Organic Chemistry Midterm Review

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ORGANIC CHEMISTRY I
Midterm Revision
Contents
Review ....................................................................................................................................................2
A Terminology Guide .............................................................................................................................3
Unsaturation, Formal Charges..............................................................................................................5
Multiple-Choices Questions ..............................................................................................................5
Answer to Multiple-Choices Questions ............................................................................................5
Hybridization ..........................................................................................................................................7
Polarity ...................................................................................................................................................8
Physical Properties ...............................................................................................................................9
Answer to Multiple-Choices Questions ......................................................................................... 10
Acid-Base Property ............................................................................................................................. 11
Multiple-Choices Questions ........................................................................................................... 11
Free-Response Questions .............................................................................................................. 13
Stereochemistry ................................................................................................................................. 14
Configurations of Double Bonds (E/Z) .......................................................................................... 15
Configurations of Stereocenters (R/S) ......................................................................................... 16
Stereochemical Relationships ....................................................................................................... 18
Answers to Multiple-Choices Questions ....................................................................................... 21
Nomenclature ..................................................................................................................................... 22
Free-Response Questions .............................................................................................................. 23
Aromaticity and Electrophilic Aromatic Substitution (SEAr) ........................................................... 24
1
Phan Tại Tính Trí và Nguyễn Lê Hoàng Phúc biên soạn.

Dehydration of Alcohols and Formation of Acetals ......................................................................... 26
Multiple-Choices Questions ............................................................................................................ 26
Nucleophilicity ..................................................................................................................................... 28
Nucleophilic Acyl Substitution ........................................................................................................... 29
Nucleophilic Substitution and Elimination of Halides ...................................................................... 30
Free-Response Questions ............................................................................................................... 32
Nucleophilic Addition to Alkyne ......................................................................................................... 35
Reaction of Organometallic Reagents .............................................................................................. 36
Hydroboration-Oxidation .................................................................................................................... 38
 Hydroboration add a hydrogen atom to the more-substituted end of a double bond, and a
boron group to the other end. Upon oxidation by peroxide anion, the boron group transform into
the hydroxyl group. ............................................................................................................................. 38
Properties and Synthesis of Carbonyl Compounds ......................................................................... 40
Properties and Synthesis of Amines ................................................................................................. 43
Advanced Topics ................................................................................................................................ 45
Review
A Terminology Guide
In organic chemistry, you will encounter a myriad of new terminologies. However, most of them
are systematic, which necessitates a thorough investigation. In general, you can, at the very least,
guess the meaning of a terminology by looking at their prefix and suffix. Here are some common
affixes that you can encounter.
Table 1. Table of Common Prefixes.
Prefix Meaning Examples
asymmetric (“not symmetric”)
a not
acyclic (“not containing cycles”)
ability ability polarizability (“ability to polarize something”)
able able, can polarizable (“able to polarize”)
anti against antibonding (“against bonding”)
carbo pertaining to carbon carbocation (“cation of carbon”)
co together coplanar (“planar together”)
cyclo pertaining to cycles cycloalkane (“alkane that is cyclic”)
dehydration (“to remove water”)
de removal
dehydrohalogenation (“to remove hydrogen and halogen”)
di two dihedral (“having two faces”)
pertaining to electricity electrochemistry (“chemistry of electricity”)
electro
pertaining to electron electrophilic (“liking electrons”)
hemi half hemisphere (“half a sphere”)
hetero different heterocycle (“cycles that contain different elements”)
homo same homogeneous (“same composition throughout”)
pertaining to water hydropower (“water energy”)
hydro
pertaining to hydrogen hydroboration (“to add hydrogen and boron”)
inter between intermolecular (“between the molecules”)
intra inside intramolecular (“inside a molecule”)
iso equal isomer (“equal in parts”)
mono one monatomic (“having one atom”)
nucleo pertaining to nucleus nucleophilic (“liking nucleus”)
poly many polymer (“having many parts”)
3
re again, back react (“to act back [a certain action]”)

tetra four tetrahedral (“four faces”)
thermo pertaining to heat thermostat (“instrument for heat regulation”)
tri three triatomic (“having three atoms”)
Table 2. Table of Common Suffixes.
Suffix Meaning Examples
to add [the root word] alkylation (“to add an alkyl group”)
ation
to transform into esterification (“to transform into ester”)
gonal pertaining to angles tetragonal (“having four angles”)
hedral pertaining to faces tetrahedral (“having four faces”)
hydrolysis (“to use water for splitting [a bond]”)
lysis to split
hydrogenolysis (“to use hydrogen for splitting [a bond]”)
meter measuring instruments thermometer (“instrument for measuring temperature”)
measurement thermometry (“measurement of temperature”)
metry
study of measuring biometry (“study of measuring biological signature”)
phile one that likes electrophile (“one that likes electron”)
philic liking electrophilic (“liking electron”)
phobic fearing hydrophobic (“fearing water”)
Unsaturation, Formal Charges

