BENZALDEHYDE

Total No.of questions in Benzaldehyde are -

In chapter Examples .................................................................. 07

Solved Examples ........................................ ............................ 15

Total No. of questions .............................................................. 22

1. INTRODUCTION C6H5 – C  N SnCl
 2 /HCl
 C6H5 – CH = NH.HCl

(a) Aromatic aldehydes are divided in two parts. 

 C6H5CHO + NH4Cl
H3 O
 
(i) Such type of aldehydes in which aldehyde
group (–CHO) is directly attached with 2.5 By Oxidation of Benzyl alcohol : –
benzene ring. C6H5 – CH2 – OH + [O] KMnO
 4  C H – CHO
6 5
H-C=O
benzaldehyde
eg. 2.6 By Catalytic oxidation of Benzyl alcohol :–
Cu / ZnO
C6H5 – CH2 – OH   C6H5 – CHO
benzaldehyde 300C
2.7 By Grignard reagent :–
(ii) Such compound in which aldehyde group in
C6H5 – MgBr + HCOOC2H5 —— C6H5 CHO
attached with side chain of a banzene ring.
CH2 -CHO ethyl formate +MgBr (OC2H5)
2.8 By dry distillation of Calcium benzoate &
eg. Calcium formate mixture :–

phenyl acetaldehyde
O O
(b) Benzaldehyde is also called as “oil of || ||
bitter almonds”. H C O O C C6H5
(c) It remains in oil of bitter almonds as Ca + Ca
amygdalin glycoside. H C O O C C6H5
|| ||
2. METHODS OF PREPARATION OF BENZALDEHYDE O O

2.1 By Ozonolysis of Styrene : –

  2C H CHO
2CaCO 3 6 5

CH=CH2 CHO
2.9 By Oxidation of Toluene : –
+ O3 Zn / H2O
 
benzaldehyde CH3
CHO
CrO3 /MnO2
2.2 By Basic hydrolysis of Benzylidene chloride:– (i) + [O] 

500C
vapour state
Cl K – OH
C6H5 – CH + C6H5CHO + 2KCl
Cl K – OH
+ H2O (ii) + [O]H2SO4 /MnO
2

2.3 By Rosenmund reaction : –
Benzoyl chloride reduces in the presence of
CHO
Pd- BaSO4 catalyst and forms benzaldehyde
Pd/BaSO4
C6H5 – C – Cl + H2   C6H5CHO + HCl
|| NOTE : If oxidation is done through basic KMnO 4
O then benzoic acid is formed.
2.4 By Stephen’s reaction : – 2.10 By Sommelet’s reaction :–
Benzyl chloride reacts with hexamethylene
When phenyl cyanide reduces by SnCl2/HCl in
tetramine (urotropine) in aq. ethanolic solution
ether solution, then intermediate aldimine is
then benzaldehyde is formed.
obtained which on hydrolysis gives benzaldehyde. C6H5CH2Cl + (CH2)6N4  C6H5CHO (60–70%)
urotropine
2.11 By Etard reaction :–
Ex.2  – CH3  CrO
 2 Cl
2 A H2 O
  B
This is also an oxidation of toluene. In this
The functional group present in B and name
chromyl chloride is used as oxidant
C6H5CH3 + 2CrO2 Cl2  C6H5CH3. 2CrO 2Cl 2 of the reaction would be –
(A) –CHO, Gattermann aldehyde synthesis.
H2O
   C6H5CHO (80%) (B) –CHO, Etard reaction.
2.12 By Gattermann reaction :– (C) –COCH3, Friedel Crafts reaction.
When benzene reacts with mixture of hydrogen (D) –CHO, Oxo reaction. (Ans. B)
cyanide and hydrogen chloride in the presence Sol. The compound ‘B; is benzaldehyde and the
of ZnCl2 catalyst, intermediate benzaldimine is reaction is called ‘Etard reaction’
formed which on hydrolysis gives benzaldehyde.

