Model-5 : Addition of Grignard reagent

Q.NO
1.
H CH, Mg Br
g+ r

(i) From the above reaction p is

sa) (b)
H-N D N

1
 (c) ()
H
H
(ii) If 'q' consists of nitrogen then 'q' is
(a) (b)
H--N-H H-C
(
(d) N-CH
(iii) r from the above reaction is
( CH, (b) CH,-D
(C) N CH3
(d)
CH,-G N
A;C;A
| 2.
Mg
THF

The major product of the above reaction is

(a)
MgCi
()
CI

3.
N=C-CH, -0CH, (0 phMgBr
(ii) H,0/H/0°C
The major product of the above reaction is
(A) (b)
PhCH-Ph+ CH3OH CH-OH
+CH,OH

(d

CH + CHg!
CH-OH
+CH

B
4.

CH,MgBr

In the given reaction, the major product is

(a) OH CH, (b)

(c) OH (d)

-CHy
 b
5. MgBr

H,o The most possible product is

DMSO

(a) (b)

(d) OH
(c) OH Ph

6.
MgBr

CHs,
H,
CH,MgBr
H.O 4

Ifp and q are the major steric approach controlled products, then p and
q are
(a) GH OH OH
(c) CH, CH,
Ph
Ph CH

CHa
(b) OH OH
(d) CH OH CH,
Ph
CH Ph OH
CHa

CH

7.
MgBr
+
H,O

The major product is

(a) OH (b) OH

(c) OH
(d)

1
8.

(0)n PhMgBr
() H,0
The products are

(a) PhC-OH + H H (b) Ph,C--OH + OH OH

(c) (d)
Ph Ph + Hó
Ph OPh+ OH OH
Ph

9
Br
() Mg
(

The major product is

(a OH
(b) OH

(c) OH
(a) OH

10.
k

CH,
Mg D,0
Br THF
CH,CHH
S-Bromo Butane
Product stereochemistry will be

(a) Retention of configuration

(b) Racemisation
(c) Inversion of configuration
(d) Retention and inversion will be observed
D
11,
)
(9 CHUI
() H;o
CH,
are
The products obtained with respect to their stereo-chermistry
(a) Racemic mixture (b) inversion product major
(c) diastereomers (d) achiral compound
(iü)
) CH,MgBr

CH, CH,CH3
The products are
(a) racemic mixture (b) diasterèomers
(c) achiral compound (d) epimers
i)c, i)c
12. *
CHO
H -OH NalO,
H-OH
CH
The final products formed are
(a) (c) (d) OH
(b)
H- -OH H- -CH,

0OH
LNH, NalO,
() OH

Thotlnal products formed are

(a) (b) (c) CO, (d)

H COOH H
1)bc 2) ab
13. * Hentify whichcompound give alkyne formation by reaction with PCl, forward by ale. NaNH; in excess.
-OH
(A) CH,CHO (B) 0 (D) CH,-O-CH,CH,
-OH

A,d
14. In which of the following reaction 3° alcohol is formed ?
+ PhMgBr (B) + 2CH,MgBr 2H
C

(C) EtO-C-OEt +
3CH,MgBr (D) H-C-CI+ 2PhMgBr 2H

A,b,c,d
15. *

OH
What are the possible combinations to
prepare given alcohol
(A) MgBr
+ CH,MgBr (B)

+ EtMgBr (D) + EtMgBr

A,b,c,d
16. *
Number of carbonyl compound with molecular formula CH,0
alcohol with CH,MgBr forward with which give racemic mixture of secondary
hydrolysis. (Including stereo)
17, *

X=mumber of structural isomer of CaHoO

reacts with PhMgBr to gave as a product.