 The unsaturation degree of the general formula of CxHyOzNtClw can be calculated using the
equation below:
2𝑥 − 𝑦 + 𝑡 − 𝑤
∆=
2
 A more sophiscated version of the aforementioned equation is excluded, and you do not have
to concern about higher-period elements (S, P, etc).
 Unsaturation degree enables you to:
o Obtain the total pi (π) bonds and rings (cycles) inside a structure. For example, the
compound C3H6 has Δ = 1, it could have 1 pi bond (propene) or 1 ring (cyclopropane).
o Exclude some possibilities when guessing a structure. For example, a compound that has
Δ = 0 cannot have any groups that is unsaturated, e.g. carbonyl groups. See the last
problem below.
o You can even use hydrogenation data to obtain the number of multiple bonds. Only double
bonds, triple bonds, and cyclopropane ring can be hydrogenated. See the second problem
below.
Multiple-Choices Questions
1. How many degrees of unsaturation does the given molecule have? C7H6ClNO2
A. Three. B. Four. C. Five. D. Other.
2. A compound C20H30 can be hydrogenated by platinum metal and hydrogen to give C20H38.
The original compound has no triple bonds. How many rings and double bonds does the
original compound have?
A. 5 double bonds and 1 rings.
B. 4 double bonds and 2 rings.
C. 3 double bonds and 3 rings.
D. None of the other answers.
3. Identify the possible functional groups of a compound having a molecular formula of
C4H10O.
A. Aldehyde/alcohol. B. Alcohol/ether. C. Ether/ketone. D. Ketone/aldehyde.
Answer to Multiple-Choices Questions
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1. C. In accord to the given equation, you can easily calculate Δ = 5. Remember to include
chlorine and nitrogen in your calculation, to create a habit, even though they cancel each other
out.
2. B. In accord to the given equation, you can easily calculate Δ = 6. The original compound has
no triple bonds, so the only feature that is hydrogenated is the double bonds. Hydrogenation
of a double bond will add 2 hydrogen atoms. As the total added hydrogen atoms is 8, we can
surmise that the original compound has 4 double bonds, which left out 2 rings.
Actually, the question should also exclude the possibility of cyclopropyl groups, that gives you
a glimpse of how tolerable the exam is.
3. B. In accord to the given equation, you can easily calculate Δ = 0. Therefore, the compound
cannot have any unsaturated functional groups, i.e. aldehyde and ketone.
Hybridization
 Hybridization is a concept you have learned in the General Chemistry I course, so it should not
bothers you. It is also one of the point givers, so please be strategic.
 In terms of determining hybridization modes, organic compounds are no more difficult than
the inorganic ones, some would even say easier.
 Choose your central atom, then rewrite the formula in the form of AX nEm, where X covers all
of the atoms/group of atoms that bond with A, and E is the notation for lone pairs. Adding up
n and m, then check for the sum: 2, 3, and 4 correspond to sp-, sp2-, and sp3-hybridization,
respectively.
 Group of atoms can be CH3, C2H5, CH=CH2, etc.
4. The hybridization of the central carbon in CH3C≡N and the bond angle CCN are:
A. sp2, 180°. B. sp, 180°. C. sp2, 120°. D. sp3, 109°.
5. What are the hybridizations of atoms 1 and 2 respectively in the following structure?
A. sp3 and sp2. B. sp2 and sp3. C. sp3 and sp. D. sp2 and sp2.
4. B. The middle carbon is the central atom. It has 2 surrounding groups (CH3 and N) and has no
lone pair, therefore its hybridization is sp and the bond angle CCN is 180o.
5. D. N (1) bonds to 2 carbon atoms and has 1 lone pair (situated coplanar to the 2 surrounding
atoms), therefore its hybridization is sp2. Do the same for C (2). Note that the hydrogen atoms
are normally not shown in the structures, but you must not forget them.
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Polarity
 Polarity is a property arises when an entity separates into two ends, one is negatively charged
and one is positively charged.
 In organic chemistry, we normally consider the polarity of a bond. Therefore, this separation
can be rationalized by the electronegativity difference of the two ends (atoms) of the bond.
The higher the difference, the larger the polarity.
 Polarity is quantify by dipole moment, which is directly proportional on both formal charges
and bond length.
 The dipole moment of a molecule can be calculated by adding the dipole moments of
individual bonds as component vectors.
 Symmetrical molecules have no polarity.
6. Which molecule has the largest dipole moment?
A. HCl. B. CCl4. C. H2S. D. CO2.
6. A. As we have mentioned before, the higher the electronegativity difference, the larger the
polarity. CCl4 and CO2 are symmetrical, so their polarities equal to zero. The electronegativity
of sulfur (2.58) is much smaller than chlorine (3.16), so we can skip the vector calculation and
conclude that the dipole moment of HCl is larger than that of H2S.
Physical Properties
 The most common physical properties to be compared are melting point, boiling point, and
solubility.
 Common intermolecular criteria for evaluation, by order of priority:
o Hydrogen bonding: If the compound are both hydrogen bond acceptor and donor, it can
form an ordered network, and therefore having both high melting point and boiling point.
Also, it will be highly soluble in water and other protic solvents. These effects diminish
when it can only accept hydrogen bonds.
o Polarity: The higher the polarity, the higher the boiling point and solubility in polar solvent.
The effect is less likely to apply to melting points and definitely inapplicable to nonpolar
solvents.
o Symmetry: The higher the symmetry, the higher the melting point, as the individual
molecules can be more orderly arranged in the solid (crystal) structure.
o Branching: Branching generally makes the molecule more spherical, which increases the
melting point (better stacking in the crystal), but decreases the surface area, hence
decreases the boiling point.
o Molar mass: When all of the criteria are absent, the higher the molar mass, the higher the
intermolecular London dispersion forces (which will not be discussed further, you can look
it up in the lectures or textbooks), therefore higher boiling and melting points.
 You will easily encounter the term volatile, it simply means “easily evaporated”, i.e. having a
low boiling point as a result.
7. Which of the following compounds will be the most volatile (having the lowest boiling
point)?
A. Acetone. B. Ethanol. C. Ethylene. D. Dimethylether.
8. Which of the following molecules has the lowest vapor pressure?
A. CH3CH2CH2CH2CH2−NH2.
B. CH3CH2CH2CH2CH3.
C. HOOC−CH2CH2CH2−COOH.
D. CH3CH2−OH.
9. Which of the following compounds has the highest boiling point?
A. 1,2-ethanediol.
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B. 2-methyl-2,4-pentanediol.
C. 2-methyl-2-butanol.
D. 2-methyl-2-propanol.
10. Which is a correct description on physical properties of alkanes?
A. Alkanes are soluble in water.
B. Melting point increases with increased symmetry.
C. Boiling point increases with branching.
D. Melting point and boiling point decrease as the number of carbons increases.
11. Which is the increasing order of boiling point?
A. (CH3CH2CH2)2O, CH3(CH2)5OH, CH3CH2CH2CH2COOH.
B. CH3COCH2CH(CH3)2, (CH3)2CHCH2COOH, (CH3)2CHCH2CH(OH)CH3.
C. H3CH2CH2CH2OH, CH3CH2CH(OH)CH3, CH3CH2CH2CH2Cl, CH3CH2CH2CH2COOH.
D. HCCH, CH2=CH2, CH3CH3.
7. C. Ethylene has no intermolecular interactions, therefore having the lowest boiling point.
Ethanol is both a hydrogen bond donor and acceptor, therefore its boiling point is the highest
among the series. Acetone arguably has higher polarity than dimethylether, therefore having
higher boiling point.
8. B. Vapor pressure quantify the tendency to change into the vapor state. Therefore, this
question’s objective is to find the most volatile compound, which is, without doubt, the only
molecule that neither donate nor accept hydrogen bonds, CH3CH2CH2CH2CH3.
9. B. Boiling points can also be evaluated by the hydrogen bonding capacity (i.e. the number of
hydrogen bond acceptor/donor groups). Both 1,2-ethanediol and 2-methyl-2,4-pentanediol
have 2 hydroxyl groups, so their boiling points are higher than the other 2 choices. Yet, 2-
methyl-2,4-pentanediol also has higher molar mass, which makes its boiling point to be higher
than that of 1,2-ethanediol.
10. B. Alkane has no other intermolecular interactions than symmetry and London dispersion
force (which can be evaluated by molar mass).
11. A. Both alcohols and carboxylic acids can create hydrogen bonds, therefore, their boiling
points are higher than that of ethers. Carboxylic acids create hydrogen bonds more effective
than alcohols.
Acid-Base Property
12. What is the best description of the Lewis acid?
A. A chemical species contains an empty orbital which is capable of accepting an electron pair;
an electron pair acceptor.
B. A chemical species that can donate a pair of nonbonding electrons; electron pair donor.
C. A chemical species that is capable of donating a proton; a proton donor.
D. A chemical species that is capable of accepting a proton; a proton acceptor.
13. How does pKa relate to Ka and acid strength?
A. the smaller the pKa, the smaller the Ka and the stronger the acid.
B. the smaller the pKa, the smaller the Ka and the weaker the acid.
C. the smaller the pKa, the larger the Ka and the stronger the acid.
D. the smaller the pKa, the larger the Ka and the weaker the acid.
14. Give a correct favorable formation of acid-base reaction?
A. The reaction favors the formation of the stronger acid and base.
B. The reaction favors the formation of the stronger acid and the weaker base.
C. The reaction favors the formation of the weaker acid and the stronger base.
D. The reaction favors the formation of the weaker acid and base.
15. Which compound is a Lewis acid?
A. BH3. B. NH3. C. CH3ONa. D. Fe2O3.
16. Which compound is not a Lewis acid?
A. AlCl3. B. NH3. C. CH3+. D. (CH3)3N.
17. What is the order of decreasing base strength for the following salts?
I sodium ethoxide (C2H5ONa).
II potassium formate (HCOOK).
III sodium benzoate (C6H5COONa).
IV sodium dichloroacetate (Cl2CHCOONa).
A. I, II, III, IV. B. II, III, IV, I. C. II, I, IV, III. D. I, III, II, IV.
18. Which group below is arranged by the order of descending acidity?
A. acetic acid, ethane, ethanol.
B. benzene, benzoic acid, benzyl alcohol.
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C. propanedioic acid, propanoic acid, 1,3-propanediol.

