RADHA SWAMI ACADEMY

CHAPTER-11 Aldehydes, Ketones and Carboxylic acids

Classification of aldehydes and ketones:
1-Aliphatic( R-CHO, R-CO-R) 2-Aromatic (C6H5-CHO, C6H5-CO-C6H5)
H H CH 3
C=O C=O C=O C=O
H CH3 CH3
Carbonyl group Formaldehyde Acetaldehyde Acetone
Carbonyl group: + -
C=O ↔ C–O
Due to the polar nature of carbonyl group, aldehydes and ketones behave as polar molecules and
possess high values of dipole moment(2.3-2.8 D).
Comparison of C = O and C=C bonds :
Similarity: 1-Both are made up of one σ and π-bond.
2-Both undergo addition rxn readily.
Dissimilarity: 1- C = O bond is polar, whereas C = C bond is non polar.
2- C = O group present in aldehydes and ketones undergo Nucleophilic addition rxn.
C = C group present in alkenes undergoes electrophilic addition rxn.
Structures Common name I.P.U.A.C name

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RADHA SWAMI ACADEMY
Structures common names I.U.P.A.C name

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RADHA SWAMI ACADEMY
Methods of preparation of aldehydes and ketones:-
1-By the oxidation of alcohols:-
𝐶𝑟𝑂3
CH3CH2OH + (O) → CH3CHO + H 2O
𝐶𝑟𝑂3
(CH3 )2CHOH + (O) → CH3COCH3 + H2 O
2-By the dehydrogenation of alcohols:-
𝐶𝑢 /573𝐾
CH3OH → HCHO + H2
𝐶𝑢 /573𝐾
CH3CH2OH → CH3CHO + H2
𝐶𝑢 /573𝐾
CH3 )2CHOH → CH3COCH3 + H2
3-By Rosenmund’s reduction:-
𝑃𝑑/𝐵𝑎𝑆𝑂4
R-COCl + H2 → R-CHO + HCl
𝑃𝑑/𝐵𝑎𝑆𝑂4
CH3COCl + H2 → CH3CHO + HCl
Note – Ketones cannot be prepared by this method.
4-By ozonolysis of alkenes:-
𝐻2 𝑂
CH2 = CH2 + O3 C2H4O3 → 2HCHO + H2O2
Ethylene ozonide formaldehyde
𝐻2 𝑂
CH3CH = CHCH3 + O3 C4H8O3 → CH3CHO + H2O2
Butylene ozonide Acetaldehyde
5-By the hydrolysis of alkyne:-
𝐷𝑖𝑙. 𝐻2 𝑆𝑂4 /𝐻𝑔𝑆𝑂4
CH≡CH + H2O → CH3CHO
𝐷𝑖𝑙. 𝐻2 𝑆𝑂4 /𝐻𝑔𝑆𝑂4
CH3C≡CH + H2O → CH3COCH3
6-From nitriles and ester:-
𝐻3 𝑂+
Stephen rxn:- RCN + SnCl2 + HCl RCH=NH → RCHO
1. 𝐷𝐼𝐵𝐴𝐿−𝐻
RCN RCHO
2. 𝐻2 𝑂
1. 𝐷𝐼𝐵𝐴𝐿−𝐻
CH3(CH2)9 – COOC2H5 CH3(CH2)9 – CHO
2. 𝐻2 𝑂
Note:- DIBAL-H (Di iso butyl aluminium hydroxide)[AlH(i-Bu)2]
7- From Acyl chlorides:-
2R – Mg – X + CdCl2 R2-Cd + 2Mg(X)Cl
2R – CO – Cl + R2-Cd 2R- CO – R + CdCl2
8- From Nitriles :-
NMgBr O
𝑒𝑡ℎ𝑒𝑟 𝐻3 𝑂+
CH2 – CH2 - C≡N + C6H5MgBr → CH3CH2 – C → C2H5 – C
C6H5 C6H5
(Propiophenone)
(1-Phenylpropanone)
Physical properties:-
1-Physical state:- Aldehydes HCHO Gas
C2 – C11 Colourless liquids
C12 – Higher Solid
Ketones C3 – C11 Colourless liquids
C12 – Higher solids
(3)

