NAME REACTIONS

(1) HALOGENATION OF THE -CARBON OF ALDEHYDES AND KETONES

Ist Acid-Catalyzed halogenation : - When Br2, Cl2 and I2 is added to an acidic solution of an
aldehyde or a ketone, a halogen replaces one of the -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
Q.1 Identify the compounds which can show iodoform reaction 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
(9) (10) (11) CI3 – CHO
O
Q.2 Complete the following given reaction :
O
O O –
I2 (1 eq.) I2 / O H
(i) Product (ii) Product
OH –(excess)

O O – –
: :

:
I2 / OH

: :
I2 / OH
:
(iii) CH3–C—C–OH Product (iv) Product
OH
Q.3 Select the compound which does not show haloform reaction is/are :

O O O
I
(A) CH3–C—O–Me (B) CH3–C C – CH3 (C) (D) O
O I

Q.4 For the reaction

1. B2H6/THF
PhCH = CH2 (X)
2. H2O2/OH
PCC(CH2Cl2)
–
(Y) OH / (Z)

(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
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
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+

Paragraph for Q.07 to Q.09

OH
conc.H 3PO 4 O3/Zn
A P1 + P2
Ph 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

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

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

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
OH O O

(i)MeMgBr(2eq)
Q.11 Ethylmethanoate (ii)H O W X
3 organic product
CaOCl 2
W CHCl 3 Y
CaOCl2
X CHCl 3 Z
Dry
Y Z Distillation
Organic product(s) + CaCO3
Which of the following organic product
( ) CH3 – CHO ( ) CH3– CO – CH3 ( ) CH3 – CH = CH – CH3 ( ) HCHO
Q.12 Correct option regarding following reaction sequence.
HgSO Ba(OH)2 NaOH
CH3 – C CH H SO 4 P Q I2 R+S
2 4
'X' 6 Ag

T
COOH
(A) T is homologue of 'X' (B) R is sodium salt of
COOH
(C) P can produce S with NaOI (D) R is sodium salt of

Q.13 Which of the following compounds(s) give a sweet smelling product having anesthetic use in presence
of Cl2, NaOH,
O
O O
(A) (B) CH3 – CH – CH3 (C) CH3 – C – OH (D) Ph – C – CH3
O I

Q.14 Reaction in which product can show positive haloform test :-

(A) CH3MgBr + PhCN (B) CH3–CH2MgBr + Ph–COOEt
H 3O (1 : 1) H3O

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

(1 : 1) NH4Cl NH4Cl
O O

Q.15 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
 ( ) ALDOL CONDENSATION
The - hydrogen of carbonyl compounds are acidic due to the fact that the anion (enolate ion) is
stabilized by resonance.

H
OH (base) O
CH2– C – H CH2= C – H CH2– C – H
O O O
3 Hydrogens enolate anion enolate anion

Base catalysed Aldol

In aqueous base, two acetaldehyde molecules react to form -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)

OH / HOH
2CH3CHO CH3 – CH– CH2– CHO CH3– CH = CH – CHO
5°C –H2O
OH
–hydroxy butyraldehyde (Aldol)

Mechanism :

H OH H –C – CH3 O H –O – H

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

O O O
OH OH
–OH H – C – CH–CH– CH3
H – C – CH = CH – CH3 H – C = CH – CH – CH3
OH Aldol
O O 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,
CH3–C–CH3 CH3– C = CH – C – CH3
CH3
( , unsaturated carbonyl compound)
O O–H OH
+
H
CH3–C–CH3 CH3 – C – CH3 CH3 – C = CH2

O–H O–H O–H O–H

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

CH3 –H

O O OH2 O OH
CH3 – C – CH – C – CH3 H CH – C – CH – C – CH
CH3 – C– CH = C – CH3 3 2 3
–H2O
CH3 H CH3 CH3
(Aldol)
Q.1 Write the product and mechanism for given reactions.
(I) CH3– CH2 – C – H (A) (B)
Dil NaOH
O

(II) O Dil NaOH (C) (III) C6H5– CH2 – CHO Dil NaOH (D)

Dil NaOH
(IV) O (E) (F) (V) C6H5– C – CH3 Dil NaOH (G) (H)
O
Q.2 Identify the intramolecular aldol product ?
O O
Dil NaOH (A) (B)
(I) CH3 – C – CH2 – CH2 – C – CH3
O

(II) Dil NaOH (E) (F)

O
Q.3 Find out the total number of possible aldol products (including and excluding stereo products).
NaOH/ HOH
(I) C6H5 – CHO + CH3 – CHO
5°C
(II) CH3 – CH = O + CH3 – CH2 – C – CH3 NaOH/ HOH
5°C
O
Q.4 Identify the structure of substrate ?
O
(I) A Dil. NaOH
A= ?

