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GRIGNARD REAGENT Page # 3
GRIGNARD REAGENT
1.1 Organometallic compounds
Organometallic compounds are the organic compounds in which a metal atom is directly attached to
carbon atom through covalent bond or ionic bond. For example
C – M or C M
(Where C is a carbon atom of an organic molecule and M is a metal atom)
If the metal atom is attahed to oxygen, nitrogen. sulphur, etc. then such an organic compound is not
reagrded as an organometallic compound. The following structural formula do not belong to the family
of organometallic compounds.
Mg/dry ether
R–X RMgX (Grignard reagent)
Mechanism
+ +
R – X + Mg Rº + X + Mg R + Mg + X R – MgX
*(RMgX is only Nucheophile)
H H H
R R R
D T Mg/Ether D T D T
R + S
R X R X XMg X
H H H
Diastereo.
Reason
R R
H O
R
D T
+2
+ Mg
Mg Function of dry ether :  Mg +2 ether
R H
O
(Plannar)
R R
RONa (sodium alkoxide). CH3COONa(Sodium acetate), CH3COOAg (Silver acetate), RSK (Potasssium
mercaptide) RNHL (N–Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.
Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compond
because sillicon is a nonmetal.
Most important examples of organometallic compounds are Grignard reagents. In Griganard reagent,
the carbon and magnesium atoms are bonded with each other through polar covalent bond and
magnesium atom is attached to halogen by ionic bond.
C – MgX (Functional part of a Grignard reagent molecule)

In organometallic compounds, the metal atom can be bonded to carbon of a hydrocarbon radical
(Saturated, unsaturated, aliphatic, alicyclic or aromatic) or carbon atom of a heterocyclic radical.
Some examples are given below.
1. Saturated Aliphatic Grignard reagent
R – MgX (Alkylmagnesium halide)
CH3 – MgI (Methylmagnesium iodide)
2. Unsaturated Aliphatic Grignard reagent
(i) Alkenyl Grignard reagent
CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard reagent
CH  C – CH2 – MgX (Propargylmagnesium halide)
3. Alicyclic Grignard reagent
MgX (Cyclohexylmagnesium halide)
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4. Aromatic Grignard reagent
MgX (Phenylmagnesium halide)
C6H5CH2MgCl (Benzylmagnesium halide)
5. Heterocyclic Aromatic Grignard reagent
N MgX (Pyridine-4-magnesium halide)
6. Heterocyclic Nonaromatic Grignard reagent
N MgX (Piperidene-4-magnesium halide)
In a Grignard reagent. X is generally Cl, Br or I (Halogen). Order of reactivity is as follows:

RMgI > RMgBr > RMgCl
Some specific examples of organometallic compounds of magnesium and other metals are as follows>
Q.1 Which of the following is not an organometallic compounds?

(A) (CH3)2Zn (B) Tetramethyllead (C) R2cuLi (D) Tetramethylsilane
Ex. Which of the following formula represents Grignard reagent?

(A) H2NMgX (B) HC  CMgX (C) R2Mg (D) Mg(OH)Br
Ans. B
Ex. Which of the following is not a Grignard reagent?

(A) (CH3)2CHMgCl (B) CH3COOMgI (C) C6H11MgBr (D) C2H5MgCl
Ans. B
1.2 Preparation
Dry and pure
RX + Mg RMgX
Ether
Ether is used as a solvent because it is a Lewis base that donates its lone pair of electrons to electron
-deficient magnesium atom, therefore providing stability to the Grignard reagent by completing the
octet on magnesium atom.
Et Et
Et – O R Et – O R
+ Mg Mg
Et – O X Et – O X
Et Et
Alkylmgnesium halide
dietherate
Ex. What is the motive of adding iodine in small amount during preparation of methylmagnesium
iodide?
(A) It acts as a catalyst (B) It converts ether into alkyl iodide
(C) It decreases the violence of the reaction (D) It acts as an electrophilic
Ans. A
Ex. The reaction of an alkyl halide and magnesium is initially very slow, but later becomes very
fast, because
(A) The rection is autocatalytic (B) The Grignard reagent formed is ether -soluble
(C) The reaction is endothermic (D) The reaction is exothermic
Ans. D
Ex. A grignard reagent is formed on reacting magnesium with