HCl + HCN  ZnCl

  2  ClCH = NH

C6H6 + ClCH = NH —— C6H5CH = NH.HCl

Ex.3 Chlororform
 
Caustic soda

H3 O
C6H5CH = NH.HCl  C6H5CHO + NH4Cl
The above reaction is –
2.13 By Gattermann Koch reaction :– (A) Electrophilic substiution
When benzene reacts with carbon monoxide and (B) Nucleophilic substiution
hydrogen chloride mixture, in the presence of (C) Free radical addition
anhydrous AlCl3, then benzaldehyde is formed. (D) Electrophilic addition (Ans. A)
CO + HCl  HCOCl Sol. Attacking species in the above reaction is
AlCl3 dichlorocarbene which is an electrophile.
C6H6 + HCOCl   
 C H CHO
6 5
HCl

2.14 By Benzoic acid :– 3. PHYSICAL PROPERTIES

HCOOH
C6H5 – COOH 
 C6H5 – CHO (a) It is a colourless liquid with a smell of bitter
MnO or TiO2,300C
almonds.
+CO2 + H2O
(b) It is insoluble in water and soluble in organic
Examples
Methods of preparation solvents.
based on
(c) It is boling point is 179ºC.
Ex.1 In Etard’s reaction toluene is oxidised to (d) It is poisonous in nature.
benzaldehyde using –
(A) H2O 2 4. CHEMICAL PROPERTIES
(B) Cl 2
(C) Chromium trioxide or CrO2Cl 2 Chemical properties of benzaldehyde are divided
(D) KMnO4 (Ans. C) in the following two types –
Sol. CrO3 or CrO2Cl 2 and a mixture of K2Cr2O7 + 4.1 Reactions of – CHO group of benzaldehyde
H2SO 4 + NaCl can also be used.
4.2 Reactions of benzene ring
4.1 Reactions of – CHO group of benzaldehyde:– (e) Oxidation :–
These reactions are also of two types – C6H5CHO  alk . KMnO 4
   C6H5COOH
4.1.1 Reactions resembling aliphatic aldehyde : benzoic acid
(a) Reaction with Hydrogen cyanide :– (f) Reaction with PCl5 :–
C6H5CHO + PCl5  C6H5CHCl 2 + POCl3
(g) Reaction with Tollen’s reagent :–
H H
| | C6H5CHO+Ag2O Tollen's reagent
  C6H5COOH+2Ag
C6H5 — C + H — CN  C6H5 — C – CN
|| | (h) Reaction with Schiff’s reagent :–
O OH
C6H5CHO Schiff 's reagent
 Pink colour
mendalonitrile
(i) Reaction with Grignard ragent :–
H

H3 O
| H H
  C6H5 – C — COOH |
| C6H5 – C + C6H5 – MgBr — C6H5–C–C6H5
OH ||
O OMgBr
mendalic acid
H
(2 hydroxy–2 phenyl ethanoic acid) |
H2 O
 C6H5 – C – C6H5 + Mg (Br) OH
(b) Reaction with Sodium bisulphite :– |
OH
H
|   diphenyl methanol
C6H5 – C  + H – OSO 2Na  (j) Cannizaro reaction :–
||
2C6H5CHO + NaOH  C6H5CH2 – OH
O 
benzyl alcohol
OSO 2Na + C6H5COONa
| (k) Tischenko reaction :–
C6H5 – C  H
2C6H5–CHO AlCl3,Al(OR)3
|   C6H5COOCH2C6H5
OH
benzyl benzoate
bisulphite compound 4.1.2 Reaction deffer from aliphatic aldehyde :–
(c) Reaction with Ammonia derivatives :– (a) Bimolecular reduction :–
(i) C6H5CHO + H2NOH  C6H5CH = NOH + H2O Zn / HCl
2C6H5CHO + 2H   
(ii) C6H5CHO + H2N NHC6H5 
C6H5  CH  CH  C6H5
C6H5CH=N –NHC6H5 + H2O | |
OH OH
(iii) C6H5CHO  semicarbazide

hydrobenzoin
Benzaldehydesemicarbazone + H2O
(b) Benzoin condensation :–
(iv) C6H5CHO  C
6H5NH2
 C6H5CH = N – C6H5
H
(Shiff’s base or anil) |
(d) Reduction :–  Alc.KCN
C6H5 – C – H + C – C6H5 
C2H5 OH
Zn /HCl Or || ||
C6H5CHO + 2H Na

