Alcohols

The functional group of an alcohol is a hydroxyl group bonded to an sp³ hybridized carbon. It can
therefore be regarded as a derivative of water, with an alkyl group replacing one of the hydrogens.

Methods of Preparation
1) Hydrolysis of alkyl halides
2) Reaction of grignard’s reagent with carbonyl compounds
3) Reaction of organolithium with carbonyl compounds
4) Reaction of Grignards Reagent with esters
5) Acid catalyzed hydration of alkenes
6) Oxymercuration - Demercuration of alkenes
7) Hydroboration – oxidation of alkenes
8) Reaction of amine with nitrous acid
9) Reduction of compounds by NaBH4 and LiAlH4
a) NaBH4
b) LiAlH4
10) From epoxides

Reactions of Alcohols
1) Acidic nature of alcohols
2) Reaction with thionyl chloride and phosphorous halides
3) Reaction of alcohol with hydrogen halides
4) Haloform test
5) Dehydration of alcohols
6) Alcoholation of alkyne
7) Acylation of alcohol
8) Esterification

Methods of distinguishing between 1°, 2° and 3° alcohols

1) Oxidation test
2) Lucas test
3) Victor Meyer’s test
4) Catalytic dehydrogenation by Cu
Primary, secondary, and tertiary alcohols

There are three major subsets of alcohols- 'primary' (1°), 'secondary' (2°) and 'tertiary' (3°),
based upon the number of carbons the C-OH carbon (shown in red) is bonded to. Methanol is
the simplest 'primary' alcohol. The simplest secondary alcohol is isopropanol (propan-2-ol), and
a simple tertiary alcohol is tert-butanol (2-methylpropan-2-ol).
Methods of Preparation:

(1) Hydrolysis of alkyl halides This reaction is useful only with reactants that do not undergo E2
elimination readily. It is really used for the synthesis of alcohols where alkyl halides are primary in
nature.

(2) Reaction of Grignard reagents with aldehydes

and ketones A method that allows for alcohol preparation with formation of new carbon bonds. Primary,
secondary, and tertiary alcohols can all be prepared and stepping up to two carbon atom also can takes
place by the help of cyclic epoxides.

(3) Reaction of organolithium reagents with

aldehydes and ketones Organolithium reagents react
with aldehydes and ketones in a manner similar to that
of Grignard reagents to form alcohols. Other reagents which are less reactive than alkyl lithium is dialkyl
cadmium, R2Cd where active species is carbanian, and forms similar kind of product.

 
(4) Reaction of Grignard reagents with esters Produces tertiary alcohols in which two of the
substituents on the hydroxyl- bearing carbon are derived from the Grignard reagent. If we want to stop
this reaction at carbonyl compound we must use less reactive reagent like dialkyl cadmium R 2Cd.
Remember the alkyl group in ester goes out finally as alcohol.

  (5) Acid catalyzed

hydration of alkenes The
elements of water add to the
double bond according to the
markonikov’s rule, by
intermediate carbocation so
rearrangement occurs.

 
(6) Oxymercuration-demercuration of alkenes
Markonikov’s addition of the elements of water to the double
bond occurs. This is a useful synthetic reaction where
rearrangements do not occur due to cyclic mercurium ion.

(7) Hydroboration oxidation of alkenes by

  B2H6 followed by H2O2 Overall reaction is
addition of water across the double bond
opposite to that of markovnikov’s rule This is a
very good synthetic method, addition is syn, and
no rearrangements are observed.

(8) Reaction of an amine with nitrous

acid
(9) Reduction of compounds by NaBH4 and LiAlH4 (Synthesis of alcohol)

(a) NaBH4

Sodium borohydride is a reducing agent. It reduces by transfer of hydride ions to substrates as in the case
of lithium aluminium hydride.

1. Reduction of carbonyl compounds and its derivatives into alcohol

In the above list it will be seen that only the carbonyl group is reduced and the other functional groups
remain unaffected. Highly selective behaviour of NaBH 4 makes it the preferred reagent for the reduction
of carbonyl groups in sensitive polyfunctional group containing compounds.

