Chapter 21-25 PDF

Chapter 2I
Carboxylic Acids
This class of compounds have the general formula

0
RCOH or RCOOH or R-CO2H

where an alkyl R is bonded to a COOH group. The functional group COOH is, in fact, made
of a carbonyl group joined to a hydroxyl group.
0
C-- + OH - COH
Carbonyl Hydroxyl Carboxyl
(present in aldeh ydes (present in (present in carbo-
& ketones) alcohols) xylic acids)
The combined group CO--OH is designated as Carboxyl which is a contraction of 'carbonyl-
hydroxyl'. Although the carboxyl group is virtually a union of one carbonyl and one hydroxyl
group, the properties of these constituent functional groups are profoundly modified due to
their mutual interaction. Thus the carbonyl of carboxyl group does not give the reactions
shown by aldehydes and ketones and its 01-1 group is definitely not alcoholic. The carboxyl
group taken as a whole shows characteristic properties and in its own is regarded as an
indepcnient functional group. Therefore, the compounds which contain the COOH group
are acidic, and are better considered as a separate class called the Carboxylic acids. They are
further termed as monocarboxylic acids, dicarboxylic acids, iricarboxylic acide etc.. according
as the number of COOH groups ptesent in the molecule is I, 2, 3 or more.
MONOCARBOXYLIC ACIDS
They contain one carboxylic group attached to a h)drocarbon group. They are called
Saturated acids or Unsaturated acids according as the hydrocarbon group to which the COOH is
bonded, is saturated or unsaturated. Thus,
CFI 5 CHCOOH CH, - CH =CH--COOK CH 3 = CH -COOH
propionic acid crotorlic acid acrylic acid
(sa,urattd) (unsaturated) (nnoaiurared)
The saturated monocarboxylic cids are also commonly referred to as Fatty acids since
many of them, particularly the higher or mbers, are obtained by the hydrolysis of fats.
STRUCTURE
Electron and neutron diffraction studies have revealed that the carboxyl group rep; csents
a planar arrangement of atoms. This shows that the carboxyhic carbon and the two oxygen
atoms in carboxylic group are rp' hybridized. The three sp' hybridized orbitrals of the
carboxylic carbon overlap with two spt orbitals of the ts' o oxygen atoms (one derived from
each oxygen) and one sp hybridized orbital of the alkyl group to form three g bonds. An op2
hybridized orbitral of one of the two oxygen atoms further overlaps with 5 orbitral of a hydrogen
479

480
Advanced Organic Chemistry
sp IJNU5ED
ORdJIALS ,A
5,b2
5,6
3 OR
N H
(a)
LA
OR
(b)
Fig. 211 (a) a skeir in of the carboxylic acid molecule (h) Delocailsed a electron cloud.
atom to form a or bond. Each of the two oxygen atoms and the carboxylic carbon are now left
with one p orbital prependicular to the a bonding skeleton. All these three unused orbitrals over-
lap so that the resulting it bond is partly delocalized between carbon and one oxygen on one
hand and the carbon and the second oxygeft on the other hand. It is illustrated in Fig. 21'I.
This delocalization explains elegantly why: (1) the CO single bond of carboxylic group is
shorter (1.36A) than the normal CO single bond (1.43A') in alcohols and ethers; and (2) the
C=O double bond in carboxylic group is slightly longer (1.23K) than the normal C=O double
bond (1,20A') in ketones and aldehydes.
/ 1434 123A
j2A
h C OH S00
H p.
l36A
ALCOHOL CARBOX YLIC ACID AE rONE
NOMENCLATURE
Broadly speaking, there are two methods of naming monocarboxylic acids.
(1 I The Common System. Many of the straight-chain monocrboaylic acids are isolated
from natural sources and were assigned common or trivial names. These came, ere usually

Carboxyllc Adds 481
derived from latin words indicating the source of the acid (See Table). It may be noted that
such names do not follow any rules except that they end in -ic acid. The acids containing five
or fewer carbon atoms are invariably referred to by their common names. The common
names for certain higher members are also still in use for convenience.
In this system, acid having a single branch of a methyl group at the end of a normal
hydrocarbon chain farthest removed from the COOH group, may be named by adding the
prefix iso . to the common name of the acid with the same number of carbon atoms (isomeric).
CH CH - CH 1 CHaCOOli CH CH CH COOH
rakric acid isovaleric acid
The higher branchedchain acids can be named as substituted derivatives of a normal parent acid.
The positions of substituents on the carbon chain are indicated by Greek letters. The first
carbon after the COOH group is designated as a, the next carbon , and so on. The carbon
atom in the COOH group is not assigned a letter,
CC--CC--C---COOH
For example,
CH, CH,
CH,CH2CHCOOH CH,CH,CHCH,COOH
a..methylbutyric and -methyIvaIeric acid
CH, CH
CHCHCHCHCH,---COOH
, 7-dimethylcaproic acid
Branched chain carboxylic acids may also be named as derivatives of acetic acid. These
derived names are obtained by naming the alkyl group or groups attached to the carbon holding
the carboxyl group and adding the suffix -acetic acid.
CH, CH1CH3 CH,
CH3 CHCH,COOH CHCHCOOH CH,CCOOH

isopropylacciic acid ethylmethylacelic acid
CIT3
trimeibyIaetic acid
fable. Systematic and Common names of some straight-chain acids
Formula JUPAC Name Common Name Source
HCOOH Methanoic acid Formic acid L, Formica= ant

CH3COOH Ethanoic acid Acetic acid L, Acelum= vinegar

CH3CH2COOH Propanoic acid Propionic acid Gr, Proton =flrst
Pion fat

CH1CH3CH,COOH Butanoic acid Butyric acid L, Butyram = butter

CH3CFT2CK1CH2COOR Pentanoic acid Valeric acid Valerian roof
CHCHSCHCH2CH2C00U 1-Texanoic acid Caproic acid L, Caper=good (fat)
CH3(C113)10C00H Dodecanoic acid Laceric acid Laurel
CH3(CH!)I4COOH Hexadenoic acid Palmitic acid Palm oil
CH3(CH5)16C00H Octadecanoic acid Stcaric acid Gr, Stear= tallow

482 Advanced Organic Chemistry
(2) The JIJPAC System. According to this system, carboxylic acids are named as
Alkanctic acids (Alkanee-t.-oic acid). The systematic name of an individual acid is derived
by dropping the final e from the name of the corresponding alkane (having same number of
(f atoms) and adding the suffix -oic acid. The systematic names of some carboxylic acids are
given in Table above.
The EUPAC system is frequently used for assigning names to higher branched-chain
and substituted carboxylic acids according to the rules given below.
(I) The longest carbon chain containing the carboxylic group is selected and the
carboxylic acid is named by replacing the 'e' of the corresponding alkane by '-oic acid'.
(2) The selected carbon chain is numbered I, 2, 3, 4 etc to indicate the position of
the side-chains attached to it. The carboxylic carbon is always given the number 1.
0
- a
CCCC COH.
5432 I
It may be noted that in the common system it is the carbon holding the COOK group which is
designated as a. while in the JUPAC system numbering starts from the carbon of the COOH
group itself.
The IUPAC names of some substituted acids are given below for illustration.
CH, CH2CHa
C14 3 CH I CHCOOH CFL. C K. - ('K -- - CK2COOH

.4 3 2 1 5 4 3 2 1
2.niethylbutaiioic ac :.;! 3-cthyl.4-meihy1hexarioic acid
'.s... .'tern, carboxylic acids may also be named as COOH-substituted
hydrocarbons. Here the parent hydrocarbon (leaving out COOK which is regarded a substituent)
is assigned name and.che suffix carboxylic acid' is added to it. Thus,
CH3 CH,CHCOOH
CH3 CH 2 CHCH 2 000I-T CF1tH3

4 3 2 1 cyctobuianccarbosylic acid
2-melhytbuane-I .carboxylic and
ISOMERISM
Like any other organic derivatives such as alcohols and alk y l halides, Carboxylic acids
show both position and chain isomerism. For example, the molecular formula C 5 l-T 13 O represents
the following isomeric carboxylic acids.
(I) CHCH 3 CHCH 2 CH 2 . COO F1 hexanoic acid
COOH
(2) CH 3CH2CH 5 HCH 2.methylpenianojc acid
COOK
(3) CH,CH,CHCH,CH, 2.ethylbutanoic acid

CH
(4) CHi -CHCHCHr_COOF1 4.me[hylpentanoic acid

CH,
(5) CFTrtjCHr'.'COOH 3, 3-dimeihylbuianoic acid
Cl-i3
CH
(6) CH.CH,--CCOON 2, 2-dirnc1hylbutanojc acid

Cl-I3

483
Ccrboxyllc Acids
While carboxylic acids (I), (2), (3) are the cases of position isomerism, the carboxylic
acids (I), (2). (3), (4), (5) and (6) illustrate chain isomerism.
same number
Carboxylic acids exhibit functional isomerism with esters containing the
of carbon atoms. For example, propionic acid is isomeric with methyl acetate and butyric
acid is isomeric both with methyl propionate and ethyl acetate.
Formula Functional isomers
CL1.0 CH1COOCH3
CHCHIC00H
methyl acetate
propionic acid
CHSO1 CHCH3CH1C00H CHCH 1 C00CH5 CHCO0CH1CH1
butyric acid methyl propionate ethyl acetate
METBODS OF PREPARATION
Monocarboxylic acids can be obtained by the following methods
(I) Oxidation of 10 alcohols and aldehydes. Primary alcohols and aldehydes on
oxidation with sodium or potassium dichromate and sulphuric acid, or potassium permanganate,
give the corresponding carboxylic acids.
(0] [0]
RCH1OH -p RCHO -v RCOOH
I' alcohol aldehyde carboxylic acid
The overall reaction with acidified dichromate may be represented as
0
a- II 3+
3RCH1OH + 2Cr101 + I6H -u 3R-4--OH + Cr + 11 1110
For example,
K1CrO2,
CHaCHtOH + 2(0] a. CHC00H + H30

ethyl alcohol acetic acid
H1S05
CH,CHO + [0] -p . CH,COOH
acetaldebyde
Similarly,
CH, CH,
l(Mn04,
I H1SO4 I
CH3CH1CH5CHCH1 OH -- 2[0] -+ CH 3CH3042 CH_C00H + H30
2.methyl . l.pentaDol room temp. 2. metbyl- l-peatanolc acid
0 KMnO4,
0
I H3SO4
CHCH3CH1CH2CH,CH1C H + [0] _-+ CH3CH3CH,CH1CH2CH2COH
hcptanol below 20 beptanoic acid
reaction). Methyl ketones on oxidation
(2) Oxidation of Methyl ketones (Jialoform
with a halogen and hydroxide ions produce a carboxylic acid containing one carbon atom less
than the starting ketone. Haloform is a byproduct. For example,
0 0 0
II Cl2 II NaOH II - +
R-CCI-11 -+ RCCCI -. RC- ONa + CHCl2
methyl kctoec NaOH sodium carboxylate chloroform
0
Cl5 -
e.g.. CH3CH,C-CH, -+ CFI 3 CH,COONa + CHCl
ethyl methyl ketone NaOH sodium propionate chloroform
484 Advanced Orguric Chemistry
(3) Hydrolysis of Esters. Esters on hydrolysis with mineral acids or alkalis yield the
corresponding carboxylic acid and alcohol.
0 HClor 0
II H2SO II
RCOR' + H 2 0 -. RCOH R'OH
ester carboxylic acid alcohol
When alkali is used, the free acid is obtained from the resulting sodium carboxylate after
acidification.
0- 0
II II -+
CH3C--0C1H6 + NaOH -f CH3C---ONa + C2H5OH
ethyl acetate sodium acetate ethyl alcohol
0 0
II -+ ii
CHaC_-ONa -4- HC! -. CH 3C--OH + NaCl
acetic acid
Many esters occur in nature and serve as sources of carboxylic acids. Oils and fats are
triglycerides of higher carboxylic acids, which on hydrolysis with alkali yield glycerol and sodium
or potassium salts of palmitic acid (C 55 H31 COI-I) and stearic acid (C 17 H31C01 H), etc. These
salts called soaps on treatment with a mineral acid could be converted to free carboxylic acids.
0
l-{.C 0C--(CH2)14CH5
o CH1OH
-#
nLuL(uH2)11CH1 + 3NaOH i CHOH + 3CH3(CH)54COONa
I
sodium palmitraic
o CF{50H (soap)
II glycerol
H i t OC (CL-I1)icH,
tripahnitin
(present in oils and fats)
H-
3CH3(CH1)4COOH
palmiijc acid
(4) Hydrolysis of Nitrites. A very good method for the preparation of monocarhoxylic
acids is the hydrolysis of alkyl nitriTes.
0 0
+HO 11- +
RCN -+ RCNH, -p RC----ONH4
alkyl nitrite amide arnm. cas-boxylate
This hydrolysis is catalysed by acid or base, and is carried by healing nitrites with aqueous
acid or alkali. When acid is used, the ammonium carbox y late formed above gives free carboxylic
acid and ammonium salt of the mineral acid.
0 0
II -+ II
.RcONH4 -- HQ -i RC--OH - NI-{4C1
When alkali is used for hydrolysis, sodium or potassium carboxylate and ammonia is produced.
The carboxylate is then decomposed with a mineral acid.
0 0
II -+ , II -
RC--ONI-1 4 + Ha -- RCONa - NH, + FJ,O
sodium carbosylaic

Carboxylic Acids 485
0 0
RC-014, 4- NaOFI RCOH + NaCI
Alkyl nitriles required in this method can be conveniently obtained from alkyl halides
by treatment with aqueous KCN solution. Hence, the conversion of an alkyl halide into nitrile
followed by hydrolysis, provides a method for preparing carboxylic acid containing one carbon
atom more than the starting alkyl halide.
KCN H+/H20
CHaCH2CH1CH2CH 2 Br - CH 3CH,CHCH iCHaCN + CH3CH2CH2CH2CH2C00H
1.1,romopeatane pentanenitrile hexanoic acid
(5) Carbonation of Organometallic compounds. This is one of the best general methods
for the preparation of carboxylic acids. An appropriate Grignard reagent or lithium reagent
is treated with anhydrous carbon dioxide. The complex adduct thus formed on hydrolysis
with a mineral acid yields the carboxylic acid. This reaction is easily carried out because the
Grignard reagent is merely poured onto dry ice.
The dry ice not only serves as a source of carbon dioxide but also provides a low tempe-
rature for the reaction. The preparation of a carboxylic acid by this method may be illustrated
by the following example.
CH3 CH, CH,
I
+Mg 1 (1) M2 I
CH3CH2CH2C_.Cl -o
CH1CHCH2CMgCl CH3CH2CHC000H
ether 1 (2)H/H20 I
CH, CH, . CH,
2.chloro-2-methylpeniane complex adduct 2, 2-dimethylpentanoic acid
Organolithium compounds can also be carbonated readily and give carboxylic acids by
similar steps.
It may be noted that, like the nitrile acid synthesis, this method also yields a carboxylic
acid containing one carbon more than was in the Starting halide,
(6) Carbonylation of Alkenes. This is a recent method for the preparation of carboxylic
acids from alkenes. The alkene is heated with carbon monoxide (CO) and steam under pressure
at 300-400C in the presence of phosphoric acid as the catalyst.
H2PO
CH,CH, - CO -i- HO CH,CHICOOH
-
cthene 300-400 propionic acid
CH,
F{ 2 1'0 4 I
C14,--CH= CH, + CO + HO,, -+ CH,CHCOOH
Propene 3004000 isobuiyric acid
(7) Catalytic Oxidation of Long-chain Hydrocarbons. The long-chain alkanes obtainable
from petroleum can be oxidised to a mixture of carboxylic acids by passing air through
at 1200 in presence of maisganou.s stearate as the catalyst. This oxidation can also be effected
by passing air into aluminium vessels containing the long-chain hydrocarbons. Thus,
02, 20
CH3CH2CH1CHICH2CHICH 1CH 2CH 3 -_^ CH3CH,CH2CH,CHCH2CHCH1COOH
noijane mantanous nonanojc acid
stearate
This is one of the most recent methods for the prcpaa'ion of long, chain carboxylic acids
needed for soap making.
(8) From Alkyl Substituted Acetoaceti. and Malowc Esters. A variety of rnonocaboytic
acids can be synthesised by the hydrolysis of suitable alkylacewacelic and malonic ester with a
concccntrated solution of ethanolic potash.

(a) From A1ky!acetocetic Esters.

HOH HO conc KOH
CH,COCH--CO 0C1H5 -+ CH 3COOH + RCHCOOH + CIHIOH
ethanolic acetic acid acid
mono Ikylaccloacetic acid
R
HOHI H conc KOH R
CH I CO -C--CO OC2HS CH 3 COOH + CHCOOH + C2H5OH
lit, ethanaljc
acid
dialkylacetoacetic ester
(b) From Alkylmalonic Esters. Alkylmalonic ester upon hydrolysis yield dicarbosylic
scids which on heating decarboxylate to yield alkylacetic acids.
R COOC2H6 (I) KOH R C0011 COOH

v -p \C< or RCH,COOH
H" CO005 H 5 (2)HCI H" 'COOH -CO 1 H" H
m000alkylmalonic acid acid
R C00C1}16 KOH R COOH A It COOH R

or "CHCooH
R' C00C2H5 (2)HCI R" COOH CO 1 R" "H R"
dialkylmalonic ester acid
PHYSICAL PROPERTIES
(I) Colour, Odour, State. The first nine monocarbosylic acids are colourless liquids,
while the higher ones are colourless waxlike solids. Further, in first three acids (C 1 to C1), formic
acid, acetic acid and propionic acid have sharp pungent odours. Butyric acid (C 4) has odour of
rancid butter. . The acids from C5 to C11 all have goatlike odour and those above C are
practically odourless.
(2) Solubility. The carboxylic group can donate hydrogen bonds at the carboxylic oxygen
and accept byogen bonds at the hydrox y lic iydrogen. Thus it is solubilized by water molecules
through extensive hydrogen bonding as illu,trated below.
0:
R 9
HBOND I;l #/80i'/D
/IBQND
The first four carboxylic acids are soluble in water, the five-carbon valeric acid is slightly
soluble, and above six carbon atoms they are insoluble. This is so as in the case of alcohols,
With the increase in size of the alkyl group, the alkanelike character dominates and solubility
declines. However, branching of the carbon chain increases the water solubility and some
branched chain acids of 5 to 6 carbon atoms are soluble in water.
All the acids are soluble in organic solvents such as alcohol, benzene, carbon tetrachloride
and ether.

Carboxylic Acids 487
(3) Boiling Points and Melting Points. The carboxylic acids have abnormally high boiling
points, even higher than those of alcohols of similar molecular weights. Thus propionic acid
(mol wt=74) boils at 1410 while n-butanol (mot wt =74) boils at 118*. This indicates greater
strength of the hydrogen bonds in acids than in alcohols. This is so because 0H of acid
H BOHD
CH 3 CCH3
ACETIC ACID DIAlER
9_ S.f.
is more strongly ionised as 0H and is also capable of forming hydrogen bonds to the rather
negative oxygen of the carbonyl dipole than just to the oxygen of another hydroxyl as in alcohols
In support of this argument, the molecular weight determination of the lower carboxylic acids by
the depression of freezing point of a solvent such as benzene, or by the vapour density method
gives about twice the molecular weight than expected for the formula R00H. This shows
that these acids exits as dimers even in the vapour state. In dimers pairs of molecWes of acid
are linked by two hydrogen bonds to form a ring structure. The presence of an eight-membered
ring has been confirmed by electron-diffraction studies (Pauling, 1934).
Ct'j(Ck),000OH
3 4 5 6 7 8 9 15
NCJM6ER OF CARBON ATOI4S -.
Fig. 211 Irregular increase in the melting points of carboxylic acid
The boiling points of monocarboxylic acids like any other series increase in regular
fashion with increasing molecular weight. The melting points of the carboxylic acids are in
general lower than the room temperature, and increase in an irregular, "sawtooth" manner.

488 Adr,ced Organic Chemstry
Table. Physical constants of carboxylic acids
C.
Name

of Formula rnp bp C Solubility
Acid g1100- of ware,

Formic acid HCOOH 8.4 101 cc
Acetic acid CH3COOH 17 118
Propionic acid CH3CH3COOH 22 141
Butyric acid CH3(CH2)C00H 4.7 163 -cc
Valeric acid CH3(CHI)3COOH 35 187 4
Caproic acid CH3(CH)4COOH - 15 205
Enanthic acid CH(CH),COOH -10 224
Caprylic acid CH3(CH1),COOH 16 238 less than I
Plargonic acid CH3(CHI)7COOH 12 254
Capric acid CHa(C11,)5COOH 31 268 -
ACIDITY OF CARBOXYLIC ACIDS

The distinctive chemical feature of the carboxylic acids is their acidity which merits a
detailed discussion. In an aqueous solution, molecules of these acids interact with water
molecules to form carboxylate ions and hydronium ions.
R-: +
APBOXYL( ACO C5PRXYLATE IO4
As indicated above, most simple carboxylic acids are only slightly ionised in water and
these are fairly weak acids. A 1 molar solution of acetic acid is ionised only to about 05% at
room temperature white a strong acid like hydrochloric acid or sulphuric acid is almost
completely ionised. Evidently water molecules are not very strong proton acceptors in relation
to carboxylic acids, which are relatively weak proton donors.
Acidity Constants The ionisation or dissociation equilibrium of a carboxylic acid,
similar to inorganic acids, may be simply written as
0 0
II il - +
RCOH ;=t RCO + H
crboa yic acid carboxylate ion
where H + represents a hydronium ion (HOy. Applying the Mass Law, the dissociation constant
or acidity constant K, for the above equilibrium can be expressed as
[RC001 IH1
K
[RCOOH]
The value of K. which is directly proportional to the concentration of hydrogen ions, is thus a
measure of acidity of the individual acid under consideration. The larger the value of K. the
greater the concentration of H ions and stronger the acid. For example the value of K. for
489
Crboxylic Acids
acetic acid is 1'8 x lO while that for HCI is 10. Thus acetic acid is a much weaker acid than
hydrochloric acid. The value of K. for ethyl alcohol is lO which has far low acidity
compared to even acetic acid.
What is the Cause of Acidity?
Resonance Effect. Delocalization of charge through resonance is the major factor which
is responsible for the relatively large acidity of carboxylic acids compared to alcohols. We see
that the alcohol and alkoxide ion produced by dissociation are each represented satisfactorily by
a single structure. In the case of a carboxylic acid, both the acid and the carboxylate ion formed
hr dissociation can exist in two canonical forms.
___ __
1kC P..0 p- R.-.0
H '4
O2H
I a EZ
4'O4'fQ111L/4(,yT EQ.UI VA LENT

(More internal energy less stable) (Less internal energy more stable)
In canonical farm II there is separation of opposite charges and some energy must be
supplied to do so. Therefore, it would contain more energy and is less stable than 1. On the
other hand, the canonical forms III and IV of carboxylate ion have equivalent structures which
are necessarily of equal stability. Thus both acid and carboxylate are resonance stabilised but
stabilisation is far greater for the carboxylate son than for the acid. The driving force for
ionisation of carboxylic acids is, therefore, due to gain in the stabilIty in going from carboxylic
acid to the more stable carboxylate ion.
Stability of Carboxylate ion. According to the resonance theory, a carboxylate ion is a
hybrid of two canonical forms as described above. These forms being of equal stability,
contribute equally and in the hybrid ion the carbon is joined to each oxygen by equivalent
"one-and-one-half" bond. In other words the negative charge of the carboxylate ion is evenly
distributed over both oxygen atoms.
1k O RC
CANONICAL FORMS OF RESONANCE

CAR BOX YLATE ION HYBRID
The fact that carhoxylate ion exists as a resonance hybrid is confirmed by physical
evidence. X-Ray and electron diffraction studies have shown the two carbon-oxygen bond
lengths in formic acid are different white in sodium formate they are equal.
l '27A -
1'23A
HC'
OH
127.4
FORMIC ACIO 300/OM FORAM TE

formic acid sodium formalc
Organic (:liernis(i N -32

490 Advanced Organic C!emsrry
Furthermore, the bond lengths in the formte ion are intermediate between those of normal
double bond and single carbon-oxygen bond.
Theory of Delocalized Electrons. The stability of the carboxylate ion can also be
explained elegantly by drawing the molecular orbital model on the same lines as that of
carboxylic acid molecule (Seepage 455).
.1
Ok. -C.
Fig. 213. Orbital Model of Carboxylate ion,

The carbon of tue carboxylic group is bonded to each of the two oxygen atoms by a
bond. The unused p orbitals of the C, 0 and 0 atoms overlap and the resulting s bond is delo-
calized over all three of them as shown in Fig. 21'3. In other words, the two T7 electrons supposed
to be forming the second covalent bond of C=0 are free to move in the region surrounding the
atomic nuclei of carbon and two oygens in the carboxylate ion. Thus the delocalized electrons
confer extra degree of stability on the carbovylate ion. This molecular orbital model also goes
to prove that both the C-0 bonds of COO ion are identical and will have bond lengths
intermediate between that of normal carbon-oxygen double bond and carbon-oxygen single
bond.
Influence of Substituents on Acidity. We have seen that the acidity of carboxylic acids
is due to their ability to release protons.
0 0
II -
RCOH - RCO + H
carboxylate ion
The force behind this dissociation is the gain in stability in going from carboxylic acid to
carboxylate ion. Thus any factor that stabilises more the carboxylate ion would facilitate the
release of protons and increase the acidity. Conversely, any factor that destabilises the
carboxylate ion would decrease the acidity. Thus electron withdrawing substiluents
(Cl, NO,, CN. etc) in a carboxylic acid would disperse the negative charge of the COO-,
stabilise it and thus enhance the acid strength. On the other hand, the presence of an electron
donating sabstitucnt such as alkyl group, would intensify the negative charge on the COO-
ion and thus destabilise it, making the carboxylic acid less acidic.
S ..... Lo.C t, I/-/

--
N
Fig, 21-4. Electron- dirg subsuluent stabilises the ion by charge dispersal,
Cirbcxyllc Acids 491
As illustrated above, the inductive effect of the various substituents modifies the acidity of
carboxylic acids. The following cases are of interest.
(a) Acidity decreases with larger alkyl groups. It will be noticed from the following
tabk, that since the electron donating inductive effect of the alkyl group increases with size of
aik'yl group, it reduces the acid strngth.
Kx 106
Formic acid HCOOH 177
Acetic acid CH,COOH 184
Propionic acid CH3CH6COOH 14
n-Butyric acid CH3CH6CH5COOH 160
(b) Acidity increases with increasing number of electron-withdrawing substituenis on the

e.carbon. The substitution of a hydrogen atom of alkyl group in a-position by a halogen atom
roduces a stronger acid since the electron withdrawing inductive effect of halogen would
stabilise the COO- ion by dispersing the negative charge. It also stands to reason that as the
number of substituted halogen atoms increases it would result in the iiicrease of acid strength.
For example,
K. x 106
Acetic acid CH,COOH 18
Chloroacetic acid C1CH6COOH 136
Dichioroacetic acid CIaCHCOOH 5530
Trichloroacetic acid CI3CCOOH 23200
(c) Acidity increases with increasing electronegativity of substituents. Chlorine being less
electronegative than fluorine produces a weaker inductive effect and hence chloroacetic acid is
a weaker acid than fluoroacetic acid. Similarly, bromoacetic acid is a weaker acid compared to
chioroacetic acid and stronger acid than iodic acid.
K6x10
lodoacetic acid ICH2COOH 67
Bromoacetic acid BrCH_COOH 125
Chioroacetic acid CICH1COOH 136
Fluoroacetic acid FCH5COOli 260
(d) Acidity declines with increasing distance between electron-withdrawing group and
COOH group. This is so because the inductive effect of the electronegative substituent
decreases rapidly with increasing distance.
)( (_ CH2 1 CH2 i4.ui.i.i CH2 14.- COON

For example,
KGX l05
Cl
2-Chiorobutanoic acid CH,CH,CHCOOH 139

Cl
3-Chlorobutanonic acid CH,CHCH5COOH 89

Cl
4Chlorobutanoic acid (,H,CH,CH,COOH 296

CHEMICAL PROPERTIES
Most of the reactions ocarbosyIic acids can be classied into four types
(1) Reactions involving removal of a proton from 0-H group by a base (:B).
(2) Reactions at the carbonyl carbon (-CO .-) involving attack of a nucleophile (:Nu).
(3) Reactions involving attack of the carboxylic group (COH or carboxylate ion (COO:-)
acting as a nucleophile upon other substrates.
(4) Reactions involving attack of a halogen on an s-carbon.
H 0
C O _(_,,_gP :a
'H
^'Nu
Fig. 21'5. Types of Reactions of Carboxylic acids iIlusi&ted.
A. REACTIONS INVOLVING REMOVAL OF PROTON FROM OH OF COOH

(1) Reaction with Metals. Metals like Na, K, Ca and Zn react with carboxylic acids to
form salts with the evolution of hydrogen.
C4R&XYUC ACiO 50DUJM3At.T
e.g., CH5COOH + Na - CH1CON + 4H1

acetic acid sodium acetate
(2) Reaction with Bases. Carboxylic acids react with inorganic bases to form the
corresponding salts.
0
0
II / ___ 1H+
+ 1418 OH .. C--0 Na
-+
e.g., HCOOH + KOH .-. HCOOK + H20
formic acid potassium
formate
CH 3COQH + NH 4 OH -'. CHCOONFi -j- HO

acetic acid ammonium
acetate
'All carboxylic acids react with sodium bicarbonate and sodium carbonate in dilute
carbon dioxide.
aqueous solutions to form sodium salts of the acids with the liberation of
2RCOOH Na 1CO3 .- 2RCOONa H 1O + CO, f
RCOOH + NaHCO 5 b RCOONa + H SO + CO,

These reactions are used as a test for the detection of carboxylic acids.

493
Carboxylic Acids
Sodium or potassium salts of long-chain carboxylic acids as palmitic acid and sicaic
acid are contents of soaps.
4-- -4
CHa(Cli,)COOH NaOH -i CH 3(CH5 ) 14COONa + H10
palmilic acid sodium palnitate
CH,(CH,),,COOH + ItOH -i CH 3(CH,),,---COO1a + HSO

stearic acid sodium stearate
The salts of carboxylic acids are crystalline solid, which are completely dissociated in
water solutions. Since they are the salts of weak acids, they are readily hydrolysed in water
solutions to give basic reaction.
RCO + HOH -- RC---OH OH
(3) Reaction Aith Organic bases. Salt formation also occurs when a carboxylic acid
comes in contact with an organic base. Thus triethylamine will react with a carboxylic acid to
give the triethylammonium salt of the acid.
0 'aHs 0 C2H5
- RCO -t- H_C21t5
C2F45
TRIETHYL 41.1/Nt TRIEIHYLA/4MON/(JM

NN
(4) Reactions of Salts of Carboxylic acids. (a) Action of Heat on Sodium salts. When
anhydrous sodium salts of carboxylic acids are heated with sodalinse (NaOH+CaO), they
decompose to form alkanes.
- + . A
CH5CO6Na + Na OH -b CH, + Na1CO1
sodium acetate methane
The above reaction which involves the removal of COO is termed Decarboxylatlon. The
decarboxylation of salts of carboxylic acids takes place by the following mechanism.
R COO t-1 RCOO- + 4 +
__ R-
.
nC ,- + CO2
R: -F H+-.___$ R1
(b) Action of Hear on Ammonium salts. Ammoniim salts when heated alone produce the
corresponding amides with the liberation of a molecule of water
- A
CH 5 COONH4 -. CHIcXNHI -F H10
ammonium acetamide
acetate
When heated with phosphorus pentoxide, nitrates or cyanides are formed.
-+ plo5
CH3COONH4 . CH,CN + 2H2O
A methyl cyanide,
acetonitrile

(C) Action of Heat on Calcium salts, The dry distillation of calcium salts of fatty acids,
except formic acid, yields ketones.
RCOO R 2+ 1.
- Ca - "C=O + CaCO3
RCOO
ketone
The dry distillation of a mixture of calcium salts of a fatty acid with calcium formate,
gives an aldehyde.
- H
RCOO . HCOO 2 1+
- Ca + - Ca .-. 2 RC=O + 2 CaCOn
RCOO HCOO aldehyde
(d) Electrolysis. When concentrated sodium or potassium salts of carboxylic acids are
electrolysed, alkanes are obtained.
CH3COO -p CH 2CO6(anode) + K(cathode)

CH,CH,
2CH3COO -. CO
K+ I-10 -+ KOH + JH3
B. REACTIONS AT THE CARBONYL CARBON INVOLVING ATTACK OF A
NUCLEOPHILE
These are the reactions of carboxylic acids in which the carbon of the carbonyl group
of COOH is attacked by a nucleophile : Nii) to form acid derivatives such as esters, acid
halides and acid amides.
0'
. + \_
- __. ,,.0 Nu ._-. 0 -- .
Nu
ACID TETRAHEDRAL 4CTh Dip/VAT/vt

AR8OYL ,iTER/4E1.I1A11
Here some nucleophile Nu (OR, Cl, NH) replaces the OH group (leaving group) through a
tetrahedral intermediate. As already discussed under aldehydes and ketones, the reactions are
catalysed by acids. Ordinarily these reactions take place more slowly than the addition to
aIdhydes and ketones because the OK group has unshared lone pair which can release electrons
to the carbonyl carbon decreasing its positive charge and thus making it less prone to
nucleophilic attack.
(I) Estenification. When a monocarboxylic acid is heated with an alcohol in the
presence of a small amount of mineral acid (HCl or H1SO4) as catalyst, it yields an ester and
water.
0 '1 0
II - H II
RCOH + R'OH RCOR' + H80
acid alcohol ester
This reaction known as esterifi cation is a reversible process. Therefore, the yield of the ester
can be ijreased by using an excess of one of the reactants, alcohol or acid. Alternatively,
water may be removed as it is formed, to drive the reaction forward.
MECHANISM. The mechanism of esterification involves the following steps
(!) Protonation of the carboxyl group by H ofe acid catalyst;
(2) This makes the carbonyl carbon more strongly electropositive which is attacked by
the nucleophile, the alcohol molecule;

'CrDoxyllc Fichls 495
(3) the transfer of proton to one of the OH groups takes place

(4) the OH group leaves as water molecule giving protonated ester ; and
(5) the resonance-stabilised protonated ester by loss of proton.

