Chapter 1

REVIEW

1.1 BONDS

What is the difference between ionic and covalent bonds? In inorganic chemistry we learned
about ionic and covalent bonds. In ionic bonding, electrons are lost by one element, a metal,
and electrons are gained by the other element, a nonmetal. The strongest bond is the ionic
bond. It is formed by an attraction of oppositely charged ions (electrostatic attraction).
Covalent bonding involves a sharing of electrons between two elements. In organic chemistry,
bonding is usually covalent and specifically the C-C and C-H bonds are nonpolar covalent
bonds. Covalent bonds are classified as polar or nonpolar depending on the difference of
Pauling's electronegativity values (see chart in front of text) of the two bonded atoms. If the
difference in electronegativities is less than 0.5, the bond is mainly nonpolar covalent and if the
difference ranges between 0.5 and 1.6 the bond is mainly polar covalent. Differences in
electronegativities greater than 1.6 usually means the bond is mainly ionic. To calculate the
∆en (change in electronegativity values) for a C-H bond we look below:

atom electronegativity value (env)*

C 2.5
H 2.1

∆en(change in env) = 0.4

*Pauling's electronegativity values are found opposite the front cover.

Therefore C-H is a nonpolar covalent bond.

1.2 HYDROGEN BONDS

Another type of bond, although weak, is very important in determing physical properties of
organic molecules. This bond is known as a hydrogen bond. For hydrogen bonding to occur a
H on one molecule must be bonded to either an oxygen (O) or a nitrogen (N) or a fluorine (F) of
an another molecule, as seen below:

CH 3 CH 2 CH 2 CH 2 O CH 2 CH 2 CH 2 CH 3
O: H
H
(hydrogen bond)

The net effect of hydrogen bonding is to associate molecules making the

molecule appear to have a larger molecular weight.

1
Remember the H on one molecule hydrogen bonds to a O (in this case) of another molecule.
In the examples below circle the molecules which would exhibit hydrogen bonding in the liquid
state:

a. HF b. CH3OH c . CH3OCH3 d. H2O e. CHBr3

When H is bonded to one of these atoms there is a marked increase in boiling and melting
points and increased water solubility. We can see the effect on hydrogen bonding by looking at
the boiling points of the following molecules in table 1.1. Note the molecular weight of these
molecules are essentially the same. All things being equal, i.e, no H- bonding, the usual effect of
increasing molecular weight is to increase the boiling point (bp), but in the examples below we
see an unusually high bp in the first molecule relative to the other two.

Why?_____________________________________________________

TABLE 1.1

CH 3 CH 2 CH 2 CH 2 OH CH 3 CH 2 OCH 2 CH 3 CH 3 CH 2 CH 2 CH 2 CH 3

MW: 74 g/mol 74 g/mol 72 g/mol

bp: 118°C 35°C 36°C

1.3 VALENCE

Valence is the number of bonds a NEUTRAL atom can form. Table 1-1 shows the valences
that make up what is known as the valence rules for a few of the more common elements. The
valence rules correspond to the number of electrons required to complete the elements
outershell.

Table 1-1

VALENCE RULES TO BE MEMORIZED

ATOM #BOND(S)

H 1
F,Cl,Br,I 1
O 2
N 3
C 4

Knowing the valence rules will allow you to draw molecules; for example, CH4O. In becoming
a molecular architect, you must follow some simple rules:

a) place the atom that can form the greatest number of bonds in the
middle of the molecule

2
 b) obey the valence rules

Let's see what we can now do with CH4O.

Of the atoms in this molecule, the atom that can form the greatest number of bonds is - C.
Surround the C as symmetrically as possible with the other atoms in the molecule. Obeying the
valence rules we obtain:

H C O H

Using the valence rules, draw structural formulas for: CO2, CI4, CH5N.

CO2 CI4 CH5N

1.4 LEWIS DOT FORMULA

In drawing a correct Lewis Dot formula use only the outershell (valence) electrons for each
atom. Sharing a pair of electrons indicates a single bond; sharing two pair of electrons
indicates a double bond; and sharing three pairs of electrons indicates a triple bond.

RULES:

a) Separate the molecule or ion into atoms. Place the atom that can form the
greatest number of bonds in the center of a polyatomic molecule

b) Write correct Lewis Dot formula for each atom

c) Without adding or subtracting electrons, share the available electrons so

that a stable molecule results, i.e., a full outershell of electrons should be
attained by all atoms.*

*The full outershell of electrons should occur when the shared electrons are counted
twice- once for each atom sharing those electrons.

Take a closer look at these rules in writing the correct Lewis Dot Formula (LDF) for CBr4.

3
 a) Separate the molecule into atoms

C Br Br Br Br

Based on carbon having the greatest number of bonds (valence rules), C is the middle atom and
the Br's are placed symmetrically around the C as seen below:

Br

Br C Br

Br

Are the Br’s symmetrically arranged around the C?

b) Write the correct LDF for each atom

..
: Br:
.
.. x ..
: Br . x Cx . Br:
.. ..
x
.
: Br:
..

(Where the dot(.) and the x indicate electrons)

How many electrons do we have around each Br? around the C?

c) Share electrons so that a stable molecule results, i.e., in this case 8

electrons around each atom.

..
: Br: ..
: Br:
.. . x. .. ..
: Br x C x. Br: ..
or : Br
.. .. .. C .. :
Br
x.
: Br
: Br:
.. .. :

The line between the C and Br's indicates a shared pair of electrons and is called a single bond.
The total number of electrons around each atom is 8, which means stablility. It is very
important in writing LDF for molecules or ions that we have a full outershell of electrons for
each atom.

In the molecule HI, we have no need to locate the atom that can form the greatest number of
bonds. Why?

In drawing the correct LDF for HI we would follow the steps above to the conclusion below:

4
 .. ..
steps (a) H (b)
I H (c)
I:x . H
.. ..I:

In step(a) the separation of atoms, in step(b) the writing of the correct LDF for each atom (x
and dots indicating electrons), and in step(c) the sharing of electrons to form a stable molecule,
ie., a full outershell of electrons for each atom.

Let's do another example together.

Draw the Lewis Dot Formula for C2H3Br
Let's separate this molecule into individual atoms keeping in mind we will place the atom that
can form the greatest number of bonds in the middle.

C C

Surround the middle atom(s) with the other atoms. One arrangement is drawn below:

H H

C C

Br Br

You may see another arrangement of atoms that obeys the valence rules. Draw that
arrangement in the space provided.

Is this similiar to your arrangement?

H Br

C C

H Br

Either framework is correct.

Using the framework above place bonds or electrons (dots and x's) around each atom-a correct
Lewis Dot formula for each atom. The shared electrons can be indicated with a line or bond.
How many electrons do you have around each atom?

5
If your molecule looks like the structure below you should proceed with exercise 1.1 if not
reread this section and work through each example.
..
H ..Br :
C=C ..
H Br
.. :

With either framework the two carbons share two pairs of electrons or a double bond.

Exercise 1.1

Try writing the LDF for CH4O, PF3, C2H4, and CS2.

In the molecule CO, we see for the first time a problem using valence rules to obtain the correct
Lewis Dot Formula. Let's see if we can draw a correct LDF for CO. We begin by separating
the atoms in the molecule, CO:

C O

Draw the correct LDF for each atom (a). Share the available electrons such that a stable
molecule results (b).

. x .
. x O xx . C . . x O xx
C . x x x
. xx

(a) (b)

In this correct LDF we see both C and O are sharing three electron pairs. The correct valence
bond formula has a triple bond between the carbon and oxygen.
:C O xx

How could this be? Carbon should have four bonds and oxygen should have two. Yes, if those
atoms were neutral. How can I tell if an atom is neutral? By calculating the atoms formal
charge.

1.5 FORMAL CHARGE

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All atoms are NOT neutral and when they are not neutral the number of bonds that atom can
form does NOT follow the valence rules. To determine if an atom is neutral, the formal
charge(FC) of each atom can be calculated using the following formula:

FC= no. of outershell(valence) e- - [no. bonds + no. nonbonding e-]

Let's calculate the formal charge for each atom in CO.

FC= no. valence e- -[ no. bonds + no. nonbonding e-]

FC(C)= 4 - [3 + 2] = -1

FC(O)= 6 - [3 + 2] = +1

The atoms in CO are not neutral. However the sum of all the formal charges do equal zero, i.e.,
[-1 + (+)1 = 0]. Therefore the molecule CO is neutral.

Exercise 1.2

Calculate the formal charge of the atoms in the following molecules or ions CS2, NH4+, CN-,
and OF2 as we did above.

1.6 ORGANIC CHEMISTRY

Organic chemistry is the chemistry of carbon containing compounds. The simplest organic
molecules contain only carbon and hydrogen and are therefore known as hydrocarbons.
There four classes of hydrocarbons:

A. Alkanes
B. Alkenes
C. Alkynes
D. Aromatics

1.7 ALKANES and HYBRIDIZATION

Alkanes are characterized by having only single bonds and they must obey the formula-
CnH2n+2 where n= number of carbons, i.e., if C=1 then the number of H must equal (2 x
1) + 2 or 4 and formula for the simplest alkane is:

CH4

Since they must contain ONLY single bonds, i.e., drawing a Lewis dot structure or using the
valence bond rules for the molecule CH4 provides us with the following structure:

7
 H

H C H

Please take your time to review these two methods to determine the types of bonds present in a
molecule. It is very important to remember that sharing a pair of electrons means a single
bond. Since we have four (4) shared pairs of electrons, we have four (4) single bonds.

In organic chemistry hybridization of the atomic orbitals is very important in determining the
shape of the molecule. Hybrization is determined by the number of single bonds and the
number of the nonbonding pair on the DESIGNATED atom, usually carbon. Each single bond
is formed by end to end overlap of atomic orbital. This end to end overlap is called a sigma
bond. The only other overlap of atomic orbitals involves a side to side overlap which is called a
pi bond. The orbitals that are used in bonding for most organic molecules are "s" and "p"
orbitals.
SINGLE BONDS ARE SIGMA BONDS

For the molecule, CH4, then there are four (4) single bonds, formed by four (4) end to end
overlaps, i.e., four (4) sigma () bonds. From the Lewis dot structure above, NO nonbonding
pairs are present on the C. The number of hybrid orbitals is equal to the number of sigma
overlaps plus the number of nonbonding electron pair on the designated atom, usually carbon.

#hybrid orbitals= number of sigma() overlaps + number of nonbonding electrons pair

From the Lewis Dot formula for CH4, four(4) sigma overlaps and zero(0) nonbonding electrons
are observed. Using the formula for #of hybrid orbitals above, we calculate four(4) hybrid
orbitals. #hybrid orbitals= number of sigma() overlaps + number of nonbonding electrons
pair

4 = 4 + 0

Therefore four(4) hybrid orbitals are required - one s and three p's or sp3.

1.8 HYBRIDIZATION AND THE MXE CONVENTION

From valence shell electron pair repulsion theory, VSEPR, we were introduced to the MXE
convention. The convention defines M to be the DESIGNATED OR MIDDLE atom; X is
defined be the atoms bonded to the MIDDLE atom, i.e., the ligands; E is defined to be the
number of nonbonding electron pair on the MIDDLE ATOM.

From the Lewis Dot Formula for CH4, the MXE convention is determined by selecting carbon
as the MIDDLE atom(M). Why carbon? Forms the greatest number of bonds.

8
 H
..H
H:C:H or H C H
..
H H

There are four(4) bromines (Br) bonded to M. There are no(0) nonbonding electrons on M;
therefore the MXE convention is MX4.

What is the MXE convention for NH3?

Always begin by drawing the correct Lewis Dot Formula. To be successful in solving this
problem remember to identify the MIDDLE atom and surround the MIDDLE atom with the
other atoms as symmetrically as possible. These steps lead to the following:

H ..
N H
H

Since nitrogen can form the greatest number of bonds in NH3, N is the middle atom (M). There
are three (3) atoms bonded to M and one (1) nonbonded electron pair on M. As a result the
MXE convention for NH3 is MX3E.

In the space provided determine the MXE for H2O.

Since hybrization is determined by the number of orbitals required or NOR, we can determine
the number of orbitals from the MXE convention.

X + E = NOR

If we determine a molecule to be an MX2, how many orbitals are required?

NOR = X + E = 2 + 0 = 2

Since the number of orbitals required (NOR) is 2 the hybridization is sp.

What is the hybridization for a molecule that has an MXE of MX3E? MX3?

Draw a Lewis Dot Formula and a valence bond formula for C2H6.

LEWIS DOT VALENCE BOND

9
What is the MXE convention? What is the hybridization?

In determining the number of sigma and pi bonds, note the number of bonds between two
atoms. If only single bonds exist between two atoms, only sigma bonds are present. A double
bond consists of one sigma and one pi bond and a triple bond consists of one sigma and two pi
bonds. It is very important to recall once again that hybridization of a designated atom is
determined by the number of sigma bonds NOT pi bonds and the number of nonbonding pair
of electrons.

What is the hybridization for each carbon (C) in C2H4?

__________________________________

Remembering that a double bond consists of one (1) sigma and one (1) pi bond, each carbon

has three sigma () bonds and no (0) nonbonding electron pair.The MXE convention around
each carbon is therefore MX3.

NOR= X + E = 3 + 0 = 3 hybrid orbitals

Three hybrid orbitals can be obtained by mixing an s with 2 p’s or sp2.

Exercise 1.3

Determine the MXE convention of the following molecules (hint draw the LDF first):

a. H2O

b. C2H2

c. PH3

d. NF3

10
 e. SO2

With the aid of Table 1.2 we may predict the hybridization or molecular shape or bond angle
or MXE convention.

TABLE 1.2

hybridization MXE convention shape bond angle

sp MX2 linear 180°

sp2 MX3 planar 120°
sp2 MX2E bent <120°
sp3 MX4 tetrahedral 109°
sp3 MX3E pyramidal 107°
sp3 MX2E2 bent 105°

Exercise 1.4

Since we just determined the MXE conventions for the molecules below, complete the
hybridization, molecular shape, and bond angles from Table 1.2.

MOLECULAR SHAPE BOND ANGLE

a. H2O

b. C2H2

c. PH3

d. NF3

e. SO2

1.9 RESONANCE

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In the course of drawing Lewis Dot formula, we recognize that we can sometimes draw two or
more structures of equal energy that obey all the rules of bonding. When this can be done by
simply moving electron pairs it is known as resonance. Resonance is an important concept in
organic chemistry. The more resonance structures we can draw, the more stable is the
molecule. For example with carbonate, CO32-, we first draw the correct LDF. In doing so we
see C can share 4 electrons (double bond) with all three oxygens (O).

We can see the movement of electrons below-note since CO3-2 has two extra electrons, the two
(*) indicates the electrons from the negative charge:
..
-2 : O
CO3
..
xx
x* C x*
: O : : O :
.. ..
resonance structures can be drawn by shifting electron pairs
as seen above. The results of shifting electron pairs are seen
in the valence bond structure below.

CO 3 -2
-
O O O-

C C C
- O - O - O O O O-

Note the double bond is being shared amongst three oxygen atoms. To represent
one resonance hybrid structure from the three resonance forms above, we need to
have one and one-third bonds between the C and each O, as indicated below:

O O

Since three oxygens are sharing a negative 2 charge, each O must have a -2/3
charge.

Benzene has a molecular formula of C6H6. Draw two structures having the formula, C6H6, and
obeying the valence rules below:

12
The resonance stuctures for benzene are shown below. It is very important for you to recognize
what each point in a ring structure means. In the case of benzene each point of the six
membered ring means one C and one H.

Benzene, C6H6
H H

C C
C H H C C H
H C
C H H C C H
H C C
C
H
H

I II

Which is represented without showing the C's or the H's below:

I II

Both structures seen above are equivalent. They differ only by the position of the double bonds
ie., electron pairs. Therefore for benzene we can draw two equivalent structures or two
resonance contributors. Please understand benzene is not the structure on the right or the
structure on the left of the double headed arrow and it is not half the time structure I and half
the time structure II. The actual structure of benzene is a hybrid of the two structures above.
We represent the two hybrids with one structure:

13
To understand hybrid ask yourself when a horse is mated with a donkey the product is a mule.
Is a mule a horse or a donkey? You are right it is neither it is a hybrid of both.

Exercise 1.5

Let's see if you can draw the indicated resonance structures for the following molecules: (hint
draw Lewis Dot formula first). Use the double headed arrows to indicate resonance structures.

a. SiO3-2(3)

b. N3- acyclic (no cyclic) structures, i.e., N-N-N (3)

c. CH2N2 use valence bond structure of C-N-N (2)

d. NO2- (2)

e. CH2=CHCH2+ (2)

1.10 ACID-BASE REVIEW

We will limit our review to the two most common concepts used to describe acids and bases.
They are (1) the Bronsted-Lowry concept for protonic acids and (2) the Lewis concept for
nonprotonic acids.

A. BRONSTED-LOWRY CONCEPT

14
An acid is defined as a H+ donor. A base is defined as a H+ acceptor. In the examples below we
will identify all the acids and the bases:

HCl + H2 O H3 O+ + Cl -
acid 1 base 1 acid 2 base 2

NH 3 + H2 O NH 4 + + OH -
base 1 acid 1 acid 2 base 2

Note in these two examples water is a base in one

reaction and an acid in the other. When one reactant
behaves both as an acid and a base dependent on
the reaction, it is called amphoteric.

In the reactions above the conjugate base to acid1 is base2. The conjugate acid to base1 is acid2.
What then is a conjugate? A conjugate acid2 is the base1 with one more H+. A conjugate base2
is an acid1 with one less H+. Therefore conjugate is one more or one less H+.

Let's take a look at the following reaction:

- -
OH + NH 3 H 2 O + NH 2

In the forward reaction, is OH- an acid or a base? Before you answer ask yourself what has
happened to the OH-?
The OH- has gained (accepted) a H+ to form HOH (H2O); therefore the OH- must be by
definition a base. What then is happening with the NH3?
NH3 is losing (donating) a H+; therefore NH3 is by definition an acid.

Now let's see if you can identify the acid and base reactants in the reverse reaction:

H2 O + NH 2 - NH 3 + OH -

H2O is a(n) . Why?

NH2- is a(n) . Why?

Exercise 1.6

15
Write the conjugate acids and bases for each of the following molecules:

a. NH3

b. OH-

c. HCO3-

d. HNO3

A good general rule is the stronger the acid or base, the weaker the conjugate base or acid and
vice versa. For example,
HCl + H2 O H3 O+ + Cl -

HCl is a strong acid, therefore its conjugate base, Cl-, is weak base. Since H2O is a weak base,
H3O+ is a strong acid.

B. STRENGTH OF ACIDS

The strength of a binary acid is related to the ease in which the proton (H+) is lost. We can
correlate the strength of the protonic acid to the periodic table in the following way:

As we go across a period from left to right, the strength of the protonic acid increases. For
example,

HF> H2O> NH3

As we go down a family, the strength of the protonic acid increases. For example,

H2Se > H2S > H2O

The strength of the acid is also related to the charge of the cation. The more positive the charge
the stronger the acid. For example,

H3O+> H2O > OH-

16
Table 1.3 is a short list of strong oxyacids.

TABLE 1.3

Strong acids
HClO4
H2SO4
HNO3
HClO3

We can also correlate acidity to Ka or –log of Ka which is pKa. The larger the pKa value the
weaker the acid. In table 1.4 is list of molecules and their pKa.

TABLE 1.4

Molecule pKa

RH (alkane) 50
alkene 44
ammonia 33
terminal alkyne 25
ROH (alcohol) 18
H2O 16
phenol 10
carboxylic acid 5

Remember basicity is opposite to acidity. Therefore a strong acid has to be a weak base. The
stronger the acid the weaker the base. For example, H2SO4 is a very strong acid and therefore
a very weak base.

C. LEWIS CONCEPT

According to the Lewis concept an acid is an electron pair acceptor and a base is an electron
pair donor.

N: + B N B

base acid
(electron pair donor) (electron pair acceptor)

Exercise 1.7

Indicate the Lewis acids and bases in the following reactions:

17
a. AlCl 3
+ Cl - AlCl 4
-

- +
b. BCl 3 + CH 3 OH Cl 3 B OCH 3
H
c. FeBr 3 + Br- FeBr 4 -

18
 Chapter 2

ALKANES AND STEREOISOMERS

2.1 ALKANES

Alkanes are named commonly and systematically. The common names are used for very
simple alkanes. The systematic name (IUPAC) is used for simple or complex alkanes. The very
first step in naming is to observe the organic compound and try to classify it, i.e., an alkane.
Table 2.1 will help you name alkanes.

Table 2.1
No. of C Formula Prefix Suffix Name

1 CH4 meth ane methane

2 C2H6 eth ane ethane

3 C3H8 prop ane propane

4 C4H10 but ane butane

5 C5H12 pent ane pentane

6 C6H14 hex ane hexane

7 C7H16 hept ane heptane

8 C8H18 oct ane octane

9 C9H20 non ane nonane

10 C10H22 dec ane decane

2.2 TYPES OF FORMULA ENCOUNTERED IN ORGANIC CHEMISTRY

A. MOLECULAR-ACTUAL COMBINATION OF ELEMENTS IN A

COMPOUND i.e. C4H10

B. STRUCTURAL-SHOWS ALL THE BONDS IN A COMPOUND i.e.

H H H H
H C C C C H
H H H H
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 C. CONDENSED-SHOWS NO BONDS BUT CONDENSES ABOVE TO BE

CH3 CH2 CH2 CH3

CAN YOU SEE HOW WE CAN CONVERT THE STRUCTURAL FORMULA TO THE
CONDENSED FORMULA AND VICE VERSA?

D. LINE ANGLE FORMULA-SHOW NO ATOMS ONLY LINE WHERE EACH END

AND POINT INDICATES CARBONS WITH THE APPROPRIATE NUMBER OF

HYDROGENS i.e.
All of these formula represent the same molecule. Let us see how we proceed to name it.

Below you see a structural formula of a molecule that contains 4 C and 10 H or C4H10.

H H H H Note the formula C4H10 obeys the

CnH2n + 2 formula of an alkane.
H C C C C H
Note all the bonds are single bonds,
H H H H either C-C or C-H, again an
indication of an alkane.
FROM THE TABLE ABOVE WHICH MOLECULE HAS
4 CARBONS? BUTANE
WHAT MOLECULAR FORMULA SHOULD AN ALKANE HAVE
THAT HAS 4C?

We may also name this molecule n-butane where the n stands for normal
or the straight chain.

You may also see it written as the condensed formula, OR as a line angle formula i.e.,

CH3 CH2 CH2 CH3 OR

Please take some time to understand the bonding in the condensed formula and the line angle
formula. Try to draw the structural formula and line angle formula from the condensed
formula in the following examples and name each:

Exercise 2.1

CH3(CH2)7CH3

CH3(CH2)4CH3

20
2.3 BRANCHED HYDROCARBONS AND ALKYL GROUPS

Unfortunately for most organic chemistry students all organic compounds are NOT straight
chain molecules. So how do we handle branched chains? We will use the PLS method . We
identify (1) the parent (P), the longest continuous chain of carbon atoms; (2) the location (L) of
any branch, i.e. substituent group, should always be indicated with the lowest possible number
and (3)the name of the substituent or substituents (S) group should always be given in
alphabetical order. Let's introduce our first substituent group, the alkyl groups. Alkyl groups
obey the formula CnH2n+1. See table 2.2 for some common alkyl groups.

Table 2.2

CH 3 CH 2 CH 3

METHYL ETHYL

CH 3
CH 2 CH 2 CH 3 CH
CH 3

PROPYL ISOPROPYL

How many different propyl groups C3H7, do you see?______

2.4 IUPAC SYSTEMATIC NOMENCLATURE

Rules

1. Select the longest continuous chain of C atoms and name it. This is your parent
hydrocarbon.

2. If there is branching, i.e., alkyl groups present, number the parent hydrocarbon in such
a way that the branch(es) are located with the lowest possible number(s) when the
numbering begins from an END of the parent hydrocarbon.

3. Number and name EACH substituent group.

4. For more than one substituent, use the alphabet to determine which substituent should
be written first. If the substituent groups are the same number each and use the prefix
di to indicate 2, tri to indicate 3, tetra (4), etc., i.e., 2,2-dimethylpropane

5. If the longest continuous chain can be obtained in more than one way,
choose the one that gives the greatest number of substituent groups.

2.5 NAMING THE MOLECULE FROM A STRUCTURE

Let's take a look at a few examples:

21
 C 4 H10

H H H H
H C C C C H =
H H H H

LINE ANGLE FORMULA

STRUCTURAL FORMULA

In this example there are no branches and a parent that has 4 carbons therefore the name of
this hydrocarbon is BUTANE.
C 7 H16

C C C C C C =

H C H

STRUCTURAL FORMULA LINE ANGLE FORMULA

In this example we see the longest continuous chain has 4 C so the parent hydrocarbon is an
alkane of 4 C or butane. Now look at the molecule and we see a branch, but what is the
location of the substituent group, i.e., on which C is the substituent? Numbering from the left
end, we see the substituent group is on the third C. Numbering from the right end, we see the
substituent group is on the second C. Which is lower? Yes 2 is less than 3 so our substituent
group is on C 2. The substituent group in this example is CH3- and its name is methyl. Let's
put it together.

P= parent hydrocarbon- hexane

L= location of substituent group- 2
S= name of substituent group- methyl

Name: 2-methylhexane

Let's try this one.

22
 CH 3
= CH 3 CHCHCH 3

CH 3

LINE ANGLE FORMULA CONDENSED FORMULA

P= parent hydrocarbon-butane
L= location of substituent groups- 2 and 3
S= substituent groups- methyl and methyl or dimethyl

Name: 2,3-dimethylbutane

Note how two numbers are separated and how numbers and letters are separated. Please use
commas and hyphens as you see above.

Why don't you try this one. Be careful!

IT MAY BE USEFUL TO DRAW EITHER A CONDENSED OR STRUCTURAL FORMULA

FIRST TO DETERMINE THE PARENT HYDROCARBON BELOW.

The longest continuous chain of carbon atoms is 5. Circle or box these 5 carbons. Therefore
the parent is pentane. There are two substituent groups that happen to be the same group.
What is that group? .
Locate the positions where the groups reside. Remember we are looking for the lowest number
or combination of numbers. The numbers are .
Now please name the molecule in the space below:

Name: ____________________

The correct name is 2,3-dimethylpentane.

2.6 DRAWING THE STRUCTURE FROM THE NAME

Draw the structure of pentane or n-pentane.

In the process of drawing the correct structure the first step is to determine the parent
hydrocarbon. In this case the parent hydrocarbon is an alkane containing five (5) carbons in
the longest continuous chain. We can then draw the structure. In condensed form it would
look like:

CH3CH2CH2CH2CH3
23
Let's try another one. Draw the structure of 3-ethyl-2-methylhexane.

Once again the parent hydrocarbon is an alkane containing six (6) CARBONS in the longest
continuous chain

C-C-C-C-C-C

On the third C from either end (in this case) is an ethyl group:

CH3CH2-

On the second C from the same end that now has the ethyl group on the third C is a methyl
group:

CH3-

Let's put it together.

CH 3

CH 3 CHCHCH 2 CH 2 CH 3 =
CH 2 CH 3

CONDENSED LINE ANGLE

Please try each of the exercises below.

Exercise 2.2

a. 3-methylpentane

b. 4-isopropyl-3-methyldecane

c. 2,7-dimethyloctane

d. 2,4,4-trimethylheptane

24
 e. 3, 4-diethyl-2, 3-dimethylnonane

All the bonds in an alkane are sigma bonds (how many sigma bonds?) forming a molecular
shape of a regular tetrahedron. The bond angles associated with this molecular shape is 109.5°.
Remember alkanes have bond angles of 109.5 and have sp3 hybridization. Predict the bond
angles and hybridizations of (a-d) above.

2.7 HALOALKANES

When we replace a (H)ydrogen atom with an atom or group of atoms, we can still apply the
same IUPAC rules we learned above. From the table below we can see how to name halogens
when they are a substituent group. The general rule is to use the stem of the halogen plus "o"
or halo.

Table 2.3

halogen prefix

F fluoro

Cl chloro

Br bromo

I iodo

If we replace a H in CH4 with a Br, we will have the formula CH3Br. If we draw this molecule
using valence bond or Lewis Dot formula, we will see:

H
.
H C Br

25
In naming this molecule we identify the parent, the location of any substituent group, and the
substituent group. In this case the parent is methane-only one carbon and the substituent
group is bromo.

The correct IUPAC name is BROMOMETHANE. Why is there no need for a number?

Let's name the following molecule having the molecular formula, C3H7F:
H H H
H C C C F
H H H

The parent has 3 carbons that are all singly bonded. Therefore the parent is propane. A
substituent group is located on the second carbon and the substituent group is fluoro.

P=propane
L= 1 answer: 1-fluoropropane
S=fluoro

Draw and name a different structural formula that has the same molecular formula, C3H7F.

Name the following molecule having the molecular formula, CH3CH2CHBr2.

H H Br
H C C C Br
H H H

The parent has 3 carbons that are all singly bonded therefore the parent (P) is propane. The
location (L) of the substituent groups must have the lowest possible numbers- 1 and 1 and the
substituent (S) group is bromo and bromo.

Using PLS system- P=propane

L=1,1 answer: 1,1-dibromopropane
S=dibromo

Now you try to name the following haloalkanes in exercise 2.3.