(A) Alkyl halide in the presence of dry ether
(B) Alkyl halide in the presence of phenol
(C) Alkyl halide in the presence of alcohol
(D) Alkyl halide in the presence of alcoholic ether
Q. 2 Grignard reagent gets stabilised in ether medium, because ether.

(A) Is a high quality solvent
(B) Restricts ionisation
(C) Favours free radical mechanism
(D) It solvates Mg+2 ion
1.3 Reactivity of grignard reagents.

It has been found out by estimation that there is 35% ionic character in carbon-magnesium bond of
grignard reagent. Therefore, there is a tendency of forming carbonion by heterolysis of this polar
coordinate bond as follows.
R MgX R + Mg X
The carbanion (a nucleophile) formed as shown above, attacks the positively, charged electrophilic
centre of other compound. Therefore. It can be said that if a Grignard reagent is regarded as the
substrate, then electrophile displaces MgX, i.e, electrophilic substitution (ESR) reaction takes place.
E
R – MgX R R – E(SE Product)
If Grignard reagent is regarded as the attacking reagent, then the nucleophilic carbonion of Grignard
reagent will attack on the other compound taken as substrate.
R + C=O R–C–O
Ex. Which of the following types of bond exists between carbon and magnesium in a Grignard
reagent?
(A) completely covalent (B) Ionic (C) Coordinate (D) Polar covalent
Ans. D
1.4 Reactions of Grignard reagent
On having same hydrocarbon radical, the order of reactivity of Grignard reagents will be as follows:
RMgI > RMgBr > RMgCl
Grignard reagent gives the following two type of reactions.
(i) Substitution Reactions.
compounds having reactive hydrogen or halogen atom give substitution products on reacting with
Grignard reagent.
Z – H + R – MgX  R – H + Z - MgX
(Where Z is an atom or group having high electron attracting capacity)
Z – H + R – MgX'  R – H + Z - MgXX'
(Where X and X' are halogen atoms)
Both the above are examples of nucleophilic substitution reaction of Z – H and Z – X (not of the
Grignard reagents).
(ii) Reactions involving addition on polar -Bond

Grignard reagents form adducts by addition on the following types of -Bonds
C = O, C=S, C = N and C  N, – N = O, S=O

Example
R – MgX + C=O  R – C – OMgX
Adduct
1.6 Synthetic Importance of Grignard reagents
1. Synthesls of Alkanes
(i) With compounds having reactive hydrogen atom
R – MgX + H – Z  R – H + ZMgX
CH3 – MgX + H – OH  CH3 – H + Mg(OH)X
C2H5 – MgX + H – OR  C2H5 – H + Mg(OR)X
C3H7 – MgX + H – OC6H5  C3H7 – H + Mg(OC5H6)X
C2H5 – MgX + H – NH2  C2H5 – H + Mg(NH2)X
CH3 – MgX + H – NR2  CH3 – H + Mg(NHR)X
C2H5 – MgX + H – NHC6H5  CH3 – H + Mg(NHC6H5)X
CH3 – MgX + H – SR  C2H5 – H + Mg(SR)X
CH3 – MgX + H – C  N  CH3 – H + Mg(CN)X
C2H5 – MgX + H – C  CH  C2H5 – H + HC  C – MgX (ethynylmagnesium halide)
CH3 – MgX + H – C  CR  CH3 – H + HC  C – MgX (Alkynylmagnesium halide)
Methane gas is released on reacting methylmagnesium iodide with a compound containing reactive
hydrogen atom. The reaction is used for estimation of reactive hydrogen atoms present in a molecule.
This method is called Zerewitinoff method of estimation of reactive hydrogen atoms.
Ex. Zerewinoff's method is used for

