Aldol - Similar Name Reaction PDF

ENTHUSE
IIT CHEMISTRY
ORGANIC CHEMISTRY
ALDOL AND SIMILAR NAME REACTION
H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-2423333
ORGANIC CHEMISTRY
NAME REACTIONS
(1) 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
H.O. 92, Rajeev Gandhi Nagar , Kota (Raj.) Mob. 97831-97831, 70732-22177, Ph. 0744-24-23333 1
www. nucleuseducation.in
Aldol & Similar Name Reaction
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) Pyruvic acid (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 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
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 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 is major organic product
(A) CH3 – CHO (B) CH3– CO – CH3 (C) CH3 – CH = CH – CH3 (D) 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, D.
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 Å (B) CH3–CH2MgBr + Ph–COOEt
H 3O (1 : 1) H3O
Å
(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
(2) 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)
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–hydroxy butyraldehyde (Aldol)
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 CH3 – 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
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) D (B)
Dil NaOH
O
(II) O Dil NaOH (C) (III) C6H5– CH2 – CHO Dil NaOH (D)
Dil NaOH D D
(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) D (B)
(I) CH3 – C – CH2 – CH2 – C – CH3
O
(II) Dil NaOH (E) (F)

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
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) D (ii)C6H5CHO
(iii) D
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)D
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
-
D
Q.12 CH 3CH = 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
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
(3) 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
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 Å
(i) C2H5ONa H3 O
Q.7 C2H5–N G H (Piperidone derivative)
CH2CH2COOEt (ii) Acidification D
(4) 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 a, b - unsaturated aromatic acids.
(i) CH3COONa,D
C6H5–CHO+CH –C–O–C–CH3 C6H5–CH=CH–COOH+CH3COOH
(ii) H /H2O,D
+
O O
–
CH3–C–O
Mech. D
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 D
Ph–CH–CH2–C–OH H2O Ph–CH=CH–COOH
O
OH O
b-Hydroxy acid
(i) (CH3CH2CO)2 O/CH3–CH2–COONa,D

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

Q.3 D
(ii) H /H2O,D
+
O CHO
O CH–COOH
(i) MeCOONa
C Å C
(ii) H3O, D
Q.4 O+F O
C C
O O
Phthalylacetic acid
(5) KNOEVENAGEL REACTION
Reaction of active methylene group with aldehyde & Ketones is known as knoevenagel reaction.
Z Å
Pyridine (i) H2O/H
RCHO+CH2 RCH = C (COOR)2 R –CH=CH–COOH
or piperidine (ii) D,–CO2
Z'
Z can be
O
CHO, COOMe, CN, NO2, C–R, SOR, SO2R, SO2 OR etc.
Mechanism :
•• Å
R3N + H2C(COOR)2 R3NH+HC(COOR)2
O O OH
Å
R3NH
R–C + CH(COOR)2 R–C–CH(COOR)2 R–C–CH(COOR)2 –H2O
–R3N··
H H H
Å
(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 Å A Q.2 C6H5CHO + H2C(COOR)2 Å B
O
O
C–Me
Q.3 HOOC – CHO + H2C(COOR)2 Å 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,D
O2N Me
O
CN
Q.7 CH2 + Ph – C – H NaOEt
D G Q.8 NO2 + Ph–NO
NO2 –
O 2N OH /
(6) MICHAEL ADDITION

Michael Addition : a-b unsaturated carbonyl compound undergo michael reaction with
compounds having active methylene. Many different nuclephile can add to a-b unsaturated
carbonyl compound. When the nucleophile is an enolate the addition reaction has a special name
MICHAEL REACTON.
Mechanism :
O
O O s O O R – CH = CH
a
–C–R
OH (base) b
R – C – CH2– C – R R – C – CH – C – R
–H2O s a, b unsaturated
carbonyl compound
O O
s
R–C O R–C O
HOH
CH – CH – CH2– C – R s CH – CH – CH = C – R
–OH
R–C R R–C R
O O
O O O
s
Q.1 CH3 – C – CH2 – C – CH3 + CH2 = CH – CH OH ?
–H O 2
O
COOEt s
CH3CH2O
Q.2 CH3CH = CH – C – CH3+ CH2 ?
COOEt
O O O
s
Q.3 CH3CH = CH – C – NH2 + CH3 – CH2 – C – CH2 – C – O – CH3 CH3O ?
O O
s
Q.4 CH3CH2CH = CH – C – OCH3 + CH3 – C – CH2 – C º N CH3O ?
O COOR s
EtONar
CH – CH3+CH2 ?
(ii) H3 O+,D
Q.5 COOR
(7) REFORMATSKY REACTION