26
Exercise 2.3

a. CH3 CH2 Cl

H H H H
H C C C C H
b.
H H Br H

c. (CH 3 ) 3 C I

d. CH3 CH2 CH2 CH2 CH(F)CH 3

e. CH3 CH2 CHCl 2

Hint: It is alway helpful to see the structure, i.e., structure (b). Draw the structural formulas
of the (a, c, d, and e).

2.8 COMMON NAMES

HALOALKANES ARE NAMED COMMONLY AS ALKYL HALIDES

In order to use a common name, we must know the name of the ALKYL GROUP that is
bonded to the halogen. If we know the name of the ALKYL GROUP we can name the
haloalkane as an ALKYL HALIDE.

RULE: Name the alkyl group plus the stem of the halogen plus the letters "ide".

For the molecule CH3Br, named above using IUPAC rules as bromomethane, could also be
named as an alkyl halide. To name this molecule as an ALKYL HALIDE we must name the
ALKYL group, i.e. CH3.

27
What have we done? When a simple alkyl group is bonded to a halogen, we name the alkyl
group plus the name of the halide.

Alkanes

Simple alkanes, we can also be named commonly. For example our

first indication that common names and IUPAC names are NOT always the same occurs with
the molecular formula, C4H10. Let's draw a couple of ALKYL HALIDES AND THE
CORRESPONDING ALKANES. To show the similiarity in naming alkanes commonly with
alkyl halides, we will show a halide with a X and the ALKANE with a H.

CH3 CH2 CH2 CH2 X CH3 CH2 CH2 CH2 H

BUTYL HALIDE BUTANE

(CH 3 ) 2 CHCH 2 X (CH 3 ) 2 CHCH 2 H

ISOBUTYL HALIDE ISOBUTANE

How can we name simple alkanes commonly?

RULE: Name the alkyl group, drop the "yl" and add "ane".

How can we tell if the alkane is simple? If we remove a H, can we name the remainder of the
molecule as an alkyl group? If your answer is yes, then we can name the alkane commonly.

If your answer is no, then we canNOT name the alkane commonly. What is our only
alternative for naming in this last case? IUPAC

Exercise 2.4

Name the following molecules commonly and IUPAC.

a. CH3 CH2 CH2 I

b. CH3 CH(F)CH 3

c. (CH 3 ) 3 CBr

d. CH3 CH2 Cl

e. CH3 CH(Br)CH 2 CH3

28
2.9 REACTIONS OF ALKANES

Because alkanes are made up of very strong single (sigma) bonds, the only reactions alkanes
undergo require a source of energy. Two reactions that alkanes undergo are combustion and
free radical substitution of a halogen (Group VIIA).

Combustion
RH + O2 __∆___> CO2 + H2O

Note: (a) RH is a standard symbol of an alkane and (b) the products of a combustion reaction
are always CO2 and H2O.

Free radical Substitution of a halogen

RH + X2 __∆ or uv__> RX + HX

Note: (a) X is usually Cl or Br and (b) the presence of an energy source in both of these
reactions.

What is the energy source in combustion? .

In the free radical substitution? .

Predict the products of the following reactions:

a. CH4 + O2 __∆___>

b. CH4 + Cl2 __∆___>

Which of the preceeding reactions will produce a haloalkane (alkyl halide)?

2.10 STEREOISOMERS

A particular isomer that deals with spatial relationships is known as stereoisomerism. With
stereoisomerism there is no difference in the order in which the atoms are connected. This is
known as the molecules connectivity. In order to deal effectively with stereoisomerism we need
to define some terms.

29
An atom that is bonded to four (4) different atoms or groups is called asymmetric, stereogenic
or a stereocenter . A carbon is asymmetric or stereogenic then if C is bonded to four different
atoms or groups, as seen below:
Q CH3

X C Z Br C CH2 CH3

Y Cl

I II

C -STEREOGENIC C IS CIRCLED IN EACH CASE

Name the four different groups or atoms bonded to the stereogenic carbon in I . Do the same
for II.

A molecule that is not superimposable on its mirror image is called chiral. To be

superimposable means that we can place one thing on top of the other so that all parts of each
MOLECULE coincide or overlap, i.e., one tube sock on top of another tube sock
or one tea spoon on top of another tea spoon. Now take your left hand and hold it up to your
right hand. Try to place your left hand or a left handed glove over your right hand or vice
versa. Are your hands superimposable? No. Since the mirror image of your left hand is your
right hand and they are NOT superimposable, they are chiral. If they were superimposable we
would call them achiral.

Exercise 2.5

Classify each as chiral or achiral.

a. shoe

b. knife

c. ear

d. a cross country ski

Stereoisomers can be divided into two categories: enantiomers and diastereomers. Two molecules
that are nonsuperimposable, mirror images are called enantiomers or an enantiomeric pair-two
stereoisomers. Twomolecules that are nonsuperimposable, nonmirror images are called
diastereomers or diasteromeric pairs-two stereoisomers. Two molecules that are superimposable,
mirror images are called meso compounds and are identical, one stereoisomer.

In order to aid us in looking at stereoisomers it is very helpful to make models.

30
 CH3 CH2
CH2 CH3
Cl C CH3
CH3 C Cl
H H

I II

Structures I and II are nonsuperimposable mirror images of 2-chlorobutane and as such are
enantiomers.

It is useful to recognize the need for an asymmetric or stereogenic C in many stereoisomers. In

fact the number of stereoisomers theoretically possible are determined by the number of
stereogenic carbon atoms (n) in the following formula:

maximum stereoisomers theoretically possible (TNS) = 2n

(where n is the number of asymmetric C or stereocenters)

For example if we have two asymmetric or stereogenic carbon atoms, i.e. n=2, the maximum
number of stereoisomers that are theoretically possible (TNS) is:

TNS= 2n = 22= 4

Exercise 2.6

Of the molecules below star (*) the carbon which is a stereogenic (asymmetric) and calculate
the maximum number of stereoisomers theoretically possible:

31
 CH2 Cl
Br H
a. C
CH3

CH2 Cl
H H
b. C
CH3

CH2 CH3
Br F
c. C
CH3

We calculate the theoretical number of stereoisomers (TNS) because meso compounds count
for only one stereoisomer. To avoid errors draw or make models of each stereoisomer to see if
a meso compound is present. Many times the actual number of stereoisomers is different than
the TNS.

2.11 Fischer Projection

Instead of using dashs and daggers as we did above, we will adopt the Fischer convention for
future molecules. The Fischer convention assume the bonds coming out (daggers) are on the
horizontal line and those in the plane and going back in the plane (dash) are on the vertical line.
For example,

CH3
CH3
H Cl = H Cl
C
CH2 Cl
CH2 Cl

tetrahedral shape Fischer projection

In the Fischer model above there is a carbon atom at the junction of the horizontal and vertical
lines.

IS THIS CARBON ATOM STEREOGENIC? To answer this question correctly we must

determine if four (4) different atoms and/or groups are bonded to this carbon. Clearly we see
H and Cl are different, but is CH3 different from CH2Cl? The answer is yes. On one C we have
3 H’s and on the other C we have 2 H’s and 1 Cl.

32
In the examples below we examine butane and 2-chlorobutane for stereoisomerism. Note how
we draw the mirror images and examine each molecule for stereogenic carbon atoms.

a. C4 H10

CH2 CH3 CH2 CH3

H H H H
CH3 CH3

The mirror images are superimposable

Note: NO assymetric carbon atoms

b. C4 H9 Cl

CH2 CH3 CH2 CH3

H Cl Cl H
CH3 CH3

The mirror images are NOT superimposable-enantiomers

Note: ONE assymetric carbon atom

Exercise 2.7

Draw all the stereoisomers of the following molecules and indicate an enantiomeric pair with
the letters "ep" and meso compounds with the letters "mc" :

Hint: It may be helpful to first calculate the maximum number of stereoisomers theoretical
possible.

a. 1,2-dichloropropane

b. 1,2,3-tribromopropane

33
 c. 1,2-dibromo-3-chloropropane

d. bromofluoroiodomethane

2.12 MULTIPLE STEREOGENIC CARBONS

If a molecule contains more than one STEREOGENIC carbon atom (stereocenter), each
stereocenter must have an absolute configuration, R or S. Let's take a close look at 2,3-

CH3 CH3

H Br Br H

H Br Br H

CH3 CH3

I II
dibromobutane below:

MAKE MODELS OF EACH STEREOSTRUCTURE AND ANSWER THE FOLLOWING

QUESTIONS.
What is the relationship of I and II?

They are mirror images that are superimposable. This is a meso compound.

What is the relationship of III and IV?

CH3 CH3

H Br Br H

Br H H Br
34
CH3 CH3
III IV
They are mirror images that are not superimposable. They are an enantiomeric pair.

What then is the relationship of I (or II) with III? with IV? They are nonmirror images with
the same connectivity and obviously not superimposable. They are each known as
diastereomeric pairs, i.e., I (or II) and III or I (or II) and IV.

One way to determine meso compounds is to look for a plane or point of symmetry within each
Fischer model. If we look closely at stereostructures I and II, we see such a plane. Please take
a close look do you see that the top half of the molecule is a reflection of the bottom half of the
molecule?

Maybe the following will help.

CH3 CH3

H Br Br H

H Br Br H

CH3 CH3

I II

The horizontal dashed line reflects the top half (above the dashed line)
on the bottom half of the molecule, i.e. a plane of symmetry. Whenever
a plane or point of symmetry is detected, you have a meso compound.

2.13 NAMING STEREOISOMERS BY ABSOLUTE CONFIGURATION

RULES:

1. ASSIGN PRIORITIES BASED ON ATOMIC NUMBER-THE HIGHER

THE ATOMIC NUMBER THE GREATER THE PRIORITY
2. ROTATE THE MOLECULE SO THE GROUP OR ATOM THAT HAS
THE LOWEST PRIORITY IS FURTHEST FROM YOUR EYE
3. OF THE REMAINING GROUPS OR ATOMS THAT ARE CLOSEST TO
YOUR EYE DETERMINE IF ROTATING FROM HIGHEST PRIORITY
TO LOWEST PRIORITY IS CLOCKWISE OR COUNTERCLOCKWISE.
IF THE ROTATION IS CLOCKWISE ASSIGN AN “R” TO THE
STEREOGENIC CARBON AND IF IT IS COUNTERCLOCKWISE
ASSIGN A “S” TO THE STEREOGENIC CARBON

35
Using the rules above, assign an absolute configuration to each stereogenic carbon in the
following stereoisomer.
CH3

H Br

H Br

CH3

Let’s begin with the circled (arrow pointing to) stereogenic carbon.

Following the rules we must first assign priorities based on atomic number around the
stereogenic carbon. Let’s look at the stereostructure redrawn below:

H
H C H

H Br

H C Br

CH3
Of the four groups/atoms bonded to the stereogenic C, the top priority is Br. What’s next? To
determine which group has the next highest priority we look for the first point of difference.
As we see the stereogenic C is bonded to C in the up or down direction-no difference. We see
the top C is bonded to H(underlined) whereas the bottom C is bonded to a Br (underlined).
This is our first point of difference. Now which has a higher atomic number Br or H? Br
(CAN WE SEE ANOTHER POINT OF DIFFERENCE?)

So our next priority is the group (G) below the stereogenic carbon.
H CBr
= G
CH3
Our priority is now set: Br> G> CH3 > H

CH3

H Br

36
 CH3 CH3

H Br
Br G
G
Secondly we must now rotate the group of lowest priority, i.e. H, so that it is furthest from our
eye.

CH3

Br G

Thirdly we must now trace the remaining groups (not H) from highest priority to lowest
priority.

THE PATH TRACED (SEE ARROW) IS COUNTERCLOCKWISE AND WE NOW CAN

ASSIGN A “S” ABSOLUTE CONFIGURATION FOR THIS STEREOGENIC C.

ASSIGN AN ABSOLUTE CONFIGURATION AROUNG THE SECOND STEREOGENIC

CARBON (*C) IN THIS MOLECULE.

CH3 G
H Br
= H * Br
H * Br
CH3
CH3
CH3

WHERE G= H Br

Following the rules the priority would be: Br > G > CH3 > H

Rotating the lowest priority (H) furthest from our eye would yield the following:
G Br G

H * Br =

CH3 CH3

Now tracing the remaining groups/atoms from highest priority to lowest priority we

Br G

CH3

37
determine the *C to be “R”.

We can now name I as (2S, 3R)-2,3-dibromobutane. Since II is the mirror image of I, the name
should be (2R, 3S) -2,3-dibromobutane. Verify this name by drawing this dibromobutane as a
Fischer projection below and analyze it as we did above:

In assigning absolute configuration to III, we once again must prioritize each stereocenter, ie.,
stereogenic C. As with I and II the second highest priority belongs to a group of atoms we
designated "G".

CH3 CH3
H * Br
= H * Br
Br H G
CH3

WHERE G= H Br

CH3
1) According to rule the priority would be: Br > G > CH3 > H

2) Rotating the atom or group of lowest priority to a position furthest from our eye we obtain:

CH3 Br CH3
H * Br =

G
G

3) Tracing the remaining groups (not the lowest priority,i.e. H) from highest to lowest priority-
Br CH3

we obtain a “S” absolute configuration.

38
Let’s list the steps to determine the absolute configuration of the second stereogenic C of
structure III.

1. ____________ 2. ______________ 3. _________________

The correct answers above should be:

1. PRIORITIZE-based on atomic number i.e. the higher the atomic number the higher
priority
2. ROTATE so the lowest priority is furthest from our eye
3. TRACE the remaining atoms/groups from highest to lowest priority.

MAKE A MODEL AND DETERMINE THE ABSOLUTE CONFIGURATION OF THE

SECOND STEREOGENIC CARBON OF STRUCTURE III.

We should find the second stereogenic carbon to also have an “S” absolute configuration.

We would name structure III (2S,3S)-2,3-dibromobutane. Since structure IV is the mirror

image of III, we would determine structure IV to be named (2R,3R)-2,3-dibromobutane.
Verify this name.

Exercise 2.8

In each of following molecules, draw all the stereoisomers indicating which are enantiomers,
diastereomers or meso compounds. It is always useful to calculate TNS. Name each
stereoisomer with a R or S as indicated. Hint: draw each stereoisomers using the Fischer
projection.

a. 1-bromo-2-chloropropane

b. 2-bromo-3-chlorobutane

c. 2,5-dichlorohexane

39
2.14 OPTICAL ACTIVITY

When plane polarized light is passed through a polarimeter, an optically active substance
causes some light to pass through the polarimeter. In order to restore a dark field, common to
optically inactive substances, the polarimeter must be rotated. If the rotation is clockwise, the
optical activity is described as being dextrorotatory (D) or (+) . If the rotation is
counterclockwise, the optical activity is described as being levorotatory (L) or (-). The
direction and the angle of rotation is called its optical activity. Chiral molecules exhibit optical
activity. If for example pure (2S,3S)-2,3-dibromobutane rotates plane polarized light -53.5°,
then (2R,3R)-2,3-dibromobutane will rotate plane polarized light +53.5°. Equal mixtures of
each stereoisomer will not rotate plane polarized light and is optically inactive, and is known as
a racemic mixture.

Exercise 2.9

Indicate which of the following stereoisomers are optically active and which would are optically
inactive:

a. (2S,3S)-2,3-dichlorobutane

b. (2R)-2-iodobutane

c. 1-iodobutane

40
1. equal mixture of 2R and 2S-2-fluorobutane

e. isopropyl bromide

41
 Chapter 3

ALKENES

3.1 THE CARBON-CARBON DOUBLE BOND

Not all molecular shapes formed by bonding carbon atoms are tetrahedral. Nor are they
always singly bonded. A new class of hydrocarbons are formed when at least one carbon-
carbon double exists in the molecule and obeys the formula CnH2n. This new class of
hydrocarbon is known as an alkene. The simplest alkene has the formula C2H4. The structural
formula would look like:

H H
C=C
H H

3.2 MXE CONVENTION AND HYBRIDIZATION

This molecule would be of the MX3 type (see table 1.2) and it's molecular shape would be a
planar triangle with bonds angles of 120°. The hybridization on either carbon atom would be
sp2.

Draw the Lewis Dot formula for C2H4.

Exercise 3.1

Using your knowledge of the valence rules and Lewis Dot formula's, draw the following
straight chain or acyclic molecules:

a. C3H6

b. C4H8

3.3 NOMENCLATURE

42
 A. COMMON

In naming alkenes it is once again imperative to identify the parent. In this case the parent is
the longest chain of continuous carbon atoms that contains a carbon-carbon double bond.

The rule for naming alkenes commonly are:

STEM OF THE PARENT + YLENE

In naming C2H4 commonly, we must identify the parent. The identity of the parent comes from a
2 C hydrocarbon. Why 2 C? The longest continuous chain of C's containing the carbon-carbon
double has 2 C. The prefix of a 2 C parent is ETH. If this is unclear see section 2.1 in chapter 2.
The rule states we must add the letters "y l e n e " and the derived name is:

ETHYLENE

B. SYSTEMATIC OR IUPAC NAME

Using the IUPAC nomenclature, the alkene is named by using the prefix to indicate the longest
continuous chain of carbon atoms containing the double bond, THE PARENT, plus the ending
"ene".
STEM OF THE PARENT + ENE

In naming C2H4 above, it very helpful to draw the structure using either Lewis Dot formula or
valence rules. Once drawn it is easy to see the longest continuous chain of carbon atoms
containing the carbon-carbon double bond is two (2). What is the prefix for the parent with
two carbons? ETH. When we add "ene", the name becomes:

ETHENE

Using the common and IUPAC rules, name the straight chain alkene having the molecular
formula C3H6. (Hint: draw the molecule)

common name:

IUPAC name:

For the straight chain alkene having the molecular formula C4H8, we run into our first problem
with position of the carbon-carbon double bond. In (I) we see the double bond between the

43
first and the second carbon. In (II) we see the double bond between the second and the third
carbon. How do we name them?

H2 C=CHCH 2 CH 3 CH 3 CH=CHCH 3

I II

In both (I) and (II), the parent has 4 C. What is the prefix that indicates four carbons (4 C)?
The prefix is but, pronounced BUTTE. The ending that we add to all alkenes is ENE. Putting
the prefix and ending together we come up with the parent name- BUTENE. But how do we
distinquish (I) from (II)? By numbering the position of the carbon-carbon double bond.
Remember give the double bond the lowest possible number.

So (I) is named: 1-butene and (II) is named: 2-butene.

Exercise 3.2
Draw and name three (3) straight chain alkenes with the molecular formula C6H12 below:

Unfortunately not all alkenes, like alkanes, are straight chained. Like alkanes, alkenes can also
have branched chains. Below we have drawn several alkenes. Circle those alkenes that are
branched.

CH 3

CH 3 CH=CCH CH 3 CH=CHCH CH 2 =CHCCH 3

3 3

CH 3 CH 3

I II III

3.4 MORE ALKYL GROUPS

It is once again very important for us to know the names of the substituent groups. Review the
alkyl groups in Table 2.2 and learn the alkyl groups in Table 3.1.

TABLE 3.1

44
 CH 3 CHCH 2
CH 3 CH 2 CH 2 CH 2
CH 3
butyl isobutyl

CH 3

CH 3 CHCH 2 CH 3 CH 3 C

CH 3
sec -butyl tert or t -butyl

It is important for you to understand that each of these groups are bonded to the parent at the
extended bond( ). For example, 4-ethyl-5,5-dimethyl-2-hexene would look like the following:

CH 3 CH 2 CHCH=CHCH 3

H3 C C CH 3

CH 3

The correct name is 4-ethyl-5,5-dimethyl-2-hexene and NOT 4-t-butyl-2-hexene. If this is

causing a problem review the IUPAC rules for alkanes. (see section 2.4 in Chapter 2)
The location of the alkyl group(s) is/are numbered from the C=C, which should have the lowest
possible number.

What is the lowest possible number for the double bond in the following line angle formula?
Name this alkene.

3.5 TYPES of CARBON ATOMS

Let's take a closer look at the substituent group in the molecule 4-t-butyl-2-heptene. The
parent 2-heptene is placed within the rectangle below.

CH 3 CH 2 CH 2 CHCH=CHCH 3

H3 C C CH 3

CH 3

45
The the circled carbon below of the substituent group is bonded to three other carbons (CH3's).

CH 3 CH 2 CH 2 CHCH=CHCH 3

H3 C C CH 3

CH 3

When one carbon is bonded to three other carbons, that type of C is said to be tert or (t) and is
indicated as- 3° C.
A secondary carbon or sec carbon atom is a carbon atom bonded to two other carbons and is
indicated as- 2°C.
A primary carbon is a carbon atom bonded to only one other carbon and is indicated as- 1°C.
In the molecule below we can clearly see 1° and 2° carbon atoms.

IF THE TYPE OF CARBON IS DIFFICULT TO DETERMINE, LOOK AT THE

STRUCTURAL FORMULA AND ASK YOURSELF HOW MANY CARBON ATOMS ARE
BONDED TO EACH CARBON.

If there is only one carbon atom in a molecule, i.e. CH4, we see no other carbon atoms are
bonded to the C of CH4. This is known as a methyl carbon.

3.6 ALKYL HALIDES AND ALKENYL HALIDES

When the extended line ( ) of the alkyl groups defined in Table 3.1 are connected to a halogen,
the molecule is commonly named as an alkyl halide. For example butyl iodide is represented
below:

CH 3 CH 2 CH 2 CH 2 I or CH 3 CH 2 CH 2 CH 2 I

Which alkyl group in Table 3.1 will have the extended bond ( ) on a 2° C?
on a 3° C?

Recalling that alkyl halides (section 2.6 in chapter 2) can also be named as haloalkanes
(IUPAC), what is the correct IUPAC name for butyl iodide?

For example we could name the following either as a haloalkane or an alkyl halide:

a. CH 3 CH 2 CH 2 Br

b. CH 3 CH 2 CH 2 Cl

46
From chapter 2, (a) is named 1-bromopropane.
Now name 1-bromopropane as an alkyl halide (common name):

When named as an alkyl halide, (b) above is named propyl chloride or n-propyl chloride.
Name propyl chloride as a haloalkane:

Exercise 3.3

See if you can now draw the structural formulas of:

a. isopropyl iodide b. sec-butyl fluoride c. t-butyl bromide

It is very important to recognize groups that contain a carbon-carbon double bond. In table
3.2, we see two very important alkenyl groups.

TABLE 3.2

CH 2 =CH vinyl or ethenyl

CH 2 =CHCH 2 allyl or propenyl

We are now able to name the following molecule commonly or IUPAC:

H2C=CHBr

Using IUPAC we name as a haloalkene. We first need to identify the parent. The parent has
two carbons in the longest continuous chain that contains the C=C. The parent is ethene. The
location of a substituent group is on carbon 1(can it be any where else?) and that substituent
group is bromo. The correct IUPAC name is:

BROMOETHENE

For simple molecules named commonly, we name the molecule as an alkenyl halide. The
alkenyl group is vinyl and the halide is bromide. Our correct common name is:

VINYL BROMIDE or ETHENYL BROMIDE

Draw the ethyl group and the vinyl group below:

47
What is the difference between the ethyl group and the vinyl group?

Draw the propyl and allyl groups. What is the difference?

Exercise 3.4

Name each of the following as a haloalkene (IUPAC) and WHEN possible, name as an alkenyl
halide (COMMON).

a. CH 2 =CHCH 2 Br

b. FCH 2 CHCH=CH 2

CH 3

c. CH 3 CH 2 CHCH=CH 2

CHCH 3

CH 2 I

d. CH 2 =CHCl

In the exercise 3.4(c), the parent containing C=C is 5, which can be obtained in different
continuous carbon chains. The correct chain is illustrated below?

CH 3 CH 2 CHCH=CH 2

CHCH 3

CH 2 I

Remember the nomenclature rules when the longest chain can be obtained in more than one
way. (See chapter 2 section 2.4)

It is useful at this point to recognize that alkanes may bond so that a straight chained (acyclic),
branched chained, or cyclic molecule may result. If a cyclic molecule results, it will obey the

48
formula CnH2n. This is the same formula for alkenes. What is the reason we see the same
formula?

_____________________________________________________________________

3.7 CYCLOALKANES AND ISOMERS

The two isomers for the molecular formula C3H6 are drawn below:

C3H6
CH 2

CH 3 CH=CH 2 and H2 C CH 2

The valence bond structures and the Lewis Dot Formula are correct. It is also obvious these
structures are different, i.e., constitutional isomers.

Remember molecules that have molecular formulas that obey CnH2n can be arranged as straight
chains, branched chains, or in the case where C is greater than 2, in cycles.

DRAW TWO CYCLIC ISOMERS OF C4H8 (THINK)

Exercise 3.5
Draw four (4) isomers for molecular formula C4H8.

a. b.

c. d.

3.8 NOMENCLATURE OF CYCLOALKANES

49
In naming cyloalkanes, we use the prefix "cyclo" plus the parent ringed alkane. For example
the cycloalkane above having the molecular formula- C3H6 is named cyclopropane. Why is it
propane? How many carbons do we have in the ring? Yes, 3.
In Table 3.3 the common cycloalkanes are drawn using the conventional shapes of these
molecules. Mentally picture a CH2 unit at each corner. Therefore, the conventional shape of
cyclopropane, C3H6, is a triangle, seen below.

Each point represents a CH2 unit.

TABLE 3.3

#C SYMBOL NAME

4 cyclobutane

5 cyclopentane

6 cyclohexane

8 cyclooctane

If the molecule is complex, we may need to name the "cyclo" as substituent group. In this case
the substituent group is a cycloalkyl. For example,

CH 2 CH 2 CH 2 Br

We would locate the parent by selecting the longest continuous chain of carbon atoms in the
straight chain (no rings). Using the PLS system we find:

P=propane
L=1,3
S= bromo and cyclopropyl

The accepted IUPAC name would be:

50
 1-bromo-3-cyclopropylpropane

Why 1-bromo and not 3-bromo? Because B comes before C in the alphabet. A general rule
that would be very useful to remember is- if two substituent groups, each having the same
priority, i.e., alkyl groups and halogens, having the same combination for lowest possible
location, the substituent that comes first in the alphabet will receive the lowest number.

All things equal, alphabetically ethyl take precedence over methyl.

All things equal, what would come first sec-butyl or fluoro? ?

REMEMBER TO USE GROUP NAMES NOT PREFIXES TO DETERMINE ALPHABETIC

ORDER AND ITALIZED PREFIXES ARE OMITTED FROM ALPHABETICAL
CONSIDERATION.

Alphabetically which would come first ethyl or dimethyl? ethyl

Look at the following examples.

FCH 2 CH 2 CH 2 Cl CH 2 CH 2 CH 2 Cl

(a) (b)

In naming (a) we recognize the parent as propane and two halogen substituent groups. No
matter which way we number, the substituents are on carbons 1 and 3. Which do we number 1
and which do we number 3? Obviously there is no priority difference between halogens or for
that matter between alkyl groups and halogens. So what do we use as a discriminator? The
alphabet. Therefore we would name (a):

P=propane; L=1,3; S= chloro, fluoro

name: 1-chloro-3-fluoropropane

Name (b).

Exercise 3.6

51
Name or draw, whichever is missing, the following molecules:

STRUCTURE NAME

CH 2 =CHCH 2

CHCH=CHCH 3

Br

3-ethyl-2-iodohexene

3.9 ANOTHER TYPE OF ISOMER

A. GEOMETRIC OR CIS/TRANS ISOMERISM

Whenever we see a molecule containing a C=C (an alkene) or cycloalkane, another isomerism
may exist. Since molecules of this type are rigid, unable to rotate freely, we are able to further
identify the atoms position relative to the C=C or the ring. If the same atoms are on the same
side of a plane passing through the C=C or the same side of a plane passing through a C-C of a
cycloalkane, we call this a cis form or simply cis.

If on the otherhand the same atoms are on the opposite side of this plane, they are known as the
trans form or simply trans.

X X X Y
plane C=C C=C plane
Y Y Y X

cis trans

How do we know when we have the possibility of cis-trans isomerism? We must look at our
alkene or cycloalkane very carefully. We must focus on the C=C or the ring itself. In order for
cis-trans isomerism to occur, the molecule must be in the form:

X X
X X

C=C or
Y Y Y Y
where X is different than Y

To determine the possibility of cis/trans isomerism with the examples below perform the
following steps:

52
 CH 3 CH 3 CH 3 H
C=C C=C
H H CH 3 CH 3

1 2

1. FOCUS ON THE CARBONS OF THE C=C. Enclose those C's.

Draw a line that passes through those C atoms.

CH 3 CH 3 CH 3 H
C=C C=C
H H CH 3 CH 3

1 2

2. CIRCLE THE GROUPS, other than the H’s, bonded to each C of the
C=C. We see two different groups or atoms on each C, i.e. CH3 and H.
In example 1, we see that each C has the same two different groups or
atoms. In this case, we see both CH3‘s above the line we have drawn
(----) and we have two H’s below the line we have drawn. We have
geometric isomerism.

We would name this molecule (cis)-2-butene NOT just 2-butene.

In structure 2, the groups bonded to each C of the C=C have been circled. On one carbon atom
there are two different groups or atoms ( CH3 and H). On the other carbon, there are the same
two groups, i.e. two CH3’s. If one carbon of the C=C does NOT have different groups or atoms
bonded to it, there is no cis-trans isomerism. So structure 2 is named:

2-methyl-2-butene.

Exercise 3.7

Draw the structure for trans-2-butene.