OH
OH
(II) A Dil.NaOH
CH3– C – CH2 C CH3 A = ?
(2 mole) 5°C
O CH3

Q.5 Complete reaction sequence :

(i) O3(1eq) (i) OH (i) OH

(I) (a) (b) (II) Product
(ii) Zn / H2O (ii) (ii)C6H5CHO
(iii)
O

Q.6 Complete the following reactions :

O OH
O
– CH3 CH–CH3
(I) (X) + (Y) OH
(II) (X) OH
CH3
OH

O
(i) OH
(III) [X]
(ii)

O
–
OH CH3MgBr Zn–Hg
Q.7 A B conc.HCl C ; the product ‘C’ is
heat CuBr
O
O

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

Q.8 Consider following intramolecular aldol condensation reaction :

O
–
OH
X ; X can be :

O O
(A) (B) (C) (D)
O O O O O O
Q.9 Product ‘E’ is :

CH3MgBr H
+ +
O3/Zn –
A B H C D OH E
(Major)
O
OH O
COONa
(A) (B)

O O

(C) (D)

Q.10 Product ‘Y’ formed in the given reaction is :

O3/Zn –
OH
X Y

O O O O

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

OH
Q.11 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

Q.12 CH 3CH = CHCHO OH

aldol
A, A is :

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

(C) CH3(CH2CH2)3CH = CH – CHO (D) None is correct

Q.13 Which one of the following will undergo aldol reaction most readily.

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

NaOH, NaOH,
Q.14 MeCHO A B ; B is :

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

(C) Me(CH=CH)2–CHO (D) Me –(CH=CH–) 4CHO
 ( ) 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
( -keto ester)
Mechanism :
O O
O
RO Na Me–C–OR (rds)
CH3 – C – OR CH2 – COOR Me – C – CH2 – COOR
–ROH
OR –R–O
O O O O
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
intramolecule then cyclization caused thus is known as Dieckmann cyclization or Dieckmann’s
condensation.
(i) EtOK (i) MeOK
Q.1 MeCOOEt A Q.2 EtCOOMe B
(ii) Acidification (ii) Acidification

(i) MeOK
Q.3 MeCOOMe + EtCOOMe C
(ii) Acidification

(i) C2H5ONa
Q.4 C6H5COOC2H5 + CH3COOC2H5 D + D'
(ii) Acidification

COOC2H5 (i) C2H5ONa

Q.5 + C6H5CH2COOC2H5 E [Cross Product]
COOC2H5 (ii) Acidification

COOPh (i) PhONa

Q.6 PhOOC F
(ii) Acidification

CH2CH2COOEt
(i) C2H5ONa H3 O
Q.7 C2H5–N G H (Piperidone derivative)
CH2CH2COOEt (ii) Acidification
 ( ) PERKIN CONDENSATION
In Perkin reaction, condensation has been effected between aromatic aldehydes and aliphatic acid
anhydrides in the presence of sodium or potassium salt of corresponding acid of that anhydride,
to yield , - unsaturated aromatic acids.

(i) CH3COONa,
C6H5–CHO+CH –C–O–C–CH3 +
C6H5–CH=CH–COOH+CH3COOH
(ii) H /H2O,
O O
–
CH3–C–O

Mech. CH3–C–O–C–CH3 O CH2–C–O–C–CH 3

–CH3–COOH
O O O O
Ph–C–H
CH3–C–OH O

Ph–CH–CH2–C–O–C–CH3 O Ph–CH–CH2–C–O–C–CH3
––
OH O O O O O

–CH3–C–OH H+/H2O
Ph–CH–CH2–C–OH H2O Ph–CH=CH–COOH
O
OH O
-Hydroxy acid

(i) (CH3CH2CO)2 O/CH3–CH2–COONa,

Q.1 H3C CHO +
A
(ii) H /H2O,

OH
(i) (CH3CO)2 O/CH3COONa,
Q.2 B C
(ii) H3O
CHO

(i) (CH3CO)2 O/CH3COONa,

Q.3 +
D
(ii) H /H2O,
O CHO

O CH–COOH
(i) MeCOONa
C C
(ii) H3O,
Q.4 O+F O
C C
O O
Phthalylacetic acid
 ( ) KNOEVENAGEL REACTION
Reaction of active methylene group with aldehyde & Ketones is known as knoevenagel reaction.

