OC - Grignard Reagent - E

JEE (MAIN+ADVANCED)
GRIGNARD REAGENTS
CONTENT
S.No Pages
1. Grignard Reagents 02 – 07
2. Exercise-1 (Subjective Questions) 08 – 10
3. Exercise-2 (Objective Questions) 11 – 23
4. Exercise-3 24 – 25
5. Exercise-4 26
6. Exercise-5 27 – 31
7. Answer Key 32 – 35
GRIGNARD REAGENT
GRIGNARD REAGENTS
Organomagnesium halides were discovered by French chemist Victor Grignard in 1900.
PREPARATION OF GRIGNARD REAGENTS
G.R. are prepared by the reaction of organic halide (RX) with Mg in dry either solvent.
RX + Mg    RMgX
Diethyl ether

ArX + Mg  ArMgX

Et 2 O

The order of reactivity of halides with Mg is :

RI > RBr > RCI
G.R. form a complex with ether solvent and formation of this complex imparts stabilityto G.R.
R R
O
R–Mg–X
O
R R
The method (which can be used for 1º, 2º and 3º alcohols) is little used in practice, since an alkyl halide
can be converted into the corresponding alcohols.
REACTIONS OF GRIGNARD REAGENTS
1. Reaction with carbonyl compounds :
GR react with carbonyl compounds to give 1º, 2º and 3º alcohols.
(a) G.R. react with formaldehyde (methanal, HCHO) to gives 1º alcohol.
H
H H H

Ether H3O
H–C=O H – C – O MgX H – C – OH + Mg
– +  H
R : MgX R R OH
1º Alcohol
(b) G.R. react with all other aldehydes to given 2º alcohols.
R' R' R' H


Ether H3O
C=O R – C – O MgX R – C – OH + Mg
 H OH
– + H H
H R : MgX OH
2º Alcohol
BANSAL CLASSES Private Ltd. ‘Bansal Tower’, A-10, Road No.-1, I.P.I.A., Kota-05 Page # 2
GRIGNARD REAGENT
(c) G.R. react with ketones to give 3º alcohols.
R' R' R' X


Ether H3O
C=O R" – C – O – MgX R" – C – OH + Mg
 H OH
– + R R
R" R : MgX OH
3º Alcohol
2. Reaction with ester :

Two moles of G.R. reacts with esters to give 3º alcohols. One mole of G.R. reacts with esters to form
ketones. Ketones are more reactive towards G.R. than esters. Therefore, as soon as a molecule of the
ketone is formed in the mixture, it reacts with a second molecule of G.R.After hydrolysis, the product is
3º alcohol, with two same alkyl groups that correspond to the alkyl portion of the G.R.
R' R' R' R'

– +
Ether –R"OMgX R : MgX H3O
C=O R – C – O – MgX C=O R – C – O MgX
 Spontaneously H OH or NH4Cl + H2 O
OR" – +
R : MgX O – R" R R
Initial product Ketone Initial product
unstable unstable
R'
R – C – OH
R
3º Alcohol
For example :
O Me
|| (i) THF,  |
C2H5 – C – O – Me + 2Me MgBr C2H5 – C – OH
Methyl propanoate (ii) H3O+ |
Me
2-Methyl-2-ol
3. Reaction with dialkyl carbonate :

Preparation of 3º alcohol containing three identical alkyl groups :
This may be prepared by the reaction between 3 mol of G.R. with 1 mol of diethyl carbonate .
O
||
H5C2 O – C – OC2 H5 or (C2 H5 O)2 C = O
For example
3EtMgBr + (EtO) 2C = O Et
Ether
Ethylmagnesium Ethylmagnesium  C– OH
bromide bromide H 3O Et
Et
4. Reaction with alkanoyl halide :
 
 O 
 || 
R  C  X
Two moles of G.R. reacts with acid halids   to give 3º alcohols.
GRIGNARD REAGENT
 
 O 
 || 
R  C  X
One mole of G.R. reacts with acid halids   to form ketones. Ketones are more reactive than
acid halides. Therefore, as soon as a molecule of ketone is formed in the mixture, it reacts with a second
molecule of G.R.After hydrolysis, the product is 3º alcohol, with two same alkyl groups that correspond
to the alkyl portion of the G.R.
R' R'
R' | –MgX2 R' – +
Ether |
C = O R – C – O – MgX Spontaneously C=O R MgX R – C – O MgX
|  | | H OH
X – + R
X R
R : MgX H3O
Initial product
Acid halide ustable R'
|
R – C – OH
|
R
3º Alcohol
For example :
O C2H5
|| (i) THF,  |
CH3 – C – O – Cl + 2 C2H5 MgBr + CH3 – C – OH
(ii) H3O |
Ethanoyl chloride
C2H5
or
R 2R'
Acetyl chloride 3–Methylpetan–3–ol
 
 O 
 || 
Two moles of G.R. reacts with formyl halides or methanoyl halides  H  C  X  to give 2º alcohols,

with two same alkyl groups that corresponds to the alkyl portion of the G.R.
H R R
H | –MgX2 – +
Ether | |
C = O R – C – O – MgX Spontaneously R MgX H – C – O MgX
|  | H–C=O
| H OH
X – + X R
R : MgX H3O
Initial product
Acid halide unstable R
|
R – C – OH
|
R
2º Alcohol
For example :
O C2H5
|| (i) THF,  |
H – C – Cl + 2C2H5 MgBr + H – C – OH
(ii) H3O |
Methanoyl chloride
C2H5
or
Formyl chloride 2R' (2º alcohol)
(Pentan-3-ol)
GRIGNARD REAGENT
 
 O 
 || 
Reaction of dialkyl cadmium (R2Cd) or dialkyl lithium cuprate with acid halides  R  C  X  gives

 
 O 
 || 
H  C  X
ketones and with formyl halides   gives aldehydes.
O O
|| THF,  ||
(i) 2R – C – X + R' 2Cd 2R – C – R' + CdX 2
O O
|| ||
THF, 
(ii) H – C – X + R'2Cd H – C – R' + CdX2
5. Reaction with anhydride :
 
 O O 
 || || 
Two moles of G.R. reacts with acid anhydride  R  C  O  C  R  to give 3º alcohol.