a-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 a, b- unsaturated acid. The overall reaction is known as Reformatsky
reaction.
O
Ph – CHO + CH2– C– OEt Zn
Å Ph – CH = CH – COOH
H3O /D
Br
Benzaldehyde Cinnamic acid
Mechanism :
Å
O O ZnBr
CH2 – COOEt Zn CH2–COOEt Ph–CH Ph–CH–CH2–COOEt
Br ZnBr Å
H3 O
OH
Br
EtOH + Zn + Ph–CH–CH2–COOH
OH D/–H2O
Ph–CH=CH–COOH
Cinnamic acid
Q.1 C6H5COCH3 + BrCH 2COOEt 1. Zn A

2. H3O ,D
Å
O (i) Zn
Q.2 (ii) PhCHO
OEt Å B
(iii) H3O ,D
Br
Ph O OEt
Q.3 + CH3CHO (i) Zn / Ether
Å C
Br (ii) H 3O ,D
O
(i)
Q.4 + BrCH2COOEt 1. Zn Å D (ii) Se / E
2. H3O
a-Tetralone
Br
(i)
Q.5 EtO – C – CH – CH2CH2CH2–CH2– CHO (i) Zn/EtÅ2O F G
(ii) H3O (ii) Se /
O
COOPh
Br
(i) Zn/Et2O
Q.6 H
(ii) CH2O
(iii)H3O ,D
Å
Q.7 O (1)Zn + BrCHCH = CH – COOCH3

Å
I
(2) H3O (3) D, – H2O
b-lonone
Matrix Match :
Q.8 Match the column-
Column - I Column - II
COOEt
(A) Ph–CHO + CH2 ¾¾¾¾
(1)EtONa
(2) H OÅ / D
® (P) Perkin’s reaction.
COOEt 3
(B) Ph–CHO + CH2–COOCH¾¾¾¾ ® (1) Zn

3
(2) H OÅ / D
(Q) Reformatskii reaction.
3
Br
(1)CH3COONa / D
(C) Ph–CHO + CH3COOCOCH3¾¾¾¾¾¾ Å
® (R) Product is a carboxylic acid with aromatic ring
(2)H3O / D
OO within the same molecule.

(D) Ph–C–C–Ph + NaOH¾¾¾
(2) HÅ
® (S) Double bond equivalent of the product formed
is less than or equal to 8.
(T) The major product cannot show optical isomerism
(8) 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
s r.d.s. s
HO 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 Os s Os
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
(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 D,KOH
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 D
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

D
(ii) DCHO NaOD
D
s 18
s
OH
Q.5 (i) Ph–CHO OD D/ DOD (ii) Ph–CHO D
KOH KOH
Q.6 (i) Ph – CHO + HCHO D (ii) Ph – C – C – H D
O O
Q.7 (i) MeCH2 – CHO KOH

D
(ii) Me2CH – CHO conc.KOH
D
Q.8 (i) Me–NO2 + HCHO KOH (ii) MeCHO – HCHO KOH

(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
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
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)
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) I 2 + Ca(OH) 2
Q.14 C – NH2 A ¾¾¾¾¾
(ii)H O
® B ¾¾¾¾¾
( i) CH 3MgBr
+
(ii) D
¾
®C ;
3
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) + CH3OH (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
(9) 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 – C6H5 OH
O O
Q.2 C–C 1. NaOH
r
O (Furil) O 2. H
O OH
s
(i) OH
Fenton
Q.3 C6H5 – C – CH – C6H5 reagent A r B.
(ii) HOH / H
O
(i) NaOH
Q.4 r
(ii) H3O
O
O
(i) NaOH
Q.5 (ii) H3O
r
O
® P1 ¾¾¾ ¾ ® P2 ¾¾¾
Fenton 's
Q.6 Ph–CHO ¾¾¾
KCN
D Reagent
NaOH
(2)H +
® P3
(10) 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 D
R – CH2 – O – C – R
Mechanism :
H H
gg r s gg r gg s
R–C = gOg + 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 ?
D
(C2H 5O)3Al
Q.2 CH3 – CH2 – CHO ?
D
Q.3 OHC – CH2 – CH2 – CH2 – CHO (C2H5 O)3Al ?