Z
Pyridine (i) H2O/H
RCHO+CH2 RCH = C (COOR)2 R –CH=CH–COOH
or piperidine (ii) –CO2
Z'
Z can be
O
CHO, COOMe, CN, NO2, C–R, SOR, SO2R, SO2 OR etc.

Mechanism :
••
R3N + H2C(COOR)2 R3NH+HC(COOR)2

O O OH
R3NH
R–C + CH(COOR)2 R–C–CH(COOR)2 R–C–CH(COOR)2 –H2O
–R3N··
H H H

(i) H2O / H
R–CH = C(COOR)2 R– CH = CHCOOH

High reactivity of the methylene group of the active methylene compound prevents self-
condensation of the aldehyde.

Q.1 CH3CHO + H2C(COOR)2 A Q.2 C6H5CHO + H2C(COOR)2 B

O
O
C–Me
Q.3 HOOC – CHO + H2C(COOR)2 C Q.4 Ph – C – H + CH2 D
Glyoxalic acid C– OEt
O

O O
Me CN
Q.5 Ph – C – H + CH3–NO2 E Q.6 C=O + CH2 F
Me COOR CH3COOH,

O2N Me
O
CN
Q.7 CH2 + Ph – C – H NaOEt G Q.8 NO2 + Ph–NO
NO2 –
O 2N OH /

H
 ( ) MICHAEL ADDITION
Michael Addition : unsaturated carbonyl compound undergo michael reaction with
compounds having active methylene. Many different nuclephile can add to unsaturated
carbonyl compound. When the nucleophile is an enolate the addition reaction has a special name
MICHAEL REACTON.
Mechanism :

O
O O O O R – CH = CH – C – R
OH (base)
R – C – CH2– C – R R – C – CH – C – R
–H2O , unsaturated
carbonyl compound

O O
R–C O R–C O
HOH
CH – CH – CH2– C – R CH – CH – CH = C – R
–OH
R–C R R–C R
O O

O O O
Q.1 CH3 – C – CH2 – C – CH3 + CH2 = CH – CH OH ?
–H O 2

O
COOEt
CH3CH2O
Q.2 CH3CH = CH – C – CH3+ CH2 ?
COOEt

O O O
Q.3 CH3CH = CH – C – NH2 + CH3 – CH2 – C – CH2 – C – O – CH3 CH3O ?

O O
Q.4 CH3CH2CH = CH – C – OCH3 + CH3 – C – CH2 – C N CH3O ?

O COOR
EtONa
CH – CH3+CH2 ?
(ii) H3 O+ ,
Q.5 COOR
 ( ) REFORMATSKY REACTION
halo esters when treated with Zn in gives organometallic halo ester which provides the
attacking Nu– for the another reactant, which is a carbonyl compound. When Nu– attacks on
carbonyl compound it gives an intermediate which upon acidic hydrolysis followed by heating,
results in formation of unsaturated acid. The overall reaction is known as Reformatsky
reaction.
O
Ph – CHO + CH2– C– OEt Zn
Ph – CH = CH – COOH
H3O
Br
Benzaldehyde Cinnamic acid
Mechanism :

O O ZnBr
CH2 – COOEt Zn CH2–COOEt Ph–CH Ph–CH–CH2–COOEt
Br ZnBr H3 O
OH
Br
EtOH + Zn + Ph–CH–CH2–COOH
OH /–H2O
Ph–CH=CH–COOH
Cinnamic acid

Q.1 C6H5COCH3 + BrCH 2COOEt 1. Zn A

2. H3O

O (i) Zn
Q.2 (ii) PhCHO
OEt B
(iii) H3O
Br

Ph O OEt
Q.3 + CH3CHO (i) Zn / Ether C
Br (ii) H 3O

O
(i)
Q.4 + BrCH2COOEt 1. Zn D (ii) Se / E
2. H3O
-Tetralone
 Br
(i)
Q.5 EtO – C – CH – CH2CH2CH2–CH2– CHO (i) Zn/Et2O F (ii) Se / G
(ii) H3O
O