0 +014 OR OH 4
II _ _ _
RCOH H q_ RC---OH RCOH I
l1)
k,__ (2) I ()
H
0 0R'
/.'\/
R H OR
_OH2j(4)
+
0 + OR
H
p Rc - ) RC
ESTE/ (5) I/
OR OR
(2) Acid Halide Formation. Carboxylic acids can be converted into .their corresponding
acid halides by reaction with phosphorus halides (PCI 5 ; PCI1 , P8r3 ) or thionyl halides (SOd1,
SOBr1).
0 0
3 RCOH + PC1 3 3 RCCI + F15P02

carboxylic acid phosphorus acid chloride phosphorus
irichioride acid
0 0
II II
RC---OH -4- PCI i RC----CI -F POCI + HCI
phosphorus phosphorus
pentachloride oxychtorlde
RCOH + SOCl 2 -+ RCCI + SO 2 + HCI t

thianyl
chloride
Of all the reagen s, thionvl chloride (or thion y l bromide) is the best and the mildest reagent for
the preparation of acid halides because the products (SO 2 , HCI or HHr) being gaseous can be
easily removed, leaving pure acid halide as the residue. Thus,
0 0
11 11
CHC1 2 COH SOd 2 -f CH J CR 1 CCI + SO, t + HCl
propionic acid propionyl chloride
CH1 11 CH3'
CHC--OH + SOd 2 -p ) CH_C_CI--SO 2 -j- HClf
CH' CH,/
iaobutyric acid . isobutyryl chloride
MECHANISM. Although detailed mechanism of the above reaction of carboxylic acid
and thionv chloride has not been established, possibly the reaction proceeds by the following
steps through the formation of mixed anhydride of carboxylic acid and chlorosiilpbonic acid

Os-
Il
0KC 11
11 1<1 1 RC CI + $02
R ' O11 + 50C12 + tCi+

D
C 1 Isi
6
MIXED AMvAlOE
Acid halides are more reactive than the parent carboxylic; acids and react readily with
alcohols, ammonia etc to form acid derivatives.
(3) Acid anhdride formation. Monocarboxylic acids undergo intermolecular anhydride
formation in the presence of a strong dehydrating agent like phosphorus pentoxide (PaOa)'
o 0 0.0
II ...... II PO6 II II
H0C--R -* R_C-0--CR
H10 acid anhydride
For example,
0 0 0 0
1'20 II II
IIII
CHC--0I +H0CCH3 -+ CH,.C_0-C_CHi
H0 acetic anhydride
acelic acid
MECHANISM involves the following three steps.
0 0
I,+
Step (1): RCOH _RC-0 + H
carboxylaic ion
0 O
0
+ I (I - .1 +
II
Step (2): RC---OH + H -. RCOH,
+
+ RC-0 -p RC-01-11
"0
Second molecule
R
0
Step (3)
C 11
ac
aCOH2
.(3)
RC RC
II II
0 0
The carboxylic acids also react with acids halides to form acid anhydrides.
0 0 0 0
Ii . . U U U
RCOH + ClC---R -p RC-0--CR' + HCI
carboxylic acid acid chloride acid anhydride
Sodium salts of carboxylic acid instead of the acid itself are used with advantage.
(4) Reduction. in general carboxylic acids are difficult to reduce either by catalytic
hydrogenation or with sodium and ethanol, However, a strong reducting agent as lithium
aluminium hydrides LiALH 4 , carboxylic acids are smoothly reduced to primary alcohols,
0
II UAIFI4
RC--OH -+ R-CH,0H
acid other primary alcohol

Corboxyltc Adds
In the first step the acid is treated with LiAlH in a solvent (ether) when a complex
almintum salt of the acid is produced with the liberation of hydrogen.
o
II . IL
K(--OH .f- LIAIH 4 -p ^
RCOAIHJ Li + H1
complex aluminium salt
Reduction then proceeds by the successive nucleophilic attack of hydride ions (H-)
derived from LiAIH 4 to the carbonyl carbon of the acid.
ro II -
1
1+
II
-
H
o
H
-
LR_-C_0AIH 1 J Li -p RC---H -* RCHOH
The overall reaction may be written as

H1O
4RCOOH + 3LiAIH 4 -, 4H 1 t + (RCHO) 5 AlLi . 4RCH2OH
MECHANISM:
QM
k.C_0A1, R-C--MH -.-- S-C-H - s-C-H . S-C-H + HO
I I
H H
C. REAcrioNs INVOLVING ATTACK OF CARBOXYLATE ION

Monocarboxylic acids react with diazometharie (a yellow gas) to form the corresponding
methyl ester.
0 0
II II
RCOH + CH 5 N 1 -H RCOCH3 + Na
diazo methyl ester
methane
The reaction proceeds at room temperature, without the aid of an external acidic or
basic catalyst. Since it takes place under mild conditions, the reaction is particularly useful for
converting an expensive carboxylic acid to its methyl ester. The fact that the only by-product
is nitrogen, makes it one of the cleanest synthetic organic reactions.
MECHANISM. The reaction takes place in two steps
(I) The transfer of a proton to diazomethane (a base).
0 0
RC O 4 Ci13NN
C.ARBOXYL4TE 11
ION(l)
(2) The carboxylale ion (1) is a good nucleophile and attacks the substrate (II) to give
methyl ester.
0 0
II +
. II
R--4--O + CH3rL4 = N --- RC-0 CH3 + N N
(I) (II) METHYL E5 71A
D. REACTIONS INVOLVING HYDOGEN OF a-CARBON

Monocarboxylic acids are attacked by Cl, and Br, in the presence of ultraviolet light to
form halogen substituted acids.
498 Advancei Organic Chemistry
H Cl
UV,A
.CCOOH -. Cl -f CCOOH + HCI
a.ciloro acid
When chlorine is passed into hot acetic acid in the presence of ultraviolet light one, two
or all the three hydrogens attached to a-carbon may be successivel y replaced by halogen atom,
UV, A
CH 5COOH + C1 2 - CH2 CICOOH + HCl
acetic acid chloroaceiic acid
UV, A
CH1 CICOOH 1 Cl, CHCl2COOH + HCI
dichloroacetic acid
UV, A
CHCl 2 COOH + C1 2 cC13COOH HCI
trichloroacetic acid
In higher acids, attack of halogens occurs randomly along the hydrocarbon chain
leading to a mixture of a, and 'y-substituted acids. Thus,
Cl Cl Cl
- Cl2
CH 3CH 2CH 2 cO 2 H CH3CU2CHCO2H + CH2 CHCH 2 C0H CH1CH1CHaCO214
butyric acid UV, A uchiorobutyric acid chlorobuiyric acid y-chlorobutyric acid
The above halogenation reactions of saturated carboxylic acids take place by the usual
free radical mechanism.
a-chloro or bromocarboxylic acids are prepared by the reaction of chlorine or bromine
on monocarboxylic acids in the presence of a small amount of red phosphorus. This is known
as Hell-Volhard-Zelinsky reaction or HYZ reaction.
Br
H
RCF{COOH Br, -p RCHCOOH + HBr

a a.brornocarboxylic
carboxylic acid acid
Br
P -I
e.g., . CH 3CIi--000H + Br5 -p CH-.-CHCOOH + HBr
propionic acid -broniopropionic acid
HYZ reaction results exclusively in a-substitution and is, therefore,. given by carboxylic
acids having a.hydrogcns.
CH,
I P
CH5 CCOOH + Br 2 -+ No reaction
CH3
trirnethylacetic acid
Since cc-halogenated acids can be conveniently converted into a variety of x-suhsriluted
carboxylic acids by treatment with nucleophiles, HYZ reaction is used for the preparation of a
variety of substituted acids.
OH
+ NaOH -, CH 3CHCOOH + NaBr

lactic acid
Br NH
CH,CHCOOH + NH 3 -- CH3CHCOOH -, NH4Br

x-broniopropionic acid . 2.aminopropionic acid
CN
+ NaCN CH3CHCOOH + NaBr

499
Acids
a.cyanoacetic acid upon hydrolysis yields methylmalonic acid.

CN
COOH
CH,CHCOOH + -)HO - CH,CH + NH
COOH
methylrnalonic acid
MECHANISM OF HYZ REACTION:
(I) The red phosphorus reacts with halogen (Br 1 ,C1 1 ) to form small amount of phosphorus
trihalide (P r 2 -.--- P8r1 ) which converts the carboxylic acid to acid halide (I). The acid halide
is feebly enshc.
,0 p nr,,,O enoiisation
RCH 5 C'' - RCH,C' RCH=C(
acid bromide "Br cooL "Br
"OH
(1) (II)
(2) Bromine enol of the acid halide (II) is then halogenated.
'-
RCi-4C + Br Br BCHC
'N8
Sr
.11 111
The intermediate It reacts with another molecule of carboxylic acid by interchange of

(3)
Br and OH to form halogenated acid.
-. RCHC + RCHIC
RCHC + RCH I C
"'Br "'OH OH "Br
I acid bromide
Dr (second molecule Br
of acid) .bromocarboxylic (IV)
(III)
acid
The acid halide (IV) generated in this step is reused in step (I).
TESTS OF CARBOXYL GROUP

A fatty acid or any other compound containing a carboxyl group can be detected by the
following tests.
(I) In aqueous solution it turns blue litmus red.
(2) Upon distillation with soda-time it will give the inflammable vapour of a hydrocarbon.
The residue in the test-tube will produce effervescence when treated with dilute hydrochloric
acid.
(3) With sodium bicarbonate solution, a carboxyl group causes effervescence due to the
evolution of carbon dioxide.
(4) When warmed with ethanol and cone sulphuric acid, a fatty acid forms an ester
which is at once detected by its fruity odour.
(5) The action of phosphorus pentachioride upon acids yields acyl chlorides and
hydrochloric acid gas. This test is also given by other hydroxy compounds.
IR SPECTRA OF CARBOXYLIC ACIDS

Since a carboxyl group is made of a carbonyl group and a hydroxyl group, the Infrared
spectra of carboxylic acids exhibit absorptions due to both these structural units. However, both
the absorption bands are displaced to lower wave number because of dimeric structure of
carboxylic acids. The 0H stretching vibration of carboxylic acids absorbs in the region 3000-
2500cm 1 relative to the free --OH of alcohols which absorbs in the region 3700-3500 cm'.
This is attributed to H.bonding which weakens the 0H bond. The carboxyl group. 00-0.
ofcarboxvlic acids absorbs in the reaion 1725-1700 cm- 1 . Acids also reveal a C-0 stretching
0H-0,
RC >CR
band at about 1250 cm 'and 0H bending absorption bands at about 1400 cm and 920 cm-
(broad).
i,cnmbci (cm
C(W '500 1000,000 1500 1300 1100 1000 900 800 700
Fig. 216. IR spectrum of Proplonic acid.
FORMIC ACID, Metkaoic Acid, HCOOH

Formic acid was first obtained in 1670 by the distillation of red ants and hence its name
(Latin: formicu.c=ant). It is present in stings of bees and wasps, as also in bristles of nettles,
The acid is found in traces in urine and perspiration.
Preparation. Formic acid may be obtained by the following methods.
(1) By the oxidation of methyl alcohol or of formaldehyde using platinum black as a
catalyst.
CH30H + [0] .. HCHO + H,0
methyl alcohol formaldehyde
HCHO + [0] -p FICOOH
formic acid
(2) By the hydrolysis of hydrogen cyanide with hydrochloric acid.
HCN + 211,0 + HCI -p HCOOH + NH1CI
hydrogen cyanide formic acid
(3) By the reduction of carbon dioxide in aqueous solution with hydrogen in the presence
of palladium black as a catalyst.
0 0
II II
HOCOH + H, - HCOH + 1120
carbonic acid formic acid
The resulting sodium formate yields free acid when treated with dilute sulphuric acid.
(5) By heating crystalline oxalic acid with glycerol (catalyst) to 120.
COOH A
HCOOH + CO
COOH (glycerol) formic acid
oxalic acid
This method is used for the laboratory preparation of formic acid. In actual practice, glycerol
is first heated at 120. Then a further quantity of hydrated oxalic acid (COOH),.2HO, is added
and the temperature is again raised to 120. The decomposition of oxalic acid takes place as
follows.

Carboxylic Adds so,
CH3OH + HOOCCOOH CH2OOCCOOH

oxalic acid I20
CHOH -. CHOH.
H2OH CI-JOF1
glycerol glyceryl monoocalate
CHSOOCCOOH CtI2O-0C-1-1
CHOH CHOH + H10
HOH CHOH
glyceryl monoformate
CHuOOCH CHaOH
I2O
CHOH + HOH CHOH + HCOOH
(from fresh formic acid
CH20H oxalic acid) CH1OH
glycerol
The glycerol set free is used over again.
LABORATORY PREPARATION. Formic acid is obtained in the laboratory by means

of the reaction between glycerol and oxalic acid as described above.
iI.LEA'1iA
Fig. 217. Preparation of aqueous formic acid.
Anhydrous glycerol (50 ml) and powdered crystalline oxalic acid (40g) are placed in a flask and
the apparatus fitted up as shown in Fig. 217. The flask is heated at 120 0 till the evolution of
carbon dioxide (marked by effervescence) ceases, The reaction flask is then cooled and a fresh
lot of oxalic acid (40 g) is added. The mixture is again heated at I20, when aqueous solution of
formic acid collects in the receiver. This is neutralised with lead carbonate. The solution
of lead formate thus produced is filtered and concentrated. The crystals of lead formate
are then charged in the inner tube of a water-cDndeflser and the apparatus fitted up as shown in
Fig. 218. Hydrogen sulphide is allowed to pass through the condenser while steam is passed
thrcigh its outer jacket. The anhydrous formic acid collecting in the receiver flask is freed from
dissolved h y drogen sulphide by distilling over fesh lead formate.

502 Advanced Orldruo CPerIty'
TEAM
DRY HYDR06EIV
5ULPID( CAlCiUM CHORID(
OLASS WO TUBE
AVDROUS
JORMiClCID
Fig. 211. Preparation of anhydrous formic acid

Anyhydrous formic acid may also be made in the laboratory by distilling a mixture of
sodium formate and sodium hydrogen sulphate.
-- + - distil
HCOONa + NaHSO 4 -. HCOOH + Na2SO4
sod formate formic acid
MANUFACTURE. (1) Formic acid is prepared industrially by heating powdered
sodium hydroxide with carbon monoxide at 150 0 under pressure of eight atmospheres.
ISO. -+
NaOH + CO o HCOONa
8 atm sod formats
pressure
Then dilute sulphuric acid is added to a slurry of crushed sodium formate and the mixture is
heated to distil the formic acid.
- +
HCOON a + H5SO4 * HCOOH + NaHSO4
formic acid
(2) Formic acid may also be produced by the acid hydrolysis of methyl formate which
is obtained by reaction of methanol and carbon monoxide at 200 under a pressure of 25-50
atmospheres.
20O.
CH5OH 4. CO HCOOCH
25-50 atm methyl formate
pressure
Fleso'
HCOOCH 1 + HO * HCOOH + CH5H
formic acid
(3) Formic acid is obtained as a byproduct in the manufacture of acetic acid from butane.
Properties. (Physical). Formic acid is a colourless, pungent smelling, hygroscopic
l.quid, bp 1008. It is soluble in all proportions at room temperature in water, ethanol and
etner. It is irritating to the mucous membranes of the eyes, nose, and throat. When brought
in contact with skin, fortnic acid cau.s blisters and burns, which are slow to heal. It has a
strong antiseptic action.
(Chemical). Formic acid is unique amongst simple carboxylic acids because it contains
an H atom instead of the alkyl group. Thus it has the structure of both a carboxylic acid and
an aldehyde.
CARBOXYL ALDEHYDE
GROOP
-- /
.r0
I -
Ht-C_-QH I
I I
I I
L_J L_ _J
Fig. 219. Two ways of viewing formic acid.

The reactions shown by formic acid are in keeping with the above structural aspect of it.

Corboxytic Acids 503
(1) Reducing properties. Formic acid can be readily oxidised to form carbon dioxide
and water:
0 0
II II
11-4--OH + 0 i HOCOH * H1 0 + CO,f
ormic acid
f carbonic acid
(unstable)
Thus like aldehydes, it reduces Fehling's solution, ammoniacal silver nitrate solution (Tollen's
reagent), and potassium permanganate solution (Tests). Both Fehling's and To]len's reagents
contain NaOH and convert formic acid into formate ion which in turn is oxidised, Thus,
HCOOH + NaOH , HCOONa + H20

formic acid sod formate
- 1+ - 2-
HCOO + 2Cu + 50H i Cu20 + C01 + 3H20
formate ion 1 red ppt
Fehting's solution -
+ a-
- 1-1
HCOO + 2Ag 330 p 2Ag4 + CO1 + 2H5O
silver mirror
Totlen's reagent
Similarly with acidified potassium permanganate, the colour is discharged
- - + 5+
5HCOO + 2MnO 4 + 6H - 2Mn + 8HSO -(- 5C01 f
Formic acid also reduces mercuric salts to mercurous salts (Test).
2HgC! 1 + HCOOH t HgaCl 5 4 + 2HCI + CO, f
mercuric mercurous
chloride chloride
Further it may be pointed out that unlike aldehydes, formic acid does not form oximi
phenylhydrazone and semicarbazone.
2) Formation of Salts. Formic acid is the strongest acid among all the members of the
homologous series. It forms salts with alkalis, carbonates and bicarbonates.
HCOOH NaHCO, HCOON + COs f + H10

sod formate
HCOOH + ItOH HCOOK + H10

pot formate
(3) Formation of Esters. Formic acid reacts with alcohols in presence of mineral acid
(as catalyst) to form esters. Thus,
H5SO4
HCOOH + CH3 OH HCOOCH 3 + H10
methyl formate
With ethyl alcohol, it produces a fruity odour of ethyl formate (Test).
(4) Reaction with PCI 5 . Formic acid when reacted with PCl 2 gives formyl chloride
which being unstable at once decomposes hydrogen chloride and carbon monoxide.
HCOOH + PCI 1 i HCOCI + POC + HCl
formyl chloride
(unstable)
HCOCI HCl + CO
(5) Reaction with Ammonia. Ammonia combines with formic acid to form ammonium
formate which decomposes on heating to-give formamide.
HCOOH NH 1 i HCOONH4
amos formtc

-+ A
HCOONH 4 -k HCONH 1 + H20
formamide
(6) Reaction of Sulphuric acid. When warmed with concentrated sulphuric acid, formic
acid decomposes to form carbon monoxide and water.
H2SO4
HCOOH HO + CO
Thus formic acid can be used as a means of storing and generating carbon monoxide.
MECHANISM:
,O H
H-C HC +H =0 C0+ M+
N
OH 0H
IORAIYI.
H CAT/ON
(7) Reactions of Salts of Formic Acid. (a) Sodium formate when heated to about 3900,
decomposes to form hydrogen and sodium oxalate.
HCOONa 3900 COONa
HCOONa COONa
sod formate sod oxalate
The free oxalic acid is produced by treatment of the product with a dilute mineral acid.
(b) The calcium formate when heated atone gives formaldehyde. However, when heated
with calcium salts of other fatty acids it gives higher aldehydes. Thus,
A
(HCOO)1Ca -p HCHO + CaCO3
calcium formate formaldehyde
A
(HCOO)1Ca + (CH 3 C00) 3Ca .-. 2CH2 CH0 + CaCO3
calcium formate calcium acetate acetaldehyde
1600 under pressure, formic acid decomposes
(8) DecarboxylatiOn. When heated above
to produce, CO 2 and H2.
> 160
HCOOH CO2 + H
under pressure
Uses. Formic acid is used
(I) for the dehydration of hides
(2) as a coagulating agent for rubber latex
(3) in medicine as a remedy for gout and neuritis
(4) as an acid for dyebaths in textile industry since ii is vcilatilised in the drying process
(5) for storing and generating carbon dioxide ; and
as an antiseptic in brewing and in flotation.
ACETIC ACID, Ethanoic Acid, CH3COOH

This is the ol dest known fatty acid. It occurs in the free and the combined state in
lain biological fluids and plant extracts. it is found in fruit juices which have become sour
Corboaylk Adds SOS
by fermentation. It is the chief constituent of vinegar and hence its name (Latin : acelum
vinegar).
MANUFACTURE
Acetic acid can be produced by any of the general methods described before. The
technical methods of preparation are
the fermentation of ethanolic liquors, Ps#O AOwwU (A
from wood distillation industry, and PAsSASE OF AIR
the modern synthetic processes.

(I) Orleans Proces In LAYER OF
France, this method is very preva. ACt TIC BACTERIA
lent and is considered to be the ON SURFACE -
easiest and most effective means of WIME

converting wine into vinegar. Acetic
bacteria are allowed to grow on the
surface of wine in a partly filled cask.
In due course wine gets converted CUTLET
into vinegar owing to oxidation with
air.
Fig. 2110. Ortcan's process.
CH1CHI0H + 0,.. --+ CHCOOH + l-J0
ethyl alcohol acetic acid
Vinegar is taken out from the bottom. The cask is again charged with fresh wine and
the process is repeated over and over again. The reaction being extremely slow, the out-put of
this process is very low but the vinegar produced is of high grade.
(2) Quick Vinegar Fermentation Process. Large quantities of vinegar, which is in reality
4-6 per cent acetic acid, are obtained from fermented liquors containing 12-15 per cent ethanol.
The aqueous solution of ethanol in contact with air and under the influence of Bacteriwn aceli
produces acetic acid.
In the Quick Vinegar Process, large woodeh vats filled with basket-work or wood
shavings impregnated with old vinegar (Bacterinm aceti) are used in series. The vats are fitted
with a perforated cover and the ethanolic solution is introduced. Inc top of the first vat and
allowed to trickle down the shavings. Air is drawn in through the holes in the lower walls of the
vessel and passes up in the opposite direction to the trickling liquid. The heat generated in the
oxidation of alcohol to acetic acid maintains the temperature at about 35 which is favourable to
the growth and activity of bacteria. The liquor leaving the bottom of each vat is introduced at
the top of the next vat. The maximum concentration of acetic acid obtained by this method is
10 per cent. The process requires 8 to 10 days for completion.
(3) From Wood Distillation Industry. Formerly the chief source to produce glacial or
pure acetic acid was pyroligneous acid obtained from the dry distillation of wood. It is a dilute
aqueous solution containing about 10 per cent of acetic acid along with a little methyl alcohol
and acetone. Acetic acid is removed from it by treatment with lime and distilling off methyl
alcohol and acetone. The aqueous solution of calcium acetate left behind is evaporated in iron
pans and the residue distilled with concentrated sulphuric acid. The distillate consists of 70-75
per cent acetic acid. To get pure or glacial acetic acid, the strong acetic acid solution is neutralised
with sodium hydroxide and evaporated. The crystals of sodium acetate thus obtained are heated
to expel the water. The anhydrous sodium acetate is finally distilled with concentrated sulphuric
acid to yield pure tic acid.
Organic Chernisiry - 33

AIR OUTLET
4- -
WOOD H
SHAVINGS
fl
cC:
(
AIR INLET
_= = =
PERFORATED
BOTTOM +
----------.-' PUM
VINEGAR
U U
Fig. 2111. Preparation of Vinegar.
(4) Modern Synthetic Methods. Now a days acetic acid is mainly manufactured from
acetaldehyde and from butane or naphtha fraction obtained from the distillation of petroleum
which contains C,C,, alkanes.
(a) From acetaldehyde by catalytic oxidation, the catalyst used being manganous acetate.
(CH1C00)2Mn
CH5 CHO CH3COOH
acetaldehyde 60 70
(b) From butane or naphtha by air-oxidation in presence of a mixture of cobalt and
chromium acetates as catalyst.
(CH1COO)CO
Cli5CH1CH1CH + O CH1COOH + HCOOH
butane 200' acetic acid (main by-
ploduct)
The main byproducts are formic acid (from butane), and formic acid and propionic acid
(from naphtha).
Properties. (Physical). Acetic acid is a colourless liquid with a sharp 'vineger odour' and
sour taste, bp 118-l', sp gr 108 at 0C. When cooled sufficiently, it forms ' like' crystals
which melt at 167'. Hence the pure anhydrous acid is usually called glacial acetic acid -
(Glacial = of ice.) It has a corrosive action on the skin and causes blisters. It is miscible with
water, ethanol and ether in all proportions, the solution in water being attended by a contraction
of volume and liberation of heat. It dissolves sulphur, iodine, and many organic substances.
(Chemical). Acetic acid is a typical fatty acid and gives all the general reactions of the
class.
(I) Action of Chlorine. Chlorine reacts with acetic acid in the presence of a catalyst
(1, S or P) giving mono-, di., and trichJroacetic acid.
Cl1 Cl1 C11
CH 3 COOH -p CH,CICOOH -.. CHCl 2 C00H -. CCI,COOH
acetic acid p P P trichioroacetic
acid
rIixyUc Acids
507
(2) Formation of Salts. It reacts with oxides, hydroxides and carbonates to form acetates
CH,COOH + NOH -. CH,CO0'ta + H10

sod, acetate
+
2CHICOOH + (NH1),C04 -i 2CH5COONH , + H 10 + CO,
amm, acetate
(3) Formation of Esters. it reacts with alcohols to form esters. Thus
CH3COOH + CI H 6 0H 4 -+ CH,COOC,H5+H10
ethyl alcohol ethyl acetate
The reaction is reversible and is catalysed by strong mineral acids.
(4) Formation of Anhydride. When the vapours of acetic acid are passed over a heated
phosphate catalyst, it yields acetic anhydride.
2CH,C0OH - p (CH3CO),O + H20
acetic anhydride
(5) Action with PC[,. It reacts with phosphorus pentachioride vigorously forming
aceiyl chloride with the evolution of HCI gas.
CHI COOH + PCI, -+ CH,COCI + POd 3 + HCI
acetyl chloride
(6) Formation of amide. Ammonium acetate decomposes on heating to form acetamide.
CHICOONH -. CH,CONHI + 11,0
acetamide
(7) Decomposition of Na-salt. Sodium acetate when heated with soda-lime yields
methane.
CHaCOONa + NaOH -. CH. + Na,CO,
methane
(8) Decomposition of Ca-salt. Calcium acetate decomposes upon heating giving acetone
(CH,COO)jCa -' (CH,)1C0 + CaCO,
acetone
(9) Electrolysis. The electrolysis of a solution of potassium acetate forms ethane.
2CH,COONa -p CH, + 2CO3 + 2Na
ethane
Uses. Acetic acid is used
(1) as a laboratory reagent, and as a solvent for carrying reactions since it remains
unattacked by oxidising and reducing agents;
(2) as a table vinegar, and also in the preparation of condiments;
(3) for coagulating rubber latex;
(4) for curing meat and fish;
(5) in medicines as a local irritant;
(6) for the manufacture of vinyl acetate, required for the production of polyvinyl acetate,
and acetic anhydhde required for making cellulose acetate.
(7) for the manufacture of acetates, acetone, and esters; ethyl acetate and amyl acetate
being used as solvents in lacquer industry.
FORMIC ACID VERSUS ACETIC ACID
0 0
II 11
HCOH CH3COH
formic acid acetic acid
Since formic acid and acetic acid contain the same functional group i.e., COOH, they
resemble each other in respect of the reactions of this group. Formic acid, however, differs
from acetic acid because it has only one H atom attached-to the carboxyl group, while in acetic
acid we have a methyl group (CH3 ) attached to the carboxyl group. The methyl group in
acetic acid shows the usual substitution reactions but the H atord of formic acid does not.
Nevertheless, the H atom of formic acid can he easily oxidised to OH and hence it shows


508
reducing properties. The chief points of resemblance and difference in behaviour of the two
acids are listed in the table below.
Table. Formic and Acetic acids compared
Acetic acid, CH1COOH

Formic acid, HCOOH
Points or Resemblance
(1) Forms salts with alkalis and cer- (1) Forms salts with metals and
tain metals; decomposes carbonates and bicarbo- alkalis ; decomposes carbonates and bicarbona-
tes with evolution of CO1.
nates with evolution of COS.
(2) Yields esters when treated with
(2) Yields esters readily when treated
with alcohols even in the absence of conc alcohols and cone H 1SO4 or HCI gas.
H1SO4 or dry HC1 gas.
(3) Reacts with PC], to form acetyl
(3) Reacts with PCI1 to form formyl
chloride which being unstable decomposes to chloride.
give CO + HCI
(4) Its ammonium salts (amm formate)

(4) Ammonium acetate on heating
when heated produces formamide. gives acetamide.
Points of Difference:
(1) It is stable to heat and conc
(1) When heated at 160 0 under pressure,
it decomposes to produce CO, + H 1 . On H5SO4.
heating with conc H 5SO 4 it gives CO + HSO.
(2) It is a weaker acid than acetic
(2) It is a stronger acid than acelic
acid.
acid.
Does not undergo substitution (3) It forms mono-, di- and tichloro-
(3)
reactions when treated with Cl, in presence of acetic acids when treated with Cl, and red
red phosphorus. phosphorus.
(4) Gives formalde yde' when its

(4) Gives acetone. when its calcium
calcium salt is heated. salt is heated.
(5) No action.
(5) Sodium formate when heated at
3900, gives sodium oxalate and hydrogen.'
(6) Methane is formed when sodium
(6) Produces H when its sodium salt is
acetate is heated with sodalime.
heated with sodalime (CaO+NaOH).
(7) Electrolysis of water sohjtiqj of (D Ethane is evolved when water

solution of sodium (or potassium) acetate is
sodium (or potassium) salt yields hy drogen.
- , electrolysed.
(8) Does not reduce Toflen's reagent;
(8) Reduces ammonical silver nitrate
solution to metallic silver; or Fehling's solution or Fehling's solution; mercuric salts ; and
to red cuprous oxide: or mercuric salts to acidic potassium permanganate.
mercurous salts ; and decolourises acidic
potassium permanganate.

uy
Carboxylic Acids
PROPIONIC ACID, Propanoic Acid, CH3CH1COOH

it occurs in small amounts in acetic acid obtained from the wood distillation industry.
Preparation. It is prepared on a large scale; (I) By the oxidation of n-propyl alcohol
with sodium dichromate and sulphuric acid.
NaiCi0,i
CHC}1ICHtOH HSO. -+ CH'CH'COOH
ii-propyl hicohol propionic a'1d
(2) The naphtha fraction of petroleum (C 4C10 alkanes) is oxidised with air under
high pressure at 200C to form propionic acid admixed with formic acid and acetic acid.
0
CH,CH,CH, -+ CHSCHCOOH
200
pressure
(3) By the reaction of ethylene, carbon monoxide and water at high temperature and
pressure in presence of phosphoric acid as catalyst.
high temp.
pressure
CH1 =CHI + CO + H 10 -+ CH3CH2COOH
H8PO4
Properties. Propionic acid is a colourless oily liquid, mp 22, bp 141. It has
acrid odour and is miscible with water, ether and ethanol in all proportions. Chemically it
gives all the general reactions of monocarboxylic acids.
BUTYRIC ACIDS
There are two isomeric butyric acids known
(1) n-Butyric acid CHICH1--CHs--COOH
CH5\
(it) Isobt1tyric acid 'CHCOOH
CH,
n-Butyric ,AcI& Butanoic odd, CHCH1CH1OOH.
It occurs in butter as glyceryl ester. The free acid is present in rancid butter and
iii perspiration. The characteristic smell of stale butter is due to the liberation of n-butyric
acid by hydrolysis of its glyceryl ester.
Preparation. (I) ,i.Butyric acid is made on a large scale by the oxidation of n.butyl
alcohol.
(0)
CH1CH5CHCH1OH - . CH1CH,CH1CO--OH
n.butyl alcohol n.butyrlc acid
(2) It is also obtained by butyric formation of carbohydrates by means of microorganism,
Bacillus butyricus.
Properties. n.Butyric acid is rancid-smelling viscous liquid, mp _47, bp 162.
It is miscible with water, ethanol and ether. It shows all the usual reactions of carboyliq
acids. it is sometimes used in the tanning industry for deliming of hides.
Isobutyric acid, 2-Me fhylpropanoiC acid, (CH1)1CHCOOH

Isobutyric acid occurs in the free state in locust bean and as methyl ester in croton oil.
Preparation (fl By the oxidation of isobutyl alcohol,
CliCH1
C 14CH1OH - ')CHCOOH
CH CHI'
isobusyl alcohol lsobtyrIc acid
(2) From isopropyl alcohol by the following sequence of reactions.

CH,,
PBr1 CH1 KCN CH, HtO CH,\
CHOH -i. 'CHBr .- CHCN - 'CHCOOH
CH/ CH, CH/ H+ CH3
Properties. Isobutyric acid is a colourless, oily liquid, bp 154. It is sparingly soluble
in water. It responds to all the typical reactions of inonocarboxylic acids.
HIGHER MONOCARBOXYLIC ACIDS
A number of higher carboxylic acids occur in nature in the form of esters with glycerol
or higher monohydric alcohols. They are generally straight-chain acids and contain even number
of carbon atoms. They are prepared by the hydrolysis of oils and fats which are the triesters
of glycerol. Still higher acids are obtained from waxes in which they are present as esters of
higher alcohols.
Table. Some Higher Monocarboxylic acids and their physical properties
jVa,ne Formula mp C bp C
Caproic acid CH,(CH,),---COOH 95 - 205

Caprylic ac.a CH,-(CH,),COOH 16 237
Capric acid CH,(CH,),COOH 31-5 270

La uric acid CH,(CH,),,COOH 44 From oils
& fats
Myristic acid CH,(CH,),,COOH 58
Pal mitic acid CH,(CH,),,---COOH 64

Stearic acid CH,(CH,),,----COOH 72
Arachidic acid CH,.(CH,),,---COOH 77

Behenic acid CH,(CH.),,---COOH 82
Lignoceric acid CH,(CH,),,COOH 83-5 From waxes
Carolic acid CH,(CH,),COOH 87-7
Melissic acid CH5(CH,)1000H 90
j
Palinitic acid, CHCOOH, and Stearic acid, C 17H35C00H, are colourless waxy solids.
They occur in most an i mal and vegetable fats from which they are prepared by hydrolysis with
steam. Palmitic acid takes its name from Palm oil and stearic acid from stear, meaning tallow.
They are insoluble in water and soluble in ethanol and ether. Their sodium and potassium
salts are the constituents of ordinary soaps. These acids are mixed with wax used for making
candles.
UNSATURATED MONOCARBOXLYIC ACIDS

The unsaturated monocarboxylic acids having a single bond in their molecule are
represented by the general formula C,H 2,_1C00H. Most of Nese acids are known by their
common names. T'eir IIJPAC names are derived by considering the longest carbon chain
containing the carb' yl group, and naming the acid as Alkenoic acid. The position of the double
bond with respect to the carboxyl group is indicated by a number. The common and IUPAC
names of a few important unsaturated monocarboxylic acids are given in the following table.

CorboxyIc Acids
511
Table. Names of some Unsaturated Carboxylic acids

Formula Common Name JUPAC Name

CR2 =CHCOOH acrylic acid prop-2-enoic acid
43 2!
CHCH = CHCOOH crotonic acid but-2-erioic acid
CH,
CH,=CCOOH methylacrylic acid 2-methyl prop- 2.cuoic acid

H $C4\ ,CH3
C= C" (igliC acid cis-2-metllylbut.2-enoic acid
2\COo}-T
H3C 32 COOH
angelic acid trans-2.mcthylbut-2-enoic add
H" cH,
CH3(CH 2)7 \ 10 9 ,(CRS)ICOOH
oleic acid cis.octadec-9.enoic acid
H" H
CH3(CH2),\ C=C/
elaidic acid trans- octadec-9-enoic acid
H" (CH,)COOH
As is clear from some of the formulae given above, the unsaturated moriocarboxylic acids
exhibit geometrical isomerism.
Unsaturated carboxylic acids of the type RCH=CH(CH),,COOH in which the double
bond and the carboxyl group are far apart (i.e., n is large), usually exhibit the properties characte-
ristic of isolated double bonds and isolated carboxyl group. But when these two functional
groups are sufficiently close together to interact strongly as in a, 3-unsatuated acids,
2
RCH= CHCOOH
(e.g., acrylic acid CH 3 =CHCOOH), an exceptional behaviour is eicountered.
Acidity. The acid strength of unsaturated monocarboxylic acids in which the double bond
and the carboxyl group are far apart, is approximatety the same as that of the corresponding
saturated analogues. But if the double bond is adjacent to the carboxyl group, then the acid
strength of the unsaturated acid is greater than the corresponding saturated acid. For example,
acrylic acid, CH2 =CHCOOH, has a Ka value of 56x lO compared with 14x lO for the
saturated analogue, propionic acid. This is due to. the fact that i-unsaturated carbon in acrylic
acid has sp2 hybridized orbitals while in propionic acid it has .cp3 hybridized orbitals. Since in
an spt hybridized orbital, the electrons are closer to the nucleus because of greater s character
than in sp3 orbitals, the sp' hybridized carbon is less electron donating than sp hybridized
carbon atom. Consequently acrylic acid is a stronger acid than propionic acid.
ACR'ILLC ACID, Prop.2-enoic acid, H2C=CHCOOH

Acrylic acid derives its name from acrolein, the corresponding aldebyde.
Preparation. It may be prepared
(I) By oxidation of acrolein with ammoniacal silver nitrate.
ammoniacal
H1 C=CHCHO + [0] . H5C=CHCOOH
acrolein AgNO3 acrylic acid
(2) By acid hydrolysis of vinyl cyanide which can be obtained from acetylene
CuCI,NH4CI,HCI H/H80
HCCH + HCN CH2=CHCN - CH=CH00OH
90' vinyl cyanide

5/2 Advanced Organic Coemistry
(3) By reftuxing a, .dibromopropionic acid with zinc in ethanol.

Br Br
I I Zn/CIHbOH
CFI2CHCOOH CH5==CHCOOH + ZnBr,
a, -dibrornopropionlc reflux
acid
(4) By distilling c3.hydroxypropionic acid with zinc chloride,
L. ZnCl
HOCHCH,COOH ------ CH 1 =CHCOOH HSO
13.hydroaypropiorsic acid
-hydroxypropionic acid is obtained from ethylene in the following manner.
+ --
HOCI KCN H+/H10
F12 C=CH2 -i HOCH ICHC1 -.4 HOCH1 CHCN - HOCH,CF{,COOH
-hydroxypropionic acid
ethylene chlorohydrin ethylene cyanohydrin
(5) From propionic acid by the following sequence reactions.
Br
P+Br1 KOH H+/H20
CH1 CCOOF1 --.+ CHCHCOOH CH1=CHCOOK CU1=CHCOOH
propEonic acid UYZ C1HOH
reaction a-bromopropiocic
acid
This is probably the best preparative method available for acrylic acid.
MANUFACTURE. (1) From ethylene cyanohydrin in the following manner.
CH1 . -i-HCN CFL1OH corc }31SO HSOdHtO
-.4 I - CH=CHCN CH,=CHCOOH
/
CH, CH1CN H2 O acrylonitrite, acrylic acid
ethylene vinyl cyanide
cyanohydrin
(2) By hydrocarbonylation of acetylene in the presence of. nickel carbonyl as catalyst.
HCCH -- CO + HSO - CH1=CHCOOH

Ha
Properties. (Physical). Acrylic acid is a colourless liquid, bp 142 1 , having a pungent

odour like that of acetic acid, It is miscible with water in all proportions. It is a stronger acid
than propionic acid and acetic acid, but is a weaker acid than formic acid.
(Chemical). Acrylic acid behaves both as an alkene and a carboxylic acid.

A. REACTIONS OF THE DOUBLE BOND
(1) On catalytic hydrogenation it gives propionic acid.
Ni
l-15C=CHCOOH + H 1 -p CHICH---COOH
propionic acid
(2) With chlorine and bromine, it forms addition products.

Br Br
Ccli I
CH1 =CHCOOH - Br, -, CH1CHCOOH
a, B-dibromopropioolc acid
(3) With halogen acids, it gives .halopropionic acids. Thus,

C}1=CHCOOH + HBr -b BrCH,CH1COOH
-bromopropionic acid
This addition takes place in defiance to Markovnikov Rule.

5)3
Carboyl7c Adds
and H1 SO4 , acrylic acid forms .hydroxypropionic

(4) On hydration in presence of HgSO 4
acid and not the Markovnikov produ.ct i.e., hydroxypropiofliC acid.
CH=CHCOOH + HOH -+ HO_CH1_-CH,-COOH
.bydroxyproPiOfliC acid
On hydroxylation with dilute potassium permanganate solution, it gives glyceric acid
(5)
which on vigorous oxidation decomposes to oxalic acid.
dii KMnO OH OH [0] COOH
CH1 =CHCOOH + H 2O + 0 I I COOH
CH1_CHCOOH
glyceric acid oxalic acid
(6) On standing, it slowly polymerizes to a glassy solid.
B. REACTIONS OF THE CARBOXYL GROUP

(I) It forms salts with metal carbonates and alkalis.
- +
2CH=CHCOOH + Na 5CO 1 -p 2CH,CHCOONa + CO, -f H1O
sod acrylite
-4
CH 1 =CHCOOH + KOH
-b CH 1 =CHCOOK + H10
On esteritication with absolute ethanol in presence of acid, it forms ethyl acrylate.
(2)
H1SO4
CH 1 CHCOOH + CaH I OH - CHCH_C0OCiHs + H10

ethyl acrylale
With phosphorus halides, it forms acryl chloride which on treatment with ammonia
(3)
gives acrylamide. I-
PCLa +2NH3
CH1=CH_OOH -+ CH=CHCOCl -+ CH,CONH, + NH4CI
acryl chloride ayIamlde
Uses. (1) Because of its irritating odour, apparent even in very low concentration, it is
added to closed sytcm of gases and volatile liquids for easy detection of leaks
(2) It is used primarily to make esters (methyl, ethyl,n-butyl) which are important
sources of plastics and other commerciall y valuable polymers.
3) Acrylonitrile, CH=CHCN, a derivative of acrylic acid, is used as a monomer in
and other acrylic fibres.
the manufacture of Acrilan, Orion,
_CH1_CH_CHr_CH_CHt_C
polymerizatloD
C C
CH1=CHCN
acrylonitlite
N N N
a portion of the Orion polymer
CH1CH=CH_COOH
CROTONIC ACID, But-2.enoic 4cid,
CH=CHC0OH, while the cis form exists as
It is the trans form of the structure CH 1
In . rnIi,nfr arid
H.0 H
H1C H
C C
HCO0H HOOC H
crotonic acid, isocrotoniC acid,
erwu-bui .2e1101c acid cis-but-2-COOic acid

Isocrotonic acid when heated at 100 0, changes to the more stable crotonic acid.
Crotonic acid occurs in craters oil in the form of its glyceryl esters.
Preparation. (I) By the oxidation of crotonald&yde with ammoniacal silver nitrate.

