01 Carboxylic Acids & Their Derivatives Theory Final E

1306 Carboxylic acids and Their derivatives
Chapter
28
Carboxylic acids and Their derivatives
Carboxylic Acids  Aldehyde can be oxidized to carboxylic acid with mild oxidising
agents such as ammonical silver nitrate solution
Carboxylic acids are the compounds containing the carboxyl
[ Ag 2 O or Ag(NH 3 )2 OH  ]
 
 
functional group  – C – OH   Methanoic acid can not be prepared by oxidation method.
 | |   Ketones can be oxidized under drastic conditions using strong
 O 
oxidising agent like K 2 Cr2 O7 .
The carboxyl group is made up of carbonyl (>C=O) and hydroxyl (–
OH) group.  Methyl ketones can also be converted to carboxylic acid through
the haloform reaction.
Classification

(1) Carboxylic acids are classified as monocarboxylic acids, R – C  CH 3  3 I 2  3 NaOH 
|| H 2O
dicarboxylic acids, tricarboxylic acids etc. depending on the number of – O
COOH groups present in the molecule.
R  C  OH  CHI 3  3 NaI  3 H 2 O
CH 3 COOH C H 2 COOH C H 2 COOH ||
| | O
CH 2 COOH C HCOOH
| (2) By Hydrolysis of nitriles, ester, anhydrides and acid chloride
CH 2 COOH (i) Hydrolysis of nitriles
Monocarbox ylic acid Dicarboxylic acid Tricarboxylic acid
HCl  OH  Rearrangem ent
(2) Monocarboxylic acids of aliphatic series are commonly known as R  C  N  HOH  R  C   
or NaOH  NH 
fatty acids such as palmitic acid (C15 H 31COOH ) and stearic acid
C17 H 35 COOH  . R C
O H O
2
 RCOOH  NH 4 Cl
NH 2 HCl
(3) The general formula for monocarboxylic acids is
Cn H 2n 1COOH or Cn H 2n O2 . Where n = number of carbon atoms. (ii) Hydrolysis of Esters
HCl
(4) The carboxylic acids may be aliphatic or aromatic depending RCOOR ' HOH  RCOOH  R' OH
upon whether – COOH group is attached to aliphatic alkyl chain or aryl Ester OH  Acid Alcohol
group respectively. (iii) Hydrolysis of Anhydrides
Methods of preparation of monocarboxylic acid O
||
(1) By oxidation of alcohols, aldehydes and ketones CH 3  C H  / OH 
O  HOH  2CH 3 COOH
[O}
RCH 2 OH  RCHO 
 RCOOH
[O] CH 3  C Ethanoic acid
K 2Cr2O7 K 2Cr2O7 Carboxylic acid ||
alcohol
O
Ethanoic anhydride
RCHO 
[O ]
RCOOH
Aldehyde monocarbox ylic acid
(iv) Hydrolysis of acid chloride and nitro alkane
H  / OH 
R  C  Cl  HOH  RCOOH  HCl
||
O
Carboxylic acids and Their derivatives 1307
85% H SO the increase in the size of the alkyl group. All carboxylic acids are soluble in
R  CH 2  NO 2 
2

4
 RCOOH
alcohol, ether and benzene etc.
(v) Hydrolysis of Trihalogen :
 The solubility of lower members of carboxylic acids is due to the
X  OH  formation of hydrogen bonds between the – COOH group and water
   H 2O
R C X  3 NaOH   R  C OH    molecules.
X  OH   Acetic acid exists in the solution in dimer form due to
intermolecular hydrogen bonding. The observed molecular mass of acetic
O acid is 120 instead of 60.
R C  3 NaX
OH
(3) Melting point
(3) From Grignard Reagent
(i) The melting points of carboxylic acids donot vary smoothly from
O one member to another.
   ||
Dry ether
O  C  O  RMgX 
 R  C  OMgX (ii) The melting point of the acids having even number of carbon
Carbon dioxide Grignard reagent H  / H 2O
atoms are higher than those containing an odd number immediately above

 RCOOH  Mg(OH )X and below them.
(4) From Alkene or Hydro-carboxy-addition (koch reaction) (iii) The acids with even number of carbon atoms have the – COOH
H 3 PO 4
CH 2  CH 2  CO  H 2 O  CH 3 CH 2 COOH group and the terminal – CH group on the opposite side of the carbon
3
5001000atm chain.
& 350C
(iv) In the case of odd numbers, the two groups lie on the same side
(5) Special methods
of the chain.
(i) Carboxylation of sodium alkoxide
CH 2 COOH CH 2
CH 2
HCl
RONa  CO  RCOONa  RCOOH
Sod. alkoxide Sod. salt Acid
CH CH CH CH COOH
(ii) Action of heat on dicarboxylic acid 3
2
3
2
COOH  CO 2 the two terminal groups lie on the the two terminal groups lie on the
R  CH   R  CH 2 COOH opposite sides of the chain same side of the chain
COOH heat Monocarboxylic acid
Substituted malonic acid
When the terminal groups lie on the opposite sides the molecules fit into
each other more closely. More effective packing of the molecule in the lattice.
(iii) From acetoacetic ester
Therefore, results into higher melting point.
CH 3 CO CHRCO O C 2 H 5 Hydrolysis CH 3 COOH
 (4) Boiling point : Boiling point of carboxylic acids increase regularly
OH H OH H  RCH 2 COOH  C 2 H 5 OH
with increase of molecular mass. Boiling points of carboxylic acids are
(iv) Oxidation of alkene and alkyne higher than those of alcohols of same molecular mass. This is due to
intermolecular hydrogen bonding between two acid molecules.
RCH  CH R   RCOOH  R COOH
[O ]
Alkene Hot alkaline
KMnO 4 Hydrogen bonding
(i)O
R  C  C  R  
3
 R  COOH  R COOH
Alkyne (ii)H 2 O O H–O
CH – C
3
C – CH 3
(v) The Arndt-Eistert synthesis O–H O

H O
R  C  Cl  CH 2 N 2  R  C  CHN 2 2
|| || Ag 2O Hydrogen bonding Acetic acid dimer
O O
Acidic nature of monocarboxylic acids
R  CH 2  COOH
(1) Cause of acidic nature
(vi) From acid amides
(i) A molecule of carboxylic acid can be represented as a resonance
Acid hybrid of the following structures.
RCONH 2  H 2 O  RCOOH  NH 3
or Alkali Acid
Amide
.. ..
RCONH 2  HNO 2  RCOOH  N 2  H 2 O O: O:
Amide Nitrous acid
|| .. | 
R  C  O H  R  C  O H
Physical properties of monocarboxylic acids
.. ..
(I) (II)
(1) Physical state : The first three members (upto 3 carbon atoms) are
(ii) Due to electron deficiency on oxygen atom of the hydroxyl group
colourless, pungent smelling liquids. The next six members are oily liquids having
(Structure II), their is a displacement of electron pair of O–H bond toward
unpleasant smell. The higher members are colourless and odourless waxy solids.
the oxygen atom. This facilitate the release of hydrogen as proton (H ). +
(2) Solubility : The lower members of the aliphatic carboxylic acid

family (upto C ) are highly soluble in water. The solubility decreases with
4
  (iii) Action with alkalies
O 
R C O  H   R  C
O
 R C O  R  C O 1 .27 A 
O O O 1 .27 A  CH 3 COOH  NaOH  CH 3 COONa  H 2 O
 Resonance hybrid  Acetic acid Sodium acetate
(iii) The resulting carboxylate ion also stabilized by resonance (iv) Action with carbonates and bicarbonates
(As negative charge is dispersed on both the oxygen atom). This 2CH 3 COOH  Na 2 CO 3  2CH 3 COONa  CO 2  H 2 O
enhance the stability of carboxylate anion and make it weaker base Sod. acetate
or strong acid. CH 3 COOH  NaHCO 3  CH 3 COONa  CO 2  H 2O
Sod. acetate
(2) Effect of substituent on acidic nature
 Reaction of carboxylic acid with aqueous sodium carbonates
(i) An electron withdrawing substituent (– I effect) stabilizes the solution produces bricks effervescence. However most phenols do not
anion by dispersing the negative charge and therefore increases the acidity. produce effervescence. Therefore, this reaction may be used to distinguish
  between carboxylic acids and phenols.
O O
GC  GC  (2) Reaction involving replacement of –OH group (i)
O O Formation of acid chloride
(I) (II) CH 3 COOH  PCl5  3CH 3 COCl  POCl3  HCl
Acetic acid Acetyl chloride
(ii) An electron releasing substituent (+ I effect) stabilizes negative
charge on the anion resulting in the decrease of stability and thus decreased 3CH 3 COOH  PCl3  3CH 3 COCl  H 3 PO3
the acidity of acid. Acetic acid Acetyl chloride
Electron with drawing nature of halogen : F > Cl > Br > I CH 3 COOH  SOCl 2  CH 3 COCl  SO 2  HCl
Acetic acid Acetyl chloride
Thus, the acidic strength decreases in the order :
(ii) Formation of esters (Esterification)
FCH2COOH  ClCH 2COOH  BrCH2COOH  ICH 2COOH
CH 3 CO OH  H OC2 H 5 Conc.H SO
2 4
Acetic acid Ethyl alcohol 

similarly :
CCl 3 COOH  CHCl 2COOH  CH 2ClCOOH  CH 3 COOH CH 3 COOC 2 H 5  H 2 O
Ethyl acetate
(Fruity smelling)
(iii) Inductive effect is stronger at -position than -position similarly at -
position it is more stronger than at  -position (a) The reaction is shifted to the right by using excess of alcohol or
removal of water by distillation.
Example: (b) The reactivity of alcohol towards esterification.
CH 3  CH 2  C H  COOH  CH 3  C H  CH 2  COOH tert-alcohol < sec-alcohol < pri-alcohol < methyl alcohol
| |
Cl Cl (c) The acidic strength of carboxylic acid plays only a minor role.
R3CCOOH  R2CHCOOH  RCH 2COOH  CH 3COOH  HCOOH
 C H 2  CH 2  CH 2  COOH
| When methanol is taken in place of ethanol. then reaction is called
Cl trans esterification.
(iv) Relative acid strength in different compounds (iv) Formation of amides
heat 
RCOOH  HOH  ROH  HC  CH  NH 3  RH CH 3 COOH  NH 3  CH 3 COONH 4 
Acetic acid Amm. acetate
 Greater the value of K or lesser the value of pK a stronger is
a
CH 3 CONH 2  H 2 O
Acetamide
the acid, i.e. pK a = – log K a
(v) Formation of acid anhydrides
 Acidic nature ( K a )  1/molecular weight CH 3 COO H
Heat CH 3 CO
HCOOH  CH 3 COOH  C 2 H 5 COOH   O  H 2O
CH 3 CO OH P2 O 5 CH 3 CO
K a Value 17.7  10  5 1 .75  10  5 1.3  10  5 Acetic acid Acetic anhydride
 The formic acid is strongest of all fatty acids. (vi) Reaction with organo-metallic reagents
 Acetic acid is less weak acid than sulphuric acid due to less ether
R' CH 2 MgBr  RCOOH  R' CH 3  RCOOMgBr
degree of ionisation. Alkane
Chemical properties of monocarboxylic acids (3) Reaction involving carbonyl (>C = O) group:
(1) Reaction involving removal of proton from –OH group LiAlH
Reduction : R  C  OH 
4
 R  CH 2  OH
(i) Action with blue litmus : All carboxylic acids turn blue litmus ||
red. O
(ii) Reaction with metals Carboxylic acid are difficult to reduce either by catalytic
2CH 3 COOH  2 Na  2CH 3 COONa  H 2 hydrogenation or Na C2 H 5 OH
Sodium acetate
(4) Reaction involving attack of carboxylic group (– COOH)
2CH 3 COOH  Zn  (CH 3 COO )2 Zn  H 2
Zinc acetate
O Cl 2 CHCOOH 2
4 Cl , red P
 Cl 3 CCOOH
||
(CO )  HCl
(i) Decarboxylation : R  C  OH 
2
R  H Dichloro acetic acid Trichloro acetic acid
When anhydrous alkali salt of fatty acid is heated with sodalime then Individual members of monocarboxylic acids
: Formic Acid or Methanoic acid (HCOOH)
CaO Formic acid is the first member of monocarboxylic acids series. It
RCOONa  NaOH  R  H  Na 2 CO 3 occurs in the sting of bees, wasps, red ants, stinging nettles. and fruits. In
Sodium salt heat Alkane
traces it is present in perspiration, urine, blood and in caterpillar's.
 When sodium formate is heated with sodalime H is evolved. 2
(1) Methods of preparation
(Exception) (i) Oxidation of methyl alcohol or formaldehyde
CaO
HCOONa  NaOH  H 2  Na 2 CO 3 CH 3 OH  O2 
Pt
 HCOOH  H 2O
Formic acid
(ii) Heating of calcium salts (ii) Hydrolysis of hydrocyanic acid : Formic acid is formed by the
heat hydrolysis of HCN with acids or alkalies.
(RCOO )2 Ca  RCOR  CaCO 3
HCl
Sodium salt Ketone HCN  2 H 2O  HCOOH  NH 3 ;
(iii) Electrolysis : (Kolbe's synthesis) NaOH
HCN  H 2O  HCOONa  NH 3
RCOONa ⇌ RCOO   Na  (iii) Laboratory preparation
CH 2OH  HO OC COOH CH 2OOC COO H
At anode 2 RCOO   R  R  2CO 2  2e  | Oxalic acid |
 H 2O CO
CHOH 
 CHOH 
2

  2H 2O | 100 120 Co | 110C
At cathode 2 Na  2e  2 Na 
 2 NaOH  H 2 CH 2OH CH 2OH
Glycerol Glycerol
Electrolysis
2CH 3 COOK  2 H 2 O  monoxalate
Potassium acetate CH 2OOCH CH 2OH
| |
CH 3  CH 3  2CO 2  2 KOH  H 2 (COOH )2 2 H 2 O
CHOH  HCOOH  CHOH
Ethane | Formic acid |
(iv) Formation of Alkyl halide (Hunsdiecker's reaction) CH 2OH CH 2OH
Glycerol Glycerol
heat monoformat e
CH 3 COOAg  Br2  CH 3 Br  AgBr  CO 2
Silver acetate CCl 4 Methyl bromide The following procedure is applied for obtaining anhydrous
formic acid.
 In Hunsdiecker reaction, one carbon atom less alkyl halide is
formed from acid salt. 2 HCOOH  PbCO3  (HCOO)2 Pb CO 2  H 2O ;
(v) Formation of amines (Schmidt reaction) Lead formate
RCOOH  N 3 H 2
4 H SO (conc.)
 RNH 2  CO 2  N 2 (HCOO)2 Pb  H 2 S  PbS  2 HCOOH
ppt. Formic acid
Acid Hydrazoic Primary
acid amine (iv) Industrial preparation : Formic acid is prepared on industrial
In Schmidt reaction, one carbon less product is formed. scale by heating sodium hydroxide with carbon monoxide at 210°C under a
(vi) Complete reduction pressure of about 10 atmospheres.
P 
CH 3 COOH  6 HI  CH 3 CH 3  2 H 2 O  3 I2 CO  NaOH 
 HCOONa
Acetic acid Ethane 210o C, 10 atm Sodium formate
In the above reaction, the – COOH group is reduced to a CH 3 Sodium formate thus formed is distilled with sodium hydrogen sulphate,
group. when anhydrous formic acid distils over.
(5) Reaction involving hydrogen of -carbon HCOONa  NaHSO 4  HCOOH  Na2SO 4
Halogenation
(2) Physical properties
(i) In presence of U.V. light
(i) It is a colourless pungent smelling liquid.
H Cl
|
U .V .
| (ii) It melts at 8.4°C and boils at 100.5°C.
 C  COOH  Cl 2 
  C  COOH  HCl
| | (iii) It is miscible with water, alcohol and ether. It forms azeotropic
 -chloro acid mixture with water.
(ii) In presence of Red P and diffused light [Hell Volhard-zelinsky (iv) It is strongly corrosive and cause blisters on skin.
reaction]
(v) It exists in aqueous solution as a dimer involving hydrogen
Carboxylic acid having an -hydrogen react with Cl or Br in the 2 2
bonding.
presence of a small amount of red phosphorus to give chloro acetic acid.
The reaction is known as Hell Volhard-zelinsky reaction. (3) Uses : Formic acid is used.
Cl , red P Cl , red P (i) In the laboratory for preparation of carbon monoxide.
CH 3 COOH 2
4
 ClCH 2 COOH 2
4

Acetic acid  HCl Chloro acetic acid  HCl (ii) In the preservation of fruits.
(iii) In textile dyeing and finishing.
(iv) In leather tanning.  The flow of alcohol is so regulated that temperature does not
(v) As coagulating agent for rubber latex. exceed 35°C, which is the optimum temperature for bacterial growth.
(vi) As an antiseptic and in the treatment of gout. Acetic acid can be obtained from vinegar with the help of lime. The
calcium acetate crystallised from the solution is distilled with concentrated
(vii) In the manufacture of plastics, water proofing compounds. sulphuric acid when pure acetic acid distils over.
(viii) In electroplating to give proper deposit of metals. (b) From acetylene : Acetylene is first converted into acetaldehyde by
(ix) In the preparation of nickel formate which is used as a catalyst passing through 40% sulphuric acid at 60°C in presence of 1% HgSO 4
in the hydrogenation of oils. (catalyst).