Hg/H O
 C6H5CH2OH O O
2 
benzyl alcohol
C6H5 – C – CH – C6H5
|| |
O OH
benzoin
 (c) Reaction with Ammonia (g) Reaction with N,N-dimethyl aniline –
H
C6H5 – C = O N H
| H H
H |
+ O = C – C6H5
+ + O = CH – C6H5
H
C6H5 – C = O N H
| H
H


Conc.H2SO4
Hydrobenzamide
(amide without – CONH2 group)
(d) Claisen condensation :–
malachite green
(i) With Acetaldehyde –
(h) Reaction with Nitromethane :–
dil. NaO H
C6H5CHO + CH3CHO     C6H5 – CH = O + H2 CH – NO2 ———
H2 O
C6H5 – CH = CH – NO2
C6H5CH = CH – CHO + H2O nitro styrene
cinnamaldehyde
NOTE :
(ii) With Acetone –
(i) Benzaldehyde reduces mercuric chloride into
dil. NaOH
C6H5CHO + CH3COCH3  
 black ppt. of mercury and it oxidises into
H2O benzoic acid.
C6H5CH = CH – CO – CH3
(ii) It does not reduces Fehling’s solution.
benzylidene acetone
(iii) Due to resonance and m-directing nature of
ethanolic NaOH
2C6H5CHO + CH3COCH3       –CHO group, benzaldehyde gives meta
2H2O
products.
C6H5 – CH = CH – CO – CH = CH – C6H5
(iv) Like nitrobenzene, benzaldehyde does not
(e) Perkin reaction :– show Friedel Craft reaction.
C6H5CHO + (CH3CO)2O  CH 3 COONa
  4.2 Reactions of benzene ring :–
 CH3 COOH
C6H5CH = CHCOOH (a) Halogenation :–
cinnamic acid
(f) Knoevenagel reaction :–
AlCl 3
+ Cl2  
It is the reaction of benzaldehyde takes place 

with malonic acid or ester and f inally
cinnamic acid is formed. m – chloro benzaldehyde
H (b) Nitration :–
| H
C6H5 – C = O + N  

H2O
H
+ HO – NO2  Conc . H SO 4
  2 

m – nitro benzaldehyde
(c) Sulphonation :–
                      C6H5 –CH =

CO
(c) + HO – SO3H 
 
2 C6H5 –CH =CH – C – OH
||
O m – formyl
cinnamic acid benzene suphonic acid
Examples
chemical reaction Ex.6 The formation of benzoin from benzaldehyde
based on
takes place in the presence of –
Ex.4 In Perkin reaction – (A) Alc KOH (B) Aq. H2SO 4
(C) Alc KCN (D) LiAlH4
(A) Benzaldehyde reacts with acetic
(Ans. C)
anhydride in the presence of sodium
acetate forming cinnamic acid.
(B) Benzaldehyde reacts with acetaldehyde alcoholic KCN
in the presence of sodium hydroxide to Sol. C6H5 – C – H + C6H5 – C –H 
|| ||
give cinnamaldehyde. O O OH
(C) Calcium salt of benzoic acid on dry |
distillation gives benzophenone. C6H5 – C – CH – C6H5
(D) None of these ||
(Ans.A) O
benzoin
Sol. Perkin reaction can be shown as – Ex.7 In which of the following crossed aldol
condensations there will be only one kind of
C6H5CHO + (CH3CO)2O  CH 3 COONa
  cross aldol formed –
C6H5CH = CH – COOH + CH3COOH (A) CH3 CHO & CH3 CH2 CHO
(B) CH3 CHO & (CH3)2 CO
(C) (CH3)2 CO & (C2H5)2 CO
Ex.5 Benzaldehyde on reaction with
(D) C6H5 CHO & CH3 CHO
CH2 = CH – CH = PPh3 forms – (Ans. D)

Sol. C6H5 – C – H + CH3 – C – H ———

(A) || ||
O O
benzaldehyde acetaldehyde
C6H5 – CH – CH2 – C – H
(B) | ||
OH O

(C)

(D) (Ans.D)

O
C - H + CH 2 = CH - CH = PPh 3
Sol.

