Aldol & Similar Name Reactions

ALLEN Aldol & Similar Name Reaction 1
ALDOL & SIMILAR NAME REACTIONS

(1) CANNIZARO REACTION
This reaction is given by aldehyde having no a- hydrogen in the presence of conc.
NaOH/D or KOH/D.
O O
s +
H – C – H KOH
D H – C – O K + CH3OH
Mechanism :
O Os O O O
HO
s r.d.s. s s
H–C–H H–C–H C CH3–O + H–C–O–H CH3OH + H–C–O
OH H H
In the presence of a very strong concentration of alkali, aldehyde first forms a doubly charged
anion (I) from which a hydride anion is transferred to the second molecule of the aldehyde to form
acid and an alkoxide ion. Subsequently, the alkoxide ion acquires a proton from the solvent.
O Os Os
s s
OH
H – C – H OH
D H–C–H H–C–H
(I)
OH O
s
s s
O H O H
s
H–C–H + C=O H – C + H–C – O
(I)
O H O H
s
s H2O s
HCH2O HCH2OH + OH
From solvent
Q.1 Which of following will not undergo Cannizaro reaction
CHO
CHO
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aldol & Similar Name Rxn\Eng\01.Theory.p65
(A) (B) (C) (D) Cl3C–CHO

O CHO Cl
AR0001
O
2 H HCHO
Q.2 Ph – C – Cl Pd –BaSO Ph – CHO (C) + (D)
4 D,KOH
Product (C) & (D) are :
(A) Ph–CO2H, Ph–OH (B) Ph–CO2–,HCO2–
(C) Ph–CH2OH, H–CO2– (D) Ph–CO2–,CH3OH AR0002
E
2 JEE-Chemistry ALLEN
CHO conc.NaOH H
+
Q.3 (A) (B)

CHO
Product (B) is :
O O
O C
CH2–O–C
(A) H2C=CH–CO2H (B) CH 2 CH2 (C) (D)H2C=C=O
C O CH2–O–C
O O
AR0003
Q.4 (i) HCHO NaOD
D
(ii) DCHO NaOD
D
AR0004
s 18
s
Q.5 (i) Ph–CHO OD / DOD (ii) Ph–CHO OHD AR0005
D
KOH KOH
Q.6 (i) Ph – CHO + HCHO D (ii) Ph – C – C – H D AR0006
O O
Q.7 (i) MeCH2 – CHO KOH (ii) Me2CH – CHO conc.KOH AR0007
D D
Q.8 (i) Me–NO2 + HCHO KOH (ii) MeCHO – HCHO KOH AR0008
(excess) (excess)
– – +
Aq.OH
A Conc. OH H
Q.9 PhCOCHBr2 B ; the compound ‘C’ is :
(A) PhCH(OH)CHO (B) PhCH(OH)COOH
(C) PhCOOH (D) None of these AR0009
Q.10 Match the column :
Column - I Column - II
(A) HCHO + NaOD (conc.) (P) DCOO– + CDH2OH
(B) DCHO + NaOH (conc.) (Q) DCOO– + CD3OH

(C) DCDO + NaOH (conc.) (R) DCOO– + CDH2OD
(D) DCHO + NaOD (conc.) (S) HCOO– + CH3OD AR0010

O O
NaOH KMnO4
Q.11 C—C—H (conc.) A B NaOH/CaO C ; Product ‘C’ is :
O
CHO
(A) (B) (C) (D)
AR0011
E
O
CºCH
D
Q.12 ¾¾¾¾¾¾¾
1% HgSO 4 / Dil.H 2 SO 4
® ¾¾¾¾
I 2 / NaOH
H+
® ¾¾ ® X ; X is :
O O O O
COOH COCH3 CH2CHO
(A) (B) (C) (D) AR0012
Q.13 The cannizaro reaction of Ph COCHO forms the product(s)

(A) PhCOCH2OH + PhCOCO2– (B) PhCH – CO–2
OH
(C) PhCO2– + PhCOCH2OH (D) Both (A) and (C) AR0013
O
P2O5 (i) I 2 + Ca(OH) 2
Q.14 C – NH2 A ¾¾¾¾¾
(ii)H O
® B ¾¾¾¾¾
( i) CH 3MgBr
+
(ii) D
¾
®C ;
3
(iii) –CHI 3
Product is:
O O
(A) C – NH2 (B) C – OH (C) C (D) C – CH2CH3
O O
AR0014
CHO
conc. KOH
Q.15
CHO
True about this reaction is / are
(A) Cannizaro name is associated with this reaction (B) It is a disproportion reaction
(C) It is a bimolecular reaction in r.d.s. (D) All of these AR0015
O3
Q.16 Zn
(A) conc.KOH (B)
(1 mole)
End product (B) of above reaction is :
+
CHO CO2– K
+
CH2OH CO2– K
(A) (B) (C) (D) +
CH2OH CH2OH CH2OH CO–2 K
AR0016
E
Q.17 The major product pair of the following reaction will be :
CHO
HCHO Products
NaOH (aq)
COONa CH2 OH
(A) + CH3OH (B) + HCOONa
CH2OH COONa
CH3OH
(C) + (D) + AR0017
HCOONa
Q.18 Reactant ‘X’ will be :
CH2OH
– +
+
COO Na
H O3 NaOH
X Y Zn Z1 + Z2 +
–
OH /
Ph – C = CH – C – Ph
CH3 O
OH OH
(A) Ph – CH – CH – Ph (B) Ph – CH – CH – CH3
CH3 Ph
CH3 OH OH
(C) Ph – CH – C – Ph (D) Ph – CH2 – CH – Ph AR0018
CH3
Q.19 An organic compound neither reacts with neutral ferric chloride solution nor with Fehling solution,
It however, reacts with Grignard reagent and gives positive iodoform test. The compound is -
[JEE-MAIN (APRIL)-2019]
OH
O O
CH3 O
CH3 CH3 C2H5
(1) C2H5 (2) (3) (4)
H CH3
OH O
O O
AR0019
E
(2) BENZIL-BENZILIC REARRANGEMENT OR BENZILIC ACID REARRANGEMENT