D. trifluoromethanesulfonic acid (CF3SO2OH), acetic acid, trifluoroacetic acid, 2,2,2-
trifluoroethanol, ethanol.
19. Which group below is arranged by the order of ascending acidity?
A.
B.
C.
D.
20. Which of the following best describes what happens in the first step in the mechanism of
the hydrogen–deuterium exchange reaction shown?
A. B. C. D.
21. Which of the following laboratory procedures is the best to separate benzoic acid from
phenol if they are both dissolved in hexanes?
A. Extraction using sodium bicarbonate.
B. Extraction using sodium hydroxide.
C. Distillation.
D. Fractional distillation.
E. Recrystallization.
12. A.
13. C. By the relation pKa = – log Ka, pKa is inversely proportional to Ka. Moreover, Ka is the direct
quantification of acid strength, so the higher it is, the stronger the acid.
14. D.
15. A. A Lewis acid is a compound that can accept an electron pair.
16. B. NH3 is not a Lewis acid, but a Lewis base, as it can only donate an electron pair and does
not accept any.
17. D. The higher the pKa of the conjugate acid, the higher the basicity. As dichloroacetic acid (pKa
= 1.35) < formic acid (pKa = 3.75) < benzoic acid (pKa = 4.19) < ethanol (pKa = 16), you can
easily deduce the descending order of base strength: sodium ethoxide (I) > sodium benzoate
(III) > sodium formate (II) > dichloroacetic acid (IV).
18. C. It is the definitive answer, as more carboxylic groups indicate higher acidity. However, the
last choice is also pedalogical, as it emphasizes the inductive effect of fluorine atoms: the
more they are, the higher the acidity.
19. D. The negative inductive effect, which increase acidity, of nitro group is higher than chlorine,
and benzoic acids (the two latter compounds) tend to be more acidic than benzylacetic acids.
20. C.
21. A. Benzoic acid (pKa = 4.19) is substantially more acidic than phenol (pKa = 9.95), therefore, it
can be effectively extracted by acid-base technique. We should use sodium bicarbonate, as
sodium hydroxide can neutralize both benzoic acid and phenol.
Free-Response Questions
22. Calculate the Ka for each of the following acids, given its pKa. Rank the compounds in order
of decreasing acidity.
HCOOH
aspirin vitamin C formic acid oxalic acid

pKa = 3.48 pKa = 4.17 pKa = 3.75 pKa = 1.19
By definition, pKa = –log Ka, then Ka = 10–pKa. By that, you can easily calculate the Kas to be 3,311
× 10-4, 6,761 × 10-5, 1,778 × 10-4, and 0,065, respectively.
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Stereochemistry
 First of all, let’s revise the Cahn-Ingold-Prelog priority rules as a prerequisite. According to CIP
rules, priorities are ranked by these criteria step-by-step:
o Atomic number (Z): The higher the atomic number, the higher the order, e.g. Br > Cl > O >
N > CH3 > H. If the first consideration does not work, move on to the second atom, and so
on, e.g. CH(CH3)2 > CH2CH2CH3 > CH2CH3 > CH3.
o Multiple bonds are assigned to “phantom atoms”, perhaps a visual representation will be
more effective: CH=O = C–O singly bonds to O–C (O–C(H)–O–C).
Configurations of Double Bonds (E/Z)