Acid anhydrides react in the same way as ester, and acid halides react with RMgX.
R O
R' | || R
Ether |
C – O – C – R' R' – C – O – C – R'
|| ||  | –R' – C – OMgX
O O O – MgX
– +
R : MgX
R'
– + |
R' – C – R R : MgX
|| R – C – O MgX
O | H OH
R 
H3O
R'
|
R – C – OH
|
R
3º Alcohol
6. Reaction of RMgX (G.R.) with oxirans (epoxides) and other cyclic ethers :
..
RMgX reacts with oxiranes or cyclic ethers via SN2 mechanism. The R  (nucleophile) of RMgX
attacks the partiallycharged C atom of oxirane ring. Since it is highly strained, the ring opens and forms
a salt of 1ºC alcohol, which gives alcohol on acidification.
GRIGNARD REAGENT
R R
+ + – + X
Et2O H3O
+ R : MgX + Mg
O  O MgX
– H OH OH
OH
5
3 4 – + THF 3 4
Ph CH2 MgBr  Ph
+  H3O
O O Mgr 2
2 1 Benzyl
Me magnesium Me H OH 1
2-Methyl Me OH
bromide
oxetane 5-Phenyl pentan-2-ol
7. Reaction with O2 :
G.R. react with O2 to give 1º alcohol

H
– + RMgX H3O
R – MgX + O = O R – O – O – MgX 2R – O – MgX 2ROH + Mg
H OH
OH
For example :
H
1. THF. 
2C2H5MgBr + O2 2C2H5OH + Mg
2. H3O Ethanol
OH
8. Reaction with acids :
RMgX gives alkane (R–H) on reaction with acids
R – MgX + H – X  R – H + MgX2
OH
R–MgX + H2O  R – H + Mg Mg
X
9. Reaction with R–CN :

RMgX gives ketone on reaction with R–CN
R R
| + |
 
R' – C = NMgX H3O
R' – C  N + R MgX R' – C = O
Ketone on further reaction with RMgX gives 3º alcohol.

R' R' R' X

Ether H3O
C=O R – C – O – MgX R – C – OH + Mg
 H OH
– + R R
R R : MgX OH
3º Alcohol
GRIGNARD REAGENT
Reaction Chart of Grignard reagent (R–Mg+X–)
HOH or ROH
2
or Ph–OH
2 NH H
O2 ,H2 O
CdCted
N
SO2,H
l imi
or R 3 or R

CS H
2 O,
l2
2 ,H O lim gBr
NH
S,H

 H2 ite 2
,
X
d
HO
R–
CO C SiCl
H limit 4 CH 2
2 ,H  O –CH=
RCHO,H2 ed
ClCH 2
O R–Mg–X R–Mg–X
Me–CH-CH2, RCOR,H2O PbCl2 ClCH2 OR
limited
H2O Ph
O HCO
H2 OEt Cl 2 CH
O CH 2, Zn ted
3O
2C
l
HC (
- i
Cl–
CH 2 lim
eq.) 2 O
OO ½ e
N,H
RCO
CN
(½ Et,H
2
Et q.)
Cl
RC
,H 2
I2
OEt
Br2
OO
O
RC
GRIGNARD REAGENT
EXERCISE-1 (Subjective Questions)
Q.1 X (
i ) CH 3MgBr
  Z
(ii ) HOH
What can be used as X if Z is
(i) CH3 – CH3 (ii) CH3–CH2–OH (iii) CH 3  CH  CH 3 (iv) CH3–CH2–CH2–OH
|
OH
OH
(v) CH2= CH–CH2–CH3 (vi)
Q.2 Number of RMgX consumed per molecule with the following reactant.
O O
|| ||
(a) PhCHO (b) Cl — C — C — OEt
CH2Cl
OH
(c) (d) SiCl4

CH3O
COCH3
Q.3 How manycycloalkyl chloride (without consideringstereoisomers) would yield 1,3-dimethyl-cyclohexane

on conversion into the Grignard reagent followed bytreatment with ethanol.
Q.4 How many grams of benzene would be produced when 135.5 gms of phenyl magnesium chloride is
treated with 224 ml of ethyne at STP?
Q.5 What is the product in the following reactions.
(a) CH
3MgBr
  A
(1eq.)

(b) PhMgBr + CH 2  C  CH 2 
 B
| |
Br Br
(c) CH 2  (CH 2 ) 3  CH 2  CHO (
i ) Mg / ether
  C
| ( ii ) NH 4 Cl
Br
GRIGNARD REAGENT
Q.6 Neither of these methods of making pentan-1,4 diol will work. Explain why not – what will happen
instead?
(i) CHO–CH2–CH2–CH2–OH MeMgBr
  CH 3  CH  CH 2  CH 2  CH 2
followed by H  | |
OH OH
CH CHO
(ii)  MgBr–CH2–CH2–CH2–OH 3
Br–CH2–CH2–CH2–OH Mg 
Et 2O followed by H
CH 3  CH  CH 2  CH 2  CH 2
| |
OH OH
Q.7 What are the products ?
(a) PhMgBr ( i ) COCl 2

 
(excess) ( ii ) NH 4Cl
O
(b) HS + PhMgBr 
(1eq.)
H
Q.8 What products would be formed in these reactions ?

(i ) EtMgBr
(a) Ph – C  CH (   A
ii ) Ph CO
(b) Br + Mg dry (i ) CO 2
 A    B.
2 ether 
(iii ) NH 4Cl ( ii ) H 3O
Cl EtMgBr
(i) Mg(1eq.), Et 2O (1 eq.)
(c) A. (d)  
 C11H18O2
Br (ii) then H  , H 2O
CHO N
(iii) H 2O
O OH
Ph
C–Cl Ph
Q.9 (
i ) xPhMgBr
  Ph
( ii ) H  HO
HO C–O–Et
OH Ph
O
What is value of 'x' ?
Q.10 How many moles of Grignard reagent required for complete reaction with following compound.
H3CO O OH
Br
O O
GRIGNARD REAGENT
Q.11 Write number of reactions which produce correct mentioned product as major product.
OH
(i) Br / H 2O
2  
Br
OAg Br
(ii) Br / CCl4
2  

O
( i ) CH MgBr
(iii) H3C – C  N  3  H 3C  C  CH 3
(ii ) H / H 2O ||
O
Ph
(iv) (
i ) PhMgBr
 
( ii ) H 2O
O OH
i ) BD 3 THF D
(v) (  
(ii ) CH 3COOT
T
(vi) HBr
 / H 2O 2
  Br
GRIGNARD REAGENT
EXERCISE-2 (Objective Questions)

[SINGLE CORRECT CHOICE TYPE]
Q.1 Consider the given organometallic compound.