18.
Me Me

+ (1) CH,MgBr(excess)
CH, CH,
(2) H,0
Number of optically active products in the reaction are -
2
19. *
OH
(i)) CHCIyNaOH
() ()
(i) H*
(Y) is double bond equivalent (DBE) of product

HO C-NH2 Br, +Z KOH NH,

(i)
() CH, K)
(Z) is number of moles of KOH consumed
So, thevalue of (X +Y+)-7 will be.
(X) is moles of grignard reagent consumed.
6
20.

l}CHMeBr conc H,SO,

|H,0 Zr:AcOH

The compound Acan be:

CHO

B)
X

D
KEY:AB

(a)
(b)

CH,OH
CH- CH,

CH,

CH,OH

CH,

OH

(c)

(d)
21, *
HBO
CH,CHO ()) CH,MgBr
() H,0 ’(A) ’(B) ’(c)
(A) and (C) are related as: (B) Position isomers
(A) ldentical (D) Opical isomers
(C) Functional isomer

22. Give the product of the following reaction.

CH-O MER
MEA
H0 (ii CH-0 Ha0

O=0
(ii) Me--Et - Ma,
H0
HSO4’ C H0
HSOA’D
OH CH,
CH, Gv) (D) CHycPh
(i) (B) (Gil) (C) B-G-E
OH CH
23. * An organic compound A(C,HBra) gives apale yellow ppt with warm ale. AgNO
solution. A on treatment with dil. KMnO4 gives a compound B(C,H;0,Br).
B on treatment with AgOH followed by heating with Br/CCl, gives a
compound of which only two mono nitro isomers are possible. A upon
treatment with LiAIH4 gives C (C,H,Br).
Ms IHCHO
ther I|H,0 PCCxThe product X' would be

CH,

CH,CHO CH; CH;

CHO

B) CHO C) D) H,0H
A)

CH,Br COOH COOAg

Br Br
Br
KMnO4 AgOlH

(A) (B) Br, /CCi,

Br Br
B
Br Br
Br
possible mono
nitro products

NO2
NO,
CH, CH¡
CH,Br MgBr
Br IHCHO
Br
Mg II H,o*
LiAlH, cther

(C) CH, CH,

(A)
CHO CH,OH
PCC
 24.
What is the major product of the reaction?
Mg,diethylether (i)HCHO
(i)H30»
Br
1)2-butanol and Mg(OH)Br 2)Butanoland Mg(OH)Br
4)Butane and Mg(OH)Br
3)2-butanol and MgHBr
B
25. *
Number of R-Mgx (grignard reagent) consumed are

H,C-o
O-Ph

(0) RMgX (excess)

H-Ca
(i) H,0®

HO

H,C-O

HC-C

26. * Choose the reagent and reactant that would produce

2-methyl-2-butanol as.the major prodsct.
() CçH_MgBr
(i) NH,CI; H,0

CH,MgBr
() NH,CI H}O

CH;MgBr
(IIT) OMe NH,CI, H,O
(a) I+Il+III (b) I+III
(c) I (d) II
A
27.
There may be something seriously wrong with the fol
lowing proposed synthesis of the drug
terfenadine.
Identify the problcm if any, and propose spccifio
nccdcd to make this route steps
workablo.
Br Mg
Ether

OH OHC

OH

OH

(a) Therc is nothing wrong

(b) In presence of -OH group, Grignard
can't be carried out synthesis
(c) N vill be involved in
participation. ncighbouring group
(d) Both (b) and (c)
B
28. *

(i)CH,MgBr ’B; Bis:

(it) a
(i)H,0
OH QH
tCH, COOH
CH, (B)| CH-OH
(C) (D)
C

29. *

Ph
Br/CCI,(1 eq) Mg/ether H/A
R ’S
H,0*
Product 'S' is

(A) (B)

11
 (C) (D)
B
Mg
Br
Br/CCI, Mg/ether Ph
Ph Ph
leq
MgBr
Br
(P)

PH
Ph
H'/A -Ph MgBr
OH AOH

30.
How many mole of griganard reagent react with following compound ?

HO
C

HS
CH,

1) 3 2) 4 3) 5 4) 6
(3)

-C-Clgroup requires 2 moleR- Mgx

-C-group requires l mole R mgx

HS- group requires 1mole R-mgx
-OH group requires ImoleR-mgx
31. Correct satementcegarding gen reacion sequence isare:
Mg
Toluene Chv Pr Ether

ÇH,
CH,-H-CH,
(E) Ris

OH
CH, H
(CR gives Lucas Test
(D) R is

117
 (8, C)

CH,
ÇH,-CI ÇH,-MgCi ÇH-H-CIH,
Mglethec 9CH-CH4o
Øt¯Úon) (i) NH,CI
Grignard
reagent
32. *