 Let us have an alkene of general formula (AC)C=C(BD). Consider the two ends of a double
bond, both has two substituents. Let A > C, B > D in terms of CIP priorities.
 If A and B, the two “superior” groups, are on the same side, the corresponding alkene isomer
will be Z, otherwise, it is E-configurated.
23. Which of the following represents (E)-3,6-dichloro-6-methyl-3-heptene?
A. B. C. D.
24. Determine the double bond stereochemistry (E or Z) for the following molecules.
A. A: E; B: E. B. A: E; B: Z. C. A: Z; B: Z. D. A: Z; B: E.
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Configurations of Stereocenters (R/S)

 For the sake of simplicity, we define stereocenter as a sp3-hybridized carbon that bonds with
four unidentical groups.
 To determine the configuration of a stereocenter:
o Identify its four unidentical groups, then rank them by the order of Cahn-Ingold-Prelog
priorities (see above).
o Left out the least-prioritized group, imagine as if it is behind the
 With n stereocenters comes a maximum of 2n stereoisomers. Emphasis on maximum, as
sometimes (e.g. tartaric acid) it is not the case. However, this is unlikely to appear in the exam.
25. How many stereogenic centers does the following compound have?
A. 0. B. 1. C. 2. D. 3.
26. Which of the following is (R)-3-hexanol?
A. B. C. D.
27. What are the absolute configurations of the carbons 3 and 6?
A. C3: S; C6: R. B. C3: R; C6: R. C. C3: S; C6: S. D. C3: R; C6: S.

28. Isoleucine is an α-amino acid that is essential in humans, meaning the body cannot
synthesize it, and must be ingested in our diet. The absolute configuration of isoleucine is
2S,3S. Give the structure of isoleucine?
A. I. B. II. C. III. D. IV.

29. Muscarine is a poisonous substance present in the mushroom Amanita muscaria. Its
structure is represented below.
How many stereoisomers does muscarine have?

A. 6. B. 7. C. 8. D. 9.
30. Muscarine is a poisonous substance present in the mushroom Amanita muscaria. It has the
configuration of (2S,3R,5S). Which of these structures is correct?

31. Which of the following sugars has the configuration (2S, 3R, 4R)?
A. B. C. D.
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Stereochemical Relationships
 Isomers are nonidentical compounds that has the same chemical formula. Be sure to check
if they are identical or not first.
 The term isomer is only meaningful when you consider more than two compounds, i.e. having
a frame of reference.
 In terms of stereochemistry, two arbitrary isomers can be constitutional isomers (same
constitution, different arrangement of atoms) or stereoisomers (same atoms and bonding,
different of how the atoms arrange in 3D-space).
 If they are stereoisomers, in turn, they can be enantiomers (mirror images) or diastereomers
(other possibilities). For example (2R,3S)-2-bromo-3-chlorobutane has 2 stereocenters, hence
4 stereoisomers. There’s only two pair of enantiomers, the rest are diastereomers.
 E/Z isomers of alkenes can be diastereomers too. They are also called geometric isomers.
 The scheme below may prove useful:
Isomers
Constitutional (structural) isomers Stereoisomers (spatial isomers)
Enantiomers (optical isomers) Diastereomers

32. Determine the relationship between the two molecules shown?
A. Constitutional isomers.
B. Enantiomers.
C. Diastereomers.
D. Identical molecules.
33. Determine the relationship between the two molecules shown?
B. Enantiomers.
C. Diastereomers.
D. Identical molecules.
34. Indicate the relationships between the two molecules as enantiomers, diastereomers, or
identical molecules?
II
III
A. I: identical molecules, II: identical molecules, III: diastereomers.

B. I: enantiomers, II: identical molecules, III: diastereomers.
C. I: enantiomers, II: enantiomers, III: diastereomers.
D. I: enantiomers, II: identical molecules, III: identical molecules.
35. Which two Fischer formulas represent a pair of enantiomers?
19
A. I and II. B. III and IV. C. I and IV. D. II and III.

36. What are the absolute configurations of groups bound to the 3 and 6 carbons.
A. 3R; 6S. B. 3R; 6R. C. 3S; 6R. D. 3S; 6S.

37. Rank the following compounds by the descending order of stability.
A. I, II, III, IV. B. II, III, I, IV. C. II, I, IV, III. D. I, III, II, IV.
38. The molecules shown below are best described as __________.
B. Enantiomers.
C. Diastereomers.
D. Conformational isomers.
Answers to Multiple-Choices Questions