(A) the estimation of reactive hydrogen atom
(B) the estimation of alkoxy group
(C ) the preparation of a higher ether
(D) the preparation of a Grignard reagent
Ans. A
(ii) with alkyl halide (coupling)

R – MgX+ X' – R'  R – R' + MgXX'
2. Synthesis of alkenes
R – MgX + X' – CH2 – CH = CH2 + MgXX'
3. Synthesis of higher alkynes

(i) Non-terminal alkynes
RMgX R"X
R' C  C – H R' – C = C = CMgX – MgX2 R'–C  C – R"
– RH
Ex. Which of the following products is formed on reacting 1-propenylmagnesium chloride with ethyl
iodide?
(A)  - Amylene (B)  - Amylene (C)  - Isoamylene (D)  - Isoamylene
Ans. B
Ex. Which of the following is obtained on the reaction of the simplest unsymmetrical alkyne with
methylmagnesium iodide?
(A) Simplest branched alkane (B) Simplest alkane
(C) Higher Alkyne (D) Isomeric Alkyne
Ans. D
Ex. Which of the following should be reacted with a Griganard reagent for preparing the thrid member
of the terminal alkyne family?
(A) An alkanal that gives iodoform test (B) Propyne
(C) Propyne followed by methyl chloride (D) Acetylene followed by ethyl chloride
Ans. D
4. Synthesis of other organometallics

4R – MgCl + 2PbCl2  R4Pb + Pb + 4MgCl2
Two important antiknock compounds, tetraethyllead (T. E. L. ) and tetramethyllead (T. M.L. ) are
manufactured by the above reaction.
2R – MgCl + HgCl2  R – Hg –R + 2MgCl2
Diallkylmercury
2R – MgCl + CdCl2  R – Cd – R + 2MgCl2
Diallkylcadmium
4R – MgCl + SnCl4  R4Sn + 4MgCl2
Tetraalkyl tin
Ex. Which of the following is the product obtained by the reaction of ethylmagnesium chloride with
lead chloride?
(A) An antiknock (B) An explosive (C) A white pigment (D) A fuel
Ans. A
5. Synthesis of Alcohols
There are following methods to obtain alcohols from Grignard reagent.
(i) From Oxygen
R – MgX + O = O  R – O – O – MgX
R – O – O – MgX + R – MgX  2R – O –MgX
R – O – MgX + HOH  R – O – H + Mg(OH)X
Primary, secondary and tertiary alcohols can be obtained by above reaction.
(ii) From Carbonyl compounds

Z Z Z
HOH
R – MgX + C=O R – C – OMgX R – C – OH
Z' Z' Z'
alcohol
(a) Primary of 1º Alcohols
Primary alcohols are formed on taking formaldehyde
H H H
HOH
H
H H
1º Alcohol
(b) Secondary or 2º alcohols
(1) From RCHO Secondary alcohols are formed of any aldehyde other than formaldehyde.
R' R
R – MgX + C=O R – C – OH
H H
2º Alcohol
(2) From formicester:
Secondary alcohols are obtained on hydrolysis of the product obtined by taking excess of Griganard
reagent and adding formic ester to it.
H H H H
RMgX RMgX
R + C – OEt R – C – OEt – Mg(OEt)X
R–C–R – Mg(OEt)X
R–C–R
MgX O MgX OMgX OH
(c) Tertiary or 3ºalcohols