(x) As a reducing agent. CH  CH  H 2O 2
4

H SO (dil.)
 CH 3 CHO
(xi) In the manufacture of oxalic acid. Acetylene HgSO 4 Acetaldehy de
Acetic Acid (Ethanoic Acid) (CH3COOH) The acetaldehyde is oxidised to acetic acid by passing a mixture of
acetaldehyde vapour and air over manganous acetate at 70°C.
Acetic acid is the oldest known fatty acid. It is the chief
Manganous acetate
constituent of vinegar and hence its name (Latin acetum = vinegar) 2CH 3 CHO  O2 
 2CH 3 COOH
70C
(1) Preparation
 Acetylene required for this purpose is obtained by action of
(i) By oxidation of acetaldehyde (Laboratory-preparation) water on calcium carbide.
CH 3 CHO 22
7
 CH 3 COOH
Na Cr O CaC2  2 H 2 O  Ca(OH)2  C2 H 2
H 2 SO 4 (O )
The yield is very good and the strength of acid prepared is 97%. The
(ii) By hydrolysis of methyl cyanide with acid method is also quite cheap.
HCl (c) By the action of CO on methyl alcohol : Methyl alcohol and
CH 3 CN  2 H 2O  CH 3COOH  NH 3
carbon monoxide react together under a pressure of 30 atmospheres and
(iii) By Grignard reagent 200°C in presence of a catalyst cobalt octacarbonyl, Co (CO) to form acetic
2 8
O acid.
||
H O H CH 3 OH  CO 
Co (CO )
  CH 3 COOH
CH 3 MgBr  CO 2  CH 3  C  OMgBr 2

2 8
Methyl alcohol 30 atm200C Acetic acid

 O  (2) Physical properties
 || 
 CH 3  C  OH  (i) At ordinary temperature, acetic acid is a colourless, corrosive
  liquid with a sharp pungent odour of vinegar. It has a sour taste.
 
(ii) Below 16.5°C, it solidifies as an icy mass, hence it is named
(iv) By hydrolysis of acetyl chloride, acetic anhydride or acetamide glacial acetic acid.
and ester (iii) It boils at 118°C. The high boiling point of acetic acid in
(a) CH 3 COOC 2 H 5  H 2 O 2
4

H SO (conc.) comparison to alkanes, alkyl halides or alcohols of nearly same molecular
Ester masses is due to more stronger hydrogen bonding between acid molecules.
This also explains dimer formation of acetic acid in vapour state.
CH 3 COOH  C2 H 5 OH
(iv) It is miscible with water, alcohol and ether in all proportions.
dil. HCl
(b) CH 3 COCl  H 2O  CH 3 COOH  HCl (v) It is good solvent for phosphorus, sulphur, iodine and many
acetylchloride organic compounds.
(3) Uses : It is used,
(c) CH 3 CO 2 O  H 2O  2CH 3 COOH
dil. HCl
(i) As a solvent and a laboratory reagent.
(v) Manufacture of acetic acid (ii) As vinegar for table purpose and for manufacturing pickles.
(a) From ethyl alcohol (Quick vinegar process) : Vinegar is 6-10% (iii) In coagulation of rubber latex.
aqueous solution of acetic acid. It is obtained by fermentation of liquors (iv) For making various organic compounds such as acetone, acetic
containing 12 to 15% ethyl alcohol. Fermentation is done by Bacterium anhydride, acetyl chloride, acetamide and esters.
Mycoderma aceti in presence of air at 30-35°C. The process is termed
(v) For making various useful metallic acetates, such as:
acetous fermentation.
(a) Basic copper acetate which is used for making green paints.
Mycoderma aceti
CH 3 CH 2OH  O2  CH 3 COOH  H 2O (b) Al, Fe and Cr acetates which are used as mordants in dyeing.
Ethyl alcohol Bacter ia Acetic acid
(c) Lead tetra-acetate which is a good oxidising agent.
It is a slow process and takes about 8 to 10 days for completion. (d) Basic lead acetate which is used in the manufacture of white
In this process, the following precautions are necessary: lead.
 The concentration of the ethyl alcohol should not be more than (e) Aluminium acetate which is used in the manufacture of water-
15%, otherwise the bacteria becomes inactive. proof fabrics.
 The supply of air should be regulated. With less air the oxidation (f) Alkali acetates which are used as diuretics.
takes place only upto acetaldehyde stage while with excess of air, the acid is
oxidised to CO and water.
2
Table : 28.1 Comparison of Formic Acid and Acetic Acid

Property Formic acid Acetic acid
1. Acidic nature,
(i) With electro-positive Forms salts, Hydrogen is evolved. Forms salts. Hydrogen is evolved.
metals
1 1
HCOOH  Na  HCOONa  H2 CH 3 COOH  Na  CH 3 COONa  H2
2 2
(ii) With bases Forms salts. Forms salts.
HCOOH  NaOH  HCOONa  H 2O CH 3COOH  NaOH  CH 3COONa  H 2O
(iii) With carbonates and Forms salts. Carbon dioxide is evolved. Forms salts. Carbon dioxide is evolved.
bicarbonates HCOOH  NaHCO3  HCOONa  H 2O  CO 2 CH 3COOH  NaHCO3 
CH 3COONa  H 2O  CO 2
2. Ester formation Forms esters when treated with alcohols. Forms esters when treated with alcohols.
HCOOH  C2 H5 OH  HCOOC2 H5  H 2O CH 3 COOH  C2 H 5 OH 2
4

H SO (conc.)
CH 3COOC2 H5  H 2O
3. Reaction with PCl 5
Forms formyl chloride which decomposes into CO and Forms acetyl chloride which is a stable compound.
HCl. CH 3COOH  PCl5 
HCOOH  PCl5  HCOCl (HCl  CO )  POCl3  HCl
CH 3COCl  POCl3  HCl
4. Heating of ammonium salt Forms formamide. Forms acetamide.
HCOONH 4  HCONH 2  H 2O CH 3COONH 4  CH 3CONH 2  H 2O
5. Heating alone it decomposes into CO and H
2 2
Unaffected
HCOOH  CO 2  H 2
6. Heating with conc. H SO 2 4
Decomposed into CO and H O 2
Unaffected
Conc.
HCOOH 
 CO  H 2O
H 2 SO 4
7. Reaction with Cl 2
in Unaffected Forms mono, di or trichloro acetic acids.
presence of red P
8. Action of heat on salts,
(i) Calcium salt Forms formaldehyde. Forms acetone.
(HCOO)2 Ca  HCHO  CaCO3 (CH 3COO)2 Ca  CH 3COCH 3  CaCO3
(ii) Sodium salt Forms sodium oxalate. Unaffected.
heat
COONa
2 HCOONa |  H2
COONa
(iii) Sodium salt with soda- Forms sodium carbonate and H . 2
Forms sodium carbonate and methane.
lime CaO CaO
HCOONa  NaOH  Na 2CO 3  H 2 CH 3 COONa  NaOH  CH 4  Na 2CO 3
9. Electrolysis of sodium or It evolves hydrogen. It forms ethane.
potassium salt
10. On heating with P O 2 5
Unaffected Forms acetic anhydride.
PO
2CH 3 COOH 2 

5
(CH 3 CO )2 O  H 2O
11. Reducing nature,
(i) Tollen's reagent Gives silver mirror or black precipitate. Unaffected.
HCOOH  Ag2O  2 Ag  CO 2  H 2O
(ii) Fehling's solution Gives red precipitate Unaffected.
HCOOH  2CuO  Cu 2O  CO 2  H 2O
(iii) Mercuric chloride Forms a white ppt. which changes to greyish black. Unaffected.
HgCl2  Hg2Cl2  2 Hg
(iv) Acidified KMnO 4
Decolourises Unaffected.
12. Acid (neutral solution) + Greenish blue colour. Unaffected.
NaHSO + Sodium
3
nitroprusside.
13. Acid (neutral solution) + Red colour which changes to brown ppt. on heating. Wine red colour.
neutral ferric chloride
Interconversions (2) Descent of series : Conversion of acetic acid into formic acid.
(1) Ascent of series : Conversion of formic acid into acetic acid.
3 CH 3 NH 2 2 CH 3 OH
N H NaNO HCl
H 2 SO 4 Methyl amine Methyl alcohol
Ca(OH ) hea t
(i) HCOOH 
2
( HCOO)2 Ca  HCHO [ O]
Formic acid Calcium formate Formaldehy de
CH3MgBr HCOOH 
 HCHO
[O ]
Formic acid Formaldehy de
CH 3 CHO 
 CH 3 CH 2 OH   CH 3 CH 2OMgBr
[O ] 2 H O
CH 3 NH 2
Acetaldehyde Ethyl alcohol H Addition product Methyl amine
Br2 / KOH

 CH 3 COOH
[O ]
CH 3 COOH  CH 3 COONH 4  CH 3 CONH 2

Aceticacid NH 3 heat
Aceticacid Amm. acetate Acetamide

H 2 Ni HI
(ii) HCHO  CH 3 OH 
 CH 3 I
Formaldehy de Methyl alcohol Methyl
iodide
KCN(Alc.)
CH 3 COOH 

 CH 3 CN H 2O
Aciticacid H Methyl
cyanide
  CH 3 COONa 
NaOH
 CH 4 
Sodalime
 CH 3 Cl
Cl 2
Sodium acetate heat Methane hv Methyl

Arndt-Eistert homologation : This is a convenient method of chloride
converting an acid, RCOOH to RCH COOH. 2
AgOH
RCOOH 
 RCOCl   RCOCHN 2
CH 2 N 2 SOCl 2
EtOH Ag2O HCOOH 
 HCHO 
[O ]
 CH 3 OH
[O ]
Formic acid Formaldehy de Na 2 Cr2 O7 Methyl alcohol
RCH 2 COOH    RCH 2 COOC 2 H 5
Hydrolysis H 2 SO 4
Conversion of Acetic acid into other organic compound

(CH CO) O 3 2
Acetic anhydride
Cl CH – CH Cl CH – CH OH CH – CHO
CH – CH
3 3
2
3 2
AgOH 3 2
[O] 3 [O] CH – COOH
hv
3
Ethane Ethyl chloride Ethyl alcohol Acetaldehyde Acetic acid
NH3
CH CH NH
KCN
3 2 2
Ethyl amine
Electrolysis
CH COCl
CH CH CH NH [H] HO CH CH COOH
CH CH CN
3
2 3 2
3 2 2 2
LiAlH
3 2
H Propionic acid
n-Propyl amine 4
+
NaOH
CH COONa Sodalime Cl AgOH [O] HCHO [O] HCOOH
3
CH 2
CH Cl CH OH
Formic acid
3
Sodium acetate Methane

4
hv Methyl chloride
3
Methyl alcohol Formaldehyde
COOH COONa
| H SO 2 4
| heat HCOONa
COOH COONa Sodium formate
NaOH Oxalic acid Sodium oxalate
Ca(OH) (CH COO) Ca heat H /Ni CH CHOHCH Conc. H SO

CH COOH3
2
3 2
CH COCH 3 3
2
3 3
2 4 CH CH= CH
3 2
Calcium acetate Acetone Isopropyl alcohol Propene
I + NaOH 500°C Cl 2
2
ClCH CH= CH
CHI 3
HC ≡ CH 2 2
Allyl chloride
Iodoform acetylene
A
CH CONH g 3 2
Br /KOH
2 CH NH 3 2
Acetamide Methyl amine

2
PCl or SOCl
5
PO [H]
NH 3
2 5
CH CN 3
CH CH NH 3 2 2
heat Methyl cyanide LiAlH 4

Ethyl amine
C2H5OH
CH COCl 3 CH COOC H 3 2 5
Acetyl chloride Ethyl acetate
Rosenmund's CH CHO HCN

OH CH CHOHCOOH
HO 3
reduction
3
Acetaldehyde CH CH 2
Lactic acid
3
H +
CN
Cyanohydrin
The sodium oxalate thus formed is dissolved in water and calcium

Dicarboxylic acids hydroxide is added. The precipitate of calcium oxalate is formed which is
The acids containing two carboxylic groups are called dicarboxylic separated by filtration. It is decomposed with calculated quantity of dilute
acids. sulphuric acid.
The saturated dicarboxylic acid are represented by the general formula COONa COO
Cn H 2n (COOH )2 where n = 0, 1, 2, 3 etc. |  Ca(OH )2  | Ca  2 NaOH
COONa COO
HO  C  (CH 2 )n  C  OH or HOOC(CH 2 )n COOH Calcium oxalate
|| ||
O O COO COOH
According to IUPAC system, the suffix-dioic acid is added to the name | Ca  H 2 SO 4 (dil.)  |  CaSO 4
of parent alkane, i.e. Alkane dioxic acid. COO COOH Calcium sulphate
Oxalic acid (insoluble)
(soluble)
Table : 28.2
Formula Common name IUPAC name (2) Physical Properties
HOOCCOOH Oxalic acid Ethanedioic acid (i) It is a colourless crystalline solid. It consists of two molecules of
HOOCCH2COOH Malonic acid 1-3 Propanedioic acid water as water of crystallisation.
HOOCCH2CH2 COOH Succinic acid 1,4-Butanedioic acid (ii) The hydrated form has the melting point 101.5°C while the
HOOC(CH2)3COOH Glutaric acid 1,5-Pentanedioic acid anhydrous form melts at 190°C.
HOOC(CH2)4 COOH Adipic acid 1,6-Hexanedioic acid
(iii) It is soluble in water and alcohol but insoluble in ether.
Oxalic Acid or Ethanedioic Acid
(iv) It is poisonous in nature. It affects the central nervous system.
COOH
| or (COOH) or (C H O )
2 2 2 4
(3) Chemical Properties
COOH
(i) Action of heat : It becomes anhydrous.
Oxalic acid is first member of dicarboxylic series.
100 105 C
It occurs as potassium hydrogen oxalate in the wood sorel, (COOH )2 2 H 2 O  (COOH )2  2 H 2 O
Hydrated oxalic Anhydrous
rhubarb and other plants of oxalis group and as calcium oxalate in acid oxalic acid
plants of rumex family.
It is found in the form of calcium oxalate in stony deposits in (a) At 200°C, (COOH )2  HCOOH  CO 2
Formic acid
kidneys and bladdar in human body. On further heating, formic acid also decomposes.
Oxalic acid present in tomatoes.
(1) Methods of Preparation HCOOH  CO 2  H 2
(i) By oxidation of ethylene glycol with acidified potassium (b) Heating with conc. H SO 2 4
dichromate
COOH H SO
CH 2 OH
K Cr O7
COOH | 2  4
 CO  CO 2  H 2 O
|  4[O] 2 2  |  2 H 2O COOH (conc .)
CH 2 OH H 2 SO 4 COOH (ii) Acidic nature
Glycol
Salt formation
(ii) By hydrolysis of cyanogen with conc. hydrochloric acid :
CN COOH COOH COOK COOK
|  4 H 2 O  
 |
2( HCl )
 2 NH 4 Cl |  KOH  |
KOH
 |
CN COOH COOH COOK COOK
Oxalic acid Acid pot. oxalate Pot. oxalate
(iii) By heating sodium or potassium in a current of carbon dioxide
at 360°C COOH COONa
COONa |  2 NaHCO 3  |  2CO 2  2 H 2 O
2 Na  2CO 2  |
heat
COOH COONa
COONa Sod. oxalate
Sodium oxalate
(iv) Laboratory preparation COOH COONa

|  Na 2 CO 3  |  H 2 O  CO 2
COOH COOH COONa
C12 H 22 O11  18[O]   6 |
HNO 3
 5H 2O
Sucrose V2 O5
COOH (iii) Esterification
Oxalic acid
(v) Industrial method COOH C H OH COOC 2 H 5 COOC 2 H 5

C H OH
| 2 5  | 2 5  |
360 C
COONa COOH COOH COOC 2 H 5
2 HCOONa   |  H2
Sod. formate Ethyl hydrogen Ethyl oxalate
COONa oxalate
Sod. oxalate
Sodium formate is obtained by passing carbon monoxide over fine (iv) Reaction with PCl : 5
powdered of sodium hydroxide.

