FUNCTIONAL GROUP

CHAPTER 7

Learning Course Outline

Naming the groups of alcohol,phenol,carbonyls, carboxyls
and amines compounds.
Write the reaction mechanism and give examples of reaction
of alcohol,phenol,carbonyls,carboxyls and amines
compounds.

NOMENCLATURE

ALCOHOL & PHENOL

Oxygen is sp3 hybridized and tetrahedral.

The HOH angle in water is 104.5.
The COH angle in methyl alcohol is 108.9.
General classifications of alcohols based on substitution on C to
which OH is attached

ALCOHOL & PHENOL

IUPAC Nomenclature
Find the longest carbon chain containing the carbon with the OH
group.
Drop the -e from the alkane name; add -ol.
Number the chain, giving the OH group the lowest number
possible.
Number and name all substituents and write them in alphabetical
order.

ALCOHOL & PHENOL

Examples of Nomenclature
3

CH3

CH3
CH CH2OH

Old: 2-methyl-1-propanol
New: 2-methylpropan-1-ol

CH3

OH

3 4

CH CH2CH3
Old: 2-butanol
New: butan-2-ol

2 1

C H3
C H3

OH

C H3

Old: 2-methyl-2-propanol
New: 2-methylpropan-2-ol

ALCOHOL & PHENOL

Alkenols (Enols)
Hydroxyl group takes precedence. Assign the carbon
with the OH the lowest number.
End the name in -ol, but also specify that there is a
double bond by using the ending -ene before ol.
OH

CH2

CHCH2CHCH3

Old: 4-penten-2-ol
New: pent-4-ene-2-ol

ALCOHOL & PHENOL

Naming Priority
Highest ranking

Lowest ranking

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Acids
Esters
Aldehydes
Ketones
Alcohols
Amines
Alkenes and Alkynes
Alkanes
Ethers
Halides

ALCOHOL & PHENOL

Hydroxy Substituent
When OH is part of a higher priority class of compound, it is
named as hydroxy.
carboxylic acid

OH
C H2C H2C H2C OOH
4

4-hydroxybutanoic acid

ALCOHOL & PHENOL

Common Names
Alcohol can be named as alkyl alcohol.
Useful only for small alkyl groups.

OH

CH3

CH3

CH CH2OH

isobutyl alcohol
IUPAC: 2-methylpropan-1-ol

CH3

CH CH2CH3

sec-butyl alcohol
IUPAC: butan-2-ol

ALCOHOL & PHENOL

Naming Diols
Two numbers are needed to locate the two
OH groups.
Use -diol as suffix instead of -ol.

hexane-1,6-diol

Glycols
1,2-diols (vicinal diol) are called glycols.
Common names for glycols use the name of the alkene from which
they were made.

IUPAC: ethane-1,2-diol
ethylene glycol

IUPAC: propane-1,2-diol
propylene glycol

Phenol Nomenclature
Phenol, C6H5OH (phenyl alcohol) has diverse uses - it gives
its name to the general class of compounds
OH groups bonded to vinylic sp2-hybridized carbons are called
enols
OH group is assumed to be on carbon 1.
For common names of disubstituted phenols, use ortho- for 1,2;
meta- for 1,3; and para- for 1,4.
Methyl phenols are cresols.
OH

Cl
3-chlorophenol
(meta-chlorophenol)

OH
H3C
4-methylphenol
(para-cresol)

CLASSES OF CARBONYL COMPOUNDS

CARBOXYLIC ACIDS
The functional group of carboxylic acids consists of a CO with
OH bonded to the same carbon.
Carboxyl group is usually written COOH.
Aliphatic acids have an alkyl group bonded to COOH.
Aromatic acids have an aryl group.
The compound named as oic acid replacing the e naming of
alkane - IUPAC
Common name of acids end in ic acid

CARBOXYLIC ACIDS
Nomenclature

CARBOXYLIC ACIDS

CARBOXYLIC ACIDS
In systematic nomenclature, the carbonyl carbon is always C-1
In common nomenclature, the carbon next to the carbonyl is the acarbon

17

CARBOXYLIC ACIDS

CARBOXYLIC ACIDS
The functional group of a carboxylic acid is called a carboxyl group

19

ALDEHYDES AND KETONES

Aldehydes (RCHO) and ketones (R2CO) are characterized by the
carbonyl functional group (C=O)
The compounds occur widely in nature as intermediates in
metabolism and biosynthesis

ALDEHYDES AND KETONES

Much of organic chemistry involves the chemistry of
carbonyl compounds
Aldehydes/ketones are intermediates in synthesis of
pharmaceutical agents, biological pathways,
numerous industrial processes
An understanding of their properties is essential