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RADHA SWAMI ACADEMY
2-Odour:- lower aldehydes unpleasant odour
Higher aldehydes pleasant odour
Lower ketones Pleasant odour
Higher Ketones Soplesant
3-Polar nature:- Aldehyde and ketones both are polar in nature.
4-Solubility:-Lower aldehydes and ketones up to C4 are soluble in water but solubility decreases
with the increase in the size of alkyl group.
H +δ -δ +δ -δ +δ R +δ -δ +δ -δ +δ
C = O …………. H O H…. C = O …………. H O H……
H R
5-Boiling point:- It higher than those of hydrocarbons and ethers of comparable molecular
masses. Due to polar nature of carbonyl group.
Chemical properties:-
A-Nucleophilic addition rxn (HCN, NaHSO3 , Grignard reagent, alcohol)
B- Nucleophilic addition rxn by loss of water (NH2OH, NH2NH2, NH2NHC6H5, NH2NHCONH2)
C-Reduction
D-Oxidation
E-Rxn involving alkyl group(Halogenation, aldol condensation, cross aldol condensation)
F-Miscellaneous rxn(Cannizzaro rxn, Tischenko rxn, PCl5, CHCl3,)
A-Nucleophilic addition rxn(HCN, NaHSO3 , Grignard reagent,)
H H OH
C=O + HCN C
H H CN
CH3 CH3 OH
C=O + HCN C
H H CN
CH3 CH3 OH
C=O + HCN C
CH3 CH3 CN
Acetone Acetone cyano hydrin
O OH
+HCN CN

Note:-Cyclohexanone forms cyanohydrin, but 2,2,6-trimethyl cyclohexanone do not forms

because presence of three methyl group on α-position offer steric hindrance and as a result,
CN- cannot attack effectively.
H H OH
C = O + NaHSO3 C
H H SO3Na
CH3 CH3 OH
C = O + NaHSO3 C
CH3 CH3 SO3Na
Acetone sodium bi sulphite
CH3 CH3 OMgCl CH3 OH
𝐻2 𝑂
C=O +CH3MgCl C → C
H H CH3 CH3 CH3
Iso butyl alcohol