200 C
CO  NaOH   HCOONa
8 10 atm
COOH COCl (5) Analytical test
|  2 PCl5  |  2 POCl3  2 HCl (i) The aqueous solution turns blue litmus red.
COOH COCl
Oxalyl (ii) The aqueous solution evolves effervescences with NaHCO 3 .
chloride
(iii) The neutral solution gives a white precipitate with calcium
(v) Reaction with ammonia chloride solution. It is insoluble in acetic acid.
COOH COONH 4 COONH 4 H 2 C 2 O4   (NH 4 )2 C 2 O4 

NH 4 OH
 CaC2 O4
CaCl 2
NH 3
|  NH 3  |  | Oxalic acid Amm.oxalate Calcium oxalate
COOH COOH COONH 4 (iv) Oxalic acid decolourises hot potassium permanganate solution
Acid ammonium Amm. oxalate having dilute sulphuric acid.
oxalate
– 2H O 2
heat (v) With hot conc. H 2 SO 4 , it evolves carbon monoxide which
– H O heat
2
burns with blue flame.

CONH 2 CONH 2 COOH
| | Malonic Acid or Propane-1,3-Dioic Acid CH 2
COOH
COOH CONH 2
Oxamic acid Oxamide or CH 2 (COOH) 2 or (C 3 H 4 O 4 )
(vi) Oxidation : When oxalic acid is warmed with acidified The acid occurs as calcium salt in sugar beet. It was so named
KMnO4 . because it was first obtained from malic acid (hydroxy succinic acid) by
oxidation.
2 KMnO4  3 H 2 SO 4  K 2 SO 4  2 MnSO 4  3 H 2 O  5[O] (1) Methods of Preparation : From acetic acid
Cl KCN ( Aq .)
COOH  CH 3 COOH 
2
 CH 2 ClCOOH 
|  [O]  2CO 2  H 2 O   5 Acetic acid P Chloroacet ic acid
 COOH 
COOH
2 KMnO4  3 H 2 SO 4  5  K 2 SO 4  2 MnSO 4  10 CO 2  8 H 2 O H O H COOH
| CH 2 CNCOOH 2
 CH 2
Pot. permangan ate COOH COOH
(Purple) Cyano acetic acid
Oxalic acid
Colourless Malonic acid
 Oxalic acid decolourises the acidic KMnO4 solution. (2) Physical Properties
(i) It is a white crystalline solid.
(vii) Reaction with ethylene glycol (ii) It's melting point is 135°C.
(iii) It is soluble in water and alcohol but sparingly soluble in ether.
OH HO O
O=C CH 2
O=C CH (i) Action of heat
heat |
2
| + | | (a) Heating at 150°C :

–H O O=C
O=C CH 2
CH
CH 2 (COOH )2  CH 3 COOH  CO 2
2 2
OH HO O
Oxalic acid Ethylene glycol
(b) Heating with P O : 2 5
Ethylene oxalate
CH 2OH H OH
COOH Zn | |
(viii) Reduction : |  4 H   |  H 2O O  C  C C  O 2 

P O
5
 O  C  C  C  O 2H 2O
COOH H 2 SO 4 COOH | | heat Carbon suboxide
Glycolic acid OH H
(ii) Reaction with aldehyde : With aldehydes, - unsaturated acids
COOH Electrolytic reduction CH 2OH COOH are formed.
2|  |  |  2H 2O
COOH 6[ H ] COOH CHO COOH Pyridine
Glycolic acid Glyoxalic acid RCH  O  H 2 C 
Aldehyde COOH heat
(ix) Reaction with Glycerol : At 100° – 110°C, formic acid is formed. RCH  CHCOOH  H 2 O  CO 2
At 260°, allyl alcohol is formed.  -  unsaturate d acid
(4) Uses : Oxalic acid (Polyprotic acid) is used, (4) Uses : Its diethyl ester (malonic ester) is a valuable synthetic
(i) In the manufacture of carbon monoxide, formic acid and allyl reagent for preparation of a variety of carboxylic acids.
alcohol. Succinic Acid or Butane-1,4-Dioic Acid :
(ii) As a laboratory reagent and as a standard substance in CH 2 COOH
volumetric analysis. | or (CH 2 )2 (COOH) or (C 4 H 6 O 4 )
2
(iii) In the form of antimony salt as a mordant in dyeing and calico CH 2 COOH
printing.
It was first obtained by the distillation of yellow fossil, resin, amber and
(iv) In the manufacture of inks. hence its name (Latin, Succinum = amber).
(v) For removing ink stains and rust stains and for bleaching straw, It is also formed in small amount during the fermentation of sugar.
wood and leather.
(1) Methods of Preparation
(vi) In the form of ferrous potassium oxalate as developer in
(i) From ethylene
photography.
CH 2 CH 2 Br CH 2 CN It was first obtained by the oxidation of fats (Latin, adeps = fat.)

||  |
Br2
 |
NaCN
   CH 2 COOH
H 2 O HCl
CH 2 CH 2 Br CH 2 CN | (i) From benzene (In industries)
Ethylene Ethylene Ethylene CH 2 COOH
bromide cyanide
Succinic acid OH
(ii) From maleic acid [catalytic reduction]
H O HNO
CHCOOH CH 2COOH 2 2
3
Ni
||  H 2  | Catalyst H BO , heat
3 3
SeO
3
CHCOOH heat CH COOH

2 Benzene Cyclohexane Cyclohexanol
 This is an industrial method.
O
(iii) Reduction of tartaric acid or malic acid
CHOHCOOH HI CH 2 COOH HI CHOHCOOH HNO
| 
 | 
 |
3
HOOC – (CH ) – COOH 2 4
P P Adipic acid
CHOHCOOH CH 2 COOH CH 2 COOH
Tartaric acid Succinic acid Malic acid
Cyclohexanone
(2) Physical properties  It is an industrial method.
(i) It is a white crystalline solid. It melts at 188 o C (ii) From tetrahydrofuran (THF)
(ii) It is less soluble in water. It is comparatively more soluble in
alcohol. CH 2 CH 2
| |  2CO  HOH  HOOC  (CH 2 )4  COOH
(3) Chemical Properties : Succinic acid gives the usual reactions of
CH 2 CH 2 Adipic acid
dicarboxylic acid, some important reactions are :
(i) Action of heat : At 300°C O
THF
CH 2 COOH CH 2 CO
300 C
|    | O (2) Physical Properties
CH 2 COOH (– H 2 O ) CH 2 CO
Succinic acid Succinic anhydride (i) It is a white crystalline solid. Its melting point is 150°C.
(ii) With ammonia (ii) It is fairly soluble in alcohol and ether but less soluble in water.
CH 2COOH CH 2COONH 4 (3) Chemical Properties
NH 3 heat
|   | 
CH 2COOH CH 2COONH 4  H 2O It shows all the general reaction of dicarboxylic acids.
Ammonium succinate (i) Action of heat
CH 2CONH 2 CH 2CO H 2
heat
|  | NH C
CH 2CONH 2  NH 3 CH 2CO HC
Succinamid e Succinimide
HOOC(CH ) COOH 2 4
heat
2
|
Adipic acid 300°C HC C = O + CO + H O
2 2
(iii) Reaction with Br 2

2
CH 2  CO CH 2  CO C
| NH  Br2  |
NaOH
N  Br  HBr
H
2
CH 2  CO 0 C CH 2  CO Cyclopentanone
(ii) Formation of Nylon-66 [Reaction with hexa methylene
Succinimid e N - bromosuccinimide diamine]
(N.B.S)
nH 2 N (CH 2 )6 NH 2  nHO  C  (CH 2 )4  C  OH
(iv) Reaction with ethylene glycol hexamethyl ene diamine || ||
HOOC  (CH 2 )2  CO OH  H OCH 2  O O
adipic acid
– nH O
CH 2 O H  HO OC  (CH 2 )2  CO OH  ....... 2
– H2 O H H O O
| | || ||
HOOC  (CH 2 )2  CO  [OCH 2  CH 2 O  OC  ( N  (CH 2 )6  N  C  (CH 2 )4  C )n 
nylon-66
(CH 2 )2  CO ]n  OH  H 2 O (4) Uses : It is used in the manufacture of several polymers.
Polyester
Unsaturated Acids : When the double bond presents in the carbon chain
When sodium or potassium salt in aqueous solution is electrolysed, of an acid is called unsaturated acid.
ethylene is obtained at anode.
Example: CH 2  CH  COOH  H  C  COOH
(4) Uses : It finds use in volumetric analysis, medicine and in the Acrylicacid ||
manufacture of dyes, perfumes and polyester resins. H C COOH
Maleic acid
Adipic Acid or Hexane-1,6 –Dioic Acid
Acrylic Acid or Prop-2-Enoic Acid
CH 2 CH 2 COOH
| or (CH 2 )4 (COOH) 2 or (C 6 H 10 O 4 ) CH 2  CH  COOH or (C 3 H 4 O 2 )
CH 2 CH 2 COOH
(i) From allyl alcohol 2CH 2  CHCOOH  Na 2CO3 
CH 2 CH 2 Br CH 2 Br CH 2
|| | | || 2CH 2  CHCO O Na   H 2O  CO 2
Br2 HNO 3 Zn
CH  C HBr  C HBr 
 C H Sodium acrylate
| | [O ] | hea t |
(v) Ester formation
CH 2OH CH 2OH COOH COOH
Conc.H SO
(ii) By oxidation of acrolein CH 2  CHCOOH  HOC2 H 5 2 
4

 H 2O
AgNO
CH 2  CHCHO  [O] 
3
 CH 2  CHCOOH CH 2  CH  COOC 2 H 5
NH 4 OH
Ethyl acrylate
(iii) From propionic acid : CH 3 CH 2COOH 


Br2 P (vi) With PCl
5
Propionic acid HVZ reaction CH 2  CHCOOH  PCl5  CH 2  CH  COCl

Acryl chloride
Alc . KOH
CH 3 CHBrCOOH 
 CH 2  CHCOOH (4) Uses : Its ester are used for making plastics such as Lucite and
 -Bromopropionic acid
plexiglass.
(iv) By heating -hydroxy propionic acid Unsaturated dicarboxylic acids
ZnCl2
C H 2  CH 2  COOH 
 CH 2  CH  COOH The molecular formula of the simplest unsaturated dicarboxylic acid
| heat,  H 2 O
OH is HOOC.CH  CH .COOH This formula, however represents two
 -hydroxy propionic acid chemical compounds, maleic acid and fumaric acid, which are geometrical
isomers.
(v) From vinyl cyanide
H  C  COOH HOOC  C  H
Cu Cl HCl
HC  CH  HCN   CH 2  CH  CN
2 2 || ||
Acetylene 90C Vinylcyanide
H C COOH H C COOH
Cis- form (Maleic acid) Trans- form (Fumaric acid)
H  H 2O

 CH 2  CH  COOH (1) Methods of Preparation of Maleic Acid
(i) By catalytic oxidation of 2-butene or benzene
(vi) From ethylene cyanohydrin
 HCN Conc.H SO
CH CH 3 CHCOOH
CH 2  CH 2  C H 2  CH 2  CN 2 
4
 ||
V O5
 30 2 2 
| |  2H 2 O
heat  H 2 O 400C CHCOOH
|
CH CH 3
OH Maleic acid
O 2 Butene
Ethylene cyanohydrin
Ethylene oxide
9 V O5
CH CO H O H
CHCOOH
C6 H 6  O 2 2 
| | O 2 | |
H  H 2O 400 C CH CO
CH 2  CH  CN 
 CH 2  CHCOOH 2 o
Benzene CHCOOH
Vinylcyanide Maleic anhydride
(acrylonitrile)
(ii) From malic acid :
Industrial method : This is a new method of its manufacture.
CH (OH )COOH heat
CHCOOH heat
CH CO
CH  CH  CO  H 2 O 

4
 CH 2  CHCOOH
Ni(CO) | | | | | O
CH 2 COOH  H 2O CHCOOH  H 2O CH CO
(2) Physical Properties Malic acid Maleic acid Maleic anhydride
(Hydroxy succinic acid) (intermedi ate)
 It is colourless pungent smelling liquid. Its boiling point is 141°C.
 It is miscible with water, alcohol and ether. CH COONa CH COOH
NaOH H  H 2O
 It shows properties of an alkene as well as of an acid. | |  | |
boil CH COONa CH COOH
(3) Chemical Properties Sodium salt Maleic acid
(i) With nascent hydrogen (Na and C H OH) 2 5 (2) Methods of Preparation of Fumaric Acid
CH 2  CHCOOH  2[H ] 
 CH 3 CH 2 COOH
Ni (i) From maleic acid :
H C COOH HCl HOOCC  H
(ii) With halogens and halogen acids : Markownikoff's rule is not ||  ||
followed. H C COOH boil H C COOH
Maleic acid
CCl
CH 2  CHCOOH  Br2 

4
 CH 2 Br  CHBrCOOH (ii) By oxidation of furfural with sodium chlorate
 ,  -Dibromopro pionic acid
HC CH HOOC C  H
CH 2  CHCOOH  HBr  BrCH 2  CH 2 COOH || ||
NaClO3
 4[O]   ||  CO 2
 -Bromopropionic acid HC C CHO H C COOH
(iii) Oxidation : In presence of dilute alkaline KMnO . 4
O
CH 2  CHCOOH  [O]  H 2 O  CH 2 OHCHOHCOOH
Glyceric acid (iii) By heating malic acid at about 150°C for long time
 On vigorous oxidation, oxalic acid is formed. CH (OH )COOH
heat
HOOC  C  H
(iv) Salt formation |  ||
CH 2 COOH 150C ,  H 2 O H  C  COOH
CH 2  CHCOOH  KOH  CH 2  CHCO O K   H 2 O Malic acid
(iv) By heating bromosuccinic acid with alcoholic potash : By heating CH 3 (CH 2 )7 CHO  HOOC(CH 2 )7 CHO
bromosuccinic acid with alcoholic potash.
It is used for making soaps, lubricants and detergents.
CH 2COOH HOOC  C  H (1) Difference between oils and fats : Oils and fats belong to the
Alc. KOH
|  ||  KBr  H 2 O same chemical group, yet they are different in their physical state.
CH .( Br)COOH H  C  COOH (i) Oils are liquids at ordinary temperature (below 20°C) while fats
(3) Physical Properties are semi solids or solids (their melting points are more than 20°C). A
substance may be classed as fat in one season and oil in another season or
(i) Both are colourless crystalline solids. Both are soluble in water.
the same glyceride may be solid at a hill station and liquid in plains. Thus,
(ii) The melting point of maleic acid (130.5°C) is lower than the this distinction is not well founded as the physical state depends on climate
melting point of fumaric acid (287°C). and weather.
(4) Chemical Properties (ii) The difference in oils and fats is actually dependent on the
Chemically, both the acids give the reactions of alkenes and dibasic nature of monocarboxylic acid present in the glyceride. Oils contain large
acids except that the maleic acid on heating forms an anhydride while proportion of the glycerides of lower carboxylic acids, (e.g., butyric acid,
fumaric acid does not give anhydride. caprylic acid and caproic acid) and unsaturated fatty acids, (e.g., oleic,
linoleic and linolenic acids) while fats contain a large proportion of
CHCOOH hea t CHCO
||  | | O  H 2O glycerides of higher saturated carboxylic acids, (e.g., palmitic, stearic acids).
CHCOOH CHCO Lard (fat of hogs) is a solid fat and its composition in terms of fatty
Maleic acid Maleic anhydride
acids produced on hydrolysis is approximately 32% palmitic acid, 18%
Both form succinic acid on reduction with sodium amalgam. They
stearic acid, 45% oleic acid and 5% linolenic acid. Olive oil on the other
undergo addition reactions with bromine, hydrobromic acid, water, etc. and
hand, contains 84% oleic acid, 4% linoleic acid, 9% palmitic acid and 3%
form salts, esters and acid chlorides as usual. With alkaline KMnO solution,
stearic acid.
4
they get oxidised to tartaric acid.