23. C.
24. D.
25. C.
26. B.
27. C.
28. A.
29. C.
30. B.
31. A.
32. A.
33. B.
34. C.
35. B.
36. A.
37. C.
38. D.
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Nomenclature
39. Rank the following substituents by the ascending order of priority.
-CH2CH3 (I) -CH=CH2 (II) -CH2Br (III) -CH=O (IV)
A. I, II, III, IV. B. I, II, IV, III. C. III, IV, II, I. D. I, III, II, IV.
40. Which of the following compounds is (S)-4-chloro-1-methylcyclohexene?
C. D.
A. B.
41. What is the IUPAC name of the given molecule?
A. 1-sec-butyl-3-methylcyclohexane.
B. 1-methyl-3-sec-butylcyclohexane.
C. trans-1-sec-butyl-3-methylcyclohexane.
D. cis-1-methyl-3-sec-butylcyclohexane.
A. (2R,3R)-2-bromo-3-chlorobutane.
B. (2S,3R)-2-bromo-3-chlorobutane.
C. (2S,3S)-2-bromo-3-chlorobutane.
D. (2R,3S)-2-bromo-3-chlorobutane.
A. 5-chloro-3,5-dimethyl-1,6-heptadiene.
B. 5-chloro-3,6-dimethyl-1,5-heptadiene.
C. 3-chloro-2,5-dimethyl-1,5-heptadiene.
D. 3-chloro-2,5-dimethyl-2,6-heptadiene.
A. 2,2,4-trimethyloctane.
B. 3,3,5-trimethyloctane.
C. 3,3,5-trimethylnonane.
D. 3-chloro-2,5-dimethyl-2,6-heptadiene.
E. None of these.
39. B.
40. A.
41. C.
42. D.
43. B.
44. B.
45. Give the IUPAC name of each of the following?
From left to right:

 2,4-dimethylpentane.
 2,2,4-trimethylhexane.
 (1S,4S)1-ethyl-4-methylcyclononane.
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Aromaticity and Electrophilic Aromatic Substitution (SEAr)

 Aromaticity is evaluated through Hückel rules. A compound is consider aromatic if it contains
a monocyclic, planar, continuously conjugated ring with (4n + 2) π-electrons.
 For simplicity sake, you will almost only encounter these two aromatic patterns. Compounds
that contain them are aromatic.
 Please revise the electrophilic aromatic substitution reaction in the lectures.

46. Which of the following compounds would be not be considered aromatic in its behavior?
A. B. C. D.
47. Choose the substituent that will direct meta addition on a benzene ring.
-CH2CH3 (I) -CH=CH2 (II) -CH2Br (III) -CH=O (IV)
A. −Br. B. −OH. C. −NH2. D. −COOH.
48. After the electrophilic aromatic substitution reaction occurs, in what position will the
bromine be directed?
A. Ortho. B. Para. C. Both A and B. D. Meta.

49. Given the reaction sequence:
The main product of above reaction sequence is:

A. B. C. D.

46. B.
47. D. Only COOH are electron-withdrawing.
48. D.
49. B. C(CH3)3 is a bulky group, so it can only end up in the para position. Alkyl substituents of the
aromatic rings that contain at least 1 benzylic hydrogen are oxidized by KMnO4 to form
carboxylic acid groups.
25
Dehydration of Alcohols and Formation of Acetals

 Alcohols can be dehydrated to form alkenes or ethers, depending on the conditions.
 High temperatures, typically over 150 oC (taken for granted), the reaction will yield alkenes.
Otherwise, the product will be symmetrical ethers.
 The reaction proceed through a carbocation intermediate.
o At moderate temperatures, another alcohol molecule will nucleophilically attack this
carbocation to form the corresponding ether.
o However, at higher temperatures, the elimination of an adjacent hydrogen atom will be
faster, forming alkenes.
 Alcohols can react with carbonyl groups to yield hemiacetals (1 equivalent) or acetals (2
equivalents). If both hydroxyl and carbonyl groups are present in a compound, they can react
intramolecularly to yield a hemiacetal, which can react with another alcohol intermolecularly
to yield an acetal.
50. Dipropyl ether could be formed when 1-propanol reacts with:
A. Sulfuric acid (catalytic amount), heat at 200°C.
B. Sulfuric acid (catalytic amount), heat at 140°C.
C. Pyridinium chlorochromate (PCC) in dichloromethane.
D. Potassium dichromate (K2Cr2O7) in aqueous sulfuric acid, heat.
51. Choose the appropriate starting compound based on the reaction conditions and the major
product shown in the figure.
A. III only. B. Either I or II. C. II only. D. IV only.

52. What is the major product in the following reaction?

53. What is the major product in the following reaction?
A. B. C. D.
27
Nucleophilicity
54. Which of the following compounds would be the best nucleophile?
A. H2O. B. CH3S−. C. CH3O−. D. NH3.
As sulfur is bigger than oxygen and are less electronegative, it is more polarizable, its electron
density is less than that of oxygen, all of which increase nucleophilicity and decrease basicity of
sulfide in compare to hydroxide.
Nucleophilic Acyl Substitution

55. What is the main product of the reaction below?
A. B. C. D.
56. What group in order of increasing reactivity in nucleophilic acyl substitution?:
A. CH3CH2CH2COOCH2CH2CH3, CH3CH2CONH2, CH3CH2COCl.
B. CH3CH2COOCH2CH2CH3, (CH3CH2CO)2O, (CF3CO)2O.
C. CH3COCl, CH3COOH, CH3COSH.
D. HCOOH, CH3CH2COOH, CH3COOH.
29
Nucleophilic Substitution and Elimination of Halides

57. What is the product of the 2,3-dibromopentane when it reacts with two equivalents of base?
A. 1-pentyne. B. 2-pentyne. C. 1-pentene. D. 2-pentene.
58. Given two reactions and the corresponding possible products below:
I II III IV
Determine the main products of each reaction.
A. I, III. B. I, IV. C. II, III. D. II, IV.
59. Predict the major product of the reaction below:
I II III IV
60. Given two reactions and the corresponding possible products below:
I II III IV
(1) and (2) are, respectively:
A. I, III. B. I, IV. C. II, III. D. II, IV.
61. Which compound undergoes substitution by the SN1 mechanism at the fastest rate?