(4)
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RADHA SWAMI ACADEMY
B- Nucleophilic addition rxn by loss of water (NH2OH, NH2NH2, NH2NHC6H5, NH2NHCONH2)
H H
C = O + H2NOH C = NOH + H2O
H Hydroxyl amine H Formaldehyde oxim
CH3 CH3
C = O + H2NOH C = NOH + H2O
H H
C H3 CH3
C = O + H2NOH C = NOH + H2O
CH3 CH3
Wolff-Kishner reduction:-
H H H
𝐾𝑂𝐻/𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 𝑔𝑙𝑦𝑐𝑜𝑙
C = O + H2NNH2 C = NNH2 → CH2 + N2
H Hydrazine H Formaldehyde hydrazone H
H H
C = O + H2NNHC6H5 C = NNHC6H5 + H2O
H Phenyl hydrazine H Formaldehyde Phenyl hydrazone
H H
C = O + H2NNHCONH2 C = NNHCONH2 + H2O
H Semicarbazide H Formaldehyde semicarbazone
Note:-There are two –NH2 groups in Semicarbazide. However, only one group is involved in the
formation of semicarbazone. Because one –NH2 group is directly attached to C=O group is
involved in resonance. Therefore the electron density on –NH2 group involved in the resonance
decreases. As a result, it cannot act as a nucleophile, and the lone pair of electrons on other
–NH2 group is not involved in resonance, thus it can act as a nucleophile.
O O O
∥
H2N – C – NH – NH2 ⟷ H2N = C – NH – NH2 ⟷ H2N – C = NH – NH2
C-Reduction:-
𝑁𝑖 𝑜𝑟 𝑃𝑡 𝑜𝑟 𝑃𝑑
→ Alcohol
𝐶𝑙𝑒𝑚𝑚𝑒𝑛𝑠𝑒𝑛′ 𝑠 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 (𝑍𝑛/𝐻𝑔 +𝐻𝐶𝑙)
C =O → Alkane + H2O
𝑊𝑜𝑙𝑓𝑓−𝐾𝑖𝑠ℎ𝑛𝑒𝑟 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛(𝑅𝑒𝑑 𝑃+𝐻𝐼)
→ Alkane + H2O + I2
D-Oxidation:-
𝑇𝑜𝑙𝑙𝑒𝑛′ 𝑠 𝑟𝑒𝑎𝑔𝑒𝑛𝑡(𝐴𝑔𝑁𝑂3 +𝑁𝐻4 𝐶𝑙)
R → R-COOH + 2Ag
𝐹𝑒ℎ𝑎𝑙𝑖𝑛𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝐶𝑢𝑆𝑂4 +𝑁𝐻4 𝐶𝑙)
C =O → R-COOH + Cu2O
𝑆𝑒𝑂2
H → CHO + Se + H2O
CHO
Glyxole
E-Rxn involving alkyl group(Halogenation, aldol condensation, cross aldol condensation)
1- Halogenation:- CH3CHO + Cl2 CH2ClCHO + HCl
CH3CHO + 3Cl2 CCl3CHO + 3HCl
Excess chloral
CH3 CH2Br
C=O + Br2 C=O + HBr
CH3 CH3
(5)
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2-Aldol condensation: - The rxn in which aldehydes and ketones containing at least one α
hydrogen atom when treated with dilute NaOH undergo self-condensation to form β hydroxyl
aldehydes or ketones is called aldol condensation.
O H H OH H H
𝐷𝑖𝑙.𝑁𝑎𝑂𝐻 𝐷𝑖𝑙.𝐻𝐶𝑙
CH3 – CH + H – CH – C =O → CH3 – CH – CH – C =O → CH3-CH =CH-CHO + H2O

O H O OH H O
𝐷𝑖𝑙.𝑁𝑎𝑂𝐻 𝐷𝑖𝑙.𝐻𝐶𝑙
CH3 – C- CH3 + H – CH – C – CH3→ CH3 – C – CH – C – CH3 → CH3-C =CH-CHO + H2O
CH3 CH3
3- cross aldol condensation:-

O H H OH H H
𝐷𝑖𝑙.𝑁𝑎𝑂𝐻 𝐷𝑖𝑙.𝐻𝐶𝑙
CH3CH2 – CH + H – CH – C =O → CH3CH2 – CH – CH –C =O → CH3CH2-CH =CH-CHO + H2O
F-Miscellaneous rxn(Cannizzaro rxn, Tischenko rxn, PCl5,SOCl2, CHCl3,NH3):-
1- Cannizzaro rxn:-This rxn is shown by those aldehydes and ketones which do not contain ∝-
hydrogen.
HCHO + HCHO + NaOH CH3OH + HCOONa
C6H5-CHO + C6H5-CHO + NaOH C6H5CH2OH + C6H5COONa
CH3 CH3 CH3 CH3
CH3 – C – CHO + CH3 – C – CHO +NaOH CH3 – C – CH2OH + CH3 – C – COONa
CH3 CH3 CH3 CH3
Cross Cannizzaro rxn:-
C6H5-CHO + HCHO + NaOH C6H5CH2OH + HCOONa
2-Tischenko rxn:-
𝐴𝑙(𝑂𝐶2 𝐻5 )3
CH3CHO + CH3CHO→ CH3COOC2H5
3-Rxn with PCl5 :- R R Cl
C =O + PCl5 C + POCl3
R R C
Benzaldehyde (C6H5CHO)
Methods of preparation:-
1-By the oxidation of benzyl alcohol:-
𝐾2 𝐶𝑟2 𝑂7 +𝐶𝑜𝑛.𝐻2 𝑆𝑂4
C6H5CH2OH + (O) → C6H5CHO + H2O
2-By the oxidation of toluene:-
𝑀𝑜𝑂3
C6H5CH3 + (O) → C6H5CHO + H2O
3-By the oxidation of toluene:-
(Etard rxn) CH3 CH(OCrOHCl2) CHO
𝐶𝑆2 𝐻3 𝑂+
+ CrO2Cl2 → →