COOH COOH (2) Physical Properties of oils and Fats
| |
H  C  OH H  C  COOH Br water H  C  Br
(i) Fats are solids, whereas oils are liquids.
Alk.KMnO4
|   || 2  | (ii) They are insoluble in water but soluble in ether, chloroform and
H  C  OH (Syn - addition) H  C  COOH (anti - addition) Br  C  H benzene.
| Maleic acid |
COOH (Cis) COOH (iii) They have less specific gravity than water and consequently float
Tartaric acid (Racemic mixture)
(Meso) on the surface when mixed with it.
COOH COOH (iv) Pure fats and oils are colourless, odourless and tasteless but
| | natural fats and oils possess a characteristic odour due to presence of other
H  C  OH H  C  COOH H  C  Br
|
Alk.KMnO

4  ||
Br water
2  | substances.
HO  C  H (Syn - addition) HOOC  C  H (anti - addition) H  C  Br
| Fumaric acid (Trans) | (v) They have specific melting points, specific gravity and refractive
COOH COOH index hence they can be identified by these oil constants.
Tarta ric acid ((Meso)
(Racemic mixture) (vi) Animal fats contain cholesterol, an unsaturated alcohol, whereas
vegetable fats contains phytosterol.
Higher fatty acids
(3) Chemical Properties : They give reactions of carbon-carbon
Palmitic, stearic and oleic acids are found in natural fats and oils as
double bonds and ester groups.
glyceryl esters.
They have derived their names from the natural source from which (i) Hydrolysis
they are prepared by hydrolysis with alkali. (a) By superheated steam
Table : 28.3
CH 2 O COC17 H 35 CH 2 OH
Name of acids Source Molecular formula | |
3H 2O
Palmitic acid Palm oil C HO COC17 H 35  C HOH  3 C17 H 35 COOH
CH 3 (CH 2 )14 COOH | | Stearic acid
CH 2 O COC17 H 35 CH 2 OH
Stearic acid Stear CH 3 (CH 2 )16 COOH Tristearin Glycerol
(meaning
tallow) (b) Base hydrolysis [Saponification]
Oleic acid Olive oil. CH 3 (CH 2 )7 CH  CH (CH 2 )7 COOH
CH 2 OCOR CH 2 OH
| |
Palmitic and stearic acids are waxy colourless solids with melting C HOCOR  3 NaOH  C HOH  3 RCOONa
| | Salt fatty acid
points 64°C and 72°C, respectively. They are insoluble in water but soluble CH 2 OCOR CH 2 OH (Soap)
in ethanol and ether. They find use in the manufacture of soaps and Fat or oil Glycerol
candles. Soaps contain sodium or potassium salts of these higher fatty acids.
(c) Enzyme hydrolysis : Enzyme like lipase, when added to an
Oleic acid has low melting point, i.e., 16°C. It is insoluble in water
but soluble in alcohol and ether. Besides the reactions of acids, it also gives emulsion of fat in water, hydrolyses it into acid and glycerol in about two or
reactions of alkenes. Two aldehydes are formed on ozonolysis. three days.
(i)O
CH 3 (CH 2 )7 CH  CH (CH 2 )7 COOH 
3

(ii)Zn  H 2 O
(ii) Hydrogenation : In the presence of finally divided nickel, at low titrating it against a standard solution of KOH using phenolphthalein as
pressure the hydrogenation process is called hardening of oils. an indicator.
(ii) Saponification value : It is a measure of fatty acids present as
O O esters in oils and fats. It is defined as the number of milligrams of KOH
|| ||
CH 2 O C (CH 2 )7 CH  CH (CH 2 )7 CH 3 CH 2 O C C17 H 35 required to saponify one gram of the oil or fat or number of milligrams
O O of KOH required to neutralize the free acids resulting from the hydrolysis
|| ||
CHO C (CH 2 )7 CH CH (CH 2 )7 CH 3 3 H

2
CHO C C17 H 35 of one gram of an oil or fat. It is determined by refluxing a Saponification
Ni , Heat
O O number of fat or oil
|| ||
CH 2O C (CH 2 )7 CH CH (CH 2 )7 CH 3 CH 2O C C17 H 35 168,000
Glyceryl trioleate or triolein (Liquid oil) Tristearin(A solid fat)
= , Where M = molecular mass
M
(iii) Hydrogenolysis [Reduction to alcohol]
(iii) Iodine value : Iodine value of a fat or oil is a measure of its
O degree of unsaturation. It is defined as the number of grams of iodine
|| taken up by 100 grams of fat or oil for saturation. For a saturated acid
CH 2  O  C  C17 H 35 glyceride, the iodine value is zero. Thus, the iodine value for a fat is low
O CH 2OH
|| | whereas for oil, it is high. As iodine does not react readily, in actual
CH  O  C  C17 H 35  CHOH  3 C17 H 35 CH 2 OH
6 H2
practice, iodine monochloride is used. Iodine monochloride is known as
200 atm |
O Octadecyl alcohol
Wij's reagent.
|| CH 2OH
CH 2  O  C  C17 H 35 (iv) Reichert-Meissl value, (R/M value) : It indicates the amount of
Tristearin
steam volatile fatty acids present in the oil or fat. It is defined as the
(iv) Drying : Certain oils, containing glycerides of unsaturated number of millilitres of 0.1 N KOH solution required to neutralize the
fatty acids having two or three double bonds have the tendency of slowly distillate of 5 grams of hydrolysed fat. It is determined by hydrolysing a
absorbing oxygen from atmosphere and undergoing polymerisation to known weighed amount (5 grams) of the fat with alkali solution and the
form hard transparent coating. This process is known as drying and such mixture is acidified with dilute sulphuric acid and steam distilled. The
oils are called drying oils. Unsaturated oils such as linseed oil are, distillate is cooled, filtered and titrated against 0.1 N KOH.
therefore, used as medium of paints and varnishes. (5) Uses
(i) Many oils and fats are used as food material.
(v) Rancidification : On long storage in contact with air and
(ii) Oils and fats are used for the manufacture of glycerol, fatty
moisture, oils and fats develop unpleasant smell. The process is known as
acids, soaps, candles, vegetable ghee, margarine, hair oils, etc.
rancidification. It is believed that rancidification occurs due to hydrolysis-
oxidation. (iii) Oils like linseed oil, tung oil, etc., are used for the
manufacture of paints, varnish, etc.
(4) Analysis of oils and fats (iv) Castor oil is used as purgative and codliver oil as a source of
(i) Acid value : It indicates the amount of free acid present in the vitamins A and D. Almond oil is used in pharmacy. Olive oil is also used
oil or fat. It is defined as the number of milligrams of KOH required to as medicine.
neutralize the free acid present in one gram of the oil or fat. It is (v) Oils are also used as lubricants and illuminants.
determined by dissolving a weighed amount of oil or fat in alcohol and
Table : 28.4 Difference between vegetable oils and Mineral oils
Property Vegetable oils Minerals oils
1. Composition These are triesters of glycerol with higher fatty acids. These are hydrocarbons (saturated). Kerosene
oil–Alkanes from C to C .
12 16
2. Source Seeds root and fruits of plants. These occur inside earth in the form of
petroleum.
3. Hydrolysis Undergo hydrolysis with alkali. Form soap and glycerol. No hydrolysis occurs.
4. On adding NaOH and Decolourisation of pink colour occurs. No effect.
phenolphthalein
5. Burning Burns slowly Burn very readily.
6. Hydrogenation Hydrogenation occurs in presence of nickel catalyst. Solid glycerides No hydrogenation occurs.
(fats) are formed.
(6) Soaps : Soaps are the metallic salts of higher fatty acids such as The oils and fats are mixed glycerides and thus soaps are mixtures of salts
palmitic, stearic, oleic, etc. The sodium and potassium salts are the common of saturated and unsaturated long chain carboxylic acids containing 12 to 18
soaps which are soluble in water and used for cleansing purposes. Soaps of carbon atoms. This process always yields glycerol as a byproduct.
other metals such as calcium, magnesium, zinc, chromium, lead, etc., are
CH 2OCOR1 CH 2OH R1COONa
insoluble in water. These are not used for cleansing purposes but for other | | 
purposes (lubricants, driers, adhesives, etc.) C HOCOR 2  3 NaOH  C HOH  R 2 COONa
| | 
Ordinary soaps (sodium and potassium) are the products of CH 2OCOR 3 CH 2OH R3 COONa
hydrolysis of oils and fats with sodium hydroxide or potassium hydroxide. Triglyceride Glycerol Soap
There are three methods for manufacture of soaps : CH 2 OH
|
(i) The cold process
C17 H 35 COOCH 2  C  CH 2 O H
|
(ii) The hot process
CH 2 OH
(iii) Modern process Pentaeryth ritol monosteara te
(7) Synthetic Detergents : The synthetic detergents or Syndets are Detergents are superior cleansing agents due to following properties.
substitutes of soaps. They have cleansing power as good or better than (i) These can be used both in soft and hard waters as the calcium
ordinary soaps. Like soap, they contain both hydrophilic (water soluble) and and magnesium ions present in hard water form soluble salts with
hydrophobic (oil-soluble) parts in the molecule. detergents. Ordinary soap cannot be used in hard water.
(ii) The aqueous solution of detergents are neutral. Hence these can
C12 H 25 OSO 3 Na C15 H 31 COONa be used for washing all types of fabrics without any damage. The solution
Hydrophobi c Hydrophili c Hydrophobi c Hydrophili c
part part part part or ordinary soap is alkaline and thus cannot be used to wash delicate
Sodium lauryl sulphate (Detergent ) Sodium palmitate(Soap) fabrics.
Some of the detergents used these days are given below: (8) Waxes : Waxes are the esters of higher fatty acids with higher
monohydric alcohols. The acids and alcohols commonly found in waxes are
(i) Sodium alkyl sulphates : These are sodium salts of sulphuric acid palmitic, cerotic acid (C25 H 51COOH ) , melissic acid (C30 H 61COOH )
esters of long chain aliphatic alcohols containing usually 10 to 15 carbon
and cetyl alcohol (C16 H 33OH ) , ceryl alcohol (C26 H 53OH ) , myricyl
atoms. The alcohols are obtained from oils or fats by hydrogenolysis.
alcohol (C30 H 61OH ) , etc.
CH 3 (CH 2 )10 CH 2 OH  HO SO 3 H 
Lauryl alcohol Sulphuric acid Waxes are insoluble in water but are readily soluble in benzene,
petroleum, carbon disulphide etc. Waxes on hydrolysis with water yields
CH 3 (CH 2 )10 CH 2OSO 2OH 
NaOH higher fatty acids and higher monohydric alcohols.
Lauryl hydrogen sulphate C15 H 31COOC16 H 33  H 2O  C15 H 31COOH  C16 H 33OH
Cetyl palmitate Palmitic acid Cetyl alcohol
CH 3 (CH 2 )10 CH 2OSO 2ONa
Sodium lauryl sulphate (Detergent ) When hydrolysis is carried with caustic alkalies, soap and higher
monohydric alcohols are formed.
The other examples are sodium cetyl sulphate, C15 H 31COOC16 H 33  NaOH  C16 H 33OH  C15 H 31COONa
C16 H 33 OSO 2 ONa and sodium stearyl sulphate, Sodium palmitate (Soap)
CH 3 (CH 2 )16 CH 2 OSO 3 Na . Unlike ordinary soaps, they do not The common waxes are:
produce OH ions on hydrolysis and thus can be safely used for woollen
–
(i) Bees wax, Myricyl palmitate, C15 H 31COOC30 H 61

garments.
(ii) Spermaceti wax, Cetyl palmitate, C15 H 31COOC16 H 33
(ii) Sodium alkyl benzene sulphonates : Sodium p-dodecyl
benzene sulphonate (S.D.S.) acts as a good detergent. It is most widely used (iii) Carnauba wax, Myricyl cerotate, C25 H 51COOC30 H 61
since 1975.
CH 3 Waxes are used in the manufacture of candles, polishes, inks, water
| proof coating and cosmetic preparations.
CH 3 (CH 2 )9 CH  CH 2  C6 H 6   CH 3 (CH 2 )9 C H  C6 H 5
AlCl3
1- Dodecene 2 - Dodecyl be nzene Waxes obtained from plants and animals are different than paraffin
wax which is a petroleum product and a mixture of higher hydrocarbons
CH 3 (20 to 30 carbon atoms). So paraffin wax is not an ester.
|
 CH 3  (CH 2 )9  C H  C 6 H 4  SO 3 Na
 (i)H 2 SO 4
Candles are prepared by mixing paraffin wax (90%) with higher
(ii) NaOH (S.D.S.)
fatty acids like stearic and palmitic. The fatty acids are added to paraffin
These long chain alkyl benzene sulphonate (L.A.S.) are most widely wax as to give strength to candles. The mixture is melted and poured into
used syndets. metal tubes containing streched threads. On cooling candles are obtained.
(iii) Quaternary ammonium salts : Quaternary ammonium salts with
long chain alkyl group have been used as detergents, e.g., trimethyl stearyl Substituted carboxylic acids
ammonium bromide. The compounds formed by the replacement of one or more
Br hydrogen atoms of the hydrocarbon chain part of the carboxylic acids by
(CH 3 )3 N atoms or groups such as X (halogen), OH or NH , are referred to as
C18 H 37 2
substituted acids. For example,

(iv) Sulphonates with triethanol ammonium ion in place of sodium
serve as highly soluble materials for liquid detergents. CH 2 ClCOOH ; CH 2 OHCOOH ; CH 2 NH 2 COOH
Chloroacet ic acid Hydroxyacetic acid Aminoaceti c acid
  
R  O  SO 2  N H (CH 2  CH 2 OH )3  The position of the substituents on the carbon chain are indicated
 
by Greek letters or numbers.
(v) Partially esterified polyhydroxy compounds also acts as
detergents. 6 5 4 3 2 1
C  C  C  C  C  C OOH
    
For example, potassium tartrate which is also precipitated by addition of CaCl . The 2
calcium salt is then decomposed with calculated quantity of dilute H SO .

CH 3 CHOHCOOH ;
2 4
CH 3 CHOHCH 2 COOH The precipitate (CaSO ) is filtered and the filtrate on concentration gives the
 - Hydroxypropionic acid  - Hydroxybutyric acid
4
2 - Hydroxypropanoic acid 3 - Hydroxybutanoic acid crystals of tartaric acid.