(1) Tertiary alcohols are formed by taking any ketone
R' R'
R'
HOH
R
R" R"
3º Alcohol
(2) Tertiary alcohols are also obtained on hydrolysis of the product obtained by taking excess of
Grignard reagent and an ester of a higher homologue of formic acid.
R R R
RMgX
R – MgX + C – OEt R – C – OEt H2O
R–C–R
O OMgX OH
Various alcohols can be prepared by changing R in the above synthesis.
(iii) From Epoxides
HOH
R – MgX + CH2 – CH2 R – CH2 – CH2 R – CH2 – CH2
O OMgX OH
Oxirane
1º Alcohol having two more C
Opening of epoxide is medium dependent
CH – CH2 – CH3
O
H /RMgX OH /RMgX
R
CH – CH2 – CH3 R –CH2 – CH – CH3
OH OH
_+
R
+
H RMgX
CH – CH2 – CH3 CH – CH2 – CH3 CH – CH2 – CH3
*
O O OH
H
–
(R attack at that carbon where charge is less in acidic medium)
OH
CH2 – CH2 – CH3 R– attack at less hindered in Basic medium
O
Ex. Primary alcohol cannot be obtained by the reaction of a Griganard reagent with
(A) The simplest alkanal (B) Dimethylene oxide
(C) Ethylene glycol (D) Oxygen
Ans. C
Q. 3 Primary, secondary and tertiary alcohols can be obtained by hydrolysis of the products formed on
reaction by a Griganard reagent with
(A) Isobutyraldehyde (B) Butanone
(C) Oxygen (D) Oxirane
Ex. Compare the reactivity of following compound with RMgX?

Ans. NAR So steric hindrance and + ve charge 
HCHO, CH3CHO, CH3 – C – CH3 , CH3 – C – Ph Ph – CHO
O O
a b c d e
a>b>c>e>d
* Aliphatic aldehyde is more reactive than aliphatic Ketone
* But aliphatic Ketone more reactive than aromatic aldehyde and ketone both
Ex. compare the reactivity with RMgX with following compounds.

CHO CHO CHO CHO CHO
CH3 Cl F O CH3
a b c d e
Ans. reactivity b > c > e > a > d
6. Synthesis of Ethers
Higher ethers can be synthesised by reacting a lower chlorinated ether with Griganard reagent.
R –MgCl + Cl – CH2 – O – R  R – CH2 – O – R + MgCl2
CH3MgCl + Cl – CH2 – O – C2H5  CH3 – CH2 – O – C2H5
Chloromethyl ethyl ether Diethyl ether
7. Synthesis of Aldehydes
Corresponding aldehyde is obtained on hydrolysis of the product obtained by reacting of formic ester
and Grignard reagent in equimolecular ratio.
H H H H
HOH – EtOH
R + C – OEt R – C – OEt R – C – OEt R–C
MgX O OMgX OH O
The above conversion can be simplified as follows for convenience.
8. Synthesis of Ketones
(i) From Alkyl cyanides
A ketimine is formed on hydrolysis of the adduct obtained by the reaction of Grignard reagent and an
alkyl cyanide, which gives ketone on further hydrolysis.
RMgX + RCN R2C = NMgX HOH R2C = NH HOH R2C = O
Ketimine Ketone
R
X
 H–C N + RMgX H – C = NMgX R – C – H + Mg
O OH
Mechanism :
H2O
R – CH = N MgX R – CH = NH + Mg(X)OH
H immine
H H
OH O H
H2 O
R – CH – NH3 R – CH – NH2 R – CH – NH2
–H
R – CH – OH R – CHO
repulsion
+
H–C H H + CN because C N
Weak acid
* Only HC  N can give aldehyde with RMgX/H2O.
H2O
 R–C N + R'-MgX R – C = NMgX R–C=O
R' R'
* All alkaly cyanide (accept HCN) gives ketone with RMgX/Water.
KCN
eg. CH3X (NSR)
R – CH3 + KX (Carbon Karne ka method)
Ex.
CH3 – C N CH3COOH + NH4
H2O2/OH or partial Hydrolysis
CH3 – C – NH2
O
Na/C2H5OH HNO2
CH3 – CH2 – NH2 CH3CH2OH + N2
Ni/H2, Na/alc, LiAlH4
X CN
eg. KCN (not possible due to partial double bond )