The base catalysed reaction of 1,2-diketones to a salt of –2– hydroxy carboxylic acid is known as
Benzilic acid rearrangement, this reaction is mainly applicable when aryl group is present on both
carbonyl carbons.
O OH
(i) OH–
Ph – C – C – Ph (ii) H+ HO – C – C – Ph
O O Ph
(Benzil) (Benzilic acid)
Mechanism :
s
O HO O O
s
Ph – C – C – Ph OH Ph – C – C – Ph HO – C – C – Ph
s
O O O Ph
OH OH
r s
HO – C – C – Ph H O – C – C – Ph
O Ph O Ph
(Benzilic acid)
O O
s
Q.1 CH3 C – C – C6H 5 OH AR0020
O O
Q.2 C–C 1. NaOH AR0021
r
O (Furil) O 2. H
O
(i) NaOH
Q.3 r AR0022
(ii) H3O
O
O
(i) NaOH
Q.4 (ii) H3O
r AR0023
O
(3) ALDOL CONDENSATION

The a- hydrogen of carbonyl compounds are acidic due to the fact that the anion (enolate ion) is
stabilized by resonance.
H 1 1
OH (base) O
gg
CH2– C – H CH2= C – H CH2– C – H
O O
gg
O
(3a Hydrogens) (enolate anion) (enolate anion)
E
Base catalysed Aldol
In aqueous base, two acetaldehyde molecules react to form b-hydroxy aldehyde called aldol.
The reaction is called Aldol condensation. The enolate ion is the intermediate in the aldol
condensation of aldehyde and ketone. Acetaldehyde for instance, forms a dimeric product aldol in
presence of a dilute base (» 10% NaOH)
1
OH / HOH D
2CH3CHO CH3 – CH– CH2– CHO CH3– CH = CH – CHO
5°C –H2O
OH
b–h y d ro x y b u tyra ld e h yd e (A ld ol )
Mechanism :
O
1 1
H OH H –C – CH3 O H –O – H
H –C – CH2 H –C = CH2 rds H – C – CH2–CH– CH3

O O1 O
OH OH
–OH1 H – C – CH–CH– CH3
H – C – CH = CH – CH3 H – C = CH – CH – CH3
OH 1 Aldol
O O
1 O H
Aldols are stable and may be isolated. They, however can be dehydrated easily by heating the
basic reaction mixture or by a separate acid catalyzed reaction. Thus if the above reaction is heated
the product is dehydrated to 2-butenal (crotonaldehyde).
Acid cataysed Aldol
In acid catalysed aldol condensation enol form of carbonyl is the nucelophile in place of enolate.
Mechanism :
O O
H /H2O,D
+
CH3–C–CH3 CH3– C = CH – C – CH3

CH3
(a,b unsaturated carbonyl compound)
Å
O O–H OH
+
H
CH3–C–CH3 CH 3 – C – CH3 CH3 – C = CH2
Å Å
O–H O–H O–H O–H
CH3– C = CH2 + CH3 – C – CH3 CH3 – C – CH2 – C – CH3

CH3 –H
Å
O O OH2 O OH
Å
CH3 – C – CH – C – CH3 H CH – C – CH – C – CH
CH 3 – C– CH = C – CH3 3 2 3
–H2O
CH3 H CH3 CH3
(Aldol)
E
Q.1 Write the product and mechanism for given reactions.