Circle the following molecule(s) that would exhibit cis-trans isomerism and name each:

CH 3 H H CH 2 CH 3
a. b. C=C
H CH 2 CH 3
H CH 3

53
The question arises as to naming a molecule that contains C=C that has four different groups
or atoms bonded to the two carbons. Let's take a look at this type of molecule.

a c CH3 CH2 CH 3
C=C i.e. C=C
b d H Cl

where a,b,c, and d

are all different atoms
or groups

B. E-Z Nomenclature

In using the E-Z nomenclature we need to prioritize atoms and groups by atomic number. If
the atomic numbers are the same continue along the group until you see the first point of
difference. In the example above, on one C of the C=C, we see a CH3 and a H. Which has a
higher atomic number C ( CH3) or H? Yes, C so CH3 has a higher priority than H. On the
other C, we see Cl and CH2CH3. Which has a higher priority Cl or C (CH3CH2)? Yes, Cl, so Cl
takes priority over CH2CH3. Now, as before enclose each C of the C=C and draw a line
through these two carbons.

CH3 CH2 CH 3
C=C
H Cl

The top priorities on each C are on opposite sides of the line (circled groups). When our top
priorities are on opposite sides of the plane (line), we identify that geometry as E (entgegen) and
if the top priorities are on the same side, we identify that geometry as Z (zussamen). The name
of this molecule is:

(E)-3-chloro-2-pentene.

Exercise 3.8

Draw (Z)-3-chloro-2-pentene.

What would we do if we had a molecule where the groups or atoms on each carbon of C=C
were different but one atom or group on each carbon was the same? Below we see an example,

54
 X X CH 3 CH 3
C=C C=C
Y Z H CH 2 CH 3

Each C of C=C has a common

group, i.e. CH 3

After circling the CH3's, we still have to prioritize the groups and atoms to be able to use the E-
Z system. Which has a higher priority CH3 or H? CH3. Which has a higher priority CH3 or
CH2CH3? Look for the first point of difference. In CH3 we see C bonded to 3 H and in CH2CH3,
we have C bonded to 2 H and 1 C. Therefore our of first point difference occurs between a
CH2-H and a CH2-C. Therefore we must decide what takes priority C (atomic number=6) or H
(atomic number=1). Our answer is C. So CH2CH3 takes priority over CH3. You may name this
molecule using either the cis/trans designation or the E/Z designation. How would you name
this molecule?

____________________________________________

(THE CORRECT NAME IS CIS OR E-3-METHYL-2-PENTENE)

Exercise 3.9

Name the following molecules:

I Cl
a. C=C
H Br

H CH 3
b. C=C
Cl CH 2 CH 3

H CH(CH 3 ) 2
c. C=C
CH 3 CH 2 CH(CH 3 ) 2

3.10 CONFORMATIONS OF CYCLOHEXANE

Unlike configurations which involves breaking bonds and moving atoms to provide different
stereostructures, conformations involve only rotating bonds without ever breaking bonds. For
example, ethane, C2H6, can rotate around a single C-C. Two conformations may result as seen
below:

55
. C C
C C

eclipsed conformation staggered conformation

Get a set of models and rotate C-C of ethane and prove this to yourself.

In looking at cyclohexane, we see the same conformations, eclipsed and staggered, as a result of
rotating a C-C in the cyclohexane molecule. The names of these two conformations of
cyclohexane are a "boat"(eclipsed) and a "chair"(staggered).

MAKE A MODEL OF CYCLOHEXANE AND SEE IF YOU CAN ARRANGE THE

MOLECULE SO ALL BONDS ARE ECLIPSED AND THEN TRY FOR THE STAGGERED
ARRANGEMENT.

CYCLOHEXANE
EACH POINT
IS A UNIT OF CH 2

CHAIR BOAT

EQUATORIAL =
AXIAL =

It is important to know that the staggered conformations are the most stable form. The
staggered conformation of cyclohexane is the chair form. For substituted cyclohexanes, the
group or atom other than H should occupy the equatorial position. For example there are two
possible chair arrangements for trans-1,2-dimethylcyclohexane.

56
 H CH 3 H H

CH 3
H
CH 3
H
H H
H CH 3
II
I

It is important for you to recognize both arrangements are in the chair form. Both structures
are trans. By circling the two C's as before one H is up and one H is down on each
conformation. If you are having difficulty seeing this with the chair conformation, the bond
that is not up is down and vice versa. On conformation (I), we have a CH3 up (axial), on the
top C, and down (axial), on the bottom C. That would infer that the H's that are down on the
top C and up on the bottom C. Now you try the same reasoning on conformation (II). What's
up? What's down?

Arrangements on whichever conformation, I or II, has CH3 groups on opposite sides, CH3 up
on one C and down on the other.
down
CH 3
CH 3

up

Groups on opposite sides means-TRANS. The most stable conformation is the one that has the
substituent groups, R, (not H) in the equatorial positions.

axial up CH 3 equatorial down

H

H CH 3
H
CH 3
CH 3 axial down H equatorial up
I II

Which structure is the most stable I or II?_____ The most stable conformation is II. In
choosing the most stable conformation, the general rule is (a) chair conformations are more
stable than the boat conformation and (b) the most stable chair conformations are those in
which the largest group is in the equatorial positions.

If a disubstituted cyclohexane has a t-butyl group and a n-propyl group and only one can
occupy the equatorial position, which one should be placed equatorial? The t-butyl is a larger
group than the n-propyl group. Therefore the t-butyl should occupy the equatorial position.

57
Draw a trans-2-isobutyl-1-butylcyclohexane below:

The isobutyl group should preferentially occupy the equatorial position.

Exercise 3.10

Circle and name the most stable conformations in the two examples below.

CH 3 CH 3

OR H3 C

CH 3

C(CH 3 ) 3 CH 3

OR

CH 3 C(CH 3 ) 3

Exercise 3.11

Draw the most stable conformation of each of the following.

a. cis-1,3-dimethylcyclohexane

b. trans-4-ethyl-1-isopropylcyclohexane

58
3.11 PREPARATION OF ALKENES

We will introduce you to three methods to prepare an alkene. A more detailed account of how
this occurs can be found in Chapter 6.

A. Dehydrohalogenation- this reaction involves a loss of a H atom

and a halogen (X) atom from adjacent carbon atoms with a
strong base, :B.

H
alcohol -
C C + :B C C + BH + X
²
X

Cl CH 3 H
EtOH C C
CH 3 C CH 2 + NaOH
² H
H
H H

B. Dehydration- this reaction involves the loss of a H atom and an

OH group from adjacent carbons with a strong acid, H+.

+
C C + H + C C + H OH + H
²
H OH

H OH
CH 3 H
CH 3 CHCH + H2 SO 4
2 ² C C
or H H
H3 PO 4

C. Dehalogenation- loss of a halogen (X2) molecule from adjacent

carbon atoms, a vicinal or vic dihalide, with Zn.

acetic
C C + Zn C C + Zn X 2
acid
X X
                              a vicinal dihalide

59
 H3 C H
HOAc
CH 3 CHCH + Zn C=C
2
H H
Br Br

OPTIONAL EXERCISE

Write a reaction that will produce an alkene from the following:

a. from a primary (1°) alkyl halide

b. from a primary alcohol (ROH)

c. from a vicinal dihalide

3.12 REACTIONS OF ALKENES

Reactions of alkenes are mainly addition reactions. The addition occurs across the π bond
leaving only sigma bonds. How do these reactions differ from those of the alkanes or
cycloalkanes?

ALKANES REACT BY

CYCLOALKANES REACT BY

A. SYMMETRIC ADDITIONS

1.Homogeneous addition reactions

Homogeneous reactions involve the addition of atoms that are

identical across the π bond of a C=C.

60
 a. Hydrogenation-addition of H2 across the π bond. The addition of H2
occurs on the same side (syn) of the molecule.

Pt
C=C + H-H C C
or Ni
H H
                                               SYN ADDITION
CH 3 CH 3
H3 C CH 3
Pt
C=C + H-H Cl C C CH 3
Cl CH 3 H H

b. Halogenation- addition of X2 across the π bond. Note X2 can only be Cl2

or Br2. The addition of X2 occurs on opposite sides (syn) of the molecule.

X
Pt
C=C + X -X C C
or Ni
X
(X=Cl or Br) ANTI ADDITION

CH 3 Br
H3 C CH 3 CCl 4
C=C + Br-Br CH 3 C C CH 3
H3 C CH 3
Br CH 3

When we add the orange bromine to an alkene, the orange color of the bromine solution fades
to a colorless product. This is a test for unsaturation i.e. a carbon-carbon multiple bond-an
alkene or alkyne(Chapter 4). We should also note that chlorine will react with an alkene, but it
does NOT have a color change. Therefore only the addition of the halogen, Br2, to an alkene
can be considered a test for unsaturaturation.

B. UNSYMMETRIC ADDITION AND MARKOWNIKOV’S RULE

2. Heterogenous addition

Heterogenous addition involves the addition of different atoms

across the π bond of C=C.

a. Hydrohalogenation-addition of a molecule HX across π

bond (where X= F, Cl, Br, or I).

C=C + HX C C X

61
 H CH 3 H CH 3
C=C H C C Cl
H + HCl
H
H H
major product

The question that arises often in the example above is "why is there a major product"? The
answer is that any time two or more products are possible, one of those products may
predominate over the others, i.e. major product.

In the example above, draw other product that could form?___________________________

Could we predict the major product? Yes.

MARKOWNIKOV’S RULE

An excellent way to predict the major product is to use Markownikov's experimental results.
Markownikov found that on unsaturated systems like alkenes the least electronegative element
will always go to the carbon of the C=C that has the most H's. Economically, it is said "money
goes to money". In organic chemistry the C that has the most H's gets the least electronegative
atom. Often the least electronegative atom is H. So we may rephase Markownikov's rule to be,
the C with the most H's (directly bonded to the C) gets the H or simply "them that has gets".
Let's apply this rule to the following examples.

2H

H CH 2 CH 3 H H
C=C + HBr H C C CH 2 CH 3
H H
H Br

1H

H CH 2 CH 3 CH 3 CH 3
C=C + HI H C C CH 2 CH 3
H3 C CH 3
H I

H CH 3
H CH 3
C=C + HF H C C CH 3
H CH 3
H F

Exercise 3.12
62
Complete the following reactions by naming the organic reactant and by drawing the
struceand naming the major product.

H CH 2 CH 2 CH 3
C=C
a. HCl ?
H H +

H CH 2 CH 2 CH 3
b. C=C ?
+ HBr
(CH 3 ) 3 C CH(CH 3 ) 2

H CH 2 CH 2 CH 3
c. C=C + HI ?
H H
                                          

CH 3
d.
+ HCl ?

CH=CH 2
e.
+ HBr ?

b. Hydration- addition of H and OH across the π bond. This

addition requires an acid catalyst.
H
H2 SO 4
C=C + HOH C C OH
(H 2 O)
an alcohol

H CH 3 H CH 3
H2 SO 4
C=C H C C OH
H + H2 O
H
H H
major product

Once again we see the addition follows Markownikov's rule. It should be noted the the addition
of HOH (water) to C=C produces a class of compounds known as alcohols, the functional group
(R-OH).
63
Exercise 3.13

Draw the structure and circle the functional group of the major organic product for the
following reactions:

H CH 2 CH 3
H2 SO 4
a. C=C HOH ?
+
H H

H3 C CH 3 H2 SO 4
b. C=C + HOH ?
H H

H CH 3 H2 SO 4
c. C=C + HOH ?
H CH 2 CH 3

c. Bisulfate addition-addition of H and OSO3H to π bond.

Further addition of H2O will convert the OSO3H to an ROH.

C=C + HOSO 3 C C OSO 3 H

(H 2 SO 4 )

H H
C C OSO 3 H + HOH C C OH

OR

H CH 3 H CH 3
C=C HOH
+ H2 SO 4 H C C OH
H H
H H

In the alternative reaction above, sulfuric acid (H2SO4) is added to propene. The second step of
this reaction follows immediately as indicated by the second arrow where the substitution
reaction produces the alcohol. This two step reaction follows Markowniknov’s rule in the first
step.

It appears in the heterogenous reactions presented so far, compared to H everything else is

more electronegative. What happens when we try to add a reactant that does not contain a H
that adds to a π bond of C=C?

64
It will be helpful to review the following rules for electronegativity. As we go across a period
left to right, the electronegativity of the atom increases. As we go down a family, the
electronegativity decreases. If in doubt, check the Pauling values at the beginning of the text.

d. Atoms other than H- addition of XY to π bond where X is

less electronegative than Y.

X R
H R
C=C + XY H C C Y
H H
H H

In the example above, neither X nor Y is a H atom. Applying Markownikov’s rule, we must
place the least electronegative atom on the C that has the most H.Reactions that add two atoms
to the C=C, neither of which is H, still obey Markownikov’s rule.

H CH 2 CH 2 CH 3 I H
C=C H C CCH 2 CH 2 CH 3
+ IBr
H H
H Br
                                       

e. Hypohalite-addition of X and OH across π bond. OH is

more electronegative than X.
H R X R
C=C + HOX H C C OH
H H
H H
                                     
H CH 3 Cl CH 3
C=C + HOCl H C C OH
H H
H H

Note once again the least electronegative atom (Cl) bonds to the C having the greatest number
of H's. How would we check that Cl is less electronegative than OH?

Exercise 3.14

Complete the the reactions on the following page by drawing the structure of the major organic
product. Name the organic reactants in each reaction.

65
 H CH(CH 3 ) 2
a. C=C + HOCl ?
H3 C CH(CH 3 ) 2

H CH 2 CH 3
b. C=C
+ BrCl ?
H H

H3 C CH 2 CH 3
c. C=C + HOI ?
H3 C H

d. + HOBr ?

CH=CH 2

e. + HOI ?

Do all alkene addition reactions obey Markownikov's rule? No. It is important for you to
recognize two reactions that add to the π bond in an anti-Markownikov manner.

3.13 ANTI-MARKOVNIKOV ADDITION REACTIONS

Anti-Markownikov addition to C=C was first explained by Drs. M.S. Kharasch and F.W. Mayo
while at the University of Chicago. They determined that the addition of HBr to a C=C is
determined solely by the presence or absence of peroxides.

With anti-Markownikov addition, the most electronegative atom bonds to the carbon with the
most H's.

A. Addition of HBr in the presence of peroxides. The symbol

for peroxides is O-O.

H CH 3 H H
O O.
C=C + HBr H C C CH 3
H H
Br H

66
 Br H
H CH 3 O O.
+ HBr H C C CH 3
C=C
H CH 3 H CH 3

B. Hydroboration-oxidation-addition of H and BH2 to the π

bond. Then OH replaces BH2 in a two step reaction.
A) Hydroboration

H CH 3
C=C
+ HBH 2 C C CH 3
H H
B H

B) Oxidation

-OH
C C CH 3 + H2 O2 C C CH 3
B H OH H

Sometimes this two step reaction is seen in one equation, as seen below:

H CH 3 H CH 3
2) H2 O2
C=C H C C CH 2 CH 3
+ HBH 2
H CH 2 CH 3 -OH
(BH 3 ) H
HO

We have indicated the second step of this reaction by placing a 2) above the arrow. The
reactants are listed next to and below the number 2.

Exercise 3.15

Look at the two anti-Markownikov additions above very carefully and then draw the structure
of the major organic product for each reaction below:

H CH(CH 3 ) 2 2) H2 O2
a. C=C + BH 3 ?
H H -OH

H3 C CH 2 CH 3
2) H2 O2
b. C=C BH 3
+ ?
H CH 2 CH 3 -OH

H3 C H
2) H2 O2
c. C=C + BH 3 ?
H3 C H -OH

67
What class of compounds have we produced from these reactions? ____

Exercise 3.16

Starting with propene see if you can prepare (synthesize) the following molecules. (Ask
yourself what reactant must I add to convert propene to:)

a. 1-bromopropane

b. 2-bromopropane

3.14 SUBSTITUTION REACTIONS

Alkenes can undergo substitution reactions by using small amounts of halogen (Cl2 or Br2) and
heat or by using a special brominating reagent, N-bromosuccinimide (NBS).

400°C
CH 2 =CHCH + X2 CH 2 =CHCH 2
2

H X

H Br

+ NBS

H
either H is replaceable

68
Exercise 3.17

Show how you would convert each of the following to 3-bromo-1-butene:

a. 1-butene

b. 1-bromobutane

c. 1,2-dichlorobutane

3.15 SUMMMARY OF REACTIONS

I. Preparation of Alkenes (section 3.11)

a. Dehydrohalogenation

H
alcohol
C=C + KX + H2 O
C C + KOH
²
X
KOH(alc)
CH 3 CH 2 CH 2 CH 2 Cl CH 3 CH 2 CH=CH 2
²

b. Dehydration

69
 H OH
acid
C C C=C + H2 O
²

OH
H+
CH 3 CHCH CH 3 CH=CH 2
+ H2 O
3
²

c. Dehalogenation of vicinal dihalides

X X
Zn
C C C=C + ZnX 2

Br Br
Zn
CH 3 CHCHCH 3 CH 3 CH=CHCH 3 + ZnBr 2

II. Symmetric additions (section 3.12a)

a. Addition of hydrogen

Pt
C=C + H H C C
or Ni
H H

Ni
CH 3 CH=CH + H2 CH 3 CHCH 2
2

H H

b. Addition of halogens
X

C C X=Cl or Br
C=C + X X
X

70
 Br
CCl 4
CH 3 CH=CH + Br2 CH 3 CHCH 2
2

Br

III. Unsymmetric additions (section 3.12b)

a. Addition of hydrogen halides

C=C + H X C C H
X=Cl, Br, or I X

CH 3 CH=CH + HI CH 3 CHCH 2
2
I

H
no peroxides
CH 3 CHCH 2 Markownikov

CH 3 CH=CH 2 + HBr Br Br

CH 3 CHCH 2 Anti-Markownikov
peroxides
H

b. Addition of water. Hydration

H+
C=C + H OH C C H

OH

CH 3 CHCH 2 Markownikov

OH
CH 3 CH=CH 2
OH
1) BH 3 ; 2)H 2 O2
CH 3 CHCH 2 Anti-Markownikov
OH -
H

71
c. Addition of sulfuric acid

C=C + H OSO 3 H C C H

HO 3 SO

CH 3 CH=CH + H2 SO 4 CH 3 CHCH 2
2
OSO 3 H

d. Addition of diatomic molecules containing no H

C=C + YZ C C Y

I
most electronegative
CH 3 CH=CH 2 + IBr CH 3 CHCH 2 atom goes to C with
the least number of H
Br

e. Addition of halohydrin

C=C + HOX C C X X=Cl or Br

OH

Br
most electronegative
CH 3 CH=CH 2 + HOBr CH 3 CHCH 2 atom goes to C with
the least number of H
OH

IV. Substitution reactions (section 3.13)

a. Halogenation

72
 CH 3 400°C
C=C + X2 C C C X X=Cl or Br
(small)

Br2 (small)

400°C
Br
CH 3 CH=CH 2 CH 2 CH=CH 2

NBS
peroxides

73
 Chapter 4

ALKYNES

Another class of hydrocarbons that obeys the formula CnH2n-2 and is characterized by having
at least one carbon-carbon triple bond is called an alkyne.

4.1 COMMON NAME

In naming alkynes, we use the common system for simpler molecules and the IUPAC for both
simple and complex molecules. The simplest alkyne has two carbon atoms and obeys the
formula C2H2 . Using the valence bond or Lewis Dot formula, we see:

HC CH

Commonly we would name this molecule acetylene. In the common system, we use acetylene as
the base name. The rule then is to name the substituent groups that are bonded to the carbon
atoms of the carbon-carbon triple bond, plus the name acetylene. For example, the molecular
formula C3H6 would be classified as an alkyne. In drawing the molecular structure, we would

C C
BASIC ACETYLENE

H C C CH3

A SUBSTITUTED ACETYLENE
see:

In naming this molecule commonly, we name the parent as acetylene and ask what substituent
group(s) do we have on the basic acetylene molecule? In the molecule listed as a substituted
acetylene above, please box or circle the carbon-carbon triple bond. This is your basic
acetylene molecule. What substituent group, (you have only one in this example), do we have
bonded to the basic acetylene molecule? The answer is a methyl group . We name this
molecule methylacetylene. In the following exercises you may find it helpful to circle the
substituent groups on the carbons of the carbon-carbon triple bond or to circle or box the
carbon-carbon triple bond.

DRAW A CARBON-CARBON TRIPLE BOND AND BOX IT BELOW:

74
 propyne
CH3 C CH

CH3 CH2 C CH 1-butyne

2-butyne
CH3 C CCH 3

Exercise 4.1

Name the following molecules commonly:

CH3 CH2 C CH

CH3 C CCH 3

CH3 C CCH 2 CH3

CH3 C CC(CH 3 ) 2

4.2 SYSTEMATIC (IUPAC) NAME

In naming alkynes systematically, we once again choose the longest continuous chain that
contains the carbon-carbon triple bond as our parent hydrocarbon. Using the IUPAC
systematic nomenclature, the alkene is named by using the prefix to indicate the longest
continuous chain of carbon atoms containing the triple bond, THE PARENT, plus the ending
"yne".

For example
HC CH

which we named commonly as acetylene would be named systematically (IUPAC) as ethyne.

WHY?
75
The longest continuous chain of carbon atoms that contains the carbon-carbon triple bond is
two. We know the prefix for a two carbon hydrocarbon is ETH and since the molecule
contains a carbon-carbon triple bond, the parent is an alkyne and the ending for all alkynes is
YNE.

In naming the following alkynes, we will follow all the rules we used with alkenes. Remember
we must indicate the position of the triple bond beginning with a four carbon alkyne. The
longest continuous chain of carbon atoms includes the carbon-carbon triple bond, as seen

propyne
CH3 C CH

CH3 CH2 C CH 1-butyne

below:

2-butyne
CH3 C CCH3

Exercise 4.2

Using the IUPAC nomenclature, please name the following alkynes:

CH3 CH2 C CH

CH3 C CCH 3

CH3 C CCH 2 CH3

CH3 C CC(CH 3 ) 2

Now try to name these.

76
 CH3 CH2 CH2 CH2 C CH

BrCH2 CHC CH
Cl

4.3 DOUBLE AND TRIPLE BOND

If both a double bond and triple bond are within the same molecule the molecule is named as
an "enyne". Look at the following examples:

CH2 =CHCH 2 CH2 C CH 1-PENTEN-5-YNE

5-HEPTEN-1-YNE
CH3 CH=CHCH 2 CH2 C CH

2-OCTEN-6-YNE
CH3 CH=CHCH 2 CH2 C CCH 3

In the first and last example above, we see we must make a choice as to which end of the chain
do we begin numbering. As you see where there is a choice in numbering, the carbon-carbon
double bond takes precedence over the carbon-carbon triple bond. In the other example above
there is no such choice, therefore we always assign the multiple bonds with the lowest possible
number combinations.

Exercise 4.3

Name the following molecules:

a. H C CCH 2 CH=CHCH 3

b. CH3 C CCH2 CH=CHCH 3

c. (CH 3 ) 3 CC CCH2 CH=CCH 3

CH3

d. CH3 CHC CCH 2 CH=CHCH2 CH2 CH3

CH3 77
e. CH2 =CHCH2 CHC CCH 3
CH3
4.4 GEOMETRIC ISOMERISM

If we take a closer look at “b” above, we can redraw this molecule showing a geometry that we
did not see originally. For example,
CH 3 C CCH 2 CH 3 CH 3 C CCH 2 H
C=C C=C
H H H CH 3

CIS TRANS

In naming these molecules, we need to include either cis or trans or possibly E or Z in the
name, i.e. cis or trans-2-hepten-5-yne. It is very important to look for geometry around the
C=C. If no geometry is indicated, then you cannot indicate cis-trans or E-Z.

4.5 PREPARATION OF ALKYNES

A. ACETYLENE FROM INORGANIC SOURCES

The simplest alkyne, acetylene (C2H2), can be prepared from inorganic

sources, calcium carbide (CaC2) and water, as seen below:

CaC2 + H2O > C2H2 + CaO

B. DEHYDROHALOGENATION OF A DIHALOALKANE

Two successive dehydrohalogenations using a strong base, NH2-, on a vicinal (vic) or

geminal (gem) will produce an alkyne. The strength of the base MUST be greater than

X X
-
78OH C=C
C C
alcohol
X ²
 the hydroxide ion (OH-). Below we see using OH- on adihaloalkane will produce a
haloalkene NOT AN alkyne.
Note the difference when a stronger base is used in the following examples:

X
-
NH2
C C C C
strong
X base
vic or gem alkyne
dihalide

Br
-
CH3 CHCHCH3 + NH2 CH3 C CCH 3

Br
2,3-dibromobutane 2-butyne
(a vic dihalide)

Cl
-
NH2
CH3 CCH 3 CH3 C CH

Cl
a gem dihalide

4.6 PREPARATION OF ALKYNES BY INCREASING CHAIN LENGTH

Alkynes like alkenes undergo mainly addition reactions. There is one major difference in that

C C H

ALKYNE WITH TERMINAL H

alkynes that have a terminal (end) H react with strong bases.

The acidity of terminal H of alkynes are more acidic than H's of any other hydrocarbon. For
that reason, we see alkynes that contain terminal H's will react with a strong base like sodium
amide, NaNH2, to produce an acetylide ion. The strength of

the base is very important so please review acid strengths and their conjugates in chapter 1.
NaOH, although a strong base, is NOT strong enough to remove the terminal H from an
alkyne. Please look carefully at the reactions on the following page:

79
 -
R C C H + NaNH2 R C C
AN ACETYLIDE

Cl -
- NH2
NH2 -
CH3 CCH 3 CH3 C C H CH3 C C

Cl METHYL ACETYLIDE

a gem dihalide
acidic H

An acetylide ion can be used to increase carbon chain length containing a carbon-carbon triple
bond as in the following reactions:
-
C C H + CH3 Cl CH3 C C H
-
NH2 CH3 CH2 Br
-
CH3 C C H CH3 C C CH3 C CCH2 CH3

acidic H

We find this reaction only occurs with certain alkyl halides and the acetylide ion. The alkyl
halides (haloalkanes) that are specific for this reaction to occur must be methyl or primary (1°).

Circle the alkyl halide above that is primary (1°) and underline the methyl halides?

How many carbons did we start with in each acetylide?

How many carbons did we wind up with in each product?

Did we increase the carbon chain length in each case?

Many times in organic chemistry we will expect you to increase carbon chain length in
preparing (synthesizing) a product. For example you may be asked to synthesize
1-butyne from acetylene and an alkyl halide.

We may approach the synthesis by drawing the product, 1-butyne.

CH3 CH2 C C H

Now we may ask ourself what reactants do we need to produce this product? Hopefully you'll
know reactions well enough to suggest the following:

-
C C H + CH3 CH2 Cl CH3 CH2 C C H

80
It is important to recognize that we are NOT finished. How do we produce acetylide from
acetylene? Remember this reaction.
- - +
HC CH + NaNH 2 ( OR NH2 ) HC C (Na )
Na is present if we write
NaNH 2 as reactant

Putting these steps together in reverse order we see the correct synthesis.

SYNTHSIS OF 1-BUTYNE BY WORKING BACKWARDS

- +
1) HC C Na + CH3 CH2 Cl HC CCH2 CH3

- +
2) HC CH + NaNH2 HC C Na

It is often easier to work synthesis in reverse order, i.e., backwards. Learn this method.

Exercise 4.4

Starting with acetylene, any alkyl halide, and any inorganic molecule try to synthesize the
following molecules:

a. propyne

b. 2-butyne

HC CH
Hint: For the molecule below how many H's will react with NaNH2?
The answer is two.

81
Now let's take a closer look at the addition reaction for alkynes.

4.7 REACTION OF ALKYNES

I. SYMMETRIC ADDITION

Homogeneous addition- addition of an identical molecule across one of the two π

bonds. If this molecule is in excess both π bonds will be attacked.

A. Hydrogenation- addition of H-H across π bond. Addition can

occur (syn) or (anti) to produce a cis or trans product.

Syn addition of H-H will produce a cis product and an anti addition of H-H will produce a

R R
Pd, BaSO
RC CR + H2
4
C C
OR
H H
P- 2
CIS PRODUCT
NH3 R H
RC CR + M
C C
M=Li, Na, or K H R
TRANS PRODUCT
trans product.

It is important to recognize that there are two different ways to obtain a

cis product. We must use one of these catalysts to prevent the further hydrogenation of the
alkene to the alkane.

How can we synthesis cis products? From hydrogenations of alkynes. Do all hydrogenations of
alkynes give cis products? NO. Try adding hydrogen to acetylene.

Be careful with the following reactions in the exercise below.

Exercise 4.5Which reactions will produce a cis product? a trans product? Draw
Pd
CH 3 CH 2 C CCH 3 + H2
BaSO 4

P-2
CH 3 CH 2 C CCH 2 CH 2 CH 3 + H2

NH 3
CH 3 C CCH 3 + Li

the structure of the major organic product for each of the reactions above.B.
Halogenation- addition of X2 across the π bond to produce an alkene. Addition
of excess reactant, X2, will produce an alkane.

82
 X
CCl 4
C C + X 2 (means 1 mol) C C
X
(a dihalo alkene)

X X
CCl 4
C C + x's X 2 (means excess) C C

X X
(a tetrahalo alkane)

Please be aware of the anti addition of the halogen to the alkyne occurs to produce a trans
product.