(b) Lithium Aluminium Hydride(LiAlH4)

Lithium aluminium hydride (LAH) is also one of the very important and useful synthetic reagent for the
reduction of carbonyl compounds along with many other compounds.

The reagent is prepared by slowly adding a calculated amount of anhydrous aluminium chloride to a paste
of lithium hydride in dry ether or THF.

The reactants and their reduction products with LiAlH4 are listed below.

(10) From epoxides

Although the chemical reactions of epoxides will not be covered in detail until the following chapter, we
shall introduce their use in the synthesis of alcohols here.
Grignard reagents react with ethyleneoxide to yield primary alcohols containing two more carbon atoms
then the alkyl halide from which the organometallic compound was prepared epoxides are open by charge
separation of carbon and oxygen, then attach with grignard reagent.

Organolithium reagents react with epoxides in a similar manner. These reactions are used to convert
lower alcohol into higher alcohol.
Epoxide rings are readily opened with cleavage of the carbon-oxygen bond when attacked by serving as
sources of nucleophilic carbon so this method can also be used for stepping up to two carbon atom. For
example

Reactions of alcohols :
Alcohols are versatile starting materials for the preparation of a variety of organic functional
groups.

Alcohols can undergo reactions involving various combinations of the bonds of carbon and
oxygen. The ionization of alcohols when they act as weak acids and the formation of alkoxides
when they react with metals are reactions that take place at the O–H bond.

The carbon-oxygen bond of alcohols is cleaved when alcohols are converted to alkyl halides or
undergo acid-catalyzed dehydration.

Some of the new reaction of alcohols that we will examine in this chapter occur by O–H bond
breaking and some by C–O bond breaking. Additionally, primary and secondary alcohols can
exhibit a third reaction type in which a carbon-oxygen double bond is formed by cleavage of
both an O–H bond and a C–H bond:

(i) Acidic nature of alcohol

Even alcohol are neutral to litmus and do not reacts with alkali like NaOH but contain active
hydrogen atom so reacts with Na or K metal.

reactivity of alcohol towards metal 1° > 2° > 3° alcohol

(ii) Reaction with Thionyl chloride and phosphorus Halides

Other reagents can also be used to avoid carbocation intermediates and minimize rearrangements
in the conversion of alcohols to alkyl halides. One of these is thionyl chloride, SOCl2. 3-Pentanol
will react with thionyl chloride in pyridine to give 3-chloropentane, and no 2-chloropentane.

This reaction is often accompanied by elimination reactions, so it does not give high yields and a
good leaving group. An intermediate chlorosulfite ester, which decomposes to give the alkyl
halide. In the presence of organic bases such as pyridine, inversion of configuration is seen for
chiral compounds.
 Another reagent that is used to substitute a halogen for a hydroxyl group with a minimum of
rearrangement is phosphorus tribromide. For example, it is used to convert the primary alcohol
isobutyl alcohol into isobutyl bromide.

The mechanism suggested for the conversion of an alcohol to an alkyl halide using phosphorus
tribromide resembles the one proposed for the conversion using thionyl chloride. Its first step is
the formation of a phosphorus- oxygen bond between the alcohol and phosphorus tribromide,
giving a phosphorus ester that has a good leaving group.
(iii) Reaction of alcohol with Hydrogen Halides

Alkyl halides, which participate in many different substitution reactions, may be prepared from
alcohols in different ways. The hydroxyl group in an alcohol can be converted into a good
leaving group so that it can be displaced by an incoming halide ion. For example, dissolving
gaseous hydrogen bromide in 1-heptanol converts the alcohol to 1-bromoheptane.

(iv) Haloform test only for 2–alkanone (by three equivalents of halogen)

(v) Dehydration of alcohols

Alcohols when are reacts with any dehydrating reagent to form alkenes with removal of water.
Intermediate carbocation formation takes place where rearrangement occurs by alkyl shift,
hydride shift and ring expansion.