(I) CH3– CH2 – C – H (A) D (B) AR0024
Dil NaOH
O
(II) O Dil NaOH (C) AR0025
(III) C6H5– CH2 – CHO Dil NaOH (D) AR0026

Dil NaOH
(E) D
(IV) O (F) AR0027
(V) C6H5– C – CH3 Dil NaOH (G) D (H) AR0028

O
Q.2 Identify the intramolecular aldol product ?
O O
Dil NaOH (A) D (B)
(I) CH3 – C – CH2 – CH2 – C – CH3 AR0029
O
(II) Dil NaOH (E) (F) AR0030

D
O
Q.3 Find out the total number of possible aldol products (including and excluding stereo products).
NaOH/ HOH
(I) C6H5 – CHO + CH3 – CHO AR0031
5°C
(II) CH3 – CH = O + CH3 – CH2 – C – CH3 NaOH/ HOH AR0032
5°C
O
Q.4 Identify the structure of substrate ?
O
(I) A Dil. NaOH AR0033
A= ?
OH
OH
(II) A Dil.NaOH AR0034
CH3– C – CH2 C CH3 A = ?
(2 mole) 5°C
O CH3
Q.5 Complete reaction sequence :
(i) O3(1eq) (i) OH
(I) (a) (b) AR0035
(ii) Zn / H2O (ii) D
(i) OH
(II) Product AR0036
(ii)C6H5CHO
(iii) D
O
E
Q.6 Complete the following reactions :
O OH
– CH3 CH–CH3
OH
(I) (X) + (Y) AR0037
(II) (X) OH AR0038

CH3
OH
O
(i) OH
(III) [X] AR0039
(ii)D
O
– CH3MgBr Zn–Hg
Q.7 OH A B conc.HCl C ; the product ‘C’ is
heat CuBr
O
(A) (B) (C) (D)
AR0040
Q.8 Consider following intramolecular aldol condensation reaction :
O
–
OH
X ; X can be :
(A) (B)
O O O O
O O
(C) (D) AR0041
O O
Q.9 Product ‘Y’ formed in the given reaction is :
O3/Zn –
OH
X Y
O O O O
(A) (B) (C) (D)
OH
AR0042
E
Q.10 Product ‘D’ is :
O
–
H /Pt CrO
CH3—C—H OH A B (excess)
2
C H SO3 D
2 4
(A) CH3–CH2–CH = CH2 (B) CH3–CH2–CH2–CHO

(C) CH3–CH2–CH2–COOH (D) CH2 = CH – CH = CH2 AR0043
-
D
Q.11 CH3CH = CHCHO ¾¾¾
OH
aldol
® ¾¾ ® A, A is :
(A) CH3(CH = CH)3CHO (B) CH3CH2CH2(CH = CH)2CHO

(C) CH3(CH2CH2)3CH = CH – CHO (D) None is correct AR00044
NaOH, NaOH,
Q.12 MeCHO A B ; B is :
(A) Me(CH=CH)3CHO (B) MeCH=CHCHO

(C) Me(CH=CH)2–CHO (D) Me –(CH=CH–) 4CHO AR0045
Q.13 For the given reaction :
+
H P (major) (i) O3 Q OH / R (Major)
(ii) H2O/Zn
OH
The (R) is :
–
CHO CHO COO
(A) (B) (C) (D)
OH
AR0046
Q.14 The major product formed in the following reaction is: [JEE-MAIN (JANUARY)-2019]
O CH2
O
dil.NaOH
H3C H+
OH
O OH
O
(1) HC
3 (2) H3 C
OH O O OH
(3) H3C
H
(4) H3C AR0047
E
Q.15 The major product obtained in the following reaction is : [JEE-MAIN (JANUARY)-2019]
CO2Et
NaOEt/D
O
O
O
O
(1) CO2Et (2)
CO2Et
O
O
(3) (4) CO2Et AR0048
CO2Et
Q.16 In the following reactions, products A and B are : [JEE-MAIN (JANUARY)-2019]

O O
dil NaOH [A]
H3C H3C CH3 H
+
H 3O
[A] [B]
D
O O O O
OH H2C OH CH3
C
H3C H H H3C H H
(1) A = ; B= (2) A = ; B=
H3C H3C H3C CH3 H3C CH3
CH3 CH3
O O O O
CH3 CH3 CH3 CH3
(3) A = CH3 ; B = CH3 (4) A = CH3 ; B = CH3
HO HO
AR0049
Q.17 The major product obtained in the following reaction is [JEE-MAIN (APRIL)-2019]
CH3 O
NaOH
¾¾¾D
®
OHC
CH3 CH3
H 3C H 3C
H H
(1) (2) (3) (4)
O CH3 O CH2
O O
AR0050
E
(4) HALOGENATION OF THE a-CARBON OF ALDEHYDES AND KETONES
I Acid-Catalyzed halogenation : - When Br2, Cl2 and I2 is added to an acidic solution of an
st
aldehyde or a ketone, a halogen replaces one of the a-hydrogens of the carbonyl compound.
Halogenation takes place through the slow formation of an enol followed by rapid reaction of the
enol with the halogen.
O O
CH3 +
H , H2O CH2I
+ I2 + HI
Mechonism :
B–
:
H : O: H
+ :
O–H H OH
Fast Fast
Step - I : CH2—C + H:B CH2—C C C + HB
Ph Ph H Ph
X
+
: :
:
OH O–H
Slow –
Step - II : X—X + CH2 = C CH2—C +X
Ph Ph
X X
+ :
O–H O
– Fast
Step - III : CH2—C + X CH2—C + HX
Ph Ph
IInd Base-Catalyzed halogenation : - In the presence of excess base and excess halogen, a methyl
ketone is converted first into a trihalo-substituted ketone and then into a carboxylic acid.
O O
– –
OH R—C—O + CHX3
R—C—CH3 X2
(Haloform)
Mechanism :
O H O O X
–
–
X—X –
:
:
R—C—CH2 + OH R—C—CH2 R—C—CH + X