Exercise 4.6

Draw the structure of the major organic product from each reaction below:
CCl 4
CH 3 CH 2 C CCH 3 + Br2

NH 3
CH 3 C CCH 3 + Li

CCl 4
CH 3 CH 2 C CCH 2 CH 2 CH 3 + x's Cl 2

CCl
CH 3 C CH + Cl 2 4

Remember in the example above the symbol x's indicates excess Cl2.

Exercise 4.7

Synthesize the following molecules from acetylene and any needed alkyl halide and any
inorganic reactant: (Hint first draw the structure of the molecule you are trying to synthesize
AND remember your reactions)

a. ethene

b. propene

83
 c. cis-2-butene

d. trans-2-butene

II. UNSYMMETRIC ADDITION

A. Hydrogen halides-addition of HX across π bond to produce a

halo alkene. Excess addition of HX will produce a dihaloalkane.

X
C C + HX (means 1 mol) C C
H

H X

C C + x's HX (means excess) C C

H X
(a gem dihalide)

H
Cl
CH 3 C C H + HCl C C
CH 3 H

major product

In predicting the major product, does it follow Markownikov's rule?

84
We see excess addition of HX to an alkyne produces a geminal (gem) dihalide. Recognize this
dihalide from a vicinal (vic) dihalide below:
X X X

C C OR C C

X
Exercise 4.8

Write the structure of a vic dichloride and a gem dibromide below:

____________________ _____________________

B. Hydration- addition of H and OH across π bond. This reaction

requires both an acid, H2SO4 and a catalyst, HgSO4 to
produce an aldehyde or ketone.
OH H O
H2 SO 4
C C + H2 O C=C C C
HgSO 4 H
H
an enol a keto form

The initial product formed by the addition of H2O to the alkyne is an enol (why enol?) which
rearranges (tautomerizes) to the keto form. Take a moment to see how this tautomerization
occurs. In the examples that follow, you will see the keto form, an aldehyde from a acetylene or
a ketone from all other alkynes, in each product. Remember the keto form is produced by a
rearrangement of the enol form.

Draw the structure for acetylene. __________________

O
H2 SO 4
CH 3 C CH + H2 O CH 3 CCH 3
HgSO 4
a ketone

O
H2 SO 4
HC CH + H2 O CH 3 C H
HgSO 4
an aldehyde

Exercise 4.9

85
Synthesize a four carbon ketone from acetylene, any alkyl halide, and any inorganic reactant.
(Hint-how do you increase C chain length?)

Exercise 4.10

Synthesize 2,3-dichlorobutane from acetylene, any alkyl halide, and any inorganic reactant.

4.8 DIENES, TRIENES AND POLYENES

These are molecules that have two (di), three (tri), or more (poly) double bonds in one molecule.
We will focus on dienes and apply our results to the other "enes".

The three types of dienes are classified as isolated, conjugated, or cumulated, as seen below:

CH 2 =CHCH 2 CH 2 CH=CH 2 ISOLATED

CH 2 =CHCH=CHCH 3 CONJUGATED

CH 2 =C=CHCH 2 CH 3 CUMULATED
86
 A. NAMING

In naming these molecules we follow the IUPAC rules for alkenes and insert the letters
"di" between the prefix of the parent and ENE. For example the isolated diene above
would be named:

1,5-hexadiene

The conjugated diene would be named:

1,3-pentadiene

You name the cumulated diene above. ___________________

B. GEOMETRIC ISOMERISM

Since we are now looking at more than one carbon-carbon double bond it is likely that
one or more of these C=C have geometric isomerism. Remember if geometric
isomerism is indicated you must include cis / trans or E/Z in the name. NOTE IF
NUMBERING COMBINATION IS THE SAME, CIS IS INDICATED BEFORE
TRANS. NOTE IF NUMBERING COMBINATION IS THE SAME AND IF BOTH
GEOMETRIES ARE THE SAME IT DOES NOT MATTER WHICH GEOMETRY IS
INDICATED FIRST, i.e. cis,cis below:

CIS

H H
C=C CH 3
CH 3 C=C (CIS,CIS)-2,4-HEXADIENE
H H
CIS

Note the boxed H’s are on the same side of the plane (________).

IF NUMBERING COMBINATION FAVORS TRANS (LOWER NUMBER) THEN

TRANS IS INDICATED FIRST IN THE NAME.
CIS
H H TRANS
C=C H
CH 3 CH 2 C=C (TRANS,CIS)-2,4-HEPTADIENE
H CH 3

Exercise 4.11

In exercise 4.11 try to name each molecule. Be sure to include geometry around the double
bonds if indicated in the structure.

87
 H H
C=C H
H C=C
H H

CH 3 H
C=C H
H C=C
H CH 3

CH 3 CH 3
C=C H
CH 3 CH 2 C=C
H CH 2 CH 3

The alternating single and multiple bonds in the conjugated systems provide for extra stability,
color, and some interesting reactions. Two such reactions are the addition of a hydrogen halide
and the addition of X2 (Cl2 or Br2) to the conjugated diene.

4.9 REACTIONS IN CONJUGATED SYSTEMS

A. Addition - addition of X2 OR HX to a conjugated diene can produce two

products.
Br

BrCH 2 CHCH 2 CH 2 Br (1,2-addition)

CH 2 =CHCH=CH 2
+ Br2
BrCH 2 CH=CHCH 2 Br (1,4-addition)
1,3-butadiene

In the 1,2-addition, the Br and the Br add across one of the two C=C of 1,3-butadiene. In the
1,4-addition, the Br and Br add to the carbons at the end of the conjugated system, i.e., at the
first and fourth carbons. The double bond is now located between carbons two and three.
Take a close look at 1,4 conjugate addition.

Exercise 4.12

When we add HBr to 1,3-butadiene we observe two products.

Draw the structure of these two products. Identify clearly the 1,2-addition and the 1,4-addition
products.

88
____________________ ____________________

89
 Chapter 5

AROMATIC HYDROCARBONS

5.1 KEKULE BENZENE

These hydrocarbons were originally named because these compounds had an "aroma". It was
soon discovered that all hydrocarbons having an aroma were not aromatic and some
hydrocarbon not having any aroma were indeed aromatic. Aromatic hydrocarbons were then
redefined as being any hydrocarbon that behaved chemically like benzene.

What then is so special about benzene? Benzene has the formula C6H6 and has unusual
stability. Benzene does NOT undergo the same addition reactions we observed with alkenes or
alkynes. In trying to draw the structure, Kekule tried several combinations of tetraenes,
diynes, and combinations of enes and ynes. For example some combinations Kekule may have

CH 2 =CHC CCH=CH 2

CH 2 =C=CHCH=C=CH 2

HC CCH 2 CH 2 C CH
tried are indicated below:

In the structures above Kekule could not explain why these structures would not undergo
normal addition reactions common to both alkenes and alkynes. In 1865 Kekule discovered the
structure of benzene and with the structure came the explanation as to why benzene would not
undergo addition reactions.

Kekule's structure for benzene was a ringed molecule that contained alternating single and
double bonds as seen below:

The two resonance structures above led Kekule to believe that the stability of the conjugated
system was indeed the reason why the double bonds must be maintained within the ring.
Therefore addition reactions would NOT occur easily and another reaction, a substitution
reaction, would be more feasible. Can we draw one resonance hybrid structure for benzene?

Yes, we can see that structure below:

90
NOTE THE CIRCLE WITHIN THE RING MEANS ALTERNATING SINGLE AND
DOUBLE BONDS. In naming substituted benzenes we can apply the following rules.

5.2 NOMENCLATURE

A. MONOSUBSTITUTED BENZENES

RULE: Name the substituent group and add the name benzene.

Some common substituent groups and names are in table 5.1.

Table 5.1
NO2 nitro
F fluoro
Cl chloro
Br bromo
I iodo

We see in the following examples this application in naming monosubstituted benzenes:

Cl
NO 2

CH 2 CH 3

NITROBENZENE CHLOROBENZENE ETHYL BENZENE

In the space below draw iodobenzene and n-propylbenzene.

iodobenzene: n-propylbenzene:

Exercise 5.1

Name the following monosubstituted benzenes.

91
 CH 2 CH 2 CH 3
______________________________________

______________________________________

______________________________________

Exercise 5.2

Draw the structures for isopropylbenzene and t-butylbenzene

isopropylbenzene: t-butylbenzene:

B. SPECIAL MONOSUBSTITUTED BENZENES

Additionally there are several monosubstituted benzenes that have special names. It is very
important that you remember these names, as seen below:

92
 CH 3 OH

NH 2
TOLUENE PHENOL ANILINE

COOH

CH 3 O

SO 3 H
BENZOIC ACID ANISOLE BENZENESULFONIC ACID

In each of the monosubstituted benzenes above, it makes no difference as to which carbon the
substituent group is bonded. The reason for this is that each carbon is equivalent, i.e. like
monosubstituted cycloalkanes.

C. DISUBSTITUTED BENZENES

In disubstituted benzenes, we see three possible combinations for two substituents

(X AND Y) to be arranged around benzene, as we see below:
X X X
Y

Y
Y
1,2 OR ORTHO (O) 1,3 OR META (M) 1,4 OR PARA (P)

1. NO SPECIAL GROUPS

If there are no special groups on the benzene ring we use the alphabet to determine the
order/numbering in naming the disubstituted benzene.

I P=BENZENE
1
L= 1,2 OR (O)
2 NO S= IODO, NITRO
2

NAME: 1-IODO-2-NITROBENZENE
OR
O-IODONITROBENZENE

93
 Br F
P=BENZENE P=BENZENE
L= 1,4 OR P L=1,3

S= BROMO, IODO S= ETHYL, FLUORO

CH 2 CH 3
I
1-ETHYL-3-FLUOROBENZENE
1-BROMO-4-IODOBENZENE

OR OR

p-BROMOIODOBENZENE m -ETHYLFLUOROBENZENE

NOTE IN EACH CASE ABOVE THE ALPHABET DETERMINES WHICH SUBSTITUENT

GROUP ASSUMES THE NUMBER 1 POSITION.
If there are no special groups and both substituent groups are identical, we use the prefix “di”
plus the name of the substituent group plus benzene.

NO 2 P=BENZENE

L= 1,2 OR (O)

NO 2 S= DINITRO = NITRO + NITRO

NAME: 1,2-DINITROBENZENE
OR
O-DINITROBENZENE

REMEMBER EACH SUBSTITUENT GROUP IS TO BE (1) LOCATED o, m, or p OR

NUMBERED (IF NUMBERS ARE USED) AND (2) NAMED.

Is the correct name for the structure below 2-difluorobenzene?

F

F
NO. THE CORRECT NAME IS 1,2-DIFLUOROBENZENE

Once again if we choose to number we must locate each substituent group with a number and
name.

Draw a meta(m) and para(p) disubstituted benzene below:

94
Exercise 5.3

Name the four disubstituted benzenes below:

____________________________________
NO 2

( CH 3 ) 3 C CH 2 CH 3

____________________________________

Cl

____________________________________
F

____________________________________
F

Exercise 5.4

Draw the structure for the following molecules:

a. m-divinylbenzene

b. 1,2-diethylbenzene

95
 c. 4-bromofluorobenzene

d. o-isopropylnitrobenzene

2. A SPECIAL GROUP IS PRESENT

In naming disubstituted benzenes it is important to recognize if a special group is substituted

on the benzene ring. For example if CH3 is one of the two substituent groups, then the special
group assumes the number one (1) position and the molecule is named as a substituted toluene
(parent).
CH3
1
2-chlorotoluene or o-chlorotoluene
2
Cl

In the following molecules, please note the special group defines the name of the parent

Br
NH 2 P=ANILINE P= PHENOL
L= 3 OR M L= 4 OR P
S= ETHYL
S= BROMO
CH 2 CH 3 OH

3-ETHYLANILINE 4-BROMOPHENOL
OR OR
M -ETHYLANILINE P-BROMOPHENOL

molecule.

96
Cautiously review each name. With disubstituted benzenes you have a choice of
nomenclatures, i.e. numbers or o, m, or p.

There are no o,m,p in naming with less than two or more than two substituents.

Exercise 5.5

Name the following disubstituted benzenes.

A. SO 3 H _____________________________________

CH 3

B.
CH 2 CH 3 _____________________________________

CH 2 CH 2 CH 3

C.

_____________________________________
F

CO 2 H

D.

NO 2 _____________________________________

How many of the molecules above had special groups?_____________

Exercise 5.6

Draw the structures of the following molecules:

97
 a. p-nitrotoluene

a. 1,3-dinitrobenzene

c. o-fluoroanisole

d. 4-bromobenzoic acid

D. MORE THAN TWO SUBSTITUENT GROUPS

When more than two substituent groups are present on benzene , their positions must be
indicated with numbers. Once again if one of the substituent groups is a special group then the
special group will be located at position 1. The parent will be derived from the special name.
If no special group is present, once again we will first use the lowest combination of numbers of
the substituent groups. If the lowest combination of numbers is not discriminating then we
would use the alphabet to determine our name.

1. NO SPECIAL GROUP

98
 LOWEST COMBINATION OF NUMBERS
I

P= BENZENE

L = 1,2,4

1 Br S= BROMO, FLUORO, IODO

F

2-BROMO-1-FLUORO-4-IODOBENZENE

NOTE OF ALL THE POSSIBLE NUMBER COMBINATIONS 1, 2, 4 IS THE LOWEST.

(AS SEEN ABOVE #1 IS FLUORINE)
ALPHABET DETERMINES NUMBER
I
P= BENZENE

L= 1,2,3
1 F S= BROMO, FLUORO, IODO
Br

1-BROMO-2-FLUORO-3-IODOBENZENE

SINCE THERE IS MORE THAN ONE WAY TO GET A NUMBER COMBINATION OF

1,2,3, WE MUST RESORT TO THE ALPHABET TO DETERMINE WHICH
SUBSTITUTION IS AT POSITION #1 (AS SEEN ABOVE #1 IS BROMINE)

2. SPECIAL GROUP PRESENT

SPECIAL GROUP IS ALWAYS OCCUPYING NUMBER 1 POSITION

OH
1 P= PHENOL
F
L= 2,5

Cl S= CHLORO, FLUORO

2-FLUORO-5-CHLOROPHENOL

99
 NH 2
1 P= ANILINE

L= 3,4

S= DINITRO
NO 2
NO 2
3,4,-DINITROANILINE

NOTE IF A SPECIAL GROUP IS PRESENT LOWEST NUMBERING COMBINATIONS

MUST HAVE THE SPECIAL GROUP AS NUMBER 1.

Exercise 5.7

Name the following multisubstituted benzenes.

CO 2 H

__________________________________
NO 2

NO 2

CH 3
__________________________________
NO 2

I __________________________________
Cl

Exercise 5.8

Draw the structures for the following multisubstituted benzenes:

a. 2,4,6-trinitrophenol (picric acid)

100
 b. 3,4-diethyltoluene

c. 2-bromo-3-nitroisopropylbenzene

E. COMPLEX BENZENES NAMED AS AN ARYL GROUP-Ar

For complex structures that contain the benzene ring it is often easier to name the benzene as a
substituent group with an aryl (aromatic) group name. The aryl group name for the benzene
ring is phenyl (Ph) and another common aryl group name is benzyl as seen below:

= Ph CH 2 = Bz

PHENYL BENZYL

Let's take a look at the following complex molecule:

CH 3 P= BUTANE
C CH 2 CH 3 L= 2,2

Cl S= CHLORO, PHENYL

2-CHLORO-2-PHENYLBUTANE

If we try to name this as a monosubstituted benzene, we will have some difficulty. The solution
is to simply treat benzene as an aryl group, given the symbol Ar. We distinquish Ar from the
alkyl group, (R). Using this symbolism ArR would be an aryl alkane or an alkyl aromatic.
What would ArX indicate? An aryl halide or a haloaromatic.

In the space below draw an aryl halide and name it.

101
Now draw 2-chloro-2-phenylpentane. Would we classify this molecule as an aryl halide? NO.
WHY NOT?

Exercise 5.9

Name the following molecules two ways: a) as an alkyl benzene and b) as an aryl alkane.

_____________________________/ _____________________
C(CH 3 ) 3

CHCH 2 CH 3

CH 3
___________________________/ ______________________

__________________________/ ________________________

In the above examples we have a choice in naming. In the exercise below there is no choice.

Exercise 5.10

Name the following molecules. Remember the symbol Ph stands for phenyl.

CHCH 2 CHCH 3

CH 3 Cl
____________________________________

102
 Ph

____________________________________
Ph

____________________________________

The names and structures for some other aromatic molecules (arenes) are listed in table 5.2
below.

Table 5.2

= BIPHENYL

CH 2 CH 2 = DI BENZYL

= NAPHTHALENE

Exercise 5.11

Draw the structure for the following arenes.

a. (3R, 4R)-3-benzyl-4-bromoheptane

103
 b. cis-2,3-diphenyl-2-butene

c. trans-1,2-diphenylcyclopropane

5.3 REACTIONS OF BENZENE

Benzene undergoes aromatic substitution reactions. In each case we will substitute an atom or
a group of atoms for a H on the benzene ring.

A. HALOGENATION-substitution of X for a H using a Lewis acid as a

catalyst.

H X
AlX 3 OR
+ X2
FeX 3
(X= Cl OR Br)
A HALOBENZENE OR ARYL HALIDE

H Cl
AlCl 3
+ Cl 2

CHLOROBENZENE
104
 B. NITRATION-substitution of an NO2 group for a H using H2SO4 to
initiate the reaction.
H NO 2
H2 SO 4
+ HNO 3

ANY H IS REPACEABLE NITROBENZENE

C. SULFONATION- substitution of SO3H group for a H using fuming

H SO 3 H
H2 SO 4
+ SO 3

H SO 3 H
²
H2 SO 4

sulfuric acid (H2SO4 + SO3) or H2SO4 and heat (∆).

The next two reactions were reported by two chemists, Friedel and Crafts. These reactions
bear their name, as we see below:

D. FRIEDEL-CRAFTS ALKYLATION-a substitution of an R, usually a

methyl (Me) or ethyl (Et), for a H using a Lewis acid.

H R
AlX 3
+ RX

(R= Me or Et)
an alkyl benzene

H CH 3
AlCl 3
+ CH 3 Cl

toluene

105
The reason we limit our alkyl halides (RX) to methyl (Me) or ethyl (Et) is that other alkyl
halides yield unexpected or many products. See limitations of Friedel-Crafts reactions in
chapter 6.

E. FRIEDEL-CRAFTS ACYLATION-substitution of an acyl group (RC=O),

for a H on a benzene ring. The reaction also requires a Lewis acid catalyst.

O
H O C R
AlX 3
+ RCCl

A KETONE

H C CH 3
O
AlCl 3
+ CH 3 CCl

Exercise 5.12

Complete the following reactions:

FeBr 3
A. + Br2

AlBr 3
B. + CH 3 CH 2 Br

O
AlCl 3
C. + CH 3 CH 2 CH 2 CCl

D. + H 2 SO 4
²

106
 CHAPTER 6
REACTIONS OF SUBSTITUTED BENZENES

6.1 REACTIONS OF SUBSTITUENT GROUPS

A useful reaction involving an alkyl benzene and either KMnO4 in a basic solution followed by
addition of acid or K2Cr2O7 in H2SO4 produces a carboxylic acid as seen below:

A. OXIDATION OF AN ALKYL SIDE CHAIN- an alkyl side chain of any

length or any number of alkyl side chains on a benzene can be oxidized to
replace the alkyl group with a COOH.

CO 2 H
R
-OH
1)
+ KMnO 4
2) H3 O+

CO 2 H
CH 2 CH 3
1) -OH
+ KMnO 4
2) H3 O+

CO 2 H
CH 3
1) -OH
+ KMnO 4
2) H3 O+ CO 2 H
CH 3

The 1) and 2) above and below the arrow indicates two different steps in the
reaction. Special attention should be paid on recognizing that any size alkyl group on the
benzene ring will be converted to COOH and this will occur for every alkyl group on the
benzene ring.

Exercise 6.1

Draw the correct product of each reaction below:

CH 2 CH(CH 3 ) 2 1) -OH
+ KMnO 4
a. 2) H 3 O+

CH 2 CH 2 CH 3
CH 3 1) -OH
+ KMnO 4
b. 2) H3 O+
CH 3
107
Another useful reaction is the reduction of the ketone to an alkyl side chain. Two reactions to
accomplish this is either a Clemmensen or Wolff-Kishner reduction.

B. REDUCTION OF AN ACYL GROUP-substitution of 2 H to replace O of

C=O, an acyl group.
CLEMMENSEN REDUCTION

O
CH 2 R
CR
Zn(Hg)

HCl

O
CH 2 CH 3
CCH 3 Zn(Hg)

HCl

WOLFF-KISHNER REDUCTION
O

CR CH 2 R
-OH

+ N 2 H4 ²

NOTE IN EACH OF THE ABOVE EXAMPLES A KETONE, AN ACYL GROUP, IS BEING

REDUCED TO AN ALKYL SIDE CHAIN.

O CH 2 CH 2 CH 3
-OH
CCH 2 CH 3
+ N 2 H4 ²

Exercise 6.2

Draw the structures of the products for the following reactions.

108
 O

CCH 3
Zn(Hg)
a.
HCl

CH 3

CCH 2 CH(CH 3 ) 2 Zn(Hg)

b. HCl

CCH 2 CH(CH 3 ) 2
-OH
c. + N 2 H4
²
CCH 3

Exercise 6.3

Starting with benzene and any alkyl or acyl halide and any inorganic reactant, synthesize each
of the following:

a. toluene

b. isopropylbenzene

109
 c. n-butylbenzene (cannot use n-butyl halide)

d. propylbenzene (cannot use propyl halide)

C. REDUCTION OF NITROBENZENE

The reduction of a nitro group on a benzene ring using either a catalytic

reducing agent like H2 and Pt or a chemical reducing agent like Mg in HCl will
produce an amino group, NH2.

H2 , CATALYST
ArNO 2 ArNH 2
OR
METAL(Mg OR Fe), H +

NH 2
NO 2
Fe

HCl

CH 3 CH 3
H2 , Pt

NO 2 NH 2

Exercise 6.4

110
From benzene and any inorganic molecule, show all the steps in preparing the following
molecules:

b. aniline

c. m-bromoaniline

6.2 REACTION AND ORIENTATION OF MONOSUBSTITUTED BENZENES

A. ORIENTATION AND REACTIVITY

Many times we will want to perform a reaction that contains a monosubstituted benzene. Will
the substitution occur o, m, or p to the existing group?
Will the reaction be activated (less difficult) or deactivated (more difficult) by
the substitutent group relative to benzene? A monosubstituted benzene that
contains an activating substituent group means the reaction will take place with milder
conditions than reacting benzene itself. A monosubstituted benzene that contains a
deactivating substituent group means the reaction will require stronger conditions than
reacting benzene itself.

In table 6.1 we see a list of substituent groups that will either be activated or deactivated and
direct ortho(o) and para(p) or meta(m).

YOU WILL BE REQUIRED TO MEMORIZE THIS TABLE.

A MONOSUBSTITUTED BENZENE

Table 6.1

111
 Y ACTIVATING DIRECTING

-OH,-NH2,-NHR,-NR2,O-; strong o and p

-OR, -NHCOR, -OCOR; moderate o and p
-R, -Ar weak o and p

Y DEACTIVATING DIRECTING

-NO2,-NR3+,-CX3(X=F,Cl) strong m
-SO3H,-COOH,-CN,-CHO, moderate m
-COR,-CONH2,-CONHR,
-CONR2 " m
-F, -Cl, -Br, -I weak o and p

Halogens are the only group that is deactivating and directs o and p.
Let's take a close look at some monosubstituted benzene reactions.

Take special note of the reaction conditions and the disubstituted products that form.

Generally if a group is activating it is going to direct ________

Generally if a group is deactivating it is going to direct ______________

ANY EXCEPTIONS TO THESE GENERALIZATIONS?___________________

112
 B. REACTIONS OF MONOSUBSTITUTED BENZENES

NOTE THE CONDITIONS FOR SULFONATING BENZENE AND THE

CONDITIONS FOR SULFONATING A MONOSUBSTITUTED BENZENE
THAT IS A STRONG ACTIVATOR AND A STRONG DEACTIVATOR.

SO 3 H

50°C
+ H2 SO 4

BENZENE
OH OH
OH
SO 3 H

+ H2 SO 4 +

SO 3 H
ACTIVATOR ORTHO AND PARA PRODUCTS

NO 2
NO 2
150°C
+ H2 SO 4

SO 3 H

DEACTIVATOR META PRODUCT

Note: TWO products are observed with an ACTIVATOR.

How many products would be produced from the nitration of toluene? 2

Draw the products below:

113
HINTS

REVIEW YOUR REACTIONS IN CHAPTER 5

REVIEW TABLE 6.1 BEFORE ATTEMPTING EXERCISE 6.4

Exercise 6.5

Complete the following reactions by drawing the correct structure of the major organic
product(s).

CH 3 FeBr 3
+ Br2
a.

NHCCH 3 FeBr 3
+ Br2
b.

NO 2

c. + H2 SO 4
²

Br

H2 SO 4
+ HNO 3
d.

Which of the reactions above would require the mildest conditions? ____
the strongest conditions? ____

C. Limitation of Friedel Crafts Reaction

1. The Friedel-Crafts alkylation does NOT occur when deactivators STRONGER than the
halogens i.e., NO2, are on the benzene ring

114
2. The Friedel-Crafts alkylation does NOT occur when the ring contains the strong activators-
NH2, NHR, or NR2.

3. Friedel-Crafts alkylations do NOT occur if the halide is aryl or vinyl.

3
4. Friedel-Crafts alkylations produce rearranged products when alkyl halides other than
methyl and ethyl halides are used as a reactant.

♦ REVIEW FRIEDEL CRAFTS ALKYLATIONS IN CHAPTER 5

The exception will occur when a tertiary halide is the reactant, a tertiary alkyl group will be
substituted on the benzene ring as seen below:

BENZENE
CH 3
H Cl CCH 3
AlCl 3
+ CH 3 CCH 3 CH 3
CH 3

t-BUTYLBENZENE

BROMOBENZENE- A MONOSUBSTITUTED BENZENE Br

Br Br CH 3

Cl CCH 3
AlCl +
3
+ CH 3 CCH 3 CH 3

CH 3 C(CH 3 ) 3

For this course we will remember this one exception and only use methyl and ethyl halides for a
Friedel-Crafts alkylations.

Exercise 6.6

115
Synthesize the following molecules from benzene, any alkyl or acyl halide and any inorganic
reactant.

a. p-chlorotoluene (hint: you may separate o from p isomers)

b. o-nitrobenzoic acid

c. m-nitrobenzoic acid

6.3 REACTION AND ORIENTATION OF DISUBSTITUTED BENZENES

When disubstituted benzenes undergo aromatic substitution reactions, the position of the H
being replaced on the benzene ring can be reinforced or opposed by the two substituent groups.
By reinforced we mean the incoming substituent group is directed to the same position on the
benzene ring, as we see below:

A. REINFORCING SAME POSITION-if Y is an ortho/para director and X is

a meta director, we see both groups, X and Y are directing an incoming
group “Z” to the same position(s). (see arrows).

116
 Y

REINFORCING

The new substituent, “Z”, can only occupy the position "o" to Y and "m" to X as we see below:
o,p-DIRECTOR

OCH 3
OCH 3
SO 3 H

+ H2 SO 4
²

NO 2
NO 2

m-DIRECTOR

Why can’t the new substituent group, “Z”,(SO3H) occupy a position para to Y (OCH3)?
Because we see the para position to Y is already occupied by X (NO2) and in organic chemistry
occupation rules.

By opposed we mean the two substituent groups are directing to different positions on the
benzene ring, as seen below:

B. OPPOSING THE SAME POSITION-if X and Y are both o,p directors or

are both meta directors, the new substituent group,”Z”, will have a choice as to
which position to occupy and most likely will occupy more than one position.
Y

OPPOSING
The new substituent may be ortho (o) to Y or ortho (o) to X. This will produce two different
trisubstituted benzenes, as seen below:

117
o,p-DIRECTOR

Br Br
Br
NO 2
H2 SO 4
+
+ HNO 3
²
NO 2
Cl Cl
Cl

o,p-DIRECTOR

NOTE IF THE TWO SUBSTITUENTS ON THE MOLECULE ABOVE WERE BOTH Br or

BOTH Cl THEN ONLY ONE PRODUCT WOULD BE OBTAINED. WHY? IF THE
ANSWER IS NOT OBVIOUS DRAW THE PRODUCTS BELOW AND NAME EACH.

Exercise 6.7

Which of the following disubstituted benzenes will BOTH substituents direct to the same

CO 2 H CH 3
OH
CH 3

A. B. C.

CO 2 H NO 2

NO 2 NO 2

D. E.

NO 2
CCH 3

O
(reinforce) (+)position(s)? Which will direct to different (oppose) (-) position(s)?
A good general rule for groups that oppose each other, the stronger activating group generally
determines the major product of the reaction.

118
MODERATE O,P -DIRECTOR

OCH 3
OCH 3

H2 SO 4
+ HNO 3
NO 2
OH
OH
MAJOR PRODUCT
STRONG O,P-DIRECTOR

Which group is a stronger activator, OCH3 or OH? OH. When p-methoxyphenol is nitrated
as above, we see the major product is a trisubstituted benzene with the NO2 ortho(o) to the OH.

OH

H3 C NO 2

ortho to OH

Exercise 6.8

Draw the structure of the major product(s) from each of the reactions below:

CH 3
O
AlCl 3
A. + CH 3 CCl

Cl O

NHCCH 3

+ H2 SO 4
B. ²
H3 C

Br
OH H2 SO 4
+ HNO 3
C.