CH3 CH(OCOCH3) CHO

𝐶𝑟𝑂3 𝐻3 𝑂 +
+ (CH3CO)2O → →
4-By the chlorination of toluene:-
CH3 CHCl2 CHO
𝑢𝑣 𝐻2 𝑂
+ Cl2 → →
(6)

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RADHA SWAMI ACADEMY
5- By Gatterman-Koch rxn : CHO
𝐶𝑂,𝐻𝐶𝑙
𝐴𝑛ℎ𝑦𝑑.𝐴𝑙𝐶𝑙3 /𝐶𝑢𝐶𝑙

Physical properties:-Colourless liquid, slightly soluble in water but readily soluble in organic
solvent (b.p: 452K).
Chemical properties:-
A-Nucleophilic addition rxn(HCN, NaHSO3)
C6H5 C6H5 OH
C = O + HCN C
H H CN
C6H5 C6H5 OH
C = O + NaHSO3 C
H H SO3Na
B- Nucleophilic addition rxn by loss of water (NH2OH, NH2NH2, NH2NHC6H5, NH2NHCONH2)
C6H5 C6H5
C = O + H2NOH C = NOH + H2O
H H
C6H5 C6H5
C = O + H2NNH2 C = NNH2 + H2O
H Hydrazine H Benzaldehyde hydrazone
C6H5 C6H5
C = O + H2NNHC6H5 C = NNHC6H5 + H2O
H Phenyl hydrazine H Benzaldehyde Phenyl hydrazone
C6H5 C6H5
C = O + H2NNHCONH2 C = NNHCONH2 + H2O
H Semicarbazide H Benzaldehyde semicarbazone
C-Reduction:-
𝑍𝑛 /𝐻𝐶𝑙
C6H5CHO + 2(H) → C6H5CH2OH
D-Oxidation:-
𝐷𝑖𝑙.𝐻𝑁𝑂3
C6H5CHO + (O) → C6H5COOH
D-Electrophilic substitution rxn:-
Nitration:- CHO CHO
Con. HNO3 + Con. H2SO4 + H2O
NO2
m- Nitro Benzaldehyde
Sulphonation:- CHO CHO
Con. H2SO4
SO3H
Carboxylic acid (R-COOH)
Methods of preparation:-
1-By the oxidation of alcohol:-
𝐾2 𝐶𝑟2 𝑂7 +𝐶𝑜𝑛.𝐻2 𝑆𝑂4
R-CH2OH + 2(O) → R-COOH + H2O

2-By the hydrolysis of cyanide:-

R-CN + 2H2O R-COOH + NH3
(7)

