CH 12 ALDEHYDES , KETONES AND CARBOXYLIC ACIDS

CARBONYL GROUP(˃C=O)
↓
----------------------------------------------------------------------------------------------------------------------------
↓

↓
RCHO
RCOR
Aldehyde
Ketone
--CHO group
> C=O gp

AROMATIC CARBONYL COMPOUNDS

↓
-------------------------------------------------------------------------------------------------------------------------------------------------------
---------------
↓
Benzaldehyde Acetophenone 2-Phenylethanal ↓
1-Phenyl-2-propanone
Functional group attached to ring
1. 3 – Methyl – Butanal

2. But – 2 – enal

3. 3 – Hydroxy – 4, 4
dimethylpentanal

4. Ethane di al

5. Propane 1, 2, 3 – tri carbaldehyde

6. Benzaldehyde

7. 3 Methyl cyclohexane
carbaldehyde

8. Pentan – 3 – one
9. 4 Nitro benzaldehyde

10. 1 pheyl ethan 1 one

11. Diphenylmethanone

12. 3 Oxo butanal

13. Butane – 2, 3 – dione

14. 1 phenyl propane 1 one

15. Benzene 1, 2 dicarbaldehyde

16. 2 methyl cyclohexanone

STRUCTURE OF >C=O GROUP

Carbon is sp2 hybridised. 3 sp2 hybrid orbitals form 3 σ bonds with O, H/R. Unhybridised p orbital forms π bond with O. O
has 2 lone pairs. Thus carbonyl C and the three atoms attached to it lie in same plane and the π electron cloud lie above and
below the plane. Bond angles are 1200
C=O is polarized due to high EN of O relative to C. Hence CO group is an electrophilic and its O , a nucleophilic centre.
High polarity of CO group is explained on basis of resonance:
PREPARATION OF ALDEHYDES AND KETONES
I Preparation of aldehydes and ketones both

1 From alcohols :
(a) By oxidation:
RCH2OH ----------- RCHO -------- RCOOH
Oxidising agents : acidified KMnO4 or K2Cr2O7, CrO3 / H2SO4

To stop reaction at aldehyde level , pyridinium chloro chromate (PCC) or Jones reagent (CrO 3/Acetone ) are used -
(Primary Alcohol) RCH2OH ----------- RCHO
(secondary Alcohol) R2CHOH ----------- RCOR
 (b) By catalytic dehydration of alcohols:
Cu/573 K
RCH2OH ----------- RCHO
Cu/573 K
R2CHOH ----------- RCOR
2 Hydration of alkynes :
1 % HgSO4
HC≡CH --------- CH2=CHOH ------- CH3CHO
H2SO4
1 % HgSO4
RC≡CH --------- RC(OH)=CH2 -------- RCOCH3
H2SO4

3.Ozonolysis of alkenes :
II Preparation of only aldehydes:
1 From RCOCl (Rosenmund’s reduction )
Pd/BaSO4
RCOCl + H2 ------------------------ RCHO
C6H5COCl + H2 ------------------------ C6H5CHO
Catalyst is poisoned by S or Quinoline to stop reaction at aldehyde level , otherwise it get reduced to alcohol
2 By reduction of RCN (Stephen reduction)

SnCl2/HCl
RC≡N + 2H --------------------------- RCH=NH------- RCHO + NH3

3 Reduction by DIBAL - H

Nitriles and esters can be reduced to aldehyde by DIBAL - H

III Preparation of ketones only:
1 From RCOCl
2RCOCl + R’2Cd ---------- 2RCOR’ + CdCl2
2 By reaction of Griganrd reagent with RCN
RC≡N + RMgX ------ R2C=NMgX --------- RCOR + NH3 + H2O
H3 O+
IV Preparation of aromatic aldehydes and ketones:
1 From Arenes: Etard reaction
Terminal C of side chain convert into CHO

2. Oxidation of methyl benzene using Chromic oxide

 2 By side chain chlorination followed by hydrolysis 4 Friedal crafts Acetylation

3 Gattermann Koch reaction 5 Reaction of RCN with RMgX

PHYSICAL PROPERTIES OF ALDEHYDES AND KETONES
1 Boiling Point :
(i) Relatively lower than that of alcohols and carboxylic acids-------- weaker dipolar attractions in
carbonyl compounds as compared to H—Bonding in alcohols and carboxylic acids
(ii) Relatively higher than that of hydrocarbons ----- strong dipolar attractions
due to polar C=O bond
(iii) B.P of ketone is higher than that of isomeric aldehyde ---- more stable ketone due to
presence of 2 R groups
2 Solubility : Upto 4 C , carbonyl compounds are soluble in water due to H-Bonding with it. With increase in
size of R , solubility decrease due to increase in non polar part