62. Which compound undergoes substitution by the SN2 mechanism at the fastest rate?

63. What is the product of the reaction below?

64. What is the product of the reaction sequence below?

65. Cyclopentanol could be prepared from NaOH with the reagent:
A. chlorocyclopentane.
B. cyclopentane.
C. cyclopentanamine.
D. methylcyclopentyl ether.
66. Which of these would react fastest with methanol via an SN1 mechanism?
A. (CH3)2C(Br)CH2CH3.
B. CH3CH2CH2CHBrCH3.
C. CH3CH2CH2CH2CH2Br.
31
D. (CH3)3CCH2Br.
57. B. However, if a strong, weakly nucleophilic base is involved, the internal alkyne can be
isomerized to the corresponding terminal derivative.
58. C.
59. D.
60. C.
61. D.
62. I.
63. A.
64. B.
65. A.
66. A. SN1 reactions of tertiary derivatives are the fastest, as they proceed through tertiary (most
stable) carbocations.
67. Predict the major organic product of each of the following reactions.
(a) (e)
(b) (f)
(c) (g)
(d) (h)
(a) (e)
(b) (f)
(c) (g)
(d) (h)
Comments:
 These are all elimination reactions.
 In thermal condition (i.e. involving heat), trans-alkene will be favored as they are more
thermodynamically stable.
 Strong, bulky bases (i.e. KOC(CH3)3) will favor the less-substituted alkene product, as
indicated by Zaitsev rules.
68. The ratio of elimination to substitution is exactly the same (26% elimination) for 2-bromo-2-
methylbutane and 2-iodo-2-methylbutane in 80% ethanol/20% water at 25°C.
(a) By what mechanism does substitution most likely occur in these compounds under these
conditions?
(b) By what mechanism does elimination most likely occur in these compounds under these
conditions?
(c) Which one of the two alkyl halides undergoes substitution faster?
(d) Which one of the two alkyl halides undergoes elimination faster?
(e) What two substitution products are formed from each?
(f) What two elimination products are formed from each?
(g) Why do you suppose the ratio of elimination to substitution is the same for the two alkyl
halides?
(a) SN1.
(b) E1.
(c) (d) R–I, as iodides are more reactive than bromides in nucleophilic reactions.
33
(e)
(f)
(g) As both substitution and elimination mechanisms proceed through a common carbocation,
the product ratio of elimination to substitution is the same for both halides.
Nucleophilic Addition to Alkyne

69. Nucleophilic addition can occur with alkynes that bear strong electron-attracting
substituents such as CF3 on the triple bond. Predict the product of the nucleophilic addition
of CH3OD to 3,3,3-trifluoropropyne. The stereochemistry of addition is anti, and the first step
in the mechanism is bond formation between CH3O− and one of the carbons of the triple
bond.
A. B. C. D.
69. A. The nucleophile (OCH3) will form a bond with the beta carbon (i.e. the carbon attached
directly to CF3 is called alpha, its neighboring carbon is called beta). This is called conjugate
addition. Since the stereochemistry is anti (H and CF3 are end up on different sides), and the
reaction performs in deuterium-containing CH3OD, the answer is A.
35
Reaction of Organometallic Reagents

 Organometallic reagents are strong nucleophiles that reacts with oxygen-containing
electrophilic functional groups (e.g. epoxide, carbonyl groups, etc.) to form corresponding
alcohols. Other examples of organometallic reactions can be viewed in further organic
chemistry courses.
 Typical examples are organolithium (R–Li) and organomagnesium (R–MgX, more famously
known as Grignard reagents), they both have a high ionic character.
70. Which of the following statements is false?
A. The base-promoted ring-opening of an epoxide using aqueous NaOH will yield a trans glycol.
B. The catalyzed ring-opening of an epoxide in aqueous acid will yield a cis glycol.
C. Treatment of an unhindered epoxide with a Grignard reagent will result in a nucleophilic
attack at the less hindered carbon.
D. A nucleophile attacks an epoxide to yield an alcohol.
71. 1-phenylethanol can be prepared by the reaction of methyl iodide and magnesium with?
A. Bromobenzene. B. Acetophenone. C. Benzaldehyde. D. Benzyl alcohol.
72. The reaction of a Grignard reagent with ethylene oxide (oxirane) followed by work-up with
dilute acid gives which of the following products:
A. A primary alcohol.
B. A secondary alcohol.
C. A tertiary alcohol.
D. Ethanol.
73. Which of the following reactions would not be a useful way of preparing 1-phenyl-2-butanol:
A. phenylacetaldehyde + ethylmagnesium bromide.
B. butanal + phenylmagnesium bromine.
C. propanal + benzylmagnesium bromine.
D. 1-phenyl-2-butanone + NaBH4.
74. Which of the following reactions would not be a useful way of preparing 2-phenyl-2-butanol:
A. 2-butanone + phenylmagnesium bromine.
B. acetophenone + ethylmagnesium bromide.
C. cis-2,3-dimethyloxirane + phenylmagnesium bromide.
D. ethylphenylketone + methylmagnesium iodide.

70. B. The epoxide will be activated by H+, becoming an electrophile that is attacked back-side to
form a trans-glycol.
71. C. Write down the reaction sequence, then it should not trouble you.
72. A.
73. B.
74. B.
37
Hydroboration-Oxidation
 Hydroboration add a hydrogen atom to the more-substituted end of a double bond, and a
boron group to the other end. Upon oxidation by peroxide anion, the boron group transform
into the hydroxyl group.
 This reaction yield an anti-Markovnikov hydration product, i.e. the hydroxyl group ends up on
a less-substituted carbon atom.
 Alkynes can also conduct this type of reaction, furnishing aldehydes (if the reactant is
terminal) or ketones.
75. What is the product of a hydroboration–oxidation reaction with 1-hexylcyclohexene?
A. 2-hexylcyclohexanol.
B. Hexylcyclohexane.
C. 3-hexylcyclohexanol.
D. 1-hexylcyclohexanol.
76. Hexanal, the major organic product isolated from the reaction of 1-hexyne with:
A. Borane (BH3) in tetrahydrofuran (THF), then hydrogen peroxide (H2O2) in sodium hydroxide
(NaOH).
B. Borane (BH3) in tetrahydrofuran, then hydrolysis in sodium hydroxide.
C. Aqueous sulfuric acid, mercury(II) sulfate.
D. Ozone followed by hydrolysis.
The final product is:
A. B. C. D.
75. A.
76. A. Sodium hydroxide alone cannot do the job. Aqueous sulfuric acid and mercury(II) sulfate
is a combination for Markovnikov-selective hydration. Ozonolysis will split our starting
material, which is not desired.
77. D. Hydroboration-oxidation furnish a primary alcohol (cyclohexylmethanol), which is oxidized

by chromium trioxide in aqueous media to yield the corresponding acid.
39
Properties and Synthesis of Carbonyl Compounds