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RADHA SWAMI ACADEMY
3-By the rxn of Grignard reagent with CO2:-
𝐻2 𝑂
R-MgX + CO2 RCOOMgX → RCOOH + Mg(OH)X
4- R-C(Cl)3 + 3KOH → R-C(OH)3 R-COOH + H 2O
− 3𝐾𝐶𝑙
5- By the hydrolysis of acid chloride, acid amide and acid anhydride:-
R-COCl + H2O R-COOH + HCl
R-CONH2 + H2O R-COOH + NH3
(R-CO)2O + H2O 2R-COOH
Physical properties:-
1-Physical state, colour and odour:-
C1 – C3 → Colourless, pungent smelling liquids.
C4 – C9 → Colourless, faint unpleasant goat like odour liquids and C10 - higher→ Colourless waxy solids
2-Solubility:-
C1 – C4 → Highly soluble in water due to hydrogen bond.
C5 - higher→ Solubility decreases. +δ -δ +δ -δ +δ -δ +δ -δ
……….H – O ……..H – O –C=O……..H – O…….H – O –C=O……
H R H R
3-B.p:- Much higher compare than those of the hydrocarbons of comparable m.m. due to
hydrogen bond.
4-M.p:- It do not vary in regular fashion. For the first ten members of the aliphatic carboxylic acid,
the acids having even no. of carbon atoms possess higher m.p. than those of the next higher
homologous containing the odd no. of carbon atoms.
CH2 COOH CH2 CH2
CH3 CH2 CH3 CH2 COOH
The zigzag chain of even no. of carbon atoms fit closely in the crystal lattice than odd no. of carbon
atoms, so they have higher m,p. A
Chemical properties:- O B
E R–C–O–H C
D
A-Rxn involving -H of –COOH(Na, NaOH, Na2CO3)
B- Rxn involving -OH of –COOH(PCl5, PCl3, SOCl2, R-OH, NH3,P2O5)
C- Rxn involving -CO of –COOH
D- Rxn involving –COOH
E- - Rxn involving alkyl group:-
A-Rxn involving -H of –COOH:- (Na, NaOH, Na2CO3) (Due to -I effect)When an electron
withdrawing group (-X, -CN, -NO2) is attached to a carboxylic group, it attract electrons from the
carbon of –COOH. This decreases electron density on the carbon atom as well as oxygen atom of
the –OH, thus release of H+ ion more easy. Due to which it show acidic character.
O Order of acidic strength :-
Cl CH2 C F > Cl > Br > I
O H FCH2COOH > ClCH2COOH > BrCH2COOH > ICH2COOH
CH3- > CH3CH2- > (CH3)2CH- > (CH3)3C-
HCOOH > CH3COOH > CH3CH2COOH > (CH3)2CH-COOH > (CH3)3C-COOH
CCl3COOH > CHCl2COOH > CH2ClCOOH > CH3COOH
HCOOH > C6H5COOH > CH3COOH
(8)

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RADHA SWAMI ACADEMY
Cl Cl Cl
CH3-CH2-CH-COOH > CH3-CH-CH2-COOH > CH2-CH2-CH2-COOH > CH3-CH2-CH2-COOH
1- 2R-COOH + 2Na 2R-COONa + H2
2- R-COOH + NaOH R-COONa + H2O
3- 2R-COOH + Na2CO3 2R-COONa + H2O + CO2
B- Rxn involving -OH of –COOH (PCl5, PCl3, SOCl2, R-OH, NH3,P2O5):-(Due to +I effect)
When an electron releasing group (Alkyl) is attached to a carboxylic group, it repels electrons
towards the carbon of –COOH. This increases electron density on the carbon atom as well as oxygen
atom of the –OH, thus release of H+ ion more difficult. Due to which it show basic character.
O
CH3 C
O H
1- R-COOH + PCl5 R-CO-Cl + HCl + POCl3
2- 3R-COOH + PCl3 3R-CO-Cl + H3PO3
3-R-COOH + SOCl2 R-CO-Cl + HCl + SO2
4-R-COOH + NH3 R-CO-NH2 + H2O
5-R-COOH R-CO
𝑃2 𝑂5 ∆
→ O + H 2O
R-COOH R-CO
C- Rxn involving -CO of –COOH:-
𝑳𝒊𝑨𝒍𝑯𝟒 (𝑷𝒂𝒓𝒕𝒊𝒂𝒍 𝒓𝒆𝒅𝒖𝒄𝒕𝒊𝒐𝒏)
Reduction:- R-COOH → R-CH2OH + H 2O
𝑹𝒆𝒅 𝑷+𝑯𝑰(𝑪𝒐𝒎𝒑𝒍𝒆𝒕𝒆 𝒓𝒆𝒅𝒖𝒄𝒕𝒊𝒐𝒏)
→ R-CH3 + H2O + I2