H
– –
O :OH
:
R—C = CH2 O X
–
R—C—CH
:
X—X
X O
X—CH—C—R
O O
X – – X—X
:
R—C—C + OH R—C—CX2 R—C—CX3

X
O H –
OH
–
:
O O :O:
– –
R—C—O + CHX3 R—C—OH + CX3 R—C—CX3
:
OH
E
Q.1 Identify the compounds which can show iodoform test and complete the reaction ?
Cl Cl
(1) Cl (2) Cl (3) Cl (4)
Cl Cl Cl
O
OH OH
(5) OH (6) (7) (8)
OH
O
O
(9) (10) (11) CI3CHO AR0051
O
Q.2 Complete the following given reaction :
O O –
I2 / O H
(i) Product AR0052
O O –
: :
I2 / OH
:
(ii) CH3–C—C–OH Product AR0053
–
: :
I2 / OH
:
(iii) Product AR0054
OH
Q.3 Select the compound which does not show haloform reaction is/are :
O O
O O
(A) CH3–C—O–Me (B) CH3–C C – CH3 (C) HO (D) I O
O I
AR0055
Q.4 For the reaction
1. B2H6/THF –
PCC(CH2Cl2) OH /
PhCH = CH2 (X) (Y) (Z)
2. H2O2/OH
(Z) is :
CH3
(A) Ph–CH=CH–CHO (B) Ph–C = C–CHO
CH3
(C) Ph–CH2 – CH = C – CHO (D) Ph–C = CH–CHO AR0056

Ph CH3
Q.5 Two isomeric ketones, 3-pentanone and 2-pentanone can be distinguished by :
(A) I2 / NaOH (B) NaOH (C) NaCN / HCl (D) 2,4-DNP AR0057
Q.6 Which of the reagent is used to convert 2–Butanone into propanoic acid -
(A) NaOH, I2/H+ (B) Tollen's reagent (C) Fehling solution (D) NaOH, NaI/H+
AR0058
E
Paragraph for Q.07 to Q.09

OH
conc.H 3PO 4 O3/Zn
A P1 + P2
Ph D H2O ( Ketone) (Aldehyde)
Q.7 Which one of the following reagent is best suitable for distinction between P1 and P2 -
(A) Braddy’s reagent (2,4 DNP) (B) NaHSO3
(C) NaHCO3 (D) NaOH / I2 AR0059
Q.8 Select the correct statement among the following -
(A) P1 will show aldol reaction & P2 will show cannizaro reaction
(B) P1 will show cannizaro reaction & P2 will show aldol reaction
(C) Both P1 & P2 will show cannizaro reaction
(D) Both P1 & P2 will show aldol reaction AR0060
Q.9 P2 conc. NaOH
+
products
(ii) H
Select incorrect statement for the above reaction -
(A) It is a redox reaction
(B) It is a disproportion reaction
(C) Two products formed are alcohol & carboxylic acid
(D) It is an intramolecular reaction AR0061
Q.10 Which of the following will give yellow precipitate with NaOH / I2
(A) Ph–CH–Me (B) CI3CHO (C) Me–C–C–OH (D) EtOH AR0062
OH O O
(i)MeMgBr(2eq)
Q.11 Ethylmethanoate ¾¾¾¾¾¾¾¾¾
(ii)H O+
® W +X
E555
F
3 organic product
W ¾¾¾®
CaOCl 2
CHCl 3 + Y
X ¾¾¾®
CaOCl2
CHCl 3 + Z
Y + Z ¾¾¾¾Dry
Distillation
® Organic product(s) + CaCO3
Which of the following organic product can be formed on dry distillation reaction
(I) CH3 – CHO (II) CH3– CO – CH3 (III) CH3 – CH = CH – CH3 (IV) HCHO
(A) I and II only (B) II and III only (C) I, II and IV only (D) II and IV only
AR0063
Q.12 Which of the following compounds(s) give a sweet smelling product having anesthetic use in presence
of Cl2, NaOH, D.
O
O O
(A) (B) CH3 – CH – CH3 (C) CH3 – C – OH (D) Ph – C – CH3
O
I
AR0064
Q.13 Reaction in which product can show positive haloform test :-
(A) CH3MgBr + PhCN Å (B) CH3–CH2MgBr + Ph–COOEt
H 3O (1 : 1) H3O
Å
(C) CH3MgBr + H–C–OMe (D) CH3MgBr + H–C–H AR0065