CH (OH )COOK CH (OH )COOK CH (OH )COO
Lactic Acid or -hydroxy propionic acid or 2-hydroxy propanoic acid 2|  Ca(OH ) 2  |  | Ca
CH (OH )COOH CH (OH )COOK CH (OH )COO
It is the main constituent of sour milk. It is manufactured by Pot.hydrogen tartrate Pot.tartra te (Filtrate) Calcium tartrate (ppt.)
fermentation of molasses by the micro-organism (Bacterium acidi lactici- CaCl2
sour milk) in presence of CaCO 3 . -2KCl
CH (OH )COO CH (OH )COOH
(1) Method of Preparation | Ca  H 2 SO 4  CaSO 4  |
From acetaldehyde : CH (OH )COO CH (OH )COOH
Tartaric acid
H O H  (ii) Synthetic method
CH 3 CHO  HCN  CH 3 CH (OH )CN 2
Electric H Br
Acetaldehy de Cyanohydrin C  H 2  CH  CH 
2
 CH 2  CH 2 
2

arc Acetylene Pd BaSO 4 Ethylene
CH 3 CHOHCOOH
Lactic acid CH 2 CN CH 2 CO 2 H
H 2O H 
(CH 2 Br)2  |
2 KCN
  |
(2) Physical Properties Ethylene bromide CH 2 CN CH 2 CO 2 H
Succinic acid
It is a colourless syrupy liquid having a sour taste and smell.
It is hygroscopic and very soluble in water. It is optically active and CHBrCOOH AgOH
CHOHCOOH
  |
Red P
|
exists in three distinct forms. Br2
CHBrCOOH CHOHCOOH
 , '-Dibromo succinic Tartaric acid
(3) Chemical Properties : It gives reactions of secondary alcoholic acid
group and a carboxylic group.
(iii) From glyoxal cyanohydrin :
CH 3 CHOHCOONa CH 3 CHOCOCH 3
Sod. Lactate | CHO CH (OH )CN H O H
CH (OH )COOH
HCN
Lactide
COOH |  | 2 |
Acetyllactic acid CHO CH (OH )CN CH (OH )COOH
CO+H2O Glyoxal Glyoxal cyanohydrin Tartaric acid
Heat
NaOH CH3COCl
Conc. H2SO4 (2) Physical Properties : It is a colourless crystalline compound. It is
soluble in water and alcohol but insoluble in ether. It contains two
HCOOH Dil. H2SO4 CH 3 CHOHCOOH HI CH 3 CH 2 COOH asymmetric carbon atoms and thus shows optical isomerism (four forms).
Formic acid
 Heat 130°C Lactic Acid  Propionic acid Natural tartaric acid is the dextro variety. It contains two secondary
CH 3 CHO
Acetaldehy de alcoholic groups and two carboxylic groups.
KMnO4 Fenton's reagent [O]
PCl5
H2SO4 Fe2+/H2O2 or Ag2O

Optical Isomerism in tartaric acid
CH 3 CHO or CH 3 COOH CH 3 CHClCOCl CH 3 COCOOH COOH COOH COOH
(4) Uses : It is used in medicine as calcium and Py
Lacty lchloride iron lactates,
ruvic acid as | | |
mordant in dyeing, as acidulant in beverages and candies, as a solvent (ethyl H  C  OH HO  C  H H C  OH
and butyl lactates) for cellulose nitrate. | | |
HO  C  H H  C O H H C  OH
Tartaric Acid. Or ,'-Dihydroxy succinic acid or 2,3-Dihydroxy- | | |
Butane-1,4-Dioic acid COOH COOH COOH
HO  C H  COOH d+ l-(Leavorotatory acid) Meso-Tartaric acid
| Dextrorotatory (Optical inactive)
HO CH COOH Tartaric acid
It is found as free or potassium salt in grapes, tamarind, and berries. Optical active
(1) Methods of Preparation (i) d + Tartaric acid-Dextro-rotatory
(i) Argol which separates as a crust during fermentation of grape (ii) l –Tartaric acid-Leavorotatory Optical active
juice is impure potassium hydrogen tartrate. Argol is boiled with limewater. (iii) Meso tartaric acid-optically inactive due to internal
Calcium tartrate is precipitated which is filtered. The solution contains compensation.
Pot. acid tartrate Potassium tartrate
CHOHCOOK CHOHCOOK
| and | C(OH )COOH
CHOHCOOH CHOHCOOK ||
It forms two series of salts C(OH )COOH
CH 3 COCOOH
Dihy droxy meleic acid
Py ruvic acid
Heat [O] Fe 2  /H 2 O 2
Fenton' s reagent
CHBrCOOH CHOHCOOH Tartronic acid + Sliver mirror (Test

| HBr | AgNO3
CHOHCOOH of tartaric acid)
CHBrCOOH NH4OH
 , 'Dibromo succinic acid Tartaric acid
CH (OH )COOH COOH
HI Heat |   
[O ]
|
olution
K 2 Cr2 O7 /H 2 SO 4
COOH COOH
Oxalic acid
(4) Uses : It is used in carbonated beverages and effervescent (2) Physical Properties : It is a colourless crystalline compound. It
tablets, in making baking powder (cream of tartar) and mordant in dyeing possesses one water molecule as water of crystallisation. It is soluble in
(potassium hydrogen tartrate), in preparing Fehling's solution (sodium water and alcohol but less soluble in ether. It is not optically active
potassium tartrate–Rochelle salt), in medicine as emetic, dyeing and calico- compound. It is nontoxic in nature. It behaves as an alcohol and tribasic
acid.
printing (tartar emetic-potassium antimonyl tartrate) and silver mirroring.
(3) Chemical properties
(5) Tests
CHCOOH With alkalies and alcohols, it
(i) When heated strongly, tartaric acid chars readily giving a smell of || forms three series of salts and
burnt sugar to produce free carbon and pyruvic acid. CCOOH esters, respectively
|
(ii) With AgNO : A neutral solution of tartaric acid gives a white
3
CH 2 COOH
ppt. which is soluble in ammonia. A silver mirror is obtained on warming Aconiticacid
the ammonical silver nitrate solution (Tollen's reagent).
Heat, 150°C
(iii) With Fenton's reagent : (H O containing a little of ferrous salt)
2 2
and caustic soda, It gives a violet colour. CH 2 COOH CH 2 COOH

| |
(iv) With Resorcinol and conc. H SO : It gives blue colour. C(OH )COOH CH3COCl
2 4
C(OCOCH 3 )COOH
| HCl |
Citric Acid Or 2-Hydroxypropane Or 1,2,3-Tri Carboxylic Acid Or - CH 2 COOH CH 2 COOH
Hydroxy Tricarballylic Acid Citric acid Mono acelyderivative
Hl
It occurs in the juice of citrus fruits such as lemon, galgal, orange,
lime, etc. Lemon juice contains 6-10% of citric acid. Fuming H2SO4 reduction
heat
(i) By Fermentation : Citric acid is obtained by carrying fermentation CH 2 COOH CH 2 COOH
of dilute solution of molasses with micro-organism, Aspergillus nigar, at 26- | |
CO CHCOOH
28°C for 7 to 10 days. The resulting solution is neutralised with Ca(OH )2 | |
to form insoluble precipitate, calcium citrate. It is decomposed by dilute CH(4)
2 COOH
CH 2 COOH
Uses : It finds use in making lemonades, as acidulant in food and
Acetone Tricarballytic acid
H 2 SO 4 . The CaSO 4 is filtered off and the solution is concentrated soft drinks dicarboxyl
and makesicthe lemon sour, as mordant in dyeing and calico
acid
under vacuum to get crystals of citric acid. printing. Ferric ammonium citrate, magnesium citrate (as an antacid and
laxative), sodium or potassium citrate are used in medicine. Ferric
(ii) By Lemon juice : It is also obtained from lemon juice. The juice ammonium citrate finds use in making blue prints.
is boiled to coagulate proteins. From clear solution, citric acid is obtained as Aromatic Carboxylic Acids
calcium salt with Ca(OH )2 .
Aromatic acid contain one or more carboxyl group (COOH)
attached directly to aromatic nucleus.
(iii) By synthetic method Examples
CH 2 OH CH 2 Cl CH 2 Cl
COOH COOH
| | |
C HOH    CHOH 
  CO CH
HCl ( g ) dil. HNO
3
3
COOH
| heat | [O ] |
CH 2 OH (in acetic acid) CH
2 Cl CH 2 Cl
Glycerol
COOH
HCN Benzoic acid O-toluic acid Phthalic acid
COOH
CH 2 COOH CH 2 CN CH 2 Cl COOH
|
H 2O / H 
|
OH
|
OH
COOH
C(OH )COOH   C  C
KCN
| | CN | CN
CH 2 COOH CH 2 CN CH 2 Cl OH NH 2
NO 2
Salicylic acid Anthranilic acid m-Nitro benzoic acid

Aromatic acid containing-COOH group in the side chain, they are
considered as aryl substituted aliphatic acid.
Examples (ix) From naphthalene [Industrial method]
CH COOH
2
CH = CHCOOH COOH COOH
[O] Soda lime
VO
2 5
COOH
(2) Physical Properties
(i) It is a white crystalline solid.
Benzoic AcidPhenyl acetic acid Cinnamic acid (ii) It has m.p. 394 K.
(1) Methods of Preparation (iii) It is sparingly soluble in cold water but fairly soluble in hot
water, alcohol and ether.
(i) From oxidation of Benzyl alcohol [Laboratory method]
(iv) It has a faint aromatic odour and readily sublimes and is volatile
CH OH CHO in steam.
2 COOH
(3) Acidity of Aromatic Carboxylic Acid : Aromatic acid dissociates to
O O give a carboxylate anion and proton.

(ii) From
Benzylhydrolysis
alcohol of nitriles or cyanides
Benzaldehyde Benzoic acid C6 H 5 COOH ⇌ C6 H 5 CO O  H 
CN COOH 
Since the carboxylate anion ( ArCO O) is resonance stabilised to a
+ 2H O
H or OH
+ –
greater extent than the carboxylic acid (ArCOOH).

2
+ 2NH 3
O O O O
Benzonitrile Benzoic acid || |  || |
(iii) From Grignard reagent Ar  C  OH  Ar  C  O H Ar  C  O   Ar  C  O
O
Resonance in carboxylic acid Resonance in carboxylate anion
|
Non - equivalent structure and  Equivalent structure and hence 
MgI C – OMgI COOH    
O hence less stable  more stable 
|
H , HO OH Effect of Substituents on Acidity : The overall influence of a
+C=O
+
+ Mg
2
substituent on acidity of substituted benzoic acids is due to two factors.

I
Phenyl mag. Addition product Benzoic acid (i) Inductive effect : If the substituent exerts–I effect, it increases the
(iv) By hydrolysis of esters
iodide acidity of carboxylic acids, while if it exerts + I effect it decreases the acidity.
H  orOH  Inductive effect affects all positions, i.e., o–, m– and p–.
C6 H 5 COOCH 3  H 2 O  C6 H 5 COOH  CH 3 OH
Methyl benzoate Benzoic acid Methanol (ii) Resonance effect : Like inductive effect, if the resonance
(v) From trihalogen derivatives of hydrocarbons producing group exerts minus effect i.e., if it withdraws electrons, it
COOH increases the strength of the benzoic acid. Similarly, if the group causes +R
CCl 3
C(OH) 3
effect it decreases the acidity of benzoic acid. However, remember that
resonance effect affects only o- and p- positions. Thus if resonance
+ 3KOH + HO 2 producing group is present in the m-position it will not exert its effect.
– 3 KCl
Benzoic acid
In case resonance and inductive effects both operate in the molecule,
Benzotrichloride Unstable
(vi) From benzene resonance effect being stronger overpowers the inductive effect.
Thus on the above basis, the following order of acidity can be
COCl COOH explained.
COCl 2
H O/NaOH [Friedel-craft reaction] NO 2
Cl OH
2
AlCl 3
(vii) From Toluene

HC COOH
3
COOH COOH COOH COOH

[O],  p-Nitrobenzoic acid p-Chlorobenzoic acid Benzoic acid p-Hydroxybenzoic acid
– NO group exerts
2
– Cl group exerts No other group – OH group exerts
KMnO /OH 4
– R and – I effects – I effects, + R + R and – I effects
or alkaline K Cr O Similarly :
 Chromic trioxide in glacial acetic acid or Co-Mn acetate can also be
2 2 7
taken in place of alkaline KMnO 4 . NO2

NO 2
NO 2
COOH
(viii) From o-xylene [Industrial method] COOH
CH CO COOH
3
[O] HOH
O COOH
VO
CH 3
2 5
CO COOH COOH
COOH
Soda
lime
Acidity is only due to electron withdrawing inductive effect of the – COOH COCl
NO group (resonance does not affect the m-position) while in the p-isomer
2
+ PCl or SOCl + POCl + HCl

acidity is due to electron withdrawing inductive as well as resonance effect. 5 2
3
The acidity of the three isomers of hydroxybenzoic acids follows the (e) Reaction with N H [Schmidt reaction]
Benzoyl Chloride
following order.
3
COOH NH
H SO
COOH
2
OH OH OH + NH
2 4
+ CO + N
COOH 3
50° C 2 2
(f) Reaction with sodalime Aniline
COOH COOH
– I effect
+ M effect COOH NaOH + CaO + CO 2
Resonance effect cannot operate and hence only the acid-

strengthening –I effect takes part with the result m-hydroxybenzoic acid is Benzene
stronger acid than benzoic acid. Like other substituted benzoic acid. (g) Reaction with anhydride O O
| |
Acidic character among benzoic acids having different electron COOH C–O–C
releasing group. 
+ (CH CO) O3 2
COOH COOH COOH COOH

(h) Reduction Benzoic anhydride
> > CH COOH > 3
> COOH CH OH 2
+ LiAlH + HO
OCH
(4) ChemicalOH
3
Properties : NH 2
CH 3
4 2
Benzyl alcohol
(i) Reactions of carboxylic group
(i) Decarboxylation
(ii) Reactions of aromatic ring
(i) Reactions of Carboxylic Group COOH CHO
MnO +CO + H O
(a) Reaction with metals + HCOOH  2 2
COOH COONa (j) Hunsdiecker reaction :

+2 Na +H in CCl4
 X 2   C6 H 5  X  CO 2   AgX
2
C6 H 5 COOAg
(b) Reaction with Alkalies Or NaHCO Or Na CO : 3 2 3
Silver benzoate (Br2 or Cl2 ) heat Phenyl halide
COOH COONa (ii) Reactions of Aromatic Ring
+ NaOH + HO 2
(a) Nitration
or NaHCO or Na CO 3 2 3 COOH COOH
(c) Formation of Esters :
Aromatic acid (benzoic acid) having no group in its ortho positions H SO
+ HNO 2 4
can be readily esterified with alcohol in presence of a mineral acid. 3
NO 2
(b) Sulphonation m-nitrobenzoic acid

COOH COOC H
H
2 5
COOH COOH
+ C H OH
+
2 5 + HO
In presence of ortho substituent the rate of esterification is greatly 2
decreased due to steric effect.

+ Fuming H SO 2 4
The esterification of the various benzoic acids :

SO H
CH COOH
3
COOH COOH COOH

HC HC 2
CH (c) Chlorination m-sulpho benzoic acid

CH 3
3
CH 3
3
; COOH COOH
Benzoic acid 2-Methylbenzoic acid 2, 6-Dimethyl 2,6-Dimethyl
benzoic acid phenylacetic acid + Cl2
Fecl 3
The substituted phenylacetic acid is easily esterified because –

COOH group is separated from benzene ring by – CH – part. Cl
2
(d) Reduction m-chloro benzoic acid

The ortho-substituted benzoic acids can be easily esterified by
treating the silver salt of the acid with alkyl halides, i.e., COOH COOH
COOH COOAg COOC H
HC
2 5
HC CH CH HC Na/amyl alcohol
3
3
3
3
3
CH
AgNO C H Br
3
3
2 5 Boil, 3H 2
This is due to the fact that in such cases the attack of the alkyl Cyclo hexanoic acid
(5) Uses : Benzoic acid is used,
group of the alkyl halides is on the oxygen atom of the COOH group
but not on the sterically hindered carbon atom. (i) in medicine in the form of its salts especially as urinary
(d) Formation of acid chloride antiseptic.
(ii) As sodium benzoate for preservation of food such as fruit juices,
tomato ketchup, pickles etc.
(iii) In the preparation of aniline blue.
(iv) In treatment of skin diseases like eczema.
(6) General Tests
(i) Benzoic acid dissolves in hot water but separates out in the form
of white shining flakes on cooling.
(ii) It evolves CO with sodium bicarbonate, i.e., it gives effervescence
2
with sodium carbonate.