O2 N

119
 Chapter 7

ALCOHOLS, ETHERS AND PHENOLS

Alcohols, ROH, are a very important functional group in organic chemistry. The alcohol
functional group provides avenues to many other functional groups, like alkenes, i.e.
dehydration reaction 3.11b. Shortly, we will see how alcohols can be converted into aldehydes,
ketones, and acids, but first it will be useful to review two methods to prepare alcohols.

7.1 Review Preparation of Alcohols, ROH (from chapter 3)

A. From alkenes-MARKOWNIKOV addition of H and OH to the π bond of C=C

using an acid catalyst, i.e., 3.12b (2)
B. From alkenes- ANTIMARKOWNIKOV addition of BH3 to π bond of C=C
followed by the addition of H2O2 in base, i.e., (3.13 (2))

Exercise 7.1

Using 2-methylpropene, prepare an alcohol using the two methods described above. Is there
any difference in the two alcohols that have just been prepared? If yes, what? If no, why not?

7.2 NOMENCLATURE

In naming alcohols, the common system and the IUPAC system are most frequently used.
There are other systems (carbinols) and familiar names that are also used in naming alcohols.
For example, CH3OH is often referred to as wood alcohol or carbinol and CH3CH2OH is often
referred to as grain alcohol or methyl carbinol.

A. COMMON SYSTEM

In naming alcohols commonly we name the alkyl or aryl group that is bonded to the OH and
add the word "alcohol". We observe the following alcohols named commonly below:
               

120
 BENZYL GROUP
METHYL GROUP ETHYL GROUP

CH 2 OH
CH 3 OH CH 3 CH 2 OH

METHYL ALCOHOL ETHYL ALCOHOL

                       BENZYL ALCOHOL

Like alkyl halides we reserve the common name for simple alcohols where the alkyl group
name is known. Also like alkyl halides we can also classify alcohols as methyl, primary (1°),

secondary (2°), and tertiary (3°). In the examples above ethyl alcohol is a primary (1°) alcohol.
The key once again is to note the type of carbon bonded to the O-H. In the aryl alcohol above
the OH is bonded to the benzyl carbon which is also primary and can be classified as benzyl,
primary carbon. This means of course that in addition to alkyl groups being classified as ie.,
methyl, aryl groups are classified also, i.e., benzyl.

BENZYL CARBON

OH CH 3

CH 3 CHCH CH 2 C CH 3
3

OH
2° CARBON BONDED TO -OH 3° CARBON BONDED
THEREFORE 2° ALCOHOL TO -OH = 3° ALCOHOL

NOTE THE PRESENCE OF A BENZYL CARBON DOES NOT MEAN AUTOMATICALLY

A BENZYL ALCOHOL. THIS IS NOT A BENZYL ALCOHOL BECAUSE THE BENZYL
CARBON IS NOT BONDED TO THE –OH.

REVIEW ALKYL (TABLES 2.2, 3.1) AND ALKENYL (TABLE 3.2) GROUP NAMES

Exercise 7.2

Name the following alcohols and classify each alcohol as methyl, primary, secondary, tertiary
or benzyl.

121
 a. CH 3 CH 2 CHOH

CH 3

b. CH 3 CH 2 CH 2 OH

c. CH 3 CHCH 2 OH

CH 3

d. CH 2 =CHCH 2 OH

CH 3
e. CH 3 CCH 2 OH

CH 3

B. IUPAC System

In the IUPAC system, alcohols are named by naming the longest, continous chain of carbons
that contains the OH-the PARENT. The alcohol is named by dropping the "e" of the parent
hydrocarbon and add "OL". As an example, methyl alcohol above, CH3OH,
would be named by identifying the one carbon hydrocarbon as methane. We would drop the
"e" and add ol. The name of this alcohol would be named by the IUPAC system-METHANOL.

Beginning with a three carbon alcohol, the location of the OH must be indicated. Using the

OH P= PROPAN OL
CH 3 C CH 3
L= 2 (LOCATION OF C
H BONDED TO -OH)
NUMBER OF CARBONS IN LONGEST
CONTINUOUS CHAIN CONTAINING
THE -OH IS 3(SEE RECTANGLE ABOVE)

IUPAC NAME: 2-PROPANOL

COMMON NAME:ISOPROPYL ALCOHOL
PLS method we name the following alcohol as:

122
Where there is substitution on the parent alcohol, the OH should have the lowest possible
number.

CH 3 P= 2-BUTANOL OR P= 3-BUTANOL

CH 3 CHCHCH 3 L= 3 OR L= 2
OH
S= METHYL S= METHYL

WHICH OF THE TWO POSSIBILITIES

DOES THE -OH HAVE THE LOWEST
NUMBER?
CORRECT NAME: 3-METHYL-2-BUTANOL

CH 3 OH P=2-PENTANOL
L= 4,4
CH 3 CCH 2 CHCH 3 S=DIMETHYL
CH 3
IUPAC NAME:4,4-DIMETHYL-2-PENTANOL

NOTE THE LOWEST POSSIBLE NUMBER COMBINATION IS NOT AS IMPORTANT AS

GIVING THE –OH THE LOWEST POSSIBLE NUMBER

In CYCLOALKANOLS the OH will most likely occupy the number 1 position. Since this is
understood it is quite common to omit the 1 in naming the parent cycloalcohols.

CH 3 P= CYCLOHEXANOL
L= 2
S= METHYL
OH
PREFERRED NAME IS 2-METHYLCYCLOHEXANOL
NOT 2-METHYL- 1-CYCLOHEXANOL

In naming alcohols whose parent hydrocarbon is an alkene, does the OH take priority over the
C=C? The answer is yes and it is named as an "enol".

For example the alcohol below is named accordingly:

P= 1-BUTEN-4-OL
OR
CH 2 =CHCH 2 CH 2 OH 3-BUTEN-1-OL

WHICH NAME HAS -OH WITH

THE LOWEST NUMBER?

CORRECT NAME: 3-BUTEN-1-OL

123
In table 7.1 is a priority list for future reference. Number 1 is the top priority.

Table 7.1

Priority Functional Group

1 -SO3H (sulfonic acid)

2 -COOH (carboxylic acid)
3 -CONH2 to CONR2(amide)
4 -COOR (ester)
5 -CHO (aldehyde)
6 -COR (ketone)
7 -OH (alcohol)
8 -NH2 to NR2 (amine)
9 -C-O-C (ether)
10 (alkyne)
11 (alkene)
12 (alkane)

Because we can have alkenyl and cycloalcohols, we also have to be concerned with the

CH 3 CH 2 H
P= 3-HEXEN-1-OL
C=C
H CH 2 CH 2 OH (TRANS)

trans-3-hexen-1-ol
possibility of cis/trans isomerism. In the examples below, we see how to name these alcohols:

NOTE BOXED ATOMS, H, OR BOXED GROUPS, CH3, ARE DETERMINING

FACTORS IN ASSIGNING EITHER CIS OR TRANS GEOMETRY.

CH 3
P=CYCLOHEXANOL
CH 3 L= 1,3
S= DIMETHYL (cis)
H
OH

cis -1,3-dimethylcyclohexanol

Exercise 7.3

124
Name the following alcohols indicating where necessary the geometry, i.e. cis:

a. HC CCH 2 CH 2 OH ___________________________

CH 3 H
C=C CH 2 OH
b.
CH 3 C=C
CH 3 H ___________________________

CH 2 CH 3
H
c.
H
OH ___________________________

d. CH 3 CH 2 CHCH=CH 2
___________________________
OH

e. CH 3 CHCH 2 CH=CCH
___________________________
3

OH CH 3

7.3 PREPARATIONS OF ALCOHOLS

A. FROM ALKENES

REVIEW SECTIONS 3.12 AND 3.13

B. FROM AN ALKYL HALIDE, RX, A SUBSTITUTION REACTION

To prepare an alcohol from an alkyl halide and hydroxide ion, we must substitute
the –OH for the halide, -X. To accomplish this the alkyl group of the alkyl halide
must be methyl or primary.

125
FOR A COMPLETE DISCUSSION ON SUBSTITUTION VS ELIMINATION SEE
APPENDIX A
A SUBSTITUTION REACTION

CH 3 I + -OH CH 3 OH + I-

NOTE THE BOXED -I HAS BEEN REPLACED WITH THE BOXED -OH

If the alkyl group, R, of the alkyl halide is secondary or tertiary the substitution reaction is
replaced by the dehydrohalogenation reaction (section 3.11a).

I H CH 3
CH 3 C CH 2 + -OH C=CH 2 + HI
CH 3
CH 3

THE DEHYDROHALOGENATION IS CLASSIFIED AS AN ELIMINATION REACTION.

HINTS IN PREDICTING ALCOHOL SUBSTITUTION AND ELIMINATION REACTIONS

SUBSTITUTION FAVORED WITH HYDROXIDE, -OH, AND ALKYL GROUPS THAT

ARE METHYL OR PRIMARY. METHYL HALIDES REGARDLESS OF
TEMPERATURE WILL ALWAYS FAVOR SUBSTITUTION REACTIONS.

ELIMINATION FAVORED WITH HYDROXIDE, -OH, AND ALKYL GROUP THAT ARE
SECONDARY OR TERTIARY

REGARDLESS OF ALKYL GROUP, EXCEPT METHYL, TEMPERATURE

FAVORS ELIMINATION

CH 3 CH 2 Br + -OH CH 3 CH 2 OH
1°RX SUBSTITUTION

CH 3 CH 2 Br + -OH CH 2 =CH 2
²
1°RX ELIMINATION

Exercise 7.4

Predict the major organic products in each of the following reactions.

Cl
-OH
a. CH 3 CHCH 3
+
²

126
 b. CH 3 CH 2 CH 2 CH 2 Br + -OH
²

c . CH 3 CH 2 CH 2 CH 2 Br + -OH

+ -OH
d. CH 2 I

To prepare different types of alcohols, 1°, 2°, etc. and also increasing carbon chain length a
Grignard reaction is often employed. A Grignard reaction involves a Grignard reagent, an
organomagnesium halide, and an aldehyde or ketone.

C. GRIGNARD REAGENTS = RMgX OR ArMgX

1. NOMENCLATURE

In the preparation of Grignard reagents it is very important to have no moisture or water

present. The reaction occurs between an alkyl or aryl halide and the metal, Mg, in an ether
solvent.

d. RULE: The Grignard reagent is named by naming the alkyl or aryl group +
"magnesium" + the name of the halide.

For example, CH3MgCl would be named by naming the alkyl group-methyl, the metal-
magnesium, and the halide-chloride. Putting this together we come up with the name:

METHYLMAGNESIUM CHLORIDE

How would you name CH3CH2MgBr?_____________________________

2. PREPARATION

ArX or RX + Mg ether > RMgX

CH3Br + Mg ether > CH3MgBr

methylmagnesium bromide

Cl MgCl
ether
+ Mg

PHENYLMAGNESIUM CHLORIDE

127
Exercise 7.5

Draw and name the product of the following GRIGNARD reactions:

ether
a. CH 3 CH 2 CH 2 Cl + Mg

CH 2 Br
b. ether
+ Mg

c. + Mg ether
H2 C=CHCH 2 Cl

D. GRIGNARD REACTIONS

1. PREPARATION OF PRIMARY (1°) ALCOHOLS FROM A GRIGNARD

REAGENT AND FORMALDEHYDE

A two step reaction involving a Grignard reagent with formaldehyde, HCHO,

will produce a primary alcohol. We will look at several reactions involving Grignard reagents
below. Take some time to look at the type of alcohol formed, i.e. 1° and the number of carbons
in the reactant aldehyde, i.e., FORMALDEHYDE and product alcohol.

Grignard reagent and formaldehyde, HCHO

O O- +MgX
ether H3 O+
HCH + RMgX RCH 2 RCH 2 OH
FORMALDEHYDE
1° ROH

128
 O
ether
HCH + CH 3 CH 2 MgCl CH 3 CH 2 CH 2 OH
FORMALDEHYDE 2) H3 O+

( 1 CARBON ) (2 CARBONS) 3 CARBON 1° ALCOHOL

MgBr CH 2 OH
O ether
+
HCH
2) H3 O+
FORMALDEHYDE benzyl alcohol

NOTE THE SECOND STEP, 2), ALWAYS INVOLVES ADDITION OF H3O+

In the examples above the carbon of the-CH2OH (boxed) is coming from the formaldehyde.
Which reactant does the ethyl and phenyl groups come from? Yes, the Grignard reagents.
Look closely at each of the reactions to see that we start with a one carbon aldehyde,
formaldehyde, and increase the carbon chain length in the resulting alcohol by the number of
carbons in the Grignard reagent.

2. PREPARATION OF SECONDARY (2°) ALCOHOLS FROM A GRIGNARD

REAGENT AND ANY OTHER ALDEHYDE BUT FORMALDEHYDE

Using a Grignard reagent and any other aldehyde EXCEPT formaldehyde in a two step
reaction will produce a secondary alcohol.

O O- +MgX OH
ether
RCH + RMgX RCHR RCHR
H3 O+ 2°ROH

OH
O ether
CH 3 CH + CH 3 CH 2 MgCl CH 3 CH 2 CHCH 3
2) H3 O+
(2 C) (2 C) (4 C 2° ALCOHOL)
sec-butyl alcohol or 2-butanol

129
Once again take a good look at how the 2°ROH is prepared. Note we began with a two carbon
aldehyde, CH3CHO, and prepared a four carbon alcohol. We increased the carbon chain
length of the secondary alcohol to four by reacting a two carbon Grignard reagent, 2 C, with a
two carbon aldehyde, 2 C.

2C + 2C = 4C

3. PREPARATION OF TERTIARY (3°) ALCOHOLS FROM A GRIGNARD

REAGENT AND A KETONE

Using a Grignard reagent and a ketone in a two step reaction will produce a tertiary alcohol.

O-+MgX OH
O
ether +
H3 O RCR'
RMgX + RCR' RCR'

R R
R'=R
or R'°R 3°ROH

O OH
ether
CH 3 MgBr + CH 3 CCH 2 CH 3 CH 3 CCH 2 CH 3
2) +
H3 O CH 3
(1 C) (4 C) (5 C 3°ALCOHOL)
2-methyl-2-butanol

NOTE THE LONGEST CONTINUOUS CHAIN OF CARBONS ATOMS, THE PARENT, IS

FOUR EVEN THOUGH THERE IS A TOTAL OF FIVE CARBONS IN THIS ALCOHOL;
THEREFORE THE NAME 2-BUTANOL.

 REVIEW ALL THE GRIGNARD REACTIONS ABOVE BEFORE PRECEEDING

WITH THE EXERCISE BELOW.

Exercise 7.6
Draw the product of the following reactions:

130
 O
ether
a. CH 3 CH + CH 3 MgCl
2) H3 O+

O
b. ether
+ CH 3 CH 2 MgBr
2) H 3 O+

O
ether
c. CH 3 CHCHCH + CH 3 CH 2 CH 2 MgBr
3
2) H3 O+
CH 3

MgCl
O ether
d. HCH +
2) H3 O+

Alcohols are a very important functional group. Being able to synthesize (make) them from the
reactions you know is paramount to you being successful in organic chemistry. Below we will
synthesize 2-pentanol from any aldehyde or ketone and any alkyl halide and/or aryl halide and
any inorganic reactant.

 STEPS TO FOLLOW IN SYNTHESIZING A MOLECULE

1. DRAW THE STRUCTURE OF THE MOLECULE YOU ARE

TRYING TO SYNTHESIZE, i.e., 2-PENTANOL

OH

CH 3 CH 2 CH 2 CHCH 3

2-PENTANOL

2. WORK BACKWARDS FROM FINAL PRODUCT TO INITIAL

REACTANTS USING KNOWN REACTIONS

NOTE THE PROCEDURE BELOW.

131
SINCE 2-PENTANOL IS A SECONDARY (2°) ALCOHOL, WE ASK THE QUESTION
HOW CAN A SECONDARY ALCOHOL BE PREPARED?
ANY ALDEHYDE EXCEPT FORMALDEHYDE AND A GRIGNARD REAGENT.
IN LOOKING AT 2-PENTANOL WE IDENTIFY THE ALDEHYDE PORTION AND
THE GRIGNARD PORTION. WITH THOSE PORTIONS IDENTIFIED THE
SYNTHESIS FOLLOWS:
OH
CH 3 CH 2 CH 2 CHCH 3

ALDEHYDE PART
GRIGNARD PART
O
OH CH 3 CH
2) H3 O+
CH 3 CH 2 CH 2 CHCH 3
Mg
2-PENTANOL CH 3 CH 2 CH 2 MgBr CH 3 CH 2 CH 2 Br
ether

Exercise 7.7

Synthesize the following alcohols from any aldehyde or ketone and any alkyl and/or aryl halide
and any inorganic reactant.

a. 1-butanol

b. 2-hexanol

c. 3-hexanol

132
 d. 3-methyl-3-hexanol

e. 2-phenylethanol

E. PREPARATION OF ALCOHOLS BY REDUCTION

Alcohols can also be prepared by reductions of many other functional groups. Aldehydes,
ketones, acids, and acid derivatives may be reduced to alcohols. The conditions to reduce
aldehydes and ketones are milder than the conditions to reduce an acid or an acid derivative.

1. REDUCTION OF ALDEHYDES OR KETONES

An aldehyde or ketone may be reduced either by using H2 in the presence of a

catalyst, eg., Pt or chemically using NaBH4.

133
 O O H
Pt
RCH + H2 RCH

an aldehyde H
1°ROH

O O H
H2 O
RCH + NaB H4 RCH
an aldehyde H

O O H
H2 O
CH 3 CH + NaB H4 CH 3 CH

ETHANOL
ALDEHYDES

KETONES

O
H2 O O H
RCR' + NaB H4 RCR'

a ketone H
R=R' 2°ROH
or R°R'

O O H
H2 O
CH 3 CCH 3 + NaB H4 CH 3 CCH 3

2-PROPANOL
Exercise 7.8

Draw the products of the following reactions:

134
 O
Pt
a. CH 3 CH 2 CH 2 CCH 3 + H2

O
CH
b. H2 O
+ NaBH 4

H2 O
c. O + NaBH 4

O
Pt
d. HCH + H2

7.4 ETHERS

Ethers as a group of organic compounds are very unreactive and are therefore used in organic
chemistry as solvents and protective groups. In naming ethers we can use the common system
and the IUPAC system.

A. NOMENCLATURE

1. COMMON NAMES- ALKYL AND/OR ARYL ETHERS

The common system is used for simple ethers where the alkyl and/or aryl group
name is known.

 RULE: name each alkyl or aryl group bonded to the -O- and add the word "ether".

CH 3

CH 3 OCH 3 CH 3 CH 2 COCH 3 CH 3 CH 2 OCHCH 3

DIMETHYL ETHER ETHYLMETHYL ETHER ETHYLISOPROPYL ETHER

OCH 3 CH 2 OCH 2

METHYLPHENYL ETHER DIBENZYL ETHER

(ANISOLE)
135
In the space below draw diethylether or what is commonly referred to as simply "ether " in
hospitals today.

2. IUPAC SYSTEMATIC NAMES-ALKOXY HYDROCARBONS

In naming ethers using the IUPAC system, we once again look for the longest
continuous chain of carbon atoms, the parent. We then locate the alkoxy,
(-OR), substituent group and then we name the alkoxy substituent group. In the
examples below look at the importance of lowest number combination and the
alphabet in naming.

P=PENTANE
CH 3 OCH 3 CH 3 OCH 2 CH 2 CH 2 CH 2 CH 3 L= 1
S=METHOXY
METHOXYMETHANE 1-METHOXYPENTANE

CH 3
P=BUTANE
CH 3 OCH 2 CH 2 CHCH L=1,3
3
S=METHOXY, METHYL
1-METHOXY-3-METHYLBUTANE

CH 2 CHCH 3
P=PROPANE
L=1,2
OCH 2 CH 3 S=ETHOXY, PHENYL

1-PHENYL-2-ETHOXYPROPANE

P=ETHENE
CH 2 =CHOCH 2 CH 3 L=N/A
S=ETHOXY
ETHOXYETHENE

Draw 4-ethoxy-2-pentanol in the space below:

136
Exercise 7.9

Name the following molecules commonly, if possible, and IUPAC.

a. CH 3 CH 2 CH OCH 2 CH 3

CH 3 ____________________________

CH 3
b. CH 3 COCH 2 CH 3
______________________________
CH 3

OCH 3
c. CH 3 CHCHCH 2 OH

CH 3 _______________________________

Br
OCH 3

d.
_______________________________

OCH 2 CH 3

e. BrCH 2 CHCHCH 2 CH 2 CH 3

Cl _______________________________

Like hydrocarbons ethers may bond in a cycle. The most common of the cyclic ethers is
oxirane or ethylene oxide, as seen below:

137
 O

OXIRANE (IUPAC)
ETHYLENE OXIDE (COMMON)

B. REACTIONS OF ETHERS

Alicyclic ethers are unreactive. Therefore we will look at reactions with acids that produce
salts or that cleave the ethers into two other molecules.

1. REACTION WITH H2SO4

A WATER SOLUBLE SALT

+
ROR + H2 SO 4 ROR + HSO 4 -

H
+
CH 3 OCH 2 CH 3 + H2 SO 4 CH 3 OCH 2 CH 3 + HSO 4 -

2. REACTION WITH EXCESS CONCENTRATED HBr OR HI

ROR' + x's HBr (conc) RBr + R'Br

CH 3 OCH 3 + x's HI (conc) 2 CH 3 I

7.5 PHENOLS

We have named phenols in chapter 4. Therefore we will limit our discussion to preparation
and reactions.

A. PREPARATION OF PHENOL

The best way to prepare phenol is through a diazonium salt. In the sequence below we will see
that a primary (1°) amine is required for the diazonium salt.

138
 NO 2 NH 2
N 2 +Cl - OH
HCl HCl, NaNO
+ Sn 2 H2 O
0°C

1°AMINE DIAZONIUM SALT PHENOL

In sequence above the second reaction contains HCl and NaNO2. The product of HCl and
NaNO2 is HNO2. Therefore HNO2 is often used in the reaction instead of HCl and NaNO2.

B. REACTIONS OF PHENOL

Because the H of the O-H is more acidic with phenols (pKa=10) than with alcohols (pKa=18),
phenols react readily with bases like NaOH.

1. ACID BASE REACTIONS

OH O-Na +

+ NaOH + H2 O

ACID BASE SALT WATER

(A PHENOXIDE ION)

2. REACTION WITH METHYL OR PRIMARY ALKYL HALIDE

O-Na + OR

+ RX

AN ALKYL PHENYL ETHER

O-Na + OCH 2 CH 3

+ CH 3 CH 2 Br

1° RX

139
Exercise 7.10

Starting with phenol and any alcohol of no more than four (4) carbons and any inorganic
reactant, synthesize the following:

a. methylphenylether

b. phenylpropylether

c. potassium phenoxide

140
d. allylphenylether

141
 CHAPTER 8
REACTIONS OF ALCOHOLS

8.1 REACTIONS OF ALCOHOLS

The alcohol functional group provides two sites for reaction to occur, RO-H or R-OH. A
reaction that involved attacking the H of the ROH is seen below in the preparation of the
alkoxide ion.

A. ALKOXIDE ION, RO-, FORMATION-AN ACID BASE REACTION

THE PROTON, H, OF RO-H IS REMOVED BY A METAL. M, A STRONG BASE

RO-H + M (Li, Na, or K) > RO- +M + 1/2 H2

CH 3 O H + K CH 3 O-K+

POTASSIUM METHOXIDE

 RULE FOR NAMING THE ALKOXIDE-NAME THE METAL PLUS THE ALKYL
GROUP MINUS THE YL PLUS THE WORD “OXIDE”

Exercise 8.1

What alcohol and metal is needed to make lithium isopropoxide?

______________________ _____________________

B. PREPARATIONS OF ETHERS

There are two methods to prepare noncyclic ethers. The best way to prepare both symmetrical
and unsymmetrical ethers is the Williamson synthesis. In preparing the ether, we must use a
methyl or primary (1°) alkyl halide with an alkoxy ion.

1. WILLIAMSON SYNTHESIS

RX + R'O - ROR'
R=Me or 1°

IF R'=R A SYMMETRICAL ETHER IS PRODUCED

IF R'IS NOT R AN UNSYMMETRICAL ETHER IS PRODUCED
SYMMETRICAL ETHER
CH 3 Br + CH 3 O- CH 3 OCH 3

UNSYMMETRICAL ETHER

CH 3 I + CH 3 CH 2 CH 2 O- 142 CH 3 OCH 2 CH 2 CH 3
Exercise 8.2

In the synthesis of t-butylethylether, a student reacted t-butyl bromide with CH3CH2O-.

Would the student observe t-butylethylether? Explain.

To prepare symmetrical ethers only, we can react an alcohol in the presence of an acid at
140°C.

2. ALCOHOL REACTION WITH ACID AT 140°

SYMMETRICAL ETHERS ONLY
140°
ROH + H2 SO 4 ROR

140°
CH 3 CH 2 OH + H2 SO 4 CH 3 CH 2 OCH 2 CH 3

DIETHYL ETHER

 TEMPERATURES OF 180°C OR GREATER WILL PRODUCE THE

CORRESPONDING ALKENE

3. PREPARATION OF OXIRANE

OXIRANE can be prepared by reacting an alkene with a peroxyacid.

CH 2 =CH 2 + CH 3 CO 3 H CH 2 CH 2

PEROXYACETIC ACID O

(PAA)

 PERACIDS HAVE ONE MORE OXYGEN THAN A CORRESPONDING ACID

i.e. PERFORMIC ACID WILL HAVE ONE MORE OXYGEN ATOM THAN
FORMIC ACID

Exercise 8.3

Draw the major product for the following reactions:

143
 140°
a. CH 3 CHCH 2 OH + H2 SO 4

CH 3

180°
b. CH 3 CHCH 2 OH + H2 SO 4

CH 3
c. CH 3 CH 2 CH 2 Cl + CH 3 CH 2 O-

d.
+ CH 3 CO 3 H

H2 SO 4
e. CH 3 CH 2 CH 2 CH 2 CH 2 OH
140°

C. SUBSTITUTION REACTIONS

1. REACTION WITH ACID CHLORIDES-reaction requires an acid

chloride like a substituted benzenesulfonyl choride, as seen below:

ACID CHLORIDES

SO 2 Cl SO 2 Cl

H3 C Br

TsCl=TOSYL CHLORIDE BsCl=BROSYL CHLORIDE

RO H + TsCl RO Ts + HCl

For example,

144
 CH 3 CH 2 CHCH 3 + TsCl CH 3 CH 2 CHCH 3 + HCl

OH OTs

CH 3 CH 3

CH 3 CCH 3 + BsCl CH 3 CCH 3 + HCl

OH OBs

The advantage of having a tosylate (OTs) group or a brosylate (OBs) group in the molecule is
that they are very good leaving groups. We can then substitute weak bases for these groups
fairly easily, as seen below:

 REACTION OF A TOSYLATE OR BROSYLATE

CH 3 CH 2 CH 2 CH 2 OTs + Cl - CH 3 CH 2 CH 2 CH 2 Cl

OTs Br

+ Br-

OBs OAc
CHCH 3 CHCH 3

+ OAc -
(acetate)

145
 TWO STEP SYNTHSISIS FROM ALCOHOL TO HALIDE

1) CH 3 CH 2 CHCH 3 + TsCl CH 3 CH 2 CHCH 3 + HCl

OH OTs

2) CH 3 CH 2 CHCH 3 + Cl - CH 3 CH 2 CHCH 3

OTs Cl

Exercise 8.4

Synthesize the following molecules from the corresponding alcohols and any other organic and
inorganic reactants.

a. benzyl choride from benzyl alcohol

b. 2-bromo-2-methylpentane from 2-methyl-2-pentanol

c. 1-chloro-2-methylpropane from isobutyl alcohol

2. OTHER METHODS FOR HALIDE SUBSTITUTION

In using phosphorus trihalides (chloride or bromide) or thionyl chloride, SOCl2, we can avoid
problems of producing other products.

HALIDE SUBSTITUTION

ROH + PX 3 OR SOCl 2 RX OR RCl

(X=Cl OR Br)

146
 CH 3 CH 2 CH 2 OH + PCl 3 CH 3 CH 2 CH 2 Cl

Cl
OH
+ SOCl 2

CH 3 CH 3

CH 3 CCH 2 OH + PBr 3 CH 3 CCH 2 Br

CH 3 CH 3

neopentyl alcohol neopentyl bromide

In the above example, neopentyl alcohol reacted with phosphorus tribromide to produce
neopentyl bromide. When this same alcohol was reacted with HBr, the product was 2-bromo-
2-methylbutane.

Br

CH 3 CCH 2 CH 3

CH 3

Reacting a phosphorus halide or thionyl chloride with an alcohol is therefore preferred to using
HBr or HCl to produce the corresponding halide. In exercise 8.5 (c) HBr is used because it will
produce the same bromide as PBr3.

Exercise 8.5

Draw the product(s) of the following reactions:

a. CH 3 CH 2 CH 2 OH + PBr 3

b. CH 3 CH 2 CHOH + SOCl 2

CH 3

CH 2 OH
c. + HBr

D. ALKENE FORMATION-see section 3.11b-A DEHYDRATION REACTION

147
 OH
180°C
CH 3 CHCH + H2 SO 4 CH 3 CH=CH 2
3

Exercise 8.6

Draw the structure of the major product(s) of the following dehydrations:

conc
a. CH 3 CH 2 OH
H2 SO 4
180°C

CH 3
OH
b. 85 % H3 PO 4

165-170°C

OH
c. 20% H2 SO 4
CH 3 CCH 3
85°C
CH 3

E. QUALITATIVE TEST FOR ALCOHOLS- THE LUCAS TEST

The Lucas test is used to determine if the alcohol is primary, secondary, or tertiary.