(1 : 1) NH4Cl NH4Cl
O O
E
Q.14 In which reaction haloform is obtained as one product :-
(A) Electrolysis of ethanolic aqueous solution of NaCl
(B) Isopropanol with bleaching powder
(C) Chlorination of methane in sun light
(D) Chloral is treated with NaOH AR0066
Q.15. Fructose and glucose can be distinguished by : [JEE-MAIN (APRIL)-2019]
(1) Fehling's test (2) Barfoed's test (3) Benedict's test (4) Seliwanoff's test
AR0067
(5) PERKIN CONDENSATION
Perkin Reaction :
Condensation reaction between aromatic aldehyde and aliphatic acid anhydride having at least two
alpha hydrogen in the presence of a base is known as Perkin reaction.
In this reaction, the anion of an acid anhydride adds to an aromatic aldehyde to produce an b aryl
a,b, unsaturated acid. In order to prevent side reactions, the base that is used to make the anion of
the anhydride is usually the sodium salt of the acid corresponding to the anhydride.
O
O O O O
CH3 – C – ONa
Ph – C – H + CH3 – C – O – C – CH3 D
Ph – CH = CH – C – OH + CH3 – COOH
Mechanism :
O
O O O O O O
CH3 – C – O N a
CH3 – C – O – C – CH3 CH2 – C – O – C – CH3 CH2 = C – O – C – CH3
O
Ph – C – H
O CH3
O – C – CH3 O C O O O O
Ph – CH Ph – CH O Ph – C – CH2 – C – O – C – CH3
CH2 – C – O CH2 C H
O O
AC2O
Acetylation
CH3
O C
O
O
Ph – CH O O + CH3 – C – O
CH – C – O – C – CH3
O O
H
O
Ph – CH = CH – C – O – C – CH3
CH3 – C – O
–CH3 – C – OH
O HOH
O O
Ph – CH = CH – C – OH + CH3 – C – OH
E
(i) (CH3CH2CO)2 O/CH3–CH2–COONa,D

Q.1 H3C CHO A AR0068
(ii) H /H2O,D
+
OH
(i) (CH3CO)2 O/CH3COONa,D
Q.2 B D C AR0069
(ii) H OÅ
3
CHO
(i) (CH3CO)2 O/CH3COONa, D

Q.3 D AR0070
(ii) H /H2O,D
+
O CHO
4. In the perkin reaction which one of the following intermediates gives compound (I)
O O
C6H 5 – CH = CH – C – O – C – CH3
(I)
O
O O O O – C – CH3
(A) (B) C6H 5 – CH
C6H 5 – CH – CH2 – C – O – C – CH3
CH2 – COO
O
O
O – C – CH3
O – C – CH 2
C6H 5 – CH O
(C) C6H 5 – CH O (D)
CH2 – C – O – C – CH3
CH2 – C – OH
O
AR0071
Paragraph for Q.no. 5-6
O
H 2/Pd – BaSO 4 (i) 'X'

Ph – C – Cl A Cinnamic acid
(ii) CH3 – C – ONa
O
CrO2Cl2
C 7H 8
(Aromatic compound)
5. Compound ‘A’ on treatment with conc. NaOH followed by acidification can give :
(A) Ph – CH2 – COOH (B) Ph – OH
(C) Ph – COOH (D) Ph – CH2 – OH AR0072
E
6. In the above reaction the reagent “X” can be :
O
Br O C – OEt
(A) (B) CH2
CH2 – C – OEt
C – OEt
O
O O O O
(C) (D)
CH3 – C – O – C – CH3 CH3 – CH – C – O – C – CH – CH3
AR0073
(6) CLAISEN CONDENSATION
Esters undergo SNAE Reaction. when attacked by a Nu– generated by the interaction of a base
(usually base related to the Alkoxy anion of ester) with one of the molecule of ester and this Nu–
attacks on another molecule. The reaction over all is considered as condensation of ester
known as claisen ester condensation.
O O O
(i) RONa
2Me – C – OR Me – C –CH2– C – OR
(ii) Acidification
(b-keto ester)
Mechanism :
O O
O
Å Me–C–OR (rds)
RO Na Me – C – CH2 – COOR
CH3 – C – OR CH2 – COOR
–ROH
OR –R–O
O O O O
Å
Å RO Na
Na Me – C = CH – COOR Me–C–CH=C–OR Me – C – CH2– COOR
Acidification
O O
Me – C – CH2 – C – OR
Some times, when two ester group are p;resent within the molecule then the condensation occurs
intramolecular then cyclization caused thus is known as Dieckmann cyclization or Dieckmann’s
condensation.
(i) EtOK
Q.1 MeCOOEt A AR0074
(ii) Acidification
(i) MeOK
Q.2 EtCOOMe B AR0075
(ii) Acidification
(i) MeOK
Q.3 MeCOOMe + EtCOOMe C AR0076
(ii) Acidification
(i) C2H5ONa
Q.4 C6H5COOC2H5 + CH3COOC2H5 D + D' AR0077
(ii) Acidification
Ethyl benzoate
E
COOC2H5 (i) C2H5ONa
Q.5 + C6H5CH2COOC2H5 E [Cross Product] AR0078
COOC2H5 (ii) Acidification
COOPh (i) PhONa
Q.6 PhOOC F AR0079
(ii) Acidification
CH2CH2COOEt Å
(i) C2H5ONa H3 O
Q.7 C2H5–N G H (Piperidone derivative) AR0080
CH2CH2COOEt (ii) Acidification D
(7) Beayer villiger oxidation
Reaction involve the oxidation of ketone to aster by treatment with per acid such as per acetic
acid, MCPBA, per trifloroacetic acid etc.
• It is a redox reaction
• Cyclic ketones are converted to lectone with ring expention.
O O
RCO3H
R—C—R' R—C—OR' + R—COOH
Mechanism
O O O–H O
H–O–O–C–R
R – C – R' R – C – R' + R – C – O – O
OH O O
R–C–O–O–C–R R–C–O–R
R
Note : In above reaction for shifting of groups migratory apptitude is applicable