CHEMICAL PROPERTIES OF ALDEHYDES AND KETONES

Ques Ketones are less reactive than aldehydes > Why ?
Ans (i) +I effect -- HCHO is most reactive. On replacing H by R , due to +I effect, +ive charge on
C of C=O decrease, so reactivity decrease. In ketones , there are 2 R groups , so more +
I so reactivity further decrease.
(ii) Steric factors --- With increase in no. of R , due to more steric hinderance to attack of Nu,
reactivity decrease
HCHO > RCHO > RCOR
If R = C6H5---- resonance stabilization ----- reactivity further decrease
RCHO> C6H5CHO > C6H5COCH3 > C6H5COC6H5
(A) Nucleophilic Addition :
(2) With NaHSO3
Mechanism :

(1) With HCN: (3) With Grignard reagent:

 H3 O+
HCHO + RMgX ------ RCH2OH (1) With ammonia derivatives
RCHO + RMgX ------ R2CHOH
RCOR + RMgX ------ R3COH
(4) With Alcohols :

(B) Replacement of O of C=O group by other groups

Control of pH : It is to be maintained at 3.5 due to
(i) If medium is too acidic, ammonia derivatives being basic in nature , react to form salt instead of desired reaction
(ii) If medium is too alkaline, protonation of C=O group do not take place .
 (2) With ammonia :
CH3CHO + NH3 ------ CH3CH(OH)NH2----- CH3CH=NH
(C) Oxidation :
(i) Aldehydes -- easily oxidised----- stronger O.A such as conc. HNO3,
acidified KMnO4 or K2Cr2O7 or weaker O.A such as bromine water, Tollen’s
reagent, Fehling’s solution and Benedict’s solution
RCHO ----------- RCOOH,
Both have same no. of C atoms due to presence of H on CO group which is
converted to OH
(a)Tollen’s reagent : Ammonical AgNO3
RCHO + 2[Ag(NH3)2]+ + 3OH-- ----- RCOO-- + 2Ag + 2H2O
+ 4NH3
(b)Fehling’s solution 1 = acidifed CuSO4, Fehling’s solution 2 = Roschelle salt or
alkaline sodium potassium tartarate
RCHO + Cu2+ ------ Cu2O ↓ + RCOO—
 (ii) Ketones ------ difficult to oxidise------ only by strong O.A
RCOR -------- RCOOH + HCOOH
In unsymmetrical ethers , Poppoff’s rule is used -- CO group stays with lower R group
CH3CH2CH2CH2COCH3 ------------- CH3CH2CH2COOH + CH3COOH √
OR ----- CH3CH2CH2CH2COOH + HCOOH x
(iii) Haloform reaction (iodoform reaction ):
Shown by CH3CHOH or CH3CHO group or the groups which convert into these groups
CH3CHO + I2 + NaOH -------- CHI3↓ + HCOONa + H2O
Yellow
CH3COCH3 + I2 + NaOH -------- CHI3↓ + CH3COONa + H2O
Yellow
Positive test Negative test
CH3CHO HCHO
CH3CH2OH CH3OH
Pentan-2-one Pentan-3-one
Propan-2-ol Propan-1-ol
Acetophenone Benzophenone
Butan-2-ol Butan-1-ol
(D) Reduction:
(1) To alcohols :
>C=O + 2H --------- > CHOH
R.A = Ni,Pt,Pd /H2, NaBH4, LiAlH4, Zn/Acetic acid, Zn/NaOH, Na/Ethanol, Al--isopropoxide
HCHO ----------------------- CH3OH
CH3CHO -------------------- C2H5OH
CH3COCH3 ------------------ (CH3)2CHOH
(2) To hydrocarbon :
>C=O ----------------------- >CH2
(a) Clemmenson’s reduction
Zn-Hg /HCl
>C=O ----------------------- >CH2
HCHO --------------------- CH4
CH3CHO ------------------ C2H6
CH3COCH3 ---------------- CH3CH2CH3
(b) Wolf Kischner reduction
NH2NH2 /KOH
>C=O ----------------------- >CH2
(c) With Red P and HI
Red P /HI
(E) Reactions due to α—H
(1) Aldol condensation: aldehyde must have α—H. HCHO and C6H5CHO donot give

(2) Cross aldol condensation:

(F) Other reactions
(1) Cannizaro reaction: No α H
(2) Electrophilic substitution: CHO and CO groups are meta directing deactivating groups
(a) Nitration