COOPh
Br
(i) Zn/Et2O
Q.6 H
(ii) CH2O
(iii)H3O

Q.7 O (1)Zn + BrCHCH = CH – COOCH3

I
(2) H3O (3) – H2O
-lonone

Matrix Match :
Q.8 Match the column-
Column - I Column - II
COOEt (1)EtONa
(A) Ph–CHO + CH2 (2) H3O / (P) Perkin’s reaction.
COOEt
(1) Zn
(B) Ph–CHO + CH2–COOCH3 (2) H3O /
(Q) Reformatskii reaction.
Br
(C) Ph–CHO + CH3COOCOCH3 (1)CH3COONa /
(R) Product is a carboxylic acid with aromatic ring
(2)H3O /

OO within the same molecule.

(D) Ph–C–C–Ph + NaOH (2) H
(S) Double bond equivalent of the product formed

is less than or equal to 8.

(T) The major product cannot show optical isomerism

 ( ) CANNIZARO REACTION

This reaction is given by aldehyde having no - hydrogen in the presence of conc.

NaOH/ or KOH/ .
O O
H – C – H KOH H – C – O K + CH3OH
+

Mechanism :
O O O O O
HO r.d.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 milecule of the aldehyde to form
acid and an alkoxide ion. Subsequently, the alkoxide ion acquires a proton from the solvent.
O O O
OH
H – C – H OH H–C–H H–C–H
(I)
OH O

O H O H
H–C–H + C=O H – C + H–C – O
(I)
O H O H

H2O
HCH2O HCH2OH + OH
From solvent

Q.1 Which of following will not undergo Cannizaro reaction

CHO
CHO
(A) (B) (C) (D) Cl3C–CHO
O CHO Cl

O
2 H HCHO
Q.2 Ph – C – Cl Pd –BaSO Ph – CHO (C) + (D)
4

Product (C) & (D) are :

(A) Ph–CO2H, Ph–OH (B) Ph–CO2–,HCO2–

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

 CHO +
conc.NaOH (A) H (B)
Q.3
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

Q.4 (i) HCHO NaOD (ii) DCHO NaOD

18

Q.5 (i) Ph–CHO OD / DOD (ii) Ph–CHO OH

KOH KOH
Q.6 (i) Ph – CHO + HCHO (ii) Ph – C – C – H
O O

Q.7 (i) MeCH2 – CHO KOH (ii) Me2CH – CHO conc.KOH

Q.8 (i) Me–NO2 + HCHO KOH (ii) MeCHO – HCHO KOH

(excess) (excess)

– – +
Aq.OH Conc. OH H
Q.9 PhCOCHBr2 A B ; the compound ‘C’ is :
(A) PhCH(OH)CHO (B) PhCH(OH)COOH

(C) PhCOOH (D) None of these

Q.10 Match the column :

Column - I Column - II

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

(B) DCHO + NaOH (conc.) (Q) DCOO– + CD2OH

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

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

 O O
NaOH KMnO4
Q.11 C—C—H (conc.) A B NaOH/CaO C ; Product ‘C’ is :

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

O
C CH
1% HgSO 4 / Dil.H 2 SO 4 I 2 / NaOH
Q.12 H
X ; X is :

O O O O
COOH COCH3 CH2CHO
(A) (B) (C) (D)

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)

O
P2O5 ( i) CH 3MgBr (i) I 2 Ca(OH) 2
Q.14 C – NH2 A (ii)H 3O
B (ii) C ;

Product is:
O O
(A) C – NH2 (B) C – OH (C) C (D) C – CH2CH3
O O

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

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

Q.17 The major product pair of the following reaction will be :

CHO

HCHO Products
NaOH (aq)

COONa CH2OH

(A) + CH 3OH (B) + HCOONa

CH2OH COONa
CH3OH
(C) + (D) +
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
CH3
 ( ) 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 :

O HO O O
Ph – C – C – Ph OH Ph – C – C – Ph HO – C – C – Ph
O O O Ph
OH OH
HO – C – C – Ph H O – C – C – Ph
O Ph O Ph
(Benzilic acid)