Migratory order for above reaction
–H > 3º > 2º > –Ph > 1º > –Me
O
Q.1 MCPBA Major product is :

COOH O O
O O
(A) (B) (C) (D) O
AR0081
O
C—Me O
18
Q.2 Me—C—OOH Major product is :
O O O O
18 18
C—OMe C—OMe O—C—Me O—C—Me
(A) (B) (C) (D)
AR0082
E
ANSWER KEY
(1) CANNIZARO REACTION
Q.1 Ans. (D)
As Cl3C–CHO given chloroform
Q.2 Ans. (C)
In crom cannizzaro reaction move reactive carbonyl compound is oxidised & less in reduced.
Q.3 Ans. (B)
Intramoecular cannizzaro followed by heating effect
Q.4 Ans. (i) CH3OD + HCOONa (ii) DCH2OD + DCOONa
18
Q.5 Ans. (i) PhCH2OD + PhCOONa (ii) Ph – CH 2 OH + PhCOONa
Q.6 Ans. (i) Ph–CH2OH + HCOOK (ii) Ph – CH – C – OK

OH O
O
Q.7 Ans. (i) MeCH2 – CH = C – C – H (ii) Me2CH – CH2OH + Me2CHCOOK
Me
OH OH OH
OH
Q.8 Ans. (i) NO2 + CH3OH (ii) + HCOOK

+ HCOOK
HO HO OH
Q.9 Ans. (B)

O OH
–
A : Ph–C–CH=O B : Ph–C–COO C : Ph–CH–COOH
H OH
Q.10 Ans. (A)®S ; (B)®P ; (C)®Q ; (D)®R
Q.11 Ans. (A)
node06\B0B0-BA\Kota\JEE(Advanced)\Leader\Che\Sheet\Aldol & Similar Name Rxn\Eng\02.Answer_Key.p65
OH
A : Ph–CH–COONa B : PhCOOH C :
Q.12 Ans. (D)
O O O
C–CH3 COOH
HgSO4 I2/NaOH
H2SO4 H
+
–CO2
Q.13 Ans. (B)

O
Q.14 Ans. (C) A : CN B : C–Me
E
Q.15 Ans. (A)

O O O
CH = O HO – C – H HO – C C–O
+ OH RDS
CH = O H–C H–C–H H–C–H
O O O–H
option A is correct.
Q.16 Ans. (B)
CHO COOK
A : CHO
B : CH2OH
Q.17 Ans. (B)

Cron cannizaro reaction
Q.18 Ans. (A)
OH
X : Ph–CH–CH–Ph Y : Ph–C=CH–Ph Z1 : Ph–C–Me Z2 : Ph–CH=O
CH3 OH O
Q.19 Ans. (1)

OH Neutral –ve
FeCl3 (FeCl3 test for
phenolic group)
CH3
Sol. RMgX +ve *Acidic H
Grigard Reaction * –C–
C–Et reagent
O
O NaOH + I2 group
+ve (CHI 3)
Iodoform Reaction
test
due –CH–CH3 group
OH
(2) BENZIL-BENZILIC REARRANGEMENT OR BENZILIC ACID REARRANGEMENT

OH OH
s
1. Ans. CH3 C – COO 2. Ans. C
C6H 5 O O
COOH
(Furilic acid)
OH OH
3. Ans. COOH 4. Ans.
COOH
E
(3) ALDOL CONDENSATION
Q.1 Ans.
OH
Q.1 (I) (A) CH3 – CH2 – CH – CH – C – H (B) CH3 – CH2 – CH = C – C – H
CH3 O CH3 O
O OH Ph
(II) (C) (III) (D) Ph – CH2 – CH – CH – C – H
OH O
O
O
OH
(IV) (E) (F)
CH3 CH3
(V) (G) Ph – C – CH2 – C – Ph (H) Ph – C = CH – C – Ph
OH O O
O O O O
Q.2 Ans. (I) (A) (B) ; (II) (E) (F)

HO OH
Q.3
Ans. Excluding Stereo Including Stereo
OH OH
(I) Ph – CH – CH2 – CHO = 2 , Me – CH – CH2 – CHO = 2