D- Rxn involving –COOH :-( Decarboxylation, Kolbe’s electrolytic, Dry distillation of Ca-salt)
1- Decarboxylation:-
𝐶𝑎𝑂 𝑁𝑎𝑂𝐻
CH3COOH + NaOH → CH3COONa → CH4 + Na2CO3
2- Kolbe’s electrolytic method:-
CH3COONa
2𝐻2 𝑂
→ C2H6 + 2CO2 + 2NaOH + H2
CH3COONa
3-Dry distillation of Ca-salt :-
HCOO
∆
Ca → HCHO + CaCO3
HCOO

CH3COO
∆
Ca → CH3COCH3 + CaCO3
CH3COO
CH3COO COOH
∆
Ca + Ca → 2CH3CHO + 2CaCO3
CH3COO COOH

(9)

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RADHA SWAMI ACADEMY
E- - Rxn involving alkyl group:-(Hell –Volhard – Zelinsky rxn)
𝐶𝑙2 (𝑅𝑒𝑑−𝑃) 𝐶𝑙2 (𝑅𝑒𝑑−𝑃) 𝐶𝑙2 (𝑅𝑒𝑑−𝑃)
CH3COOH → CH2ClCOOH → CHCl2COOH → CCl3COOH
Benzoic acid(C6H5COOH)
Methods of preparation:-
𝐶𝑜−𝐴𝑐𝑒𝑡𝑎𝑡𝑒
1-By the oxidation of toluene:- C6H5CH3 + (O) → 2C6H5COOH + 2H2O
𝐶𝑎(𝑂𝐻)2
2-By the hydrolysis of tri Chloro toluene:- C6H5CCl3 + 3H2O → 2C6H5COOH + 3HCl
𝐾𝑀𝑛𝑂4
3- By the oxidation of benzyl alcohol:- C6H5CH2OH + 2(O) → 2C6H5COOH + H2O
𝑇𝑜𝑙𝑙𝑒𝑛′ 𝑠 𝑟𝑒𝑎𝑔𝑒𝑛𝑡
4- By the oxidation of Benzaldehyde:- C6H5CHO + (O) → C6H5COOH
5- By the hydrolysis of benzonitrile:- C6H5CN + 2H2O C6H5COOH + NH3
Physical properties:-
1-It forms white shining leaflets having m.p 395K.
2-It is sparingly soluble in cold water but readily soluble in hot water, benzene and ether.
3-Its vapour are irritating and cause sneezing and coughing.
Chemical properties:-
1- 2C6H5COOH + 2Na 2C6H5COONa + H2
2- C6H5COOH + NaOH C6H5COONa + H 2O
3-C6H5COOH + PCl5 C6H5COCl + HCl + POCl3
4- C6H5COOH + SOCl2 C6H5COCl + HCl + SO2
1- C6H5-COOH C6H5-CO
𝑃2 𝑂5 ∆
→ O + H 2O
C6H5-COOH C6H5-CO
Benzoic anhydride
7-Electrophilic substitution rxn:-
Halogenation:- COOH COOH
𝐹𝑒𝐵𝑟3
+ Br2 → + HBr
Br
Nitration:- COOH COOH
𝑐𝑜𝑛𝑐. 𝐻2 𝑆𝑂4
+ HNO3 → + H2O
Conc. NO2
Sulphonation:- COOH COOH
𝑆𝑂3
+ H2SO4 → + H2O
SO3H
m-sulpho benzoic acid
Note:-Benzoic acid do not undergo Freidel crafts rxn, due to presence of strong –COOH group.

[10]

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