(I) (CH3)2Hg (II) (CH3)2Zn (III) (CH3)2Mg (IV) CH3Li
The correct decreasing order of ionic character is
(A) I > II > III > IV (B) II > I > III > IV (C) I > III > II > IV (D) IV > III > II > I
Q.2 The order of reactivity of alkyl halide in the reaction R–X + Mg  RMgX is
(A) RI > RBr > RCl (B) RCl > RBr > RI
(C) RBr > RCl > RI (D) RBr > RI> RCl
MgBr OH
Q.3 +  A
O – Ph
(A) (B) (C) (D)
Q.4 14CH =CH–CH

2 3 NBS
 Mg
 / ether D O
 2 Product(s)
CCl4 / Peroxide
Product(s) is / are:
(A) 14CH2= CH–CH2–D (B) CH2 = CH– 14CH2–D
(C) Both of these (D) None of these
Q.5 On conversion into Grignard followed by treatment with ethanol, how many alkyl halides (excluding
stereoisomers) would yield 2-methyl butane.
(A ) 2 (B) 3 (C) 4 (D) 5
(2)
O OH
C
O (3)
H
H
Q.6 S
(1) RMgX
 (2 moles )
 
C

CH
(4)
Deprotonation will occur from the following positions:
(A) 1,2 (B) 1,3 (C) any two positions (D) 1,4
Q.7 How many litres of methane would be produced when 0.595 g of CH3MgBr is treated with excess of
C4H9NH2
(A) 0.8 litre (B) 0.08 litre (C) 0.112 litre (D) 1.12 litre
GRIGNARD REAGENT
D O
Q.8 1
equivalent Mg
  X 
2
 Y; Y is
ether
(A) (B) (C) (D) None of these
Q.9 CH3—CH—CH2 CH

3MgCl

H 2O
O
(A) CH 3  CH  CH 2OH (B) CH 3  CH  CH 2  CH 3
| |
CH 3 OH
(C) CH 3  CH  CH 3 (D) HO – CH2 – CH2 – CH2 – CH2 – OH
|
CH 3
r1
Q.10 (i) + Ph Mg Br  Ph CH2 CH2 OH
O
r2
(ii) + Ph Mg Br  Ph CH2 CH2 CH2 OH
O
(A) r2 > r1 (B) r1 > r2 (C) r1 = r2 (D) r1 = 2r2
Q.11 What will be the order of reactivity of the following carbonyl compounds with Grignard's reagent?
H H CH3 Me3C
(I) C = O (II) C=O (III) C=O (IV) C=O
H CH3 CH3 Me3C
(A) I > II > III > IV (B) IV > III > II > I
(C) II > I > IV > III (D) III > II > I > IV
Q.12 Order of rate of reaction of following compound with phenyl magnesium bromide is:
O O O
|| || ||
Me  C  Cl Me  C  H Me  C  O  Et
I II III
(A) I > II > III (B) II > III > I (C) III > I > II (D) II > I > III
Q.13 Select the correct order of decreasing reactivity of the following compounds towards the attack of
Grignard reagent
(I) Methyl benzoate (II) Benzaldehyde (III) Benzoylchloride (IV)Acetophenone
(A) II > III > I > IV (B) III > IV > II > I
(C) III > II > IV > I (D) II > IV > I > III
GRIGNARD REAGENT
Q.14 Which of the following reacts faster with RMgX.

O O O O
|| || || ||
(A) R  C  Br (B) R  C  H (C) R  C  OEt (D) R  C  NH 2
Q.15 Select the correct order of reactivity towards Grignard reagent for nucleophilic attack.
O O
|| ||
(A) R  C  R > R  C  H
(B) CH 3  C  H > Cl  C  H
|| ||
O O
O O
|| ||
(C) CH 3  C  O NO2 < CH 3  C  O
O O
|| ||
(D) R  C  OR > R  C  NR 2
Q.16 The reaction of 1 mole each of p-hydroxy acetophenone and methyl magnesium iodide will give
O O
(A) CH4 + IMgO C—CH3 (B) CH3–O C—CH3
OMgI MgI
O
(C) CH3–C OH (D) CH3O C—CH3
CH3
Q.17 (R) - 2-Bromooctane (

i ) Mg
 X
( ii ) CO 2
( iii ) H 
X is
(A) (B)
(C) A and B both (D) None of these
Q.18 In which one of the following reaction products are not correctly matched in
(i) CO2
(A) RMgX + CO2 Carboxylic acid
(ii) H
(B) RMgX + C2H5OH  Alkane
(C) RMgX + CH3CH2Cl  Alkene
(D) RMgX + Cl O  Ether
GRIGNARD REAGENT
Br
14
NaHCO
Q.19 Mg
 (A) (  (B)  3  (C) gas
i ) CO 2
( ii ) H  / H 2 O
Product C is
(A) CO (B) 14CO2
(C) CO2 (D) A mixture of 14CO and CO
2 2
O
||
CH 3 CCH3 
Mg H
Q.20 CH3–CH=CH2 Limited
  Br2
       P (Major Product)
Dry ether
  NH 4Cl
End product of above reaction is

CH 2
||
(A) CH 2  CH  CH 2  C  CH 3 (B) H 2C  CH  CH  C  CH 3
|
CH 3
OH
|
(C) H 2C  CH  CH 2  C  CH 3 (D) H 2C  CH  CH 2  CH  CH 2  OH
| |
CH 3 CH 3
Br
Q.21  1
. Mg / ether
   Product (s)