CH,,CHCHCHO [0] -i CHICH=CH_.COOH
crolonakiehyde crotonic acid
(2) By heating acetaldehyde and diethyl malonate in the presence of diethylamine or

pirperidine (Knoevengal Reaction) followed by hydrolysis and decarboxylation.
H
COOC1H6 piperidine C0OC2H
CH-CO + H5C
-h CHCH=C/ + H 20
acelaldthyde COOCH5 s . COOCH5
eq KOH (hot)
acidify COOK
C0 + CHCH=CH_CO0H - CH5._CHC<"
180-199 "COOK
Properties. Crotonic acid is a colourless solid, nip 72. Like acrylic acid, it gives reactions
both of an alkerie and carboxylic acid. On bromination with N
. bromosuccjnimjde (NBS), it
forms y-bromocrotonjc acid.
CHCo light
CH5 CHCH--COOH
crotonlc acid
+ I \NBr -* BTCHICHCH..COOH
CHaCO 7-bromocrotonic acid
NBS
OLEIC ACID, Cis-heptadec.8. ene. /.carboxyljc acid,

CH(CHcH CH(CH1)7COOH
It occurs abundantly as glycery[ esters in oils and fats. Olive oil, coconut oil, Cotton
seed oil, linsed oil etc all contain oleic acid,
Preparation,
Oleic acid can be prepared by the hydrolysis of olive oil with sodium
i y droxide when sodium salts of oleic, palnsitic and stearic acids are obtained.
CHOCO_.C15H 4.
CHOH CnH16COO_Na'
od stearate
CH-0 ..f. 3NOc{ I(HOH + C17H15CO(5N
god oleaie
CHIOCO--C11H
oIepa1mtoatearin CH0H C55H11COONa
glycerol sod palmitare
(olive oil)
The water soluble mixture of sodium salts obtained above is treated with lead acetate
when the corresponding lead salts are precipitated out. The mixture of lead salts so formed is
then treated with ether which dissolves lead oleate leaving behind lead palmitate and lead stearate.
The etheral solution of lead oleate is evaporated, and the resulting lead oleate is decomposed with
mineral acid to get free oleic acid. The solution is then extracted with ether and dried over
fused calcium chloride. Ether is distilled off and the residue upon further distillation under
reduced pressure yields pure oteic acid.
Properties (Physical). Oleic acid is a colourless, odourless liquid, bp 26. When cooled
it solidifies to form crystals, mp 1i. it is insoluble in water but is readily soluble in ethanol
and ether. In air, it rapidly becomes yellow due to oxidation.
sts
Carboxyflc MIda
Properties
(Chemical). Chemically oleic acid behaves both as an acid and an alkene.
(1) Reduction. On catalytic reduction, it forms stearic acid.
Ni
CH 2 (CT1) 7 CFL=CH--(CH 1 ) 7COOH - H 2 -i CH3(CH2)7CHICH,--(CH,),COOH
otcic acid In, stearic acid
(2) Bromhiation. On bromination, it gives 9, 10-dibromostearic acid.
Br Br
CH 2(CH 2 ) 7 CH=CH(CH,),.COOH + Br 2 -. CH3(CH2)7CHCH(CH5)7COOH

9, 10-dibromostearic acid
(3) Oxidation. Oleic acid when treated with cold dilute alkaline potassium permanganate
gives 9, lOdihydroxystearic acid which upon further oxidation yields pelargonic acid and azelaic
acid.
a!k. KMnO1
CH 5 (CH 2 ) 7 CH=CH(CH,),COOH + HSO +0
cold
OH OH
I 1 (01
CH 5 (CH 5 ) 7 CHCH--(CFI.) 7 COOH .-+ Cll(CH 1 ) 7 COOH HOOC(CH1),COOH
9, 10-dlhydroxystearic acid petaronjc acid azelaic acid
(4) Ozonolysls. When reacted with ozone, oleic acid forms the corresponding ozonide
which when decomposed with zinc and water gives pelargonic aldehyde and azelaic acid half
aldehyde.
CP4 j (LM 2 ) CM CHlCMsl?C0H.#O3 CH3(CH2)7_CH I CH(CPI2)7C00M

OLEIC ACID I
\Q
c:,1
OZCNIOE
HO
p.. CH)CH,CHO + 0 H ( CH 217COO44
Pfc4R60N/C AZELA'C ACID HALF

ACID AL.OEHYOE
(5) Conversion to trans form. Oleic acid exhibits geomet rical isomerism. Ordinary acid
is the cis form and when this is treated with nitrous acid, it is converted into its trans form
elaidic acid.
CH2(CHa)i H CH,(CH1)7 H
C HNO1 C
C C
HOOC(CH,) /\ H H (CH1)7COOH
oleic acid, mp 16 etaidic acid, mp 51
(6) Addition with Alkalis. Oleic acid reacts with NaOH or KOH to form salts known
as soaps.
(3 0
NaOH --I.
CH,(CH I ), CH CH(CFL)7 COH - CH,(CFI2>, CH =CH(CHa)rCONa

oleic acid sodium oleate (soap)
516 * Advanced Organic Chemistry
QUESTIONS
I What are carboxylic acids? Write the Structure of the functional group present in them and why it
is named as carboxyl'.
2. (a) Discuss in brief the orbital structure of carboxylic acids. Why the CO single bond length in
alcohols (143 X) is greater than in carboxylic acid (116 A).

(6) X-ray diffraction of sodium formate shows both CC) bonds of the carboxylate anion to be equal
in length (1-27 A). How do you account for this
3. Describe the various systems of naming carboxylic acids. Give two examples to illustrate each
system.
4. Write the possible structural formulae and names of monocarboxylic acids having the molecular
formula C4 H 1504. Also, illustrate the functional isomerism of carboxylic acids with esters.
S. Describe the general methods of preparation of monocarbonylic acids.
6. Describe the physial properties of fatty acids? How do you explain the relatively high solubility of
these acids in water? How is it that carboxylic acids have abnormally high boiling points
7. Write a note on the acidity of fatty acids? What is the cause of their acidity? Explain why the
OH group of an acid is more acid than that of an alcohol.
8. (a) Discuss in brief the effect of substituents on the acidity of monocarbosylic acids.
(b) Arrange the following carboxylic acids in order of increasing acidity and briefly giving reason for
your answer.
(i) acetic, formic, butyric and propionic acids. (ii) a, 0, T-flUOtobutyriC acid.
(ii:) a-fluoro., u.bromo., a-chloro., a.iodoacetic acids. (iv) mono-, di- and trichloroacetic acids.
9.Give systematically the genera' reactions of monocarboxylic acids, with special reference to esteri-
(ceation, acid chloride formation and acid annydride formation.
10. Given equations for three general swlhodx xl prcpanng carboxylic acids. how will you convert
ml RCOOH into RCH 2COOH and (6) RCOOFI into RCH10H (Pandicherry IdS,c 1993)
II. Give one method of preparation of acrylic acid. (Osma,iiaBSc, 1994)

12. What is Vinegar ? How is it prepared (MarisraiBSc, 1994)

13. Describe the Quick Vinegar Process (Inviore uSc, 1993)
14. Explain - Formic acid ii. stronger than acetic acid. (Madras BSc. 1994)
15, Explain Acetic acid is stronger than propionic acid but weaker than monochlomacetic acid. (Delhi BSc, 1994)
16. Explain l'hrichloroscetic acids i mach stronger acid than acetic acid.
(Sau gut BSr. 1993; Bundelkiswid BSc, 1994; Madurai BSc. 1994)
17. Arrange the following compounds in order of Increasing solubility in water
(a) CII 3 CEI 1 CFI1CH3 (b) CH 5CH2CH 1CFI2COOH (c) CEI3CH2CH2CH2CH2O11
Answer, (a) < (c) <(Li)
IS. Arrange the following compounds in order of increasing acidity
(a) CH3COOH (Li) BrCH 2COOIt (C) Br2CHCOOH
Answer. (a) < (b) < ( C)
19. Arrange the following compounds in order of increasing acidity,
(a) CH3CH1COOH (Li) O2 IS1CH2CH2COO1f ; (c) CH 3 CH(NO2) COOH
Answer. (a) < (Li) < (c) Compounds (Li) and (c) are stronger acids than (a) because NO2 is an electron-withdrawing
sutmtituait. Compound (c) is a stronger acid than (Li) because the NO2 group in (c) is closer to the carboxyl group.
20. Discuss the rnechsnismofestenBcatinnofcazbosylicaeids. (Kerala BSc, 1993;Osma,sa BSc Hans, 1994)
21. How will you distinguish between butyric acid and 1-henene 7 (Calicui /lSe, 1994)
Hint. Add few drops o(brominc in carbon tetrachloride toeach compound iii separate test tubes. I-Hexene, anunuisturated
compound, will give a positive test (discolouratioe). whereas 1-butyric acid gives a negative test (solution stays red-brown).
22. Compound (A), C 5H7CI, reacts with alcoholic KOH to give (B), C5H6 . 4S the major product. Compound (B)
decolounsen Br2/C04 solution, Reaction of (A) with Mg in dry ether and subsequeist treatment with CO 2 and the dilute acid gives a
compound, (C), whose molecular formula's C 4H802. When we add compound (C) to aqueous NaHCO5 solution, bubbles are evolved.
Identify (A), (B). and (C).
Answer. (A) is lsopropyl chloride; (B) is Propene; and (C) is 2 .Methylpeotunoic acid.
Chapter 22
Dicarboxylic Acids
As the Dame implies, th dicarboxylic acids contain two carboxyl groups (COOH) in
their molecules. Of these most important are those which carry the carboxyl groups at the two
ends of the saturated carbon chain. The general formula for such Saturated dicarboxylic acids is
(CH(COOH), or HOOC_-(CH,).COOH
where there are is carbon atoms bonded strongly each to each in a chain. n=O for the first
member, oxalic acid.
00 COOH
or Oxalic acid
H0.tLOH
COOH
O 0 - C
II II Malonic acid
HO_C_CH1C--OH or CH/OOH
C00H
0 0
II II ?}ht_CO0H
or Succinic acid
HO_C_cH,_CH,C-0H
CH,COOH
0 0
II CH,COOH
II Giutaric acid
H0C_CHi_CHrCHr"COH or CH,
\CHc0OH
0 0
CH,CH---000H
or Adipic acid
CH1CH1---cOOH
NOMENCLATURE
Most of the dicarboxylic acids are known by their common names which indicate the
source from which they have been isolated, in the IUPAC system they are named are Alkanediolc
acids. The suffix .djo,c acid is appended to the name of the alkane containing the same number of
carbon atoms as the dicarboxylic acid. The position of the two carboxyl groups is indicated by
Arabic numerals if necessary while naming the substituted acids. For example,
43 2 1
I-IOOCCH,---CK 1--COOH I,4.butanedioicacld, or butaoedioic acid
butane-I. 4-dioic acid
65432 I
HOOCCH1 CH 1CH1CHaCOOH i, &icaanedioic acid. or bexanedjoic acid
bcxane'-I, 6-dioic acid
517
518 . Advanced Organic Chemistry
An alternative scheme is to regard the carboxyl group as a substituent when the name of
the acid is obtained by adding the suffix carboxylic: acid. For example,
3 2 I
HOOCCH1 --CH--C H1 ---COOl1 I, 3-proanedicarboxyIic acid or propone-I, 3 .dicarboxytic acid
In the common system the names of the substituents are indicated by Greek letters
y etc. The meaning of substituted acids according to the two systems is illustrated below.
Structure Common Name JUPAC Name
Br
5 4 3 12 I
HOOCCHICH,--CH--COOH a.bronioglutaric acid 2-bromo-pentane-1, 5
a' a dioic acid
CH,
5 4 3 2 I
HOOC. CH2 _CEI . CR,COOH 3 , 3dimerhyllutaric 3, 3 .dimethyl-pentane.1, 5
a' a acid -dioic acid
CK
ci ci
6 5 4 3 2
HOOCCHCH,CH,CH - COO , '-dichloroadipic 2, 5-dichloro-hexane.I, .6
a' f a acid -dioic acid
PHYSICAL PROPERTIES
(1) All the dicarboxylic acids are crystalline solids, their boiling points being much
higher ,than the corresponding saturated monocarboxylic acids.
(2) The lower members are sufficiently soluble in water but are only slightly soluble in
organic solvents. The solubility in water goes on decreasing with increase in molecular weight.
This is attributed to the fact that hydrogen bonding with water molecules becomes less effective
as the insoluble hydrocarbon part of the molecule prcdoninates with rising molecular weight,
thus reducing the solubility. None of the dicarboxylic acids is steam-volatile.
(3) The melting points of dic.arboxylic acids follow the Alternation or Oscillation Rule
from one member to the other. The melting point of an 'even acid' (having even number of
carbon atoms) is always higher than that of the 'odd acid' lying immediately below and above
it in the series.
..
2 3 4 s 6 7 5 9 10 2
NuMgeR OF CA801V 470M3 -.-
Fig. 221. Graph showing alternation of melting points in the series
of dicarboxytic acids.
DlcarboxyIlc Acid: 519
This phenomenon of alternation is probably due to the fact that the carbon chains of
dicarboxylic acids are arranged in the zigzag fashion (Fig. 222). This view has been confirmed
by X-ray examination of dicarboxylic acids. As a result of this zig-zag orientation, the carboxyl
groups of an dodd acid' lie on the same side of the carbon chain while of an even acid' lie on
the opposite sides of the chain
CH7
(I)
O'COOH
Fig. 222, Arrangement of carbon chains in odd' and even' acids.

Structures (I) and (3) represent 'odd acids' while (2) and
(4) represent even acids'.
Thi latter arrangement permits closer packing of the molecules in the crystal lattice and
evidently strong-!r intermolecular force exist between the chains. This makes the melting point
or even acid .igher than those of 'odd acid'
It s further interesting to note from Fig. 22-1. that a minimum melting point is found
with three-carbon dicarboxylic acid. This minimum may be a consequence of two opposing types
of intermolecular attraction stablising the crystal lattice. As the carbon chain increases in length,
the molecules become more alkanclike, and hydrogen bonding becomes less effective in holding
the large molecules in po F itlon in the crystal lattice, but the, forces of attraction between the
hydrocarbon chains (van der Waals forces) become more and more predominant as the chain
lengthens. t the dicarboxylic acid with five carbons, these opposing forces counterbalance and
melting point is minimum
(4) Acidity. The dicarboxylic acids are much stronger than the monocarboxylic acids.
This is expected since a carboxyl group being electron-attracting its presence close to another
carboxyl group facilitates the release of the first proton. This inductive effect falls off sharply
as soon as the carboxyl groups are separated by more than one saturated carbon atom (CH1).
Thus oxalic acid (K1 =5400x lO') is stronger than malonic acid (K= 140x lO s) in which the
carboxylic groups are farther apart. When two or more methylene groups intervene, the two
carboxyl groups have little effect on each other. For example, succinic acid (K.=6-4x IO)
is only slightly stronger than acetic acid (K1 =l'76x lO s). Hence the acid strength of
dicarboxylic acids decreases with increase in molecular weight.
Dicarboxyic acid ionise in two steps
HOOCCOOH + H SO HOOCCOO +
OOC.COOH + H 10 OOCCOO + HO
Since in the second ionization, a proton has to be removed front a negatively charged spieces
containing an electron-donating substituent i.e., COO, the equilibrium lies to the left. As
a result olthis equilibrium, oxalic, mlonic and succinic acids are weaker in their second
onisation than formic, acetic and propiortic acids respectively.

520 AdvQnced Organic Chemistry
Table. Physical Properties of some Dicarboxylic acids
First ionisation Second ionisation

Formula Name M, C constant constant
K1 x 10 at 25 K. 1 x10' at 25

1 896
HOOCCOOH Oxalic acid 5400 52

HOOCCH,COOH Malonic acid 135 170 023

HOOC(CH1)ICOOH Succinic acid 185 68 024

H00C(CH,)C00}l Glutaric acid 98 46 028

H00C(CH)C00H Adipic acid 151 38 023

H00C(CHC00H Pimelic acid 105 3.5 027

H00C(CH2)6C00H Suberic acid 144 30 039

HOOC(CH,)7COOH Azelaic acid 106 29 039

HO0C(CHC00H Sebacic acid 134 26 040
METHODS OF PREPARATION
The methods of preparation of dicarboxylic acids are analogous to those used for
monocarboxylic acids. Here we have to develope two COOH groups instead of one for the
monocarboxylic acids. Consequently, difunctional substrates would be the most suitable
starting materials.
(I) By the oxidation of glycols or hydroxy acids with KMnO 4 or K,Cr,O,.
K2Cr,071
,CH5OH H5S0 COOH
(CH, + 4{0J -.-.. (CH,). / + 2H10
CH2OH or KMaO4J COOH
glycol OH dicarboxylic acid
CH2OH KjCr,07 COOH
e.g.,
CH1OH
I + 4(0) -i.
H2SO4 COOH
+ 21-110
ethylene glycol oxalic acid

Similarly,
,CH 2OH K,C407 . ,COOH
(CH).( + 2[0] -* (CH,),,(' + HO
C0OH H2SO4 C00H
hydroxy carboxylic acid dicarboxylic acid
K,Cr,O, COOFI
e.g., CH,/
CH,( + 2[0] s. CH/ + 11,0
C00H H2SO4 C001H
..hydroxyproplocsIc malonic acid
acid
(2) By the hydrolysis of dinitriles or cyano-monocarboxylic acids having the cyano
group at the other end of the chain, with boiling dilute hydrochloric acid.
CN . boil COOH +-
(CH,),,{ + 4H,0 + 2HCI - (CH,),.( + 2NH4CI
CN C0OH
dinitrile dicarboxylic acid
CH,CN - bolt CH,COOH
e.g., I
CHICN
+ 41120 -. 2HCI..._.,
CHICOOH
I 2NHCI
ethylene auccinle acid

cyanide

blcarboy(ic Adds 52!
This provides a method for obtaining dicarboxylic acids of alkenes as follows.

H 2 Bra in CH 2 Br KCN CI-ICN H 2 OfHCI CHCOOH
I -+ I -* I
CF! 2 Cdt CH,Br CF{2CN boil CH2COOH
ethylene ethylene ethylene succinic acid
bromide clinic
Similarly,
reflux COOH
(CHI .), ' CN 1 0 + HCI -# (CH,). cooH + NH4CI
COOF1 + F1
cyanocarboxylic acid
7 CN + - reflux ,COOH
e.g., CH.H2 / 0 + HCl--i CH + NH4CI
COOH "COOH
cyanoacelic acid malonic acid
(3) By the action of silver or zinc on halogenated monocarboxylic esters A Wurtz

type reaction takes place. For example,
I CH 2 CU 2 COOC2 H CH2CHC00C1112
2Ag - I 2AgI
I CHCH 1COOC-2 H 6 CHICH8COOCaH
ethyli lodopropionate diethyl adipate
CHCH,COOC2 H 2 j- CHZCHZCOOH
I + 2H 2 0 ------f I + 2C1HSOH
CII 2 CFI 2 COOC,H 6 hydrolysis CH2CHSCOOH
adipic acid
(4) By electrolysis of salts of acid esters of lower dicarboxylic acids (Crum-Brown and
Walker Electrolytic method).
2 IOOqCF! 2 ),,COOC 2 H 5 -p 2 K .- 2 OOC(CHZ),ICOOCZFJ6

At cathode:
2K 4 2e -# 2K; 2K + 2HS O c 2KOli + H2
At anode:
- 2e (CH,),, COOC2H
2 OOC(CH 2 ) N COOCO H S -* 2 OOC (CHCOOCI H 5 - -- 2 CO
(CH 2),, COOCH1
(CH t)nCOOCHr. H4 (CH I ), COOH
+2H0 I +2C2HuOH
(CH 2 )COOC-2 H 5 L (CH,),, COOH
Thus succinic acid can be prepared by electrolysis of potassium ethyl malonate.

+- electrolysis CH2 CO005 H 5 [JO CH2COOH
2 KOOCCHCOOC 2 H 6 -
pot ethyl malonate
____+ -i- 2 C2H6OH I
CHICOOCaHC H CH2COOH
diethyl succinate succisic acid
(5) By treating Grignard reagents obtaired ficin the corretpordieg dihalcalk y ocs, with
solid carbon dioxide and sLbsequent b)drolysis. Thus glutaric acid can be prepared ficm
I 3-dibromopropanc,
CH 1 Br Mg CH2M8Br solid CFT1COOMgBr H 10 CE-T,(OOH
CH I ( -b C14/ s CHI -. CH/
CH 2 Br ether CH,MgBr CO 5 "CH5COOMgBr H+ CH2C00H
0.dibromopropane glutaric acid
Organic CIieunistr -34

522 Advarced Organic Chemistry
(6) By oxidation of unsaturated fatty acids. For example, oleic acid when treated with
}1NO 3 or permanganate solution or ozone gives peJargonic acid and azelaic acid.
KMnO
)
CH,( CHCH= CH(CHI 7COOH -p CH3(CH2 )COOH + H00C(CH,)7C00H
olcic acid pelargonic acid azelaic acid,
nonanoic acid, nonane-1 9 .dioic acid
(7) By oxidation of cyclic alkenes and cyclic ketones with HNO3 or KMu04 /0H or
K5Cr10,fH1S0
CH X1Cr01 COOH
(CH.) ' II + 4(0) -+ (CH1)(
'CH H1SO C00H
cyclic .lkcoc dicarboxylic acid
1 CH, }1N01 1COOH
(CH,)a( I + 3[0) + (CH,)(
C00H
For example, cyclohexene or cyclobexane on oxidation with nitric acid yields adipic acid.
(8) Dicarboxylic acids can be conveniently synthesised with the help of acetoacetic ester
or better malonlc ester.
(a) From acetoacetic ester
CII0Na ClCH5C00CH
CH1C0CH1C00C1H5 - CH5C0CHNaC00C3 H -+
accoac.dc ester. (NaC))
ethyl acetoacetats
CH5COOC1H5 CHC00H
I 2HAO +
CH 5COCHCOOC1 H, CH1COOH
CHICOOH
succinic acid
(b) From molonic ester:
COOC3H 5 CaH5ONS C00C1H
2 CH/ 2 dNa"
cO0C2H cooc2H5
niatonic ester sodio diethylmalonate
.Sodio diethylmalonate is then reacted with 1,2 . dibromoethane, the resulting ester
hydrolysed, and the free tetracarboxylic acid heated to yield the desired dicarboxylic acid.
CU5 Br Na CH(C00C1H5), HacH(c00c5H5)2 2HaO CII2CH(COOH)1

I -4
CH,jBr Na CH(COOC1H5h CHCH(C0005H CH1CH(COOH)a
1, 2 - d i b rom oich an tctraetbyl carboxylate tetracarbosylic acid
A CHaCH1COOH
ccH1CH2C00H
adipic acid
CHEMICAL PROPERTIYS
When the two COOH groups are separated by a chain of more than five carbon atoms,
they react more or less independently. Therefore the dicarboxylic acids, (CH 2)(C00H),, in
which n>5, give normal reactions of monocarboxylic acids twice over. However, in the lower
members where the COOH groups are closer together the possibilites of mutual interactions
increase. Thus many of their reactions depend on the distance apart of the COOH groups i.e.,
on tne value of n.

Dlrcarboxyllc Acids
523
(1) Reactions of the COOH groups. One or both the carboxyl groups may react with
appropriate reagents to form mono- or di-derivative. Thus* oxalic acid gives the following salts,
esters, acid chloride, and acid aniide.
COONs Z Na

+NaO l-i
-p
COOH Na
sod hydro . sod cialala
gea oxalate
cO0C2 H5 COOC1H1
+ 2C,H1OH/H+ _,
COOH COOCIHI
ethyl hydrogen diethyl oxalate
COOH oxsiite
OOH COONH4 rNH,

oxalic acid I
+NHOH .-, I - '
COOH OH
1mm hydro. oxamic acid
Len oxalate
COCI NH4OH H1
+sOd! I -4 s.
I
COd
ozalyt ozarnlde
CH,
chloride -
The two COOH groups can also be made to react successively with different reagents to
yield 'mixed derivatives'. For example,
COOH C,)OH COOCsHj soa 1 ooc,
4I
COOH H COOH (0c!
ethyl hydrogen mixed derl,idve
ozaiste
COOH NH 4 OHZ NH4 t CONH 5 oc ONH1

I
COOH H -RIO COOH COd

1mm hydrogen oxamic add mixed derjvavc
oxalate adid
These mixed derivatives are useful intermediates in organic synthesis.

(2) Action of Beat on Dicarboxyllc adds. The nature of product formed when a
dicarboxylic acid is heated depends on the number of carbon atoms intervening the two carboxyl
groups. Thus, these acids can be divided into three groups on the basis of the effect of heat on
them.
(1) Those with one or no Intervening carbon. The dicarboxylic acids in which the two
COOH groups are ]inked directly to each other or to the same carbon atom, when heated split
out a molecule of carbon dioxide from one of the COOH groups to form nionocarboxylic acids.
Thus oxalic acid and malonic acid decompose to give formic acid and acetic acid respectively.
HiOCdOOH - i HCOOH ,+ CO,

oxalic acid IO fonnic acid
COOH
H5C( -b CHI COOR + CO1
"COOR l' acetic acid
malonjc acid -
524 Ad v anced Organic Chemistry
(ii) Those with two or three intervening carbons. The dicarboxylic acids in which the two
COOH groups are separated by two or three carbo,n atoms, eliminate a molecule of water to form
cyclic anhydrides. Uhus succinic acid and glutaric acids when heated one or preferably with
acetic anh y dride yield succinic anhydride and glutaric anhydride respectively.
CH,COOCH,CO
H ,,
I -. ')O+HO
CU,COOH 00-150' CH,CO"
succinic acid succisic anhydride
/CHCO--OH A CH1CO\
H,C -+ H C" + HO
" CHCOOH too .jso CH,CO
glutaric acid glutaric anhydride
Such a reaction occurs where five or six-membered ring anhydrides can be formed.
(iii) Those with four or five intervening carbons. The dicarboxylic acid in which the two
COOH groups are separated by four or five carbon atoms upon heating alone or distilling with
acetic anhydride form cyclic ketones. Thus adipic acid and pimelic acid when heated at 300'
yield cyclopcntanone and cyclohexanone respectively.
CHCH2COOH CH,CH1
-.4 C=O+CO1+H1O
CHCFL 1 COOH 300' CH1CH/
adipic acid cyclopeotanoce
,CHaCHr'COOH A ,CHCH1
HC'- HIIC( + CO + H30
cH1CH,--cooH 300' CH1CH(
pimelic acid cyclohecanone
The calcium salts of the above acids also give the respective cyclic ketones.
H,CCH,---COO A HCCH 1+ 1-
Ca -+ +
H1 CFICoO - HCH3
calcium adipate cyctopentanose
CH1 CH2---COO A CH,CH, 1+

H,C - ca -.+ HC<( "c=o + ca CO3
CH1CH,COO 300' CH1CH,/
calcium pimelata cyclohexanone
The results of action of heat described in (2) and (3) above are summarised by Blancs
Rule which states that 1, 4- and 1, 5-dicarboxylic acids yield cyclic anhydrides on healing
whereas I, 6-and I, 7-dicarboxylic acids afford cyclic ketones. This rule is often useful for deter-
mination of the ring size,
(ir) Higher dlcarboxylic acids. Those acids where the two COOH groups are separated
by six or more carbon atoms, on heating form small amounts of ketones but the major product
is a linear polymeric anhydride resulting from intermolecular dehydration.
0 0
II A
HOC---(CH),C---OH -.4
dkar boxylic acid
where n ) 5
HOC(CH,),--C-0 C(CHj).C-0_C_ CH,).C-0111

jZ
linear polymer anhydride

525
Dicarboxylic Acids
(3) Oxidation. The dicarhoxylic acids are, in general, stable to oxidising agents.
However, oxalic acid is oxidised with acidified potassium permanganate solution to give carbon
dioxide and water.
COOH KMnO4
I OOH +10] - 2CO2+H10
C H2SO4
(4) Acyloin Reaction. Higher dicarboxylic acids form acyloins when heated with sodium
in boiling xylene followed by acid hydrolysis.
Na/ -+ ,C.OH ___ ,C=0
,COUH xytene ,_ONa H5OjH+
(CHuj( Ii - .- ( CH' (CH.)./
(CK5)( "CHOII
"COOH boil "CONa La "COH
acyloin
with Cl, or Br2 , the corresponding

(5) Halogenation. When a hot higher acid is treated ,
halogenated acids are obtained. For illustration,
CH'COOFI CHCICOOH Co, COOK
OOH
as I Cl2 I
or (CH,).., - ( CH 1 ), (Ct-I2).
(CH2)
La I
excess

CI-11CO()H CHCI -COOH CCI9COOH
COOH halogenated acid
dicarboxydc acid
INDIVIDUAL MEMBERS
OXALIC ACID, Ethane-I, 2-dioic acid, (COOK)5

This acid has long been knowi' and is widely distributed in the plant kingdom. It
occurs as potassium hydrogen oxalate in the wood sorrel (Oxalis ace/use//oh It is also present
ax calcium oxalate in many other plants such as spinach, rhubarb, sweet potatoes, cabhagd.
grapes and tomatoes. Ammonium oxalate is present in urine.
Preparation. Oxalic acid may be obtained by the oxidation of glycol and also by the
hyo olysis of cyanogen.
CH1OH K1r207 cOOH
I + 4[0] . + 2H20
CH2011 H1SO tOOH
ethylene gl ycol oxalic acid
CN bolt COOt-I
+ 2NH1CI
+ 4H10 + ?HCI -.-
CN COOl-I
cyanogcn
LABORATORY PREPARATION- in the Jaborixtory, oxalic acid is prepared by the
oxidation of cane sugar i.e., sucrose with concentrated nitric acid in presence of vanadium
pentoxide as the catalyst.
HNO5 COOK
C11 H21011 + 18[0] -+ 6 I + 5H20
sucrose V505 COOK
This oxidation is usually conducted in a fume cupboard since copious oxides of nitrogen are
produced during the reaction.
Oxalic acid is prepared industrially
M .\NUFACI'URE. (I) From Sodium formate. produced. This is then
by heating sodium formatc rapidly at 375 when sodium oxalate is
converted to calcium oxalate by treatment with lime which when reacted with dilute sulphuric
acid forms oxalic acid.
526
Advanced Organic Chemistr y
E--COON 37 cOONa
HcOONa OONa
sad ozalate
cOONa LW
"Na + Ca(OH), Ca + 2NaOH
coo,
calcium oxalate
COO COOH
I ""Ca+1s4 I +CaSO4
coo/ COOH (insoluble)
oxalic acid
(2) By direct combination of CO 2
and metallic sodium at 3600.
o COONa
2CO5+2Na -i I
COONa
sod oxilate
Sodium oxalate is worked for oxalic acid as in method (1),
(3) Oxalic acid is also obtained commercially by the oxidation of carbohydrates such as
glucose, sucrose, starch, cellulose with nitric acid in the presence of a catalyst (ferric sulphate,
vanadium pentoxide),
COOH
CH 2 0 6HNO3 31 -+ + 6N0 + 6HSO
dextroseOoH
(4) Formerly, oxalic acid was obtained on a large scale by heating saw dust (cellulose)
at 240-250 with a concentrated solution of sodium hydroxide. The sodium oxalate thus
produced was converted to oxalic acid a's described in method (1). This method is now
obsolete.
Properties, (Physical).
Anhydrous oxalic acid (HOOCCOOI-J), is a colourless,
odourless, white powder with a marked acid taste, It crystallises from water as the dihydrate
(HOOCCOOH.214,0) in the form of colourless prismatic crystals. The melting point of the
hydrated acid is 101 50, while that of the anhydrous acid is 1895. The crystals of oxalic acid
show efflorescence in air and the hydrated acid becomes anhydrous when carefully heated to
150. It is soluble in water and ethanol, and practically insoluble in ether. It is an active
poison.
(Chemical). (I) Acidity. Oxalic acid is the strongest of all the dicarboxylic acids,
being even stronger than phosphoric acid.
(2). Formation of Salts. It gives the usual replacement reactions of the two carboxyl
groups, forming two series of salts, esters, amides and acid halides. (See general reactions
of dicorboxylic acids)
(3) Action of Heat. When heated alone, oxalic acid decomposes above its melting point,
giving formic acid and carbon dioxide.
190-200
HOOCCOOH -+ HCOOH + CO
formic acid
(4) Aclion with Glycerol. It reacts with glycerol to form formic acid or allyl alcohol
depending on experimental conditions, (See Glycerol)
.
(5) Action with H 2 SO. Oxalic acid when seated with sulphuric acid decomposes to
yield a mixture of CO 5 , CO and water.
H1SO4
1-I00C--000H -+ CO, + CO + HSO
A
(6) Action with Ethylene glycol. When heated with ethylene glycol, it forms ethylene
Oxalate, a cyclic compound.

Dlcarbaxyltc Acids 527
0=C,__0H HO I-, CM
0C
7N012
+ I + 2H2O
OCNCH2 O CH
OH HO N0
OXALIC GLYCOL ETHYLEN( OXALATE
AdO
(7) Action with PCI1 . With PCI 5 , it forms oxalyl chloride. But if an insufficient
quantity of P0 1 is used, oxalic acid decomposes via the intermediate half acid chloride.
COOH Fci, COCI
I I 4 CO, +CO+FICI
tOOH COOH
Intermediate
COOH p a s COCI
I I.
OOH excess COCI
oxalyl chloride
(8) Oxidation. Oxalic acid when treated with potassium permanganate and dilute
sulphuric acid at 600, is oxidised to carbon dioxide and water.
COOH
2KMnO4 + 5 1 + 3H 1 SO4 '----* K 1 SO4 + 2MnSO1 + loCo + 8H20
COOH
Since this reaction is quantitative and oxalic acid is easily available in pure state, the substance
is used in volumetric analysis for standardising potassium permanganate solutions.
Uses, Oxalic acid is used
(1) For removing ink stains and for bleaching straw for hats and for removing rust since
it reduces ferric compounds to mere soluble ferrous salts
(2) As a mordant in dyeing and calico printing;
(3) As a standard substance in volumetric analysis
(4) As ferrous oxalate in photographic developers;
(5) As potassium ferric oxalate, K3 Fe(C104 ) 3 , platinum prints in photography , and
(6) For the preparation of allyl alcohol and formic acid in the laboratory.
MALONIC ACID, Propane-I, 3-dioic acid, CH5(COOH),

Malonic acid was so named because it was first obtained by the oxidation of malic acid
(hydroxysuccinic acid).
Preparation. It is ordinarily prepared from sodium chloroacetate by the following
sequence of reactions.
+ -
CICH2COOH + NaHCOa s CICH5COONa + H30 4- CO
chioroacetic acid
+ + - - + +-
ClCH5C661sla + KCtN -p NCCHCOONa + KCI
sod cyanoacctatc
NCCH,COON 2HCI + 2H 20 -p HOOCCH 5COOH + 1'tH4ClNkl

malonic acid
Properties. Malonic acid is a white crystalline solid, mp 135C. It is soluble in water
mci ethanol but is practically insoluble in ether. It gives all the usual reactions of dicarboxylic
scids.
(I) Action of Heat. When heated to 140-150 or when refiuxed in sulphuric acid
mliitinn it loses A molecule of CO, to j,roduce acetic acid.

140lW
HOOCCH,COOH -p CH,COOH + CO,
matonic acid acetic acid
The decarboxylation probably occurs by the following mechanism
CH. 0
HOC 4 JC = O II
QcV21 Iu,rtt P
cO+ I CH3 C-011
ALETIC ACID
H OH
[ j

15CNi( ACID INTERMEDIATE
(2) Action with P 205. When heated with P105 , inalonic acid gives a small amount of
carbon suboxide.
HO H
I I Pio6
O=CCC=-O -b O=C=C=C=O 2HO
a carbon suboxide
H -OH
Carbon suboxide is a diketonc and combines with water to give back the malonic acid
md also with ethanol to yield diethyl malonate,
(3) Action with Aldehydes. When a pyridine solution of malonic acid and an alde!ide
is heated, ; -unsaturated acid is obtained,
COOH pyridine
RCHO . - -, RCH=CHCOOH + CO H20
aldehycic , -uasacurated acid
(4) Addition with Nitrous Acid, Malonic acid on treatment with nitrous acid, foilowed
by hvdrolyis
- gives nsesoaaic add.
- COOH H 10 coon H,01 H+ COON
HON=O + H 2C( -+ 1-{ON=C" -+ O=C(
COOH "COOn "COOlI
mesoxalie said
(S) Action with Bromine. A suspension of malonic acid in ether when treated with bromine
affords monobromomalonic acid.
COOK COOH
H1C( + Br 5 -' BrHC" + HBr
"COOH COOH
mossobrornomalonic
acid
Uses. Eth y l malonate is very useful for the synthesis of a variety of organic compounds.
SUCCNIC ACID, Butane-I, 4.dIoic acid, HOOCCH,----CU2COOH
Succjrsic acid was first obtained as a result of distillation of the fossil resin amber and
hence its name (Latin, succinum=ansber). It occurs widel y in nature in numerous plants and
unripe fruits. It is also produced in small amount during the alcoholic fermentation of sugar.
Preparation. (I) Succinic acid is prepared from ethylene bromide by treating wish.
potassium cyanide and subsequent hydrolysis of ethylene cya aide,
CHBr 2KCN CH 1 CN H5OJHCI CH1COOK
+1
C'H,Br CHICN hydrolysis CH1COOH
ethylene ethylene sticcinic acid
bromine cyanide
(2) By heatinir malic or tartaric acid in a sealed tube with hydriodic acid and red
519
btcdrboxyllc Acids 1
CH(OH)COOH red p CH1COOH

+2HI - +12 H2O
CH1 COOH A CH2COOII
matic ocid succinic acid
CH(OH)COOF{ red CII1C0OH
CHOH)COOH A CHJCOOII
(3) It is prepared commercially by the catalytic reduclion of maleic acid.