(b) Halogenation

(c) Sulphonation
DISTINCTION BETWEEN ALDEHYDES AND KETONES
S.No. TEST ALDEHYDE KETONE
1 Sample + Tollen’s reagent + heat Grey ppt turning to silver mirror No reaction

2 Fehling’s solution 1& 2 + sample + heat Red ppt No reaction

3 Sample + Schiff’s reagent Pink colour No reaction

4 With NaOH Brown resinous mass No reaction

5 With alcohols in presence of dry HCl Form acetals easily Do not form
ketals easily

CARBOXYLIC ACIDS
--COOH GROUP
ALIPHATIC CARBOXYLIC ACIDS -- RCOOH
AROMATIC CARBOXYIC ACID ----- ArCOOH
Aliphatic monocarboxylic acids are known as fatty acids (higher ones exist in natural fats)
STRUCTURE OF CARBOXYLIC ACIDS
Bonds to carboxylic C lie in 1 plane and are separated by 120 0. This carbon is less electrophilic than carbonyl C
PREPARATION OF CARBOXYLIC ACIDS
(1) From primary alcohols :on oxidation
RCH2OH -------- RCHO ------- RCOOH
C6H5CH2OH ----------- C6H5COOH
(2) From alkyl benzenes

(3) From Nitriles and Amides

RC≡N + H3O+ ------- RCONH2
RC≡N + 2H3O+ ------- RCOOH + NH3
RCONH2 + H3O+ ------- RCOOH + NH3
C6H5CONH2 + H3O+ ------- C6H5COOH + NH3
(4) From Grignard’s reagent
O=C=O + RMgX --------- O=C(R)---OMgX ------- RCOOH + Mg(OH)X
(5) Ester Hydrolysis
RCOOR’ + H3O+ ------- RCOOH + R’OH
(6) From olefins
CH2=CH2 + CO + HCl ------- CH3CH2COOH
RCH=CH2 + CO + HCl ------- RCH2CH2COOH
(7) From acid derivatives
RCOCl + H2O ----------- RCOOH + HCl
(RCO)2O + H2O ----------- 2RCOOH

PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS

(1) Solubility : (i) soluble in water due to H-bonding with it (ii) With increase in R , solubility decrease
(2) Boiling Points : (i) Very high -- dimeric structure as a result of H-Bonding
(ii) Acids have higher B.P than alcohols --- more polar O—H bond in acids
(iii)Aromatic acids have higher B.P than aliphatic ----- symmetrical structure
and close packing in aromatic ones.
(3) Melting points : (i) In first 10 members , alternation effect is observed. M.P of carboxylic acids with even no. of C atoms
is
higher than the lower and higher acid with odd no. of C atoms due to symmetrical arrangement and close packing of acid
with even no. of C atoms
/\/COOH (4 C) , /\COOH (3 C), /\/\COOH (5C)
(ii) M.P of aromatic acids > aliphatic acids due to close packing
CHEMICAL PROPERTIES OF CARBOXYLIC ACIDS
(A) Reactions involving cleavage of O—H bond:
(1) Acidic nature: RCOOH ------- RCOO-- + H+

Positive and negative both charges in

structure II of RCOOH which require
charge separation so RCOOH is less
stable. In carboxylate ion only
negative charge which is deispersed
on 2 EN O atoms so RCOO—is more
stable than RCOOH----- loss of H+
easy---- acidic nature