2. CH 3CHCH 2CH 3. H 3O
| ||
OH O
Select the product from the following
I: II : CH 3CHCH 2CH III :

| ||
OH O
(A) III (B) I, III (C) I, II (D) II, III
Q.22
( i ) CH CN
RMgX  3   (A) ( i ) RMgX
 (B) will be
( ii ) H 3O  (ii ) aq. NH4Cl
(A) 1° ROH (B) 2° ROH (C) 3° ROH (D)Alkene
O
||
Q.23 C 2 H 5O  C  OC 2 H 5 2  A. Product A formed
CH 3MgBr

(A) is ethyl acetate
(B) further react with CH3MgBr/H2O+ to give acetone
(C) further react with CH3MgBr/H2O+ to give t-butyl alcohol
(D) Cannot give pinacol when treated with Mg followed by H2O
GRIGNARD REAGENT
Q.24 Which of the following is incorrect.

O
O
C ||
(A) Cl OC2H5 CH3MgX
    CH 3  C  OC 2 H 5
(1eq )
O
OC2H5 ||
C 2H 5MgX
(B) CH3–C OC2H5     CH 3  C  OC2 H 5
(1eq )
OC2H5
S S
|| H3O 
||
(C) CH3MgX + C = S  CH 3  C  SH
O O
||  ||
(D) CH3MgX + C = O H
3O
 CH3  C  OH
O
Q.25 MgBr + H–C–Cl  product.
O
||
(A) C  CH3 (B) CH2CH=O
(C) CH = O (D) CH  CH 3
|
CH  O
( i ) CH CN (i ) RMgX
Q.26 RMgX  3  (A) (   (B) will be
ii ) aq. NH4Cl
(ii ) aq. NH 4Cl
(A) 1° ROH (B) 2° ROH (C) 3° ROH (D)Alkene

Q.27 Compounds are shown with the no. of RMgX required for complete reaction, select the incorrect option
(A) CH3COOC2H5 1
(B) CH3COCl 2
(C) HOCH2COOC2H5 3
(D) 4
Q.28 The number of moles of grignard reagent consumed per mole of the compound
is:
(A) 4 (B) 2 (C) 3 (D) 1
Q.29 How many moles of Grignard reagent will be required by one mole of given compound?
O
SH
HO C – OEt
C – Cl
CH2–CH2 O
Cl
(A) 7 (B) 6 (C) 8 (D) 5
GRIGNARD REAGENT
O
||
Q.30 CH2=CH C  H (
i ) CH 3MgBr / CuCl
    Product (1, 4 addition). It is
( ii ) H 3O 
OH
|
(A) CH 2  CH  C  H (B) CH 2CH  CH  CH 3
| |
CH 3 OH
(C) CH3CH2CH2CHO (D) none
Q.31 In the reaction sequence:
(i ) CH MgBr / CuCl
 3    (X) Major + (Y)
(ii ) H 2O / H 
(X) & (Y) respectively are

OH CH3 OH
(A) , (B) ,
CH3
(C) , (D) ,
O (i) CH 3MgBr
|| + P
(ii) H3O
Q.32 CH3CH = CH  C  CH 3 .
(i) CuI,CH 3MgBr
+ Q
(ii) H3O
OH OH
| |
(A) P is CH3CH = CH  C  Me Q is CH3CH = CH  C  Me
| |
Me Me
O OH
|| |
(B) P is CH 3CH  CH 2  C  CH 3 Q is CH3CH = CH  C  Me
| |
CH 3 Me
(C) P is CH 3CH  CH  C(CH 3 ) 2 Q is (CH 3 ) 2 CHCH 2C  CH 3

| ||
OH O
(D) P is (CH 3 ) 2 CHCH 2C  CH 3 Q is CH 3CH  CH  C(CH 3 ) 2

|| |
O OH
GRIGNARD REAGENT
( i ) CH MgBr conc.H SO
(i ) O
Q.33 C – H  3   24  3  P
( ii ) H 2O  ( ii ) H 2O / Zn
O
P is / are
O
|| H H
(A) O + CH 3  C  H (B)
O O
O
(C) O (D) O
O
H3C H
Q.34 C—C (
i ) PhMgBr
  Product(s)
( ii ) H O
2
H O CH3
Product(s) is / are ..........
Ph
Ph
H3C H
H3C H
(A) H CH3 (B) + en
H CH3
OH
OH
Ph Ph
H CH3 H3C H
(C) +en (D)
H CH3 H3C H
OH OH
Mg / Ether 
Q.35 Br   D/D 2O
 Major product
Br
Major product is.........
(A) D (B) OD
D OD
(C) OD (D) D
D OD
GRIGNARD REAGENT
O NaI (acetone)
|| P
Q.36 H 3C  C  CH 2  Cl CH3MgBr
(1 eq.)
Q
P and Q are respectively.
O¯ Na  O
| ||
(A) H 3C  C  CH 2  Cl H 3C  C  CH 2  CH 3
|
I
O O
|| ||
(B) H 3C  C  CH 2  I H 3C  C  CH 2  CH 3
O O
||
(C) H 3C  C  CH 2  I H3C – C CH2
CH3
O¯ Na  O
|
(D) H 3C  C  CH 2  Cl H3C – C CH2
|
I CH3
Q.37 Which method is not a good method for preparation of ketone
(A) H 3C  C  Cl + (CH3)2 Cd 
||
O
(B) H 3C  C  Cl + (CH3)2 CuLi 

||
O

(C) H3C – C  N + CH3 MgX  H/
H 2O

(D) H 3C  C  Cl + CH3MgBr 
||
O
Q.38 H 3C  CH 2  C  OCH 3 (

i ) PhMgBr ( excess )
    P, P is
|| (ii ) H 2O
O
CH 3 Ph Et CH 3
| | | |
(A) Et  C  Ph (B) Et  C  Ph (C) Et  C  Ph (D) Et  C  CH 3
| | | |
OH OH OH OH
GRIGNARD REAGENT
O
||
( i ) CH 3MgBr (1eq.) i ) Sia 2 B H Ph COO H
Q.39 HC  CH     (
i ) CH 3MgBr (1eq.)
  (      

( ii ) CH I 3 ( ii ) EtI ( ii ) CH 3COOH
Final product is
H Et H3C Et
C C + en C C + en
(A) (B)
H 3C O H H O H
CH3 CH3
H OH H H
+ en + en
(C) H OH (D) H OH
Et Et
Q.40 Which statement is correct.