CHCOOFI Ni CF1.COOH
I I -1 TT -*
CHCOOH CFIJCOOH
rnaleic acid iucetnic acid
Properties. Suc'inie acid forms white monoclinic prisnis, mp ISa. It is moderately
soluble in water and sparingly soluble in ether. II .vcS all the thual reactions shown by
dicarbosylic acids listed earlier,
(I) Action with Alkalis. It reacts with NaOU and KOFI to form two series of salts.
CII5COONa NaOH CH1COOH KOH CH5COOK
C I-1COONa CH,COOH CH2COOK

' ' I hydrogen succinic acid pot succinate
siicciate
Action with PCI1. When ireated with phosphorus pentachloride, it form s sucCiri)l
cliloi idC.
CHICOOH CH2COCI
^ 2PC1 5 -4
+ 2POCI 3 -- aHCI
CH5CQOH CHCOCI
succinyl chloride
inic .2iliydride
'Succinic acid, however, an rreatment with thioisyl clrtordc ' Ves We'
instead or succinyl chloride.
(3) Action of Heat. When heated above its melting point, succinic acid sublimes largi'I
and the rest being converted into the anhydride.
CFTaCQOH CB CO
I ) .i HO
ci-i1cooi g CHrCO"
succinic anhydride
Excellent yield of auccinic anhvdride can, however, be obtained by distilling
succinic
acid with acetic anhydride or acetyl chloride or phosphoryl chloride.
C 1112110i in presence
(4) Action with Ethanol. Suecinic acid when refiuxed with absolute
of cone H 2SO4 gives diethyl succinate.
CHCOOH H1SO4 CH2CO005H5
2CH s OH 7H20
CH ICOOH CH1CO005H5
diethyl gucciSate
so..Iium or
(5) Electrolysis of Na or K salts. The electrolysis of a strong solution of its
potassium salt yields ethylene.
CHICOOK elcctrolylis C11,,,

I , 2CO 2 -- O
2K H r. 112
('Ii COOK CH, alcatl1s5de
ii
02 ano,js'
hated in a current of d. in ii. inq

(6) Action with mmonia. When succinic acid is
or with ammontutu c1b5iu1c succinimide is produced.

530 Advanced Organic chemistry
CH,cOOH CH,CO +N111 CH,CO
CH,COOH H 1 0 CH,CO
I '
CHCO'NH+H2O
succinic anhydride succinimide
Succinimide when treated with an alkaline solution of Br 1 at 00, forms N bromo
succinimide (NBS) which is a valuable reagent for allylic bromination.
CH,00 NaOH CH CO\
I
CHI CO'
)NH + Br, -.--+ ' )NBr + HBr
0' CHICO'
N-bromosuccinimide
(NBS)
(7) Action with Glycol. When heated with excess of ethylene glycol, succinic acid for?ns
polyesters commonly referred to as Alkyd esters, These esters are acidic in character due to
succinic acid residues at the end of the chain.
HOOC(CH,)aCOOH + H0CE-I,CH 2 0H + HOOC(CH2 ) 3COOH + HOCH 2CH2 0H +...
I
HOOC_(CHl)a_CO[_O_(CHO_O_CO_(CHI)a_CO_]::H
polyester
Uses. Succinic acid is used for the manufacture of polyeseter resins.
GLUTARIC ACID, Pentane-1, 5-dioic acid, HOOC(CH2)3COOH
Glutaric acid was prepared from Glutamic acid as follows, and hence its name.
NH, OH
I HNO,
H00CCH,CH1 CH000H -' H00CCH2CH2CH000H
I
glutamic acid a-hydroxygtutaric acid
Ht
-.4 HOOCCI-I2CH,CH2COOH
glutaric acid
It is not a commercial product and is made in the laboratory by the following synthetic
methods.
(I) By hydrolysis of trimethylene cyanide,
,CH,CN boil ,CH2COOH
H1 C' + 4H2 O + 2HCI -p H,C( + 2NHCl-
CH,CN "CH,COOH
trimethylene cyanide glutaric acid
(2) By oxidation of cyclopentanone with nitric acid,
CH,CH, HNO, ,CH,COOH
C=O + 3[0] -.+
CH2CH, CH,COOH
cyclopentanone glutaric acid
(3) By the action of methylene iodide on monosodiomalonic ester (See Malonic ester).
Properties. Glutaric acid is a crystalline solid, mp 98. Like succinic acid, this acid
also loses a molecule of water when heated alone, or with acetic anhydride or thionyl chloride.
CH,COOH A JCH200
.-* H2C" O + HaO
CH,COOH CH1 CO"
glutaric acid glutaric anhydride
ADIPIC ACID, Hexane-1, 6-dioic acid, H00CCH2CH2CH2---000H
This acid got its name from the fact that it was first obtained by the oxidation of fats.
(Latin, adeps=f t).
Preparation, (I) It can be prepared by the reaction of monosodiomalonic ester with
ethylene bromide (See malonic ester)
(2) It is obtained commercially by the oxidation of cyclohexanol prepared from phenol,
or cyclohexanone with nitric acid in the presence of SeO 2 catalyst.

DiccrboxyUc Ac7d 53!
OH 0
CN2CH_ COOH
RA (,'EYM HNO3 HNO3
0 3
a
. - ,
AD/P/C ACID
PHENOL CYCIOHEXAWOL CYCLOHEXANONE
(3) It is also prepared on a large scale by the reaction of tetrahydrofuran with c. -

monoxide and water.
CH,CH, CH,CH,--COOH
I
CH,CH1 '
0+2C0+H0
CHICH, COOH
tetrabydro(uran idipic acid
(3) Now a days adipic acid is produced by the catalytic oxidation of cyclohexane (Obtain-
ed by catalytic reduction ol' benzene) in two steps. In the first step cyclohexane is converted to
cyclohexaone by air-oxidation in the presence of cobalt catalyst at 100 under a pressure of 150
psi. In the second step the cyclohexanone is oxidised to adipic acid with the help of nitric acid.
C
BENZENE CYCtOI/IXANE
a
CYCWH(XANONE
Properties. Adipic acid is a crystalline solid, mp 150. When heated in presence of

AD/P/C ACID
Ba(OH)2 , it is converted into cyclopentanone.

CHCH--c00H
-- CHCH, ,
I -
ao nhydri e
I )C=0+CO3+H20
C}iCH000H 280-300
CI12CH3"
adipic acid cyclopentanone
Upon heating with acetic anhydride, it gives iinear polymeric anhydride.
(x +l)H00C(CH)4C00H + x(CHC0)20
adipic acid acetic
0 0 10
HOOC(CH1)4CC (CH2)---CO-- (CH 2)4 COOH xCHCOOH
^_ x1
poly adipic) anhydride
Adipic acid undergoes condensation polymerisation wills I, 6-diaminohcxane
(hexamethylcoediamine) to give a polyatnide, Nylon 6, 6. It is one of the most popular of the
synthetic fibres and is so named because in each repeating unit its molecule contains six carbons
in the amine fragment and six in the acid fragment.
o
0 0
II II
X H0C--(CH)4----C--0H + x H I N(CHI )6NH, -4
adipic acid hcxamelhylcnedianiine
0 0 0
I II II
C_(CH1 )4 _ .--NN(CHNHC(CH2)1_C. NH(CH 2)6NH + 2x H10
X
Nylon, 6,6

UNSATURATED DICARBOXYLIC ACIDS
The two simplest and the most important dicarboxylic acids are
I?.
1-1 \/ COH HCOH
HOC"H
0 0
mateic acid fumaric acid
For convenience of writing, they may be represented as
HC---COOH HCCOOH
HC--COOH HOOCCH
mjlcic acid fumaric acid
(cis form) (trans form)
These acids furro the classical example for illustrating geometrical isomeriem. Only one
of them i.e., rnaieic acid when heated above its melting point readily yields a c y clic anhydride
and hence this acid must be the ri g -isomer. Therefore the other acid, Fumaric acid, is the
trans-isomer. Fumaric anhydride is unknown When fumaric acid is heated for long periods
of time, it is slowly transformed into rnaleic anhydride by rotation about the double bond and
elimination of a molecule of water. During this process, energy Is absorbed, as shown by heats
cf combustion of the two acids: maeic acid 326 3 kcaljinole ; fumaric acid 3201 kcalJmolc.
Thus [umaric acid is the more thermodynamically stable isomer, as its heat content is lower
by 62 kcal)mnole.

0 0
HCN OH

N V HN/

g 0
4ALI/C ACiD M1LE/C ANb/VOIc'E
0 o c
H II

\ 7C
C7OH
() _____ C
C
OHC
N H.
Ii
C
0
IC/MAR/C AC ID MALEIC ACID MAtE/C ANHYDR/DF

Dlcarboxytic Acids
ACIDITY OF MALEIC AND FUMARIC ACIDS

It might be thought at the first sight that the two acids might be of equal strength
i
since they l iave identical structures But actually maleic acid (Ka = 1,420 .' 10) is a much
x 10). This is due to the fact that the malcate
stronger act, than fuinaric acid (Ki1 =93
ion left after the removal of a proton is stabilized by hydrogen bonding due to the close
proximity of the two carboxyl groups whereas this is not possible for the fumarate anion.
Thus maleate ion is stabilised by resonance and also by hydrogen bonding, fumarate ion is
stabilised only by resonance. This greater stability of maleate anion relative to fumarate anion
accounts for the higher acidity of maleic acid over furmaric acid.
0
0
11
IHN/ II 0 i_
NH I II
J
0
MALEIC ACID NY06EN BONDED
MALEArE ION
0 0
Hc
CZOH
H+
HO C
H C
0
0
FUMA,'ATE /0/V
FL/MAR/C Ec/D
(NO HYDROCEN 80ND/NG)
The second dissociation of fumaric acid occurs more readil y than that of male acid
(Ka,=008X l0 and 36x 10 respectively) since it is diffiU1t to remove a proton from the
negatively charged cyclic system of maleate anion.
MALEIC ACID, cis-Ethylene-1, 2-dicarboxylic acid,
H COH H COOH
HGCOOH
C or
or
HC---COOH
H'OH H/\COOH
0
It does not ccur in nature and hence is a synthetic compound.
Prepartiofl. (I) By heating malic acid rapidly at 258 to form maleic anhydride which
is then hydrolysed with boiling water to give nialeic acid.
+o CHCOOH
HO_HCOOH HO HCOOH H2 0 HCO\
I O . II
CHCOOH A cHCO7 boil CHCOOH
CH,C OH A rnateic acid
malic acid maleic acid maleic anhydride
(intermediate)

S34 Advanced Organic Cheinlitry
(2) By heating bromosuccinic acid with ethanolic potash.

BrCI-ICOOH ethanol CHCOOH
+ KOH -+ if + KBr + llO
CHICOOB CHCOOH
bromosuccinjc acid maleic acid
(3) It is prepared commercially by the oxidation of benzene with air at 4004500
presence of vanadium pentoxide (V,0 5 ) as catalyst, followed by hydrolysis of maleic anhydride
formed.
V106 HC +HO CHCOOH
+ 44O -. ,CO,"
10D
benzene
I 0 -+
400-4W HC00 CHCOOH
maleic anhydride maine acid
boil
Properties. Maleic acid crystallises in large colourless prisms, mp 130. It is freely

soluble in cold water. It gives the reactions of two COOH groups linked to adjacent carbon
atoms as also of alkenes i.e., carbon-carbon double bond.
(I) It forms two series of salts, esters, amide and acid chloride,
CHCOON CHCOOCIH5 CHCONH1 CHcOCI

II -+ II if II
CHCOONa CHCO0051714 CHCONHI CHcOC1
sod maleate diethyl maleato maleamide maleyl chloride
(2) Action of Heat. When heated alone or with acetic anhydride, it forms maleic'
anhydride
CHCOOH A CHCO
II '\o+Ho
CHCOOH 430 CHCO/
nialek anhydride
On prolonged heating at 150 maleic acid isomerises to fumaric acid.
HCCOOH HCCOOH
HCCOOH 150. HOOCC---IJ

malcic acid fumaric acid
This isomerisation presumably occurs via
the intermediate diradical as discussed in before I
acid. (3) Action with HBr. Maleic acid reacts with hydrogen bromide to form bromosuccinic
CHCOOH Br HOOH
H +HBr I
CHCOOH CH3COOH
monobromosuccinic acid,
or bromosuccinjc acid
(4) Action with Bromine. Bromir: .solved in Cd 4 0
CUCOOH adds to the C=C bond of maleic
acid producing a mixture of (+) and (-) dibromosuccinic acid (Racemic Mixture),
H H Br
l,C0QH HO0C H /81.
C=C + Bt ---+ .0 C + CC.
H'i
HOOC COOH HOOC Br Br COOR
MALI( A(
(+)-giBpopjosuCCINi( xcio (j -DIBROMOSuCCINIC ACID
MECHANISM. The addition proceeds by trans-mechanism so that the two bromines add from
opposite sides of the nlanar C=C bond.
Step I. Bromine adds to the C=C bond to form the bromonium ion and a bromide ion.

fJlcorboxyllc Acids
H H Br
C==C + Br + CC + Br
/ H"J' 'H
HOOC COOH HOOC COON
MALEIC ACID
BROMONIUM ION
Step 2. The bromonium ton undergoes nucleophilic attack by bromide ion in two ways. When the
attack occurs at (2-2, (+)- form of dibroinosuccinic acid iij is produced. When the attack occurs at C-, (-)
form of dibromosuccinic acid (2) is formed.
Br u
COOH
Qtt5(h
.0 at C-2 -C
H'j
Br' HOOC Br
/ \ ()-oIsnoMosucciNIc ACID (1)
Br
H
HOOC COOH
HOOCH Br
attack \`
at C-1
/
Br COOH
- OIBROMOSU(CINI( ACID (2)
(5) Action with Alkillne KMnO4 .. When treated with alkaline potassium peruldnganaw
solution (or with 0s0 4 ), it undergoes hydroxylation to produce mesotartaric acid.
COOH
HCCOOH ICMnO1 H OH
II +H10+O
HC000H alkaline H OH
COOH
mesa-tartaric acid
(6)Reduction. When reduced with hydrogen using Raney nickel as catalyst, it gives
succinic acid.
CHCOOH Raney Ni CHCOOH
-fH1 + I
CHCOOH CH2COOH
succinic acid
Uses. Maleic acid is used
(1) to inhibit rancidity in milk powders, oils and fats
(2) to prepare rnaleic anhydride for making varnishes and lacquers.
FUMARIC ACID, tram-ethylene.1,2-dicarboxylic acid
0
H\/ COH H\/COOH
C C H.--COoH
1 or 1
c . HOOCC--H
H0CH HOOC"H
a
Funiaric acid occurs in many plants. . .

536 Advanced Orgonic Chemistry
Preparation (I) By heating malcic acid for a long time at 150'.

(2) B y dchydrishromination ct bromosuccinic acid with ethanolic potash.
BrCUCOOfJ c(hanot }ICCOOH
KOU -+ + KBr + H20
CH,COOH IIOOHC--H
broimoxuccinic acid furnaric acid
(3) By conckqation of inalonic acid with glyoxytic acid in the presence of pyridine as a
base Kooevenagcl Reaction), followed bydecarboxylation at 1301400.
,COOH pyridin JCOOFI HOOCC.EJ
HOOCCHO- FiC' -. HOOCCH=C'
gIyoxIic acid "COOlI "COOH CO HCCOOH
malonic acid futnaric acid
(4) Industrially, fumaric acid is prepared by boiling maleic acid with hydrochloric acid
or sodium hydroxide.
Properties. Fumaric acid is a colourless solid, mp 287. It is slightly soluble in water.
Chemically, fumaric acid behaves both as an alkenc and a dibasic acid.
(I) Formation of Salts. It forms two series of salts, esters, amides and acid halides. For
example,
NOOCCH H4C100CCH J-I1NOCCH

if -+ II ii
CHCQONa CHCOOC2H5 CHCONFI,
sodium fumarate dielhI fumarate fumaramido
(2) Reduction. When reduced with sodium amalgam, furnaric acid yields succinic acid
(Cf. maleic acid).
HooCH Na-Hg/H2O CHCOOF1
ii, -.--_._.......+
CHCOOU CHCOOH
un:aric acid succin acid
(3) Oxidation. WI: fl oxidised with dilute potassium permanganate, it forms dl-mixture
of tartaric acids since the addition takes place in a ds fashion.
(4Action with Ur. Fumaric acid adds a molecule of hydrogen bromide to form
hromosuccinic acid.
H CCOO U BrCHCOOH
i-HB- -,
HOOCCH CH,COOH
funiarjc acid bromosuccinic acid
(5) Action with Bromine. When treated with BI- 2 in Cd 4 or CH2COOH, lumaric acid Fives
ycvo . dihromosuccinic acid.
H COOH Br COOH
C C' + Br, -' C - C

\ H'j
HOOC H HOOC Br
fuilARic ACID ,o-CI9ROplOSL'CtIiiC ACID (t

537
Corboqltc Acids
MECHANISM. Like maleic acid, fumanc acid undergoes trans-aUUItion wan oromine.
Step 1. Bromine adds to the C=C bond to from bromonium ion and bromide ion.
,COOH
Br2 ,C'C 4 Br
/ WJ V"CooH
HOOC H HOOC H
FUMARIC ACID BROMONIUII ION
Step 2. The nucleophile (: Br) formed above attacks at CI or C-2 to produce (2) and (3) as the
products.
Br C00F4
attack
at C-2
\
Br HOOC Br
CC +
H' J' 2"-COOH
H
}100C
Br
H00
attack/
C (3)
at [-1
/ "-COOH
Br H
The structures (2) and (3) represent the same compound (I), as can be seen by rotating any one of
the two through I SO'- The compound will not be optically active since a plane of symmetry can be drawn
through the molecule.
(6) Coinerslosi to Mitivic anhydride. It does not form anhydride of its own, but when
heated to 230', fumaric acid gives inaleic anhydride.
HCOOH 20 HC---COOH A HC--CO -
II 11 "0
HOOCC---H Isomerisatlon HCCOOH
(emaric acid maleic acid mateic anhydride
QUESTIONS
1. What are saturated dicarboxytic acids? Write the structural roriwlac and names of the members of
this class containing Iwo to six caibon atoms.
2. Write out all the possible isomeric dicarboxtrllc acids of molecular fornuls C,H,,0 4 and name them
aemwsn$ to WPAC 1)15cm.
3. DescrIbe the cneral methodsofprepenlioo mzidpcoperties of ,llplsstk dicaeboxyllciclda. How do
you explain alternation in their mdulog points. -
4 Describe briefly the action of heat on dkarboxyllc aclds:snd their calcJurti alla.
S. How is oxilic add obtained ? mention its properties and sees. In what respects does It differ
from tuccioic add.
6. Describe the preparation and properties of pioxitsic acid,
7. How Is malonlc acid syrthesised? Describe the action of heat on the acid.
t Give the general methods of preparation of aliphatic saturated dicarboxylic icld. What is iJi
action of heat on the dicarboxylic acids where the two carboxygroups are separated b y none one, two and three
carbon atoms.
Orgaisic Chemislry - 35

38 Adyanced Organic Chemistry
9. Discuss the preparation, properties, *ad U1901 of malosun acid.

)Jswajs BSc 11, 1987)
10. Write a dote on; Action of heat an dioarbox,11 0 ecidi,
Udaipor BSe II, 1938)
11. Give one method of manufacture, easy three ftaotions, and two usea of oxslia acid.
Ransasaa B& 11, l9dlj
12. Row wilt you synthesi.e -
13. Discuss the pepauarjou, properties. and uses of monic acid.
(Jzwajp BSc, 1993)
14. Write a note on. Action of heat ondicazbouylic acids.
(Sambealpur9Sc. 1993)
IS. Give one method of manufacture, any three reactions, and two uses of oxalic acid,
(Karnataka RSc, 1994)
16. How will you synthesise
(a) Malonse acid from chioroacetic acid and (b) Saccinjc acid from ethylene
(Pwijab BSc, 1994)
Hint. (a) (i) C1 2, (is) NaCN, (iii) H 20/H'/lsea(; and (b) (i) NaCN, (u)
H201H/heat. For (b) carbonation of Gsignard reagent
riot a suitable method her ussr the presence of COOH group in chioroacetic acid prevents the formation of a Grignard reagent
17. How is succouc acid prepared from ethylene? What happens
w hen succimc acid is heated I (Mo4ros diSc. 1994)
18. How will you disnnguisls heiwects oxalic acid and succinic acid?
(Dibraguth diSc Hurts, 1994)
19. (a) How isoua1ic acid prepdinlrbnc,.
(b) flow will you syntheriisc mulonic acid from ellta&d?
(Saugar BSc. 1993; Manipur BSc, 1994 Gulbarga diS(. 1994)

Chapter 23
Substituted Carboxylic Acids
These are the derivatives of inonocarboxylic acids in which one or more hydrogenatoms
in the hydrocarbon chain have been substituted by other atoms or groups. Thus the subs..
tituted acids are bifucictional compounds in which one of the two functions is a COOH
group and the other a halogen atom or a group such as OH, NH,, NO 2 etc. They are called
halo acids, hydroxy acids, amino acids, nitro acids aftef the name of the substituent in the
hydrocarbon chain.
COOH LCOOH ."OOH . .+MH

chioro acid hydroxy acid amIno acid nitro acid
NOMENCLATURE
(1) The Common Names of substituted acids are derived by prefixing ebloro, hydroxy.
amino etc., to the trivial name of the corresponding monocarboxylic acid, according as the
substituent in the hydrocarbon chain is Cl, OH, NH,, etc. The position of the substituent
is indicated by Greek letters a, , , etc., when the carbon adjacent to COON is designated
as a.
(2) In the 1UPAC System a given substituted acid is named by prefixing ehioro,
hydroxy, amino etc., to the systematic name (as alkanoic acid) of the parent carboxylic acid.
The position of the substituent is shown by Arabic numerals I, 2, 3, 4 etc, the number 11'
being assigned to carbon of COOH group.

Formula Common Names JUPAC Names

ClCH,COOH chioroacetic acid chlorocthanoic acid

HOCH1--COOH hydroxyacetic acid hydroxyethanoic acid

H,NCH1-000H aminoacetic acid
1.
aminoethanoic acid
3 2 I
CH,CHBrCOOH e .bromopropionic acid 2-broniopropanoic acid
a
HOCH,CH, COON -hydroxypropionic acid 3-hydrox\propanoic acid
H,NCHICHS CH,....COOH ?.aminobutyric acid 4-aminobutanoic acid
We will now discuss the halo acids and hydrosy acids at length in this chapter. In
amino acids, the amino group is present in the hydrocarbon chain of a casboylcc acid.
Therefore, this class of substituted acids will he better discussed after the treatment of
alipbatic,amnies and alongwith Proteins of which amino acids are the building blocks,
539

1. HALOCAROXYLIC ACIDS
Halo acids or Halogen-substituted acids are those in which one or more H atoms of
the hydrocarbon chain of a monocarboxylic acid are replaced by halogen atoms (F, Cl, Br
or I). They are classed as a, p . or y-halogeno acids according as the halogen is attached to
a, or y carbon of the chain with respect to COOH group. For e%ample,
Cl
CICH,COOH ,CHCOOH, CI CCOH
chioroacetic acid CV I
dichioroacetic acid Cl
trichioroacetic acid
F
CH,_(!iICOOH BrCH1 CH5COOH ICH,CH,--CH,-COOH

-Ouoropropionic acid -brornopropionic acid '-iodobutync acid
Of the a, 1, y halogen acids, a-acids are the most important.
A. FOR a-HALO ACIDS:
(1) a-chloro and a-bromo acids are prepared conveniently by Hell-Vohlard-Zeiinsky
(HVZ) Reaction in which a given monocarboxylic acid is treated with chlorine and bromine
in presence of red phosphorus. Thus,
red P
CH3COOH + Cis C1CHOOH + HCI
acetic acid chioroacetic acid
Br
red
CH,-CH,COOH + Br, - p CH3CH.COOH HBr
propionic acid -bromopropionic acid
The second and the third a-hydrogens (if any) can be replaced successively by using
excess of chlorine or bromine,
Cis Cl a, Cl
CICH,COOH - CHCOOH -.-. C1CCO0H
chloroacctic acid red P Cl" red P Cl/
dichioroacetic acid trichtoroacctic acid
This reaction proceeds only when there is a a-hydrogen atom in the substrate
carlxylic acid.
(2) a-Chloro acids can also be produced by the reaction of suiphuryl chloride on the
corresponding carboxylic acid in presence of iodine as catalyst.
CH,CHI COOH + 2SO,Cl, 2S0, + 2HCI + CH,HCOCi

propfoaic acid
Cl
H2O.boil I
-+ CHICCOOH
(HO) a-bromopropioaic acid
(3) a-Chloro and bromo acidran also be obtained by halogenation of an alkyimalonic
acid followed by decvboxylation.
Br Br
I COOH Bri paued . I COOK 140-150' I
CH,CH( -_. CH.C/ -_. CH,.CRCOOH +CO,
'COOK into hot acid 'COON a-bromopropionie acid
methylmalonic acid

541
Substituted Carboxylic Adds
(4) lodo acids can be synthesised by treating chioro or bromo acids with potassium
iodide in acetone or methanol solution.
Br I
..- acetone or I
. CHCH---COOH + KBr
+-
CH3CHCOOH + K!
a.bromopropionic acid methanol a-iodopropionic acid
(5) By the action of hydrogen halide or phosphorus halide on a hydroxy acid.

OH Br
CH,CHCOOH + HBr -. CH,CHCOOH - HSO

lactic acid, a.bromopropionic acid
a-hydrosypropioriiC acid
B. FOR 3-HALO ACIDS:
(I) 3-Halo acids may be prepared by the addition of hydrogen halides to a, p-unsaturated
carboxylic acids.
+. CH5COOH
CH 3 =CHCOOH HBr -^ Br._CH,CH,COOH
+
acrylic acid .brcmopropionic acid
It is an anti-Markovnikov reaction.
(2) By the addition of halogen acids to x, 1s-unsaturated aldehydes followed by oxidation
of the .haIoaldehyde produced (anti-Markovnlkov product).
401
CH, CHCHO -- HCI + C1CH 1CH1 CH0 ClCHa_CHCOOH
acrolein .chloropropionaldehYdC HNOa !-chloropropiooic acid
(3) By refluxing alkene cyanohydrins with 40% hydrobromic acid.
HOCHCH,---CN + 21Br + H 2 O p Br_CH,CH,COOH NH4Br

ethylene cyanobydrin .bromopropioic acid
(4) By oxidation of alkene halohydrins with cone nitric acid.

(01
ClC FI 1 CHCFl 1 ---OH -+ Cl_CH,_CH,CH2COOH
tiimei byleise chtorohydrl cone HNO3 -chlorobulyric acid
(5) By the action of a hydrogen halide or phosphorus halide on a hydroxy acid.

CH 5OH_CHrCO0H + HBr CH1BrCH1COOH + H2O.
.bydroxypropioniC acid .bromOpWpjOfllC acid
C. FOR y.HALO ACIDS:

(1) yHalo acids may be prepared by the addition of halogen acids to , y.unsaturated
carboxylic acids (anti.MarkovnikOv addition).
CH=CH-_CH,COOH + iBr f Br_CH1_CH,CH1COOH

but-3. enoic acid y-bromobutyriC acid,
(a 0, T-unsaturated acid) 4.bromoblitailoic acid
(2) By heating y-hydroxy acids with conc halogen acids or by treatment

with phosphorus
halides, or with SOX, (SOCI 5 or SOBr5).
HO_CHa_CHr_CH 1 COOH + ItCI - CI_CH,CH,CL3j001

.hydroxybutyric acid y-clIorcbutyric acid
D. FOR a., AND i-HALO ACIDS:

(I) All types of halo acids can be prepared by heating appropriately substituted bydroxy
acids with halogen acids or phosphorus halides or SOX, (XCI, Br).
However, a, p, and i-iodo-

acids are obtained by treating the corresponding chioro or bromo acids with potassium iodide in
acetone or methanol (Finkelstein Reaction).
CH1OH
BrCH 2 CHCH,00OI f KI -0 l CHr--CH,--CH, COOIj + KBr
i . bromobvtyric acid y.Jodjobiyrk acid
(2) Any halo carboxylic acid may be prepared by the use of Hunadlecker Reaction.
For example, y-bromobutyric acid is prepared from ethyl hydrogen glutarate according to
the following sequence of reactions.
CH 2 COOC2 H AgsO 1CH2COOC1H
CH, -p .CH,( - +
\cH1cooc1 H, moist 'CH,COOA g
ethyl hydrogen glularaic
Br, in,CH,COOC 2 H, +-
_...^ CH ,/ AgBr + CO,
CC) 4 "CH2Br
CHCO0C2H, H2O!fi CH2C00H
CH, -+ CH/
' "CH2Rr boil CHBr
13 -bromobutyric acid
PROPERTIES OF HALO ACIDS
Halo carboxylic acids are stronger acids than the parent carboxylic acids. This is due
to the electron-withdrawing inductive effect (I effect) of the halogen atom. The increased
elecron withdraw] from the 0 H bond of the acid favours the release of proton from the
carboxylic group.
'S
fr CiCC--o + H4
/
CI, C
The inductive effect is the greatest with the maximum number of a-fluorine atoms and hence
trnfluoroacetic acid is the strongest organic acid known. This inductive effect decreases as the
halogen is removed farther away fcom the COOH group, thus lowering the acidity of the acid
concerned.
Halo acids give the reactions of both a cirboxylic acid and alkyl halide.
ClCH2---+COQH
ALKYL HALIDE CARBOXYL
FRAGMENT GROUP
(1) Substitution Reactions of Halogen atom. The halogen atom in an a-halo acid is
more reactive than it is in an alkyl halide, and hence can be substituted by a variety of
nucleophiles such as OH, OR, CM, I, NH, ;NH3, R etc. These reactions generally take
_ _
place by a bimolecular nucleophilic substitution (SN 2) mechanism as shown below.
P P
NC) + C
)- (
HO ---is p c
+
H
H CO,H
CO2 __
N
MAJi5/7/Opj STATE

Substituted Carboxyllc Acids 54
The halo acids can be regard.ad as valuable intermediates for conversion of saturate
monocarboxylic acids into a wide range of substituted acids such as amino-, bydroxy . , cyano
acids etc. Some of these nucleophilic reactions are stated below.
+ AgOH -+ HOCH1COOH + AgCI

moist hydroxyacetic acid
ethanol
+ AgNO3 + 02NCHaCOOH + AgCI
nitroacetic acid
methanol
+ KI + 1CH2COOH + KCI
or acetone iodoaceiic acid
CICH5COOH
chioroacetic acid ethanol
- KCN * NCCH 2COOH + KCI
- cyanoacetic acid
ethanol
+ 2NH 3 p I-T2N CftCOONU 4 +HCI
amm aminoacetate
H/l{O
ftN. CHCOOH 4- NH4CI
- -aTnisoacetic acid
Similarly -, y . and 6-halo acids show many reactions of alkyl halides but here thr
halogen atom is less reactive than it is in x halo acids.
(2) Reaction with Alkalis. The behaviour of halo acids with aqueous alkalis is
particularly interesting inasmuch as it depends upon the position of the halogen atom on thr
carbon chain.
(i) -i-ialo acids are hydrolysed to give the corresponding hydroxy acids.
Br 011 OH
CHaCH2CHCOONa CHaCHaCHCOOH
CU5 CH5CHCOOH + NaOH a-hydroxybutyric acid
a-bromobuiyric acid
(ii) a-Halo acids are similarly converted into the corresponding .hdroxy acids which
on further boiling with alkali eiiminatc a molecule of water to form a, 3-unsaturated acids.
Br OH
r
aq NaOH, bolt - . H10
CH3_CHCH5C0O11 CH3CFJ--CH1COONa
.bromobutyrir acid t4a15r, l-tO [
H/H5O
C1-1_CL-I=CH.COONa + CH3_Cl1=CHCOOH
crotonic acid
(ill) y- and 6-halo acids are convened into y and -lactones respectively.
Cl -
CH--
'O
I + NaCl
+ Nas)ht -.--. H I C( I
i-ctslorobutyric acid 'CH'CO

Br
C"'--O
'CO NaBr
CH 2 CF1 1 H 2_ CH 2_CO0 H + NaOH -----. HIC.(
broiflOpentanonic acid .
(!) ti-halo acids give the corresponding c-hydroxy acids.
(1)NaOH
BrCH 1C}I 1CH 1CH,CFJ3 C00H -,. HOCE{1CH2CH.CH,cH3COQH
-t- NaUr
c.bromocaproic acid (2) H c-hydroaycaproic acid
MONOCHLOROACETIC ACID, Monachlorocihanoic acid, CIC112C001-1
Preparation. (I) It is prepared industrially by passing chlorine into glacial acetic acid
at 100 in the presence of red phosphorus (HYZ reaction).
red
CHaCOOH + Cl, --+ ClC FI 2 COOH + HCI
acetic acid l chtoroacetic acid
(2) It is 1so obtained by agitating t rich loroethylene with 90 0/" H2SOI.

cii CI CI
I 1t2SO1 I I hydrolysis
HC=CCl + HO --* F-ICC--Cl
Lrichloroethytene, I j +H20. HCi
1, 1, 2-trichloroethene
H OH
C1 OH Cl.
I I -H20
HCCOH HCC'
II I
H 01 H
unstable chtoroaoeijc acid
Properties. Monocliloroacetjc adl is a crystalline solid, mp 62, It is soluble in wale

and ethanol and has corrosive action on the skin. It responds to all the general reactions 0
halo acids descrit,ed earlier. It is readily esteritied with absolute ethanol and uIphui ic acid.
it2SO4
CLCH.COOH C-1-4 OP ClCJ-I 2COOC 2 H, + I-{O
ethy. hIoroacetate
Ethyl chioroacetate when shaken with aqueous amnwni-a, is converted into chloroacetair, de.
The latter on dehydration with P 10 5 gives chloroacetonitrile.
CkCH2COOC,FJa NH 3 CICH2CONH5 C1HON

chioroacetamide
PiO
CIC}I *CON}4 - .ClC}ICN
H10 chtoroacetonitrlte
Chloroacetic acid is used for the synthesis ofglycine and of the dye known as indigotin.
Cl
DICHLOROACETIC ACID, Dith ioroethanoic acid, CHCOOH
Cl'
Preparation, it is obtained by adding calcum carbonate to a warm aqueous solution

of chloral hydrated followed by addition of sodium cyanide. The function of sodium cyanide
is not completely understood but presumabl y it helps in splitting out HC] from the chloral
hydrate molecule yielding unstable enol which readily ketonises to dichioroacetic acid,
CI OH CI OH
I I
2 ClCCOH + CaCO2 - 2 ClC= COFF + CaC1 5 + C01 H,0.
I11 unstable enol (A)
CI H

ubsUWted Carboxyhc kias
CIOH
I I ketoiil,ea Cl..
C!C=COH - 'CHC-011
(A) aNacN CV
dichioroacejic icid
Properties. Dichioroacetic acid is a colourless liquid, bp 190. It is soluble in water.
When carefully hydrolysed with dilute alkali, it gives glyoxylic acid.
H
Cl NaOH HO I CHO
"CHCOOH-l-2H10 "CHCOOH -.----,. O=CCOOH or
ci" 2HCI HO" glyosylic acid COOH
able
When hydrolysed with cone NaOH (or KOH) it gives sodium oxalate and glycollate as
under these conditions glyoxylic acid first produced undergoes Cannizzaro Reaction.
CHO (conc NaOH) CH IQH COOH
+HO -+ +
COOH COOH COOH
glyoxylic acid glycollic acid oxalic acid
INaOH jNaOH
CH1OH COONa
COONa COONa
sod glycollate sod oxalate
TRICHLOROACETIC ACID, Trichioroethanoic acid, CI3CCOOH

Preparation. It is obtained b y oxidising chloral hydrate With cone nitric acid.
CI OH C1
H HNO3 H
CIC--COH + (0] - ClCCOH + HSO
(!:l
chloral hydrate trichloroacetic acid
Properties. Trichloroacettc acid is a colourless crystalline solid, mp 58. It is soluble

in water. Upon hydrolysis with boiling water or with dilute alkali, it gives chloroform and
carbon dioxide.
ci o ci
1+11
COH I Ci4 -f- c07
TRICHLORO ACETIC CHL OROORM

4CIO
The ease with which cc bond is broken here is due to the inductive effect of the three
chlorine atoms which weakens the bond appreciably. The possible mechanism is:
00
tnhIr\ ___
Cl-i-C--L--COH - CO + CHCia
CI
HYDROXYCARBOXYLIC ACIDS
Organic compounds which contain an alcoholic OH group and a COOH group within
a single molecule are called bydroxycarboxylic acids or simply hydroxy acids. They could be
regarded as derived from carboxylic acids by replacement of one or more hydr.ogens in the
hydrocarbon part of the molecule by corresponding number of OH groups. Thus we have
mono-, di-, tri-, or polyhydroxy acids according as one, two, three or many hydrogen atoms of
the carbon chain are replaced by OH groups. Unlike halo acids, hydroxy acids cannot contain
more than one OH group on the same carbon, since the presence of two or three of them
would make the molecule unstable.
Some hydroxy acids are found in nature and are of biological importance. The most
significant of these is lactic acid (x . hydroxypropionic acid, which is the acidic constituent of
sour milk and also an important muscle metabolite. Other common hydroxy acid is citric
acid, the sour component of citrus fruit and also an important biochemical intermediate.
Tartaric acid is yet another well-known member of this class which occurs in grapes, tamarind
and other fruits.
NOMENCLATURE
Hydroxy acids are named as hydrox y derivatives of the parent carboxylic add. In the
Common System, the position of OH group k indicated by a, 3, y etc, while in the JUPAC System
it is shown by a number placed before the prefix hydroxy, Some hydroxy acids which occur
in nature get their trivial names from the name of the source.
Table. Names of some Hydroxy acids.
HOCHlOOH hydroxyacetic acid hydroxyethanoic acid

glycollic acid
CH,CHOH.00H a-hydroxypropionic acid; 2-hydroxypropionic acid

lactic acid
CF110HCH,---COOH -hydroxypropionic acid 3-hydroxypropionic acid

hydracrylic acid
CH(OH)COOH a, a'-dihydroxysuccirtic acid 2, 3 .dihydroxybutanedioic acid

tartaric acid
cH(OH)COOH
CH(OH)COOH a. hydroxysuccinic acid; 2-hydroxybulanedioic acid

malic acid
H5COOH
CHCOOH
(Of)_COOH citric acid 2-hydroxypropane-1, 2, 3-

tricarboxylic acid
CH1COOH
It may also be noted that monohydroxy acids are class'd as a-Hydroxy acids, -Hydroxy
acids, y-Hydroxy acids and &-Hydroxy acids depending on the fact whether the OH is bonded
to the a, A, y or 8 carbon of the chain with respect to the COOH group.