LUCAS TEST TO DISTINQUISH ALCOHOLS

A. PRIMARY (1°)ALCOHOL DOES NOT REACT WITH LUCAS REAGENT,

HCl and ZnCl2.

ZnCl 2
CH 3 CH 2 OH + HCl NO REACTION

1° ROH ROOM TEMP

B. SECONDARY (2°) ALCOHOLS-REACTS TO PRODUCE A CLOUDY

SOLUTION WITHIN FIVE (5) MINUTES.

ZnCl 2
CH 3 CHOH + HCl CH 3 CHCl
CH 3 ROOM TEMP CH 3

2° ROH CLOUDY ~5 MIN.

148
 C. TERTIARY (3°) ALCOHOLS-REACT TO PRODUCE A CLOUDY
SOLUTION IMMEDIATELY.

CH 3 CH 3
ZnCl 2
CH 3 COH + HCl CH 3 CCl
CH 3 ROOM TEMP CH 3

3° ROH CLOUDY IMMED

Exercise 8.7

Describe a simple chemical test to distinquish between 1-butanOL and the following (be sure to
indicate what would be seen):

a. 1-butene

b. sec-butyl alcohol

c. isopentyl alcohol

d. 3-methyl-3-hexanol

F. GLYCOL or DIOL FORMATION

A. Alkenes react with cold, dilute KMnO4 or OsO4 to produce a cis diol or
glycol.

149
 R R C R
C=C + KMnO 4 OR OsO 4 HO
H H C R
HO

SYN ADDITION
Syn additions always add across the double bond on the SAME side.

B. Alkenes react with peroxyacids, RCO3H, to produce trans diols or

glycols. (See table 8.1 for symbols of peroxyacids)
R
H
HO C
R R H
2) H+ OR -OH
C=C + RC O3 H C OH
H H H2 O
R

PEROXYACID ANTI ADDITION

In the peroxyacid addition to the alkene, the reaction requires either aqueous acid or base in
order to obtain the trans diol. For example we can control stereochemistry as we see below:

COLD
+ KMnO 4
H2 O

OH OH
CIS -1,2-CYCLOHEXANEDIOL

H+
+ CH 3 CO 3 H
OH
H2 O
PAA
OH
TRANS -1,2-CYCLOHEXANEDIOL

Remember unlike syn addition, ANTI addition adds across the double bond on OPPOSITE
sides.

Table 8.1

PEROXYACID SYMBOL

PERACETIC ACID PAA

PERBENZOIC ACID PBA
PERFORMIC ACID PFA

150
Exercise 8.8

Draw the structures of the product(s) for each reaction. Name each product paying particular
attention to stereochemistry, eg., R or S, cis or trans.

CH 3 H
H2 O
a. C C + KMnO 4
H CH 3

H H
b. C C H2 O
+ KMnO 4
CH 3 CH 3

O
CH 3 H
H+
c. C C + CH 3 COOH
H CH 3 H2 O
PAA

O
H H H+
C C + HCOOH
d.
H2 O
CH 3 CH 3
               PFA

e. + OsO 4

 In looking at your products in (a-d) above can you make a general statement about syn
or anti additions to symmetrical alkenes? For example syn addition to the trans alkene
above produces an enantiomeric pair. Syn addition to the cis alkene above produces a
meso compound. What can you say about anti additions to the above alkenes?

G. MILD OXIDATION OF A METHYL OR PRIMARY ALCOHOL

Methyl or Primary (1°) alcohols

1. ALDEHYDES

Methyl and primary alcohols can be oxidized to carboxylic acids with strong oxidizing agents,
ie., K2Cr2O7 in H2SO4 (Jones reagent) or KMnO4 in a neutral or basic solution. To stop the

151
primary alcohol oxidation at the aldehyde, we must use a special mild oxidants, ie., PCC,
pyridinium chlorochromate.

H2 SO 4
RCH 2 OH + K2 CrO 7 RCO 2 H
CARBOXYLIC ACID

CH 2 Cl 2
RCH 2 OH + PCC RCHO
ALDEHYDE

Take a close look at these two reactions. Take special note of the different products from the
different reactants. In table 8.1 is a list of strong and mild oxidizing agents. What functionality
difference occurs when a 1°ROH is oxidized with a strong rather than a mild oxidizing agent?

_______________________________________________________________________

Table 8.2 COMMON OXIDIZING AGENTS

STRONG (Sox) MILD (Mox)

K2Cr2O7 Cu, 250°

KMnO4 PCC
Ag2O

2. KETONE FORMATION-OXIDATION OF A SECONDARY ALCOHOL

Secondary (2°) alcohols

Secondary alcohols are oxidized by any oxidizing agent to produce a ketone.

OH O
Sox
RCHR RCR
OR
2°ROH Mox KETONE

OH O
PCC
CH 3 CHCH 2 CH 3 CH 3 CCH 2 CH 3
CH 2 Cl 2
3. ALCOHOLS THAT CANNOT BE OXIDIZED

Tertiary (3°) alcohols

152
Tertiary alcohols CANNOT be oxidized by any oxidizing agent.

OH
Sox
RCR NR
OR
R Mox
3°ROH

OH
PCC
CH 3 CCH 2 CH 3 NO REACTION
CH 2 Cl 2
CH 3

Let's take a look at the following reactions:

H2 SO 4
CH 3 CH 2 CH 2 CH 2 OH + K2 Cr 2 O7 CH 3 CH 2 CH 2 CO 2 H

1° ROH carboxylic acid

CH 2 Cl 2
CH 3 CH 2 CH 2 CH 2 OH + PCC CH 3 CH 2 CH 2 CHO

1° ROH aldehyde
OH O
H2 SO 4
+ K2 Cr 2 O7

2° ROH ketone

OH
K2 Cr 2 O7
CH 3 CCH 2 CH 3 NO REACTION
H2 SO 4
CH 3
(Jones reagent)
3° ROH

In the preceeding examples, we see the effect of an oxidizing agent on an alcohol.

 Take special note of these reactions.

Take a moment to review - what is the product when we oxidize:

a. a primary alcohol with a strong oxidizing agent _______________________

153
 b. primary alcohol with a mild oxidizing agent _________________________

c. a secondary alcohol with a mild or strong oxidizing agent _________________

d. a tertiary alcohol with a mild or strong oxidizing agent ___________________

Exercise 8.9

Predict the products of the following reactions.

K2 Cr 2 O7
a. CH 3 OH
H2 SO 4

CH 2 Cl 2
b. CH 3 CH 2 CHCH 3 + PCC

OH
OH CH 2 Cl 2
c. + PCC
CH 3

CH 2 OH
OH -
d. + KMnO 4
2) H3 O+

OH
H+
e. + K2 Cr 2 O7

10. PREPARATION OF A ESTER-AN ALCOHOL REACTION WITH

A CARBOXYLIC ACID

When an alcohol is reacted with a carboxylic acid using a mineral acid catalyst an ester is
produced. This reaction is not particularly the best method to produce an ester as will be seen
in Chapter 12.

O O
H+
RO H + RC OH RC OR + HOH

154
 O O
H+
CH 3 CH 2 OH + CH 2 CH 2 COH CH 3 CH 2 COCH 2 CH 3 + HOH

In the reaction above an ester is formed from an alcohol and an acid. Inspect the ester and
identify which part of the ester is coming from the acid and which part is coming from the
alcohol.

A Reaction Wheel

Below we see a reaction wheel. Notice how each reaction is completed by answering what is
missing (?).

( CH 3 CH 2 OCH 2 CH 3 )

? CH 3 COOH
H2 SO 4 ? ( KMnO)
140° 4 O
PCl 3 PCC
( CH 3 CH 2 Cl ) ? CH 3 CH 2 OH ? ( CH 3 CH )
CH 2 Cl 2
?
(H 2 SO 4 , ? ( CH 3 COH, H + )
180°C)
O
CH 2 =CH 2
CH 3 COCH 2 CH 3

8.10

Complete the reaction wheel BELOW by drawing the correct structures ?(A-H). If no reaction
is possible write NR and if more than one product can be expected draw the structure of the
major product.
O

CH 2 OCCH 3

? (E)
? (F)
PCC, CH 2 Cl 2

CH 2 Br CH 2 OH COOH
? (G) ? (A)

PCl 3
? (H)
? (B)
CH 2 OCH 2
CH 3 C C-

H2 , P2
? (C) ? (D)
155
 CHAPTER 9

ALDEHYDES AND KETONES

Aldehydes and ketones make up a group of compounds known as carbonyls. Carbonyl

compounds contain the C=O, the carbonyl group. Aldehydes have the general formula,
O

                                                               RCH

and ketones have the general formula,

O

RCR'
WHERE R=R' OR
R DOES NOT EQUAL R'

ALDEHYDES

Aldehydes are named both commonly and systematically, IUPAC. Common names requires
knowledge of the common name of the carboxylic acid. In table 9.1 is a list of the common
names of the first five carboxylic acids.

Table 9.1

#C Formula Common name

1 HCOOH formic acid

2 CH3COOH acetic acid
3 CH3CH2COOH propionic acid
4 CH3CH2CH2COOH butyric acid
5 CH3CH2CH2CH2COOH valeric acid

9.1 NOMENCLATURE

A. COMMON NAME

In naming aldehydes commonly, we identify the longest, continuous chain that contains the
aldehydel group, CHO, by naming the corresponding common name of the carboxylic acid,
dropping the "ic" and adding the word "aldehyde".
O O
O
CH 3 CH CH 3 CH 2 CH
HCH

PROPIONALDEHYDE
                    FORMALDEHYDE ACETALDEHYDE

156
Staying with the common system, we identify the location of a substituent group by using a
letter from the greek alphabet. The alpha carbon () is located next to the aldehydic carbon,
CHO, the beta carbon () is located next to the alpha carbon, the gamma carbon () is located
next to the beta carbon, etc. The substituent group is named as before. Below we will see each
carbon assigned α−ε and some examples. Learn these locations and the corresponding greek
letters for the common system.
ε δ γ β α O

C C C C C C H
                                                     
O
CH 3 CH 2 CHCH 2 CH P= valeraldehyde
L= β
Cl S= chloro
β- chlorovaleraldehyde

O
P= propionaldehyde
CH 3 CHCH L= α
CH 3 S= methyl

                             α- methylpropionaldehyde

Exercise 9.1

Draw the structures of the aldehydes indicated below:

a. δ--hydroxyvaleraldehyde

b. α-bromobutyraldehyde

c. α,β-dimethylvaleraldehyde

d. γ,γ -dichlorobutyraldehyde

e. α-iodo-α-methylpropionaldehyde

B. IUPAC NOMENCLATURE

157
The IUPAC systematic nomenclature involves identifying the parent-the longest continuous
chain of carbon atoms containing the aldehyde, CHO, functional group. Name the
corresponding hydrocarbon of the same number of carbon atoms inclusive of the aldehyde
functional group, drop the "e" and add "AL". For example, the following aldehydes would be
named using IUPAC rules as indicated:

O O O

CH 3 CH CH 3 CH 2 CH CH 3 CH 2 CH 2 CH

ethanal propanal butanal

CH 3 (CH 2 ) 5 CHO

                                    heptanal

What do you see about aldehydes that is different with alcohols or alkenes or alkynes? Yes, the
location of the aldehyde functional group is NOT located with a number. Why? ______

Substituent groups are located with a number, NOT A GREEK LETTER, and named
according to the PLS system.
O
*
C C C C C C
6 5 4 3 2 1 H
*
Note: The aldehydic carbon (C ) assumes the number 1
                     position

Draw an aldehyde that has a total of 4 carbons.

See how we name the following:

158
 O P = hexanal

CH 3 CHCH 2 CH 2 CH 2 CH L= 5
S= methyl
CH 3
5-methylhexanal

I OH O P= pentanal
L= 3,4,4
CH 3 CCHCH 2 CH S= hydroxy, iodo, methyl
CH 3
3-hydroxy-4-iodo-4-methylpentanal

CH 3 CH 2 H P= 2-penten al
L= 3
C=C S= methyl
CH 3 C=O

                           E-3-methyl-2-pentenal

Exercise 9.2

Draw the structures for the following aldehydes:

a. 3,3-dibromobutanal

b. 2,4-dimethylheptanal

c. trans-2-hexenal

d. 2-phenylpropanal

e. 3,5,5-trimethyloctanal

159
 KETONES

In addition to both common and IUPAC nomenclature, the simplest ketone is known by a
familiar name. That ketone and its name is indicated below:

CH 3 CCH 3

                                                                   ACETONE

9.2 NOMENCLATURE

A. COMMON NAME

In the common system we alphabetically name each alkyl or aryl group bonded to the carbonyl,
C=O, group followed by the word ketone. In the examples below, we see the common system is
used to name simple ketones:
O O

CH 3 CCH 3 CH 3 CCH 2 CH 2 CH 3

DIMETYL KETONE METHYL PROPYL KETONE

O O

CH 3 CH 2 CCH 3 CH 2 CCH 2

ETHYL METHYL KETONE

DIBENZYL KETONE

B. IUPAC NOMENCLATURE

For both simple and more complex ketones, we use the IUPAC system. In the IUPAC
systematic nomenclature, we once again identify the longest, continuous chain of carbon atoms
that contains the carbonyl group, C=O. Name the corresponding hydrocarbon of the same
number of carbon atoms, drop the "e" and add "ONE". This then is the parent. The location
of the C=O must be given the lowest possible number, beginning with the five carbon
unsubstituted ketone. The substituent groups are numbered and named, as before, in the PLS
system, as seen on the next page:

160
 O
P=PROPANONE
CH 3 CCH 3

PROPANONE

O
P=2-PENTANONE*
CH 3 CCH 2 CH 2 CH 3

2-PENTANONE

O
P=2-PROPANONE *
CH 2 CCH 2
L=1,3

S=DIPHENYL

1,3-DIPHENYL-2-PROPANONE

O OH P=2-PENTANONE *
L=4
CH 3 CCH 2 CHCH 3
S=HYDROXY
4-HYDROXY-2-PENTANONE
* NOTE LOCATION OF CARBONYL MUST BE INDICATED

Exercise 9.3

Name the following ketones both commonly and IUPAC.

Remember NOT all ketones can be named commonly but these are simple enough that they can
indeed be named both ways.

a. CH 3 CH 2 CCH 2 CH 3

b. CCH 3

c. CH 3 CCHCH 3

CH 3
O

(CH 3 ) 2 CHCC(CH 3) 3
             d.

161
 C. CARBONYL GROUP AS A SUBSTITUENT GROUP

The C=O can be named as the substituent group, oxo. For example in the molecule below the
aldehyde functional group takes precedence over the ketone functional group and we write the
following name:
O O P=PENTANAL *
L=4
CH 3 CCH 2 CH 2 CH
S= OXO
4-OXOPENTANAL

                                     * NOTE NO NEED TO LOCATE ALDEHYDE POSITION

D. SPECIAL CARBONYL NAMES

O O

CCH 3 CH

BENZALDEHYDE
                                          ACETOPHENONE

9.3 PREPARATIONS OF ALDEHYDES AND KETONES

We have learned several reactions in previous chapters that allowed us to prepare aldehydes
and ketones. Below is a review of those reactions:

 From an ALKYNE-requires addition of H and OH across a π bond

forming an enol form which tautomerizes to a keto form.
(CHAPTER 4)

H O
H2 SO 4 OH
C C + H2 O C C C C
HgSO 4 H
H
ENOL KETO
O
H2 SO 4
CH 3 C CCH 3 + H2 O CH 3 CH 2 CCH 3
HgSO 4
BUTANONE
                          2-BUTYNE

 From OXIDATION OF ALCOHOLS- primary (1°)alcohols are oxidized to

aldehydes and secondary (2°) alcohols are oxidized to ketones and tertiary (3°) alcohols canNOT be
oxidized. (CHAPTER 8)

162
 OXIDATION
H C OH C O

ALDEHYDE OR KETONE
                                            1° OR 2° ALCOHOL

O
PCC
CH 3 CH 2 CH 2 OH CH 3 CH 2 CH
CH 2 Cl 2
1-PROPANOL (1° ROH) PROPANAL

OH O
Jones reagent
CH 3 CHCH 2 CH 3 CH 3 CCH 2 CH 3
(CrO 3 , H 2 SO 4 )
sec- BUTYL ALCOHOL BUTANONE

OH Jones reagent

CH 3 CCH 3 N.R.

CH 3
t -BUTYL ALCOHOL (3° ROH)

 From FRIEDEL CRAFTS ACYLATION-reaction of a benzene with an

acid chloride in the presence of a Lewis acid. (CHAPTER 5)

CR
O
AlCl 3
+ RCCl
OR R=Ar
A KETONE

O CH 3
CH 3
CH 3
CCH 3
O
AlCl 3
+
+ CH 3 CCl

CCH 3
O
9.4 REACTIONS OF CARBONYLS

163
Several reactions of aldehydes and ketones have been presented in earlier chapters. We have
presented reduction reactions and Grignard reactions for your review on the following page:

 REDUCTION of aldehydes and ketones-using a reducing agent to

prepare a primary (1°) or secondary (2°) alcohol. (CHAPTER 8)

O OH
H2 , Pt
RC RC
OR NaBH 4 , H 2 O H
                                                  

O O H
H2 , Pt
CH 3 CH CH 3 CH

H
AN ALDEHYDE
A 1° ALCOHOL
O O H
NaBH 4 , H 2 O
CH 3 CCH 2 CH 2 CH 3 CH 3 CCH 2 CH 2 CH 3

H
A KETONE
                                   A 2° ALCOHOL

We can also reduce aryl ketones using either the Clemmensen or Wolff-Kishner reductions, as
seen below:

O Zn(Hg), HCl
(CLEMMENSEN)
CR
OR N 2 H4 , -OH
                                     (WOLFF KISHNER)

• GRIGNARD REAGENTS-reaction with formaldehyde produces

primary (1°) ROH; with any other aldehyde produces a secondary (2°)
ROH; and with a ketone produces a tertiary (3°) alcohol.

O OH
2) H+
CH 3 CH 2 CCH 3 + CH 3 MgBr CH 3 CH 2 CCH 3

CH 3
KETONE GRIGNARD REAGENT
                                        3° ALCOHOL

Exercise 9.4

Draw the major product for each of the following reactions:

164
 H+
a. CH 3 CH 2 CH 2 C=O + CH 3 CH 2 MgCl

O
CCH 2 CH 3
HCl
b. + Zn(Hg)

H2 SO 4
c. CH 3 CH 2 C CCH 3 + H2 O
HgSO 4
              

A. CYANOHYDRIN ADDITION of H and CN across the π bond of

the C=O. The H will add to the O and the CN will add to the C.

C O + HCN C OH

CN
CARBONYL CYANOHYDRIN

O H

CH 3 CH + HCN CH 3 C OH

CN
ETHANAL CYANOHYDRIN
                                               ETHANAL

 RULE- IN NAMING CYANOHYDRINS SIMPLY ADD THE WORD

“CYANOHYDRIN” TO THE STARTING ALDEHYDE OR KETONE

B. ADDITION OF ALCOHOLS/DIOLS-Acetal formation-addition of

alkoxy groups across the π bond of the C=O by reaction with excess
alcohol in the presence of an acid.

165
 O OR'
H+
RCH + x's R'OH RCH
AN ALDEHYDE OR'
AN ACETAL

OCH 3
O
dry HCl CH 3 CH 2 CH
CH 3 CH 2 CH + x's CH 3 OH
OCH 3
PROPANAL
          DIMETHYL ACETAL OF PROPANAL

Another method of producing an acetal directly without using excess

alcohol is by using ethylene glycol (a diol) instead of an alcohol:
CH 2 CH 2

O
H+ O O
RCH + HOCH 2 CH 2 OH R H
C
A CYCLIC ACETAL
                     AN ALDEHYDE ETHYLENE GLYCOL

In the formation of an acetal, we require excess alcohol to produce the diether functional
groups. The ether functional group is unreactive and the acetal for that matter is used to
protect the aldehyde from reacting.

In the following example, we see how we use these protecting groups in the synthesis of
pentanal:

3-Pentenal has two functional groups within the molecule, can you name them?

O OCH 3
x's CH 3 OH
CH 3 CH=CHCH 2 CH CH 3 CH=CHCH 2 CH
HCl OCH 3

DIMETHYL ACETAL
OF 3-PENTENAL

H2 ,Pt
O OCH 3
HCl
CH 3 CH 2 CH 2 CH 2 CH CH 3 CHCHCH 2 CH
OCH 3
H H
                         

Why did we need to protect the aldehyde? Because the aldehyde can also be reduced by
hydrogen to a primary alcohol, an unwanted reaction.

166
In the space below show how you would reduce the aldehyde group without reducing the C=C
double bond, i.e. prepare 3-penten-1-ol.

C. IMINE FORMATION-addition of a H and a NHG* (where G can

be an H, an alkyl group, or any other atom or group)* to the π bond of
the C=O. Reaction involves a loss of H2O in the second step.
OH
- HOH
C=O + RNH 2 C C=NR
N H

1° AMINE R IMINE
ADDN PRODUCT
O
- H2 O
CH 3 CH + H2 N CH 3 C=N

H
                                  

If we replace R or Ar bonded to the N with other atoms or groups (G), we produce other C=N
compounds. In table 9.2 we indicate the names and formulas of these C=N compounds.

Table 9.2

G-NHG* Formula Name of product

and name of product

167
 NH 2 OH C NOH OXIME
HYDROXYLAMINE

NH 2 NH 2 or N 2 H4 C NNH 2 HYDRAZONE

HYDRAZINE

NH 2 NH
C NNH PHENYLHYDRAZONE

PHENYLHYDRAZINE

NH 2 NH NO 2 C NNH NO 2 ???

O2 N O2 N

2,4-DINITROPHENYLHYDRAZINE

The name of the imine from 2,4-dinitrophenylhydrazine has the initials 2,4-DNP. Can you
guess it’s name?

Exercise 9.5

Draw the major product of reacting hexanal with:

a. excess methyl alcohol with HCl

b. HCN

c. NH2OH

168
 d. Ag2O (mild oxidizing agent)

e. NaBH4

D. REACTIONS TO DISTINQUISH CARBONYL COMPOUNDS

In addition to the nitrogen derivatives mentioned in Table 9.2 to identify both aldehydes and
ketones, a relative simple reaction to distinquish an aldehyde is known as the Tollens test. The
reagent in this reaction is known as the Tollen's reagent, a silver diammine complex, and
produces a silver mirror, i.e., Tollens silver mirror test. An aldehyde will react with Tollens
reagent in a glass reaction vessel in such a way as to coat the inside of the glass vessel with
metallic silver, a silver mirror. The following reaction is an example of Tollens simple test to
identify an aldehyde:

TOLLENS TEST

O O

RCH + Ag(NH 3 ) 2 + -OH RCO - + Ag + NH 3 + H2 O

TOLLENS REAGENT SALT OF A

CARBOXYLIC ACID

In this reaction we observe that the Tollens reagent is a mild oxidizing agent and we produce
the oxidized product, the ammonium salt of the carboxylic acid and the reduced product,
metallic silver (Ag).

Another reaction that distinquishes methyl ketones from other carbonyls is known as the
iodoform test. The iodoform produced is a yellow precipitate (ppt). Below we see some
examples:

169
 O - O
OH
RC CH 3 + I2 RCO - + CH 3 I
IODOFORM
METHYL KETONE
(YELLOW PPT)

O - O
OH
-OCCH + CH 3 I
CH 3 CCH 2 CH 3 + I2 2 CH 3

IODOFORM
(YELLOW PPT)
O -
OH
C + I2 NO REACTION
                       

Once again iodine in base acts as a oxidizing agent. When present the methyl ketone is oxidized
to the salt of the carboxylic acid. Why is there no reaction with benzophenone (diphenyl
ketone)? It is NOT a METHYL ketone.

In the following example, we will distinquish between acetaldehyde and acetic acid:
O O

CH 3 CH + Ag(NH 3 ) 2 + -OH CH 3 CO - + Ag
O

CH 3 COH + Ag(NH 3 ) 2 + -OH NO OBSERVABLE CHANGE

Exercise 9.6

Using a simple chemical test distinquish between the following pairs of molecules. Be sure to
show reactions and what will be observed.

a. butanone and butyric acid

b. propionaldehyde and propene

c. 3-pentanone and 2-pentanone

170
 d. acetophenone and benzaldehyde

e. 1-butanol and 2-butanol (think)

E. CLEAVAGE REACTIONS OF ALKENES

Some cleavage reactions of alkenes that are useful preparations of aldehydes and ketones and
also helpful in determining structures of alkenes are (1) reaction with hot KMnO4 in base and
(2) reaction with ozone (O3) followed by reaction with zinc in acetic acid. This latter reaction is
known as ozonolysis.

O R
R R" -OH
R " CO - + C=O
C=C + KMnO 4
SALT OF R'
R' H ²
CARBOXYLIC KETONE
ACID

R R" R
O
2) Zn, H + C=O
C=C + O3 +
R " CH R'
R' H
ALDEHYDE KETONE

CH 3
CH 3 H O
2) Zn, H + C=O
C=C + O3 CH 3 CH + CH CH
3 2
CH 3 CH 2 CH 3
          ETHANAL BUTANONE

Many times in organic chemistry knowledge of the products can lead to the identification of the
reactant. This is true of the products of ozonolysis. We could identify the alkene reactant by

171
(1) simply arranging the carbonyl products such that the oxygens (O) are facing each other as
we see below:
CH 3
CH 3
C=O O=C
CH 3 H

(2) NOW BOX THE TWO OXYGENS

CH 3
CH 3
C=O O=C
CH 3 H

(3) ERASE BOTH OXYGENS AND CONNECT

THE DOUBLE BONDS BETWEEN THE TWO CARBONS

CH 3 CH 3
CH 3 CH 3
C= =C C=C
CH 3 H CH 3 H
                                   

We see then if the products of ozonolysis of an unknown alkene were one mole of acetone and
one mole of acetaldehyde, the alkene reactant would have been:

2-methyl-2-butene

Exercise 9.7
Identify the alkene when the products of ozonolysis are:

a. two moles of propanone

b. one mole of acetone and one mole of propanone

c. one mole of acetaldehyde and one mole of butanone

d. two moles of butyraldehyde

172
 e. one mole of hexanedial (only product-think)

Synthetically aldehydes and ketones provide convenient pathways to a variety of alcohols. It is

vital to identify the type of alcohol, i.e., 1°, 2° or 3° and how to obtain the proper chain length.

For example, let's try to synthesize 3-methyl-3-heptanol from benzene, any alcohol, any alkyl
halide, and any inorganic reagent. It is always a good idea to draw the final product first, i.e.,
3-methyl-3-heptanol:
Draw 3-methyl-3-heptanol.

OH
CH 3 CH 2 CCH 2 CH 2 CH 2 CH 3 ( A 3° ALCOHOL)

QUESTIONS CH 3

1. What do we need to prepare

+
a 3° alcohol? A ketone and a H
Grignard reagent.
2. Which ketone and which
Grignard reagent? From + ClMgCH
CH 3 CH 2 C O 2 CH 2 CH 2 CH 3
2-butanone and n-butyl
magnesium chloride. CH 3
3. How would we prepare 2-butanone n-butyl magnesium chloride
2-butanone and n-butyl
magnesium chloride?
From the givens.
CrO 3 , H + Mg, ether

CH 3 CH 2 CHCH 3 ClCH 2 CH 2 CH 2 CH 3
OH
2-butanol (a 2° alcohol)

GIVEN GIVEN

Notice since benzene was not required in this synthesis we did not use it. Remember use only
those reactants that are needed. If you are not given a reactant, you must prepare it.

Exercise 9.8

173
Given benzene, any alkyl halide of no more than 5 carbons and any inorganic reactant,
synthesize the following organic molecules:

a. 2-phenyl-1-ethanol

b. 2-heptanol

c. 2-methyl-3-pentanol

d. diphenylmethanol

174
e. 1,1-diphenyl-1-ethanol

175
 Chapter 10

CARBOXYLIC ACIDS AND THEIR DERIVATIVES

Carboxylic acids, RCOOH, are weak acids and are very important in organic chemistry. The
functional group is the carboxyl group,
O

R CO H

Although we observe an alcohol (OH) and a carbonyl (C=O), the carboxyl group is a
combination of C, H, and O atoms written as COOH. Derivatives of carboxylic acids
substitutes another atom or group of atoms for the OH of the carboxyl group. For example an
ester substitutes an alkoxy group, OR' for the OH or RCOOR', an acid chloride substitutes a
Cl for the OH or RCOCl.

10.1 NOMENCLATURE OF ACIDS

Acids can be named both commonly and IUPAC. Acids are named commonly from the Latin
or Greek word. In chapter 9, we introduced you
to the first five common acid names. In table 10.1 we will introduce you to the first ten
common acids. These names must be memorized.

