2.2.

3 Alcohols
 Alcohols are compounds whose molecules have a hydroxyl group (-OH)
attached to a saturated carbon atom.
 General formula: R-OH
 Compounds in which a hydroxyl group is attached to an unsaturated
carbon atom of a double bond (i.e., C=C–OH) are called enols.
 Compounds that have a hydroxyl group attached directly to a benzene ring
are called phenol.
 Alcohols are classified as primary (10), secondary (20), and tertiary (30)
depending upon wether the –OH group is attached to a primary, a
secondary, or a tertiary carbon.

1
Nomenclature of Alcohols (IUPAC System)

 Parent Hydrocarbon is the longest continuous chain that contains the –OH
 Change the name of the alkane corresponding to this chain by dropping the
ending –e and adding the suffix –ol.
 Number the chain in direction that gives functional group the lowest
number
 If both a substituent and a functional group are present, the functional
group gets the lower number
 If the functional group gets the same number when counted from both
directions, use direction which gives the substituent the lower number
 If there is more than one substituent, cite substituents in alphabetical order

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3
Physical properties of alcohols

 Lower alcohols are colourless, toxic liquids.

 They have a characteristics smell.
 Boiling points of alcohols increase regularly with the increase in the
number of carbon atoms.
 Boiling points of alcohols are much higher than those of the corresponding
alkanes.
 Lower alcohols (C1 to C3) are completely soluble in water. As we go
higher in the series, the water solubility falls rapidly.

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2.2.4 Ethers
 Ethers are a class of compounds which contain an oxygen atom bonded to
two alkyl groups.
 General formula: R-O-R’
 They are further designated as symmetrical ethers or unsymmertrical
ethers according as the two alkyl groups attached to the oxygen are same
or different.

Nomenclature of Ethers
Common name
 The two alkyl groups attached to oxygen are named in alphabetic order and
the word ether is added.
 If the two alkyl groups are same, the prefix di- is used.
CH3-O-CH2CH3 = Ethyl methyl ether CH3-O-CH3 = Dimethyl ether

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IUPAC name

 In this system, ethers are named Alkoxyalkanes.

 The larger of the alkyl groups is considered to be the alkane.
 The name of the alkane is prefixed by the name of the alkoxy group and
position number.

 Names of some common alkoxy groups (RO-) are given below:

CH3CH2CH2O- propoxy
 

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7
 Physical properties of ethers

 Dimethyl ether and ethyl methyl ether are gases. All other are colorless
liquids with pleasant odors.
 Lower ethers are highly volatile and very flammable.
 Boiling points of ethers show a gradual increase with the increase in
molecular weight.
 Ethers have lower boiling points than isomeric alcohols. This is because
ether molecules cannot form hydrogen bonds with each other as they have
no –OH groups.
 Ethers are slightly soluble in water. This is because they can form
hydrogen bonds with water.

 Ethers are excellent solvents because they are inert, unreactive and polar
molecules.

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2.2.5 Epoxides
 Epoxides are cyclic ethers in which the molecules contain a three-membered
ring involving an oxygen atom and two carbon atoms.
 Unlike most ethers, epoxides (compounds in which the C-O-C unit forms a
three-membered ring) are very reactive substances.
 For the most part, cyclic ethers behave like acyclic ethers.
 The chemistry of the ether functional group is the same, whether it’s in an
open chain or in a ring.

 Common cyclic ethers such as tetrahydrofuran and dioxane, for example, are
often used as solvents because of their inertness, yet they can be cleaved by
strong acids.

 The strain of the three-membered ring gives epoxides unique chemical

reactivity. 9
Nomenclature of epoxides
IUPAC
 Epoxides may be named as -epoxy derivatives of alkanes.

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2.2.6 Amines
 Amines are alkyl or aryl derivatives of ammonia.
 Amines are classified as primary (RNH2), secondary (R2NH), tertiary
(R3N), or quaternary (R4N+) depending on the number of organic
substituents attached to nitrogen.

Nomenclature of Amines
Common name
 Amines named as alkylamine
 Amines bearing two or three similar alkyl groups are indicated by the
prefix di- or tri-
 Amines bearing dissimilar alkyl groups are named as the N-substituted
derivative of the larger alkyl group.
 Aromatic amines are called Anilines
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 Cont..