SubsUwted C4rboxy!k Acids 547
(I) By the hydrolysis of the corresponding halo acid with moist silver oxide (AgOH)
or dilute sodium carbonate solution.
Br OH
CHI(HCOOH + AgOH - CH2CH--00OH

a-bromopropionic acid a-hydroxypropionic acid
(2) By the action of nitrous acid (sodium nitrite and dilute mineral acid) on amino
acids.
HINCH3COOH + HO--NO -b H0CH2COOH + N3 + H30

aminoacetic acid, bydroxyacctic acid,
glycinc gIyoIlic acid
Since naturally occurring amino acids are i.derivatives, this method is particularly useful
for the preparation of cz.hydroxy acids.
(3) hydroxy acids are best prepared by Cyanohydrin Synthesis. An aldehyde or a

ketone is first converted to cyanohydrin by addition of HCN to it. The cyanohydrin ic then
hydrolysed to give the hydroxy acid.
0 OH OH
I
H+H3O
RCH + HCN -.--- RCCEN -._ RCHCOOH
aldehye boil a-hydrozy acid
H
canobydrin
OH OH
I
I
e.g., CHsC--H + HCN - CH(CNCH,CH-COOH
-+
acelaldehyde boil lactic acid
H
acetaldehyde
cyanohydrin
(4) By the controlled oxidation of glycols with dilute nitric acid. Thus,
dii HNO1
HOCH3CH3OH + 2[01 _- HOH 3CCOOH + H10
glycollic acid
dill HNO3
CH,CHOHCH 1OH + 2(0] CH,CHOHCOOH + H30
1, 2-propane-diol lactic acid
(5) By reduction of the available dicarboxylic acid by the following sequence of re-
actions.
CH,COOHcH3 cooc5H5 NIJC5HaOH CH1OH

I
CH,COOH
succinic acid
+C1H1OH.I
CH1COOH
ethyl hydrogen
I.
y-hydroxybtyr acid
- ZCOOH
succinatc
The reduction of half-esters of dicarboxylic acids is particularly useful for the prepara-
tion of T-hydroxy acids.

(6) -hydroxy acids can be prepared by Reformatsky Reaction.
0 OZnBr
H Zn
CHC--CH, + BrCH,COOC2H, CHF_cLCHICOOC,H,
acetone ethyl bromoacetate
CH,
OH
HjHO I
CH,C--CH,COOH
CH5
34ydroxy-3-metbylbutanoic acid
Similarly, y. hydroxy acids can be obtained by taking -bromo-esters instead of a.bromo-
esters.
(7) a-, 3-., y- or 8-hydroxy acids may be synthesised by the catalytic reduction of the
respective keto esters. Thus,
H2, Ni hydrolysis
CH3C0CH2C00C1H5 +.CH3CHOHCH,COOC,H, -f CH8CH0HCH2C00H
ethyl acetoacetate OO, (I) KOH -hydrosybutyric acid
pressure (2) Hf
PHYSICAL PROPERTIES
The hydroxy acids are colourless, crystalline solids or syrupy liquids. Their melting
and boiling points are much higher than those of the corresponding monocarboxylic acids. They
are more soluble in water than the parent carboxylic acids and alcohols, because both 'he func-
tional groups OH and COOH present in them can form hydrogen bonds with water. Many
hydroxy acids, but not all, exhibit optical isomerism.
Acidity. The hydroxy acids are stronger acids than the corresponding monocarboxylic
acids. This is so because the strongly electronegative hydroxy group withdraws electrons from
the carbon of the carboxyl group, thus facilitating the ionisation of the proton.
H 0 HO
1111 __
- Ho-c.---C-0 + H
H H
HYDROXYACETIr ACID HYORO, 1A ETA If

ION
Thus hydroxyacetic acid (K.-14-76x 10 3) is a considerably stronger acid than acetic

acid (K.., 18 x 10- 5). Since the inductive effect due to the hydroxy group diminishes rapidly
as it is farther removed from the COOH group, the acid strength falls. 3-Hydroxypropjoaic acid,
HOCH1 CH,COOH, is only .lightly more acidic than acetic acid.
CHEMICAL PROPERTIES
1-lydroxy ac,ds would be expected to display the reactions of thealcohoiic OH group and
of the COOH group. The two functional groups, OH and C0OH, do not interfere with each
other and react independently when they are widely separated. In case a given reagent can
react with only one function ; only one will react, and if it reacts with both functions, both will

Substituted Carboxylic Acids 549
react, Thus hydroxy acids give a variety of derivatives as illustrated below.
QH
- 4.
+ NaOH, - RCH(CH,).COONa + HO
sod salt
ONa
+ Na -, RH(CH,)CO0N + HO + JH,
QH
H5SO4
+ C;H;OH ---+ RCH(CH;)pCOOCH; + HP
ctbyl eater
(
OH OH
OH I -+PA I
RCH(CH5).COONH4 -..R.-CH(CFI;)piCONHs
+ NH 3
animsalt A amide
R H(CH5),,COOH
hydroxy acid Cl
I
+ SOCI3 -* RCH(CH,),,COCI -. R
H0
or PC], monocbloro acid chloride
A.
-- 2111 s RCH1(C112),.000H H
saturated acid
0
dii HO
+ [0J ---# R(CH,)..0001i + H1.,
keto acid
OCOCHZ
+ CH 5COCI -, RCH(CH,),COOH + nd
ester carboxylic acid
In the above reactions of hydroxy acids, the alcoholic OH and COOH groups react
independent of each other. In addition, the hydroxy acids give reactions in which the two
functions, the hydroxy group and the carboxylic group may react with each other to form esters.
These reactions are very interesting because the nature of the product formed depends on the
relative position of the hydroxy group to the carboxyl group in the molecule.
Action of Heat on Hydroxy adds. As already observed, the alcoholic ON *nd COOH
present in a hydroxy acid may react to form an ester. The type of ester obtained depends on
the relative location of the two functions on the carbon chain. Also, the ester formation may take
place between the OH and COOH of the same molecule (intramolecular esterification) or two
different molecules (intermolecular esterification) of a hydroxy acid. The action of heat on
-, J3-, y.hydroxy acids is given below.

(I) a-Hydroxy Acids on heating give cyclic esters known as Lietides. This name was
onginally assigned to the cyclic diester obtained from lactic acid.
Here the ester formation takes place between two molecules of the hydroxy acid so as
to get a stable six-membered ring in the product.
R\ D R\
HO" OH a/ \n
U /
HO /00 4II0 ' CH
CH \
O' R
\R
a-.hydroxy acid
a lactide
(2 molecules)
This lactic acid undergoes intermolecular esterification to form a lactide as follows.
CH,CHC/O
HO" "011 -* cH;7cH_c
c :
HO ,OH
"CCHCH1 2H30 ,>C_CHCHZ
0/
lactic acid Wide
(2 molecules)
Similarly, glycollic acid yields the lactide commonly known as glycollide.
(2) f3-Hydroxy acids are not converted to cyclic esters on heating. On the other hand,
when heated alone or treated with a strong mineral acid, -hydroxy acids undergo elimination
of a molecule of water to yield unsaturated acids. The a, -unsatuatcd acid, rather than the
, y-unsaturated acid, is formed preferentially because the a, a-unsaturated acid is more stable
due to conjugation between the carbon-carbon and the carbon-xygen double bids,
0
I B a or H+ B a II
CH-cH-CH--.COOH CH3-CH=CH-C...0H
HO crotonic acid
(a, B-unsaturated acid)
OH H
-h ydroxybutyiic acid
This reaction is similar to dehydration of an alcohol to an alkene.
(3) y-Hydroxy acids when heated undergo an intramolecular estrification to form a
five-membered cyclic ester or internal ester known as a lactonc.
CH._C
B a HSO
H1-CH-CH,-OOH -+ >0
A C0-b{1
()H
y-hydroxybutyric acid y-butyrolactotse
The lactone produced from a y hydroxy acid is known as a y.!ac:one.
(4) 8-Hydroxy acids also undergo an intramolecular estrification spontaneously to form
a six-merhbered cyclic ester or internal ester, known as a S-lacione.
H10
CH_C/<
CU_CH,- .CH,_CH_COOH ---+ H,C< /0
OH CHI--CH
l-hydroxvlic acid alcrolactone
Substituted Carboxylic Acids
The reactions (3) and (4) which yield a lactonc are termed Lactonlsatloa.
(5) c-Hydroxy acids, in which carboxyl and hydroxy groups are separated by five
carbons
have little tendency to form lactones since the cyclic structure would bc required to have seven
members, an unstable structure. Instead, they undergo intermolecular estrjfication to form
linear polyesters.
HOCH,)5-OH 1-0--(CH,^ L1 + n H10

c-hydroeycaprojc acid a linear polyester
The higher hydroxy acids with larger number of carbon atoms between OH and COOP also
form linear polyesters.
Reactions of Laclones. The reactions of lactones will be particularly useful in the study
of carbohydrates later on.
(I) Free lactones are rather reactive compounds and in contact with water the ring opens
and they produce the parent y- or -hydroxy acid.
H2CC
/1
HCCOH
1
Ha CCR1OH
H2CCH5 y-bydroxybutyrjc acid
ybutyrolactone
(2) When a lactone is treated with a base, the ring opens to form the salt
of the
corresponding hydroxy acid However, acidification reforms the ring.
0
CHICH, \ NaOH CF15CH1C--0'ta
HC( C=O =
11+ 'CH.OH
sod hydroxyalerate
(3) Reduction of the lactones with sodium anialgam gives the respective saturated
monocarboxylic acid with the opening of the ring structure.
A0 0
HCC--OH
/
0 + 2H -+
H10 "s
HICCH,
ibutyrolactone mbuyric acid
(4) When treated with boiling halogen acids, lactones give the corresponding halo acids.
0
HsC_t H5CCOH
I )O+HBr -+ I
HCCH,--Br
H2CCH, TbrOirio-a-bUtyriC acid
Tbutyrolactooc

GLY(OLLIC ACID, Hydroxyacetic acid, 2 .Hydroxye:hanoic acid, HOCH1COOH

It is the simplest hydroxy acid known and occurs in unripe grapes, sugar cane and beet.
\Prepar.tioa. (1) Glycollic acid is prepared by the hydrolysis of chtoroacetic acid with
boiling lil alkali, followed by acidification with dii hydrochloric acid.
-+
CICH 1 000H 4- 2t4aOH -p HOCH 5COONa + NaCl + H10
sod glycollate
+
HOCH1COONa + HCI -+ HOCFJ 1COOI{ + NaCl
glycollic acid
(2) Technically it is obtained by the electrolytic reduction of oxalic acid

00
- Ii It
HO--CC-01-1 - 4[H] - 1-10CI!CO0H
oxalic acid glycollic acid
(3) According to a recent method, glycollic acid is manufactured by heating a mixture of
form;tldehyde, carbon monoxide and water at 1600_I 100 under pressure in presence of sulphuric
acid as catalyst.
H
I
HC =0 + Co +%0 -+ HOCH1COOH
11+
ormaldehyde
f A giycolllc acid
Properties. (Physical). Glycollic acid is a white crystalline solid, mp 800. It is readily

soluble in water, ethanol and ether. It is a stronger acid than acetic acid though weaker than
chioroacetic acid.
(Chemical). It gives the reactions of both a primary alcohol and a nionocarboxylic acid.
(1) As a primary alcohol, glycollic acid gives the following reactions.
HNO3 [0]
I +0 a HOOCCHO -+ HOOCCOOH
maid) oxalic acid
glyoxytic 11NO3
HBr - 1, HOOCCH 5Br HO

FIOOC CH1OH a-bromoacciic acid
glycoltic acid
I L
+ 21-11 9 HOOCCHs + I + HO
(red P) ccicadd
+ CH3C0CI - HOOCCH1OCOCH1 + HQ
acet$glycolilc acid
(2) As carboxylic acid, it forms salts with alkalis and decomposes bicarbonates as also
carbonates. In pre'ence of cone: 111SO4, glycollic acid reacts with alcohols to form esters.
HO CH 1COOH + NaOH HOCH1COON + I{0

sod gtycollatc
HSO4
HO CHCOOH + CH 3OH HOCH1COOCH, + HSO
methanol methyl glycollaic.

55:
Suatltuted Corboxyt Ic Acids
With PCl and Na, the reaction takes place at both the hydroxy group and carboxy
(3)
group independently to form di-derivatives.
3 + 2HCI
HO_CH,COOH + 2PC1 6 -' Cl CH 2 COCI + 2P0C1
glycollic acid chioroacetyl chloride
HOCH,_COOH + 2Na -. NaOCH,COONa + H1
disodlum glycollatc
On heating, two molecules of glycollic acid eliminate two molecules of water tc
(4)
form a lactide called glycollide.
/ OH HO A 0C
HIC\ / CH S .. HC(' CHa
+
OH HO
0
glycollide (a laclide)
When warmed with concentrated sulphuric acid, it forms formaldehyde and carbor,
(5)
monoxide.
HO_CH1C0011 HCHO + CO + H10
I.
glycollic acid formaldehyde
Uses. Glycollic acid is used chiefly in cloth printing ; and as a synthetic reagent.
CHCHO}I---COOH
LACTIC ACID, c.HydroxyprOpiOfliC acid, 2 . 11ydroxvpropaisOic acid,
Lactic acid is the main constituent of sour milk and hence its name - (Latin, lac=milk).
It is found in the blood and muscle tissue shere it is formed by the decomposition of glycogen
(C4 11 1105)n. This reaction furnishes energy needed for muscular work. The lactic acid produc-
ed in muscles due to work is then reconverted into glycogen during rest.
Lactic acid molecule is dissymmetric and, therefore, exhibits optical isomerism. Ordinary
lactic acid prepared in the laboratory or industry is the racemic mixture. d-lactic acid or
sarcolactic acid )sarx, meaning flesh) is obtained from fatigued muscles by extraction with
solvents. 1-lactic acid is prepared by the fermentation of lactose, glucose or sucrose under the
influence of the enzyme Rhiwpus Oryzase.
CH, CH,
HCOH HOCH
OOH COOH
()-lacdcacid (+)-lacticaCid
or 2 (R)-H y droxyproplotslC acid or 2 (S)HydrOxYPfOPlOolC acid
Preparatloa. Lactic acid may be prepared by the following methods:

(1) By bromirsating propionic acid and hydrolysing the resulting 2-bromoprOpiOniC acid
by heating with dilute sodium hydroxide solution.
QH
Br, (l)NOH I
CHrCHr. COOH -, CH,CHCOOH CHHC0O14
pcoplonlc acid s-bromopropionk. acid (2) Nfl lactic acid
reacting ace.lde
(2) By the hydrolysis of acetaldehyde cvanc,hydrin which is obtained by
hyde wig HCN (lndEstriat).
9H Q1{
HCN bydrolysis I I
CH.CH=O - CH,CHCN -+ CI-i,--CHCOOH
acet.ldthyda (KCN+H(.I) acetsidcbyde H, boll lactic acid
cyamikiydrin
Organic Chemistry - 36
Advanced Organic Chemiry
(3) By the oxidation of propylene glycol with dilute nitric acid.

OH OH
UNO3 I
CH,CH--CH2OH + 2(0] -+ CHCE-10001-1 + H2O
propylene glycol lactic acid
(4) By the fermentation of Sucrose. Lactic acid is obtained on a commercial scale by
c fermentation of sugar by the microorganism Bacillus acidii lactit (BAL).
C11 H2 011 + H 2 0 -. CH I20. + Col-1120a

sucrose glucose fructose
BAL
C.H15 0. -. 2CH3CHOHCOOH
tactic acid
In actual practice, a dilute solution of molasses is treated with sour milk (which contains
L) in presence of CaCO 2 . Thus fermentation is carried in almost neutral medium at 35-40,
hich conditions are congenial for the growth of micro-organism. As the lactic acid is
roduced, it combines with CaCO, to form insoluble calcium lactate. The calcium lactate
filtered off and decomposed with a calculated quantity of dilute sulphuric acid. The lactic
id set free in the aqueous solution is recovered by distillation in vacua'.
Lactic acid is also. made industrially by first hydrolysing it to glucose and then carrying
e fermentation as described above.
Properties. (Physical). Lactic acid il a colourless crystalline solid. The two
antimeric forms melt at 53, while the racemate has the melting point 18. At ordinary
uperature, the commercial lactic acid is a syrupy liquid having sour taste. It is hygroscopic
id
miscible with water, ethanol and ether in all proportions. Optically pure lactic acid has
specific rotation of +382 (for dextrorotatory) and 382 (for laevorotatory).
(Chemical). Lactic acid is a monocarboxylic acid as well as a secondary alcohol.
,SECONDARY
ALCOHOL
GROUP
'Ho
'II I
cu c, I CHOH - cOoH
i
ow" I
5(cofioA/y I CIR80Xy
4 1COH01 GROUP I GROUP
Thus lactic acid gives all the reactions characteristic of a carboxylic group and a
condary alcohol group.
(I) Formations of Salts and Esters, Being a monobasic acid, lactic acid reacts with
Ikolis and alcohols to form salts and esters respectively.
CH5 CHOH.CooH + NOH -, CH 5CHO}(--000N + HSO

lactic acid sodium lactate
dry Ha
CH,( HOHCOOH + CH 5 OH -+ CHsCHOH--COOCH, + H10
gas methyl lactate
oth sodium and methyl lactate are laevorotatory. Similarly, with ethyl alcohol in the
resence of cone HSO 1 , lactic acid forms ethyl lactate, CH3CHOHCOOC2H5.
Substituted Carbox1llc Acids 555
(2) Action of Heat. On heating it forms a cyclic ester called lactide.

2
O-
OH HOOC
/ A
CH,CH CH,CH
HCCH1 -p HCCH + 2HO
+
COOHHO" fO
lactic acid (2 moles) 0

lactide
1300, lactic acid
(3) Action with H,SO4. When heated with dilute sulphuric acid to
decomposes to yield acetadehyde and formic acid.
OH . 0
CH,CHCOOH -+ CHCH=O + HCOH

lactic acid 130 acataldehyde formic acid
If heated with conc ! 15S01 , the decomposition takes place in the above manner but th
formic acid produced decomposes frthcr to yield carbon monoxide and water (Test).
QH
I coecffS0a
CH3CH--cOOH - CHCH=O + CO + 11,0
lacticacid A
(4) Action with PCI,. Both the OR and COOL-I groups are attacked by phosphorus
pentachloridc giving lactyl chloride.
OR
CH 3CCOOH + 2PC1, -. CH1(HCOCl + 2 POCI, + 2HCI

lactic acid lactyl chloride
Lactyl chloride is obtained as a clear product when thionyl chloride is employed
instead of PCI,.
(5) OxltIon. When oxidised with a weak oxidising reagent such as silver oxide
(Ag,O) or Fenton's reagent (H2O,/Fe'), lactic acid forms pyruviqacid.
CH,CHCOOH + Ag,O -, CH,_,CCOOH + HO + 2 Ag

lactic acid pyruvic acid
With potassium permanganate, lactic is oxidised to give acetic acid by fission of the
molecule.
OR
I EM004
CHaCBCOOH + 210 1 -.. CH,COOH + CO, + H.O
lactic add acetic add
(6) Redictlon. Lactic acid is reduced to propionic acid wi n heated withh.oic
acid.
OR I
126' I
CH,CHcOOIJ + RI ---# CH,CHcOOH + 1110
lac add s-lodopropionlc acid
I 126'
CHCHc0OH + HI CH,CH,COOH + Is
proplonic acid

(7) Jodolorm Reaction. Like other organic compounds containing the group
CH,CHOH--, lactic acid also forms iodoform when treated with iodine and alkali.
CH,CHOHCOOH + I, CHICOCOOH + 2H1
pyruvic acid
CFI3CO--COQH + 60H + 31 s 2 C1 3COCOOH + 6 H10

triiodopyruvjc acid
C13COCOOH + 2NaOH -. CHI 3 + ( COONa) + H10
jodoform sod oxalate
Uses. Lactic acid is used (1) as a mordant for dyeing wool ; (2) for deliming of
hides in tanning; (3) as acidulaat in candles ; (4) as calcium and iron lactate in medicine to
make up the deficiency of calcium and iron in body ; (5) as ethyl and butyl lactate which are
employed in plastic industry.
HYDRACRYLIC ACID, -Hydroxypropionic acid, HOCI12CH1---COOH
It is isomeric with lactic acid.
Preparation. (I) By the hydrolysis of -chIoropropionic acid with moist silver oxrA
ClCHyCHCOOH + AgOH -i HOCH,---Cff5--COOH + AgBr
-chloropropionIc acid hydracrylic acid
(2) By the hydrolysis of ethylene cyanohydrin, which is obtained from ethylene
chlorohydrin.
KCN NaOH
HOCH,CH,---CI -+ HOCH I CH,--CN -+ HOCH,CH,--COOH
ethylene chiorohydrin . hydrolysis . hydracrylic acid
Properties. Hydracrylic acid is a colourless syrupy liquid and gives the usual reactions
of a primary alcoholic OH group and COOH group. It is not optically active since it does not
contain an asymmetric carbon atom. When heated alone or with dilute sulphuric acid, it
loses a molecule of water to produce acrylic acid.
9H I
CH1 CHCOOH -.-. CH=CHCOOH + H10

hydracrylic acid acrylic acid
Upon oxidation with chromic acid, hydracrylic acid yields malonic acid.
,CH5 OH K20207 JCOOH
H,C( + 2[01 -+ H3C( + H10
COOH H2SO4 COOH
hydracrylic acid malonic acid
Here the primary alcohol group (CJI1OH) is oxidised to a carboxyl group (COOH).
SOME HYDROXY POLYCARBOXYLIC ACIDS

MAUC ACD, Monohydroxeeln1c acid, 2-hydroxybulane-1, 44oic acid,
HOOCCHOHCHI--cOOR.
It was first isolated by Scheels in 1785 from green apples. Its calcium salt (calcium acid
malate), commonly called Sugar Sand crystallises when maple sap is concentrated by evapotion.
It also occurs in fruit juice obtained from grapes, berries Qf the mountain ash and many other
fruits.
Preparation. (I) Malic acid is best prepared from green mountain-ash berries. The
extract thus obtained is treated with lime when malic acid is precipitated as insoluble calchi
malate. Calcium malate is then filtered off and is decomposed with calculated quantity of dilu
sulphuric acid.

ubstStute Carboxyflc Acids

It is produced technically by heating maleic acid (obtained from benzene) with
(2)
dilute sulphuric acid under pressure.
HSO, HO-CH--COOH
CH COOH QH
+1
CH_COOH H under Press ure
CH,COOH
malic acid
m1cic acid
It may also be prepared by the partial reduction of tartaric acid with hydriodic acid.
(3)
HO_CHCOOH
HO_CHCOOH +H20+1.
+2H1 - I
ciI.-COOH
HO CHCOOH
malic acid
tartaric acid
by the hydrolysis of bromosucciflic acid with moist
(4) It is prepared in the Laboratory
ilver oxide.
Br.CHCOOII HO_CHCOOH
AgOH -* AgBr
CH COOH
CH,COOH
malic acid
bromoauCCiOIG acid
Malic acid contains an asymmetric carbon in its molecule and
Properties. (Physical).
hence it exhibits optical isomerism.
H
HOCCOOH HOOCCOH
(H!COOH
(KCOOfl
(.-.).walic acid (-1)-matte acid
Malic acid obtained from natural sources is laevorotatory i.e., () ; the acid prepared by
reduction of (+)_tartraric acid with HI is dextrorotatory i.e., (-f-) while the synthetic
malic acid is raceinic mixture i.e.
maliC acids are colourless solids with mp lOO n th -acid
Both (-) and (+) .
melts at 130. (.._).malic acid is deliquescent solid, readily soluble in water and ethanol.
On the other hand, (+)-malic acid is slightly less soluble in water.
Malic acid gives the reactions expected of a secondary alcohol group
(Chemical).
and two carboxyl groups present on adjacent carbon atoms.
CHOH,
When reduced with hydriodic acid, it yields succinic acid.
(I) Reduction with HI.
HO_CH---COOH H2COOH
+2111 ---p +H2O+1,
I
CH10004 ^H,COOH
malic acid succinic acid
a molecule of water to form maleic anhydride

(2) Action of Heat. On heating, it loses
and furnaric acid. This behaviour is characteristic of .hydroxy acids.
A H_cOoH H CO
HO_CHCOOH A HOOCCR
n
HC--COOH HCCOOH HCCOt
CH5 COOH 11O maleic anhythldc
fuinaric acid maleic acid
malic acid
an a.hydroxy and a .hydroxy acid.
It may-be noticed that malic acid is both
HOOC_CHsjH_COQH or 1100C_CH1_H-000H
OH TH
malic acid - an -hydroxy acid inalic acid - a M,oxy acid
Such acids generally behave as -hydroxy acids and not as a.hydroiy acids. Hence on heating
they lose a molecule of water rather than forming lactides.

558
Advancel Organic Chemistry
(3) Oxidation. On careful oxidation, it is converted into oval-acetic acid which exhi-
bits keto-enol tautoincrism.
HOCHCOOH -coou HOCCOOH
I +(0)+ II
CH,COOH H10 O=1HlCOOH CH- COOH
(kcto form) (enol form)
oxal-acetic acid
Uses. Malic acid is used in medicine as a purgative and also a remedy for sore-throat.
It is also used as a food acidulant.
TARTARIC ACID, , z'-dihydroxysuccjnjc acid, 2, 3 . dihydroxy6:aj,e.1 4-dioic acid,
HOOC_CHOH_CHOH_(JJOH
(+)-Tartarric acid is the most widely distributed plant acid. It occurs in grapes,
tamarind and in other fruits either free or as potassium acid tartarate. During the later stages
- of fermentation of grape juice to wine, the potassium acid tartarate is thrown out as a reddish-
brown crust csllcd argol. In 1769 Scheele first isolated tartaric acid from 'argol' and even today
this continues to be the chief source of industrial acid.
Isolation from Argol. Argol (reddish brown) is crude potassium acid tartarate It is
recrystallised to give a purer form (white) called Cream of tar tar. This is dissolved in boiling
water and the solution nearly neutralised with milk of lime. The potassium acid tartarate reacts
with lime to give normal potassium tartaratc and insoluble calcium tartarate.
cH(oH)cool CH(OH)COOKCH(OH)COO
2I
CH(OH)COOH
+ Ca(OHh -p - + + I - Ca2 + 2H20
CH(OH)COOK CH(OH)COO
p01 acid tartarate POE Lfl5fliC calcium tartarate
(solable) (insoluble)
The precipitated calcium tartrate is filtered ott' and calcium chloride added to the filtrate
when a fresh crop of calcium tartarate is obtained.
cH(OH)COOK CH(OH)COQ
+CaC!1 , I Ca+2J(Cl
CH(OH)COOK CH(OH)COO
(soluble) (insoluble)
The calcium tartarate from the two lots is combined and decomposed with calculated
quantity of dilute sulphurj acid
CH(OH)COO + CH(OH)COOH
I - Ca + HISO4 -.
+ CaSO4
- CH(OH)COO CH(OH)COOH (insoluble)
tartaric acid
The precipitated calcium sulphate is removed by filtration and crystallised when tartaric
acid is obtained as a white crystalline material,
Syntheses. (I) Tartaric acid can be synthesised by th e following steps.
CH H5 CH, Bra CH1 Br KCN H1 CN H3S0/H+
H * I
CH Pd/EaSt) 4 CHs (CCI I) CH,Br (C2HSO}I) I
CH2 CN hydrolysis
(acetylei) ethylene ethylene ethylene
bromide cyanide
R5cooH Bra/red p Br. CH-_COOH AgOH HOCH_COOH
- I
CH,COOH HVZ readion BrCHCOOH HOC}I
succinic acid dibromoaucuic acid CH
- tartaric acid
Acetylene can, in turn, be synthesised from elements (2C -l-H---.CFICH) by passing hydpgen
through an electric arc, Thus the above synthesis of tartaric acid is, in fact,- its total sy?h.

55
substituted Corboxyllc Add
Another synthesis of tartaric acid starting from ethylene is outlined below.
(2)
o CR0 HCN H(0FI)CN H1OJH+ HOHCOOI
CH I (ItO+O) CH IOH
5 CH(OH)CN CH(OH)C001
CH I KMnO4 CH2OH HN0 CR0 glyoxat cyanohydrin tartaric acid
ethylene glyorat
obtained ,rom glyceraldehyde by Killian i.Fischer synihesi.
(3) Tartaric acid may also
COOH COOH
CN
CH=0 I
hydrolysis, Ba(OH)2 CHOH HNO CROH
+HCN CHOH (1)
CHOR
41CHOH
I
(2) acidification, 11 1SO 4 H0H oxidation CHOH
CU2OH 00H
CHOH CH1OH
tartaric acid
glyceraldehyde
Properties. (Physical). It is the classical example of a compound containing twi
asymmetric carbon atoms.
H
H-- c000R
H0C-000H
H
Thus it exhibits thc phenomenon of optical isomerism and exists in four forms dexiro-
inevo-, mesa- and racemic.
C OOH C0OH COOH
HOCH HCOH H?OH
HC--OH HO-CH HCOH
COOH COOH COOH

(-)-tartaric acid (4-).tartaric acid ,neso-tartaiic acid,
(S, S)-tartaric acid (R, R)-tartaric acid (R, S)-tartaric acid
Natural tataric acid is (+)-tartaric,acid.
(+.)-ta r a ric acid forms colourless monoclinic prisms without any water of crystallisation
It melts at 170 and is soluble iq water and ethanol but insoluble in ether. An aqueous solutiot
of (+)- tartaric acid, upon heating, is rendered optically inactive owing to racemisation.
(Chemical). Tartaric acid is both a dicarboxylic acid and a disecondary alcohol,
J.100C_CHOH_CHOHCOOH
Therefore, it shows the reactions of two secondary alcohol groups (CHOH) and twc
:arboxyl groups. Some typical reactions of tartaric acid are described here.
(I) Formation of Salts. -Tartaric acid being a dibasic acid forms two series of salts
icid tartarates and tartarates, when heated with alkalis, carbonates and bicarbonates.
HOCRCOOK. HOCHCOOK
HOCHCOOH HOCHCOOK
pot acid tartaraic normal potassium tartarate
It also forms mixed salts e.g.,
+ - +
HOCHCOO(SbO)
HO-SH_COO Na
HOCH006-K+ HOCUCOOK
sod pot tartarate pot anilmonyl tartaraie
(Rocheile salr) (Tartar emetic)

(2) Action or Heat. When heated above its melting point, tartaric acid loses a molecule
water to produce tartaric anhydride.
HOHCooH HOHco
HOCHCOOH HOH---CO
tartaric anhydride
However, if tartaric acid is heated strongly, tartaric acid decomposes with smell of
urnt sugar to produce free carbon (Test), and pyruvic acid.
HO.cHCOOH
CHJCOCOOF-I + CO, + H2O
HOCH---00OH pyruvic acid
Pyruvic acid is also produced vhen tartaric acid is heated with potassium hydrogen
ilphate at 210-220'.
)CH--COOH KHSO r CHCOOH
cHt_cooHl_co,
I I I s CH,COCOOH
)CHCOOH 2lO-22O HOC_COOH O=CCOOH J pyruvic acid
When heated with cone H,SO,, tartaric acid deposits carbon rapidly and a mixture of
.0, CO,, SO, and H 2O is produced (Test).
(3) Action with Mr. Tartaric acid when treated with !-IBr gives a, a'-dibromosuccinic
A by replacement of hydroxy groups by bromine atoms.
H0CHCOOH BrCHCOOH
-(-2FIBr -.---, +214,0
}{OCHCOOH Br(HCOOH
, a'-djbromouccjyj
acid
(4) Reduction, Tartaric is reduced first to malic acid and then to succinic acid when
eated with concentrated hydriodic acid.
HOHCOOH HOCHCOOH
+2Hl -. I +H2O+1,
HOCHCOOFI CH,COOH
malic acid
HOCHCOOH CH,COOH
CH, COOH
+2H1 - I
CH,COOH
+H2O+1,
succinic acid
(5) Oxidation. Tartaric acid is very, sensitive to oxidising agents. When heated with
nrnoniacal silver nitrate solution, it is donverted to tartonic acid and a silver mirror is
iirmed.
4AgNO3 + 4NH1 0H -p 4AgOH + 4NH4NO,
2AgOH -p 2A&0 + 2H,0
HOCH--COOH HOCHCOOH
I + 2Ag,0 -i I + 4A8 + CO11 f + H2O
H0CHCOOH COOH silver
tartonic acid mirror
Fenton reagent (Fe3 /H,02), oxidises tartaric acid to dthydroxy maleic acid.
}10CHCOOH Fe3+/H2O, HOCcOOH

I
HOCHCOOH
+[O] -.. H2O
HOCCOOH
h'droxymajejc acid

Substituted Carboxylic Acids 561
With strong oxidising agents like IINOS, tartaric acid is converted first to tartonic acid
and then to oxalic acid.
HOCHCOOH (01 HOCHCOOH oj cOOH
I -p 1
HOCH00OH HNO1 COOH COOH
tartonic acid oxalic acid
(6) Formation of Complexes; Fehling solution. Like other polyhydroxy compounds,
tartaric acid prevents the precipitation of hydroxides of heavy metals owing to the formation
of soluble complex salts. An excellent example of such a complex is provided by the well-
known reagent called Fehling Solution. This reagent contains copper sulphate, Rochelle salt
and sodium hydroxide. The insoluble Cu(OH) 2 first formed goes into solution due to the
formation of the complex. The unoccupied 4s and 4p orbitals in the copper (II) ion serve as
the electron pair acceptors for the electron pairs on the hydroxyl oxygen of tartarate ion.
The.chelate formed by the coordination of this bidentate anion and copper (II) ion is depicted
below.
( OH HO
I - 1 I I II - I
O.-CC--O O_._c_CO +
Cu I 6Na
IIII
OH HO
I
L )
SODIUM CL/PRITARTRATE
The formation of this complex in Fehling solution lowers the concentration of Cu(II)
ions to an extent that it does not permit the formation of the insoluble Cu(OH),. On the
other hand, copper (I) ions do not form a chelate with tartaric acid and hence the brick red
copper (1) oxide is precipitated as the copper (11) ions are reduced to Cu(l) ions by an aldehyde
or some other easily oxidisable substance.
Uses. Tartaric acid is used (I) as acidulant in making sweet drinks ; (2) S'eidljjz
Powder used as a laxative contains tartaric acid in a white wrapper and a mixture of the
Rochelle salt and sodium bicarbonate in blue wrapper; when the powders are dissolved
separately and mixed, carbon dioxide is evolved; (3) Baking Powders contain potassium acid
tartarate and sodium bicarbonate ; on mixing with dough they produce carbon dioxide during
the baking process, which leads to an open te7ture in bread and cakes ; (4) Sodium potassium
tartarate is also used in the communication industry (microphone crystals) and in making of
mirrors ; (5) Fehling soluzion containing Rochelle salt is used for detecting reducing functions
in organic compounds (aldehyde test) ; (6) Tartar emetic, pot antimonyl tartarate, when
administered orally causes mansea and vomiting, and hence its use as an eliminant for poisons.
It is also used as a mordant in dyeing.
CITRIC ACID, -hydroxytricarba11yIIc acid, 2-hydroxypropane-1, 2, 3-Iricarboxylic acid,
HOOCHCH1OOH
OOH
Citric acid occurs in many fruits, especially unripe fruits of the citrus family e.g.,
lemons, galgals and oraliges. Lemon juice contains about 7-10% of citric acid.
Preparation. Citri acid is prepared on a large scale by the following methods.
(I) From Lemoh. The juice of the lemons or galgals is extracted and is boiled to
coagulate the proteinous matter. The coagulated material is filtered off and the filtrate
neutralised with lime while the solution is boiling. The precipitated calcium citrate is collected


562
by filtration and is decomposed with a calculated amount of dilute sulphuric acid. The calcium
sulphate thus precipitated is removed by filtration and the solution of citric acid evaporated
to crystallisation.
(2) From Mola.sses.' A dilute solution of molasses or sucrose or glucose, is formed by

in presence of ccrt.iifl
microorganisms such as Citromycvs pfefferianus or Aspergillu.s wentii
inorganic salts. The mechanism of this fermentation is not completely understood. However,
Krcps has advanced an elegant suggestion that the incomplete fermentation of carbohydrates
gives rise to pyruvic acid. One molecule of this acid is decarboxylatel to acetaldehyde which
then gets oxidised to acetic acid and a second molecule is converted to oxal.acettc acid.
Finally, the acetic acid condenses with oxal.acetic acid to form citric acid.
r CH 5 CHO s CH3COOH acetic acid
acetaldehyde
(i) 4OLASSES - CH3COCOOH
pyruvic acid
HOOC_CH1CO--00OH
oxal-acetic acid
H2COOH
?HaCOOH
(ii) O=CCOOU Ho__COOH
I
4
CH3COOH CE - COOH
citric acid
Synthesis Citric acid may also be produced by synthesis involving the following steps.
(I) (2) (3)
HCl CHCI CH2CI
CHIOH
HCI I cit FINO, KCN I OH
I C=O C'
CHOH -b CFIOI-i
controlled oxidation ethatiolic CN
I CH2Cl
CH2OH
conditions cu5c1 CH,Ci
I, 3 .glycerol 1, 3-dichloro- 1, 3-dichloroacetorie
glycerol acetone cyanohydrin
dichiorohydrin
(4)
CH, COOH
11o11t10H
.- C'
hydrolysis "COO H
Clln.COOH
citric acid
Properties (Physical). Citric acid forms large prismatic crystals containing one molecule
of water of crystallisation. The hydrated acid loses its water of crystallisation when heated to
130', and then melts at 153. It is readily soluble in water and ethanol but sparingly in ether.
Citric acid is not optically active since its molecule does not have an asymmetric carbon atom.
(Chemical). Citric acid is a hydroxytribasic acid and behaves accordingly. It gives

reactions of both e-hydroxy and (3-hydroxy acids, since the OH is situated a- to one COOH
group and - with respect to to the other two COOH groups.
H,_coOH aCHr-COOH
II
H COOH ' Ho.COOH
CH,COOH eH1COOH
as a.hydroxy acid
ice -hydroay arid
Given below are a few typical reactions of citric acid.