Table 10.1

No. Carbon Atoms Formula Common name

1 HCOOH formic acid

2 CH3COOH acetic acid
3 CH3CH2COOH propionic acid
4 CH3(CH2)2COOH butyric acid
5 CH3(CH2)3COOH valeric acid
6 CH3(CH2)4COOH caproic acid
7 CH3(CH2)5COOH enanthic acid
8 CH3(CH2)6COOH caprylic acid
9 CH3(CH2)7COOH pelargonic acid
10 CH3(CH2)8COOH capric acid

Fatty acids which are quite common in soaps are even numbered carboxylic acids. Most soaps
contain 16 or 18 carbon atoms. Is acetic acid a fatty acid?

A. COMMON NAMES

In naming acids commonly we need to remember that the location of substituents groups are
given with a Greek letter. This is identical with the common naming of substituted aldehydes.
Let's take a look at some examples.

176
 COMMON NAMES

CH 2 COOH
a. cyclohexylacetic acid
or
α-cyclohexylacetic acid

b. CH 3 CH 2 CH 2 CH 2 CH 2 COOH
             caproic acid
COMMON NAMES

c. CH 3 CH 2 CHCH 2 COOH β-bromovaleric acid

Br

CH 3 CH 2 CH 2 CHCH 2 CHCH 2 COOH β-ethyl- δ-methylcaprylic acid

d.
CH 3 CH 2 CH 3

CH 2 CH 2 CH 2 COOH γ -aminobutyric acid

e. NH 2
              

Exercise 10.1

Write the correct structure for the following molecules:

a. γ -chlorobutyric acid

b. β−hydroxy--methylvaleric acid

c. cyclopropylacetic acid

d. ε -methyl−δ-oxocapric acid

e. α-aminoacetic acid (glycine)

177
Exercise 10.2

Name the following molecules commonly:

a. CH 3 CH 2 CHCOOH

CH 3

b. CH 3 (CH 2 ) 5 COOH

Cl

c. CH 3 CH 2 CCH 2 CH 2 COOH

Cl
                        
CH 3

d. CH 3 CH 2 CCH 2 CHCOOH

OH CH 3
O
e. CH 3 CCH 2 COOH
                       

B. IUPAC NOMENCLATURE

In naming acids systematically using the IUPAC system, we identify the longest, continuous
chain of carbon atoms including the carboxylic C. Name the parent by naming the
corresponding hydrocarbon, drop the "e" and add the letters "oic" plus the word acid.
Remembering to number the location of each substituent group and naming each substituent
group, we can use the PLS system to correctly name the following molecules:

CH 3 CH 2 CH 2 COOH P=BUTANOIC ACID

a.

Cl P=HEXANOIC ACID
b. CH 3 CH 2 CCH 2 CH 2 COOH L=4,4
Cl S= DICHLORO
4,4-DICHLOROHEXANOIC ACID
CH 3
P=HEXANOIC ACID
c. CH 3 CH 2 CCH 2 CHCOOH
L=2,4,4
OH CH 3
S= HYDROXY, DIMETHYL

4-HYDROXY-2,4-DIMETHYLHEXANOIC ACID
                 

178
In looking at the differences between the common and IUPAC systems of naming acids, you
should notice as with the nomenclature of aldehydes that the locations are indicated with a
greek letter in the common system and indicated with a number in the IUPAC system. The
carboxyl carbon is the number 1 carbon in the IUPAC system and in the common system the
carbon adjacent to the carboxylic carbon is the carbon.

Exercise 10.3

Draw the correct structure for each of the following molecules:

a. 3-bromopentanoic acid

b. 4-isopropylhexanoic acid

c. 2,4,6-trimethyloctanoic acid

d. 5,5-difluoroheptanoic acid

e. 3-oxobutanoic acid

Explain what is wrong with the following names:

a. 3-hydroxybutyric acid

b. ε -dibromopentanoic acid (Be careful with this one)

c. 2,4-methylbutanoic acid

179
Exercise 10.4

Write the correct IUPAC name for each of the following molecules:

CH 3

a. CH 3 CH 2 CHCOOH

Cl

b. CH 3 CH 2 CHCH 2 CH 2 COOH

CH 3
c. CH 3 CH 2 CCH 2 CH 2 CHCOOH

CH 3 OH
              
d. BrCH 2 COOH
O

e. HCCH 2 CHCOOH

CH 2 CH 3
              

Exercise 10.5

All of the names on the following page are INcorrect, explain why these names are NOT
possible.

a. 3-bromocaprylic acid

b. 2,4-dimethylbutanoic acid

c. δ−iodopentanoic acid

d. α-oxo-4-chloroheptanoic acid

e. α,β-ethyl-methylvaleric acid

C. CYCLIC CARBOXYLIC ACIDS

Acids that are directly bonded to a cyclic system are named and by naming the corresponding
cyclo hydrocarbon plus the words "carboxylic acid. "

180
Benzoic acid has the carboxyl group on benzene, but we can also name benzoic acid using the
rule above as seen below:

COOH

cyclohexanecarboxylic acid

COOH cyclopropanecarboxylic acid

COOH

benzoic acid or benzenecarboxylic acid

                           

Because of the ringed system we have to be concerned with geometric

isomerism as seen below:

COOH
trans-2-methylcyclopropanecarboxylic acid

CH 3

Exercise 10.6

Write the correct structure for each of the following molecules:

a. 3,5-dimethylcyclohexanecarboxylic acid

b. cis-2-methylcyclobutanecarboxylic acid

c. o-nitrobenzoic acid

d. 2,3-dichlorocyclopropanecarboxylic acid
181
 e. trans-3-ethylcyclopentanecarboxylic acid

f. 1-iodocyclopropanecarboxylic acid

Exercise 9.7

Name the following molecules:

a. COOH
                             
COOH

b.

Cl

COOH
c.
Cl

COOH
d.

CH 3

COOH
e. CH 3

                            

182
 D. DICARBOXYLIC ACIDS

Two carboxyl groups within one acid molecule is named both commonly and IUPAC in table
10.2. IUPAC naming requires identifying the longest, continuous chain of carbon atoms that
contains both carboxyl groups- the parent. Name the hydrocarbon plus the prefix "di" plus
"oic" plus the word acid. Pay special attention to the common names of the alkene dioic acids.

In the space below draw a 4 C alkane dioic acid and a 4 C alkene dioic acid:

Table 10.2

STRUCTURES COMMON NAME IUPAC NAME

HOOCCOOH OXALIC ACID ETHANEDIOIC ACID

HOOCCH 2 COOH MALONIC ACID PROPANEDIOIC ACID

HOOCCH 2 CH 2 COOH SUCCINIC ACID BUTANEDIOIC ACID

HOOC COOH
C=C MALEIC ACID CIS-2-BUTENEDIOIC ACID
H H

H COOH
C=C FUMARIC ACID TRANS-2-BUTENEDIOIC ACID
HOOC H

Some common aromatic dicarboxylic acids are listed below:

COOH
COOH
COOH

COOH
COOH
COOH

                       phthalic acid isophthalic acid terephthalic acid

10.2 PREPARATION OF CARBOXYLIC ACIDS

In reviewing the preparations of carboxylic acids, we should remember the following two
oxidations:

183
  OXIDATION OF AN ALKYL SIDE CHAIN on a benzene ring-
using a strong oxidizing agent, i.e., KMnO4, to produce the benzoic
acid.

-OH

R + KMnO 4 COOH
2) H+
                                      
CH 3 COOH
OH -
+ KMnO 4
2) H+

CH 2 CH 3 COOH
-
OH
+ KMnO 4
2) H+

CH 2 CH 3 COOH
-
OH
+ KMnO 4
2) H+
CH 2 CH 3 COOH
                                

 OXIDATION OF PRIMARY ALCOHOLS- -using a strong oxidizing agent to produce a

carboxylic acid.
H+
CH 3 CH 2 CH 2 OH + K2 Cr 2 O7 CH 3 CH 2 COOH

Note: a three carbon primary alcohol produces a three carbon

                                    carboxylic acid

Exercise 10.8

Synthesize the following carboxylic acids from benzene, or any alcohol of no more than five (5)
carbons and any inorganic reagent.

a. m-bromobenzoic acid

b. butanoic acid

184
c. hexanoic acid

d. α-chloroacetic acid

e. p-aminobenzoic acid

A. OTHER PREPARATIONS OF CARBOXYLIC ACIDS

1. REACTION OF A GRIGNARD REAGENT-reaction with CO2

followed by acid hydrolysis to produce a carboxylic acid with a one
carbon chain increase.

185
 2) H+
RMgX + CO 2 RCOOH

2) H+
CH 3 CH 2 MgCl + CO 2 CH 3 CH 2 COOH

2 C Grignard 3 C carboxylic acid

2) H+
MgBr + CO 2 COOH
                                          

2. HYDROLYSIS OF A NITRILE-reacting a nitrile with water in the

presence of an acid or base.

+ H2 O H+ RCOOH + NH 3
RC N -
or OH
acid contains
alkyl nitrile one more C than
or alkyl group
a cyanide
NAMING NITRILES (CYANIDES )
A CYANIDE IS SIMPLY NAMED BY NAMING THE ALKYL
OR ARYL GROUP PLUS THE NAME "CYANIDE".
A NITRILE IS NAMED COMMONLY BY NAMING THE COMMON
ACID FROM WHICH IT IS DERIVED, DROP THE "IC" AND
ADD "ONITRILE"
A NITRILE IS NAMED SYSTEMATICALLY BY NAMING THE ACID
FROM WHICH IT IS DERIVED, DROP THE "OIC" AND ADDING
"ENITRILE"
H+
CH 3 CH 2 CN + H2 O CH 3 CH 2 COOH
PROPION ONITRILE PROPIONIC ACID
PROPAN ENITRILE PROPANOIC ACID
ETHYL CYANIDE

Please notice in the examples above that the nitrile is named from the corresponding acid. We
should therefore include the carbon of the CN in naming the parent..

In the following molecules we have how many C?

C-C-C-C-C-C answer: 6

CH3-CH2-CH2-CH2-CH2-CN answer: ____

Therefore the IUPAC name is hexanenitrile.

What is the common name?

186
Exercise 10.9

Name the following molecules either commonly or IUPAC:

a. CH 3 CN

b. CH 3 CHCN

CH 3

c.

CN

d. CH 3 CH 2 CH 2 CH 2 CH 2 CN

e.
CN
               

Draw the correct structures of the following molecules:

f. 3-chloropropanenitrile

g. 2,4-dimethylpentanenitrile

h. 2-cyclopropyl-3-bromohexanenitrile

i.αmethyl-
 γ -hydroxyvaleronitrile

187
 j. δ ,δ difluorocapronitrile


Exercise 10.10

Draw the major product(s) of the following reactions, where no reaction write NR:

H+
a. CH 3 CH 2 CN + H2 O

MgBr
b. 2) H+
+ CO 2

H+
c. CH 3 CHCH 2 CH 2 CN + H2 O

CH 3

CH 2 CH 2 CH 2 CH 3
d. OH -
+ KMnO 4
+
2) H

2) H+
e. CH 3 CN + CO 2
                          

In the preparation of a nitrile (cyanide) it is important to remember that cyanide, CN-, is a

strong nucleophile. We may therefore react CN- with a methyl or primary (1°) alkyl halide to
produce an alkyl nitrile via an Sn2 reaction, as seen below:

RX + CN - RCN
an alkyl nitrile

CH 3 CH 2 CH 2 Cl + CN - CH 3 CH 2 CH 2 CN
butyronitrile or butanenitrile
                                propyl chloride

Exercise 10.11

Synthesize the following acids from any alkyl halide and any inorganic reactant.
188
a. butyric acid

b. hexanoic acid

c. 3-methylbutanoic acid

d. cyclohexanecarboxylic acid

e. acetic acid

189
 10.3 REACTIONS OF CARBOXYLIC ACIDS

When carboxylic acids are reacted with bases like sodium hydroxide, a salt of the carboxylic
acid and water are produced, as we see on the next page.

A. SALTS OF CARBOXYLIC ACIDS

RCOOH + NaOH RCOO -Na + + H2 O

salt of acid

CH 3 COOH + NaOH CH 3 COO -Na + + H2 O

COMMON acetic acid sodium acetate

or or
         IUPAC ethanoic acid sodium ethanoate

In naming salts, we name the metal plus the name of the acid minus "ic" plus ATE

COOH COO -K+

+ KOH + H2 O

benzoic acid potassium benzoate

How would you name the lithium salt of propionic acid? Yes, lithium propionate. How would
you name the calcium salt of pentanoic acid?

In a true saponification (soap making) reaction, the salt that is formed is the salt of a fatty
acid. A fatty acid is a carboxylic acid that has an even number of carbon atoms. Soaps
usually have between 12 and 18 carbon atoms. In a true saponification (soap making)
reaction, the soap that is formed must have:

1) a polar end AND

2) a nonpolar end

The large number of carbons C16 -C18) insures a nonpolar (hydrocarbon) end for the soap.
The ionic end (salt) provides the polar end.

Draw a soap below:

190
191
 Chapter 11

AMINES

Amines are organic bases and as a base will accept a proton (H+) from an acid or donate
electron pairs to an acid. Although amines are much weaker bases than hydroxide or alkoxide
ion, they are much stronger bases than alcohols, ester, etc. The strength of a base will be
directly proportional to the availability of the electron pairs. The more available the electron
pairs the stronger the base, i.e., 3° amine is more basic than a 2° amine or generally:

.. .. .. ..
RNR > RNH > RNH > HNH

R R H H

1°
                                            3° 2° AMMONIA

Notice amines are classified as 3°, 2°, or 1° based on the number of non H groups on the N. The
strength of a base, like an acid, can also be determined by pKb values. The smaller the pKb
value the stronger the base. In table 11.1 is a list of some common pKb values. Notice the
range of most amines are between 3 and 13.

Table 11.1
Amine pKb

Methylamine 3.4
Dimethylamine 3.3
Ethylamine 3.3
Diethylamine 3.0
n-Propylamine 3.4
Di-n-propylamine 3.1
Aniline 9.3
Diphenylamine 9.0
Triphenylamine 13

Exercise 11.1

Circle the strongest base in each case below:

a. methylamine or dimethylamine

b. aniline or methylamine

c. diethylamine or n-propylamine

d. triphenylamine or aniline

e. methylamine or ethylamine

192
11.1 NOMENCLATURE

A. COMMON

Simple alkyl amines are named by naming the alkyl group(s) bonded to the nitrogen (N) plus
the word "amine". More complicated amines are named by naming the parent hydrocarbon
(P), locating the amine substituent group (L) and naming the amine as an "amino" substituent
group (S). In the examples below we will see simple and complex amines:

SIMPLE AMINES

1° 2° 3°

CH 3 NH 2 CH 3 NHCH CH 3 NCH 3
3

CH 3
METHYLAMINE DIMETHYLAMINE TRIMETHYLAMINE

CH 3 CH 2 NH 2 CH 3 H2 NHCH 3
CH 3 CH 2 NCH 3

ETHYLAMINE ETHYLMETHYLAMINE CH 3
ETHYLDIMETHYLAMINE
CH 3

CH 3 CNH 2 CH 3 NHCHCH 3
N
CH 3 CH 3

t -BUTYLAMINE
ISOPROPYLMETHYLAMINE

                         TRIPHENYLAMINE

COMPLEX AMINES

CH 3
P=HEXANE
CH 3 CH 2 CHCH 2 CHCH 3 L=2,4
NH 2 S=AMINO, METHYL

4-AMINO-2-METHYLHEXANE

FI

CH 3 CH 2 CCHCH 2 CH 2 CH 3 P=HEPTANE
L=3,3,4
NHCH 3
S=N-METHYLAMINO,FLUORO, IODO
3-(N-METHYLAMINO)-3-FLUORO-4-IODOHEPTANE

H2 NCH 2 CH 2 CH 2 COOH P=BUTANOIC ACID

L=4
4-AMINOBUTANOIC ACID
                    S=AMINO

B. IUPAC (CHEMICAL ABSTRACT (CA))

193
Name the parent hydrocarbon drop the “e” and add the word amine. Use the PLS method for
substituted amines.

CH 3 P=2-PROPANAMINE

CH 3 NH 2 CH 3 CH 2 NH 2 CH 3 CNH 2 L=2

ETHANAMINE CH 3 S=METHYL
METHANAMINE

                     2-METHYL-2-PROPANAMINE

CH 3
P=1-BUTANAMINE
CH 3 CH 2 CHCH 2 NCH 3
L=N,N,2
CH 3 S=TRIMETHYL

                                    N,N,2-TRIMETHYL-1-BUTANAMINE

C. AROMATIC AMINES

Aromatic amines are named as derivatives of aniline as we see below:

I F

NH 2 NH 2 NH 2

Br I I Cl
M-BROMOANILINE 2,3,5-TRIIODOANILINE 3-FLUORO-5-CHLOROANILINE

CH 3 HN O2 N NCH 2 CH 3
CH 3

       N-METHYLANILINE P-NITRO-(N-ETHYL-N-METHYL)ANILINE

D. NOMENCLATURE OF AMINE SALTS

In naming salts it is very important to distinguish an alkyl from an aryl amine. If the amine
salt is derived from an alkyl amine, it is named as an ammonium salt. If the amine salt is
derived from an aryl amine, it is named as an anilinium salt. Below we observe both:

194
 SALTS OF ALKYL AMINES

CH 3 CH 2 CH 3
+ +
CH 3 NCH 3 Cl - CH 3 NH Br-
CH 3 H

TETRAMETHYLAMMONIUM CHLORIDE ETHYLMETHYAMMONIUM BROMIDE

SALTS OF ARYL AMINES

CH 3
+ +
NCH 3 NO 3 - NH 3 I-
CH 3

ANILINIUM IODIDE
     TRIMETHYLANILINIUM NITRATE

Amine salts that have four alkyl or aryl substituent groups (R or Ar) on the N are called
quaternary ammonium salts. If the four groups are different, we once again observe
stereoisomerism, i.e., R or S.

Exercise 11.2

Draw the structures of the following molecules:

a. propanamine

b. 3-amino-1-butanol

c. N,N-diisopropylpentanamine

d. p-nitro-N-methylaniline

e. ethylsec-butylammonium hydroxide

195
 f. 3-amino-2-phenylhexane

g. benzylamine

h. (R)-benzylethylmethylphenylammonium ion

11.2 PREPARATION OF AMINES

In the preparation of amines you will see most of the reactions yield primary (1°) amines. For
this reason it is imperative that you learn how to prepare not only primary (1°) but also
secondary (2°) and tertiary (3°) amines.

A. SUBSTITUTION REACTIONS -a reaction of a methyl or primary

alkyl halide with ammonia or an amine.

CH 3 CH 2 Br + HNH 2 CH 3 CH 2 NH 2 + HBr

AMMONIA 1°AMINE
                                      1°RX

The following reactions will begin with general reactions followed by specific reactions. Look
carefully at each reaction.
RX + NH 3 RNH 2
1°AMINE

R'X + RNH 2 R'NHR

1°AMINE 2°AMINE

R ' X + RNHR R'NR 2

2°AMINE 3°AMINE
+
R'X + R''NR 2 R'NR 2X -
3°AMINE
R''
                                       QUATERNARY AMMONIUM SALT

196
 CH 3 Cl + NH 3 CH 3 NH 2
1°

CH 3 CH 2 CH 2 Br + CH 3 NH 2 CH 3 CH 2 CH 2 NHCH 3

2°
Cl * NHCH 3

+ CH 3 NH 2

O2 N NO 2 O2 N NO 2
2°
*REQUIRES A STRONG
                        DEACTIVATOR O AND P

Exercise 11.3

In the above examples we prepared a primary (1°) and two secondary (2°) amines, how would
you prepare the tertiary (3°) amine, ethyldimethylamine?

B. REDUCTION OF ARYL NITRO COMPOUNDS using tin (Sn) or

iron (Fe) in a mineral acid, i.e., HCl.

HCl
NO 2 + Sn NH 2
2) -OH
1° AMINE

HCl
Br NO 2 + Sn Br NH 2
2) -OH

                                  1° AMINE

This particular reduction yields the very important primary aromatic amine, aniline. This
primary aromatic amine can be converted to an aromatic diazonium salt which can be
converted to many other functional groups, i.e., phenols.

197
 HCl
NO 2 + Sn NH 2
2) -OH
1° AMINE

NH 2 + NaNO 2 + HCl N 2 +Cl -

0°C
(HONO)
DIAZONIUM SALT

N 2 +Cl - + H2 O OH

                                PHENOL

Other very useful diazonium salt reactions producing a variety of aromatic compounds are
seen following:

CuCl (Br) H3 PO 2
(Br) Cl N 2 +Cl - H
H2 O
CuCN
CHLOROBENZENE HBF 4 BENZENE
OR BROMOBENZENE KI ²
F

CN FLUOROBENZENE
BENZONITRILE I

IODOBENZENE

In looking at the reactions above it is important to note the preparations of the fluoro and
iodobenzenes and the preparation of benzene. Both bromo and chlorobenzenes were prepared
before using a Friedel-Crafts reaction.

Write the Friedel-Crafts reactions for both the chlorination and the bromination of toluene
below.

198
Suppose we were asked to synthesize o-iodotoluene from toluene and any inorganic reagent or
reactant. What would we do? Work backwards!

KI HONO
CH 3 CH 3 CH 3
0°C
I N 2 +Cl - NH 2

Sn, HCl

CH 3 CH 3

NO 2

Take a moment to look at each step in the sequence of reactions above.

Exercise 11.4

With these steps in mind, synthesize p-iodotoluene and m-iodotoluene (Hint: how do you
remove a group and replace it with a H).

C. REDUCTION OF A NITRILE using H2 and the catalyst Ni.

Ni
RCN + H2 RCH2 NH 2
                                                

199
 Ni
CH 3 CH 2 CN + H2 CH 3 CH 2 CH 2 NH 2

CH 2 Cl + CN - CH 2 CN

BENZYL CHLORIDE PHENYLACETONITRILE

Ni
CH 2 CN + H2 CH 2 CH2 NH 2

                      2-PHENYLETHANAMINE

In the examples above we see how to convert a 2 carbon nitrile (can you name it) to a three
carbon amine. We also see how to convert benzyl chloride to the corresponding nitrile using
the strong nucleophile cyanide (CN-) to replace the good leaving group chloride (Cl-). Once we
have prepared the phenylacetonitrile, we can prepare the corresponding amine or we could
prepare the corresponding carboxylic acid (how?). Remember nitriles can be hydrolyzed (H2O
in acid or base) to the corresponding carboxylic acid, as seen
below:
RCN H+ OR -OH RCOOH
OR + H2 O OR
ArCH 2 CN ArCH 2 COOH
                                   

D. REDUCTION OF AN AMIDE using catalytic hydrogenation (H2) or

chemical reduction using LiAlH4.

O
LiAlH 4
RCNH 2 RCH 2 NH 2
-OH
2)

O
LiAlH 4
CH 3 CH 2 NH 2
CH 3 CNH 2
2) -OH

O
LiAlH 4
CNH 2 CH 2 NH 2
-OH
2)
                                        

Exercise 11.5

200
Starting with benzene, toluene, and/or any alkyl halide and any inorganic reagent or reactant,
synthesize the following molecules:

a. N,N-dimethylaniline

b. N-ethylbenzylamine

c. phenylacetic acid

d. n-butylethylamine

e. N-ethyl-2-phenylethylamine

201
11.3 REACTIONS OF AMINES

A. REACTION WITH A MINERAL ACID to produce a salt.

HX RNH 2 X -
RNH 2 +
H
AMINE SALT
+
CH 3 NHCH 3 + HCl CH 3 NHCH 3 Cl -

H
DIMETHYL AMMONIUM CHLORIDE
H
+
NCH 3 + HNO 3 NCH 3 NO 3 -

CH 3 CH 3

                              DIMETHYL ANILINIUM NITRATE

B. REACTION WITH AN ACID CHLORIDE to produce an amide.

O O

RNH 2 + RC Cl RC NHR + HCl

N-SUBSTITIUTED AMIDE
                                      1° AMINE
O O

CH 3 NHCH + CH 3 CCl CH 3 CNCH 3

3

2° AMINE CH 3

N.N-DISUBSTITUTED AMIDE
O

NCH 3 + CH 3 CCl NO REACTION

CH 3

                                       3° AMINE

 Please note the tertiary (3°) amines will NOT react with an acid halide

C. REACTIONS WITH METHYL AND PRIMARY ALKYL HALIDE to

produce secondary (2°) and tertiary (3°) amines. (SEE 11.2 A)

D. REACTION WITH NITROUS ACID (HONO)

202
 ArNH 2 + HONO ArN 2 +X -
0°C
1°AMINE DIAZONIUM SALT

RNHR' + HONO RNN O

0°C
R OR R'=Ar R'

N-NITROSOAMINE
2°AMINE

CH 3

NHCH 3
+ HONO NN=O

N-METHYL-N-NITROSOANILINE

CH 3 NHCH + HONO CH 3 NN=O

3

CH 3
N-METHYL-N-NITROSOMETHANAMINE

NR 2 + HONO O=N NR 2

3°Ar AMINE P-NITROSOAMINE

E. REACTION WITH ALDEHYDES AND KETONES-Reductive Amination

Aldehydes and ketones react with ammonia, primary (1°) amines and secondary (2°) amines to
produce primary (1°) amines, secondary (2°) amines, or tertiary (3°) amines, respectively, as
seen below:

R H2 , Ni R
C=O + NH 3 CH 2 NH 2
OR NaBH 3 CN
1°AMINE

R H2 , Ni R
C=O + RNH 2 CH 2 NH R
1°AMINE 2° AMINE

NaBH 3 CN R
R CH 2 NR 2
C=O + R 2 NH
2° AMINE
3° AMINE
O NaBH 3 CN
CH 3 CH + CH 3 CH 2 NH 2 CH 3 CH 2 NHCH 2 CH 3
                        

203
Let's see how we could synthesize 3-(N-methylamino)pentane from 3-pentanone and any alkyl
halide and any inorganic reactant or reagent.

CH 3 CH 2
CH 2 NHCH 3
CH 3 CH 2

O
H2 ,Ni CH 3 CH 2 CCH 2 CH 3

NH 3
CH 3 Cl CH 3 NH 2
                      

REACTIONS THAT GIVE AROMATIC AMINE SUBSTITUTION

 (Review aromatic substitution reactions; CHAPTER 6)

IN THE SPACE BELOW NITRATE 1,3-DINITROBENZENE AND P-NITROTOLUENE.

Since the amine functional group is a very strong activator that directs ortho (o) and para (p),
it is important for us to be aware of specific reactions that will produce the desired products, as
seen below:

204
 Br
Br2
Br NH 2

Br
NH 2 2,4,6-TRIBROMOANILINE

STRONG ACTIVATOR O
O
(O,P DIRECTOR) CH 3 CCl
NHCCH 3

MODERATE ACTIVATOR
(O,P DIRECTOR)
Br2

O
H2 O
Br NH 2 Br NHCCH 3
-OH

P-BROMOANILINE

It is very important to observe each reaction for if we desire the mono substituted bromo (p-
bromo) product we cannot accomplish it with direct bromination of aniline. Because the
acetamino (NHCOR) group is a weaker activator than the amino group, we can obtain the para
bromo product by hydrolyzing the acetamino group in our final step above.

Exercise 11.6

Draw the structure of the missing (?) reactant or product for each of the reactions below:
O
a. CH 3 CH 2 CNHCH + ? CH 3 CH 2 CH 2 NHCH
3 3

b. CH 3 CH 2 CH 2 CH 2 NHCH + HONO ?
3

NH 2

c. + HONO ?
0°C
CH 3

d. CH 3 CH 2 CN + ? CH 3 CH 2 CH 2 NH 2

NCH 3

e. CH 3 + HONO ?

                    

205
Aminoacids are the basic structural unit of a protein. A protein consists of many α-aminoacids.
Since there are 20-22 α-amino acids, we see many combinations are possible. In table 11.2 we
see some α-amino carboxylic acids and their common names. Note the α-refers to the position
of the amino group relative to the carboxyl group.Because the molecule contains both a basic
group (NH2) and an acid group (COOH) the actual molecule will appear as a zwitterion or
dipolar ion. In table 11.2 we list the unionized form followed by some zwitterions.

RCH 2 CHCOO -

+ NH 3

A ZWITTERION OR
                                                     DIPOLAR ION

Draw the zwitterion of α-aminoacetic acid.

Table 11.2

H2 NCH 2 COOH GLYCINE (GLY)

CH 3 CHCOOH (ALA)
ALANINE
NH 2

NH 2

CH 3 CHCH 2 CHCOOH LEUCINE (LEU)

CH 3
NH 2

CH 3 CH 2 CHCHCOOH ISOLEUCINE (ILEU)

CH 3
                         

In each case a zwitterion or dipolar ion would exist, i.e.,

206
 -
+NH 3 CH 2 COO Glycine
-
CH 3 CHCOO
Alanine
+ NH 3

-
CH 2 CHCOO
Phenylalanine
NH 3
+

- Cysteine
HSCH 2 CHCOO

                                          +NH 3

Exercise 11.7

Draw the zwitterion for Leucine and Isoleucine. Draw the unionized form for Phenylalanine
and Cysteine. Draw α, β and γ aminoacid.


Another important aminoacid is p-aminobenzoic acid or PABA. PABA is required to continue

the growth cycle of bacteria. It is also very common in sun tan lotions.
Let's say we would like to synthesize p-aminobenzoic acid from benzene, any alkyl or acid
halide and any inorganic reagent or reactant. We start by drawing our product and working
backwards.