(iii) Neutral ferric chloride gives a buff coloured precipitate.
(iv) When warmed with ethyl alcohol and a little conc. H SO , a fragrant OH
2 4
odour of ethyl benzoate is obtained. COOH

Salicylic acid [O-Hydroxy benzoic acid];
(v) When heated strongly with soda lime, benzene vapours are
evolved which are inflammable. Salicylic acid is present in many essential oils in the form of esters.
Oil of winter green is a methyl ester of salicylic acid.
Cinnamic Acid [-Phenyl acrylic acid]
CH = CH – COOH (1) Methods of preparation
(i) Kolbe Schmidt reaction
ONa OCOONa OH
(i) By Perkin's reaction
CO 2 Rearrangement COONa
125°C, Pressure
CH COONa
C6 H 5 CHO  (CH 3 CO )2 O 
3

180C Sodium Sodium phenyl Sodium salicylate
C6 H 5 CH  CHCOOH  CH 3 COOH phenoxide carbonate
dil. HCl
(ii) By Claisen condensation
C H ONa ' OH
C6 H 5 CHO  CH 3 COOC 2 H 5 2 5  COOH
H 2O
C6 H 5 CH  CHCOOC 2 H 5 
Ester H
It is a commercial method. The reaction yields o- and p-
bothacid
Salicylic
C6 H 5 CH  CHCOOH  C 2 H 5 OH isomers. Salicylic acid is more volatile and separated by steam distillation.
(iii) By knoevenagel reaction
(ii) Reimer-Tiemann reaction
NH
C6 H 5 CHO  CH 2 (COOH )2 
3

heat OH OH OH
+CCl + KOH Heat Dil. HCl
C6 H 5 CH  CHCOOH  CO 2  H 2O 4
COOK COOH
(iv) Industrial method
200 C (iii) From benzene derivatives
C6 H 5 CHCl 2  H 2 CHCOONa 
 C6 H 5 CH  CHCOOH  NaCl  HCl
Benzal chloride Sodium acetate
Cl OH
(2) Physical Properties (a)
Fuse with
(i) It is a white crystalline solid and its melting point 133°C. COOH NaOH COOH
(ii) It is sparingly soluble in water. o-Chlorobenzoic acid
(iii) It exhibits geometrical isomerism.
SO K OH
C6 H 5  C  H C6 H 5  C  H (b)
3
Fuse with
|| ||
KOH
H  C  COOH HOOC C  H COOH COOH
Trans - form Cis- form o-Sulphobenzoic acid
(Cinnamic acid) (Allo cinnamic acid)
Cinnamic acid (stable form) occurs in nature both free and as esters OH Chromic
OH
(c) + [O]
in balsams and resins. acid
COOH
CH OH
(3) Chemical properties Salicyl alcohol
2
Oxidation
C H CHO + C H COOH
OH OH
6 5 6 5
CrO Benzaldehyde Benzoic acid

3
(d) PbO/NaOH
+[O]
Reduction
CH 3 COOH
C H CH CH COOH o-Cresol
Na(Hg)/H O 6 5 2 2
-Phenyl propionic acid

NH 2
N Cl
Reduction (e) NaNO /HCl 2
C H CH CH CH OH COOH
2
LiAlH
6 5 2 2 2
0°C COOH
4
3-Phenyl propyl alcohol Anthranilic acid
– 10°C Anthranilic acid
C H CH = CHCH OH
6 5 2 heat HO2
Cinnamyl alcohol
OH
Soda lime
C H CH = CH
distilled
6 5
Styrene
2
COOH
Br
C H (CH) COOH
6 5 2
2
C H CHBrCHBrCOOH
6 5
Cinnamic acid Dibromocinnamic acid

OH Cl
PCl
(2) Physical properties 5
COOH COCl
(i) It is a colourless needle shaped crystalline compound. Salicylic acid
o-Chlorobenzoyl chloride
(ii) Its m.p. is 156°C. (vii) Bromination
(iii) It is sparingly soluble in cold water but readily soluble in hot OH

OH Br Br
water, alcohol, ether and chloroform. Br water
2
(iv) It is steam volatile. COOH

Salicylic acid
(v) It is poisonous in nature. However, its derivative used in Br
medicine internally and externally as antipyretic and antiseptic. (viii) Nitration 2,4,6,-Tribromophenol
(3) Chemical properties OH

OH
(i) Reaction with Na CO , NaHCO or NaOH ON
2 NO
2 3 3 Fuming HNO 3
2
O COOH
|
C – OH COO Na Salicylic acid NO
– +
Aq. Na CO 2 3
2
2,4,6,-Trinitrophenol
OH Phthalic acid [1,2,-Benzene dicarboxylic acid]
OH
Salicylic acid
Mono sodium salicylate COOH
Aq. NaOH
COOH
COONa There are three isomer (ortho, meta, para) of benzene dicarboxylic
acid.
ONa COOH
(ii) Reaction with alcohols or phenolsDisodium salicylate COOH COOH
OH OH COOH
+ CH OH HCl(gas) +H O
3 2
COOH
COOH COOCH
Methyl salicylate
3
COOH
Salicylic acid
Methyl salicylate is an oily liquid (oil of winter green) with pleasant Benzene-1,2-dicarboxylic acid Benzene-1,3-dicarboxylic acid Benzene-1,4-dicarboxylic acid
(Phthalic acid) (Isophthalic acid) (Terphthalic acid)
material. It is also used in medicine in the treatment of rheumatic pain and as a (1) Methods of preparation
remedy for aches, sprains and bruises. It is used in perfumery and as a
(i) By the oxidation of o-xylene :
flavouring. It is used for making of iodex.
CH CH COOH
OH OH 3
[O] 3
[O]
POCl KMnO
+ C H OH 6 5
3
CH 4
COOH COOH
COOH COOC H o-Xylene
3
6 5 o-Toluic acid Phthalic acid

Salicylic acid
Phenyl salicylate (salol) (ii) From naphthalene (Industrial method) : It is known as aerial
Salol is a white solid m.pt. 43°C. It is a good internal antiseptic. It is oxidation.
used in making of toothpastes. Salol absorbs ultraviolet light and its main
use now is sun-screening agent and stabiliser of plastics. Fuming H SO CO NaOH COONa
2 4
O
HgSO ,300°C CO COONa
(iii) Decarboxylation
4
Naphthalene Phthalic anhydride

COOH
 + CO 2
OH OH COOH
Salicylic acid Phenol
(iv) Acetylation (2) Physical properties COOH
OH OCOCH 3
(i) It is colourless crystalline compound.
+ ClCOCH 3
Pyridine
COOH (ii) Its melting point is not sharp (195–213°C).
Salicylic acid Acetyl chloride
COOH
Aspirin (iii) It is sparingly soluble in cold water but soluble in hot water,
(Acetyl salicylic acid)
alcohol, ether, benzene etc.
 Aspirin is a white solid, melting point 135°C. It is used as
antipyretic and pain killer (analgesic action). (3) Chemical properties
(v) Reaction with ferric chloride solution NaOH
COONa
OH
FeCl COOH
3
Violet colouration
Solution Acid salt
COOH
Salicylic acid NaOH
(vi) Reaction with PCl 5
COONa
COONa
Disodium phthalate
C H OH COOC H 2 5
2 5
COOH
 The important derivatives are given below :
Group replacing – OH Name Structure
(X  F, Cl, Br, I) Acyl halide O

||
R  C X
 NH 2 Amide O
||
R  C  NH 2
OR  ester O
||
R  C  OR 
( R  may be R )
OOCR anhydride O O
|| ||
R  C O  C  R
Reactivity
Acyl derivatives are characterised by nucleophilic substitution
reactions.
Nu Nu
R R .. |
C  O :  : Nu  C O
. . :  R  C  O : L

L .. L
Intermediate
O
||
(L  X , NH 2 , O  C  R or OR)
The relative reactivities of various acyl compounds have been found to
be in the following order:
O O
R || || O O
C  O  R  C O  C R  R  C  R C
X OR NH 2
Out of acid halides, the acid chlorides are more important ones.
The overall order of reactivity can be accounted for in terms of the
following three factors:
(i) Basicity of the leaving group (ii) Resonance effects and (iii)
Inductive effects.
(i) Basicity of the leaving group : Weaker bases are good leaving
groups. Hence, the acyl derivatives with weaker bases as leaving groups are
more reactive. Chloride ion is the weakest base while – NH 2 is the
strongest base. Thus, acyl chlorides are most reactive and amides are least
reactive.
(4) Uses : It is used in the manufacture of plastics, dyes and other (ii) Resonance effect : The leaving group in each case has an atom
compounds such as phthalic anhydride, phthalimide, anthraquinone and with lone pair of electrons adjacent to the carbonyl group. The compound
exists, therefore, as a resonance hybrid.
fluorescein etc.
O O
Acid derivatives || |
RC  R  C
The compounds which are obtained by replacing the OH of the .. 
 L L
carboxylic group by other atoms or groups such as X ,  NH 2 , – OR and
This makes the molecule more stable. The greater the stabilization, the
O  C  R are known as acid derivatives. smaller is the reactivity of the acyl compound.
||
O However, acyl chlorides are least affected by resonance. Due to lower
stabilization, the acid chlorides are more reactive as the loss of Cl is
 R  C  group is common to all the derivatives and is known as easier. Greater stabilization is achieved by resonance in esters and amides
||
O and thus, they are less reactive.
acyl group and these derivatives are termed as acyl compound.
(iii) Inductive effect : Higher the –I effect, more reactive is the acyl (iv) Reaction with benzene (acylation) : This reaction is called friedel
compound. Inductive effect of oxygen in ester is greater than nitrogen in craft reaction.
amide, hence ester is more reactive than an amide. COCH 3
O
Acyl Halides R  C  CH 3 COCl 
3

Anhyd. AlCl
 HCl
Cl
where R may be alkyl or aryl group. Acetyl chloride Acetopheno ne
(1) Methods of Preparation COC H 6 5
(i) From carboxylic acid :

RCOOH  PCl5  RCOCl  POCl3  HCl  C6 H 5 COCl   
Anhyd. AlCl3
 HCl
3 RCOOH  PCl3  3 RCOCl  H 3 PO3 Benzoyl chloride

Benzophenone
(ii) Industrial method : By distilling anhydrous sodium acetate (v) Reaction with ammonia or amines :
heat
3CH 3 COONa  PCl3  3CH 3 COCl  Na 3 PO3 CH 3 COCl  2 NH 3  CH 3 CONH 2  NH 4 Cl
Acetyl chloride Acetamide
heat
2CH 3 COONa  POCl3  2CH 3 COCl  NaPO3  NaCl C6 H 5 COCl  2 NH 3  C6 H 5 CONH 2  NH 4 Cl
Sodium acetate Acetyl chloride Benzamide
heat
(CH 3 COO )2 Ca  SO 2 Cl 2  2CH 3 COCl  CaSO 4 However, acyl chlorides react with amines to form substituted
Calcium acetate Sulphuryl Acetyl chloride amides.
chloride
O
(iii) With thionyl chloride : ||
CH 3 COCl  H 2 NC 2 H 5  CH 3 C  NH  C2 H 5
RCOOH  SOCl 2  RCOCl  SO 2  HCl N - Ethyl acetamide
This is the best method because SO 2 and HCl are gases and easily CH 3 COCl  (C2 H 5 )2 NH  CH 3 CON (C2 H 5 )2  HCl
N, N -Diethyl acetamide
escape leaving behind acyl chloride.
(2) Physical properties : The lower acyl chloride are mobile, colourless (vi) Reduction :
liquid while the higher members are coloured solids. LiAlH or
CH 3 COCl 
4
 CH 3 CH 2 OH
Acyl chloride have very pungent, irritating order and are strong NaBH 4 Ethanol (Primary alcohol)
lachrymators (tears gases)
Pd / BaSO
They fume in air due to the formation of hydrochloric acid by CH 3 COCl  H 2 

4
 CH 3 CHO  HCl
hydrolysis.
They are readily soluble in most of the organic solvent. Acyl chloride This reaction is called Rosenmund reaction.
don't form intermolecular hydrogen bonding. Therefore, their boiling points (vii) Reaction with organocadmium compounds (formation of
are lower than those of their parent acids. ketones)
2CH 3 COCl  (CH 3 )2 Cd  2CH 3 COCH 3  CdCl 2

O O O Dimethyl Acetone
| || Cadmium
||
R  C  Cl  : Nu   R  C  Cl  R  C  Cl  2C6 H 5 COCl  (CH 3 )2 Cd  2C6 H 5 COCH 3  CdCl 2
| | Acetopheno ne
Nu Nu
(viii) Reaction with diazomethane
 
Cl  H  HCl O O
||  ||  
(i) Hydrolysis : CH 3 COCl  HOH  CH 3 COOH  HCl CH 3  C  Cl  2C H 2  N  N  CH 3  C  CH  N  N
Acetyl chloride Acetic acid Diazometha ne Diazoaceto ne
C6 H 5 COCl  H 2 O  C6 H 5 COOH  H 2 O O
Benzoyl chloride Benzoic acid ||
H 2O
(ii) Reaction with alcohols (alcoholysis)  CH 3 CH 2 C  OH
( N 2 )
CH 3 COCl  CH 3 CH 2 OH  CH 3 COOCH 2 CH 3  HCl
Ethyl acetate
(ix) Reaction with water
AgNO / H O
C 6 H 5 COCl  C 2 H 5 OH 
aq NaOH or
 C 6 H 5 COOC 2 H 5  HCl CH 3 COCl 
3
2 CH 3 COOH  AgCl  HNO3
Benzoyl chloride Ethyl alcohol Pyridine Ethyl benzoate
(x) Reaction with chlorine
This reaction is called Schotten Baumann reaction.
Red P
(iii) Reaction with salts of carboxylic acid CH 3 COCl  Cl 2 
 Cl  CH 2  CO  Cl  HCl
Mono- -chloroacet yl chloride
O O
|| || (xi) Reaction with Grignard reagent
CH 3 COCl  CH 3 COO  Na  
Pyridine
 CH 3 C  O  C  CH 3
Acetic anhydride
I (iii) By partial hydrolysis of alkyl cyanide :
CH 3 CO Cl  IMg CH 3  CH 3 COCH 3  Mg
Methyl magnesium iodide Acetone Cl Conc. HCl
CH 3 C  N  CH 3 CONH 2
H 2 O / OH  Acetamide
(xii) Reaction with KCN
(iv) By heating carboxylic acid and urea
H O
CH 3 COCl  KCN  CH 3 COCN 2 CH 3 COCOOH
heat
Acetyl cyanide Pyruvic acid H 2 N  C  NH 2  R  C  OH  R  C  NH 2  CO 2  NH 3
|| || ||
(xiii) Reaction with Salicylic acid O O O
Amide
OH OOCCH 3 (2) Physical properties