Substituted Corboxylk Acids 563
(1) Formation of Sills. Citric acid forms three series of salts

-4- -+ -+
9 2 COOK CH1COOK CH!COOK
I
HOCCOO H HOCCOOH
I
HOCCOOK
I I -+ -
CH2COOH C112COOK CHCOOK
monopotassium citrate dipotassium citrate tipotassium citrate
(2) Acetylation. It reacts with acetic anhydride or acetyl chloride to form monoacetyl-
citric acid.
CH,COOW H5COOH
1-IO---CCOOH + CH 3CO-0--00CH 5 - CH3COOCOOH + CF1COOH
acetic anhydride
CII2COOH CIIaCOOH
citric acid monnacctykitric acid
(3) Reduction. The alcoholic OH group in citric acid molecule is reduced b y the action
of hydriodic acid to yield tricarballylic acid.
CH2COOH CHCOOH
reflux I
HOCHCOOH 4- 2111-, (H 2 COOH HO + CO
CH2COOH C1-1,COOH
citric acid iricarballytie acid
(4) When heated to I 5O, citric acid eliminates a molecule of water to produce Aconitic
acid, thus behaving as a 3-hydroxy acid.
CH5COOH CHCOOH
I5II
U_?_COOH
_copH + HO
CH5COOFI CHICOOH
aconjtjc -acid
(5) Like u-hydroxy acids, citric acid when -heated with fuming H 2 S05 gives acetone
dicaboxylic acid. -
CH 5COOH CHaCOOH
fuming H1504 I
HOC--COOH
--------- C=O
CH2COOH CH,COOH
citric acid acetone dicarboxytic acid
(6) Formation of Complex salts Benedict Solution. Like tartaric acid, citric acid also
forms soluble complex salts and thus prevents the precipitation of hydroxides of heavy metals.
Benedict solution which contains copper sulphate, sodium carbonate and sodium citrate, provides
an excellent example of complex formation. The structure of the complex is similar to that
of the complex formed by tartaric acid.
OOCCHI -"Q 2y0_CO\ /cHcOO

C
1
NCH 2CO10 J
300/tiM CUPRIC/[RATE
564
The formation of this complex lowers the concentration of Cu (II) ions to such an extent
that it does not permit the precipitation of insoluble tu(0F1h. On the other hand, since Cu(I;
ions do not for n a chelate (of the type shown above) with citric acid, the brick red copper (I)
oxide is preciiitated when Cu (II) ions are reduced to Cu (I) ions by an aldehyde or any other
easily oxidisable substance.
Benedict solution is more stable than Fclsling solution and is not affected by substances
like creatine and uric and which are present in urine. Hence it is to be preferred for detecting
and estimating glucose in urine.
Uses. Citric acid is used : (I) as acidulant in foods and soft drinks (2) as a mordant
in dyeing ; 3) for cleansing metals as it forms complexes with metals ; (4) Sodium citrate is
added to milk given to babies as it prevents the curdling of milk in stomach and thus makes it
more digestible ; (S) Magnesium citrate is used in medicine as an antacid and laxative
(6) Ferric ammonium citrate on exposure to sunlight changes to ferrous salt and is, therefore,
used in making blue prints' paper; (7) Citric acid esters . (tributyl ci(rate) are good plasticizers
for lacquers and varnishes.
QUESTIONS
1. What are substituted acids? How are they named?

2.. Describe the methods of synthesis of haLo acids. What is the action of alkalis an these acids.
general methods for the synthesis of hydtoxy acids. Give a brief survey of their
3. Enumerate the
.4tysical and chemical properties.
a, B, r-hydroxy acids on heating.
4. Describe the characteristic behaviour of
How can you prepare lactic acid 7 Explain its isomerism.
5.
(Artnornal: BSc 111, 1980)
6 Discuss the action of heat on a. B, and rhydroxy acids.
(1) What is the action of heal on lactic acid? Depict a method for its synthesis from ethanol.
7. (Colicut BSc Iii, 1980)
How will you distinguish between a, R and y-hydrXy acids 2
(ii)
Citric acid from propane-1, 2, 3-trial. (Dams ras BSc lii, 1980)
Outline the snthesio of
g 9 How is lactic acid prepared 2 Describe its properties invoting the --OH as well as(Delhi
COOH groups.
BSc II, 1980)
10 (a) How is Citric acid obtained from lemons ? Give its two important uses.
(iisaipur BSc 11, /981)
How will you distinguish between ci4ic acid and tartanc acids 7
(h) 2 Establish the constitu-
What is the chicISOulce of citric acid? How is it obtained in the pure state (North Eastern BSc, 1981)
11. y ?
lion of citric acid. Is citric acid Optically active 7 if not, wh
Indicate in which particular physical property do the isomeric lactic acids differ
12. (a)(1,) How do you obtain tactic acid from (/) acetaldebyde (ii) actone.
the product obtained on beating malic sod. The product of
(c) Predict the organic structure of
this reaction is further heated with I, 3-butadienC. Prodict the structure of the latter product.
(Andhra BSc 11, 1981)
What happens when lactic ishCatrd 1 (Modurai BSc, 1993)

53.
What happens when ci(flC arid is heated at I50C2 (Krra(aBSc. 1993)
14.
t)eccnbc the synthais and one use of (a) Lactic acid. and (b) Tartaric acid, I Udaipur BSc, 1994)
15.
(Delhi BSc, 1994)
16. . How is lactic acid paJed? What happens when lactic acid b5 healed ?
17. Write a note on: Action of hex Ofla,B.YY&o5Y (Mysore BSc, 193; Agra BSc, 1994)
1K. Flow is tartaric acid prepared How does tatMic reart with:- (a) To&as reagent (b) Fenton's reagent. and (c) Acetyl
(SwigarRSc, 1994)
chloride,
Chapter 24
Functional Derivatives of Carboxylic Acids

Acid Halides, Anhydrides, Esters and Amides
The derivatives of monocarboxylic acids discussed in this chapter are those which are
formally obtained by replacing the OH group of the carboxyl function by another reactive
atom or group, say G.
0 0
OH U
RCOH -. RC--G
carboxylic acid +0 acid derivative
Here 0 can be a halogen -x (Cl, Br, 1), -O--CO---R, OR or NH, and the respective
classes of carboxylic acid derivatives are designated as Acyl halides, Anhydrides, Esters and
Ainldes. The structural relationthips among these classes of compounds are summarised in the
Table below.
0
Table. Functional Derivatives of Carboxylic acids, RC--OH
Class General formula Q Specific Example
-
0 0
II
Acyl halide, or RCX 'Cl CH1CCl
Acid halide Br,! tcetyl chloride
0 0. 0 0 0
I U Ii II I
Acid anhydride RC-0CR O--C----R CH1C-4)--,CCH,
acetic anhydride
0

Ester RC--OR OR CH-4C-0cH,CH1
stbytace

0 0

Acid amide RCN' or NH, CU-4--NH,
0
RCNH
ORBITAL STRUCTURE
As described above, the carboxylic acid derivatives are characterised by the presence of
IL carbonyl group, CO, and a group G which may be X, OCO--R, ..-OR Or NH,.
565
The Structure of these derivatives is primarily the structure of the carbonyl group, though this
structure is modified somewhat by the group 0 attached to carbonyl carbon Let us discuss the
orbital structure of acid derivatives by taking example of acyl halide.
Like aldehydes and ketones, the carbonyl carbon in acyl halide is sp' hybridized. Its
one sp orbital overlaps with a sp3 orbital of the carbon of the alkyl group, and the remaining
two sp1 overlap with half-filled p orbitals on the halogen (say Cl=3p' 3p', 3p') and oxygen
atom ( 2p', 2p, 2p',). The unhybridized p orbital on the carbonyl carbon and on the oxygen
atom being parallel overlap to form a 7t bond. The carbon and oxygen are thus joined
by a double bond (i.e., one a bond and one it bond. This orbital picture of an acid halide n
depicted in Fig. 241.
It
2
Sp3-55)b2 c,8OND
R - --
S/2
6

'6
)cc 0
P141
=
(7*
^1 2 Oe
Sb2p a BOND I 0 80N0

Fig. 241. Orbital Model of AeyI halide.
Since the carbonyl carbon utilizes its sp a orbitals to form three a bonds, the angl es
LRCX, LRcO and LXCO are approximately of 120. Evidently the part of the molecule
",",,,,'
V V
1. IL
Fig. 242. Orbital structure of RCO---O showing the rinhybridid p orbitib of carbonyl C and Os.
also, nf cow G.
Fuhcflon? Derixotives of CorboxHc AddsAdd halides, Anhydrides, Esters and Amides
immediately surrounding the carbonyl group is flat i.e., the carbonyl carbon, the oxygen, the
group R and the group G( X) are all in one plane. The orbital model of anhydrides, esters,
and amides is exactly similar to that of acyl halides. Thus, in general, the orbital model of an
acid derivative, RCO---G, could be represented as tin Fig. 242.
The atom of the group G 5 C1 in acyl halide 0 in anhydrides and esters N in amides)
directly bonded to the carbonyl carbon has lone pair of electrons in p orbitals. This p orbital
may also overlap with p orbital on carbon and oxygen (of C=O) to provide additional bonding
as shown in II and [it of Fig. 342. This additional bonding depends on the electronegativity of
the atom of G directly linked to the carbonyl group.. Greater the electronegativity, lesser the
additional overlapping. The group G mentioned above contains either a halogen or oxygen or
nitrogen which is directly bonded to the carbonyl group. Since the electro negatives of these
atoms follow the order halogen > oxygen > nitrogen, this additional bonding is important only
with amides.
In valence bond terms, the additional bonding implies that carboxylic acid derivatives
may be represented by resonance structure as shown below.
/110
R_CQ
REACUON MECHANISM. Acid derivatives undergo nucleophilic substitution

reactions because the carbonyl carbon is electron deficient on account of greater electronegativity
of the oxygen atom bonded to it. These reactions take place by the following steps.
0
- (1) Attack by Nucleophilc (i'u) on RC--G
c--
Nu
TETRAhEDRAL
/A'TER,49EO/4Tr
0
(2) Loss oft) with formation of R(!_Nu
RC+
Nu
5118571fl' TED
PRWcr
G=X, 0COR, OR, and NH1'; Nu may be R--&H,: Nil, or 11,0 in the
reaction of acyl halides or anhydrides to form esters, amides and carboxylic acids.


SoB
RELATIVE REACTIVITIES
Experience has shown that the acyl halides are much more reactive than the other
derivatives in respect of their nucleophilic substitution reactions. Let us illustrate it by taking
example of basic hydrolysis of the acid derivatives which takes place as
0 0
II - 11 20 II -
CH,CG + OH -i CH,COH + G
acid derivative acetic acid leaving
group
The differences in reactivity of the various acid derivatives are presumably due to the basicity
of the leaving group G as is clear from the following Table,
0
Table. Relative reactivities of Acid derivative CHCG and Basicity of 0.
- Relative reactivity towards
Acid Derivative G Basic hydrolysis K, of G
0 Reacts explosiveiy at 10-It

-
CH,C --Cl Cl room temperature
acetyl chloride 0
O 0 0 *
II II II - Reacts rapidly at 0 l0'
CH,CO--CCH3 CH,CO room temperature a
a
acetic anhydride 0
0 U 10k'
- Reacts slowly at a
room temperature U
CH,C--O--CH,Cl-I, CEI,CH,O
ethyl acetate
0 10+10
- Hydrolysis requires
'CH,CNH, NH, prolonged heating
acetamide
The ease with which a nucleopnilic substitution in an acid derivative takes place,
depends on two factors.
(I) The Electrooegatlity of C. Greater the elec'ronegalivity of group C more polar
would be the CG bond, and the cath,a of the carbonyl group becoming more electron
deficient thereby. This facilitates the nucleophilic attack. We know that the electro-
negativities of the groups 0 follow the sequence -x > 000R > OR> NH,.
Therefore, acid halides should be more reactive than anhydrides; anhydrides in turn should
be more reactive than esters which again should be more reactive than amides.
(2) Reso.asce Stabilisation. Lesser the electronegativity of the group G, more would
be the resonance stabilisation as represented below.
P'0 4 R__C

Functional Derivatives of Carboxylic AddsAcid halides, Anhydrides, Esters and Amides 569
Greater the double bond character between the carbonyl carbon owing to resonance, greater
would be the electron density at the carbonyl carbon. Thus a high degree of stabilization
results in a slower nucleophilic attack. Hence the reactivity of the acid derivatives with
nucleophilic reagents should also follow the order : acid halides> anhydrides> esters> amides.
Both the 'clectronegativity' and 'stabilisation' factor reinforce each other and support
the fact that relative stabilities actually follow the sequence
0 0 0 0 0
II II II II II
RCX > RCOCR > RC .--OR > RCNH,
acyl halide anhydride ester &,nide
ACYL HALIDES
Acyl halides (sometimes called acid halides) are the derivatives of carbox) lie acids in
which the OH of COOH group has been replaced by a halogen atom (X).
0 0
1 OH
RCOH v. RCX where X = Cl, Br, I
acid +X acid halide
Further, they are named as acyl chlorides, acyl bromides and acyl iodides according as
X=Cl, Br or I respectively. Because of the exceptional reactivity of the acyl chlorides, it is
seldom necessary to prepare and use the more reactive acyl bromides and iodides. For the
matter of that, these derivatives have not received much attention and our discussion of acyl
halides will be limited almost exclusively to the acyl chlorides.
The typeformula of acyl chlorides is
0
R%,%,i or RCOCl or RCOCI
and COCl is the functional group.
NOMENCLATURE
Acid chlorides are named after the name of the parent carboxylic acid. Both in the
Common and IUPAC systems, the ending ic acid is replaced by -yl chloride. The Common
and IUPAC names of a few acyl chlorides are given below.
0
HCCl (unstable) formyl chloride methanoyl chloride
0
CH1CCl acetyl chloride ethanoyl chloride
0
CH5CH5CCl propionyl chloride propanoyl chloride
.0
CTlaCiICHiCCl n .butyryl chloride butanoyl chloride
,
CI-I--CCl isobutyryl chloride 2.methylpropanoyl
CH/ chloride
The common names of acyl chlorides containing more than live carbon atoms in a
chain, are obtained by replacing the ending -Ic acid by -oyl chloride. Thus laurie acid
CH 3 (CH,) 1C00H, gives rise to lauroyl chloride and not lauryl chloride. In order to avoid
confusion, it is advisable to use !UPAC names for higher acyl chlorides.
Organic Cliensk r - 37

(I) By the action of Phosphorus chlorides and Thionyl chloride on Carboxylic acids, Acid
chlorides are prepared by the action of phosphorus trichloride (PCI 3), phosphorus pentachloride
(PCI 6 ) or thionyl chloride (SOCJ2) on a carboxylic acid.
3 RCO--OH + PCI6 -, 3 RCOCI + HIPO,
acyl chloride phosphoric
acid
RCOOH + PCI 6 .- RCOCl + POd 1 + HCI
phosphoryl
chloride
RCOOH + Sod 6 i RCOCl + SO t + HCI f
The choice of reagent used for the conversion of a particular carboxylic acid is governed by
the boiling points of the products. If the acyl chloride has a very low boiling point (e.g., acetyl
chloride, bp 520), PCI, is used and the chloride is easily separated by distillation from
phosphorus acid (H3 P0 1 ) which decomposes at 2000. If the acyl chloride has a very high
boiling point, PCI 5 can be used as the fractional distillation gives first POCI 1 (bp 1070) and
then the acyl chloride, With propionyl chloride which has an intermediate boiling point (800),
thionyl chloride is suitable as the gaseous SO, and HCl pass off first leaving the pure acyl
chloride behind.
Examples:
3 CHI COOH + PCI 1 - 3 CH,COCI + HIP03
acetic acid acetyl chloride
CH J CH I CFI,COOH + SOd 1 -, CH,CHI CH,CO--CI + SO 1 t + HCI t
n'butyric acid n'buIyryl chloride
(2) By the distillation of Salts of Carboxylic acids with PCI3 , FOCI6 or SO 1CI,. Acyl
chloride may be prepared by distilling the salt of a corresponding carboxylic acid with either
phosphorus trichloride (PCI 3), phosphor y l chloride (POd 3 ), or sulphuryl chloride (SO,Cl,).
Thus,
3 CH,CONa + PCI 3 --, 3 CH3 COCI + Na3PO3

sodium acetate acetyl chloride
- +
2 CH3 CH5COONa4- FOCI, i 2 CH1 CH,COCI + NaCl + NaPO3
sodium propriouate propionyt chloride
(CFI,COO)5Ca4 + SO5CI I -, 2 CH,CO---C1 + CaSO6

calcium acetate acetyl chloride
This method is particularly useful for industrial preparation of acyl chlorides since salts
of acids are cheaper than the, acids themselves.
PHYSICAL PROPERTIES
(1) The lower acyl chlorides are mobile, colourless liquids while the higher members
are colourless solids.
(2) Acy] chlorides have very pungent, irritating odours and are strong lachrysnators
(tear gases),
(3) Since they contain no hydrogen attached to oxygen,, hydrogen bonding between
their molecules or with water is not possible. Evidently the boiling points of acyl chlorides are
much lower than those of carboxylic acids having equal number of electrons. Thus propionic
acid with 40 electronc boils at 1410, while acetyl chloride with 42 electrons boils at 520.
(4) The boiling points of lower members record a rise in boiling with rising molecular
weight and the higher acyl halides being solids have higher melting points. Thus,
Acetyl chloride Propionyl chloride 'n-Eutyryi chloride Stearyl chloride
bp 52'C bp 80'C bp 102C sep 22*C

Functional DerivatIves of Carboxylic AcIds-Acid halides, Anhydrides. Esters and Amtdes 571
CHEMICAL PROPERTIES
Acyl halides are most reactive of all acid derivatives of carboxylic acids. The high elec-
tronegative character of chlorine atom increases the partial positive charge on the carbonyl car-
bon by withdrawing electrons from it. This makes the carbonyl carbon increasingly susceplible
to the attack of nucleophiles. The elect roph ilici ty of the carbonyl carbon is thus enhanced
to such an cxtent that even weak nucleophiles such as water and alcohols can also successively
attack the carbonyl group. As a result, acyl chlorides readily give a variety of nucleophilic
subsitution reactions in which the Cl atom is replaced by other atoms or groups.
6-
..*0
[ol 0
HI - I II I II
R-C- Cl+:Y-H R - C-al -+ I R - C I -+ R-C-Y
I I I
+Y-Hj +Y-Hj suesTiluTto
ACTI CHLORIDE L L PRODUCT
Here Y-H is any nucleophilic reagent such as water, alcohol, etc. The process where-
by an acyl group substitutes a replaceable H atom in n organic molecule (Y- H), IS called
Acylation. Thus introduction of an acetyl group in an organic molecule is called AcetyItIon,
CH,-CO-CI + H-Y CH,-CO---Y
-p + H-X
acetyl chloride acetyl derivative
Some important nucleophilic substitution reactions of acyl chlorides are given below.
(1) Hydrolysis. Acyl chlorides undergo hydrolysis to give back the parent carboxylic
acid when treated with water.
0 0
R-C--Cl + H,0 -p R-C-OH + HCI
acyl chloride carboxylic acid
0 0
II II
e.g., CH-C--Cl + H 1 0 CH3-C-OH + HCI
acetyl chloride acetic acid
Thus, when the stopper is removed from a bottle of acetyl chloride, white fumes are
seen owing to the formation of HCI with moist air.
This reaction is of no practical value since acyl chlorides themselves are prepared
from carboxylic acids,
(2) Esterification. Acyl chlorides react readily with alcohols and phenols to from
esters.
0 0
11 1
R'-OH -, R-C-O-R' + HCl
acyl chloride alcohol or ester
phesol
0 0
II II
e.g., CH5-C--Cl + CH 8 CFI 1-OH -i CH,_C-O--H 1 CH 5 + HC1
ethyl acet10
CH-C-Cl + C 1 H-0H - C11 5--0-C.H -I- HCI

phenci phenyt acetate
iioiikc th: acLl . atalyseJ esterifitioo of carboxylic acides, this reaction is irreversible
and the ester is obtained in excellent yield.

(3) Ammonolysls or Amide formation. Acyl chlorides react vigorously with ammonia to
form acid amides.
o o
II II
RCCI + NH, -i RCNH, + HCI
acyl chloride acid amide
o o
11 11
e.g., CH,CC1 + NH, -- CH,CNH, + HCI
acetyl chloride acetamide
HCI produced in the reaction reacts with a second molecule of NH, to give NHCI.
+ -
NH, + HCI -. NH4CI
Primary and secondary amines react similarly to produce mono- and di-N.substitutcd
amides,
0 0
II II
R11Cl + RNH1 RCNHR + HCI
1' amine m000-N-substituted
amide
RNH1 + HCI I-
RNH, Cl
0 0
e.g., CH,C--Ct + CH,NH 1 ; CH5CNH--01 3 + HCI

methylamine N-methylacctarnidc
(4) Thioester formation. Thioalcohols react with acyl chlorides to form thioesters.
RCCl + R'SH -i RC--SR' + HCI

thiol tbiocstcr
0 0
e.g., C111t1Cl + CHrSH o CH1 --SCH 3 + Ed

methasethiol methyl thtoacctate
(5) Anhydride formation. Acyl halides react with anhydrous sodium salts of carbo-
xylic acids to form acid anhydrides.
o o o o
II +- 11 It II + -
RCCI + NaO---CR -, RCO--CR + NaCI
acyl chloride sod earboxylatc acid anhydride
0 0 0 0
II +.
e.g., 03 1C---1-1 + NaOCCH, CH1C-0CCH, + NaCI
acetyl chloride sod acetate acetic anhydirdc
+- -
(6) Peroxide formation. Acyl chlorides react with sodium peroxide, NaOONa, to
form organic peroxides.
0 0 0
II +- -+ II II
2 CH,C--Cl + NaOONa -, CH 1C.-0-0-4C1:1 1 + 2 NaCl
acetyl chloride acetyl peroxide
(7) Reaction with Organometailic Compounds. Acyl chioride rcsjt with Grignaid icagcats
in ether solution to form ketones.

Functional Derivatives of Carboxylic AcidsAcid halides, Anhydrides, Esters and Amidez 573
r
OMgBr 0
- + II
3 MgBr --4 RCCl v RCCH + Mg(Br)CI
R_bC_Cl + CH
1 KETONE
ITHYLMAN(SIUM
ACYL HALIDE CH 3
BROMIDE
However, better yield of ketone is obtained by taking organocadmiuni compound in

place of Grignard reagent. Thus,
0 0
II 1 5-
CH5 CCl + CH 1CH 1 CdCI -+ CH 1 C-0I1 CH 5 -)- CdCI,
ethylcadium chloride ethyl methyl ketone
(8) Reaction with Diazomethane. Acyl chlorides readily react with diazomethane to
give diazoketones. For example,
o 0
ii - + II- +
CH,C--C1 + 2 CH,NN - CH,CCH-NN + CH 1CI + Nit
acetyl chloride diaaocncthane diazoacelone
if the diazoketone thus obtained is warmed with water in presence of Ag 10 as catalyst, the
next higher homologue of the parent acid of acyl chloride is produced. This method of
converting a carboxylic acid to its next higher homologue via the acyl chloride, is referred to
as Armdt-Etstert Synthesis.
MECHANISM:
- + WOLFF
Cu( CHN N -P- O=C=CH C4
ARRAN6EM(NT A
/ET(NE
0
H20 II
) H0C--CH2CH
PROP/ON/C ACID
(9) Reduction. Acyl chlorides may be reduced either to aldehydes or alcohols with
certain specific catalysts.
(a) To Aldehyde:. Acyl chlorides when reduced with Ha in presence of palladium
(supported over BaSO5) as catalyst, form aldehydes. This reaction is commonly known as
Roaeninund's Reduction. For example,
0 0
Ii Fd-BaSO4 II
CHaC---Cl + H 1 - CH,CH + HCl
1001S0 acetaldebyde
The function of SaSO is to act as 'poison' and reduce the activity of the catalyst to the extent
that the reaction stops at the aldehyde stage,
(b) To Alcohol:. Reduction of acyl chlorides with LiAIH 4, leads to the formation of
alcohols.
0 II
II LiAIH4
RC--CI -p RCOH + HC[
H
V alcohol

S74 Advanced Organic ChemIstry
MECHANISM:
co Qf4 H
- L_fl
aC- ci +/ H -.-. R -0.1 - RC--- )- RC-0
H
_____
I
P R--C---OH
(Hct)
H
1 0 ALCOHOL
The complete reaction involved in the reduction of acyl chloride with LIAIH 4 may be
represented as
2RCOCI + LiAIH 4 -+ (RCH!O)ILIAICI,
(RCH0) I LIAIC1 + 2HCI -i 2RCHOH + LiCI + AlCl
1 alcohol
(10) Friedel.Crafts Reaction. Acyl chlorides offer a convenient method for introducing
acyl groups into the nucleus of the beozenoid compounds in presence of anhydrous Ala, as
'cittlyst. This reaction called &Iede! . Crafis Acylation will be discussed in detail in the
chapter on Aromatic hydrocarbons.
0
11
0
ii anh. A105 /C_R + HCl
+ 1
alkyl phenyl ketone
/C_CHs + HCI
V anh, Aid,
e.g., CH1CC1 + -.
0]
..ctophenone
(ii) Halogenation Hell.Volhard-Zelinsky Reaction. Acyl chlorides undergo chlorination
or brorninatiori much readily than aliphatic hydrocarbons and hydrocarboxylic acids. Further,
only . hilogens are substituted by halogen atoms. The greater reactivity of acyl chlorides
towards halogenation is presuinibly due to greater acidity of -H atoms because of the
inductive effect of both the carbonyl group and chlorine atom.
HO
ii Ii
RCCC1 + Cl, =2 R Q-0 + HCI
(l
acyl chloride -chloro.acyi
chloride
MECHANISM. The halogenation of acyl chlorides probably occurs through the
following steps.
H,*O + H 0 H 0H
H H0
+H I II
R'CCCl RC=C_Ci RC7C__Ci R---CCI -f- Cl
1-
'Cl-!Ci
ci

575
runctlonal Derivatives of CarboxylicAcids Ac id halides, Anhydrides. Esters and Amldes
In actual practice, free carboxylic acids are themselves chlorinated in the presence of
a small amount of phosphoric trihalides. The reactions are
3 RCH--COOH + PCI 3 - 3 R_CH,COCI + H3P03
acyl chloride
RCH,COCL + Cl, -* R._CHCICOCI + HC1
R_CHCICOCI + RCH 3--COOFI R_CHCI.COOH + R_CH2COCI
(reused)
Because of the last reaction, only a small amount of acyl chloride is needed to convert a large
amount of an acid to its a-halo derivative. This method for preparing a-halo acids is called
Hell- Volhard-Zelinsky Reaction.
FORNIYL CHLORIDE, Methanoyl chloride, HCOCl
Formyl chloride is the first member of the class. It is unstable and is not known to
exist at ordinary temperature. There is evidence of its existence at low temperature (-80).
A mixture of carbon monoxide and hydrogen chloride, however, behaves as formyl chloride
in its reactions.
0
C=O: + HCI -. HCCa

forrnyl chloride
(unstable)
This mixture is frequently used for introducing a formyl group (fortnylalion) into the beozene
ring in presence of anhydrous AICI, (Gatterman Koch Aldehyde Synthesis).
CR0
ash. AICb
CO + HCI +
beozaldehyde
ACETYL CHLORIDE, Ethanoyl chloride, CH3COC1

Acetyl chloride is the most important acyl chloride. Since the abbreviation for the
acetyl-group(CH,CO) is 'Ac', acetyl chloride may be written as AcCl or AcC1 for
convenience.
Preparation. Acetyl chloride is prepared in the laboratory by the action of phosphorus
trichloride on glacial acetic acid.
3 CH,COOH + PCI, - 3 CH,COCI + H3PO,
acetic acid acetyl chloride
Properties. Acetyl chloride is a colourless pungent smelling liquid, bp 52. It is soluble
in ether and chloroform. It fumes in moist air due to the formation of hydrogen chloride
through hydrolysis. . It responds to all the general reactions of acyl chlorides discussed before.
+ H 10 -. CH 3 00OH + HC1
acetic acid
H3 + HCI
+ CH 30H - CH3CO--OC1
eihy acetate
+ NH, -p CH,CONH, + HCI
acetamide
o
11 + CH 8 SH - CH 3COSH + HCI
CH3C--C1 thioacelic acid
acetyl chloride + CH,MgI - CH 1.COCH 3 + MgICL
acetone
+ LiAIH4 -p CFI3CH,OH + HCl
ethanol
AICI,
+ C5 H, - CH,_COC.H1 + HCI
anhyd. acetophenone
S76 AdvanCed Organic Chemlstiy
Uses. Acetyl chloride is largely used as an acetylating agent i.e., to introduce the
group CH 17 CO in organ c molecules. It is also used to estimate and detect the presence of
OH group in organic compounds.
ACID ANHYDRIDES
Formally speaking acid anhydrides may be derived by the elimination of a molecule of
water from two OH groups of the two molecules of a carboxylic acid.
0 0 0 0
ii II II II
RCO--H + HOCR -+ RCOCR + H10
two carboxylic acid molecules acid anhydride
Evidently, acid anhydrides are made of two acyl groups (RCO) connected through
an oxygen bridge, The functional group co_oco, present in anhydrides is called the
Anhydride function.
o 0 o 0
II II II
R-.-.C---O---CR R.COC-_R R00--0--00a
CV(. -7 ACYL ANh'YDR/D'/14'CT/2A/

GROUP / CrRO1YP
OXYGEN
In addition to the abve general formulas, the acid anhydrides may also be represented
as (RCO)1 0, to economise space and time.
The acid anhydrides may be Simple or Mixed anhydrides according as the two acyl groups
attached to the oxygen bridge are same or different,
0 0 0 0
II II
RCOCR
simple anhydride mixed anhydride
Almost all the monocarboxylic acids form their corresponding anhydrides, only formic
acid, HCO 01-1, is an exception. Hovevcr, mixed anhydrides of formic acid and other
carboxylic acids are known. For example,
0 0 0 o
II It II It
HC 0--H +H OC--CH -. HC_O_C...CH5 + H10
formic acid ' acetic acid acetic formic anhydride
NOMENCLATURE
Both in the Common and IUPAC Systems, acid anhydrides are named by dropping the
word 'acid' foin the name of the parent acid and adding the word anhydride'. For naming the
mixed anhydrides the first words of the names of the two parent acids are written in alpha.
betical order and then the word anhydride is added once only, The common and IUPAC names
of a few typical anhydrides are listed below.
Formula Common Name IUP4C Name
CH,.COOCOCH acetic anhydride ethanoic anhydride
CCH 100-0--COC HCU3 propionic anhydride propanoic anhydride
CFlCH.CI{1CO-0COCHCFI2CH3 butyric anhydride butanoic anhydride
HCOOCOCH, acetic formic anhydride ethanoic methanoic
anhydride
CH,CO-000CI{CH3 acetic pronlonic anhydride cthanoic propanoic
anhydride
CHCOOCOCH,CH ICHI acetic butyric anhydride ethanoic butanoic an-
hydride

Functional Derlyatly es of Corboxyllc AcidsAcid halides, Anhydrides, Esters and Amides 577
METHODS OF PREPARA'UON
(I) By reaction of an Acid chloride with Sodium carboxylate. Acid anhydrides are best
prepared by the ncicophilic displacement of chlorine from acid chlorides by carboxylale ion.
0 0 0 0
IIC ______ II II
C---Ci /+ Na+0._CR )- RC_--0--CR 1- Na Ci
lC/ CML OkYDE 50D/o'41 C4R8OXY- A619 A trnx9R/L9F
e.g., CH'COCl .- NaOCOCH -. CH,COO----COCH 2 + NaCl

acetyl chloride sod acetate acetic anhydride
Mixed anhydrides can also b prepared by this method when an acid chloride is reacted
with sodium salt of another acid. Thus,
- +
CH,CO-Cl + CHaCHaCO ON a . CH500-0--00CEI1CH5+NaCL
acetyl chloride sod propionate acetic propionic anbydrido
This is a very general method for preparing acid anhydrides. The reaction proceeds
smoothly and yields are ecelIent. However, the most serious limitation arises from the fact
that unsymmetrical anhydrides are unstable and disproportionate easily.
(2) By reaction of Carboxylic acids with Acetic anhydride. High-molecular-weight add
anhydrides are prepared by distilling the corresponding carboxylic acid with acetic anhydride.
0 0 0 0 0 0
II 1 tI 11 ii Ii
CHIC---0.--CCH 1 -- 2RCOfl = RCOCR + 2CH,COH
acetic anhydride acid acetic acid
(bp 140) (bp 118)
Acetic acid boils at a lower temperature than the carboxylic acid and acetic anhydride and is the
lowest boiling crmponent of the equilibrium mixture. As acetic acid is removed during distil-
lation, the retction is forced to the right and proceeds to completion. This method of pre-
paration is applicable to the preparation of simple anhydrides only. It is preferred over the
method (I) because of the low cost anl availability of acetic anhydride.
MECH.kN[Ss1. This exchange reaction probably occurs through the nucleophilic
attack of the carboxytic acid onto the earbony) carbon of acetic anhydride.
cii__J__o__ C CH 3 RC--0--.C--CH3 + CH3COOH
ACETIC NWIYDf19f (INTERAIEDIA To

#Clo
R_Cf_C__CH3 -4- 000H

E) 4- RCOCR + CHaCOGH
11 11
0 0 ACID A 0
(SECOIvOMOLEa/LE) HIGNOR ACID
A4WYO1k'/DE
PHYSICAL PROPERTIES
(1) Excepting formic anhydride, which is unstable, the lower members of the series
are colourless mobile liquids with a sharp pungent odour. The higher members are colourless
crystalline solids.
(2) Their boiling points rise with increase of molecular- weight as for members of any
other class of compounds. Thus acetic anhydride boils at 140, propiofliC anhydride at i

and butyric anhydride at 198. Relatively high boiling points of anhydrides are attributed to
the larger size of the anhydride molecule compared to the acid molecule which results in larger
van der WaaIs interactions and the higher boiling point. The anhydrides, however, do not form
hydrogen bonds to an appreciable extent.
(3) They are only slightly soluble in water but dissolve in ethanol and ether. Their
insolubility in water is also due to the fact that they do not form hydrogen bonds with water
molecules. The large resonance energy (30 kcal) resulting from the overlap of p orbitals of
oxygen and carbon atoms prevents the localization of negative charge on oxygen necessary for
hydrogen bonding.
Table. Physical properties of some Acid anhydrides
Name Formula mpC hpC sp gr
gfmol, 20C
Acetic anhydride (CFIaCO)zO 73 140 1081
Propionic anhydride (CEIaCH2CO)aO 45 167 l0l2
Butyric anhydride (CEI1CH2CH2CO)20 75 1995 0968
Isobutyric anhydride [(CHCHCOJIO 535 182 0952
Valerie anhydride [CH3(CHC0110 56 2275 0921
Stearic anhydride [CH3(CH2)1,CO],0 72
CHEMICAL PROPERTIES
Acid anhydrides give reactions analogous to those of acyl chlorides because the latter
could be very much regarded as mixed anhydrides of HCl and RCOOH. Thus they react with
the sane nucleophilic reagents as the acid chlorides but with less vigour. This should be so
because the group RCOO in an anhydride is less strongly electron attracting than the
Cl atom in acid chloride RCOCI, and hence making the carbonyl carbon less positive.
Some typical reactions of acid anhydrides are mentioned below. The reactions (1), (2) and (3)
are examples of nucleophilic displacement reactions.
(1) Hydrolysis, They react with water slowly to produce the corresponding acids.
0 0 0 0
II II 11 II
RCOC--R + H,0 .- RCOH + RCOH
acid anhydride original acid (2 molecules)
e.g., CH100-0--COCH5 + H 10 .- CH100OH + CH00-0H
acctic anhydride acetic acid (2 molecules)
MECHANISM:
PCO + R C OH p P C OH + R-OH
TWO MOLECULES OF ACID

ANHYDRIDE
(2) Alcoholysis. Acid anhydrides react with alcohols to form esters.

0 0 0 0
II II ii
RC-0--C- R + R'OH -i RCOR' - RCOH
alcohol eater acid
e.g.,
CH300-000CH3 + CI }1OH - CH,00-0C2H5 + CHCO0H
acetic anhydride ethyl alcohol ethyl acetate acetic acid
Similarly, acid .nhydrides also react with phenols to give esters.