207
 COOH

NH 2
HNO 3 p-aminobenzoic acid
H2 SO 4
HCl, H O
2
NO 2
COOH
Sn, HCl

NHCCH 3

O
NH 2
O KMnO 4

AlCl 3
CH 3 CCl
CH 3

CH 3 Cl
AlCl 3

NHCCH 3 NHCCH 3

O O
        

In looking at the synthesis why did we convert the amino group (NH2) to the acetamino group
(NHCOCH3)? Right it is much less reactive but more importantly aniline will NOT undergo a
Friedel-Crafts reaction. (See exceptions to a Friedel-Crafts reaction)

Exercise 11.8

From benzene, any alkyl or acid halide and any inorganic reactant or reagent, synthesize the
following molecules:

a. m-aminobenzoic acid

b. m-fluorobenzoic acid
208
c. m-iodobenzamide

d. p-aminobenzenesulfonic acid

e. p-aminobenzenesulfonamide (sulfanilamide-the first sulfa drug)

209
 Chapter 12

DERIVATIVES OF CARBOXYLIC ACIDS

Reactions of carboxylic acids produce the various derivatives of carboxylic acids, i.e., esters.
Derivatives of carboxylic acids all share the carbonyl, C=O, group, but differ in what is
substituted for the OH. For example esters substitute an alkoxy group, OR, or a phenoxy
group, OPh, for the OH. Acid chlorides substitute a chloride, Cl, for the OH. In naming
derivatives the name of the carboxylic acid is always used minus the "ic" ending plus the
appropriate ending. Esters end with the letters "ATE", acid chlorides end with the letters
"YL", and amides end with the word "amide" to name a few.

ACYL OR ACID HALIDES

Acyl or acid halides (Cl or Br) are very reactive and are preferred as a reactant to produce
some products, eg. esters.

12.1 NOMENCLATURE

In naming acid halides, we drop the "ic" of the corresponding carboxylic acid and add the
ending "YL" plus name the halide. For example the acid chloride, benzoyl chloride, is shown
below with the appropriate reasoning:

COOH CCl

BENZOIC ACID BENZO YL CHLORIDE

From benzoic acid we would name the corresponding acid chloride by dropping
the "ic" of the acid and adding the letters "YL" plus the name "chloride".

ACID CHLORIDE COMMON NAME IUPAC

O

CH 3 CCl acetyl chloride ethanoyl chloride

CH 3 CH 2 CH 2 CCl butyryl chloride butanoyl chloride

CH 3 CHCH 2 CCl β-methylbutyryl chloride 3-methylbutanoyl chloride

CH 3

210
Exercise 12.1

Draw the structures of the following acid halides:

a. butanoyl bromide

b. α-methylvelaryl chloride

c. benzoyl bromide

d. 3-bromopropanoyl bromide

e. heptanoyl chloride

12.2 PREPARATIONS

Acid halides are prepared from the corresponding carboxylic acids or acid derivatives using
thionyl chloride, SOCl2, (acid chloride) or with phosphorus trihalide, PX3, (acid chloride or
acid bromide).
O

RCOOH + PX 3 RCX

X=Cl or Br

CH 3 COOH + PBr 3 CH 3 CBr

acetic acid acetyl bromide

O
COOH CCl

+ SOCl 2

                            

12.3 REACTIONS

Reactions of acyl halides provides a very convenient way to prepare a variety of functional
groups, as seen below:

1. Ketone-Friedel-Crafts acylation reaction with benzene

211
 O

CCH 3
O
AlCl 3
+ CH 3 CCl

                                    

2. Esters-reaction with an alcohol or a phenol

O O

RCX + R'OH RCOR'

                                           an ester
O O

CH 3 CH 2 CCl + CH 3 OH CH 3 CH 2 COCH 3

O O
CCl COCH 2 CH 3
+ CH 3 CH 2 OH

                       

3. Amides-reaction with ammonia or a derivative of ammonia,

eg. an amine

O O

RCX + NH 3 RCNH 2

an amide

O O

CH 3 CH 2 CH 2 CCl + CH 3 NH 2 CH 3 CH 2 CH 2 CNH

CH 3
an amine an N-substituted amide

O
O
CH 2 CBr
CH 2 CNCH 3

+ CH 3 CH 2 NHCH 3 CH 2 CH 3

                        an N, N-disubstituted amide

Exercise 12.2

Draw the major product for each of the following reactions:

212
 O

a. CH 3 CH 2 CCl + CH 3 NH 2
O

(CH 3 ) 2 CHCBr + (CH 3 ) 2 NH

b.

c. CH 3 + (CH 3 ) 2 CHCBr
          
O

d. CCl + CH 3 OH

e. OH + CH 3 CH 2 CCl
              

ESTERS

Esters are usually nice smelling and are often used as flavoring agents. Esters have the
general formula RCOOR' where the R' may be identical to or different from R. In looking at
the ester as compared to the acid, we see an carbonyl (RC=O) and an alkoxide (OR') or
possibly a phenoxide (OPh).

12.4 NOMENCLATURE

In naming esters, we name the the R' or Ph group first followed by the name of the carboxylic
acid minus the "ic" ending and adding the ending "ate".

COMMON IUPAC
O

CH 3 CH 2 COCH METHYL PROPIONATE methyl propanoate

3

O
CH 3 CH 2 COCH 2 CH 3 ethyl propionate ethyl propanoate

O
CH 3 CH 2 CO phenyl propionate phenyl propanoate

CH 3 CH 2 CH 2 CH 2 CO CH 3 METHYL VALERATE METHYL PENTANOATE

           

213
 12.5 PREPARATION

Esters can be prepared from carboxylic acids AND acid chlorides.(see above reactions) In
planning a synthesis of an ester, the preferred method would be to use the acid chloride
because of the reactivity and the lack of an equilibrium reaction.

EQUILIBRIUM REACTION ( )
O
COOH
COCH 3
H+
+ CH 3 OH

                  
REACTION GOES TO COMPLETION ( ) -NO equilibrium

O O

CCl COCH 3

+ CH 3 OH

                   

Note the presence of the acid catalyst, H+, in the equilibrium reaction and the absence of a
catalyst in the reaction that goes to completion.

Exercise 12.3

Synthesize methylbutanoate using (a) the corresponding carboxylic acid and alcohol; (b) the
corresponding acid chloride and alcohol.

Exercise 12.4

Synthesize the following molecules from benzene, any alkyl or acyl halide and any inorganic
reagent or reactant:

a. benzoic acid

214
 b. 2-phenyl-1-ethanol

c. methyl benzoate

d. acetophenone (methylphenyl ketone)

e. sodium 2-phenylacetate

12.6 REACTIONS

Esters are not as reactive as acid halides. Therefore heat or catalysts like acids or bases are
common in ester reactions. Esters react with water (hydrolysis), with other alcohols
(transesterification), with ammonia or an amine (ammonolysis) or with a base like NaOH
(saponification-soaps) to produce cleavage products like carboxylic acids, esters, amides or
salts respectively as seen below:

215
 1. ALKOXY CLEAVAGE REACTIONS

H2 O
RCOOH + R'OH (hydrolysis)
H+

R''OH
RCOOR' RCOOR'' + R'OH (transesterification)
H+
O
NH 3 (ammonolysis)
RCNH + R'OH
2
heat

H2 O
RCOO -Na + + R'OH (saponification)
NaOH ,
heat
O O
heat
CH 3 COCH 2 CH 3 + CH 3 NH 2 CH 3 CNHCH + CH 3 CH 2 OH
3

O O
heat
CH 3 COCH 2 CH 3 + NaOH CH 3 CO -Na + + CH 3 CH 2 OH
H2 O
O O
H+
CH 3 COCH 2 CH 3 + CH 3 OH CH 3 COCH + CH 3 CH 2 OH
                     3

216
Exercise 12.5

Complete the following reactions by drawing the structure of the missing product or reactant
(?):
H+
a. CH 3 CH 2 COOH + ? CH 3 CH 2 COOCH 2 CH 2 CH 3

O
heat ?
b. COCH + CH 3 CH 2 NH 2
3

H+
c. CH 3 CH 2 CH 2 COCH 3 + H2 O ?

O O
H2 O
d. CH 3 CH 2 COH + ? CH 3 CH 2 CO -Na +
heat

H+
CH 3 COOCH + CH 3 CH 2 OH ?
               e. 3

2. REDUCTION of an ESTER-using LiAlH4 to produce a primary

(1°) ALCOHOL
ether
RCOOR' + LiAlH RCH 2 OH + R'OH
4
2) H+

ether
CH 3 CH 2 COOCH 3 + LiAlH 4 CH 3 CH 2 CH 2 OH + CH 3 OH
2) H+
                                

3. GRIGNARD REACTION of a ESTER -to produce a tertiary

(3°) alcohol, as is seen below:

OH
ether
RCOOR' + 2 R''MgX RCR''
2) H+
R''

OH
ether
CH 3 COOCH 2 CH 3 +2 CH 3 CH 2 CH 2 MgBr CH 3 CCH 2 CH 2 CH 3
2) H+
CH 2 CH 2 CH 3

                      3°ROH
217
 AMIDES

Amides are the least reactive of the derivatives of carboxylic acids. They are classified as
primary (1°), secondary (2°), or tertiary (3°) depending on the number hydrogens (H) on the
N.

O O O

RCNH 2 RCNHR RCNR 2

                        PRIMARY SECONDARY TERTIARY

12.7 NOMENCLATURE

Amides are named either commonly or IUPAC by dropping the "ic"(common) or "oic"
(IUPAC) of the corresponding carboxylic acid and adding the word amide.

PRIMARY AMIDES

O O O

CH 3 CNH 2 CH 3 CH 2 CNH 2 CH 3 CH 2 CH 2 CH 2 CNH 2

COMMON: acetamide propionamide valeramide

IUPAC: ethanamide propanamide pentanamide

SECONDARY AMIDE TERTIARY AMIDE

O O

CH 3 CNHCH CH 3 CNCH 3
3
CH 3
N-methylacetamide N,N-dimethylacetamide

O O O
CNH 2 CH 3 CHCNH 2 CH 3 CHCNH

CH 3 CH 3 CH 3
α-methylpropionamide α,N-dimethylpropionamide
benzamide

Notice how N substitution differs from C substitution in naming the last two examples.

Exercise 12.6

218
Draw the structure for the following amides. Indicate if they are primary (1°), secondary (2°), or
tertiary (3°).

a. N-ethylbenzamide

b. hexanamide

c. 2-ethylpentanamide

d. N-ethyl-N-methylpropionamide

e. 2,3-dimethylbutanamide

12.8 PREPARATION

From a carboxylic acid or an acid halide using ammonia or an amine. The preferred method
would be to use an acid halide because of its reactivity, i.e. an acid chloride and an amine (see
reaction below). If a carboxylic acid is used heat must be supplied, as seen below:
O
heat
RCOOH + NH 3 RCNH 2
O
heat
CH 3 CH 2 COOH + NH 3 CH 3 CH 2 CNH 2
O O

CH 3 CCl + CH 3 CH 2 NH 2 CH 3 CNH CH 2 CH 3
                                    

12.9 REACTIONS

Hydrolysis or alcoholysis of an amide to produce the corresponding carboxylic acid or

ester. respectively. Amides are not very reactive, however amides can be converted to
the corresponding acids or ester under severe conditions, heat and acid or base
catalyst.

219
 HYDROLYSIS

O
heat
+ HOH RCOOH + NH 3
RCNH 2 + -
H or OH
ACID
ALCOHOLYSIS
O
heat + NH 3
R'OH RCOOR'
RCNH 2
+
H+ or OH -

                            ESTER

Reduction of amides to produce an amine with LiAlH4. This is a very

good reaction to produce amines (Chapter 11).

O
ether
RCNH 2 + LiAlH 4 RCH 2 NH 2
2) OH -
                                     
O
CH 2 NH 2
CNH 2
ether
+ LiAlH 4
2) OH -
                           

Exercise 12.7

Using benzene, any alkyl halide and any inorganic reactant synthesize :

a. benzoic acid

b. methyl benzoate

220
 c. benzamide

d. benzoyl chloride

e. N-methylbenzylamine

Exercise 12.8

Complete the reaction wheel on the following page by drawing the correct structure for the
unknown (?). If there is no reaction write NR and if there is more than one product formed
draw the structure of the major product:

221
 O

? CH 3 CH 2 CH 2 CCl

NH 3 ,
heat ?
CH 3 OH LiAlH 4 , ETHER
? CH 3 CH 2 CH 2 COOH ?
H+ 2) H +
?
CH 3 OCH 3 O
? CH 3 CH 2 CH 2 COCHCH 3

CH 3
                         

222
 APPENDIX A

ELIMINATION vs SUBSTITUTION

If we react several alkyl halides with hydroxide ion, OH- we observe different products. With
methyl and primary (1°) alkyl halides, we observe substitution products. In this case the
products are alcohols.

RX + OH - ROH + X-

CH 3 Cl + OH - CH 3 OH + Cl -

-
CH 3 CH 2 Br + OH - CH 3 CH 2 OH + Br

With secondary (2°) and tertiary (3°) alkyl halides, we observe elimination products. In this
case the products are alkenes.

X R
RCCH 3 + -OH C=CH 2
+ X-
R
R
3° RX ALKENE

CH 3 CHCl + -OH CH 3 CH=CH 2

+ Cl -
CH 3

2° RX
CH 3 CH 3
CH 3 CBr + -OH C=CH 2 + Br-
CH 3
CH 3
                           

 Predicting Substitution Reactions or Elimination

For substitution or elimination reactions to occur several factors come into play. One, as
mentioned above, was the type of alkyl halide we were reacting. The second factor is the
strength of the base, i.e., OH-. Generally as we go across a period from left to right basicity
decreases, eg. F-< OH-< NH2-< CH3-.

As we proceed down a family the basicity decreases, eg. I-< Br-<Cl-< F-.

223
Generally the more negative the charge of the ion the stronger the base, eg.
O-2 is a stronger base than OH-.

Exercise A1

Circle the strongest base in each set.

a. O-2 or S-2

b. CH3- or SiH3-

c. H2O or NH3

d. NH3 or NH2-

In table A1 below lists some strong and weak bases. It would be very helpful to know which
bases are strong and which are weak.

Table A1

STRONG BASES WEAK BASES

CH 3 - CH 4

NH 2 - NH 3

-OR i.e. -OCH ROH i.e. CH

3 3 OH

-OH H2 O

HC C- HC CH

                            

The term bulky is sometimes used to describe a base. What is a bulky base? A bulky base is a
base that is highly substituted, i.e., a tertiary carbon as seen below:

224
 -
A BULKY BASE OF THE TYPE RO MEANS

CH 3

CH 3 CO -

CH 3

HIGHLY SUBSTITUTED AT THIS POSITION

                             

The third factor in deciding if a substitution or elimination will occur is the leaving group. A
leaving group is that atom or group of atoms that is removed (leaves), during the course of a
reaction. Good leaving groups are weak bases. For the most part alkyl halides provide a good
leaving group. What is that leaving group? ____ Is it a strong or weak base? ____

In addition to these three factors, temperature is important in distinguishing substitution from

elimination. A good general rule is increasing temperature favors elimination reactions.

 With these factors in mind we need to ask the following questions and from our
answers we can predict a substitution or an elimination reaction:

RX + Y- ------> ?

1. Is X- a good leaving group? If the answer is not yes then there is NO

reaction.

2. If R is methyl (CH3), then we will observe a substitution product. Can we have an

elimination product with one carbon?

3. If R is primary (1°), is Y a bulky base OR A STRONG BASE WITH NO HEAT

(a) If the answer is yes then we will observe a SUBSTITIUTIONproduct.

OR

(b) If the answer is no then we will observe an ELIMINATION product.

4. If R is secondary (2°) or tertiary (3°), is Y a strong base AND WEAK ``

NUCLEOPHILE?

(a) If the answer is yes, then we will observe an elimination product.

OR

(b) If the answer is no, then we will observe a substitution product.

Let's apply these rules to the following examples:

225
 -
a. CH 3 Cl + OH CH 3 OH + Cl -

- -
1. Is Cl a good leaving group? Yes, Cl is a weak base.
2. Is R a 1°, 2°, or 3°? Neither R is methyl
3. THE ONLY PRODUCT OBSERVED IS FROM SUBSTITUTION

- CH 3
b. CH 3 CHBr + OH C=CH + H2 O + Br-
2

CH 3 H
- -
1. Is Br a good leaving group? Yes, Br is a weak base.
2. Is R a 1°,2°, or 3° alkyl group? R is a 2° alkyl group.
-
3. Is OH a strong base? Yes.
4. The major product observed is from elimination.
                   

Exercise A2

Indicate the products as, i.e., substitution (S) or elimination (E) or no reaction (NR), for of the
following reactions:

a. CH 3 CH 2 I + HC C-

CH 3

b. CH 3 C Br + HC C-

CH 3
                      
c. CH 3 CHF + H2 O

CH 3

d. CH 3 OH + Cl -
                      

 Elimination Reactions to Produce Alkenes

In planning synthesis, we are often presented with a situation where we know one reaction will
occur, but we want another reaction to occur. This is exactly the situation that occurs with the
following reactions:

226
 CH 3 CH 2 Cl + -OH CH 3 CH 2 OH + Cl -

We would correctly predict the major product to be the

substitution reaction.

How could we force this reaction to yield as its major

product the elimination reaction?

a. use a bulky base:

CH 3
CH 3 CH 2 Cl + CH 3 CO - CH 2 =CH 2

CH 3

OR

b. use a strong nonbulky base with heat

alcohol
CH 3 CH 2 Cl + OH - CH 2 =CH 2
heat

                        .

We see we can control our product, substitution or elimination, by choice of reactants (bases)
and by controlling temperature. If we choose a strong, nonbulky base and heat, we observe a
product that we recognize as an alkene. The formation of the alkene occurs when the base
removes the proton (H+) from the carbon atom immediately adjacent to the carbon atom
bonded to the halogen, as seen below:
B:
H
2 1
CH 3 C CH 2

H Cl

Note the numbers above carbon atom (1) bonded to the halogen,
the α carbon, and the adjacent carbon atom (2), the βcarbon.
This process is called a 1,2 or β elimination with every step
occurring simultaneously, a concerted process described below:

As the base, B:,abstracts the H+ from C (2) the electrons left on

                          C (2) form a π bond with C (1) and the halide is eliminated.

This type of reaction is known as a dehydrohalogenation.

Since dehydrohalogenations yield alkenes, it is important that we learn a relation between

substitution pattern and alkene stability. The general rule is the greater the number of bonded

227
alkyl groups, not H, to the C=C the greater is the alkene's stabitity. Another way of saying the
same thing is the more highly substituted the alkene the more stable is the alkene.
Table 2 lists the relative stabilities of alkenes.

Table 2
R R R R RH H R R R H HH H
C=C > C=C C=C
> > C=C > C=C > C=C > C=C
R R R H R H R HH HR HH H
tetrasubst trisubst disubst monosubst unsubst

i.e.
CH3 CH3 CH3 H H CH3 H H
C=C > C=C > C=C > C=C
CH3 CH3 CH3 H CH3 H CH3 CH3

 Dehydrohalogenation-a reaction that eliminates a H and a

X and produces an alkene.

alcohol
RX + OH - C=C + H2 O + X -
heat

alcohol H3 C H H3 C CH 3
CH 3 CH 2 H
CH 3 CH 2 CHCH 3 C=C + C=C + C=C
OH -, heat H CH 3 H H
Cl H H
trans and cis-2-butene are major products very minor product

Of the two products-cis and trans, trans is the major product

In the example above, we see three organic products. The major product is the 2-butenes and
of the 2-butenes, the trans is more stable than the cis. In addition to heat you also notice
alcohol may or may not be present in these reactions. Alcohol is used to keep the organic
reactants and products in solution.

 SATZEFF’S RULE

In the nineteenth century a Russian chemist, A.N. Saytzeff, found that in the majority of the
elimination reactions he studied, the most stable or the most highly substituted alkene was
produced. Whenever an elimination occurs that produces the most stable alkene, Saytzeff's
rule is obeyed and many times the alkene is referred to as Saytzeff's product.

In dehydrohalogenation reactions, it is useful to remember the strong bases and the need for
alcohol and heat to produce the desired product.

The desired product from the dehalogenation of 2-chlorobutane is:

228
 TRANS-2-BUTENE

Draw the SAYTZEFF product from the dehalogenation of 2-bromo -2-methylbutane?

Exercise A3

Predict the product of the following dehydrohalogenations:

a. alcohol
CH 3 CH 2 CH 2 Cl + CH 3 O-
heat

CH 3
alcohol
b. CH 3 CHCHCH + OH -
3
heat
Cl

alcohol
c. CH 3 CHCH 3 + CH 3 CH 2 O-
heat
Cl

CH 3
alcohol
d. CH 3 CBr + CH 3 O-
heat
CH 3
                        

 Stereochemistry of Elimination

Does the H and the X eliminate from the same side (syn) or from opposite sides (anti) of the
alkyl halide? The answer is anti and can be seen in the elimination of HX from several
cyclohexyl halides.

Show what you think is meant by anti elimination by dehalogenating cis-1-chloro-2-

methylcyclohexane. (Hint: draw the cis-1-chloro-2-methylcyclohexane first)

229
Now check your answer by looking at the following anti eliminations:

H heat
+ :B(base)

CH 3 CH 3
-
heat
H + OH

H H
Cl 3-methylcyclohexene-major product

H
CH 3 + OH - CH 3 CH 3
heat
CH 3
H Cl H
major product

CH 3
heat
CH 3 + OH - no rxn (no anti H to Cl)

H
H Cl
                       

 Dehydration-a reaction that eliminates H and OH (H2O)from an alcohol

to produce an alkene.

Remember the use of an acid is very important in this reaction to produce a good leaving
group.

What do you think is the good leaving group?

Why is it important to have a good leaving group?

230
 heat
ROH + H2 SO 4 or H 3 PO 4 C=C + H2 O

CH 3 H3 C CH 3
CH 3 CHCHCH 3 + H3 PO 4 C=C
heat
H CH 3
OH

OH
heat
+ H2 SO 4

                          only product

In the second example above, Saytzeff's rule is the answer to why 2-methyl-2-butene is the
major product. So we see Saytzeff's products occurs with molecules other than just alkyl
halides.

• Debromination of Vicinal Dibromides-the eliminaton

of Br and Br from vic dibromide to produce an alkene.

In the example reactions below draw a box around the two bromines (Br) in the reactant, the
dibromide, that are going to be eliminated. Do you see that a carbon-carbon double bond is
required for each carbon to have four bonds.

acetone
C C + 2 NaI C=C + I2 + 2 NaBr
Br Br

acetic acid
C C + Zn C=C + ZnBr2
or ethyl alcohol
Br Br

HOAc
CH3 CHCHCH3 + Zn CH3 CH=CHCH3
(acetic acid)
Br Br
                

231
Exercise A.4

Draw the major organic product(s) for the following reactions:

HOAc
a. CH 3 CHCHCH 2 CH 3 + Zn

Br Br

b. heat
+ H2 SO 4

OH

CH 3 heat
+ H3 PO 4
c. CH 3 COH

CH 3

d. CH 2 CHCH 3+ HC C-
Cl
                                

 Elimination to Produce an Alkyne

Two successive dehydrohalogenations of a vicinal (vic) or geminal (gem) dihaloalkane will

produce an alkyne. The base that must be used to effectively dehydrohalogenate a haloalkene
must be stronger than hydroxide, -OH, i.e., -NH2. In the following examples look closely at
each reaction. In reaction 1, step one hydroxide ion, (OH-), is used to remove the first H and
the subsequent halide and the second step amide, (NH2-), is used to remove the second H and
the subsequent halide to obtain the alkyne. In reaction 2, a one step reaction using the strong
base amide removes both H's and halides in a single reaction.

REACTION 1 AND REACTION 2

232
 H H CH 3 H
1. + OH -
C=C
CH 3 C CCH 3
Br CH 3
Br Br

CH 3 H
+ -NH 2 CH 3 C CCH 3
2. C=C
Br CH 3
                 
OR IN 1 STEP

H H
+ x's -NH 2 CH 3 C CCH 3
CH 3 C CCH 3

Br Br
                             

In the examples above the dihalide is vicinal.

Exercise A.5

Write the two step reaction for the dehydrohalogenation of a gem dihalide to produce an
alkyne AND a one step dehydrohalogenation of a gem dihalide to produce an alkyne.

We can now extend our synthesis problems to include these new reactions, as you see below:

Synthesize acetylene from ethyl alcohol, C2H5OH, and any inorganic reactant.

233
 Br Br
x's -NH 2
HC CH H2 C CH 2

CCl 4 Br2

H2 C=CH 2

heat H2 SO 4

CH 3 CH 2 OH
                                            
Exercise A.6

Synthesize the following molecules from the given molecule, any alkyl halide of no more than
two carbons and any inorganic reagent or reactant:

a. 1-bromopropane from ethyl alcohol, CH3CH2OH

b. 2-butyne from 2-bromobutane

c. 2,2,3,3-tetrachloropentane from 2-iodopentane

d. 3-phenyl-1-chloropropane from benzene

234
NUCLEOPHILIC SUBSTITUTIONS-Sn

In a substitution reaction, the reactant that is replacing the leaving group is called a
nucleophile or (nucleus loving). Since the nucleus is positively charged, the nucleophile is either
negatively charged or has electron pair that are readily available for bonding. The strength of
the nucleophile is a very important factor in substitution reactions. Generally the stronger the
nucleophile the faster the substitution. The strength of a nucleophile, like basicity, generally
decreases as we go across a period from left to right and unlike basicity, increases in strength as
we go down a family. In table A.3 is a list of strong and weak nucleophiles.

Table A.3

NUCLEOPHILES
Strong Weak
I-(in acetone), SH-, H2O, ROH (i.e. CH3OH)
R-(i.e. CH3-), OH-, F-(in acetone), Cl-,
NH2-, OR- (i.e. OCH3-) HSO4-, NO3-
OAc-, CN-

 Type of Sn Reaction

When a weak nucleophile substitutes at a 2° or 3° carbon, the reaction is known as an Sn1 and
when a strong nucleophile bonds to a methyl or 1° carbon it is known as an Sn2 reaction.

Substitution Reactions to Produce Other Functional Groups

Alcohols- A substitution reaction of alkyl halide, RX, with a hydroxide ion or

H2O. With a methyl or primary (1°) RX, we must use -OH and with secondary
(2°) or tertiary (3°) RX, we must use H2O.

Remember a halide, X-, is a good leaving group and as a good leaving group can undergo
nucleophilic substitution readily.

235
 RX + -OH ROH + X-
R=1° OR METHYL

RX + H2 O ROH + HX

                                     R=2° OR 3°

Which of the examples above would be classified as an Sn1? Sn2?

 Ethers- a substitution of alkyl halide, RX, with an alkoxide ion, RO- or an alcohol, ROH. With
a methyl or primary (1°) RX, we must use -OR and with secondary (2°) or tertiary (3°) RX, we must
use ROH. (SEE ETHERS)

Exercise A.8

Synthesize the following molecules from benzene, any alkyl halide, and any inorganic reagent.

a. 1-bromo-2-phenylethane

b. CH3CH2OCH2CH2CH3

236
 c. 3,3,4,4,-tetrabromohexane

CH 2 CH 2 CH 2 OH

d.

e. CH 3 CCH 2 CH 2 CH 3
                                   

237
 APPENDIX B

MECHANISMS

 MECHANISM­COMPLETE STEP BY STEP DESCRIPTION OF WHAT OCCURS 
FROM REACTANTS TO PRODUCTS

1. FREE RADICAL MECHANISM HAS THREE STEPS

1. INITIATION

2. PROPAGATION

3. TERMINATION

CHLORINATION OF METHANE

uv
Initiation: Cl 2 2 Cl .
or ²

Propagation: Cl . + CH4 CH3 . + HCl ²H= 1 kcal

CH3 . + Cl 2 CH3 Cl + Cl . ²H= 26 kcal

Termination: CH3 . + Cl . CH3 Cl

OR
CH3 . + CH3 . H3 CCH 3
Calculate the ∆H(rxn) for :

CH 4 + Cl 2 CH 3 Cl + HCl

REACTION PROFILE FOR THE PROPAGATION STEPS

238
 [R H X]
[R X X]
R. + X2
E Ea HX
RH + X .

-²H
RX + X .

REACTION COORDINATE

2. IONIC MECHANISM

A. ELECTROPHILIC ADDITION REACTIONS

C=C + E Nuc C C

E Nuc
TWO STEP MECHANISM

C=C C C+ C C
E+ E Nuc - E Nuc

A. HOMOGENEOUS ADDNS

1. CATALYTIC HYDROGENATION

Pt or Ni
C=C + H2 C C
or Pd
H H
syn addn

2. HALOGENATION

239
 X

C=C + X2 C C
(X=Cl or Br X
sometimes I) anti addn

TWO STEP MECHANISM

X- X
C=C C C C C
X+ X- X
+ X
halonium ion

B. HETEROGENOUS ADDITIONS

1. HYDROGEN HALIDES

C=C + HX C C
(X=Cl or Br X H
or I) Markownikov addn

2. ACID CAT HYDRATION

H+
C=C + HOH C C H

OH
Markownikov addn

THREE STEP MECHANISM

C=C C C C C H
+
H+ H + OH

. . .. H
O . . ..
O
H H
H H

240
ALL IONIC MECHANISMS INVOLVE THE FORMATION OF A CARBOCATION-A
CARBON WITH A POSITIVE CHARGE OR SLIGHTLY POSITIVE CHARGE IN THE
CASE OF A CYCLIC THREE MEMBERED INTERMEDIATE I.E. HALONIUM ION.

241