In smaller ring always ring expansion takes place due to molecular strain and they tends to
convert to high stability with large ring.
In Dehydration of alcohols

(vi) Alcoholation of alkyne

When alcohols reacts with alkyne in the presence of BF3 and HgO, according to markonikoff’s
rule they forms ethers.
(vii) Acylation of alcohol

When alcohol reacts with acylhalide and anhydride substitution of hydrogen atom by acyl group
is known as acylation of alcohols.

(viii) Reaction with CH2N2 or CH2CO

(ix) Esterification

When acid reacts with alcohol in the presence of of ester’s takes place with fruity
smell. Striking feature is removal of –OH group from acid so water contains isotopic oxygen
comes from acid molecule.

Methods of distinguishing between primary, secondary and tertiary alcohols

(a) Oxidation test

(b) Lucas test

(c) Victer meyer test (best method)

(d) Catalytic dehydrogenation by Cu/300°C.

(a) Oxidation with sodium Dichromate (Na2Cr2O7)

Primary and secondary alcohols are easily oxidized by reagents containing chromium (VI). For
low-molecular-weight alcohols that are water-soluble, water solutions of sodium dichromate in
the presence of acid are used. A primary alcohol such as n-butyl alcohol is oxidized first to an
aldehyde, which is oxidized further by the same reagent to a carboxylic acid.

This process is not of practical use for preparing aldehydes from primary alcohols because it
undergo further oxidation (except for a few cases where the aldehyde that is formed has a boiling
point low enough that it can be distilled out of the reaction mixture).

A secondary alcohol, for example sec-butyl alcohol, is oxidized to a ketone, which usually does
not undergo further oxidation due to absence of reducing hydrogen. For a ketone to be oxidized,
carbon-carbon bonds would have to be broken because there are no more carbon-hydrogen bonds
available on the carbonyl carbon atom.

The tertiary alcohol tert-butyl alcohol is not oxidized by acidic sodium dichromate solution. The
carbon atom bearing the hydroxyl group in this alcohol does not have a hydrogen atom on it.
Here, too, carbon-carbon bonds would have to be broken to allow oxidation to take place.

The oxidizing solution in the above examples, an acidic solution of sodium dichromate, contains
a variety of species in equilibrium. Most important of these is the acid chromate ion, HCrO4¯.
(b) Lucas test: Alcohols react with concentrated hydrochloric acid in presence of anhydrous
zinc chloride to form alkyl halides.

The three types of alcohols undergo this reaction at different rates. The rates of reaction with
Lucas reagent
[conc. HCl + ZnCl2 (anhydrous) follow the following order:

Tertiary alcohol > Secondary alcohol > Primary alcohol

Lucas test is based on this order because formation of intermediate carbocation takes place. An
unknown alcohol (monohydric) is mixed with conc. HCl and ZnCl2 at room temperature. The
alkyl chloride formed is insoluble in the medium; thus the solution becomes cloudy before it
separates as a distinct layer.

The following observations are made:

(a) If cloudiness appears immediately, the alcohol is tertiary.

(b) If cloudiness appears within 5–10 minutes, the alcohol is secondary.

(c) If the solution remains clear, i.e., on cloudiness is formed the alcohol is primary.

Note: Primary alcohols do not react with Lucas reagent at room temperature. It requires high
temperature.
(c) Victor Meyer’s test: In this test, the following steps are involved:

(i) Alcohol is reacted with conc. HI or red phosphorus and iodine to form the corresponding
alkyl iodide.

(ii) Alkyl iodide is treated with silver nitrite when corresponding nitroalkane is formed.

(iii) Nitro alkane is treated with nitrous acid (NaNO2 + H2SO4) and the solution is made alkaline
by addition of excess of caustic soda.

(d) Catalytic dehydrogenation: It involves the passing of vapours of alcohol over reduced
copper at 300°C and the product thus formed is identified.

(i) Primary alcohols give aldehydes (dehydrogenation).

(ii) Secondary alcohols give ketones (dehydrogenation).

(iii) Tertiary alcohols form olefins (alkenes). This is dehydration.