Functional O.rWOtivu of Carboxylic AcidsAcid halides, Anhydrides, Esters

and Amides 579
() Ammonolysis. Acid anhydrides react with concentrated aqueous ammonia to give

acid amides.
0 0 0 0
II II II
RC--OCR + NH 3 -. RCNH, + RCOH
acid amide acid
e.g., CH,-CO_OCOCF1 3 + NH 3 -' CF1 3CONHa + CH3COOH
acetic anhydride acelamicic
With primary and secondary amines, acid anhydrides form mono- and di-N-substituted
amides respectivel y . For example,
CH 3CO-0COCH 3 + H 3NCH3 -p CH 3CONHCH, + CH1COOH
acetic anhydride methylamine N.rncthylacctamide
CH,
CH3C00COCEI3 HN1CU1 ( -p CH3CON( + CH3COOH
acetic anhydride CF13
dimetbylamine N, N.dimethylaceiamide
(4) Reaction with dry HCl, Acid anhydrides react with dry hydrogen chloride to form
acyl chlorides.
0 0 0 0
II Il II II
R.C_OCR + HCI -p RCC1 + RCOH
acyl chloride
_CO_000--CHa + HCI CH,00CI + CH3COOH
e.g., CH 3
acetic anhydride acetyl chloride
(5) Reaction with Aldehydes. When reacted with aldehydes, acid anhydrides form
aikylidene esters. For example,
0COCH,
CH2 OO0O3 + CH5 CH ' O - CHCH
acetic anhydride acetaldehyde \OCOCH,
ntliylidene acetate
(6) Reaction with Nitrogen Pentoxide, Acid anhydrides react with nitrogen pentoxide
(N 1 O) to produce acyl nitrates which are useful nitrating agents. Thus,
CH,CO--O CO--C H, + NiO,-p 2 CH,CO-0NO,
acetic anhydride acetyl nitrate
(7) Reaction with Phosphorus Peatachioride. With PC],, acid anhydrides yield acyl
chlorides. Thus,
CHrC0_0_C0 Ha + PCI 1 2 CH3CO---C1 + POCI,
acetic anhydride acetyl chloride
(8) Frledel-CrsFt.s Acyistion. Like acyl chlorides, acid anhydrides are used for the intro-
duction of an acyl group into the molecule of a bcnzenoid compound in presence of anhydrous
aluminium chloride. / COCH3
+ CH,C0-0COCH 1
(1) anliyd A1c
I.
Q + CHCO0H
(2) Ha acetopbenone
benzene
(9) Reduction. Acid anhydrides when reduced with LiAIH 4 produce alcohols. For example
CH,CO---O00CF1 3 + 2(H1 2 CHrCH3--OH + H2O

acetic anhydride in ether at 25 ethyl alcohol
Use: Acid anhydrides are widely used as acylating agents in industrial and laboratory
synthesis. They are somewhat less reactive than acid chlorides and are more easily handled
and stored. For this greater convenience in handling and availability, the acid anhydrides are
preferred over acid chlorides as acylating agents.
0 0
II I)
ACETIC ANHYDRIDE, Ethanoic Anhydride, CH3C--0--C--CH1
It is the simplest aliphatic anhydride and is an important industrial chemical,

580
Advnced Organic Chemistry
Preparation. (I) Acetic anhydride is prepared conveniently in the laboratory by

distilling a mixture of anhydrous sodium acetate and acetyl chloride.
- + distil .1.
CH.-L,--CO---ONa + CH,00CI -.- CH,CO--OCOCH, + NaCI
sod acetate acetyl chloride acetic anhydride
(2) By pyrolysis of ethylidene diacetate which is in turn obtained by passing acetylene
into glacial acetic acid in presence of mercury salts (Industrial).
H-0COCH,
+ Ug+ ,OCO---CH, distil
HCC--H -' CH,CH' - (CH,CO)3 0 + CFI,CHO
+ 800 OCOCH, acetic anhyride acct.aldcbyde
H-0COCH, ethylidene djacctate
(3) By passing ketene through glacial acetic acid. The ketene required for the process
is obtained by pyrolysis of acetic acid or acetone (Industrial).
0
II (C1H5)P...0
CH,C--CH, -+ CH,=C=0 + CH,
acetone 700 ketoe
0 0 0
CH,C---OH + CH,=C=O -. CH3C-04CH,
acetic acid ketene acetic anhydride
(4) By oxidation of acetaldehyde. Acetic anhydride is also manufactured by the oxida-
tion of acetaldehyde with air in presence of cobalt acetate-copper acetate catalyst.
o Co(OAc), 0 0 0
II Cu(OAc)a II CHICHO II II
CH,CH + O -_,. CH,.00_0_H -_. CEI3C-4)C_CH,+H10
acetaldehyde 50-70, 60 psi
Properties. Acetic anhydride is a colourless, neutral and pungent smelling Liquid,
bp 1395C. It is sparingly soluble in cold water but in readily soluble in ether and benzene. It
gives reactions similar to those of acetyl chloride, but is much less reactive.
+ H 2O -p 2CH,C00H
acetic acid
+ 2CI H2 OH -p CHICOOCIH,
ethyl acetate
+ NH, - CH,CONH, + CH,COOH
acetatnide
+ MCI -. CH,COCi + CH,COOH
acetyl chloride
+ PCI, -. CH,COCl + POd,
acetyl chloride
CH, C--OCCH, + N,0, -i 2 CH5COONO,
acetic anhydride Iacetyl nitrate
+ CipH, -p CH,.00---CH, + CH5COOH
acetophenonc
+ CH,CHO - CH,CH(OCOCH,),
ethylidene diacetato
+ 2(H) -. 2 CH,CH2 OH + H,0
ethyl alcohol
+ [0] - CHIcO-_0_0_cO_CHI
acetyl peroxide
Uses. Acetic anhydride ii used (I) as an acet y latin g anent (21 in the nreparation of
medicines like aspirin and phenacetin ; and (3) for the manufacture of two important plastics,
cellulose acetate and polyvinyl acetate.
Fithcrionai Derivatives of Carboxylic AcidsAdd halides, Anhydrides, Esters and Amides 581
ESTERS
Esters are the derivatives of carboxylic acids in which the OH of carboxyl group is
replaced by alkoxy group (OR').
0 0
1 OH II
R. COH - RCOR
acid -FOR' ester
The general formula for esters is represented as
0
RCOR' or RCOOR' or RCOOR'
The functional group of esters which determines their characteristic behaviour may be
written as
0
--OR' or CO-0R' or simply COOR'
Esters are by far the most important class of acid derivatives and are widely distributed in
nature. The active ingredient responsible for pleasant flavour and odour of a fruit or flower is
often an ester. For example, amyl acetate is present in bananas, octyl acetate in oranges, amyl
propionate in apricots, ethyl' butyrate in peaches, n-butyl butyrate in pineapples, and isoasnyl
isovalerate in apples. Animal and vegetable fats and oils are esters derived from glycerol and
higher fatty acids. These will be discussed separately in a subsequent chapter.
NOMENCLATURE
Esters are named in a manner similar to salts of carboxylic acids. The common name
of an ester RCOOR' is derived by naming the alkyl group R' first which is followed by the name
of the fragment RCOO as a separate word. The name of fragment RCOO is obtained by
replacing .ic acid of the name of the parent acid (RCOOH) by -ate in the common system and
by -aic acid in the IUPAC system. The common and IUPAC names of a few simple esters are
given below for illustration.

0

CH,COCH1CH1 ethyl acetate ethyl ethanoate
0

CH1CH2COCH2CH, ethyl propionate ethyl propanoate
0

CHCH5C1J1C-0CFl5CHCH1 propyl butyrate propyl butanoate
CH o CH,
I I
CH3CHCH8COCH1CH4CHCH isoamyl isovalerate isopentyl 3-methylbutanoate
ISOMERISM IN ESTERS
In addition to the chain isomerism of the hydrocarbon groups, esters exhibit Metamerism
and isomerism with acids. For example, the molecular formula C,HaOs represents two isomeric
esters ani one acid.
0 0 0
U II
CHC OCH ICEJ2 CR5CHCOCH CH3CHCFU4COH
ethyl acetate methyl propionate bulanoic acid
Ethyl acetate and methyl propionate differ in respect of the carbon atoms about the ester
group COO, and are called metamers.

Esters can be prepared by the following general methods.
(1) Esterlfication. Esters are usually prepared by boiling a mixture of carboxylic acid and
an alcohol in presence of a mineral acid catalyst, such as cone 1I 2SO or HCI gas This reaction
is commonly known as Fischer.Speir esterification procedure.
0 0
H+
RCOH + R'OH = RC--0R' + H,0
acid alcohol ester
0 0
11
e.g., CH ICH ICOH + CH 3CH IOH = C113CiJCOCH 1 CH 3 + H20
propionic acid ethyl alcohol ethyl propionate
This reaction is reversible and withone mole of a straight-chain acid and one mole of a
primary alcohol, the equilibrium is established when about 66% conversion to ester has taken
place. Better yields are obtained by using excess of the carboxylic acid or alcohol which displaces
theequilibrium to the right. Usually alcohol is employed in excess since it is cheaper. Alter-
natively, equilibrium can be shifted to the right by removing one of the products i.e., water as
soon as it is formed. This can be accomplished by carrying out the esterification in benzene or
toluene and removing the water by azeotropic distillation with solvent.
Esters are also obtained when a mixture of the vapour of an acid and an alcohol is passed
over heated thoria.
o 0
1 ThO, II
RCOH + R'OH -i R-C--OR' + HaO
300
(2) Alcoholysis of Acid chlorides and Acid anhydrides. Esters are conveniently prepared by
the action of alcohols on acid chlorides or acid anhydrides.
(a) R00---Cl + R'OH -p R00-0R' . HCl

acid chloride ester
e.g., CFI300--Cl + CH s OH -. CHaCO-0C C H b + HCl
acetyl chloride ethyl alcohol ethyl acetate
RCO
(b) ')0 + R'OH -i RCO--OR' + RCOOH
R00 alcohol eater acid
acid anhydride
CH1CO\
e.g., )O + CH,OH -i CH,CO-0CH, + CHJCOOH
CH 1 CO' ethyl alcohol ethyl acetate
acetic anhydride
Acid anhydrides, however, react a little slowly than acid chlorides which are preferred on
a laboratory scale.
(3) Silver Salt method. Ester may be prepared by treating the ethanolic solution of an
ethyl halide with silver salt of an appropriate carboxylic acid.
R00OA + R'X -. R00-0---R' + AgX

silver salt alkyl halide ester
e.g., CHCHa00_0A + C2 H5 Br a CH3 CH200-0C2 H + AgBr

silver propionate ethyl bromide ethyl propionate

Functional Derivatives of Carboxylic AcidsAcid halides, Anhydrides, Esters and Amldes 533
Although sodium salts of carboxylic acids also give satisfactory yields, the use of silver
salts gives improved yields. Sodium or potassium salts of carboxylic acids, however, produce
excellent ,yields of esters when treated with a dialkyl sulphate in alkaline solution.
-+ R'O 0 KOH K0 ,O
R00--0K-- -p R00OR' + )S'
pot salt of acid R'O" 0 ester R'O' NO
dialkyl sulphate alkyl potassium
sulphate
- CH5-00 KOH -+
e.g., CHI00-0i + ')S .s CFI 500-0CH3 + CH3-0--S0,--OK
pot acetate CHIO/ '0 methyl acetate methyl potassium
dimcihlyl sulphate sulphate
(4) Addition of an Acid to Alkene. Esters are produced when the solution of an alkene in
conc sulphuric acid is treated with a carboxylic acid. This method is particularly suitable for
the preparation ofesters of tertiary alcohols.
H
H5SO4 I
H5CC=CH1 + CH,COOH = CH500-0C--CH5
len- butyl acetate

(5) By the addition of Diazomethane to Carboxylic acids. Methyl esters can be prepared
conveniently when an ethereal solution of diazomethane is added to the solution of a carboxylic
acid in ether.
- +
R00OH + CHINEN -4 R00---OCH3 + N1
acid djazomethine methyl ester
This reaction proceeds even below 0 and gives quantitative yield of esters. This
method is, however, suitable only for laboratory preparation because of the difficulty encountered
in preparing and handling the reagent.
(6) Tlsclienko Reaction. Esters may also be prepared by treating the application of
TLschenko Reaction when two molecules of an aldehyde in the presence of aluminium ethoxide
Al(0C1 H react by mutual reduction and oxidation to form an ester.
0=HCR'
+ A1(OC1H1)3
R00H R00-0CH1R
(2 molecules of ester
aldehyde)
AI(OC%Hsh
e.g., 2 CH5CH3CHO -+ CH5CH100OCH,CH1CH5
propiosaldehyde propyl propionate
PHYSICAL PROPERTIES
(I) The lower members are volatile liquids, lighter than water, and having pleasant
odours that are usually described as fruity. The higher esters are colourless wax-like solids.
(2) The boiling points of the methyl and ethyl esters are lower than those of parent
acids because association through hydrogen bonding does not occur in esters (hydroxyl groups
are absent). Esters with unbranched chains have higher boiling points than their branched.
chainisomers.
The inability of the esters to forn hydrogen bonds is evident from the fact that their
boiling points are comparable to acid chlorides of similar molecular weights.
584 Advocd Organic Chemistry
Compound Formula mol WI bp C

0
Butyl chloride CH,CH,--.CH1b.--CI 106 101
0
Butyl formate Ht-0CH,CH,.-CH,CH, 102 107
0
Propyl acetate CHCOCH,CH,CIJ1 102 102
(3) Low-molecular-weight esters are fairly soluble in water. For example, methyl
formate dissolves up to the extent of 30 g/100 g of water at 25'. Water solubility of esters
decreases with Increasing hydrogen chain. On the other hand, all esters are soluble in most
organic solvents (ethanol, ether, benzene, etc.)
The water-solubility of esters is explained by hydrogen bonding between molecule of an
ester and water molecules,
Table. Physical properties of some Esters
Solubility
Name Structure bp 'C g1100 g HO at 20C
0
Ethyl formate H-4--OC1H5 54 miscible in all
proportions
0
Ethyl acetate CEJ--OC1H5 77 739 (25C)
0
Ethyl propionate CH3CH 2--4OC1 H5 99 175
0
Ethyl butyrate CHCHCH1tOC2H5 120 051
0
Ethyl vaterate CU3CFI1C}1CH,COC1H1 145 022
0
Ethyl caproate CHsCH*CH2CH3CEIr-.COC1FI6 168 0063
0
Ethyl enthanate 189 0030
Esters or Acetic acid:
0
Methyl acetate CH,---0CH1 57 244
Ethyl acetate CH,COCH1CH1 77 739 (25C)

0
n.Propyl acetate CHI__!OCH2CH1CH1 102 189
0
n.Butyl acetate CH,COCH1CH1CH,CH1 125 10 (22C)

Functional Derivatives of Carboxylic AcidsAcid halides, Anhydrides, Esters and Amides 585
CHEMICAL PROPERTIES
Esters give nucleophilic substitution (or S) reactions analogous to the acid halides and
anhydrides since the carbonyl carbon in their molecule is electron deficient and carries a partia
positive charge.
06 0
R C It--CNu --lb- R--CNu + :

+ - ^u
^-t^
co_a ALKOXY ION

(LEAVING
GROUP)
The esters undergo SN reactions considerably less readily than acid halides and
anhydrides. This is due to two reasons:
(1) Esters are resonance hybrids of two canonical fc.ms.
c11
RC--O R 4 RC=CR
As a result of this resonance, the carbonyl carbon is not as electron deficient (or positive) as in
acid halides and anhydrides. This makes esters less prone to nucleophilic attack.
(II) Alkoxide ions '-OR) are much stronger bases than halide ions (X) and carboxylate
ions (RCOO-); and hence these are poor leaving group3 relative to X- ions and RCOO- ions,
Nevertheless, esters undergo a good number of S N reactions. A few reactions charac.

teristic of esters are discussed below.
(I) hydrolysis. Esters are hydrolysed by boiling with mineral acids or alkalis.
(a) ACID HYDROLYSIS. An ester can be hydrolysed to give the parent carboxylic
acid and alcohol by using mineral acid (H2S0 or MCI) as catalyst.
0 0
R--C--OR' + 1110 RCOH + R'OH

Cow carboxylic acid alcohol
0 0
II II
e.9. 1 CH5C-0CH1CH5 + H 10 CHI.COH + CH,CH1OH
ethyl acetate acetic acid ethyl alcohol
The above reaction is reversible and is exactly opposite of esterification. In order to hydrolyse
most of the ester, the equilibrium must be pusLd to the right by using large excess of water
(one of the reactants). For this reason acid hydrolysis is seldom convenient,
(b) ALKALINE HYDROLYSIS (Saponification). When an ester is treated with an

alkali (NaOH or KOH) as catalyst, the hydrolysis yields the parent alcohol and sodium salt of
the carboxylic acid.
0 0
1 +- Ho Il -f
RCOR' + NaOH .+ R CONa + R'OH
ester a sod salt alcebol
0 0
U + - H10 II - +
CHr_CHr_C_0CH5CH5 + NaOH , CH 5CH,C-0Na + CH1CH5OH
thyl proplonate
e A sod propionate
Organic Clieniistrv - 38
686 . Advanced Organic Cemst'
Alkaline h y drolysis of ester is also known as saponification since the reaction was first used
for the preparation of soaps from the esters of higher fatty acids (oils and fats). The term
saponification, in fact, comes from the Latin Sapo='soap', and onis= fy' i.e., to make soap.
Unlike acid-catalysed hydrolysis of esters, the base-catalysed hydrolysis resulting in the

formation of salts is irreversible and proceeds to completion. It is, therefore, more efficient
than acid hydrolysis. Further, since one equivalent of a base is required for each equiialent
of the ester, the reaction can be employed for the quantitative estimation of esters. A known
weight of an ester is reuluxed with excess of a standard alkali and the unreacted alkali at the
end of the reaction is titrated with a standard acid using phenolphthalein as indicator.
MECHANISM. The hydrolysis of an ester in theory can proceed by either the

cleavage of the ester group at the CO bond or at OR' bond. Thus when the hydrolysis
is carried with water containing the isotope O il instead of 016 , the reaction can foflow either
of the two possible courses.
0 0
It 11:
______ is /
Course 1: Rc--o_rs * C--OH + k-0H
ACID ALCOHOL
0 0
IIII
Course 11: __C__O.j.iR' -----a.- RC-0.ti +
Is ACID ALCOHOL
141.0_Il
Experimentally it is found that most esters on hydrolysis produce the acid containing O.
Therefore, it stands to reason that the bond CO is broken during hydrolysis. The exact
mechanism of ester hydrolysis involves the steps described below,
Acid Hydrolysis. The acid hydrolysis being ,a reversible reaction, its mechanism is
exactly the reverse of the acid-catalysed esterificatton of carboxylic acid. However, for
recapitulation it is mentioned below.
(i) Protonation of carbonyl oxygen to give cation I which is mesomeric with cation II.
/
rkC---O 4- 11 R__C---O
II
(ii) Attack by nucleophile water molecule and proton transfer.
R:i;,

Functional Derivatives of Carboxylic Acids"Acid halides, Anhydrides, Esters and Atnides 587
(iii) Elimination of R'OH and formation of original acid.

1H
( ROw
I-.
1C - _CO + H
I 4GW
Alkaline Hydrolysis. The nucleophile OH attacks the carbonyl carbon which bears
partial positive charge, to form anion I. The anion 1 splits off an alkoxy anion and givd the
corresponding acid 11. The alkoxy anion then extracts a proton from the acid II giving acid
anion and alcohol.
-.
co 0
a- 1COH
OH
I,
OR
OR
ESTER AN/ON (I)
(it) acOH ____- CUI-I -I- 0 1

____ 1
CL
01 ACID(g) ALKOXYAVIO'V
0 0
uiti
II- II -
ICUH + OR - IC U + RON
ACID 9 ACID AN/DIV ALCOHOL
Alkaline hydrolysis is reversible because of the irreversibility of step (iii).
(2) Alcoholysis; Transesterlficatlon, An ester RCOOR' can react with an alcohol

R"OH to give a new ester RCOOR".
0 0
II II
RCOR' + R"OH RCOR" + RIOH
ester alcohol new ester
Here the 'alcohol residue' (OR') of the original ester has been replaced by the 'alcohol
residue' (OR") of the reacting alcohol. The formation of a new ester by mutual exchange or
transfer of 'alcohol residue' is termed Trsnesterlfication. The reaction is catalysed by acids
(HCI or HSO4 ) or bases. The most effective catalyst is a trace of the sodium alkoxide
corresponding to the reacting alcohol (R"OH). Transesterification is a reversible process and
is pushed to completion by using a large excess of the alcohol. It is generally used for
preparing the ester of a higher alcohol from that of a lower one, since the lower alcohol
produced in the reaction can easily be removed by distillation giving better yield. For example,
-.4.
C1H2ONa
CH,CO-0C5H5 + C 3H70H CH3COOC,F17 + CIHSOH
ethyl acetate propyl alcohol propyt acetate ethyl alcohol

Advonced Oganf c Cernis(ry

588
Base-catalysed transesterification is preferred to acid-catalysed reaction since in the

former case the reaction proceeds to completion.
MECHANISM. The mechanhm of transesterification is probably similar to the
corresponding hydrolysis reaction of esters, the reacting alcohol taking the place of water.
The base catalysed reaction proceeds by the following mechanistic pathway.
R"O
+ OR'
OR
(3) Ammonolysis. Esters react with ammonia, in either concentrated aqueous or ethanolic
solution, to form acid amides.
0 0
II . II
RCOR' + NH, p RC--NH, + R'OH
ester acid amide
e.g., CH 3 00-0C1 H5 + NH CH,CONH,

+ + C,H5OH
ethyl acetate acetainide
However, the reaction is much slower than with acid chlorides or anhydrides, and
amides are therefore more easily prepared from esters.
The mechanism of ammonolysis of esters is essentially the same as that given for the
acid chlorides and anhydrides.
(4) Reaction with Grignard Reagents. Grignard reagents react with esters to form an
addition product which decomposes to form a ketone.
0 /
-- .+. RC--R+ R0M9X
R11
ADDUCT
The resulting ketone at once reacts with more Grignard reagent to form halomagnesium salt
which upon hydrolysis gives the corresponding tertiary alcohol.
OH
o OMgX
I
II I
RC--R"
HO
p RCR" + Mg(OH)X
? alcohol
Formic asters when reacted similarly produce secondary alcohols.
(5) Reaction with Hydsoxylainine. Esters react with hydroxylaminc in presence of strong
bases e.g., ethanolic KOH to give the correspondiug hydroxamic acids.
O 0
II II
RCOR' + H1N0H -.. RC---NHOH + R'OH
ester bydro'aniic acid
These compounds produce deep purple complexes with ferric ions. This reaction, therefore,
forms the basis gf detection of ester groups in organic substances.
(6) Reduction, Esters can be reduced to alcohols by a variety of reagents such as

lithium aluminium hydride, sodium and ethanol, or by catalytic reduction,

589
Functional Derivatives of Carboxylic AcldsrAcid halides, Anhydrides, Esters. and Amides
RCO--R' + 4[H] LiAlH R--OH + R'OH

ester
11 alcohol
0
II L1AIH,
iCH2_ C1{r_0 1 + CH3OH
e.g., CH1 CHCH1_ C_0C1a + 4(H] --* CHaCH n.butyt alcohol
methyl butyrate
The reduction of esters to alcohols with sodium and and alcohol is commonly known as
Bouvesult-Blanck Reduction. This reduction is particularly important because while converting
an ester into alcohols it does not reduce ethylenic linkage if present in the ester molecule.
Thus,
Na(CH2011
CH3(CH2)1C CH(CH I)rCIIaOH J. CHOH
CH3(CH1)7CH=CH(CH1)7_C0OClHa 41H] oleyl alcohol butyl
butyl oleatc alcohol
The esters can be reduced with molecular hydrogen with copper chromite catalyst at
280-300 and at 100-300 atmosphere pressure (Adkin's Method). The catalytic reduction of
long-chain carboxylic acids to form long-chain alcohols is used in the manufacture of
detergents.
Cu chromite
+ 2H1 CH3(CH,)10C1hi01 + CH3OH
CH 3(CHz) 1 oCO_0 t 3
lauryl alcohol
methyl laurate 280-300'
300 atm
The mechanism of reduction of esters probably involves nucleophilic attack on the
carbonyl carbon by the hydride ion (H-) or another electron donor.
(7) Pyrolysis of Esters. Esters which have a hydrogen atom on .carbon of the
alkoxy group when heated to 500' lose a molecule of an acid to form an alkene. Esters of
primary alcohols are converted to 1-alkenes and acid.
R00O H
I 500'
CH,CHR' RCOOH + CH,CHR'
acid 1-alkene
aP
ester
e.g., CH,CO-0 H
II 500'
+ CH1=CHC3
CH1 _CH_CH 5 Clu, -' CHC00 11 1-butene
n-butyl acetate acetic acid
In this reaction the R00-0 group and a hydrogen on adjacent carbon are eliminated as
acid. It may be noted that with primary alcohol esters, pyrolysis affords a single alkene.
With secondary and tertiary alcohol esters where elimination of acid may take place in more
than one direction, a mixture of alkenes is produced. Acetates are commonly employed for the
reaction.
MECHANISM. The pyrolysis of esters occurs through a cyclic transition state.
H OH
'- -<.3--
H H1
(___-0 R -
NV Q
0 AL)t(Nf Ac)O
CYCLIC TRAN31TION
E3TE1
5MTE

590 Advanced Organic Chernstry
(8) Acyloln formation. Esters react with sodium metal in a suitable solvent such as
benzene or toluene to give bimolecular reduction products called acyloins.
-+
o NaO ONa 0. ?H
1 I I H10 II
2 CH1 COC,H 6 + 4Na e CH 3CCCH1 -, CHICCHCH1
acetom
(an acyloin)
It may be noted that acyloins are compounds in which the grouping CHOH--CO is
flanked by alkyl groups. The reaction occurs on the surface of the sodium metal and is rather
similar to the bimolecular reduction of ketones to pinacols.
(9) Claisen Ester Condenutioo. Esters which contain x.hydrogen atom react with
themselves, undergoing a reaction very similar to aldol condensation. In the presence of
strongly basic reagents such as sodium ethoxide, metallic sodium or sodamide, two molecules
of the ester eliminate a molecule of alcohol to form a ketone.
- OR 0
C1HSON V I U
RCH--COR' + HCHC---OR' ; RCH1--CCH-_C_0p. + ROH
cater second molecule .keto ester alcohol
of ester
This specific type of condensation reaction shown by esters was discovered by Ludwig Claisen
(1887) and is named after him.
The best example of Claisen Ester Condensation is the preparation of ethyl acetoacetate
from ethyl acetate in the presence of sodium ethoxide,
0 0 -+ o o
II II C,H6ONa II II
CH1C--0C5H1 -F HCH--4---0C1115 z . CH,CCH,L;.001H1
ethyl acetate (2 molecules) ethyl acotoacetate,
acetoacetk ester
Ethyl acetoacetate is a valuable synthetic reagent and will be discussed in detail at a later stage.
Since the Claisen reaction described above is reversible, the alcohol must be distilled
as fast as it is produced so that equilibrium is shifted to the right to give good yield of the keto
ester.
MECHANISM. The mechanism of Claisen Ester Condensation may be illustrated by

taking example of the formation of acetoacetic ester from ethyl aeetate. It involves the
following steps.
(i) a-hydrogen atoms being weakly acidic and in the presence of a strong base such as
sodium ethoxide (C1 HSONa) reacts to forms the ester anion I.
(ii) The ester anion [is a strong nucleophile which then attacks the carbonyl carbon
of a second ester molecule to produce the anion II.
(iii) The anion I1 eliminates an etboxide.ion to yield the -keto ester.

HO 0
C1 HSO + HC--C--0C1H5 : CH,.. C-0C1 H5 + CIH1OH
cthoxide ion ester anion (I)
I-I
ethyl acetate
59!
Functional Derivatives of Carboxylic AcidsAcid halides, Anhydrides, Esters and Amrdes
:0: 0
CH 3
I
CJl 2 C 0C2H
CH 3C"+ El Co--- C2k,
QC2H 0C2N5
3ECOftJL? E5Te AN/OW fi

.4OLEC.IL
flb -
"-0- I
a
______________ - II
o
CH 5 _C_C 2_ C-0C 5 C2t40 + CH3_CCHC_0C1HS
^1 C, H,
USES OF ESTERS
(I) Esters are extensively used for preparing flavouring essences e.g., ethyl formate in
raspberry essence and isoamyl acetate in pear essence.
(2) They are used in artificial scents.
(3) Esters (ethyl, butyl and pentyl acetates) are used as industrial solvents, especially
for cellulose nitrate in the formulation of lacquers, and also for oils, paints, varnishes and
gums.
(4) They are also used as solvents for drugs and antibiotics. Butyl acetate is empi
loyed to extract penicillin from 'fermentation broth'.
(5) High boiling esters are used as softening agents (plasticizers) for resins and plastics.
ETHYL ACETATE, Ethyl ethanoate, CH4_LOCH1CH1

It is the ethyl ester of acetic acid and is a typical member of the class.
Preparation. (I) Ethyl acetate is prepared on a large scale and also in the laboratory
by refluxing glacial acetic acid and absolute-ethyl alcohol in presence of a few drops of conc
H,SO4 as catalyst.
H,SO4
CH00--OH + C 5 H 5OH CH,.CO-0C1H1 + H20
acetic acid ethyl acetate
It can also be prepared by passing a mixture of glacial acetic acid and ethyl alcohol in
vapour form over a suitable catalyst such as thorium oxide or titanium dioxide at 150-300*.
(2) It is also prepared by adding active anhydride or acetyl chloride to ethyl alcohol.
CHa_CO_0C0CH3 + CaHOH CHC0OCH5 + CH3COOFI
acetic anhydride ethyl acetate
CH,00--Cl + C,HaOH - CH 5-COOCH + HCI
acetyl chloride
(3) It can be obtained by heating acetaldehyde with aluminium ethoxide.
Al(OC1Ha)s
2 CH,CHO CH,CO-0C1H5
acetaldehyde
Properties. Ethyl acetate is a colourless liquid, bp 78. It has a characteristic fruity
odour. It is sparingly soluble in water but readily soluble in organic solvents. It gives all the
general reactions of esters. A few typical reactions of ethyl acetate are summarised as follows.

H-fH2O
CH,COOH + C5H2OH
acetic acid ethyl alcohol
NaOH -+
CH,CO--ONa + C,H2OH
sod acetate
NaJC,H5OH
2 CII, - CH,OH
or LIAIH4 ethyl alcohol
fl concNH,
CH,COC,H 1 - CH,CONH,
ethyl acetate acetamide
CH,
(I) CH,Mgl I OC1H,
CH,C---OH + Mg"
(2) H2OJH+
CH,
teri-butyl alcohol
pa,
CH,COCl + C1 H,CI + POCI,
acetyl chloride ethyl chloride
C2H2ONa
CH,COCH,CO OCH,
ethyl acctoacetate
Uses. Ethyl acetate is used (I) in the preparation of artificial fruit essences; (2) as a
solvent for lacquers (3) as a solvent in the ebbulioscopic method for determining molecular
weights and (4) in the preparation of acctoacetic ester (ethyl acetoacetate) which is a veritable
organic synthetic reagent.
ACID AMIDES
In this class of derivatives of carboxylic acids, the OH of the carboxyl group is replaced
by an amino group, NH,.
0 0 0
II OH 1
RCOH -. KCNH, or RCN(
carboxylic acid -I-NH, acid amide "H
These compounds arc known as Acid amides or Amides, Evidently, the simple amides may be
represented by the general formula RCONH,, when the amide group, CONH,, acts as
the functional group. The hydrogen atoms of the arnido group on substitution by alkyl group
(R) give rise to the Substituted amides.
0 0 0
11, H Ii II ,R' ii
RCN( -p RCN' -. RCN'
amide "H +R "H +R'
mono-N'substjtuted di-N-substjtuted
amide amide
The alkylamino group, NHR, and dialkylamino group, NR,, are functional groups of mono-
-substituted and di . N-substituted amides respectively. In general, the functional group of
amides may be written as
A00E L/4'MAGF
- CN OP - cN(
and the carbon-nitrogen bond is called the Amide linkage. This bond is very stable and is found
in the repealing units in protein molecules, nylon and many other industrial polymers.

Functional Derivatives of Carboxyilc AcidsAcid halides, Anhydrides, Esters and Amides .593
Alternatively amides could also be considered as derived from ammonia by replacement

of one, two or three H atoms by acyl group,(30)
RCO. They are designated as primary (ll
amide, secondary (2) amide, and tertiary amide according as 1, 2 or 3 acyl groups are
attached to the N atom.
H H OCR OCR.
HNH RCONH RCONH RCONOCR

ammonia 1' amide 2' amide ? amide
The diacyl derivatives of ammonia and primary amines are also called Inildes
OCR OCR OC CO
I I N
RCONH RCONR or CO t'
CON
diacyl ammonia diacyl p-amine __
(imide) imide group
Cyclic imides of succinic acid and phthal ic acid are important
CO
CHICO
')NH
dH,ro
- CO
succinimide
phthalirnide
In this chapter we will discuss only the simple amides or 1 amides, RCONH2,
which are important as a class.
STRUCTURE OF AMIDES
In amides both the carbonyl carbon and the nitrogen are sp'- hybridized. 'Ihe three spt
orbitals of carbon overlap with a sp l orbital of the alkyl group, a sp 2 orbital of nitrogen and a p
orbital of oxygen to form three ci bonds. The remaining two sp 2 orbitals of N overlap with s
orbitals of two hydrogens to produce two NH a bonds. Further, the half-filled p orbitals on car-
"N
si-s

(BEFORE OVERLAP) (AFTER OVERLAP)
if
Fig. 243. Orbital Model of Amidc.
e
boo and oxygen being parallel overlap to form a bond of the carbonyl group. Sinc tile p orbital
on N containing the lone pair of electrons is also parallel to the p orbital on carbon, the additional
594 Adanced Qgunic Che'ii:St!Y
overlap also becomes possible. In vie' of this additional overlap, the molecular orbital picture
of an amide as compared to that of an acyl halide is modified as illustrated in Fig. 43. In
valence bond terms the additional overlap in amide may be visualised as a resonance hybrid of
forms I and II.
RC
/ NH2
NH 2 NH2
I II 132A
The additional overlap shortens the carbon-nitrogen distance in amides to 132 A as

against the normal carbon-nitrogen single bond distance of 147 A. This suggests a significant
contribution of the dipolar ion II towards the actual structure of amide,
NOMENCLATURE
The Common Names of amides are derived from the trivial name of the parent carbo-
IUPAC System,
xylic acid by dropping the suffix -ic and and adding the word amide. In the
amide, When
the -oic acid of the name of the corresponding acid is replaced by the word
alkyl groups are attached to the nitrogen atom, they are so indicated by the capital N. The
common and IUPAC names of a few amides are listed below for illustration.
Table Common and IUPAC names of some Amides
Formula Common Name !UPAC Name
HCNH3 formamide methanamide
CH,CNH1 acetamide ethanamide
CH3CH3C-14H propionamide propanamide
CH3CII1CH1_CNH1 n-butyrarnide butanamide
CH3CHCNH2 isobutyrarnide 2-rnethylpropanamide
0
,CH3
CH3CN / W-methylacetaniide N.inethylethanamide
CR
CH,CN" N, N.dimethylacctamide N, N-dimcthylethanamide
\CH,

Functional Derivatives of Carboxy1c AcidsAcid halides, Anhydrides, Esters and Amides 595
(1) By Pyrolysis of Ammonium salts of Carboxylic acids. The simple amides can be
prepared by heating the ammonium salt of the corresponding acid at 170 230'. The am-
monium salt dehydrates to form the amide.
o 0
II - + 170-230' II
RCONH4 -.-- RCNH, HSO
amm carbozylate acid amide
Alternatively, ammonium salt of the relavent carboxylic acid can be heated in an inert solvent
to get the amide. For example, acetamide is generally made by refluxing a solution of ammonium
acetate in glacial acetic acid.
O 0
- + in CH5COOH
CH,CONU, - CH,C--NH I + H2O
amos acetate reflux acetamjde
(2) By Partial Hydrolysis of Alkyl Nilriles. Acid amides are obtained by the controlled
or partial hydrolysis of alkyl nitriles.
0
RCN + H20 -p RC-1-4l{1
nitrile amide
This can be effected by dissolving the nitrile in cold concentrated sulphuric acid and pouring
into water, or by shaking with concentrated hydrochloric acid. Forrnamide may thus be
prepared by the partial hydrolysis of hydrogen cyanide.
0
HC=N + HSO -.
hydrogen cyanide (ormamide
(3) By Ammonolysis or Acid chlorides, Acid anhydrides and Esters. The most important
general method for preparing amides is by treating acid chiorides, anhydrides or esters with a
concentrated solution of ammonia.
0 0
II II
RC CI + 2NH1 _+ RCNH, + NH4CI
acid chloride amide
0 0 0 0
II II II
RCO--CR + 2N1T 3 -p RCNH + RCONH4
acid anhydride
R00R' + NH, RCNHa + R'OH

ester
Acid chlorides in general are readily available add are commonly used. For example,
acetainide is conveniently and quickly prepared by the action of ammonia on acetyl chloride.
CH3 COC] + 2NFJ3 -+ C11 3 CONH, + NH4c1

acetyl chloride acetamide
The reaction of ammonia on esters is reversible and is of practical value in the case of
simple esters only it proceeds best with methyl esters.
(4) By heating Carboxylic acids with Urea. When a carboxylic acid is heated with urea.
an exchange reaction takes place to form an jtcid amide.
596
0 0 0
0 II
II II II
H 1 NCNH, + RC--OH RCNH1 + H2NC-0H
acid amide carbamic acid
urea (unstable)
0
H 1 NCOH .-_, CO, + NH3
Since the carbamie acid is decomposed to carbon dioxide and ammonia (both gases), and
are thus removed from the reaction mixture, the above reaction proceeds to completion.
PHYSICAL PROPERTIES
(mp 2-5),
(1) With the exception of formamide which is a liquid at ordinary temperature
all amides are white crystalline solids having sharp melting points.
(2) Pure amides are odourless. The unpleasant smelt associated with simple amides is
due to the presence of impurities. As ordinarily prepared, acetamide smells of mice but the
smell disappears after recrystallisation from acetone.
3) The amides have abnormally high boiling points and melting points. Thus their boiling
points are much higher than the acids from which they are deri"ed, eventhough their molecular
1000 while formamide
weights are almost identical. For example, formic acid (mol boils at
(mol wt 45) boils at 211'. Acetic acid (mol wt 60) boils at 118' while its amide i.e., acetamide
(mol wt 59) boils at 222 0 . The high boiling points of amides are due to the polar character of
their molecules And the formation of hydrogen bonds between the oxygen atom of one molecule
and the amine-hydrogen atom of another molecule.
H k-80ND H H K
I
O=C_NH-----OCN--H----.O=CNH---- O=CNH--
I
S
I
S
I
It
I
It
(a portion of the hydrogen-bonded network oramide RCONII1)
The stronger intermolecular forces caused as above raise the boiling point of amides,
Because of the salt-like dipolar character and complete association in the solid state, the
amides are crystalline solids with melting points higher than the corresponding acids of compar.
able molecular weights.
(4) Lower amids up to those made of five or six carbon atoms are very soluble in water
and are deliquescent. All amides are soluble in organic solvents. Amides owe their large solubility
to association with water through hydrogen bonding and ionic character of their molecules.
--- I I
HYDROGEN 8OiVO
O=CN---H------OH- ----O=C---.N----H----- OH-
H
1
K. N
AMIDE WATER AMIDE WATER
The water-solubility goes on decreasing as the molecular weight increases because of the
increasing hydrocarbon part (R) of the molecule.