B
Mg Cyclopentadienone The product is
Eher
For the reaction BI

A) B) oD)
C
8r
Diels-Alder
Mg
Reaction o
Br

33.
CH3
(1) NBS
H-c-CH CH3 OsO4 ’(C)
(2) Mg/ether >(A) (B)
H,0,
CH3-CHy Br
Product (C) is
OEt OEt
H-
OH OH
(a) (b)
OH OH

OEt
H

OH
(c) (d) Both (a) and (b)
OH

B
34. * How many aldehydes with M.F. CH2 can give geometrical isomers on reaction with
hydrazine where n = 1to 5 (including all).

H
35. *
The following conversion is caricd out usiung

Me Me

cO,H

(A) hydroboration-oxidation followed by Jones oxidation

(B) Wacker oxidation followed by haloforn1 reaction
(C) oxyercwation-demercuration followed by Jones oxidation
(D) ozonolysis followed by haloform reaction

36. * HO

To synthesize -CH-CH
CHa
(A)

Which of the following reactants cannot be suitable:

(A) (B)

CH-CH. CH-MgBr CHa CH,CH,MgBr

(C) CHO
(D) MgBr
CH,ÇHMgBr
HC -CH-CH3
H,-CH3 \

37. Which of the following pairs of the compounds can be

used as starting mnaterials in the synthesis of 2-phenyl
2-pentanol?
(a) CH,(CH,),Br and PhCOOH
(b) (CH),CHCH,Br and PhCOCH,
(c) PhBr and CH3CH,CH,COCH3
(d) PhBr and (CH,),CHCH,COCH,

38. Which of the following Grignard reaction will fail to

occur as written?

(a) H C=CCH,- -H + CH,MgBr

OH
Hydrolysis,H CEC-CHz H
H3
+ CHzMgBrHydrolysis

OH

-H + CH3MgBr Hydrolysis
QH
CI
H
CHy
 (d) + CH;MgBrHydrolysis

ÖH
ABC
39. * Which of the following is correct for the final product of the given
sequence of reaction :
MgBr
ÇH,-Oh HIO, P, (0) H,O
’ P 0PCC
(i) CH,MgBr,>P,(Final product)
(ii) H,0
(A)Compound P, on oxidation with
(B) Compound P, on rcaction with I, (CrOo, + H.SO,) gives a compound which gives 2,4 DNP
+ NaOH gives yellow ppt. test
(C)Compound P,on reaction with cerric
(D)Compound P, on reaction with MnO, ammonium
gives
nitrate give red colouration
carboxylic acid
ABC
40.
CH, =CHCHCH,CH,0H MnO2 y À. Ais
OH

(A) CH, =CHCCH,CH,OH (B) CH, =CHCHCH,CHO

OH
(c) CH2 =CHCCH,CHo (D) CH2 =CHÇCH,ÇOH

A
41. There may be something seriously wrong vith the fol
lowing proposed synthesis of the drug terfenadine.
Identify the problcm if any, and propose specific steps
needed to make this routc workable.

Br Mg
Ether

ÓH OHC

OH

OH

(a) Therc is nothing wrong

(b) In presence of -OH group, Grignard synthesis
can't be carried out
(c) N will be involved in ncighbouring group
participation.
(d) Both (b) and (c)
B
 inacive (co
0optically aclive alcohol is oxidized by Jones' reagent (H,CrO) to an optically
42. *
ketone. Which of the followingcompounds meets these facisr

OH
(A) (8) (D)
OH

43. *
Which sequence of reaction would produce 2-brömo
2,3-dimcthyl butanc from acetonc and 2-bromopropanc?
Br () Li-THF
(a) (ii) Acetone HBr, 0°C
(iii) HCI, H,0
Br
(b) (i)
CH,ONa
(i) H,0* HO -Br
CH,OH
Br
(c) (i) Mg, Ether
(ii) Acetone
(iii) HCI, H,O -fon Mg, Ether
Br?
Br
(i) Mg, Ether ()Li, THF
(d)
(ii) Acetone (ii) Brz
(ii) HCI, H,0
A
44. 9. Choose the najor product of the following
quence.
reaction se
OH PBrs Li 1, CO, SOCI) CH,OH
2. Ht