 ClOCCH 3  + HCl
COOH COOH (i) Physical state : Formamide is a liquid while all other amides are
solids.
Salicylic Acetyl salicylicacid
acid (Aspirin) (ii) Boiling points : Amides have high boiling points than the
(xiv) Reaction with ether corresponding acids.
Acetamide Boiling points 494 K
ZnCl
CH 3 COCl  C 2 H 5 OC 2 H 5 
2
 Acetic Acid Boiling points 391 K
Diethyl ether anhy.
Benzamide Boiling points 563 K
CH 3 COOC 2 H 5  C 2 H 5 Cl Benzoic acid Boiling points 522 K
Ethyl acetate Ethyl chloride The higher boiling points of amides is because of intermolecular
(xv) Reaction with sodium peroxide (Peroxide formation) hydrogen bonding
O O O H R H R H R
||    || || | | | | | |
2CH 3  C  Cl  N a O  O N a  CH 3 C  O  O  C  CH 3  2 NaCl .......... H  N  C  O......... H  N  C  O......... H  N  C  O
Acetyl chloride Acetyl peroxide (iii) Solubility : The lower members of amide family are soluble in
(xvi) Reaction with hydroxylamine and hydrazine water due to the formation of hydrogen bonds with water.
CH 3 COCl  H 2 NOH  CH 3 CONHOH  HCl
Hydroxyl Acetyl hydroxylamine (i) Hydrolysis
amine (hydroxami c acid) Slowly
CH 3 CONH 2  H 2 O  CH 3 COOH  NH 3
CH 3 COCl  H 2 NNH 2  CH 3 CONHNH 2  HCl
Hydrazine Acetyl hydrazine CH 3 CONH 2  H 2O  HCl    CH 3 COOH  NH 4 Cl
Rapidly
(4) Uses CH 3 CONH 2  NaOH   CH 3 COONa  NH 3

Far more rapidly
(i) As an acetylating agent. (ii) Amphoteric nature (Salt formation)

(ii) In the estimation and determination of number of hydroxyl and It shows feebly acidic as well as basic nature.
amino groups. CH 3 CONH 2  HCl(conc.)  CH 3 CONH 2 .HCl
(iii) In the preparation of acetaldehyde, acetic anhydride, acetamide, Acetamide hydrochlor ide
(only stable in aqueous solution)
acetanilide, aspirin, acetophenone etc.
2CH 3 CONH 2  HgO  (CH 3 CONH )2 Hg  H 2 O
O Acetamide Mercuric Mercuric acetamide
Acid Amides R  C Oxide
NH 2
1
CH 3 CONH 2  Na   CH 3 CONHNa 
Ether
H2
where, R  CH 3 ,  CH 2CH 3 ,  C6 H 5 Sodium acetamide 2
(1) Methods of preparation (iii) Reduction
CH 3 CONH 2  4[H ]  CH 3 CH 2 NH 2  H 2O
LiAlH4
(i) Ammonolysis of acid derivatives
Acetamide Ethylamine
CH 3 COCl  2 NH 3  CH 3 CONH 2  NH 4 Cl
Acetamide C6 H 5 CONH 2  4[H ]    C6 H 5 CH 2 NH 2  H 2O
Na / C 2 H 5 OH
Benzamide Benzylamine
(CH 3 CO )2 O  2 NH 3  CH 3 CONH 2  CH 3 COONH 4
Acetamide Amm. acetate
(iv) Dehydration
CH 3 CONH 2  CH 3 C  N  H 2O
P2 O5
C6 H 5 COCl  NH 3  C6 H 5 CONH 2  HCl Acetamide heat Methyl cyanide
Benzoyl chloride Benzamide
C6 H 5 CONH 2   C6 H 5 C  N  H 2O
2 5 P O
(ii) From ammonium salts of carboxylic acids (Laboratory Method) Benzamide heat Phenyl cyanide
Heat
CH 3 COONH 4  CH 3 CONH 2  H 2 O C6 H 5 CONH 2 
 C6 H 5 C  N
SOCl 2
Acetamide Phenyl cyanide
 Ammonium acetate is always heated in presence of glacial acetic (v) Reaction with nitrous acid
acid to avoid the side product ( CH 3 COOH ) .
(i) From carboxylic acid [Esterification] : Laboratory method.
CH 3 CONH 2  HONO    CH 3 COOH  N 2
NaNO 2 / HCl
Aceticacid O O
|| H ||
 H 2O
+
R  C  OH  H OR  R  C  O R  H 2 O
Ester
C6 H 5 CONH 2  HONO 
 C6 H 5 COOH
NaNO 2 / HCl
Ether
Benzoic acid
CH 3 COOH  CH 2 N 2  CH 3 COOCH 3  N 2
 N 2  H 2O Acetic acid Diazometha ne Methyl acetate
Ether
(vi) Hofmann bromamide reaction or Hofmann degradation : This is C6 H 5 COOH  CH 2 N 2  C6 H 5 COOCH 3  N 2
an important reaction for reducing a carbon atom from a compound, i.e., Benzoic acid Diazometha ne Methyl benzoate
CONH 2 is changed to  NH 2 group.  With diazomethane is the best method.
Br2 (ii) From acid chloride or acid anhydrides
CH 3 CONH 2  CH 3 NH 2
Acetamide NaOH or KOH Methyl amine (p-) CH 3 CO Cl  H OC 2 H 5  CH 3 COOC 2 H 5  HCl
Acetyl chloride Ethyl alcohol Ethyl acetate
This reaction occurs is three steps:
O CH 3 CO
||
O  CH 3 CH 2 OH  CH 3 COOCH 2CH 3  CH 3 COOH
CH 3 CO
CH 3  C  NH 2  Br2  KOH  CH 3 CONHBr  KBr  H 2 O Acetic anhydride Ethyl alcohol
Ethyl acetate
Acetobroma mide
C6 H 5 CO Cl  H OC2 H 5  C6 H 5 COOC 2 H 5  HCl
O Benzoyl chloride Ethyl alcohol Ethyl benzoate
||
CH 3  C  NHBr  KOH  CH 3 NCO  KBr  H 2 O (iii) From alkyl halide :
Methyl isocyanate
C2 H 5 Br  CH 3 COOAg  CH 3 COOC 2 H 5  AgBr
CH 3 NCO  2 KOH  CH 3 NH 2  K2CO 3 Ethyl bromide Silver acetate Ethyl acetate
Methyl amine (iv) From ether :
CH 3 CONH 2  Br2  4 KOH  CH 3 NH 2  2 KBr  K 2 CO 3  2 H 2 O CH 3  O  CH 3  CO 
3
 CH 3 COOCH 3
BF
Methoxy methane 350 K Methyl acetate

 In this reaction a number of intermediates have been isolated; N-
  (v) From Tischenko reaction :
bromamides, RCONHBr; salts of these bromamides [RCONBr ] K ;
CH 3  C  H  O  C  CH 3 25
  CH 3  C  OC2 H 5
3 Al(OC H )
Isocyanates, RNCO. || | ||
 Nitrene rearranges to form isocyanate. O H O
(vii) Action with alcohol : (2) Physical properties
(i) Physical state and smell : Esters are colourless liquids (or solids)
HCl
CH 3 CONH 2  CH 3 OH  CH 3 COOCH 3  NH 4 Cl with characteristic fruity smell. Flavours of some of the esters are listed
70 o C methyl acetate below :
(viii) Reaction with grignard reagent Ester Flavour Ester Flavour
CH 3  Mg  Br  CH 3  CONH 2  CH 4  CH 3  CONH  MgBr Amyl acetate Banana Isobutyl formate Raspberry
CH MgBr
3 Benzyl acetate Jasmine Ethyl butyrate Pineapple
Amyl butyrate Apricot Octyl acetate Orange
  OMgBr
 OH 
| | (ii) Solubility : They are sparingly soluble in water but readily soluble in
CH  C  NH   H 2O / H 
  CH 3  C  NH  MgBr organic solvents such as alcohol, ether etc.
 3
|
2  Hydrolysis |
 CH 3  CH 3 (iii) Boiling points : Their boiling points are lower than the
 Unstable  corresponding acids because of the absence of hydrogen bonding. i.e., ethyl
acetate = 77.5 C. o
- NH3

 O  (i) Hydrolysis :
 ||
 CH 3 COOC 2 H 5  H 2 O
dil. acid
CH 3 COOH  C 2 H 5 OH
CH 3  C  CH 3 
 Acetone  Ethyl acetate Acetic acid Ethyl alcohol
 
CH 3 COOC 2 H 5  NaOH  CH 3 COONa  C 2 H 5 OH
(4) Uses Ethyl acetate Sod. acetate Ethyl alcohol
(i) In organic synthesis. The compounds like methyl cyanide, Hydrolysis of ester by alkalies (NaOH) is known as saponification
Methylamine and ethylamine can be prepared. and leads to the formation of soaps
(ii) In leather tanning and paper industry.  This reaction (saponification) is irreversible because a resonance
(iii) As a wetting agent and as soldering flux. stabilized carboxylate (acetate) ion is formed.
Amides such as dimethyl formamide (DMF), dimethyl acetamide  The acid hydrolysis of esters is reversible.
(DMA) are used as solvents for organic and inorganic compounds. (ii) Reaction with ammonia (ammonolysis) :
CH 3 CO OC2 H 5  H NH 2  CH 3 CONH 2  C2 H 5 OH
Esters, R  C  OR Ethyl acetate Acetamide
||
O (iii) Reduction
These are the most important class of acid derivatives and are widely LiAlH
CH 3 COOC 2 H 5  4[H ] 
4
 2C2 H 5 OH
distributed in nature in plants, fruits and flowers. or Na / C 2 H 5 OH
(1) Methods of preparation
COOC 2 H 5 CH 2 OH O O
|| ||
LiAlH 4
 4 H   C 2 H 5 OH CH 3  C  OC2 H 5  H  CH 3  C  NHOH  C 2 H 5 OH
base
HNOH
or Na / C 2 H 5 OH Ethyl acetate Hydroxyl amine Hydroxamic acid
(ix) Reaction with hydrazine

Ethyl benzoate Benzyl alcohol CH 3 COOC 2 H 5  H 2 NNH 2  CH 3 CONHNH 2  C2 H 5 OH
Hydrazine Acid hydrazide
 Reduction in presence of Na / C2 H 5 OH is known as Bouveault (x) Halogenation

Blanc reduction. CH 3 COOC 2 H 5  Br2   CH 2 BrCOOC2 H 5  HBr
Red P
 The catalytic hydrogenation of ester is not easy and requires high   Bromoethyl acetate
temperature and pressure. The catalyst most commonly used is a mixture of (xi) Reaction with HI
oxides known as copper chromate (CuO.CuCr2 O4 ) . CH 3 COOC 2 H 5  HI  CH 3 COOH  C 2 H 5 OH
Aceticacid Ethyl alcohol
O
|| (4) Uses
R  C  OR  2 H 2   RCH 2 OH  ROH
CuO .CuCr 2 O 4
525 K , 200  300 atm (i) As a solvent for oils, fats, cellulose, resins etc.
(iv) Reaction with PCl or SOCl (ii) In making artificial flavours and essences.
5 2
(iii) In the preparation of ethyl acetoacetate.

CH 3COOC2 H5  PCl5  CH 3COCl  C2 H5 Cl  POCl3 (5) General Tests
(i) It has sweet smell
CH 3 COOC 2 H 5  SOCl 2  CH 3 COCl  C2 H 5 Cl  SO 2
Acetyl chloride Ethyl chloride (ii) It is neutral towards litmus
(iii) A pink colour is developed when one or two drops of
C6 H 5 COOC 2 H 5  PCl5  C6 H 5 COCl  POCl3  C2 H 5 Cl phenolphthalein are added to dilute sodium hydroxide solution. The pink
Ethyl benzoate Benzoyl chloride colour is discharged when shaken or warmed with ethyl acetate.
(v) Reaction with alcohols : On refluxing ester undergoes exchange of (iv) Ethyl acetate on hydrolysis with caustic soda solution forms two
compounds, sodium acetate and ethyl alcohol.
alcohols residues.
CH 3 COOC 2 H 5  NaOH  CH 3 COONa  C2 H 5 OH
O H O
R C  ROH R C  ROH
+
OR (Excess) OR

CH3 CO
CH 3 COOC 2 H 5  CH 3 OH  CH 3 COOCH 3  C 2 H 5 OH Acid Anhydride O or (CH3 CO)2 O
CH3 CO
Ethyl acetate Methyl acetate
 This reaction is known as alcoholysis or trans esterification.

(1) Method of preparation
(vi) Reaction with Grignard reagents (i) From carboxylic acid
O  OMgBr  O O O O
||  |  || ||
Quartz tube
|| ||
CH 3  C  OC 2 H 5  CH 3 MgBr  CH 3  C  OC 2 H 5  R  C  OH  H O  C  R  R  C  O  C  R  H 2 O
  Porcelain Acid anhydride
C2H5OMgBr
Ethyl acetate |
chips 1073 K
 CH 3 
P O
C6 H 5 CO OH  H OOCC 6 H 5 4 

10

OMgBr O heat
| ||
CH 3  C  CH 3 
 CH 3  C  CH 3 CH 3 MgBr
O O
| || ||
CH 3 C6 H 5  C  O  C  C6 H 5  H 2 O
H +
HO
2
Benzoic anhydride
OH (ii) From carboxylic acid salt and acyl chloride [Laboratory method]
|
CH 3  C  CH 3 CH 3 COONa  CH 3 COCl 
 CH 3 COOCOCH 3  NaCl
Py
| Aceticanhydride
CH 3
o
3 alcohol
C6 H 5 COONa  C6 H 5 COCl 
 C6 H 5 COOCOC 6 H 5 Py
(vii) Claisen condensation Benzoic anhydride
O
||
 NaCl
C H O  Na 
CH 3  C  OC2 H 5  H  CH 2 COOC 2 H 5 2 
5


Ethyl acetate (2 molecules)
(iii) From acetylene
O CH CH 3
HgSO 4 Distill
|| |||  2CH 3 COOH  |  
CH 3  C  CH 2 COOC 2 H 5  C 2 H 5 OH CH CH (OOCCH 3 )2 heat
Ethyl acetoacetate
(  - ketoester)
(viii) Reaction with hydroxyl amine

CH 3 CO AlCl
CH 3 CHO  O (CH 3 CO )2 O  C6 H 6 
3
 C6 H 5 COCH 3  CH 3 COOH
CH 3 CO Benzene Acetopheno ne
Aceticanhydride
(iv) From acetaldehyde : (viii) Reaction with acetaldehyde

CH 3 CHO  O 2 
 2CH 3  C  O  O  H
Cobalt
(CH 3 CO )2 O  CH 3 CHO  CH 3 CH (OOCCH 3 )2
acetate || Acetaldehy de Ethylidene acetate
O
(ix) Reduction
 (CH 3 CO )2 O  H 2 O
LiAlH
(2) Physical properties (CH 3 CO )2 O 
4
 CH 3 CH 2 OH
Ether Ethyl alcohol
(i) Physical state : Lower aliphatic anhydrides are colourless liquids
(x) Action with ether :
with sharp irritating smell. The higher members of the family as well as the
aromatic acid anhydrides are solids in nature. CH 3 CO O.COCH 3  C 2 H 5  O  C2 H 5  2CH 3 COOC 2 H 5
Diethyl ether Ethyl acetate
(ii) Solubility : They are generally insoluble in water but are soluble
in the organic solvents such as ether, acetone, alcohol, etc. (xi) Action with N O 2 5
(iii) Boiling points : The boiling points of acid anhydrides are higher O
than those of carboxylic acids because of the greater molecular size. CH 3 COOCOCH 3  N 2 O5  CH 3  C  O  N
|| O
(3) Chemical Properties O
(4) Uses : Acetic anhydride is used
(i) Hydrolysis :
(i) as an acetylating agent.
O O
|| || (ii) For the detection and estimation of hydroxyl and amino group.
CH 3  C  O  C  CH 3  H 2 O  2CH 3 COOH
Aceticanhydride Aceticacid (iii) in the manufacture of cellulose acetate, aspirin,
(ii) Action with ammonia phenacetin, acetamide, acetophenone, etc.
(CH 3 CO )2 O  2 NH 3  CH 3 CONH 2  CH 3 COONH 4 NH 2

