Carboxylic Acids And Derivatives, Alkanoic Acids.

Derivatives of carboxylic acids(acyl halides, acid anhydrides, esters and amides)

are derived from a carboxylic acid by the replacement of the hydroxyl group of

.the carboxyl group of the carboxyl function by another atom or group

All these carboxylic acid derivatives contain the acyl group, R-CO- and may be

.converted to carboxylic acids by hydrolysis

Nomenclature:
i- Common names:
Are derived from the common names of the corresponding aldehyde by changing
suffix aldehyde by ic (acid)

e.g no of C Acid Aldehyde

HCOOH 1 Formic Formaldehyde
CH3COOH 2 Acetic Acetaldehyde
CH3CH2COOH 3 Propionic Propionaldehyde
CH3CH2CH2 COOH 4 Butyric Butyraldehyde
CH3CH2CH2CH2 COOH 5 Valeric Valeraldehyde

:IUPAC Name
alkane alkanoic acid

the carboxyl group is the principal group in the parent

compound, taking precedence over other substituents in the
name. The carboxyl group must be at the beginning of the chain
and no number is needed for the group
 Cyclic acids add “carboxylic acid” to the name of the cyclic
hydrocarbon.

Acyl groups are named by replacing the –ic acid ending of the
corresponding carboxylic acid by –yl.

CH3CO- acetyl group CH3CH2CO- propionyl group

ethanoyl Propanoyl
 Acidity of carboxylic
acids acids is due
The acidity of carboxylic
to:
• 1-Resonance effect:
Any factor that stabilizes the conjugate
- base of an acid more than it stabilizes
the
acid itself will increase the strength of the acid.

The greater acidity of carboxylic acids, when compared with alcohols, arises
from the extra resonance stability of the carboxylate anion (COO-).

O
O O
R C R C = R C
+
O H O H O H

O
O O
R C R C = R C
O O O H
 •2-The Inductive effect:
The carbonyl group is an electron withdrawing attracting electrons away
from the negatively charged oxygen; the carboxylate anion is stabilized, and
in the meantime helps proton removal.
In general carboxylic acids have about the same acid strength regardless
of the length of the chain, but the acid strength is increased or decreased
by the presence of electron-withdrawing or electron-donating substituents
in the molecule.

electron donation decreases acidity by destabilizing the

resulting
carboxylate anion while electron withdrawal increases acidity
by
stabilizing the resulting carboxylate anion.
 *The inductive effect is
additive:
Cl3-C-COOH > Cl2-CH-COOH > Cl-CH2COOH > CH3COOH

Increasing acid strength

**The more electronegative the substituent the stronger the

acid:
F-CH2COOH > Cl-CH2COOH > Br-CH2COOH > CH3COOH

The influence of the inductive effect upon acid strength decreases with
an increasing number of atoms between the carbonyl group and the
electronegative group.

Increasing acid strength

 Preparation:
1) By Oxidation:
As previously mentioned, oxidation of alkenes, alkynes, alcohols and
aldehydes gave carboxylic acids.

2-From Alkyl Halides

. This is achieved in either of two ways:
• a-By Carbonation of Organometallic reagents:

This synthesis is applicable to primary, secondary, tertiary and allyl halides

which have no groups incompatible with a Grignard, or alkyl lithium reaction such as OH,
NH, SH,CN or C=O.
 • b-By Hydrolysis of Nitriles:

This method is most effective with 1o alkyl halides. Secondary alkyl halides react
more slowly and give somewhat lower yields; while elimination is the only reaction
observed with 3o alkyl halides. .

Physical Properties
The boiling points of acids are higher than those of other functional compounds of
.comparable mol. wt
The carboxylic acids have been found to consist largely of dimers; two hydrogen
bonds per molecule are found, accounting for the high boiling points of this class of
compounds.
 The water solubility of carboxylic acids is greater than that of
the corresponding alcohols. .The water solubility might be
ascribed to the additional oxygen atom that is present in a
carboxylic acid consequent increase in its ability to act as an
acceptor species in hydrogen bond formation.
 Reactions of the Carboxyl
Group:
Aldehyde& Ketones Carboxylic acid

The tetrahydral intermediate usually accept proton The tetrahydral intermediate usually eject a leaving
to form Addition product group to generate C=O to form Substitution product

The C=O attached to H or R group form strong The C=O attached to leaving group which is more
covalent bond electronegative than C make C-L bond is a weak bond

H- or R- are poor leaving group L can be easily protonated and become good leaving
group
OH H2O Cl HCl
OR ROH NH2 NH3
 Reactions of the Carboxyl Group:
Nucleophilic substitution at the Carboxyl Carbon:
Addition-Elimination Mechanism:
:a)Acid-catalyzed Addition-Elimination

b)Base-catalyzed Addition-Elimination
There are 2 places where bonds can be broken and made with preservation of the acyl
:group

• A-Reaction in which the hydrogen atom of the carboxyl group is involved:

• 1-Salt Formation:
Carboxylic acids react with inorganic bases to form
salts.

The name of the salt is formed by naming the cation, followed by the name of the
acid in which the –ic ending has been changed to –ate.

e.g. CH3COONa = sodium acetate, sodium ethanoate.

ii) Methyl Ester Formation (via Diazomethane):
 Reactions in which the intact hydroxyl groupof the carboxyl is
involved:
II) Reactions of the Alkyl Group:
-Halogenation of Carboxylic Acids: Hell-Volhard-Zelinsky Reaction
(HVZ Reaction):

Mechani
sm:
 The HVZ reaction is of a synthetic value in that the  halogen can be displaced
.by nucleophilic substitution to give other substituted derivatives

• A-Conversion to -Hydroxy Acids;

•B-Conversion to -Amino Acids:

• C-Conversion to ,-Unsaturated and -Halogenated Acids:

 The addition of HBr to acrylic acid appears to be anti-Markovnikov due to
the presence of the electron-withdrawing carboxyl group. Also, the acrylic
acid molecule has a conjugated system and the 1,4-addition that can result
leads to the formation of resonance stabilized allylic carbocation.
 d) Conversion to Dicarboxylic
Acids.

III) Miscellaneous Reactions:

1-Reduction:

RCOOH RCH2OH i) LiALH4/THF

ii) H+, H2O

Mechani
sm:
 2)Oxidation
All acids, except formic acid, are extremely resistant to oxidation, but prolonged
heating with oxidizing agents ultimately produces carbon dioxide and water.

3)Decarboxylation.
When the acid or its sodium salt is treated with sodalime,an alkane is
formed.

RCOONa+ + NaOH (CaO) R- H + Na2CO3