O O
Q.1 CH3 C – C – C6H5 OH

O O
Q.2 C–C 1. NaOH
O (Furil) O 2. H

O OH
Fenton (i) OH
Q.3 C6H5 – C – CH – C6H5 reagent A B.
(ii) HOH / H

O
(i) NaOH
Q.4
(ii) H3O
O

O
(i) NaOH
Q.5 (ii) H3O
O

KCN Fenton 's NaOH

Q.6 Ph–CHO P1 Reagent P2 (2)H
P3
 ( ) TISCHENKO REACTION /CONDENSATION
(1) This reaction takes place between two molecules of aldehydes.
(2) Reaction is catalysed by aluminimum ethoxide.
(3) This is a two-step reaction, i.e., redox reaction followed by ester formation. Thus this
reaction is extension of Cannizzaro reaction.
O
(C2H 5O)3Al
R – CHO + R – CHO R – CH2 – O – C – R

Mechanism :

H H

R–C = O + Al(OC2H5)3 R–C = O–Al(OC2H5)3 R–CH=O R–CH = O–C–O–Al(OC2H 5) 3

H R
Hydride ion
O transfer

R–CH2–O–C–R + Al(OC2H5)3
Ester

(C2H 5O)3Al
Q.1 CH3 – CHO ?

(C2H 5O)3Al
Q.2 CH3 – CH2 – CHO ?

Q.3 OHC – CH2 – CH2 – CH2 – CHO (C2H5 O)3Al ?

(C2H5O)3Al
Q.4 CH3CHO + CH3–CH2–CHO ?
 (11) COREY HOUSE SYNTHESIS

Reaction of Gilman’s reagent with alkyl halide gives alkane as one of the product which is known
as Corey House synthesis,

[R2Cu] Li R' – X
R' – R + RCu + LiX
Gilman reagent
(Lithium dialkyl cuprate)

To obtained good yield of alkane, the alkyl halide R’ – X must be either a methyl halide,
a primary alkyl halide, or a secondary cycloalkyl halide. (Best CH3X, if possible)

Preparation of Gilman reagent:

2Li Cu–X,
R–X –LiX
R Li –LiX
[R2Cu] Li
(2 mole) Gilman reagent
(alkylLithium)

Complete the following reaction sequence :

Li CH3CH2CH2CH2CH2I
Q.1 (A) Cul (B) (C)
Et2O

CH3CH2CH2CH2Br Li (D) Cul CH3CH2CH2CH2CH2Br

(E) (F)
Et2O

Cl2 Li
Q.2 (A) (B) ; (B) (C)
h

CuCl CH3Cl
(C) (D) ; (D) CH3– CH– CH2 – CH3

CH3

(i) Li CH3–Cl
Q.3 CH3 – CH2 – Br (A) (B)
(ii) CuBr,

(i) Li CH –CH2–Br
Q.4 I (ii) CuI (A) 3 (B)
 CH3–CH–CH3
Cl (C)

Q.5 CH3 – CH2 – Br Li (A) CuBr (B) O

(i)
(D)
(ii) H

Q.6 How can you prepare following compounds using corey house synthesis.

(i) CH3 (ii) CH2 = CH – CH2 – CH3 (iii) CH2

14
Q.7 (CH3 )2 CuLi CH 2 CH – C H 2 – Cl

Q.8 (CH3)2CuLi + CH3 – CH – CH2 (A) H (B)

Q.9 (CH3)2CuLi + (A) H (B)

Q.10 (CH3)2CuLi + CH2 = CH – C – H (A) H (B)

Q.11 Which of the combination of Gilman’s reagent & alkylhalide will be most suitable for preparation
of following compounds.

CH3 CH3
(i) CH3 – CH2 – CH3 (ii) CH3 – C – CH3 (iii) CH3 – C – Ph
CH3 CH3

CH3 CH3
(iv) (v)

Q.12 Identify the product of following reactions :

CH2 CH3
–
(a) CH3 – C – CH2 – Cl + (CH3)2CuLi (b) (CH3)2CuLi + CH2 = C – CH – CH – CH 3
14 O
 (12) BENZOIN CONDENSATION

The Benzoin Condensation is a coupling reaction between two aldehyades that allows the preparation
of -hydroxyketones.

O O
|| ||
–
H CN |
H2O/EtOH OH 92%
Benzoin

Mechanism of Benzoin Condensation

–
O O OH
|| | CN | CN
CN H 2O
H H H
–
OH

A strong base is now able to deprotonate at the former carbonyl C-atom.