D
(C2H5O)3Al
Q.4 CH3CHO + CH3–CH2–CHO D ?
(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,
s r
[R2Cu] Li R' – X R' – R + RCu + LiX
D
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,D 1 Å
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 D D
CH3CH2CH2CH2Br Li (D) Cul CH3CH2CH2CH2CH2Br

(E) (F)
Et2O D D
Cl2 Li
Q.2 (A) (B) ; (B) (C)
hu
CuCl CH3Cl
(C) (D) ; (D) CH3– CH– CH2 – CH3
D D
CH3
(i) Li CH3–Cl
Q.3 CH3 – CH2 – Br (A) (B)
(ii) CuBr, D D
(i) Li CH –CH –Br

Q.4 I (ii) CuI (A) 3 D 2 (B)
D
CH3–CH–CH3
Cl (C)
Q.5 CH3 – CH2 – Br Li (A) CuBr (B) O

D
(i)
(D)
(ii) Hr
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 ®
r
Q.8 (CH3)2CuLi + CH3 – CH – CH2 (A) H (B)
O
r
Q.9 (CH3)2CuLi + (A) H (B)
r
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
–d
(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 a-hydroxyketones.
O O
|| ||
–
H CN |
H2O/EtOH OH 92%
Benzoin
Mechanism of Benzoin Condensation
–
O O OH
|| 1 | 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
1 CN H
CN OH CN
O1 OH
O
H –
O O O
– – ||
OH CN
CN H2O CN
OH OH OH
ORGANIC CHEMISTRY
ANSWER KEY
(1) HALOGENATION OF THE a-CARBON OF ALDEHYDES AND KETONES

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 (A,B)
Q.4 (C)
X : PhCH2CH2OH Y : PhCH2CHO Z : Ph–CH2–CH=C–CHO
Q.5 (A) Ph
Q.6 (A)
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

a 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 (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)
H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831, 70732-22177, 0744-2423333 24
ORGANIC CHEMISTRY
Q.11 (A)
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 (A,B,C)
O O O COONa
P : CH3–C–CH3 Q : CH3–C=CH–C–CH3 R: S : CHI3 T : HCºCH
Q.13 (A,B,D)
O O O O
Cl
Å Å
OH ONa OH ONa
Cl CHCl3+
Cl2 CCl3 ONaÅ
O O
O O
Q.14 (A,B,C,D)
Q.15 (A,B,C,D)
(2) ALDOL CONDENSATION
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
ORGANIC CHEMISTRY
O O O O
Q.2 (I) (A) (B) ; (II) (E) (F)

HO OH
Q.3 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 – 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
q O
O O O
(ii) (iii)
Q.7 (C)
Intramolecular aldol condensation the 1,4-additon and finally clemmesion reduction.
Q.8 (D)
ORGANIC CHEMISTRY
Q.9 (D)
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 (B)
Ozonolysis followed by intramolecular aldol.
Q.11 (C)
(A) CH3–CH–Cl2CHO (B) CH3CH=CH–CH=O
OH
(C) CH3CH2CH2CH2OH (D) CH3CH2CH2COOH
Q.12 (A)
Q.13 (A)
Q.14 (A) OH
Q
CH3CHO + CH2 – CHO CH3 – CH – CH2 – CHO CH3 – CH = CH – CHO
–H 2O
OH
D CH2–CH=CH-CHO
CH3(CH=CH)3–CHO CH3 – CH = CH – CH – CH2– CH = CH
–H 2O
CHO
(3) CLAISEN CONDENSATION
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-a-oxalyphenyl
acetate
COOEt
Q.7 (G) C2H5–N O C2H5–N O
1-Ethyl-4-piperiodone
ORGANIC CHEMISTRY
(4) PERKIN CONDENSATION
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
(5) KNOEVENAGEL REACTION
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
(6) MICHAEL ADDITION

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
ORGANIC CHEMISTRY
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–CºN
O
O
CH–CH2–COOH
Q.5 CH3
(7) REFORMATSKY REACTION
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
a-Naphthylacetic acid
COOH
COOH COOH CH 2OH
OH
Q.5 (F) (G) Q.6
COOH Q.8 (A)-RST, (B) -Q,R,S,T (C)-P,R,S,T (D) R,T