* *
OH OH
* – COCH = 4
(II) CH3 – CH – CH CH3 – CH – CH2 – CHO = 2
3
* *
CH3
OH OH
CH3 – C * – COCH = 4 ,
CH CH3 – CH – CH2 – CO – CH2 = 2
*
3
*
CH3
CH2CH3 CH3
OH OH
CH3 – CH – CH2 – COCH2CH3 = 2 , CH3 – C – CH2 – CHO = 2

* *
CH2CH3 CH2–CH3
E
O
Q.4 Ans. (I) (II) CH3 – C – CH3
O O
O
C–H
Q.5 Ans. (i) (a) (b) C–H (ii) CH – C6H 5
CH2 – CH2 – C – H
O O
O
O
H3C
Q.6 Ans. (i) X = Y = CH3 – C – H
O
O O O
(ii) (iii)
Q.7 Ans. (C)
Intramolecular aldol condensation the 1,4-additon and finally clemmesion reduction.
Q.8 Ans. (D)
Q.9 Ans. (B)
Ozonolysis followed by intramolecular aldol.
Q.10 Ans. (C)
(A) CH3–CH–Cl2CHO (B) CH3CH=CH–CH=O
OH
(C) CH3CH2CH2CH2OH (D) CH3CH2CH2COOH
Q.11 Ans. (A)
Q.12 Ans. (A)
OH
Q
CH3CHO + CH2 – CHO CH3 – CH – CH2 – CHO –H 2O
CH3 – CH = CH – CHO
OH
D CH 2–CH=CH-CHO ]
CH3(CH=CH)3–CHO CH3 – CH = CH – CH – CH2– CH = CH
–H2O
CHO
Q.13 Ans. (A)

P : Q : Me–CH=O R : Me–CH=Ch–CH=O
Q.14 Ans. (1)
Sol. Aldehyde reacts at a faster rate than keton during aldol and stericall less hindered anion will be
O
a better nucleophile so sefl aldol at CH3 – C – H will be the major product.
Q.15 Ans. (4)
E
Q.16 Ans. (4)
O O
Sol. O OH
–
O
C– H C–H + H 2O
O O
H2O
HO O–
H H
(A)
D –H2O
O
(B)
Q.17 Ans. (4)
CH3
CH3 O
NaOH
Sol. OHC
D
Intramolecular
aldol condensation
O
(4) HALOGENATION OF THE a-CARBON OF ALDEHYDES AND KETONES

Q.1 Ans. (1 , 2 , 5 , 7 ,8, 9 , 11)
O O
– – –
Q.2 Ans. (i) CH3–COO + CHI3 ; (ii) O – C –C – O + C H I 3 ; (iii)
–
C O O + C H I3
Q.3 Ans. (A,B,C)
Q.4 Ans. (C)
X : PhCH2CH2OH Y : PhCH2CHO Z : Ph–CH2–CH=C–CHO
Ph
Q.5 Ans. (A)

Q.6 Ans. (A)
O
+
C–C–C–C NaOH
I
CHI3 + CH3CH2COONa H
CH3CH2COOH
2
Q.7 Ans. (B)

OH
O
conc.H3PO4 O3/Zn O
Ph Ph + Ph–C–H
H 2O
(A)
Ketone Aldehyde
(P1) (P2)
E
NO2
(A) Both ketone & aldehyde react with braddy's reagent H2N NH NO2 2, 4 dinitrophenyl hydrazine.
(B) With NaHSO3 only aldehyde give crystalline bisulphite adduct whereas hindered ketone is unable react.
(C) NaHCO3 will not react any of them.
(D) Both P1 & P2 are unable to form idoform with NaOH/I2
Q.8 Ans. (A)
H a Hydrogen
O
O
For aldol aH should be present i.e. H P1 where as P2 Ph C H will give
cannizaro's as there is no. aH in P2.

Q.9 Ans. (D)
O O
conc.NaOH
Ph–C–H +
Ph–C–OH + Ph–CH2–OH
H
The above reaction is intermolecular redox reaction. In which desprotionation is taking place as
a result of which 2 different products are formed from singlet reactant.
Q.10 Ans. (A,B,C,D)
Q.11 Ans. (C)
O
(i) 2MeMgBr
H–C–OEt + MeCH–OH + EtOH
(ii) H3O
CrOCl2
CHCl3 + (MeCOO)2Cl (HCOO)2Cl + CHCl3
O O O
Me–C–H + Me–C–Me + H–C–H
Q.12 Ans. (A,B,D)

O O O O
Cl
Å Å
OH ONa OH ONa
Cl CHCl3+
Cl2 CCl3 ONaÅ
O O
O O
Q.13 Ans. (A,B,C,D)

Q.14 Ans. (A,B,C,D)
Q.15. Ans. (4)
Sol. Seliwanoff's test is used to distinguished aldose and ketose group.
E
(5) PERKIN CONDENSATION
Q.1 Ans. H3C CH = C – COOH