ÇH,
OH
OH
(a) (b)
H3C
OMe
(c) | (d)
CHs
45. PB n gEt,OR
OH

Choose the corect statenment (s)

a) A is position isomer of isopropyl chloride

b) B can act both as base as well as nucleophile

c)C is CH,CH(D).CH,

d) Cis CH,CH.CH,ND,
B

46. In which of the following reactions, the products are represented correctly (Given
each reaction is taking place under suitable experimental conditions)

OH

A)

OH
HI
B) Cold

LiAIH,
C)
OH
(major)

D) Na NH,
R-OH
HO

ABC
47. In the reaction sequence X| is ketone;
CH,
-CH-C0OH then X will be
X KMn0, /OH® /AHOOC-(CH, ,
a) b) c) ACH, d) CH, Ú CH,

B
acid
Ketones (or) aldehydes on oxidation gives carboxylic
 48.
lCenlifly the rea tion which can nt ghve3Alcohol CH,-Cl\-C-CH,
OH

) CHCHMg'Br CH-Mg'B
()

(C)CH-G (0 CH,CH,-Mg'Br(2ea). 0) CH-Mg'Br(2-eq)

)

CH-Cihl.o-cH, CH-MaBr
-CH,-o
SN-AE CH-CHd-CH CHMOBIL, CH-CH-CH,
H,
By Nucleophilic
49, addition reaction '

A+ B(gas)
EtMgBr
Product is Product

(H- CH,
(eYRacemic mixture of Ph--CH, -CH,
(o Et
C zptcaly pure)

Hint- First step is

50. EtMgBr
The
decarboxylation
from top and bottom
product obtained via face.
to result ketone
and second step is
oxymercuration Nucleophilic addition of
(A) CH,CH,-C-CH, (HgSO,-H,SO) 1-butync would be
of
(C) (B) CH,CH,CH,CHO
CH,CH,CHO + HCHO (D)CH,CH,COOH +
A
HCOOH
51. Choose the sequence of the
following to get

(a) OH NaBH, sOCi,, Mg ) HCHO

(üi) H,0
PCC
(b) NaBH4 SOCl, Mg ) HCHO

PCC
(C) NaBH4 SOCI, Mg 0 HCHO
(i) H,0
(d -H NaBH SOClh Mg (O)
H,C,0,
HCHO
(üi) H,o
PC
B

1177
52.
In which of the following rcactions the predominant
product would be 2-pentanone?
(a) OH PCC ) CH,MgBr PCC
() H,o
(b) CH,CN(excess) () CH,CH,CH,MgBr
(i) H,0*
(c) (i) CH,MgBr
CH,CH,CH,CO0C,Hs(excess) (iü) H,0
(d) CN (excess) () CH,MgBr
(i) H,0"
A,B,C,D
Passage - II
Grignard addition to carbonylcompounds is a specific case of nucleophillic addition
reaction which leads to formation of all type of alcohols (1, 2° &3°). In this addition tne
Strongly nucleophilic Grignard reagent uses its electron pair to form a bond with the C
atom of > C=
group, where one e pair of > C=O group, shifts out towards oxygen.
It results in the formation of an intermediate species in which alkoxide ion associated
with Mg"and X. Now addition of a ag. HX causes protonation of this species to
alcohol. give
53. *

-CHO,(A) CH,MgBr
H,0* (B)
Here the product (B)can be given as
OH CH,

-CH-CH, -CH-CH,
a) OH
b OH

CHOH QH CH,

-CHO CH,OH
c) d)
C

54. *
Aldehydic group alone protected
In which of the following reaction product formed is correctly given?
 OH
( (i)*-MgBr
(m)Hzo+

OH

CH,

(I) L D
BrvgCH,

MgBr
P Hð

OH
C=0
Pl

C
)

H
(u)
(ü)Hz0+ d) I, I,
b) II, III c) 1, III
a) I, II

D
Conceptual
S5 *

()CH, M¸Br (1eq)1-P+Q

(i) Hot

Here P and Q are respectively:

C,H,OH
CH,OH b)
a) , CH, cOoC,H,
cooc,H,
d) CH,OH
C,H,OH

substitution
B CH3MgBr followed by intramolecularnucleophilic
>C=0 reacts with followingreaction.
ofthe
56. Give the product CH-0 MB ’R
(ii) CH-0 H0
H20

(iv) Ph- - Me M H,SO4 D

HSOL’C H20
(iii) Me- -Et MB 1179
H0
57.
-OH
(A) 0CH;MÍl
()H,o*
CH,0
The structure of the compound (A) is

(A) (B)

-CHO (D) All the above

(C)

58. * Consider the following sequence of rcactions.