OH OH OH OH
| CN – |– – | |
OH CN
H CN CN
H 2O
–

A second equivalent of aldehyde reacts with this carbanion, elimination of the catalyst regenerates
the carbonyl compound at the end of the reaction

OH OH OH
| H2O
CN H
CN OH CN
O OH
O

H –
O O O
– – ||
OH CN
CN H2O CN
OH OH OH
Q.1 (1 , 2 , 5 , 7 , 9 , 11)
– O O
COO
Q.2 (i) ; (ii) CH3–COO– + CHI3 ; (iii) O–C–C–O + CHI3 ; (iv) COO + CHI3

Q.3

Q.4
X : PhCH2CH2OH Y : PhCH2CHO Z : Ph–CH2–CH=C–CHO
Q.5 Ph

Q.6
O
+
C–C–C–C NaOH
I
CHI3 + CH3CH2COONa H
CH3CH2COOH
2

Q.7 (B)
OH
O
conc.H3PO4 O3/Zn O
Ph Ph + Ph–C–H
H 2O
(A)
Ketone Aldehyde
(P1) (P2)
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 (A) H Hydrogen

O
O
For aldol H should be present i.e. H P1 where as P2 Ph C H will give
cannizaro's as there is no. H in P2.
Q.9 (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 (A,B,C,D)
Q.11
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
O O O COONa
P : CH3–C–CH3 Q : CH3–C=CH–C–CH3 R: S : CHI3 T : HC CH

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

Q.14 (A,B,C,D)
Q.15

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 (I) (A) (B) (II) (E) (F)

HO OH

Q.3
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 – CH3 = 2
3
* *
CH2CH3 CH3

OH OH

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

* *
CH2CH3 CH2–CH3
O

Q.4 (I) (II) CH3 – C – CH3

O O

O
C–H
Q.5 (i) (a) (b) C–H (ii) CH – C6H 5
CH2 – CH2 – C – H
O O
O
O
H3C
Q.6 (i) X = Y = CH3 – C – H
O
O O O
(ii) (iii)
Q.7 (C)
Intramolecular aldol condensation the 1,4-additon and finally clemmesion reduction.

Q.8 (D)
Q.9
Me OMgBr Me OH
(A) Ph–C=CH–CH–CH3 (B) Ph–C=CH–CH–Me
Me O
(C) Ph–C=CH–CH–CH2 (D) Ph–C–Me are of the product

Q.10
Ozonolysis followed by intramolecular aldol.
Q.11
(A) CH3–CH–Cl2CHO (B) CH3CH=CH–CH=O
OH
(C) CH3CH2CH2CH2OH (D) CH3CH2CH2COOH
Q.12 (A)
Q.13 (A)
Q.14 OH
CH3CHO + CH2 – CHO CH3 – CH – CH2 – CHO CH3 – CH = CH – CHO
–H 2O
OH
CH2–CH=CH-CHO
CH3(CH=CH)3–CHO CH3 – CH = CH – CH – CH2– CH = CH
–H 2O
CHO

O O O O
Q.1 Q.2 *

CH3
(R / S)

Q.3 4 products Q.4 C6H5COCH2COOC2H5, CH3COCH2COOC2H5

Ethtl benzolyacetate

Q.5 C6H5–CHCOOC2H5 Q.6 * C OPh

O
COCOOC2H5 (R / S)
Diethyl- -oxalyphenyl
acetate

COOEt
Q.7 (G) C2H5–N O C2H5–N O

1-Ethyl-4-piperiodone
 OH O O
Q.1 H3C CH = C – COOH Q.2
CH 3 CH–CH2–COOH
(B) OH (C)

Q.3
O CH=CH–COOH Q.4 CH3COOCOCH3

Q.1 CH3 – CH = CH – COOH Q.2 C6H5 – CH=CH – COOH

Cinnamic acid Cinnamic acid

O
C – Me
Q.3 HOOC – CH = CH – COOH Q.4 Ph – CH = C
C – OEt
O

Me CN
Q.5 Ph – CH = CH – NO2 Q.6 C=C
Me COOR

NC NO2
Q.7 C = CH – Ph
O2N Q.8 O2N CH3 + O = N–Ph
–
OH /
NO2

NO2

O2N CH = N–Ph

NO2

O
CH2 – CH2 – CH O
Q.1 CH3 – C – CH – C – CH 3 Q.2 CH3–CH–CH2–C–CH3
O O
O
CH(–C–OCH2CH3)2
 O O
Q.3 CH3–CH–CH2–C–NH2 Q.4 CH3–CH2–CH–CH2–C–O–CH3
O O
CH3–CH2–C–CH–C–O–CH3 CH3–C–CH–C N
O
O
CH–CH2–COOH
Q.5 CH3