ALDEHYDES AND KETONES

Aldehydes are named by replacing the terminal e of the
corresponding alkane name with al
The parent chain must contain the CHO group
The CHO carbon is numbered as C1
If the CHO group is attached to a ring, use the suffix
carbaldehyde

ALDEHYDES

KETONES
Replace the terminal -e of the alkane name with one
Parent chain is the longest one that contains the ketone group
Numbering begins at the end nearer the carbonyl carbon
The carbonyl is assumed to be at the 1-position in cyclic ketones:

KETONES

If a ketone has a second functional group of higher priority

25

KETONES
Common Names:
IUPAC retains well-used but unsystematic names for a few ketones

Carbonyl as Substituent
On a molecule with a higher-priority functional
group, a ketone is an oxo and an aldehyde is a
formyl group.
Aldehydes have a higher priority than ketones.

AMINES
Organic derivatives of ammonia, NH3
Nitrogen atom with a lone pair of electrons, making amines both basic
and nucleophilic
Occur in plants and animals

AMINES
Classes of Amines
Primary (1): Has one alkyl group bonded to the nitrogen (RNH2).
Secondary (2): Has two alkyl groups bonded to the nitrogen
(R2NH).
Tertiary (3): Has three alkyl groups bonded to the nitrogen (R3N).
Quaternary (4): Has four alkyl groups bonded to the nitrogen and
the nitrogen bears a positive charge (R4N+).

AMINES
Quaternary Ammonium Salts

The nitrogen atom has four alkyl groups attached.

The nitrogen is positively charged.

AMINES
Common Names

Common names of amines are formed from the names of the

alkyl groups bonded to nitrogen, followed by the suffix -amine.

AMINES
IUPAC Names
Name is based on longest carbon chain.
The -e of alkane is replaced with -amine.

AMINES
Amine as Substituent

On a molecule with a higher-priority functional group, the amine

is named as a substituent.

AMINES
Aromatic Amines

In aromatic amines, the amino group is bonded to a benzene

ring.
Parent compound is called aniline.

AMINES
Heterocyclic Amines
When naming a cyclic amine, the nitrogen is assigned position number 1.

REACTION

REACTION : ALCOHOLS
Types of Alcohol Reactions

Dehydration to alkene
Oxidation to aldehyde, ketone
Substitution to form alkyl halide
Esterification
Tosylation
Williamson synthesis of ether

Summary Table

1) Dehydration of Alcohols to Yield Alkenes

The general reaction: forming an alkene from an alcohol through loss
of O-H and H (hence dehydration) of the neighboring CH to give
bond
Specific reagents are needed

Dehydration with POCl3

Phosphorus oxychloride in the amine solvent pyridine can lead to
dehydration of secondary and tertiary alcohols at low temperatures
An E2 reaction via an intermediate ester of POCl2

2) Oxidation Of Alcohols
Can be accomplished by inorganic reagents, such as KMnO4, CrO3,
and Na2Cr2O7 or by more selective, expensive reagents

Oxidation of Primary Alcohols

To form aldehyde: pyridinium chlorochromate (PCC, C5H6NCrO3Cl) in
dichloromethane
Other reagents produce carboxylic acids

Oxidation of Secondary Alcohols

Effective with inexpensive reagents such as cromic acid reagent,
Na2Cr2O7 in acetic acid
PCC is used for sensitive alcohols at lower temperatures
Product is ketones

3) Substitution Of Alcohols
Conversion of alcohols into alkyl halides:
- 3 alcohols react with HCl or HBr by SN1 through carbocation
intermediate
- 1 and 2 alcohols converted into halides by treatment with SOCl2 or
PBr3 via SN2 mechanism

Reactions of 1 and 2 alcohols

5) Esterification

Reaction of an alcohol and a carboxylic acid produces an ester.

Sulfuric acid is a catalyst.
The reaction is an equilibrium between starting materials and
products, and for this reason the Fischer esterification is seldom
used to prepare esters.

Esterification cont..
Reaction of Alcohols with Acyl Chlorides

The esterification reaction achieves better results by reacting

the alcohol with an acyl chloride.
The reaction is exothermic and produces the corresponding
ester in high yields with only HCl as a by-product.

6) Tosylation

Alcohols can be converted to tosylate esters (ROTs) through a

condensation with p-toluenosulfonic acid.
The tosylate group is an excellent leaving group.