78. Propanoic acid could be formed when 1-propanol reacts with:
A. Sulfuric acid (catalytic amount), heat at 200°C.
B. Sulfuric acid (catalytic amount), heat at 140°C.
C. Pyridinium chlorochromate (PCC) in dichloromethane.
D. Potassium dichromate (K2Cr2O7) in aqueous sulfuric acid, heat.
79. Which of the following is not capable of oxidizing a secondary alcohol to a ketone?
A. Pyridinium chlorochromate (PCC).
B. K2Cr2O7.
C. CrO3, H2SO4, acetone.
D. Lithium aluminum hydride (LiAlH4).
80. Which of the isomeric C4H10O alcohol(s) can be prepared by hydrogenation of aldehyde?
A. Butan-1-ol.
B. Butan-1-ol and butan-2-ol.
C. 2-methylpropan-2-ol and 2-methylpropan-1-ol.
D. Butan-1-ol and 2-methylpropan-1-ol.
81. 1-propanol could be prepared from the reaction of propanal with:
A. Lithium aluminum hydride, followed by water.
B. Sodium borohydride, methanol.
C. Hydrogen (nickel catalyst).
D. All of the above.
82. Aldehyde could be prepared by:
A. Reduction of carboxyl compounds and oxidation of primary alcohols.
B. Reduction of carboxyl compounds and oxidation of secondary alcohols.
C. Oxidation of carboxyl compounds and oxidation of primary alcohols.
D. Oxidation of carboxyl compounds and reduction of primary alcohols.
83. Which of the following reactions would NOT produce a carboxylic acid?
A. CH3CH2MgBr + CO2(g) →.
B. CH3CH2CH2OH + CrO3 + H2SO4 →.
C. CH3CH2CHO + KMnO4 →.
D. CH3CH2CH2OH + PCC →.
84. There are various methods that can be used for the preparation of carboxylic acids.
A. By using primary alcohols and aldehyde.
B. From nitriles and amides.
C. By using Grignard reagents.
D. All mentioned methods are correct.
One of the final products is:

A. HCOOH. B. OCH-CHO. C. CH3CH2CHO. D. CH3CH2COOH.
What is the compound C?

A. (CH3)2CH-COCH3.
B. (CH3)2CHCH2CHO.
C. (CH3)2CHCH2COOH.
D. (CH3)2CH-CO-CH2OH.
87. Which of the following reaction sequences would be best for converting cyclohexanol to
methylenecyclohexane, (CH2)5C=CH2:
A. (i) H3PO4 & heat; (ii) CH2I2 + Zn(Cu).
B. (i) PCC in CH2Cl2; (ii) CH3MgBr; (iii) H3PO4 & heat.
C. PCC in CH2Cl2; (ii) (C6H5)3P=CH2.
D. CH2N2 & heat.
78. D. 1-propanol can be viewed as a reduced form of propanoic acid, so it can produce the acid
upon oxidation with a strong oxidant like potassium dichromate. All primary alcohol oxidation
to corresponding carboxylic acid should be conducted in aqueous media, as water will form
gem-diol with the aldehyde intermediate, this gem-diol is further oxidized as an alcohol,
furnishing acids.
79. D. Only lithium aluminium hydride is a reductant.
80. D. The reduction product of an aldehyde is a primary alcohol.
41
81. D. All three choices are reductants of carbonyl group to alcohol.

82. A. Isn’t that obvious.
83. D. PCC normally oxidize alcohols to carbonyl groups only.
84. D. Acids can be prepared by oxidation of primary alcohols and aldehydes, hydrolysis of nitriles
and amides, and addition of Grignard reagents to carbon dioxide.
85. D. Please revise alkylations of terminal alkynes (by deprotonation-nucleophilic substitution)
and ozonolysis of alkynes (yielding corresponding acid fragments).
86. B. Please revise the properties of carboxyl derivatives.
87. B. Please see the sequence below:

Properties and Synthesis of Amines

88. Given the reaction and the corresponding possible products:
CH3COO- CH3COOH
I II III IV
(1) and (2) are, respectively:
A. I, III. B. II, III. C. I, IV. D. II, IV.
89. What reagent(s) will successfully complete the synthesis reaction shown below?
C6H5CH2CHO → C6H5CH2CH=NCH(CH3)2
A. (CH3)2CHNH2, strong acid.
B. (CH3)2CHNH2, strong base.
C. (CH3)2CHNH2, mild acid.
D. (CH3)3CNH2, mild acid.
90. Which reaction or sequence of reactions would best accomplish the following synthesis?
A. CH3NH2, acidic catalysis & heat.