Urea or Carbamide O  C
Acetamide Amm. acetate NH 2
(iii) Acetylation : Acetic anhydride react with compound having Urea may be considered as diamide of an unstable and dibasic
active hydrogen. carbonic acid from which both the hydroxyl groups have been replaced by
 NH 2 groups.
(CH 3 CO )2 O  C 2 H 5 OH  CH 3 COOC 2 H 5  CH 3 COOH
Ethyl alcohol Ethyl acetate
OH NH 2 NH 2
 OH  OH
(CH 3 CO )2 O  H 2 NC 2 H 5  CH 3 CONHC 2 H 5  CH 3 COOH OC  O  C  O  C
 NH 2  NH 2
Ethyl amine N  Ethyl acetamide OH OH NH 2
Carbonic acid Carbamic acid, Urea, diamide of
(Monoamide ) carbonic acid or
(CH 3 CO )2 O  HN (C 2 H 5 )2  CH 3 CON (C 2 H 5 )2  CH 3 COOH carbamide
Diethylamine N , N  Diethyl acetamide
 First time isolated from urine in 1773 by Roulle and hence the
(CH 3 CO )2 O  H 2 NC 6 H 5  CH 3 CONHC 6 H 5  CH 3 COOH name urea was given.
Aniline Acetanilide
 It was the first organic compound synthesised in the laboratory
OH OOCCH 3 from inorganic material (by heating a mixture of ammonium sulphate and
(CH 3 CO )2 O    CH 3 COOH potassium cyanate) by Wohler in 1828.
COOH COOH
Salicylic acid Acetyl salicylic acid (Aspiriin)
 This preparation gave a death blow to Vital force theory.
(iv) Action of dry HCl  It is the final decomposition product of protein's metabolism in
man and mammals and is excreted along with urine.
(CH 3 CO)2 O  HCl  CH 3 COCl  CH 3 COOH
 Adults excrete about 30 grams of urea per day in the urine.
(v) Reaction with chlorine (1) Method of preparation
(CH 3 CO )2 O  Cl 2  CH 3 COCl  CH 2 ClCOOH (i) From urine : Urine is treated with conc. nitric acid where crystals
Acetyl chloride Monochloro acetic
acid of urea nitrate CO(NH 2 )2 .HNO 3 are obtained.
(vi) Reaction with PCl 5

2CO (NH 2 )2 .HNO 3  BaCO3  2CO (NH 2 )2  Ba(NO 3 )2  H 2O  CO 2
Urea nitrate Urea
(CH 3 CO )2 O  PCl5  2CH 3 COCl  POCl3

(ii) Laboratory preparation
(vii) Friedel craft's reaction
(a) Wohler synthesis NH 2 CONH 2  HNO 3 (conc.)  NH 2 CONH 2 .HNO 3
Urea nitrate
2 KCNO  (NH 4 )2 SO 4  2 NH 4 CNO  K 2 SO 4
Potassium cyanate Ammonium sulphate Ammonium cyanate 2 NH 2 CONH 2  H 2 C2 O4  (NH 2 CONH 2 )2 H 2 C2 O4
Oxalic acid Urea oxalate
NH 4 CNO  NH 2 CONH 2
Isomeric change
Ammonium cyanate On heating Urea

Urea is a stronger base than ordinary amide. It is due to the
resonance stabilization of cation, the negatively charged oxygen atom is
 The solid residue is extracted with alcohol and the extract capable of coordination with one proton.
evaporated when the crystals of urea are obtained. It can be recrystalised
 
from water. H2N NH 2 H2 N NH 2 H2N NH2
(b) From phosgene or alkyl carbonate C  C  C
|| | |
 OH OH
Cl  2 NH  O  C NH 2 OH
OC 3  2 HCl
Cl NH 2
Carbonyl chloride
(Phosgene)
Urea
 An aqueous solution of urea is neutral.
(ii) Hydrolysis
OC 2 H 5 NH 2
OC  2 NH 3  O  C  2C 2 H 5 OH
OC 2 H 5 NH 2 NH 2  H OH OH
Aq. alkali or
Ethyl carbonate (urethane) Urea
OC 
 O  C  2 NH 3
acid
(iii) Industrial method NH 2  H OH OH Ammonia
Urea Carbonic acid
(a) By partial hydrolysis of calcium cyanide 
CO 2  H 2O
heat
CaC 2  N 2  CaCN 2  C NH 2 CONH 2  2 NaOH  2 NH 3  Na 2 CO 3
Calcium Calcium
Carbide cyanamide
An enzyme, urease, present in soyabean and soil also brings
o hydrolysis .
The cyanamide is treated with dilute sulphuric acid at 40 C where
partial hydrolysis occurs with the formation of urea. NH 2 CONH 2  2 H 2 O  (NH 4 )2 CO 3  2 NH 3  CO 2  H 2 O
Ammonium carbonate
H SO H O
CaCN 2 2
4
 H 2 NCN 2 H 2 NCONH 2 (iii) Action of heat
 CaSO4 Cyanamide (H 2 O 2 ) (Urea)
NH 2CO NH 2  H HNCONH 2   NH 2CONHCONH 2  NH 3
heat
or (Two moleculesof urea) Biuret

Urea is identified by the test known as biuret test. The biuret
o
CaCN 2  H 2 O  H 2 SO 4   NH 2 CONH 2  CaSO 4
40 C residue is dissolved in water and made alkaline with a few drops of NaOH.
When a drop of copper sulphate solution is added to the alkaline solution of
(b) From carbon dioxide and ammonia biuret, a violet colouration is produced.
150  200 C
CO 2  2 NH 3   NH 2 COONH 4
o
when heated rapidly at 170 o C , polymerisation takes place:
Ammonium carbamate
NH 2CONH 2   NH 3  HOCN (H  N  C  O)
heat
Cyanic acid
o
  NH 2 CONH 2
heat (140 C)
 H 2O Urea 3 HOCN  (HOCN )3 or (H 3 N 3 C3 O3 )
Polymerisa tion
(2) Physical properties : Urea is a colourless, odourless crystalline H

o
solid. It melts at 132 C . It is very soluble in water, less soluble in alcohol C
but insoluble in ether, chloroform and benzene.
O=C C=O
Crystal structure: In solid urea, both nitrogen atoms are identical.
or
 
H2N NH 2 H2 N NH 2 H2N NH2 H N N–H
1.37 Å C  C  C C
|| | |
O O O O
Cyanuric acid
This indicates that C  N bond in urea has some double bond (iv) Reaction with nitrous acid
character.
O N OH
(3) Chemical Properties NaNO2 HCl
H 2 N  CO  N H 2  2 HNO 2  
(i) Basic nature (Salt formation): It behaves as a weak monoacid
HO N O
base (Kb  1.5  10 14 ) . It forms solt with strong acid.
H 2 CO 3  2 N 2  2H 2 O NH  C  O
Carbonic acid OC  2C 2 H 5 OH
 NH  C  O
H 2O CO 2 Parabanic acid
(Oxalyl urea)
(v) Reaction with alkaline hypohalides
NH  H C 2 H 5 O  CO NH  CO
NaOH  Br2  NaOBr  HBr
OC  CH  O  C CH
NH 2 CONH 2  3 NaBrO  N 2  2 H 2 O  CO 2  3 NaBr NH  H HO  C NH  CH 3
CH3 4  Methyl urecil
(vi) Reaction with acetyl chloride or acetic anhydrides
NH 2 CONH 2  CH 3 COCl  NH 2 CONHCOCH 3  HCl (xiii) Reaction with formaldehyde
Acetyl chloride Acetyl urea (Ureide) HCl CH O
CH 2  O  NH 2 CONH 2  CH 2 (OH )NHCONH 2 
2

NH 2 CONH 2  (CH 3 CO )2 O  NH 2 CONHCOCH 3 Formaldehy de Monomethylol urea
Acetyl urea heat
CH 2 (OH )NHCONH (OH )CH 2  Resin
 CH 3 COOH Dimethylol urea (Urea - Formaldehy de)
Aceticacid (4) Uses
(vii) Reaction with hydrazine (i) Mainly as a nitrogen fertilizer. It has 46.4% nitrogen.
NH 2CONH 2  H 2 N . NH 2  
o
 NH 2CONH . NH 2  NH 3
100 C (ii) In the manufacture of formaldehyde-urea plastic and
Urea Hydrazine Semicarbazide semicarbazide.
(viii) Reaction with ethanol (iii) As animal feed.
heat (iv) For making barbiturates and other drugs.
H 2 NCO NH 2  H OC 2 H 5  H 2 NCOOC 2 H 5  NH 3
Ethanol Urethane
(v) As a stabilizer for nitrocellulose explosives.
(5) General Tests
(ix) Reaction with chlorine water
(i) When heated with sodium hydroxide, ammonia is evolved.
NH 2 NHCl
(ii) When heated gently, it forms biuret which gives violet
OC  2Cl 2  O  C  2 HCl colouration with sodium hydroxide and a drop of copper sulphate solution.
NH 2 NHCl (iii) Its aqueous solution with concentrated nitric acid gives a white
Urea Dichloro urea
precipitate.
(x) Dehydration
(iv) On adding sodium nitrite solution and dil. HCl (i.e.,
NH 2 CONH 2  SOCl 2  H 2 N  C  N  SO 2  2 HCl  H 2 O HNO 2 ) to urea solution, nitrogen gas is evolved and gives effervescence
(xi) Reaction with fuming sulphuric acid due to carbon dioxide.
NH 2CONH 2  H 2 SO 4  SO 3  2 NH 2 SO 3 H  CO 2
sulphamic acid
Oleum
(xii) Formation of cyclic ureides
O
||
NH H C2 H 5 O C
OC  CH 2  
PCl3
NH H
Urea
C2 H 5 O C
||  Oxidation of 1° alcohols and aldehyde cannot be carried out with
O alkaline K Cr O since under these condition K CrO is formed which does
2 2 7 2 4
Diethyl malonate not act as an oxidising agent.

O
||
 During oxidation of alkyl benzenes with alkaline KMnO or acidified 4
NH  C K Cr O , the aromatic nucleus remain intact but each side chain oxidised
2 2 7
OC CH 2  2C 2 H 5 OH to –COOH group irrespective of its length. The ease of oxidation of alkyl
NH  C benzenes follows the order.
||
Toluene > Ethyl benzene > Isopropyl benzene.
O
Barbituric acid Tert butyl benzene however does not undergo oxidation to give benzoic
(Malonyl urea)
acid since it does not have any benzylic H-atom.
 Carboxylic acids are stronger acids than phenols since carboxylate ion is
NH H C 2 H 5 O CO better stabilized by resonance than phenoxide ion.
OC   PCl3
 The melting points of carboxylic acids show oscillation or
NH H C 2 H 5 O CO alternation effect, i.e. melting point of an acid containing even number of
Urea
Diethyl oxalate
carbon atom is higher than the next lower or higher homologue
containing odd number of carbon atom, due to greater symmetry and
close packing of molecules in the crystal lattice.
 Carboxylic acid do not give the characteristic reaction of the
carbonyl group. The reason being that due to resonance, the double
bond character of the C = O bond in carboxylic acid is greatly reduced as
compared to that in aldehyde and ketone.
 The boiling point of acid derivatives follow the order.
RCONH > (RCO) O > RCOOH > RCOOR > RCOCl.
2 2
 The boiling point of acid chloride and ester are lower than those of
their parent acid due to absence of H-bonding in their molecule.
 The boiling points of acid anhydrides are higher than those of the
acids from which they are derived because of stronger Vander Waal’s
forces of attraction owing to the larger size of their molecules.
 The melting points and boiling points of acid amide are much
higher than those of the acids from which they are derived due to strong
intermolecular H-bonding even though their molecular masses are almost
identical.
 Aromatic acid chlorides are less reactive than aliphatic acid
chlorides primarily due to greater electron donating effect of the
benzene ring over alkyl group which tends to reduce the electron
deficiency of aromatic acyl carbon.
 Phthalimide and succinimide on treatment with Br –KOH undergo
2
Hofmann bromamide reaction to form anthranilic acid and -

aminopropionic acid respectively.
 Urea acts as a monoacidic base.
 Malonic acid on heating with P O gives carbon suboxide (C O ).
2 5 3 2
 Tamarind contain tartaric acid which does not exist in nature.

 Baking powder is a mixture of sodium bicarbonate and cream of
tartar i.e. acid potassium hydrogen sulphate.
 Smell of ammonia in public urinals is due to hydrolysis of urea
present in urine by the enzyme urease present in atmosphere.
 Tartar emetic (i.e. potassium antimony D(+) tartrate is used to
cause nausea and vomiting during treatment of poisoning.
 Magnesium citrate is used as an antacid.
 Succinic acid was prepared by the distillation of amber.
 Malic acid is found in apples, grapes etc.

01 Carboxylic Acids &amp; Their Derivatives Theory Final E

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01 Carboxylic Acids &amp; Their Derivatives Theory Final E

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1306 Carboxylic acids and Their derivatives

(v) The Arndt-Eistert synthesis O–H O

(2) Solubility : The lower members of the aliphatic carboxylic acid

Acetic acid Ethyl alcohol 

in the hydrogenation of oils. (catalyst).

Methyl alcohol 30 atm200C Acetic acid

Table : 28.1 Comparison of Formic Acid and Acetic Acid

CH 3 COOH  CH 3 COONH 4  CH 3 CONH 2

Aceticacid Amm. acetate Acetamide

Sodium acetate heat Methane hv Methyl

Conversion of Acetic acid into other organic compound

Ethane Ethyl chloride Ethyl alcohol Acetaldehyde Acetic acid

Sodium acetate Methane

Methyl alcohol Formaldehyde

Ca(OH) (CH COO) Ca heat H /Ni CH CHOHCH Conc. H SO

Calcium acetate Acetone Isopropyl alcohol Propene

Acetamide Methyl amine

heat Methyl cyanide LiAlH 4

Rosenmund's CH CHO HCN

The sodium oxalate thus formed is dissolved in water and calcium

(iv) Laboratory preparation COOH COONa

(v) Industrial method COOH C H OH COOC 2 H 5 COOC 2 H 5

powdered of sodium hydroxide.

COOH COONH 4 COONH 4 H 2 C 2 O4   (NH 4 )2 C 2 O4 

burns with blue flame.

| + | | (a) Heating at 150°C :

CH 2 CH 2 Br CH 2 CN It was first obtained by the oxidation of fats (Latin, adeps = fat.)

CHCOOH heat CH COOH

(iii) Reaction with Br 2

(iii) From propionic acid : CH 3 CH 2COOH 

Propionic acid HVZ reaction CH 2  CHCOOH  PCl5  CH 2  CH  COCl

they get oxidised to tartaric acid.

(i) Bees wax, Myricyl palmitate, C15 H 31COOC30 H 61

substituted acids. For example,

calcium salt is then decomposed with calculated quantity of dilute H SO .

2 - Hydroxypropanoic acid 3 - Hydroxybutanoic acid crystals of tartaric acid.

H2SO4 Fe2+/H2O2 or Ag2O

CHBrCOOH CHOHCOOH Tartronic acid + Sliver mirror (Test

and caustic soda, It gives a violet colour. CH 2 COOH CH 2 COOH

Salicylic acid Anthranilic acid m-Nitro benzoic acid

greater extent than the carboxylic acid (ArCOOH).

substituent on acidity of substituted benzoic acids is due to two factors.

(vii) From Toluene

COOH COOH COOH COOH

taken in place of alkaline KMnO 4 . NO2

+ PCl or SOCl + POCl + HCl

(f) Reaction with sodalime Aniline

Resonance effect cannot operate and hence only the acid-

COOH COOH COOH COOH

COOH COONa (j) Hunsdiecker reaction :

can be readily esterified with alcohol in presence of a mineral acid. 3

(b) Sulphonation m-nitrobenzoic acid

decreased due to steric effect.

The esterification of the various benzoic acids :

COOH COOH COOH

CH (c) Chlorination m-sulpho benzoic acid

The substituted phenylacetic acid is easily esterified because –

(d) Reduction m-chloro benzoic acid

with sodium carbonate.

odour of ethyl benzoate is obtained. COOH

CrO Benzaldehyde Benzoic acid

-Phenyl propionic acid

Cinnamic acid Dibromocinnamic acid

(iii) It is sparingly soluble in cold water but readily soluble in hot OH

01 Carboxylic Acids & Their Derivatives Theory Final E

01 Carboxylic Acids & Their Derivatives Theory Final E