CH = CH - CH = CH2
+ (C 6 H5)3 P = O
 SOLVED EXAMPLE
Ex.1 Keto-enol tautomerism is shown by – Ex.4 Benzaldehyde may be prepared from phenyl
(A) C6H5CHO magnesium bromide by it's reaction with –
(B) C6H5CO.CCl3 (A) HCHO (B) Acetonitrile
(C) C6H5COC6H5 (C) Ethyl formate (D) Air
(Ans.C)
(D) C6H5COCH2COCH3 (Ans.D)
Sol. Benzaldehyde may be prepared from phenyl
Sol. Keto- enol tautomerism is shown by
magnesium bromide by it's reaction with ethyl
C6H5COCH2 COCH3 as follows : formate
O O O
|| || ||
C6H5 – C – CH2 – C – CH3  H – C – OC2H5 + C6H5 MgBr 
keto
OMgBr O H
OH O | |
H2 O
| || H – C  OC2H5    H  C  OH
C6H5 – C = CH – C – CH3 | |
C6H5 C6H5
enol
Ex.2 Hydrolysis of benzylidene chloride with aq. H O
2
   C6 H5 CHO
acid gives –
(A) Benzoic acid (B) Benzyl alcohol CHO
(C) Benzaldehyde (D) Benzhydrol Ex.5 PCl
5
  A
(Ans.C)
Hydrolysis of benzylidene chloride with aq. Hydrolysis
acid gives benzaldehyde : The compound A is –
(A) Benzyl chloride
Cl OH (B) Benzotrichloride
CH CH
| Cl OH (C) Benzylidene chloride
|
2H O (D) Benzoyl chloride (Ans.C)
Sol.
2
 
[HCl]H2O Sol. C6H5 CHO  PCl
 5
 C6H5 CHCl2
benzylidine
chloride unstable H2 O
 C6H5 CHO
CHO PCl 5
| Ex.6 C6H5 COOH    A + POCl3 + HCl
Compound A can also be formed by treating