(A) Cyclopropane can not decolourise bromine water
(B) Toluene can be prepared by decarboxylation of benzoic acid
(C) Methane gas evolve after reaction of CH3MgBr with H2O
(D) is non aromatic compound.
Q.41 Which reaction will give diastereomeric products.

CH3
(A) H Br Mg
 / ether
 (
i ) O2
 (B) (
i ) BD 3 .THF
 
(ii ) CH 3COOT
( ii ) H 2O
Et
O
(C) (
i ) CH 3MgBr
  (D) Br

2
( ii ) H 2O CCl 4
Q.42 H 3C  C  CH 3 ( 
i ) CH 3 MgBr conc .H SO / 
  2 4 2   
Br / H 2 O Na
Cyclic compound (X)
|| ( ii ) H 2 O  H2
O
X is-
CH3
(A) H3C — C — CH2 (B) H3C — CH — CH – CH3

O
O
(C) H3C — CH2 — CH – CH2 (D) H3C — CH — O
O CH2 — CH2
GRIGNARD REAGENT
O
Q.43 (
i ) Mg ( Hg )
  J (Major).
(ii ) H 2 O
O
J is
OH
OH
(A) OH (B)
OH
OH
(C) OH (D)
OH
OH
[MULTIPLE CORRECT CHOICE TYPE]
Q.44 Which of the following reacts with Grignard reagent to give alkane?
(A) nitro ethane (B) acetyl acetone
(C) acetaldehyde (D) acetone
Q.45 Nucleophilic addition of Grignard reagent cannot occur in

O O O O
|| | | || ||
(A) CH 3  C  C  CH 3 (B) CH 3  C  CH 2  C  CH 3
O O
|| || O
(C) CH 3  C  CH 2  CH 2  C  CH 3 (D)
O
CH 3
|
conc. H 2SO 4 NBS CH 3 CH  MgI
Q.46 H 3C  CH 2  CH  CH 3    X + Y        Product(s)
|  CCl4 / peroxide SN 2
OH
Product(s) are:
CH 3
|
(A) (B) H 3C  CH  CH  CH  CH 2
|
CH 3
(C) H 3C  CH  CH 2  CH  CH  CH 3 (D) H 3C  CH  CH  CH  CH 2  CH 3
| |
CH 3 CH 3
GRIGNARD REAGENT
Q.47 Select the correct order of reactivity towards Grignard reagent for nucleophilic attack.
O O
|| ||
(A) R  C  R > R  C H
(B) Cl  CH 2  C  H > CH 3CH 2  C  H
|| ||
O O
O O
|| ||
(C) CH 3  C  O NO2 < CH 3  C  O
O O
|| ||
(D) R  C  OR > R  C  NR 2
Q.48 (
i ) PhMgBr
  Product.
(ii ) NH 4Cl
Me
Products in this reaction will be
(A) Stereoisomers (B) Enantiomer (C) Diastereomers (D) Geometrical isomers
OH
Q.49 Carbonyl compound (X) + Grignard reagent (Y) Me Ph
Et
X , Y will be
O O
|| ||
(A) Et  C  Ph , Me Mg Br (B) Me  C  Ph , Et Mg Br
O O
|| ||
(C) Me  C  Et , Ph Mg Br (D) Et  C  Ph , Et Mg Br
O
||
Q.50 C 2 H 5O  C  OC 2 H 5 2  A. Product A formed
CH 3MgBr

(A) is ethyl acetate
(B) further react with CH3MgBr/H2O+ to give acetone
(C) further react with CH3MgBr/H2O+ to give t-butyl alcohol
(D) Can give pinacol when treated with Mg followed by H2O
GRIGNARD REAGENT
Q.51 In which of the following reactions 3°alcohol will be obtained as a product.

O
||
(A) MgBr (excess) + H  C  Cl  

H
O
||
(B) PhMgBr (excess) + CH 3  C  Cl  

H
O O
|| ||
(C) CH3MgBr (excess) + CH 3  C  O  C  CH 3  

H
O
||
(D) CH3MgBr (excess) + Cl  C  O  Et  

H
Q.52 Which reactions will not produce Grignard reagent as final product.
Br
(A) Mg
 / ether
 Mg / ether
(B) HO – CH2 – CH2 – CH2 – Cl  
Br
Mg / ether
(C) H 3C  C  CH 3 Mg
(Hg )
 (D) Br Br  
||
O
Q.53 Which statement(s) is / are incorrect?

(A) Grignard reagent reacts with H2O to form alcohol
(B) Aldehydes are more reactive than ketones towards Grignard reagent
(C) H 2C — CH 2 on reaction with Mg/ether and then with O2 followed by acidification
| |
Br Br
gives CH 2 — CH 2
| |
OH OH
 
(D) CH 3 is a strong Nu  then N H 2
Q.54 Which reaction(s) produce(s) ketones as major product ?