H,SO, healc 2. Zn, H,O
Ketone A 1.2.CH,0,H,Mgs BH,0
The ketone (A)is:
(A) (B).

B
59. What is the product of the reaction bclow?
CHO

NaCN,cthanol
then,dil.HCI

Br
OH
OH ÇN OH HCI
H+CN H+H HLCI

a) (b) (d)

Br CN
Br Br
A

60. Choose the correct statement about the following car

bonyl compounds.
(A) (B)

(C)
than
(a) Ketone (A) reacts faster with methyl lithium
aldehyde (C)
borohydride
(b) Ketone (A) reacts faster with sodium
than aldehyde(C)
aluminium hy
(c) Ester (B) reacts faster with lithium
dride than ketone (A)
lithium aluminium
(d) Aldchyde (C) reacts faster with
hydrie than ketone (A)
D
61.
N-OH

HsO4 ma<or producl

Identify the strucBure of 'P'
ÇONH,
ÇONH,
NH
NH (C) (0)
(A) (B)
Caprolactum

Passage
iodoform test, undergoes reaction with MeMgBr
A carbonylcompound P, which gives positive
lcads to a dicarbonyl compound
followed by dehydration to give an olefin Q. Ozonolysis of Q
predominantly S.
R, which undergocs intramolccular aldol reaction to give
P
I.McMgur 1.011 S
2.7n.l20 2.A
2,H*,H,)

62. The structure of the carbonyl compound P is

Me

Me

Et Me

B
63. The structure of the products Qand R, respectivcly, are

(A) -Me
COMe
Me Me
Me Me

(B)
CHO
MoMe .Me Me

H
CHO
Met. Me E
Me

CH,
CHO
Me Me Et

A
64. Thc'strdcture of thc product Sis (JEE 2009)

(B)
Me MeMe

Passage
Read the following reaction

H NaOEt
(mixture of monochloro derivatives) -R (mixture)
NBS
R(mixture) s(mixture)
aq. NaOH
T(mixture)
Note:From P' to 'Q
aSsume that chlorination is happening at the carbons adjacent to a conjugative
65.
One of the compounds in the mixture T' is system
OH
OH
OH OH

OH
A) B) OH C) H
D)
OH

66.
Total no. of isomers in mixture 0' on the basis of above mentioned
A) 2
assumption
B)4 C) 6 D) 8
C
67.
On treating mixture 'S' with strong base, product obtained is
OH
OH OH
OH

A) B) C) D) Br

B
OH OH
OH OH

Cl,
hy

1182
 HO HO

+
NBS ->

Br
HO

Br
Br
Br

HO
HO. Br HO

Caq. NaOH corresponding mixture of alcohols

68. 1) X is used in bristles For brushes

2) X is used in tyre cords
Final organic 3) X is used in manutacture of
substance unbreakable crockery
statements of (X) 4)) X is used in oilseals, tank lining

2
Toras Process
N0
NOH NH
HCI

nyon 6

69. *

) PAMgBr (eses) (A)

(2) H,o

Product(A) is:
OH OH

C) Ph-C D)
B)
Pli-C-Pl,
A)
Ph
Plh- -Pl Ph

KEY:B

11
 Ph OMgBr
+ PhM gBr -
PhMgBr OMgBr

OH

Ph
Ph Ph
P Ph

70.

Ç-CH,
MeMgCI
(1 mol) "P"
"P" is:
OH
CH3-(-CH3
(A) CH (B)

(C)
(D)

71. -CsHs

CzH;ONa Identify the correct statement about product

A) It is a ketoaldehyde B) It exhibits tautomerism

C)It is a sodium salt of carboxylic acid D) It is an ethyl ester
B

Ph Ph

-Fh

118