 the chlorine with the following compound in
H2O
the absence of halogen carrier –
benzaldehyde
(A) C6H5 COOH (B) C6H5 CHO
Ex.3 Reduction of benzoyl chloride with Pd and (C) C6H5 CH2OH (D) C6H5COOC2H5
BaSO4 produces – (Ans.B)
Cl2
(A) Benzoic acid (B) Benzaldehyde Sol. C6H5 CHO  
 C6H5 COCl + HCl
(C) Benzoyl cyanide (D) Benzyl alcohol
(Ans.B) Ex.7 Which of the following compounds would not
form a silver mirrior with Tollen’s reagent –
Sol. C6H5 – C – Cl + H2 Pd/BaSO4
  (A) R.CHO (B) Ar.CHO
|| (C) CH3.CO.R (D) RCHOHCOR
O (Ans.C)
C6H5 – C  H + HCl Sol. Aromatic aldehydes as well as -hydroxy
||
O ketones are oxidisable by Tollen’s reagent
Ex.8 Benzaldehyde and formaldehyde differ from is named as –
acetaldehyde in their reaction with – (A) Claisen condensation
(A) NaOH (B) Perkin reaction
(B) HCN (C) Knoevenagel reaction
(C) 2,4-Dinitrophenyl hydrazine (D) Aldol condensation (Ans.A)
(D) Semi carbazide
(Ans.A) Sol. C6H5 – C – H + CH3 – C – O – C2 H5
|| ||
Sol. Benzaldehyde (C 6 H 5 – CHO ) and O O
formaldehyde do not have -hydrogen atoms
so they give disproportionation reaction with C H O
2 5
   C6H5 – CH = CHCOOC2H5
NaOH but CH3CHO does not give it.
ethyl cinnamate (ester of --
Ex.9 When an aldehyde was heated with alkali, unsaturated acid)
part of it was converted into an alcohol and
The reaction is called as ‘Claisen
part of it into an acid. The aldehyde is –
condensation’
(A) An aliphatic aldehyde other than
Ex.12 Benzaldehyde reacts with acetaldehyde in
formaldehyde
the presence of a base to give –
(B) An aliphatic aldehyde or salicylaldehyde
(A) Crotonaldehyde (B) Cinnamaldehyde
(C) An aromatic aldehyde other than (C) Crotonic acid (D) Cinnamic acid
salicylaldehyde (Ans.B)
(D) An aromatic aldehyde or formaldehyde
(Ans.D) Sol. Benzaldehyde reacts with acetaldehyde in
the presence of a base to giv e
Sol. The aldehydes which do not have -hydrogen cinnamaldehyde. It is called crossed Aldol
atoms show disproportionation reaction.
condensation or Claisen's condensation
These aldehyde may be aliphatic aldehyde
(formaldehyde) or aromatic aldehyde. CHO
|
Ex.10 Product obtained on the addition of an aqueous
alkali to benzaldehyde followed by acid OH
+ CH3CHO 
hydrolysis is – H2O

(A) Benzoic acid (B) Benzyl alcohol benzaldehyde acetaldehyde

(C) Benzyl benzoate (D) All of the above
(Ans.D) CH=CH.CHO
Sol. When an aqueous alkali solution is added to |
benzaldehyde Cannizzaro's reaction takes
place and the products formed are potassium
benzoate and benzyl alcohol . Potassium cinnamaldehyde
benzoate on acidic hydrolysis produces
benzoic acid , Which further reacts with Ex.13 Which of the following acid show cis - trans
benzyl alcohol produces benzyl benzoate isomerism
(A) Benzoic acid (B) Pthalic acid
C6H5CHO C6H5CH2OH + C6H5COOK (C) Cinnamic acid (D) None of these
benzyl potassium (Ans.C)
alcohol benzoate Sol cis-trans isomerism is shown by cinnanmic
acid. It exists into two isomers as follows-
C6H5COOH + C6H5CH2OH 
C6H5CH2. OOCC6H5
benzyl benzoate
Ex.11 The reaction
cis - cinnamic acid
CH3 COOC2H5 / C2H5O 
C6H5CHO   
C6H5CH = CH – COOC2H5
trans - cinnamic acid
Ex.14 In the reaction between benzaldehyde and Ex.15 Which of the following will undergo aldol
formaldehyde, point out the wrong statement condensation –
(A) Benzaldehyde is reduced to benzyl Acetaldehyde Propanaldehyde
alcohol (1) (2)
(B) Formaldehyde is oxidised to formic acid Benzaldehyde rideuterosacetaldehyde
(C) Benzyl formate is formed (3) (4)
(D) The reaction is known as crossed aldol (A) 1 (B) 1, 4
condensation (C) 1, 2, 4 (D) All of them
(Ans.D) (Ans.C)
Sol. In the reaction between benzaldehyde and Sol. CH3CHO CH3CH2CHO
formaldehyde the wrong statement is that the (1) (2)
reaction is known as crossed aldol
condensation. Actually the reaction is called C6H5CHO CD3CHO
Crossed Cannizaro's reaction. (3) (4)
(1)OH  Benzaldehyde has no -hydrogen atom,
C6H5CHO + HCHO   remember that CH3CHO and CD3CHO both
( 2)HCl
behave similarly in chemical properties.
benzaldehyde formaldehyde
C6H5CH2OH + HCOOH
benzylalcohol formic acid