Et Et
| | conc.H SO ( i ) PhMgBr ( excess)
(A) Me  C — C  Me  24  (B) H3C – C  N    
 
| |  (ii ) H / H 2O
OH OH
NH2
HO
(C)
( CH 3 ) 2 Cd
C – Cl    (D) HNO
2 
O
GRIGNARD REAGENT
[PARAGRAPH TYPE]
Paragraph for question nos. 55 to 56
( i ) CH MgBr ( excess) (i ) BH .THF HBr
Ph – C  N  3     A  3  B conc .H 2SO 4
  D  E
(ii ) H / H 2O ( ii ) CH 3COOH  H 2O 2
(i) PhMgBr
(ii) H2O
C
Q.55 What is C?
C — OH
(A) (B)
CH3
C — CH3 C — OH
(C) (D)
OH CH3
Q.56 E is
CH 3
|
(A) Ph  CH 2  CH 2 (B) Ph  C  CH 2  Br
| |
Br H
CH 3 CH 2  Br
| |
(C) Ph  C  CH 3 (D) Ph  C  CH 2
|
Br
GRIGNARD REAGENT
EXERCISE-3
(JEE ADVANCED Previous Year's Questions)
Q.1 Write the structural formula of main organic product formed when ethyl acetate is treated with double the
molar quantity of methyl magnesium bromide and the reaction mxiture is poured into water.
[JEE 1981]
Q.2 Identify the major product. [JEE 1993]

C6H5COOH + CH3MgI  ? + ?
Q.3 Predict the major product. [JEE 1994]

( i ) CH MgBr ( excess )
C6H5– CH2COCH3  3    
(ii ) H
Q.4 Which of the following is an organometallic compound? [JEE 1997]

(A) Lithium methoxide (B) Lithium acetate
(C)Lithiumdimethylamide (D)Methyl lithium
Q.5 (CH3)3CMgCl on treatment with D2O produces [JEE 1997]

(A) (CH3)3CD (B) (CH3)3COD (C) (CD)3CD (D) (CD)3COD
Q.6 C 4 H 8O 2 CH MgBr

3 P, the product 'P' will be [JEE 2003]
Ethyl ester ( excess )
(A) (B) (C) (D)
Q.7 Order of rate of reaction of following compounds with phenyl magnesium bromide is: [JEE 2004]
Ph  C  Ph Me  C  H Me  C  Me
|| || ||
O O O
( I) (II) (III)
(A) I > II > III (B) II > III > I (C) III > I > II (D) II > I > III
CH 3
|
Q.8 Ph – MgBr + CH3  C  OH  A [JEE 2005]
|
CH 3
CH 3 CH 3
| |
(A) (B) CH 3  C  OPh (C) (D) CH 3  C  Ph
| |
CH 3 CH 3
GRIGNARD REAGENT
Q.9 Identify the reaction mechanism : [JEE 2011]
Q.10 The major product in the following reaction is [JEEAdvance 2014]

O
. CH 3MgBr , dry ether , 0C
Cl 1  
CH3 2. aq. acid
O OH
(A) H3C (B) H C CH3
CH3 2 CH3
CH3
(C) (D)
O CH2 O CH3
Paragraph for question nos. 11 & 12
In the following reactions : [JEEAdvance 2015]

C8 H 6 Pd BaSO4
 C8 H8 i
. B2H 6
  X
H2 ii. H 2 O 2 , NaOH , H 2O
 H 2O
 HgSO 4 , H 2SO 4
C8 H 8O i
. EtMgBr , H 2O
      Y
ii. H  , Heat
Q.11 Compound X is
O OH
(A) CH3 (B) CH3
OH
CHO
(C) (D)
Q.12 The major compound Y is
(A) CH3 (B) CH3
CH2 CH3
CH3
(C) (D) CH3
GRIGNARD REAGENT
EXERCISE-4
(CBSE Previous Year's Questions)
Q.1 Describe how the following conversions can be brought about :

Bromo benzene to benzoic acid [CBSE 2008]
Q.2 Give the mechanism of addition of grignard reagent to carbonyl compound. [CBSE 2009]
Q.3 Explain the mechanism of the following reactions: [CBSE 2009]

Addition of Grignard's reagent to the carbonyl group of a compound forming an adduct followed
by hydrolysis.
Q.4 How are the following conversions carried out? [CBSE 2010]
Methyl magnesium bromide to 2-methylpropan-2-ol.
Q.5 How would you account for thefollowing: [CBSE 2010]

Grignard reagents are prepared strictly under anhydrous conditions.
Q.6 How would you bring the following conversion ? [CBSE 2011]
(a) Methanal to ethanal (not more than 3 steps)
(b)Acetone to tert-butyl alcohol
(c) Propanal to butanone
GRIGNARD REAGENT
EXERCISE-5 (Rank Booster)
[SINGLE CORRECT CHOICE TYPE]

Q.1 How many litres of ethene would be produced when 2.62 g of vinyl magnesium bromide is treated with
224 ml of ethyne at STP.
(A) 0.224 litre (B) 0.08 litre (C) 0.448 litre (D) 1.12 litre
Q.2 Br–CH2–CC–CH2–Br Mg

 BrMg–CH2–CC–CH2–MgBr
( excess)
Et 2O
Product
The major product is:
(A) Br–Mg–CH2–CC–CH2–Br (B) Cyclobutyne
(C) —(CH 2  C  C  CH 2—
)n (D) CH2 = C=C=CH2
(1) CH 3MgX
Q.3 O
(2) NH 4Cl
Product is
(A) Enantiomer (B) Diastereisomer (C) Meso (D)Achiral
Q.4 CH 3CCH 2 CH 2 CH 2Cl   A, A is

CH MgBr (1eq .)
3
||
O
CH 3
|
(A) CH 3CCH 2 CH 2 CH 2Cl (B) CH 3CCH 2 CH 2CH 2CH 3
| ||
OH O
(C) (D)
O O
|| ||
Q.5 CH 3CCH 2 CH 2 COCH 2CH 3 (
i ) CH3MgBr ( one mol )
     A,A formed in this reaction is
(ii ) H3O 
OH O O O
| || || ||
(A) CH 3CCH 2 CH 2COCH 2CH 3 (B) CH 3CCH 2 CH 2CCH 3
|
CH 3
CH 3 CH 3
| |
(C) (D) CH 3CCH 2 CH 2 CCH 3
| |
OH OH
GRIGNARD REAGENT
CH MgBr (1 eq.)
Q.6 3   ?
The product is:
(A) (B) (C) (D)
Q.7 CH2 = C = O (

i ) Br2
 C4H8O
( ii ) CH 3MgBr
( 2 equi )
(A) (B) (C) (D)All of these
Q.8 Which of the following reacts with 4 moles of RMgX.
COCl CH2–Cl
ROC
(A) (B)
CHO COOEt
OH CC – H
EtO
O OCH3
(C) O (D) O
H RN
O
Et
GRIGNARD REAGENT
[PARAGRAPH TYPE]
Paragraph for question nos. 9 to 11
Consider the given reaction and answer the following questions
COOCH3
MeMgBr
  Products
O OCH3 ( excess )
O SH
||
O
Q.9 No. of RMgX consumed in the reaction is