Substitution and Elimination Reactions

Using Tosylates

7) Alkoxide Ions: Williamson Ether Synthesis

Ethers can be synthesized by the reaction of alkoxide ions with

primary alkyl halides in what is known as the Williamson ether
synthesis.
This is an SN2 displacement reaction and as such, works better
with primary alkyl halides to facilitate back-side attack.
If a secondary or tertiary alkyl halide is used, the alkoxide will
act as a base and an elimination will take place.

REACTION : PHENOLS
Undergoes the same reaction of aromatic substitution.
Type of rxns:
Formation of ether
Cleavage of alkyl aryl ethers
Bromination
Nitration

1) Formation of Ether
Phenol can be converted to ether through Williamson synthesis
Phenols react with alkyl halides in alkali solution to form phenyl
ethers
The alkali first forms the phenoxide ion which react with aklyl
halide

Ar-OH

NaOH

OH

Ar-Ona
ONa

NaOH

CH3

R-X

Ar-O-R + NaX
OCH2CH 3

CH 3CH 2I

CH3

CH3

2) Cleavage Of Aklyl Aryl Ethers

Alkyl aryl ether reacts with strong acid such as HI and HBr
produce alkyl halide and a phenol

Ar-O - R

conc. acid

Ar-O-R + NaX

HBr
H3C

OCH3

H3C

OH

3) Bromination
Hydroxyl group is powerful activating group and o,p director
Phenol reacts with bromine water (aqueous bromine) to give
precipitate of 2,4,6-trinitrophenol
OH

OH
3Br

Br

Br

H2 O

HBr

Br

If the reaction carried out in carbon disulfide (CS2) at low

temperature, monobromination of phenol can be formed.
OH

OH
Br2
CS 2

OH
Br

+
CH3

4) Nitration
Phenol reacts with dilute nitric acid to yield mix of o,p product
OH

OH
HNO 3

OH

O 2N

H2SO4

NO 2

If phenol reacts with concentrated nitric acid, picric acid is formed

OH

OH
conc HNO3

NO 2

O 2N

NO 2

REACTION: CARBOXYLIC ACIDS

Preparing Carboxylic Acids
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7
gives a substituted benzoic acid
1 and 2alkyl groups can be oxidized, but tertiary groups are not

From Alkenes
Oxidative cleavage of an alkene with KMnO4 gives a carboxylic acid
if the alkene has at least one vinylic hydrogen

From Alcohols
Oxidation of a primary alcohol or an aldehyde with CrO3 in aqueous
acid

1) Fischer Esterification

Reaction of a carboxylic acid with an alcohol under acidic

conditions produces an ester.
Reaction is an equilibrium; the yield of ester is not high.
To drive the equilibrium toward the formation of products, use a
large excess of alcohol.

2) Synthesis of Amides

The initial reaction of a carboxylic acid with an amine gives an

ammonium carboxylate salt.
Heating this salt to well above 100 C drives off steam and forms
an amide.

3) LiAlH4 or BH3 Reduction of Carboxylic

Acids

LiAlH4 reduces carboxylic acids to primary alcohols.

The intermediate aldehyde reacts faster with the reducing agent
than the carboxylic acid.
Borane can also reduce the carboxylic acid to the alcohol.

4) Synthesis of Acid Chlorides

The best reagents for converting carboxylic acids to acid

chlorides are thionyl chloride (SOCl2) and oxalyl chloride
(COCl2).
They form gaseous by-products that do not contaminate the
product.

5) Conversion of Carboxylic Acids to

Ketones

A general method of making ketones involves the reaction of a

carboxylic acid with two equivalents of an organolithium reagent.

REACTION: ALDEHYDE & KETONE

The partial positive charge on the carbonyl carbon causes that carbon to
be attacked by nucleophiles:

An aldehyde has a greater partial positive charge on its carbonyl carbon than
does a ketone:

Aldehydes Are More Reactive Than Ketones

Steric factors contribute to the reactivity of an aldehyde.
The carbonyl carbon of an aldehyde is more accessible to the nucleophile.
Ketones have greater steric crowding in their transition states, so they have
less stable transition states.

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1) Formation of Acetals

2) Oxidation of Aldehydes

Aldehydes are easily oxidized to carboxylic acids.

3) Reduction using Sodium

Borohydride

NaBH4 can reduce ketones and aldehydes, but not esters,

carboxylic acids, acyl chlorides, or amides.

4) Reduction using Lithium Aluminum

Hydride
OH

O
R

R(H)

LiAlH4
ether

R(H)

aldehyde or ketone

LiAlH4 can reduce any carbonyl because it is a very strong

reducing agent.
Difficult to handle

5) Additon of Hydrogen
Hydrogen cyanide adds to aldehydes and ketones to form cyanohydrins:
+

HCN