IUPAC name
 Drop the final -e ending from the alkane name and adding the suffix -amine.
 Amines have a lower priority than do alcohols, which in turn are lower than
carbonyls when the amine is a substituent, it is termed an amino group.

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13
Physical Properties Amines
 Lower aliphatic amines are gases with fishy odour.
 Primary amines with 3 or more carbon atoms are liquid and higher ones
are solid.
 Primary amines are more strongly associated with each other through
hydrogen bonding hence are of higher boiling points.
 Secondary amine can also associate through hydrogen bonding but to a
lesser extent.

 Tertiary due to non availability of hydrogen atoms can not form hydrogen
bonds hence are of lowest boiling point amongst amines.
 Thus the decreasing order of boiling point is 1° > 2° > 3°.

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 Cont..
 Amines can form hydrogen bonds with water and are soluble in water. As
the size of hydrophobic alkyl group increases solubility decreases.
 Amines that have fewer than six or seven carbon atoms are soluble in
water.
 Primary and secondary amines are more soluble than tertiary because they
have more H-bonding with water.

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2.2.7 Aldehydes and Ketones
 A carbonyl functional group (C=O) is a carbon double bonded to an
oxygen atom.
 An acyl functional group (R_C=O) consists of a carbonyl group attached to
an alkyl or an aryl group.

 Carbonyl group-containing compounds can be classified into two broad

classes:
 one group includes compounds that have hydrogen and carbon atoms
bonded to the carbonyl carbon, (aldehydes and ketones)
 and the other group contains an electronegative atom bonded to the
carbonyl carbon.(carboxylic acids and their derivatives)

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 Cont…
 The simplest aldehyde is formaldehyde (CH2O). It is the only aldehyde
without an alkyl group attached to the carbonyl carbon.
: O:
H C H

formaldehyde

 All other aldehydes, such as acetaldehyde (CH3CHO), have one alkyl

group and one H attached to the carbonyl carbon.
: O:
CH3 C H
acetaldehyde

 All ketones have two alkyl groups attached to the carbonyl carbon.

: O:

C
H3C CH3

dimethyl ketone
(acetone)
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 Common Names of Aldehydes

 In the common system, aldehydes are named from the common names
of the corresponding carboxylic acid.
 The ‘ic acid’ ending is replaced with ‘aldehyde’.
Structure IUPAC name Common name Structure IUPAC Common name
HCO2H methanoic acid formic acid HCHO methanal formaldehyde
CH3CO2H ethanoic acid acetic acid CH3CHO ethanal acetaldehyde
CH3CH2CO2H propanoic acid propionic acid CH3CH2CHO propanal propionaldehyde
CH3(CH2)2CO2H butanoic acid butyric acid CH3(CH2)2CHO butanal butyraldehyde
CH3(CH2)3CO2H pentanoic acid valeric acid CH3(CH2)3CHO pentanal valeraldehyde
CH3(CH2)4CO2H hexanoic acid caproic acid CH3(CH2)4CHO hexanal caproaldehyde

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 Cont..
 Substituents locations are given using Greek letters (, , , , ) beginning
with the carbon next to the carbonyl carbon, the a-carbon.

O OH O O
CH3CHBrCH2C H CH3CHCH2CH2C H CH2C H
       
-bromobutyraldehyde -hydroxyvaleraldehyde -phenylacetaldehyde

IUPAC System
 Select the longest carbon chain containing the carbonyl carbon.
 The -e ending of the parent alkane name is replaced by the suffix -al.
 The carbonyl carbon is always numbered “1.” (It is not necessary to
include the number in the name.)
 Name the substituents attached to the chain in the usual way.
 If the aldehyde group is a substituent on a ring, the suffix -
carbaldehyde is used in the name

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 Cont..

Naming system of ketones

Common system
 Common names of ketones are obtained by simply naming the two alkyl
groups attached to the carbonyl group and adding the word ketone.

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IUPAC System
 Select the longest carbon chain containing the carbonyl carbon.
 The -e ending of the parent alkane name is replaced by the suffix -one.
 Number the chain starting with the end closest to the ketone group (i.e. the
carbonyl carbon should have the lowest possible number).
 Name the substituents attached to the chain in the usual way.