RCOOH turns blue litmus red Δ

RCOOH + NH3 -------- RCOONH4 --------- RCONH2

Effervences
Expressing acidic strength

K x [H2O] = Ka
pKa = --log Ka
Higher the Ka ------ lower pKa -----
stronger the acid
Lower the Ka ------- higher pKa ---- weaker
the acid
Comparison of acidic strength
(i) RCOOH > ROH
RCOO—is more resonance stabilised than RCOOH , so equilibrium shifts in forward direction releasing large amount
of H+ ions so show acidic character.
ROH is more stable than RO—so release of H+ is difficult so less acidic.
(ii) RCOOH > C6H5OH
RCOOH and RCOO--- are more resonance stabilized than C6H5OH and C6H5O—respectively so RCOOH are stronger
acids than C6H5OH
 There are 2 EN O atoms in carboxylate ion for dispersal of negative charge while only 1 EN O atom in phenoxide
ion so RCOO—is more stable than C6H5O— ion
Effect of substituents on acidic character
(a) If –I group is attached to COOH group
------- electron density on C and O of COOH decrease
------- O of COOH is more EN
------- attracts shared pair from O—H bond
------- release of H+ is easy
------- RCOO—more stable due to charge dispersal
------- more acidic character
Eg ClCH2COOH > CH3COOH
(b) If +I group attached to COOH group
------- electron density on C and O of COOH increase
------- O of COOH is less EN
------- attracts shared pair from O—H bond to less extent
------- release of H+ is difficult
------- RCOO— less stable dur to intensification of charge
------- less acidic character
Eg HCOOH > RCOOH
(c) With increase in number of –I groups , acidic character increase
Eg Cl3CCOOH > Cl2CHCOOH > ClCH2COOH > CH3COOH
(d) With increase in distance of –I group from COOH , acidic character decrease
C—C(Cl) –COOH > C(Cl) ---C—COOH
(e) Ph< I<Br< Cl< F<CN<CO2<CF3 ------ --I groups
(f) HCOOH > CH3COOH > CH3CH2COOH > (CH3)2CHCOOH > (CH3)3CCOOH
(g) Presence of phenyl or vinyl group increase acidic character
C6H5COOH > RCOOH
(h) Effect of substituents on acidic character of Benzoic acid
(i) + I group
-- I group
Destabilise benzoate ion
Stabilise Benzoate ion
Acidic character decrease
Acidic character increase
(ii) Both effects are more at para than meta.
(iii) o isomer is more acidic in –I or + I substituents
Benzoic acid< m- Nitrobenzoic acid< p-Nitrobenzoic acid < o-Nitrobenzoic acid
Benzoic acid> o-Methoxybenzoic acid > m- Methoxybenzoic acid > p- Methoxybenzoic acid
(B) Cleavage of C—OH bond:
(1) Formation of acid anhydride : By dehydration
P2 O5
2RCOOH ------------------ (RCO)2O + H2O
(2) Esterification : H2SO4
RCOOH + R’OH --------------- RCOOR’ + H2O
Mechanism:
 (3) Reaction with P- halides, SOCl2 :
3RCOOH + PCl3 --------------- 3RCOCl + H3PO3
RCOOH + PCl5 ---------------- RCOCl + HCl + POCl3
RCOOH + SOCl2 --------------- RCOCl + SO2 + HCl
(4) With NH3 :
RCOOH + NH3 ---------- RCOONH4 ----------- RCONH2
(C) Reactions due to COOH group:
(1) Reduction:
(a) Partial reduction to alcohols : RCOOH ---------------- RCH2OH
RA
RA = LiAlH4, CuCr2O4.
NaBH4 is not used
(b) Complete reduction to alkane: red P
RCOOH + 6HI -------------------------- RCH3 + I2 + H2O
(2) Soda lime decarboxylation : CaO
RCOONa + NaOH -------------------------- RH + Na2CO3
(3) Kolbe’s electrolysis :
2RCOOK ------------- 2RCOO-- + K+
2RCOO-- --2e-- -------- 2RCOO ------ RR + 2CO2
K+ + OH-- ------------- KOH
(4) Dry distillation of Ca salt of carboxylic acids
(HCOO)2Ca -------------- 2HCHO + CaCO3
(RCOO)2Ca + (HCOO)2Ca -------------- 2RCHO + CaCO3
(RCOO)2Ca ---------- RCOR + CaCO3
(5) Hundsdiecker reaction
RCOOAg + Br2 ------- RBr
(D) Reactions due to R group:
(1) Oxidation : Strong OA as KMnO4 and weak OA as H2O2 oxidise β H to OH
C—C—C—COOH -------- C—C(OH)—C—COOH
SeO2 oxidise α H to OH
C—C—C—COOH -------- C –C—C(OH)---COOH
HCOOH reduce Fehlings solution and Tollens reagent
HCOOH + Ag2O ------- Ag + CO2 + H2O
HCOOH + CuO -------- Cu2O + CO2 + H2O
(2) Hell Volhard Zelinsky (HVZ) reaction: α H is halogenated
Cl2/P Cl2/P Cl2/P
CH3COOH
(3) Electrophilic ------ :CH2ClCOOH ----- CHCl2COOH ---- CCl3COOH
substitution
COOH is meta directing deactivating group
Aromatic carboxylic acids do not give Friedal Craft’s reaction as COOH group is deactivating and catalyst anhyd.
AlCl3 gets bonded to COOH group
 DISTINGUISHING TESTS
Test Alcohol Phenol
Carboxylic acid
1 With blue litmus No reaction turns red
turns red
2 With NaHCO3 No reaction No reaction
Effervences
3 With Neutral FeCl3 No reaction violet colour No