(A) 4 (B) 5 (C) 6 (D) 7
Q.10 How many product will be fromed in given reaction (excluding stereo)
(A) 2 (B) 3 (C) 4 (D) 5
Q.11 Which of the following reaction will give the same Hydrocarbon formed as one of the product in the
above reaction.
(A) EtMgBr + Me – OH  (B) PhMgBr + Me – OH 
(C) MeMgBr + Ph – OH  (D) MeMgBr + CH3 – CHO 
[MULTIPLE CORRECT CHOICE TYPE]

OH
Q.12 Carbonyl compound (X) + Grignard reagent (Y) Me Ph
Et
X , Y will be
O O
|| ||
(A) Et  C  Ph , Me Mg Br (B) Me  C  Ph , Et Mg Br
O O
|| ||
(C) Me  C  Et , Ph Mg Br (D) Et  C  Ph , Et Mg Br
HO OEt
2 CH3MgX
Q.13 NH4Cl
P1 + P2
Identify P1 & P2.

O HO Me
(A) CH4 (B) (C) (D)

O
GRIGNARD REAGENT
Q.14 Select the correct statement:

(A) 1,4-dibromobutane react with excess of magnesium in ether to generate di-Grignard reagent.
(B) 1,2-dichlorocyclohexane treated with excess of Mg in ether produces cyclohexene.
(C) Vicinal dihalides undergo dehalogenation to give alkene when heated with Zn dust or Mg.
(D) 1,3-dichloropropane by treatment with Zn dust or Mg forms cyclopropane.
( i ) CH ONH
Q.15 2CH3MgBr ( 2 
3
ii ) H 
(A) CH3–O–NH–CH3 (B) CH3–NH–CH3

(C) CH3–NH2 (D) CH3–OH
[SUBJECTIVE]
Q.16 4.6 g of a polyhydric alcohol was treated with an excess of methy magnesium bromide to produce 3.36
litre of CH4 at STP. Calculate number of –OH group present in the alcohol.
(molecular weight of alcohol = 92)
Q.17 Calculate number of molecules of Grignard regent consumed by 1 molecule of following compound.
H
O
O O
O
HO NO2
Q.18 (reaction-1)
( i ) x CH3MgBr
   
( ii ) H3O
( i ) y CH MgBr
  
3

 (reaction-2)
( ii ) H3O
O OH
|| | (reaction-3)
Et  O  C  O  Et ( i ) z PhMgBr
  Ph  C  Ph
(ii ) H  |
What is the value of x + y + z = ? Ph
GRIGNARD REAGENT
Q.19 Addition of phenyl magnesium bromide to 4-tert-butyl cyclohexanone gives two isomeric tertiaryalcohol
as product. Both alcohol yield same alkene when subjected to acid-catalyzed dehydration. Suggest a
reasonable structure for these two alcohol.
4-tert-butyl cyclohexanone
Q.20 Organic halide having carbonyl, cyanide , epoxy , OH , – NH2 , – NHR , –CO2H , –SO3H , –SH ,
– CCH group cannot be used to prepare grignard reagent. Explain why?
Q.21 Conversion : HCCH  CH3–CCD

Ph–Br  Ph–D
Q.22 (a) Unlike other esters which react with Grignard reagents to give tertiary alcohols, ethyl formate
O
||
(HCOCH 2CH 3 ) yields a different class of alcohols on treatment with Grignard reagents. What kind of
alcohol is formed in this case and why?
O
||
(b) Diethyl carbonate (CH 3CH 2 OCOCH 2 CH 3 ) reacts with excess Grignard reagent to yield alcohols of a
particular type. What is the structural feature that characterizes alcohols prepared in this way?
GRIGNARD REAGENT
ANSWER KEY
EXERCISE-1
Q.1 (i) CH3–Cl (ii) H  C  H (iii) CH 3  C  H
|| ||
O O
CH3
C=O
(iv) (v) CH2=CH–CH2–Cl (vi)

O
Q.2 1434
Q.3 0005
Q.4 1.56 gms
Q.5 (a) + CH4 + MgBr2
(b) CH 2  C  CH 2 

| |
Ph Br
(c) (
i ) Mg / Ether
 
(ii ) NH 4Cl
Q.6 Due to acidic hydrogen
Q.7 (a) Ph3C–OH (b) PhH
OH
|
Q.8 (a) EtH + Ph 2 C  C  C  Ph
(b)
(c) 
(d)
Q.9 5 Q.10 6 Q.11 3
GRIGNARD REAGENT
EXERCISE-2
Q.1 C Q.2 A Q.3 A Q.4 C Q.5 C Q.6 A Q.7 C

Q.8 D Q.9 B Q.10 B Q.11 A Q.12 A Q.13 C Q.14 D
Q.15 D Q.16 A Q.17 C Q.18 C Q.19 C Q.20 B Q.21 C
Q.22 C Q.23 C Q.24 B Q.25 C Q.26 C Q.27 A Q.28 A
Q.29 A Q.30 C Q.31 B Q.32 C Q.33 D Q.34 D Q.35 C
Q.36 C Q.37 D Q.38 B Q.39 B Q.40 C Q.41 C Q.42 A
Q.43 C Q.44 AB Q.45 BD Q.46 BC Q.47 BD Q.48 ACD Q.49 ABC
Q.50 CD Q.51 BCD Q.52 ABCD Q.53 AC Q.54 ABCD Q.55 D Q.56 A
EXERCISE-3
O
||
H O
Q.1 CH 3  C  OC 2 H 5  2CH 3MgBr  
2
 ]
OH
|
C6 H 5  CH 2 — C — CH 3
Q.2 C6H5COO¯ Mg I + CH4 Q.3 |
CH 3
Q.4 D Q.5 A Q.6 A Q.7 B Q.8 A
O O CH2–Cl O
|| CH3MgI
Ph  C  CH 2  CH 2  CH 2  Cl   Ph – C – CH2CH2 Cl 