Q.7 (I) ,
(8) CANNIZARO REACTION

Q.1 (D)
As Cl3C–CHO given chloroform
Q.2 (C)
In cross cannizzaro reaction move reactive carbonyl compound is oxidised & less in reduced.
Q.3 (B)
Intramolecular 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.6 (i) Ph–CH2OH + HCOOK (ii) Ph – CH – C – OK

OH O
ORGANIC CHEMISTRY
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 (B)
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 (A)
OH
A : B : PhCOOH C :
Ph–CH–COONa
Q.12 (D) O
O O O
C–CH3 COOH
HgSO4 I2/NaOH
H2SO4 H
+
–CO2
Q.13 (B)
Q.14 (C)
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
ORGANIC CHEMISTRY
Q.17 (B)
Cross cannizaro reaction
Q.18 (A)
OH
Ph–CH–CH–Ph Ph–C=CH–Ph Ph–C–Me
X: Y : Z1 : Z2 : Ph–CH=O
CH3 OH O
(9) BENZIL-BENZILIC REARRANGEMENT OR BENZILIC ACID REARRANGEMENT
OH OH
s
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
(10) TISCHENKO REACTION /CONDENSATION
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
(11) COREY HOUSE SYNTHESIS
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
s
CH3–CH–CH2 r
(C) CH3 – CH – CH2 Li (D) CuLi
CH3
CH3 3
ORGANIC CHEMISTRY
s r
Q.3 (A) [CH3CH2]2 CuLi (B) CH3 – CH2 – CH3
s
r
Q.4 (A) CuLi (B) CH2–CH3
2
O
Et
sd rd s r
Q.5 (A) CH3 – CH2 Li (B) [CH3CH2]2 CuLi (C) CH3 – CH – CH3 (D)
Et
Q.6 (i) [Ph]s2CuLir CH3–Cl Ph–CH3
s r CH3–Cl
(ii) CH2–CH–CH2–CH3
Ph–CH2–Cl
s r
(iii) [Ph]2CuLi Ph–CH2–Ph
14
Q.7 CH3 – CH 2 – CH = CH 2
Q.8 not available
Q.9 (A) CH3 – CH – CH2 – CH3 (B) CH3 – CH – CH2 – CH3

s
O Lir OH
Q.10 (A) CH3 – CH2 – CH = C – H (B) CH3 – CH2 – CH2 – C – H
sOLir O
s r
Q.11 (i) [CH3 – CH2]s2 CuLir + 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
IIT CHEMISTRY
ENTHUSE
Child Help Line No. 1098, Hope Society Kota + 91-72443 33666

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ENTHUSE

R—C—CH2 + OH R—C—CH2 R—C—CH + X

R—C—C + OH R—C—CX2 R—C—CX3

Q.4 For the reaction

Paragraph for Q.07 to Q.09

Q.8 Select the correct statement among the following -

Q.9 P2 conc. NaOH

Q.12 Correct option regarding following reaction sequence.

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

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

Q.15 In which reaction haloform is obtained as one product :-

(2) ALDOL CONDENSATION

Base catalysed Aldol

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

(II) Dil NaOH (E) (F)

Q.5 Complete reaction sequence :

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

Q.6 Complete the following reactions :

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

Q.8 Consider following intramolecular aldol condensation reaction :

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

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

(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

COOC2H5 (i) C2H5ONa

COOPh (i) PhONa

(i) (CH3CH2CO)2 O/CH3–CH2–COONa,D

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

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

(6) MICHAEL ADDITION

(7) REFORMATSKY REACTION

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

Q.7 O (1)Zn + BrCHCH = CH – COOCH3

(B) Ph–CHO + CH2–COOCH¾¾¾¾ ® (1) Zn

OO within the same molecule.

is less than or equal to 8.

(T) The major product cannot show optical isomerism

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

Q.1 Which of following will not undergo Cannizaro reaction

Product (C) & (D) are :

(A) Ph–CO2H, Ph–OH (B) Ph–CO2–,HCO2–

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

Q.4 (i) HCHO NaOD

Q.7 (i) MeCH2 – CHO KOH

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

(C) PhCOOH (D) None of these

Q.10 Match the column :

(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

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

End product (B) of above reaction is :

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

(A) + CH3OH (B) + HCOONa