Fttpctlonal Derivati v es of CarboxyIc AcidsAdd halides, Anhydrides, Esters and Arnldez 597
Table. Physical properties of some simple Amides.
Name Formula nip C bp C Solubility in water
Formamide HC0Nl1 25 210

Acetamide CHC0NHI 82 222 very soluble
Propionarnide CH3CH2CONH2 79 213 soluble
Butyramide CU3CHCHCONl-I 115 216 soluble
Valeramide CHCHCFI1CH2C0NH2 106 sublimes soluble
Caproamide CH 8 (CH 2)I CON I-I, 100 sublimes slightly soluble
CHEMICAL PROPERTIES
Acid amides give the following general reactions.
(1) Basic and Acidic Character. Amides are resonance hybrids of the following canonical
structures.
0
L. ____
!- 'RCN---H OR RCNH
6+
I I
H
HYBRID
Becauseof the delocalization of the non-bonding electron pair of N atom over the system
0C--N it is relatively unavailable for accepting a proton, Hence amides are neutral or weakly
basic in character in contrast to amines in which the electron pair of N atom is fully available
for protonation.
AVAILABLE RELATIVELY UNAVN48LE

0 (DUE ro DEL OCALIZA 1/ON
'R P'OTO4'A 7/ON
OVER 0-C -N
ii !'
RCNH
RP4---H
H 14
37RON6LY BASIC (WEAKLY 8A31C)
Furthermore, as a consequence of the delocalizalion of the non-bonding electron pair of

N atom, 0 atom acquires a partial negative charge and N gets a partial positive charge as shown
above in the hybrid structure. Thus similar to carboxylic acids, amides will be expected to
evidence acid character. The N-H bond is weakened as a result of delocalization of the electron
pair and thereby the release of proton (H 5 ) is facilitated. Thus acid amides act as very weak
acids.
The fact that amides behave both as very weak bases and acids, is shown by the foil -)wing
reactions.
(a) As Weak Bases amides form salts with strong mineral acids which are only stable in
the aqueous solutions.
+
.5- , 0H 10H -
RC' + HCI -+ RC' +--+ RC" Ci
NH2 NH,
amide
Thc i in agreement with the fact that amides being resonance hybrids the protona
tion takes place at the negative 0 atom rather than at N atom which carries a positive charge.
This is also supported by NMR studies of amides.

598 Advanced Organic Chemistry-
(b) As Weak Acids amides react with sodarnide (NNH 1 ) in ether solution to form salts
of .ie stronger acid. Here the proton attached to N atom is released in the reaction.
Ii ' - I II
ro 1
- I
2RCNH, -4- NaNH, -b 21 RCNH INa + NH,
amide sodamide L salt J
Amides also form mercury salts with mercury oxide.
RCONH
2RCONH1 + HgO -, Hg + H10
amide RCONH"
mercury salt
(2) Hydrolysis. On boiling with water, amides are hydrolysed to give the parent acid and
ammonia. The hydrolysis takes place rapidly in a minera' acid (usually nd) and far more
rapidly in an alkali such as sodium hydroxide.
0 0
Ii 0+ II
RCNH, + H 20 -b RCOH NH4
(HO)
O - 0
II OR II -
RCNH, + HO -, RCO + NI-Is
MECHANISM. The reaction takes place by the same mechanism as the hydrolysis of
esters and acid halides.
(a) Acid Hydrolysis:
+
0 ,vOH OH OH OH
H L -H4 '4+ I +
RCNH 2 RC--NH2 R CNH ? -- RC--NH3
.111 IV - fr
R _CJ H-_H OH
ON
+
-p I--C=O -4 NHa
(b) Base Hydrolysis:
RC--NH' R-2-NH -.. R c -E + NH

LH
(3) Reaction with Nitrous Acid. Amides when treated with nitrous acid and dilute HCI
give a quantitative yield of nitrogen and the parent carboxylic acid.
0 0
II HO
RCNH, + HONO - RCOH + N 1 + H10
amidc nitrous acid carboxylic acid
In actual practice, sodium nitrite and dilute HO are used for the above reaction. Thus,
HCI
CH,CONH 1 + HONO p CH,COOH + N 1 +.H,0
This reaction of amides is analogous to that given by primary aliphatic amines.

Functional Derivatives of Carboxylic AcidsAcid halides, Anhydrides, Esters and Amides 599
(4) Reduction. Amides may be reduced to primary amines either with sodium and
ethanol or with lithium aluminium hydride (L1AIH4).
0
II Na/C2HOH
RCNH 1 + 4[H] -+ RCH,NH, + H,0
or Li All-I 4 I' amine
(5) Dehydration. Amides when heated with phosphorus pentoide or thionyl chloride
(SOd 1 ), lose a molecule of water to form the corresponding nitriles,
0
II POa
RCNH, -_., RCN + H,0
or SOCl 2 1' nitrite
Formarnide is converted to hydrogen cyanide and water by passing its vapour overthoria
or pumice at 400'.
0
II ThO,
HCNH, -p HCN + HO
400 hydrogen
cyanide
(6) Hofmann Degradation. When an amide is treated with bromine (or chlorine) in
alkali solution, it is converted to a primary amine that has one carbon less than the starting
amide,
0
II H20
RCNH, + Br, + NaOH -, RNH,
amide r amine
This reaction which was discoveied by Hofmann in 1882 and results in the formation of a
primary amine by elimination of carbonyl group (one carbon) from an amide, is often referred
to Ifofmaran Degradation. The overall reaction of the amide with bromine in the presence of
three equivalents of alkali may be represented by the equation
H10
R00NH, + Br, j- 3 NaOH -p RNH, + 2NaBr + NaFICO 1 + 1110
amide I' amine
Hofmann degradation is particularly useful for stepping down any homologous series by one
carbon atom less.
MECHANISM. The mechanism of Hofmann degradation involves the following
steps
(I) Base-catalysed brornination of amide produces N-bromoamide.
0 0
II H10 II
RC---NH, + Br, + NaOH - RCN--Br + NaBr + H,0
(ii) The N-bromoamidc then reacts with alkali (NaOH) to give acyl nitrene ion.
+ 87r + o
H ACYLNf7(N(
(lrn.srA8L 1)
The nitrogen atom of nitrene ion has only six electrons and the ion is highly unstable.
(iii) R group or nurene then migrates (or rearranges) to form a relatively stable inter-
mediate, called Isocyanate.
600
0.
Ici-,- k-
I.5OCYA NATE
(Iv) The isocyanate finally reacts with water to give unstable carbamic acid which
eliminates a molecule of CO, to yield the primary amine.
r
Rl=C=O + }IO ' I R" OH
lsocyaciate I i' astirte
H
caxbamic acid
(uMsiabte)
Since the key step (W) in the above mechanism involves rearrangement, the overall
reaction resulting in a primary amine is also called Hofinaun Rearrangement. This reaction is
Bromarnide Reaction because 'bromoamide' is an important inter-
often referred to as Hofmann,
mediate as shown in the first step of the mechanism.
ACTAMIDE, Ethanamide, CH1.CNH1
This amide corresponds to acetic acid, CH5COOH.
Preparation.
(I) By heating ammonium acetate in presence of glacial acetic acid.
CH,COONH - CH,CONH, + H5O

amm acetate aceaaanlde
By allowing a mixture of ethyl acetate and concentrated aqueous ammonia to stand
(2)
at room temperature for a few days, and then distilling the reaction mixture.
CHrCO_OCaHs + NH, p CH,CONH, +C5H4OH
ethyl acetate acetamide
This is a convenient method for preparing acetamide in the laboratory.
(3) By partial hydrolysis of acetonitrile with alkaline H10.

NaOU
CH1 CEN + HO p CH,CONH,
acetooltrile acetamide
Properties. Acetamide forms long colourless needles, mp 82* , bp 223'. As ordinarily
prepared in the laboratory, it has a smell of mice but the pur substance is odourless. It is
very soluble in water and ethanol.
Acetamide gives all the general reactions typical of amides.
-+
+ NaOH -. CH 'COONa + NH,
sod acetate
4-
CI{1_C0NH5
I + HC1 .i CH,COOH +
acetic acid
acetamide
'
+ P501 CH,CN + H10
I acetonitrije
+ Br, + NaOHCH,--NH,
'
methylamine
+ NaNO1 + HC1 CH3CO--OH + N, 4 H10

acetic acid
Functional berivativen of Carboxylic AcidsAcid halides, Anhydrides, Este,s and Arnldes 601
QUESTIONS
I. Write type formulas or acyl halides, acid anhydrides, esters and acid amides. Indicate the functional
groups of these acid derivatives.
2. Discuss the orbital Structure of derivatives of carboxylic acids. What are the relative reactivitien
of acid chlorides, acid anhydrides, esters and acid amides, and explain.
3. Describe the general methods of preparation of acid choridps. How can you obtaia n.butyryl
chloride in the laboratory using thionyl chloride.
4. "The boiling points of acyl chlorides are much lower than those of carboxylic acids having equal
number of electrons." Illustrate and explain.
5. How is it thatacid chlorides readily give a variety of tsucleopbilic substitution reactions? Offer a
general mechanismfor such reactions.
6. Write notes on the following reactions of acid chlorides.
(a) Hydrolysis; (b) Esterification ; (c) Ammonolysis; (d) Anhydride formation; (e) Roseurnund's
Reduction.
7. Describe Hell . Volhard . Zelinsky Reaction for preparing a-Halo acids. Give the mechanism of this
reaction.
8. Give the methods ''f preparation and properties of (a) Acetyl chloride ; and (b) formyl chloride.
9. Why are the anhydrides so named? Write their structural formula and label in it ho 'oxygen
bridge' and the 'anhydride function'.
10. Describe the general methods of formation of acid anhydrides. How will you synthesise acetic
propionic anhydride?
11. How do you explain: (a) Relatively high boiling points of acid anhydrides ; and (b) The insolubility
of acid anhydrides in water.
12. Write notes on the following reactions of acid anhydrides: (a) Hydrolysis ; (b) Alcoholysis
(c) Ammonolysis ; and (d) Friedel-Crafts Acylation.
13. Give the methods of preparation, properties and uses of acetic anhydride.
14. Write the type formula of the derivatives of carboxylic acids known as esters. Mark out the
functional group in this formula.
15. What types of isomerism are shown by esters 7 Write the structural formulas of the esters and acids
which the molecular formula C 5 H 1505 represents. Give their common and IUPAC names.
16. Give the general methods of preparation of carboxylic esters. Write a note on Tiachenko reaction
taking example of the preparation of propyl propionate.
17. "The boiling points of the methyl and ethyl esters are lower than those of parent acids." Illustrate
and explain.
18. Why are esters lens reactive than acid halides and anhydrides ? Illustrate by taking example of
hydrolysis. Give the mechanism of alkaline hydrolysis of esters, Why is it irreversible reaction?
19. Write notes on the following reactions of esters. Transesteri6cation, Bouvcault . Blanck reduction,
Claiscn enter condensation and Pyrolysis.
20. Enumerate the uses of esters in everyday life and industry.
21. Give two nsetlsochi of preparation, and the reactions of esters. :a1,eut BSc, 1994)
22. (a) Discuss the mechanism ofacid-catalysed hydrolysis of esters.
(b) Give one method of preparation and two reactions of acid chlorides. (Sougar BSc. 1993)
23. Discuss the mcchanism of alkaline hydrolysis of ethyl acetate. (Karrisrzaka BSc. 1994)
24. What are acid amides 5 Give one method of their preparation and two reactions of acid amidec.)RajasthaR (DC, 1994)
25. Give the preparation of ethyl acetate. (Madras ltSc, 1994)
26. Discuss the nxchanssin of cstcrilicauon al carboxylic acids. ifle(hs ld,Vc Hons. 1994)
27. Wnic a note on: Hydrolysis of esters. i0smania SSc Ho.ns, 1994)
28. Discuss the mechanism of acid-catalyscsl hydrolysis of esters (Madras BSc. 1993: Berhampar BSc, 19554)
29, Es p lain wlsv the boil tn point of eth y l acetate is 87T lower than that of butyric acid even though the molecular weights
of the two compounds are the same (Rajasthan TDC. 1993)
Answer. Butyric acid has a much higher boiling point than ethyl acetate because is the acid there are strong intermolecular
forces of attraction (hydrogen bonds) No h y drogen bonding is possible among molecules of [he ester.
30. A neutral organic compound, (A), of molecular formula C 0H 120, was saponified to give compounds (B)and (C). After
acidification of Use reaction mixture, an acid, (B). was isolated and found to have a molecular weight of 88 (C) gave a positive todolorm
test and reacted with Lucas reagent to produce an alkyl halide after beating for several hours What two smictutes are possjble for (A I'
.5.rvt"xr. The )Acee)dbc eithcrcthyl hussnoate or ethyl 2.rrwthylpropanoate.
(.)r'gait ic (1'Iicriii.s rv - 39
Chapter 25
Esters of Inorganic Acids
The term ester is applied to compounds obtained by the reaction of an alcohol with an
acid. Thus, even though the acid reacting with alcohol is inorganic, the product is an ester. Hence,
the esters derived from inorganic acids such as sulphuric acid, sulphurous acid, nitric acid, nitrous
acid, carbonic acid, phosphoric acid, boric acid etc., are referred to as Inorganic Esters. Theoreti-
cally, these esters are to be regarded as the derivatives of inorganic acids in which one or more
ionisable H atoms are replaced by as many alkyl groups. For example,
o o
HON=O -. RON=O
+
nItric acid alkyl niirale
o 0
II II
HOSOH -i RO-.-SOR
+2R
O 0
sulphuric acid dialkyl sulphate
o o
II 311 II
HOP-014 .s ROPOR
+3R
OH OR
phosphoric acid trialkyl phosphate
Truly speaking, the alkyl halides are also inorganic esters of hydrogen halides (HCI,
HBr, HI). But they differ from the esters of other inorganic acids in flue sense that they do not
contain oxygen atom. Furthermore, alkyl halides are versatile synthetic reagents and almost all
classes of organic compounds can be prepared from them. lheca'use of these reasons, alkyl halides
merit a separate treatment. Here we will discuss esters of inorganic acids other than those of
hydrogen halides.
In general, inorganic esters have properties similar to those of organic esters. They can
be prepared by
(a) the reaction of an alcohol with an inorganic acid chloride
(b) the reaction of an alcohol with inorganic acid
(C) the reaction of an alcohol with an inorganic anhydride.
The first method is a general one, while the other two methods fail when the inorganic
acid is wek.
NOMENCLATURE
Esters of inorganic acids are named like salts, the name of alkyl group being substituted
for that of the metallic atom. Thus the name of an individual ester is written as two separate
words, the first being the name of the alkyl group and second the name of the acid residue
602
Esters of Inorganic Acids eui
obtained by removal of replaceable H atoms of acid. The esters derived from di. and sri-basic
acids are named as their di- and rri-alkyl salts. The names of a few inorganic esters given in the
Table will illustrate their nomenclature.
Table, Names of some Inorganic Esters,
Formula Acid Group Name of Acid Group Name of Ester
0
cii
CH,O S---OH OS--OH hydrogen sulphate methyl hydrogen
sulphate
0
0 0

CHI_0_LO_CHI 0s-0- sulphate dimethyl sulphate
0 0
0 0
1+
C,}15O--N=O 0N nitrate ethyl nitrate
C4H1-0N=O O.--N=0
nitrite n.butyl nitrite
0 0

C1HOL_0c1H1 oJo sulphite diethyl sulhite
0

CH6-0_&-.0_C,j{5 carbonate dietbyl carbonate
C1Ha-_0LO_C1H5
0P-0 phosphate triethyl phosphate
OCIH1
r
CH-0---0CH5
borate triethyl borate
ESTERS OF SULPHURIC ACID

Sulphuric acid forms two series of esters namely acid and normal esters according as one
or both the replaceable H atoms have been substituted by alkyl groups.
o 0 0
II 2H II H II
ROS-0R f-
4 +2R
HO---&--0H -, R-0S-0H
ii R
o 0 0
dialkyl sulphate sulphuric acid alkyl hydrogen sulphate
(a normal ester) (an acid ester)
Amone the esters of entphurc acid. ethyl hydrogen sulphate, dimethyl sulphate acd
diethyl sulphate are important.
ETHYL HYDROGEN SULPHATE, Ethyl Sulphuric 4cid,CH,CH1_OS05OH
It is the acid ester of sulphuric acid, H0S0 5OH, and may be prepared b) the
-
following methods,
(I) By beating ethyl alcohol with excess of cone H I SO4 at lOO.
CH,CH 1 OH - H0S0 5--OH CH3CH1O---S01OH + HSO
ethyl alcohol sulphuric acid ethyl hydrogen sulphate


604
(2) By passing ethylene through conc sulphuric acid at about 100 (Industrial).
100
CH 1 CH, + H0SO0 H * CHiCHaOSOr'H
ethylene sulphuric acid ethyl hydrogen sulphate
However, in the presence of cuprous or silver salts, the reaction can be carried at a
lower temperature.
Properties. (Physical). Eth y l hydrogen sulphate is an odourless oily liquid, miscible
with water in all proportions. it cannot be distilled without decomposition and hence it does
not have a characteristic boiling point.
(Chemical). Ethyl hydrogen sulphate behaves both as an acid and an ester. its chief
reactions are
(I) Acidic Nature. It is a genuine acid and is capable of exchanging their as yet unre-
placed hydrogen for metals in the usual manner. Thus ethyl hydrogen sulphate decomposes
carbonates and bicarbonates to liberate carbon dioxide.
-4.
2 CH,-0S0 1 -0H + K 2 C01 . 2 C,H 5O. S02OK + CO t + H2O
ethyl hydrogen sulphate ethyl potassium sulphate
C5H1OS05OH + NaHCO 5 p C1H5OSO,-6Na + CO, + HSO

ethyl codiurn sulphate
Sodium and potassium derivatives of ethyl hydrogen sulphate are very reactive and are tiled to
prepare alkyl halides, thioalcohots and ethyl thioethers.
+- p-+ __Pr CHCl4 2 81 + k55O

K Br + CH3CF42O--S02OK
ErHYL
+ BA'OMIO(
(_) .
K Sil + CH3CH1JO-502OK a-- CH 3 CH 2 SH + K254
EfilyL
TIIIOALCOHOL
-
K2S + CH 3 C11 2 _0_S02- 1( -P'- CR 2 CH 3_ S_CH2C + 2K250
ETHYL
THIQETHER
(2) Hydrolysis. Ethyl hydrogen sulphate when heated with boiling water is hydrolysed
back to ethyl alcohol and sulphuric acid.
p CH 5CH 5OF1 + H5SO4
CH 3 CH 5_OS01 --O--H + H SO ethyl alcohol
ethyl hydrogen sulphate
(3) Action of Heat. When heated alone, it decomposes to give diethyl sulphate and
sulphuric acid.
a .LlLII'0\ ,O
2 CH 5CH1_0S0 5OH ' + HIS0
ethyl hydrogen sulphate CH3C45-0" "0
diethyl sulphate
(4) Action with H1SO4. When heated with excess of sulphuric acid at 170, it produces
ethylene.
H2SO4
.., .- r1'J4
eth y l hydrogen sulphate
1700 ethylene

605
Esters of inorganic Acids
MECHANISM. The probable mechanism of this reaction is
.1- -
HOSO,OH H + OS01OH
CH2CR2 + H0_S0 2 _0H + oS02---0H

'T'4_1)_CH2__0S00
+ - HO-_SOaOH or H1SO4
H + 0S0 2OH
sulphuric acid
When reacted with ethyl alcohol at 140 0 , ethyl hydrogen sul-
(5) Action with alcohol.
phate yields diethyl ether. 1400
CH5CH1OCH,CH5 + H2SO4
CH,CH,_0_50s_0 H + CH3CH1-0H diethyl ether
ethyl alcohol
ethyl hydrogen sulphate
MECHANISM:
CHCH 2 O H + CH 3 CH - S010H
H
ETHYL ALCOHOL
4 CH 3 C141 -0 CH 2 CI1 3 +
OIETIIIL tIMER
Ethyl hydrogen sulphate is frequently used to prepare ethyl halides, ethyl thio-
Uses.
alcohol and ethyl thioether in a fairly good yield.
CH5OSO3O
DIMETHYL SULPHATE, Methyl Sulphate,
It is the most important ester of sulphuric acid on account of its great value as a
methylating agent.
Preparation. (I) Dimethyl sulphate is prepared by heating methyl alcohol with an
excess of concentrated sulphuric acid when methyl hydrogen sulphate is produced. Methyl
hydrogen sulphate is then distilled under reduced pressure to yield dirnethyl sulphate.
CH,OH + H0S01---0H - CH 3 -0S0,-0H + H2SO

methyl hydrogen sulphate
methyl alcohol
C" 'O 0
2 CH,_OSO,OH -i . + H1SO4
reducedCEI3 -0' No
pressure dimethyl sulphate
(3) it may also be obtained by heating methyl iodine with silver sulphate.
CH'O0
2 CBl + Ag 1SO4 -p 'S( + 2 Ag!
CH IO / '0
dimethyl sulphate
prepared by passing sulphur trioxide (2 moles) into cooled methyl
4) Technically it is
alcohol (I mole).

606 Advanced Organic Chenistry
CH.-0.H 0 CH 00
+ sos -+ "5/ + H1SO4
CH,OH "0 CH,"O o
dlmethyl sulphate
methyl alcohol
Properties (Physical). Dimethyl sulphate is a colourless, odourless heavy liquid, bp 1800.

It is immiscible with water, Dimethyl sulphate is a very poisonous compound. Its vopours, even
in low concentration, strongly attack the mucous membranes. The eyes and throat are parti-
cularly susceptible and' may suffer severe damage.
(Chemical), Dimethyl sulphate is a typical ester. It is saponified by boiling with

alkalis, forming methyl alcohol and a salt of sulphuric acid. Thus,
CH,-0 0
+ 2 NaOH -. 2 CH I OH + Na1SO4
CH,O / '0 methyl alcohol
d)rnethyl sulphate
As Methylatlng Agent. In the presence of sodium or potassium hydroxide, dimethyl

sulphate reacts with hydroxy and amino Compounds wherely the replaceable H atom in them
is substituted by methyl group. This reaction which is referred to as Methylation may be repre-
ted by the following equations.
CH,O 0 + - aO 0
ROH +
hydrosy
-
CH,O/ '0
+ NaOH - R-0CH5 + + H2O
methyl ether CH,O' '0
COPd,
sod methyl sulphate
H
I CH,-0,O NaO O
I
RN--H + + NaOH -p RNCH, + + HSO
1 amine CH,O / '0 alkyl methylamine CH,O/'0
nod methyl sulphate
Although only one of the two methyl groups takes part in the reaction, dimetbyl
sulphate is a valuable methylating agent. In this respect it is superior to methyl iodide since It
reacts with greater rapidity and gives better yields. Dimethyl sulphate is particularly effective
for the metbylation of phenols and carbohydrates, though amines, thiols and carboxylic acid
may be methylated with it.
Examples. (a) Methylation of phenols to give methyl phenyl ether.
OH CH1 0 0 Na
I0 H -p 1?;T.o CH 0
CO)
phenol
+
CH,O// '0
dimethyl sulphate

'-.9
methyl phenyl ether
+
CH10' NO
H,0
or aolole
1ECHAN1SM. Metbylation of phenol is a itucleophilic substitution reaction and

follows the following mechanism.
+ NaOH + H10

Esters of lnorgonlc Adds 607
0
ONa CH3\ /0
+
+ __ CH30Q
CN3/N0
METHYL PHENYL
ETHER
(b) Methylatioii of aniline to give N-methylaniline.
H
_I!4_-CH5 0
!'ta0
CH 3O 0 \S/ H2O
NH
D+ + NaOH + C0/
CH 2-0/ o
( Amethylaniline
aniline
MECHANISM:
H +
F + H
CHO
ON:YThH3-1
H
j
H
CH, + CH,-0S0 1 -0N + H20

[_CHt}_S0t_0H30H .
Similarly, Nmethylafli1ifle in presence of excess of dimethyl sulphate would react further

to give N, N.dimethylanilifle.
Carbbxylic acids upon methylation with dirncthyl sulphate in presence of sodium
(c)
hydroxide give methyl esters,
0 o
0+ NaO,. O
CH,-0
+ NaOH -+ RC-0CH + )S + H10
RCOH +
methyl carboxylate CH 30" '0
CH,O / 'o
Thiols may also be methylated with dimethyl sulphate in presence of sodium

(d)
hydroxide.
4-
Nab 0
CH,-0 ,0
3 CH,SCH + + H10
CHCH2SH + "S' + NaOH * CH
ethyl methyl thiol CH 3O' "0
ethanethiol CH3-0' o
dinietnyl sulphate
The methylation of carbohydrates will be discussed in the Chapter on Carbohydrates'.
Uses. Dimethyl sulphate is a valuable methylating agent and is particularly useful for
determin ing the size of the ring in carbohydrates.

DIETHYL SULPHATE, Ethyl Sulphate, CH1CHOSO-0_CfJ1CH3

It may be prepared by the same methods as applicable to dimethyl sulphate. However,
industrially diethyl sulphate is produced by passing excess of ethylene into cold conc 111SO4.
HO,O CH,CH, \ ,O
2 CH,=CH2 --
ethylene HU7 '0 cl-ccE-3, '0
sulphuric acid dietyl sulphate
(excess)
Properties and Uses. Diethyl sulphate is a colourless, odourless, heavy liquid, bp 208.
It is not poisonous. Its reactions are similar to those of dimethyl sulphate discussed earlier.
Its a good ethylating agent and is used for introducing ethyl groups into bydroxy and amino
compounds.
ESTERS OF NITRIC ACID
Since nitric acid has only one replaceable hydrogen atom, it forms only one type of
esters commonly known as Alkyl Nitrates.
o 0
I H
or HON=O -p R-0N=0
+ -fR +
alkyl nitrate
(esters)
Triese esters are unstable and sometimes especially in contact with nitric acid decompose
violently. Of the esters of nitric acid only ethyl nitrate is important and will be discussed
here. -
ETHYL NITRATE, CEI3 CH 5-0NO i or CH1CHONO
It may
may be prepared by the following methods.
(1) By the action of concentrated nitric acid in presence of urea '
and at low
temperature.
urea
CH 5 CHOH + H0NO, -. CHCHaO_NOa + H10
ethyl alcohol nitric acid ethylnirrate
Urea is added to destroy any nitrous acid formed as a result of the reduction of nitric acid by
ethyl alcohol.
NH,CONH, 2 HONO -i CO2 f + 2N1 t + 3H2O
(2) By heating ethyl iodide with ethanolic silver nitrate solution.
ethanol
CH 2 CH 2 I + AgON0 1 -k CHsCH2 -.-
O_NO,+ Agi
ethyl iodide silver nitrate ethyl nitrate
Properties. (Physical). Ethyl nitrate is a colourless, pleasant smelling liquid, bp 881.
It is hea icr than water in which it is practically insoluble.
(Chemical). Chemically it behaies like a tpicaI ester.
(I) Hydrolysis. On boiling with water, ethyl nitrate is hydrolysed to form ethyl alcohol
and nitric acid.
CH3CI-1 2ON01 + HOH -p CH 1CH2 OH + HONO,
ethyl nitrate ethyl atcoholJ
(2) Reduction. When reduced with tin and hydrochloric acid, it is Converted to ethyl
alcohol and hydroxylanuine.
e,,,url
CH1CH 2O---NO2 + 6[H] -+ CHaCH2OH
+ NH 2OH + H10
ethyl nitrate ethyl alcohol hydroxylamirie

609
Es ters of Inorganic Acids
This reaction shows clearly that in ethyl nitrate molecule, the ethyl group is linked to nitrogen
through an oxygen atom
ESTERS OF NITROUS ACID
Like nitric acid, nitrous acid has only one replaceable hydrogen atom and, therefore,
forms only one type of esters known as Alkyl Nitrites.
H
H-0N=O - p R-0N=O
nitrous acid + R alkyl nitrite
Of these esters of nitrous acid, only ethyl nitrite and isoamyl nitrite are important.
ETHYL NITRITE CH3CH2-0N=O

It may be prepared : (I) By the distillation of a mixture of ethyi alcohol, sodium
nitrite and conc HCI or H2SO4,
NaNO + HCI p NaCl + H-0N- O
nitrous aei
CHCH1OH + H-0N=O - CH 3CH2 ON=O + H10
ethyl alcohol ethyl nitrite
(2) By the action of nitrogen trioxide (nitrous anhydride) on ethyl alcohol.

2CHCH2OH + O=N-0N=O f 2CH3CH 1ON=O + HO
ethyl alcohol nitrogen trioxide ethyl nitrite
(3) By the reaction of ethyl iodide with potassium nitrite,

CHCHI + KNO S p CH 3CH-0N=O + [(I
ethyl iodide ethyl nitrite
Properties. (Physical). Ethyl nitrite is usually gaseous at ordinary temperature. Upon

cooling, it becomes a colourless liquid, bp 17 g . It has a characteristic smell of apples. It is
soluble in water. -
(Chemical). Its reactions are similar to those of ethyl nitrate.

(1) Hydrolysis. Upon hydrolysis with alkalis (NaOH or KOH) ethyl nitrite forms
ethyl alcohol and nitrous acid.
CH5CH1 ON=O + HOH p CHCH 2OH + HON=O
ethyl nitrite ethyl alcohol
HON=O + NOH i N0N=O or NaNO2

sodium nitrite
(2) Reduction. When reduced with tin and hydrochloric acid, ethyl nitrite yields ethyl
alcohol and ammonia.
SnfHCI
CHCHONO 1 6[H] i CHCH 1 OH NH + HO
ethyl nitrite ethyl alcohol
The above reaction furnishes evidence that in ethyl nitrite molecule, the ethyl group is not
directly linked to the N atom but is joined to it through 0 atom.
Uses. (I) Ethyl nitrite is easily broken and reacts with organic compounds in the sam
way as nitrous acid does and is used with advantage in 'organic synthesis as the reaction cat5
be c3rricd ei in thc absenec of water ; (2) It accelerates the pulse rate and lowers the blood
pressure and is, therefore, used as medicine for the treatment of asthma and heart diseases,
Cli,
ISOAMYL NITRITE, CH,CHCH,CH 1 -0r = 0

It can be prepared (I) By healing a mixture of isoamyl alcohol, sodium nitrite and
conc H1SO4.
NaNO2 + H,S0 NaHSO4 + HON0
Cli, Cli,
"CHCH,ClI,OH .- H-0N=O CHCHCH !ON0 + H2O
CH,/ Cli,' isoamyl nitrite
iaoamyl alcohol
(2) By passing nitrogen trioxide into hot isoaml alcohol.

CH, CH,
2 ,CHCH,CH,CH,-0H + 0 = N-0N= 0 42 CHCH1CH,-0N= 0+ lI0
CH/ nitrogen trioxide CHI/ isomeSbyl nitrite
tsoamyl alcohol
Properties and Uses. Isoamyl nitrite is a yellow liquid having pleasant smell, bp 98.
Chemically it behaves like ethyl nitrite, This is also used as a source of nitrous acid in organic
synthesis and is preferred to ethyl nitrite which is a gas at room temperature. The inhalation of
a few drops of isoamyl nitrite dilates the peripheral blood vessels, accelerates the heart rate and
lowers the blood pressure. Isoamyl nitrite has been used as a valuable drug to relieve spasms
of the arteries in angina pictoris.
ESTERS OF CARBONIC ACID
These are called alkyl carbonates as they are the derivatives of carbonic acid.
H0 ZH 1W
co .-., \c_o
HO' +2R RO"
carbonic acid dliikyl carbonate
Alkyl carbonates can be prepared by the action of phosgene on alcohols or on sodium

alkoxides. Thus
C1 H5-6a Cl CIH&_O\
+ \ c=o -. + 2NaCI
C,H5-0a CI"
sod ethoxide phosgene diethyl cathonate
Dialkyl carbonates are colourless liquids,
)C=0 dimethyl carbonate bp 90-91C

Cli,'
CI HI\ - -
ULCLUI UUfliIG 1hO k.
C,H'
tThey react with Grignard Reagents to give tertiary alcohols. Thus,

R
C,H5-0
3 RMgX + )C0 .-. RCOM8X + 2 CH,OMgX

Eaten of Inorganic Acids 6!!
R R
RC---OMgX -+ R,OH + MgXCI
R
It
3 alcohol
ESTERS OF BORIC ACID"
These are called alkyl borates,

OH OR
3H
HOBOH -p ROBOR
boric acid +3R trialkyl borate
Alkyl borates are prepared by reaction of alcohols with boric acid, Sometimes I-1 5SO4 is added
as a catalyst.
OH OCH1
HO_bOH + 3CHOH -+ CH 2O_LOCH I + 3H5O

boric acid methyl alcohol tritnethyl borate
They are colourless liquids,

(CH1 O),B trimethyl borate bp 72C
(C1H10)5 3 triethyl borate bp 120C
Alkyl borates hydrolyse rapidly to regenerate boric acid and the corresponding alcohol.
They burn with a green flame. This forms the basis of a qualitative test for boric acid or its
salts,
ESTERS OF PHOSPHORIC ACID
These are called alkyl phosphates and are derived by replacement of three H atoms of
phosphoric acid,
o o
II 3M
HOPOH -p . ROPOR
+3R
OH OR
phosphoric acid trialkyt phosphate
Alkyl phosphates are obtained by the reaction of the corresponding alcohol and phos-
phorous oxychioride in the presence of pyridine.
0 0
II pyridine II
3 C,H 6OH + C1Cl -+ CI H6O'OC2 H6 + 3HCI
Cl OC1H,
phosphorous trietbyl phosphate
ozychioride
They are high boiling colourless liquids,

(CH,-0)1 P=O trimethyl phosphate bp 1972C
(C1 H5-0)1P=O triethyl phosphate bp 216C

QUESTIONS
I, What are inorganic esters 9 Why alkyl halides are discussed separately from them?
2 Give the formula and name of one ester of sulphuric acid, nitric acid, nitrous acid, carbonic acid,
phosphork acrd, boric acid and sulphurous acid
3. Give the preparation, properties and uses of ethyl hydrogen sulphate.
4. How is dimerhyl sulphate prepared ? Write a note on its utility as a tnethylating agent. Give the
mechanism of the methylation of phenol and aniline.
S. Write the prepararsion, properties and uses of: (a) diethyl sulphate (b) ethyl nitrate.
6. How can ethyl nitrite be produced ? Give its reactions and uses.
7. Write a note on : (a) isoantyl nitrite ; (b) diethyl carbonate ; (c) trialkyl borate; (d) trialkyl
phosphate.
0. Describe the prcpl ation and uses of dimethyl sulphate.
9. Give two properties of alk yl nitntes. (Andhra 8Sr, 1993)

10. What happens when alkyl nitrites are treated with ammonia? (Agra 8k, 1994)

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Chapter 2I

This class of compounds have the general formula

RCOH or RCOOH or R-CO2H

Carboxyllc Adds 481

CH3 CHCH,COOH CHCHCOOH CH,CCOOH

Formula JUPAC Name Common Name Source

HCOOH Methanoic acid Formic acid L, Formica= ant

CHCHSCHCH2CH2C00U 1-Texanoic acid Caproic acid L, Caper=good (fat)

CH3(C113)10C00H Dodecanoic acid Laceric acid Laurel

CH3(CH!)I4COOH Hexadenoic acid Palmitic acid Palm oil

CH3(CH5)16C00H Octadecanoic acid Stcaric acid Gr, Stear= tallow

C14 3 CH I CHCOOH CFL. C K. - ('K -- - CK2COOH

CH3 CH 2 CHCH 2 000I-T CF1tH3

(3) CH,CH,CHCH,CH, 2.ethylbutanoic acid

(4) CHi -CHCHCHr_COOF1 4.me[hylpentanoic acid

(5) CFTrtjCHr'.'COOH 3, 3-dimeihylbuianoic acid

(6) CH.CH,--CCOON 2, 2-dirnc1hylbutanojc acid

CHaCHtOH + 2(0] a. CHC00H + H30

(a) From A1ky!acetocetic Esters.

mono Ikylaccloacetic acid

R COOC2H6 (I) KOH R C0011 COOH

R C00C1}16 KOH R COOH A It COOH R

Carboxylic Acids 487

ACETIC ACID DIAlER

NCJM6ER OF CARBON ATOI4S -.

Fig. 211 Irregular increase in the melting points of carboxylic acid

Table. Physical constants of carboxylic acids

Acetic acid CH3COOH 17 118

Propionic acid CH3CH3COOH 22 141

Butyric acid CH3(CH2)C00H 4.7 163 -cc

Valeric acid CH3(CHI)3COOH 35 187 4

Caproic acid CH3(CH)4COOH - 15 205

Enanthic acid CH(CH),COOH -10 224

Caprylic acid CH3(CH1),COOH 16 238 less than I

Plargonic acid CH3(CHI)7COOH 12 254

Capric acid CHa(C11,)5COOH 31 268 -

ACIDITY OF CARBOXYLIC ACIDS

APBOXYL( ACO C5PRXYLATE IO4

4'O4'fQ111L/4(,yT EQ.UI VA LENT

CANONICAL FORMS OF RESONANCE

FORMIC ACIO 300/OM FORAM TE

Organic (:liernis(i N -32

Fig. 213. Orbital Model of Carboxylate ion,

S ..... Lo.C t, I/-/

(b) Acidity increases with increasing number of electron-withdrawing substituenis on the

)( (_ CH2 1 CH2 i4.ui.i.i CH2 14.- COON

2-Chiorobutanoic acid CH,CH,CHCOOH 139

3-Chlorobutanonic acid CH,CHCH5COOH 89

4Chlorobutanoic acid (,H,CH,CH,COOH 296

492 Advanced Organic Chemistry

A. REACTIONS INVOLVING REMOVAL OF PROTON FROM OH OF COOH

form salts with the evolution of hydrogen.

C4R&XYUC ACiO 50DUJM3At.T

e.g., CH5COOH + Na - CH1CON + 4H1

CH 3COQH + NH 4 OH -'. CHCOONFi -j- HO

2RCOOH Na 1CO3 .- 2RCOONa H 1O + CO, f

RCOOH + NaHCO 5 b RCOONa + H SO + CO,

CH,(CH,),,COOH + ItOH -i CH 3(CH,),,---COO1a + HSO

RCO + HOH -- RC---OH OH

- RCO -t- H_C21t5

TRIETHYL 41.1/Nt TRIEIHYLA/4MON/(JM

494 Advanced Organic Chemistry

CH3COO -p CH 2CO6(anode) + K(cathode)