Ph
Q.9
H3C
CH3
Q.10 D Q.11 C Q.12 D
GRIGNARD REAGENT
EXERCISE-4
Br MgBr COOH
Mg/dry (i) Dry ice
Q.1 ether (ii) H3O
+
Bromo Benzoic
benzene acid
O OMgBr OH
|| | |
Q.4 CH 3MgBr  CH 3  C  CH 3  CH 3  C  CH 3 H
2O
 CH 3  C  CH 3
Methyl magnesium bromide | |
CH 3 CH 3
2 methylpropan  2ol
Q.5 Grignard reagents are very reactive. They react with moisture present in the starting materials.i.e.
R–X and Mg.
R–MgX + H – OH  R – H + Mg (OH) X
Therefore, Grignard reagents must be prepared under anhydrous conditions.
CH3MgBr H2O [O]

Q.6 (a) HCHO CH3CH2OMgBr CH3CH2OH + CH3CHO
K2Cr2O7/H
Addition Ethyl alcohol Ethanal
product
CH3 CH3
+
CH3MgBr H , H2O
(b) CH3 – C = O Dry ether CH3 – C – OMgBr –Mg(OH)Br CH3 – C – OH
CH3 CH3 CH3
Acetone Addition product 2-Methylpropan-2-ol
(i) CH3MgBr K2Cr2O7/H2SO4

(c) CH3–CH2 –C– H CH3CH2CH – CH3 CH3CH2CCH3
Dry ether or Cu/573 K
O +
Propanal (ii) H2O/H OH O
Butan-2-ol Butan-2-one
GRIGNARD REAGENT
EXERCISE-5
Q.1 C Q.2 D Q.3 A Q.4 C Q.5 C Q.6 D Q.7 A

Q.8 D Q.9 C Q.10 C Q.11 C Q.12 ABC Q.13 AB
Q.14 ABCD Q.15 CD Q.16 0003 Q.17 0005 Q.18 0012
Q.19 Geometrical isomer will formed
Q.20 Not required
 
LiO or Na  CH Cl  
Q.21(a)HCC–H   H  C  CNa 3 H  C  C  CH 3  3  
CH MgBr
 BrMg–CC–CH3
liq.( NH3 )
D–CC-CH3
D 2O
(b) Ph–Br Mg
 Ph–MgBr  Ph–D
Q.22 (a) Formate gives aldehydes & other esters gives ketones.
— H O
(b)  R3C– O MgX 
  R3C – OH + Mg
2
3
MgX

 2 RO
GRIGNARD REAGENT
NOTES

OC - Grignard Reagent - E

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

OC - Grignard Reagent - E

Uploaded by

Copyright:

Available Formats

JEE (MAIN+ADVANCED)

PREPARATION OF GRIGNARD REAGENTS

ArX + Mg  ArMgX

The order of reactivity of halides with Mg is :

REACTIONS OF GRIGNARD REAGENTS

1. Reaction with carbonyl compounds :

GR react with carbonyl compounds to give 1º, 2º and 3º alcohols.

(a) G.R. react with formaldehyde (methanal, HCHO) to gives 1º alcohol.

(b) G.R. react with all other aldehydes to given 2º alcohols.

R' R' R' H

(c) G.R. react with ketones to give 3º alcohols.

R' R' R' X

2. Reaction with ester :

R' R' R' R'

3. Reaction with dialkyl carbonate :

5. Reaction with anhydride :

G.R. react with O2 to give 1º alcohol

9. Reaction with R–CN :

Ketone on further reaction with RMgX gives 3º alcohol.

Reaction Chart of Grignard reagent (R–Mg+X–)

EXERCISE-1 (Subjective Questions)

(v) CH2= CH–CH2–CH3 (vi)

(c) (d) SiCl4

Q.3 How manycycloalkyl chloride (without consideringstereoisomers) would yield 1,3-dimethyl-cyclohexane

Q.5 What is the product in the following reactions.

Q.7 What are the products ?

(a) PhMgBr ( i ) COCl 2

Q.8 What products would be formed in these reactions ?

What is value of 'x' ?

EXERCISE-2 (Objective Questions)

Q.1 Consider the given organometallic compound.

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

Q.4 14CH =CH–CH

(A) (B) (C) (D) None of these

Q.9 CH3—CH—CH2 CH

Q.14 Which of the following reacts faster with RMgX.

Q.17 (R) - 2-Bromooctane (

(C) A and B both (D) None of these

End product of above reaction is

I: II : CH 3CHCH 2CH III :

Q.24 Which of the following is incorrect.

(A) 1° ROH (B) 2° ROH (C) 3° ROH (D)Alkene

Q.31 In the reaction sequence:

(X) & (Y) respectively are

(C) P is CH 3CH  CH  C(CH 3 ) 2 Q is (CH 3 ) 2 CHCH 2C  CH 3

(D) P is (CH 3 ) 2 CHCH 2C  CH 3 Q is CH 3CH  CH  C(CH 3 ) 2

(B) H 3C  C  Cl + (CH3)2 CuLi 

Q.38 H 3C  CH 2  C  OCH 3 (

Q.40 Which statement is correct.

(D) is non aromatic compound.

Q.41 Which reaction will give diastereomeric products.

(A) H3C — C — CH2 (B) H3C — CH — CH – CH3

[MULTIPLE CORRECT CHOICE TYPE]

Q.45 Nucleophilic addition of Grignard reagent cannot occur in

Q.51 In which of the following reactions 3°alcohol will be obtained as a product.

Q.53 Which statement(s) is / are incorrect?

Q.54 Which reaction(s) produce(s) ketones as major product ?

Q.2 Identify the major product. [JEE 1993]

Q.3 Predict the major product. [JEE 1994]

Q.4 Which of the following is an organometallic compound? [JEE 1997]

Q.5 (CH3)3CMgCl on treatment with D2O produces [JEE 1997]

Q.6 C 4 H 8O 2 CH MgBr