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24
 Physical Properties of Aldehydes and Ketones
 In general, aldehydes and ketones have higher boiling points than
hydrocarbons because they are more polar and the dipole–dipole attractive
forces between molecules are stronger.
 But they have lower boiling points than alcohols
 because, unlike alcohols, two carbonyl groups can’t form hydrogen bonds
to each other.

 Aldehydes and ketones can form hydrogen bonds with the protons of OH
groups.
 This makes them more soluble in water than alkenes, but less soluble than
alcohols.

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2.2.8 Carboxylic Acids and Their Derivatives
 Carboxylic acids are organic acids characterized by the presence of at least
one carboxyl group (-COOH).
 The general formula of a carboxylic acid is R-COOH OR R-CO2H.
 A carboxyl group (-COOH) is a functional group consisting of a carbonyl
(C=O) and a hydroxyl (-OH).
 They are weak acids.
Nomenclature of Carboxylic Acids
 Common system
 The common names are usually derived from the Latin or Greek word that
indicates the original source of the acid.
 They do not follow any rule except that all common names of acids end in
–ic acid.

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IUPAC system
 Simple carboxylic acids derived from open-chain alkanes are
systematically named by replacing the terminal -e of the corresponding
alkane name with -oic acid.
 The -CO2H carbon atom is numbered C-1.
 Cycloalkanes bonded to -COOH are named as cycloalkanecarboxylic
acids.
 Aromatic acids are named as benzoic acids.

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Physical properties of carboxylic acids
 Lower carboxylic acids (up to C-10) are liquids with sharp or disagreeable
odor. Higher members are wax-like solids and almost odorless.
 They have sour taste.
 Carboxylic acids have higher boiling points than alcohols of similar
molecular weight.

 Smaller carboxylic acids (1 to 5 carbons) are soluble in water, whereas

higher carboxylic acids are less soluble.

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 Acid Halides (Acyl Halides)
 Acid halides are the derivatives of carboxylic acids in which the –OH
group of the carboxylic acid has been replaced by a halogen atom.

Nomenclature of Acid Chlorides

 They are named by adding the word “chloride” after the name of the
acyl group.
 To name the acyl group, replace the –ic acid ending of the IUPAC name
of the corresponding carboxylic acid by –yl.
Preparation of Acid Chlorides
 In the laboratory, carboxylic acids are converted into acid chlorides by
treatment with thionyl chloride, SOCl2.

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 Acid Anhydrides, RCO2COR′

• Symmetrical anhydrides of unsubstituted monocarboxylic acids and cyclic

anhydrides of dicarboxylic acids are named by replacing the word acid
with anhydride.

• Unsymmetrical anhydrides—those prepared from two different carboxylic

acids—are named by citing the two acids alphabetically and then adding
anhydride.

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 Ester
 Esters are derivatives of carboxylic acids in which the –OH group has
replaced by –OR group.

 Esters are among the most widespread of all naturally occurring

compounds.
 Many simple esters are pleasant-smelling liquids that are responsible for
the fragrant odors of fruits and flowers.
Nomenclature of Esters
 The name of an ester is of two words.
 The name of the alkyl group attached to carboxyl oxygen is the first word.
 The second word is the name of the parent acid with the endig “-ic acid”
changed to “-ate”

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 Amides
 Amides are derivatives of carboxylic acids in which the OH group of the
COOH group has been replaced by NH2, NHR, or group NR2.

 Amides, like esters, are abundant in all living organisms. Proteins, nucleic
acids, and many pharmaceutical agents have amide functional groups.
 The reason for this abundance of amides is that they are stable to the
aqueous conditions found in living organisms.
 Amides are the least reactive of the common acid derivatives and undergo
relatively few nucleophilic acyl substitution reactions.

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Nomenclature of Amides
 Amides are named by using the acid name, replacing “oic acid” (IUPAC)
or “ic acid” (common) with “amide”.

 If a substituent is bonded to the nitrogen, the name of the substituent is

stated first (if there is more than one substituent bonded to the nitrogen,
they are stated alphabetically), followed by the name of the amide.
 The name of each substituent is preceded by a capital N to indicate that
the substituent is bonded to nitrogen.

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