B. CH2=NH, acidic catalysis & heat.
C. (i) NH3, acidic catalysis & heat; (ii) CH2I2 & Zn(Cu).
D. (i) HCN & NaCN; (ii) LiAlH4 in ether.
89. A. Amides are hydrolyzed to corresponding amines and carboxylic acids. In an alkaline
solution, however, the carboxylic acid cannot exist as the free acid, but the salt (carboxylate)
form.
90. C. Primary and secondary amine can condense with carbonyl groups in the presence of mild
acids. If the solution is strongly acidic, the condensation product (imine or enamine) can be
hydrolyzed.
43
91. D. First, HCN and NaCN is the combination that add hydrogen and cyanide group to a carbonyl
group (review the addition reaction of carbonyl groups). LiAlH4 will reduce the cyanide to
corresponding amine, just like the reduction of carbonyl groups to alcohols.
Advanced Topics
91. What is the product of the following pinacol rearrangement reaction?
A. C. D.
B.
92. Base on the pinacol rearrangement in the preceding problem, if we keep the reaction
condition, predict the product starting from the vicinal diol below. Note that the reaction will
form the more stable carbocation intermediate of the two possible carbocations.
A. D.
B. C.
93. Tridecane [CH3(CH2)11CH3] is a major component of the repellent that the stink bug
Piezodonis guildinii releases from its scent glands when attacked. What fatty acid gives
tridecane on decarboxylation?
A. CH3(CH2)10COOH. B. CH3(CH2)11COOH. C. CH3(CH2)12COOH. D. CH3(CH2)13COOH.
94. Classify the carbon in adamantane that is oxidized in forming the major product?
A. Primary. B. Secondary. C. Tertiary. D. Quaternary.

95. Assuming a selectivity analogous to that observed in the microbiological oxidation of 4-
methyloctane by Pseudomonas oleovorans, which of the following is expected to give two
constitutionally isomeric alcohols on oxidation?
45
A. Heptane.
B. 3-Methylheptane.
C. 4-Methylheptane.
D. 4,4-Dimethylheptane.
96. Female German cockroaches convert the alkane shown to a substance that attracts males.
CH3CH2CH(CH3)(CH2)7CH(CH3)(CH2)16CH2CH3
Oxidation at C-2 of the alkane gives the sex attractant, which has a molecular formula C31H62O
and the same carbon skeleton as the alkane. What is the structure of the sex attractant?
A. CH3CH(OH)CH(CH3)(CH2)7CH(CH3)(CH2)16CH2CH3.
B. CH3CH2CH(CH3)(CH2)7CH(CH3)(CH2)16CH(OH)CH3.
C. CH3C(=O)CH(CH3)(CH2)7CH(CH3)(CH2)16CH2CH3.
D. CH3CH2CH(CH3)(CH2)7CH(CH3)(CH2)16C(=O)CH3.
97. A typical steroid skeleton is shown along with the numbering scheme used for this class of
compounds. Specify in each case whether the designated substituent is axial or equatorial.
(a) Substituent at C-1 cis to the methyl groups.

(b) Substituent at C-4 cis to the methyl groups.
(c) Substituent at C-7 trans to the methyl groups.
(d) Substituent at C-11 trans to the methyl groups.
(e) Substituent at C-12 cis to the methyl groups.
(a) Equatorial.
(b) Axial.
(c) Axial.
(d) Equatorial.
(e) Equatorial.
98. Biological oxidation of hydrocarbons is a commonly observed process.
(a) To what class of hydrocarbons does the reactant in the following equation belong? What is
its IUPAC name?
(b) Identify by IUPAC locant the carbon that is oxidized in the formation of each product.
(c) How are alcohols A, B, and C related? Are they constitutional isomers or stereoisomers?
(a) The reactant is a bicyclic (i.e. having 2 rings) molecule. Its IUPAC name is spiro[2.5]octane.
(b)
Alcohol A: spiro[2.5]octane-4-ol, i.e. oxidation occurs on the 4 carbon.
Alcohol B: spiro[2.5]octane-5-ol, i.e. oxidation occurs on the 5 carbon.
Alcohol C: spiro[2.5]octane-6-ol, i.e. oxidation occurs on the 6 carbon.
(c) Constitutional isomers.
47

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Answer to Multiple-Choices Questions ......................................................................................... 25

re again, back react (“to act back [a certain action]”)

Unsaturation, Formal Charges

C. propanedioic acid, propanoic acid, 1,3-propanediol.

aspirin vitamin C formic acid oxalic acid

Configurations of Double Bonds (E/Z)

Configurations of Stereocenters (R/S)

A. C3: S; C6: R. B. C3: R; C6: R. C. C3: S; C6: S. D. C3: R; C6: S.

A. I. B. II. C. III. D. IV.

How many stereoisomers does muscarine have?

A. I. B. II. C. III. D. IV.

Constitutional (structural) isomers Stereoisomers (spatial isomers)

Enantiomers (optical isomers) Diastereomers

A. I: identical molecules, II: identical molecules, III: diastereomers.

A. I and II. B. III and IV. C. I and IV. D. II and III.

A. 3R; 6S. B. 3R; 6R. C. 3S; 6R. D. 3S; 6S.

Answers to Multiple-Choices Questions

From left to right:

Aromaticity and Electrophilic Aromatic Substitution (SEAr)

 Please revise the electrophilic aromatic substitution reaction in the lectures.

A. Ortho. B. Para. C. Both A and B. D. Meta.

The main product of above reaction sequence is:

Answer to Multiple-Choices Questions

Dehydration of Alcohols and Formation of Acetals

A. III only. B. Either I or II. C. II only. D. IV only.

A. I. B. II. C. III. D. IV.

Nucleophilic Acyl Substitution

Nucleophilic Substitution and Elimination of Halides

A. I. B. II. C. III. D. IV.

A. I. B. II. C. III. D. IV.

A. I. B. II. C. III. D. IV.

A. I. B. II. C. III. D. IV.

Nucleophilic Addition to Alkyne

Reaction of Organometallic Reagents

Answer to Multiple-Choices Questions

The final product is:

77. D. Hydroboration-oxidation furnish a primary alcohol (cyclohexylmethanol), which is oxidized

Properties and Synthesis of Carbonyl Compounds

One of the final products is:

What is the compound C?

81. D. All three choices are reductants of carbonyl group to alcohol.

86. B. Please revise the properties of carboxyl derivatives.

87. B. Please see the sequence below:

Properties and Synthesis of Amines

A. CH3NH2, acidic catalysis & heat.

A. Primary. B. Secondary. C. Tertiary. D. Quaternary.

(a) Substituent at C-1 cis to the methyl groups.

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