Académique Documents
Professionnel Documents
Culture Documents
Carboxylic Acids
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
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,
(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
Cl-i3
CH
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,
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.
486 Advanced Organic Chemistry
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.
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.
(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
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
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
C.
Name
of Formula rnp bp C Solubility
Acid g1100- of ware,
Formic acid HCOOH 8.4 101 cc
R-: +
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
1k O RC
l '27A -
1'23A
HC'
OH
127.4
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.
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
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.
(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
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
(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
C2F45
(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.
0'
. + \_
- __. ,,.0 Nu ._-. 0 -- .
Nu
'CrDoxyllc Fichls 495
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
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
496 Advanced Organic Chemistry
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
-
MECHANISM:
QM
k.C_0A1, R-C--MH -.-- S-C-H - s-C-H . S-C-H + HO
I I
H H
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
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
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
Br NH
CN
499
Acids
'-
RCi-4C + Br Br BCHC
'N8
Sr
.11 111
-. 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).
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
H2OH CI-JOF1
glycerol glyceryl monoocalate
CHSOOCCOOH CtI2O-0C-1-1
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.
iI.LEA'1iA
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
(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 NH 1 i HCOONH4
amos formtc
504 Advanced Organic Chemistry
-+ 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 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.
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
Organic Chernisiry - 33
506 Advanced Organic Chemistry
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
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
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.
(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).
uy
Carboxylic Acids
jVa,ne Formula mp C bp C
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.
CorboxyIc Acids
511
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.
CuCI,NH4CI,HCI H/H80
HCCH + HCN CH2=CHCN - CH=CH00OH
90' vinyl cyanide
5/2 Advanced Organic Coemistry
5)3
Carboyl7c Adds
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
514 Advanced Organic Chemistry
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.
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
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
OZCNIOE
HO
p.. CH)CH,CHO + 0 H ( CH 217COO44
(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.
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
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
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.
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
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
CHICN
+ 41120 -. 2HCI..._.,
CHICOOH
I 2NHCI
blcarboy(ic Adds 52!
(4) By electrolysis of salts of acid esters of lower dicarboxylic acids (Crum-Brown and
Walker Electrolytic method).
(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.
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
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
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
(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
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
INDIVIDUAL MEMBERS
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.
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
CHOH)COOH A CHJCOOII
(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.
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
C
BENZENE CYCtOI/IXANE
a
CYCWH(XANONE
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
532 Advanced Organic Chemistry
The two simplest and the most important dicarboxylic acids are
I?.
1-1 \/ COH HCOH
HOC"H
0 0
mateic acid fumaric acid
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
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
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
(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,
(5) Action with Bromine. When treated with BI- 2 in Cd 4 or CH2COOH, lumaric acid Fives
ycvo . dihromosuccinic acid.
H COOH Br COOH
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
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.
3 2 I
CH,CHBrCOOH e .bromopropionic acid 2-broniopropanoic acid
a
HOCH,CH, COON -hydroxypropionic acid 3-hydrox\propanoic 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
METHODS OF PREPARATION
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.
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
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
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.
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
(1)NaOH
BrCH 1C}I 1CH 1CH,CFJ3 C00H -,. HOCE{1CH2CH.CH,cH3COQH
-t- NaUr
c.bromocaproic acid (2) H c-hydroaycaproic acid
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
C1 OH Cl.
I I -H20
HCCOH HCC'
II I
H 01 H
unstable chtoroaoeijc acid
Ethyl chioroacetate when shaken with aqueous amnwni-a, is converted into chloroacetair, de.
The latter on dehydration with P 10 5 gives chloroacetonitrile.
Cl
DICHLOROACETIC ACID, Dith ioroethanoic acid, CHCOOH
Cl'
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
(!:l
chloral hydrate trichloroacetic acid
ci o ci
1+11
COH I Ci4 -f- c07
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
546 Advanced Organic Chemistry
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.
CHCOOH
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
METHODS OF PREPARATION
(I) By the hydrolysis of the corresponding halo acid with moist silver oxide (AgOH)
or dilute sodium carbonate solution.
Br OH
(2) By the action of nitrous acid (sodium nitrite and dilute mineral acid) on amino
acids.
Since naturally occurring amino acids are i.derivatives, this method is particularly useful
for the preparation of cz.hydroxy acids.
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,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.
548 Advanced Organic Chemistry
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
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
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
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.
550 Advanced Organic Chemistry
(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.
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
HNO3 [0]
I +0 a HOOCCHO -+ HOOCCOOH
maid) oxalic acid
glyoxytic 11NO3
(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.
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
Organic Chemistry - 36
Advanced Organic Chemiry
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).
,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.
OH . 0
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
(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.
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
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
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
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)
Advanced Organic Chemistry
(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.
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
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.
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.
CH,COOH eH1COOH
as a.hydroxy acid
ice -hydroay arid
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.
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
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
566 Advanced Organic Chemistry
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
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
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.
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
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.
Formula Common Name JUPAC Name
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
METHODS OF PREPARATION
(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,
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
572 Advanced Organic Chemistry
(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
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
- + 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
o 0 o 0
II II II
R-.-.C---O---CR R.COC-_R R00--0--00a
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
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.
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
+ 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
580
Advnced Organic Chemistry
+ 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.
Formula Common Name JUPAC Name
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.
METHODS OF PREPARATION
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.
(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.
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
(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
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
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,
(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
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,
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.
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
R:i;,
Functional Derivatives of Carboxylic Acids"Acid halides, Anhydrides, Esters and Atnides 587
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)
0 0
uiti
II- II -
ICUH + OR - IC U + RON
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
(4) Reaction with Grignard Reagents. Grignard reagents react with esters to form an
addition product which decomposes to form a ketone.
0 /
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.
589
Functional Derivatives of Carboxylic AcldsrAcid halides, Anhydrides, Esters. and Amides
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
(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.
(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.
:0: 0
CH 3
I
CJl 2 C 0C2H
CH 3C"+ El Co--- C2k,
QC2H 0C2N5
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.
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.
592 Advanced Organic Chemistry
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
"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
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.
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
METHODS OF PREPARATION
(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
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
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
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
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.
H 14
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
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.
Advanced Organic Chemistry
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.
Preparation.
(I) By heating ammonium acetate in presence of glacial acetic acid.
4-
CI{1_C0NH5
I + HC1 .i CH,COOH +
acetic acid
acetamide
'
+ P501 CH,CN + H10
I acetonitrije
+ Br, + NaOHCH,--NH,
'
methylamine
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
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
(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
(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
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.
(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
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.
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
+ NaOH + H10
Esters of lnorgonlc Adds 607
0
ONa CH3\ /0
+
+ __ CH30Q
CN3/N0
METHYL PHENYL
ETHER
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 .
Uses. Dimethyl sulphate is a valuable methylating agent and is particularly useful for
determin ing the size of the ring in carbohydrates.
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. -
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
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.
(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,
610 Advanced Organic Chemistry
Cli,
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.
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
C1 H5-6a Cl CIH&_O\
+ \ c=o -. + 2NaCI
C,H5-0a CI"
sod ethoxide phosgene diethyl cathonate
Eaten of Inorganic Acids 6!!
R R
R
It
3 alcohol
Alkyl borates are prepared by reaction of alcohols with boric acid, Sometimes I-1 5SO4 is added
as a catalyst.
OH OCH1
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,
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
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.