CH 3
OH O O
Q.2 Ans.
CH–CH2–COOH
(B) OH (C)
Q.3 Ans.
O CH=CH–COOH
Q.4 Ans. (A)
Q.5 Ans. (C, D)
Q.6 Ans. (C)
(6) CLAISEN CONDENSATION
O O
Q.1 Ans.
O O
Q.2 Ans. *
CH3
(R / S)
Q.3 Ans. 4 products

Q.4 A ns. C6H5COCH2COOC2H5, CH3COCH2COOC2H5
Ethtl benzolyacetate
Q.5 Ans. C6H5–CHCOOC2H5
COCOOC2H5
Diethyl-a-oxalyphenyl
acetate
O
Q.6 Ans. * C OPh

O
(R / S)
COOEt
Q.7 Ans. (G) C2H5–N O C2H5–N O
1-Ethyl-4-piperiodone
(7) Beayer villiger oxidation
Q.1 Ans.(B)
Q.2. Ans.(D)

Aldol &amp; Similar Name Reactions

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Aldol &amp; Similar Name Reactions

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ALLEN Aldol & Similar Name Reaction 1

ALDOL & SIMILAR NAME REACTIONS

Q.1 Which of following will not undergo Cannizaro reaction

(A) (B) (C) (D) Cl3C–CHO

Product (C) & (D) are :

(A) Ph–CO2H, Ph–OH (B) Ph–CO2–,HCO2–

(C) Ph–CH2OH, H–CO2– (D) Ph–CO2–,CH3OH AR0002

Q.3 (A) (B)

(C) PhCOOH (D) None of these AR0009

Q.10 Match the column :

(A) HCHO + NaOD (conc.) (P) DCOO– + CDH2OH

(B) DCHO + NaOH (conc.) (Q) DCOO– + CD3OH

(C) DCDO + NaOH (conc.) (R) DCOO– + CDH2OD

(D) DCHO + NaOD (conc.) (S) HCOO– + CH3OD AR0010

Q.13 The cannizaro reaction of Ph COCHO forms the product(s)

End product (B) of above reaction is :

(A) + CH3OH (B) + HCOONa

Q.18 Reactant ‘X’ will be :

(2) BENZIL-BENZILIC REARRANGEMENT OR BENZILIC ACID REARRANGEMENT

(3) ALDOL CONDENSATION

H –C – CH2 H –C = CH2 rds H – C – CH2–CH– CH3

CH3–C–CH3 CH3– C = CH – C – CH3

CH3– C = CH2 + CH3 – C – CH3 CH3 – C – CH2 – C – CH3

Q.1 Write the product and mechanism for given reactions.

(II) O Dil NaOH (C) AR0025

(III) C6H5– CH2 – CHO Dil NaOH (D) AR0026

(V) C6H5– C – CH3 Dil NaOH (G) D (H) AR0028

(II) Dil NaOH (E) (F) AR0030

(II) (X) OH AR0038

(A) (B) (C) (D)

Q.9 Product ‘Y’ formed in the given reaction is :

(A) (B) (C) (D)

Q.10 Product ‘D’ is :

(A) CH3–CH2–CH = CH2 (B) CH3–CH2–CH2–CHO

(A) CH3(CH = CH)3CHO (B) CH3CH2CH2(CH = CH)2CHO

(A) Me(CH=CH)3CHO (B) MeCH=CHCHO

Q.16 In the following reactions, products A and B are : [JEE-MAIN (JANUARY)-2019]

R—C—CH2 + OH R—C—CH2 R—C—CH + X

R—C—C + OH R—C—CX2 R—C—CX3

(C) Ph–CH2 – CH = C – CHO (D) Ph–C = CH–CHO AR0056

Paragraph for Q.07 to Q.09

(C) CH3MgBr + H–C–OMe (D) CH3MgBr + H–C–H AR0065

(i) (CH3CH2CO)2 O/CH3–CH2–COONa,D

(i) (CH3CO)2 O/CH3COONa, D

H 2/Pd – BaSO 4 (i) 'X'

Note : In above reaction for shifting of groups migratory apptitude is applicable

Q.1 MCPBA Major product is :

(A) (B) (C) (D) O

Q.6 Ans. (i) Ph–CH2OH + HCOOK (ii) Ph – CH – C – OK

Q.8 Ans. (i) NO2 + CH3OH (ii) + HCOOK

Q.9 Ans. (B)

Q.13 Ans. (B)

Q.15 Ans. (A)

Q.17 Ans. (B)

Q.19 Ans. (1)

(2) BENZIL-BENZILIC REARRANGEMENT OR BENZILIC ACID REARRANGEMENT

Q.2 Ans. (I) (A) (B) ; (II) (E) (F)

(I) Ph – CH – CH2 – CHO = 2 , Me – CH – CH2 – CHO = 2

CH3 – CH – CH2 – COCH2CH3 = 2 , CH3 – C – CH2 – CHO = 2

Q.4 Ans. (I) (II) CH3 – C – CH3

Q.13 Ans. (A)

(4) HALOGENATION OF THE a-CARBON OF ALDEHYDES AND KETONES

Q.5 Ans. (A)

Q.7 Ans. (B)

Aldol & Similar Name Reactions

Aldol & Similar Name Reactions