Q.1 C6H5–C=CH–COOH Q.2 Ph – CH = C – COOH

CH3 CH3
(E/Z) (E/Z)

CH–CH3 HO CH 2COOH CH2–COOH

Q.3 Ph
OH
Q.4 (D) ,(E)
O
-Naphthylacetic acid
COOH
COOH COOH CH 2OH
OH
Q.5 (F) (G) Q.6

COOH Q.
Q.7 (I) ,

Q.1
As Cl3C–CHO given chloroform
Q.2
In cro cannizzaro reaction move reactive carbonyl compound is oxidised & less in reduced.

Q.3
Intramo ecular cannizzaro followed by heating effect
Q.4 (i) CH OD + HCOONa (ii) DCH2OD + DCOONa
3

18
Q.5 (i) PhCH2OD + PhCOONa (ii) Ph – CH 2 OH + PhCOONa

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

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

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

+ HCOOK
HO HO OH
Q.9
O OH
–
A : Ph–C–CH=O B : Ph–C–COO C : Ph–CH–COOH
H OH
Q.10 (A) S ; (B) P ; (C) Q ; (D) R
Q.11
OH
A : B : PhCOOH C :
Ph–CH–COONa

Q.12 O O
O O
C–CH3 COOH
HgSO4 I2/NaOH
H2SO4 H
+
–CO2

Q.13 (B)
Q.14
O
A : CN B : C–Me

Q.15 (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 (B)

CHO COOK

A : B :
CHO CH2OH
Q.17
Cro cannizaro reaction
Q.18
OH
Ph–CH–CH–Ph Ph–C=CH–Ph Ph–C–Me
X: Y : Z1 : Z2 : Ph–CH=O
CH3 OH O

OH OH
Q.1 CH3 C – COO Q.2 C
C6H 5 O O
COOH
(Furilic acid)

O O OH OH
Q.3 (A) Ph – C – C – Ph (B) Ph – C – COOH Q.4 COOH

Ph

OH
Q.5
COOH

O OH O O OH
Q.6 (P1) Ph – C – CH – Ph (P2) Ph – C– C – Ph (P3) Ph – C – COOH
Ph

O
O O
O
Q.1 CH –C–O–C H Q.2 CH3–CH2–C–O–CH2–CH2–CH3 Q.3 Q.4 4 products
3 2 5

Q.1 (A) CH Li, (B) (CH ) CuLi, (C) CH –CH CH CH CH CH , (D) CH CH CH CH Li,
3 3 2 3 2 2 2 2 3 3 2 2 2

(E) (CH3CH2CH2CH2)2CuLi, (F) CH3CH2CH2CH2 – CH2CH2CH2CH2CH3

Q.2 (A) CH3 – CH – CH2 (B) CH3 – CH – CH2 – Cl

CH3 CH3

(C) CH3 – CH – CH2 Li (D) CH3–CH–CH2 CuLi

CH3
CH3 3
Q.3 (A) [CH3CH2]2 CuLi (B) CH3 – CH2 – CH3

Q.4 (A) CuLi (B) CH2–CH3

2
O
Et
Q.5 (A) CH3 – CH2 Li (B) [CH3CH2]2 CuLi (C) CH3 – CH – CH3 (D)
Et
Q.6 (i) [Ph]2CuLi CH3–Cl Ph–CH3

(ii) CH3–Cl
CH2–CH–CH2–CH3

Ph–CH2–Cl
(iii) [Ph]2CuLi Ph–CH2–Ph

14
Q.7 CH3 – CH 2 – CH = CH 2

Q.8

Q.9 (A) CH3 – CH – CH2 – CH3 (B) CH3 – CH – CH2 – CH3

O Li OH
Q.10 (A) CH3 – CH2 – CH = C – H (B) CH3 – CH2 – CH2 – C – H
OLi O

Q.11 (i) [CH3 – CH2]2 CuLi + CH3 – Cl (ii) [Me3C]2 CuLi + CH3 – Cl

Ph
(iii) Me C– CuLi + Me–Cl (iv) CuLi + Me–Cl (v) CuLi + Me–Cl
Me 2 2 2

CH3
Q.12 (a) CH3 – C – CH2 – CH3 (b) CH3 – CH2 – C = CH – CH – CH3
CH 2
OLi
14