+ KX
CH2X CH2CN
eg. KCN
* Benzene gives ESR reaction not FSR
eg. CH2 = CH – Br + KCN CH2 – CH – CN (not possible due to partial double bond )
(ii) From carboxylic esters (other than formic ester)

Ketone is formed on taking R' in place of H of formic ester.
R' R' R' R'
HOH – EtOH
R + C – OEt R – C – OEt R – C – OEt R–C
MgX O OMgX OH O
The above reaction sequence can be simplified as follows for convenience.
R + EtO – C – R' R – C – R' + EtO – MgX
MgX O O
Ex. Which of the following is formed on the reaction of one mole of acetyl chloride with one mole of
methylmagnesium chloride?
(A) 2-Butanol (B) Acetone (C) Isobutyl alcohol (D) t-Butyl alcohol
Ans. B
Q.4 Which of the following is formed on the reaction of one mole of acetyl chloride with two mole of
methylmagnesium chloride followed by hydrolysis?
(A) 2-Methyl-1-propanol (B) 1-Butanol (C) tert-Butyl alcohol (D) Acetone
(iii) From carboxylic acid chlorides
Formyl chloride is unstable. Therefore, acetyl chloride is regarded as the first member of this family.
R' R' R' R'
R + C – Cl R – C – Cl HOH R – C – Cl –HCl R–C
MgX O OMgX OH O
or
R – MgCl + Cl – CO – R' R – CO – R' + MgCl2
(iv) From carboxylic acid amides
Ketones are formed on reacting acetamide or its higher homologue with Grignard reagent, followed by
hydrolysis of the product.
R' R' R' R' R'
HOH – H2O H2O
R + C – NH2 R – C – NH2 R – C – NH2 R – C = NH R–C=O
-NH3
MgX O OMgX OH
9. Synthesis of carboxylic acids

A carboxylic acid is formed on hydrolysis of the adduct formed by passing carbon dioxide in the
ethereal solution of a Grignard reagent.
R – MgX + C = O R – C – OMgX HOH R – C – OH
–Mg(OH)X
O O O
10. Synthesis of carboxylic acid esters
Higher esters are formed on reacting the chlorinated ester of lower carboxylic acid with grignard
reagent.
RMgCl + ClCH2COOEt RCH2COOEt + MgCl2
11. Synthesis of mercaptans

Alkanethiols, i.e. mercaptan is formed on hydrolysis of the product obtained by adding sulphur to the
ethereal solution of Grignard reagent.
HOH
R – MgCl + S R – S – MgCl R – S – H + Mg(OH)Cl
12. Synthesis of phenols

Phenol is obtained on hydrolysis of the product obtained by reaction of arylmagnesium bromide with
oxygen.
C6H5MgBr + O = O C6H5O – OMgBr
C6H5O – OMgBr + C6H5MgBr 2C6H5 – OMgBr
C6H5 – OMgBr + H2O C6H5 – OH + Mg(OH)Br
Other phenols can be prepared by taking any aryl (Ar) group in place of phenyl group.
O=O Ar–MgBr
Ar – MgBr Ar – O – OMgBr 2Ar – O – MgBr
HOH
Ar – OMgBr ArOH
For example, on taking p-toluenemagnesium bromide p–cresol is formed in the end.
(i) O = O
(p) CH3 – C6H4 – MgBr (p) – CH3 – C6H4 – OH (p – Cresol)
(ii) HOH
p – Toluenemagnesium bromide
Q. 5 Which of the following compound reacts with methylmagnesium iodide to form n-Butane?
(A) n -Butyl alcohol (B) n - Propyl alcohol (C) Isopropyl iodide (d) n - Propyl chloride
Q. 6 Which of the following reactions froms an unsaturated Grignard reagent?

(A) RMgX + C2H2 (B) RMgX + CH3C  CCH3
(C) HC  CNa + RMgCl (D) RMgX + CH2 = CHCl
Q.7 Which of the following compound is formed on hydrolysis of the product obtained on the reaction of
ethylmagnesium iodide and propanone?
(A) tert-Amyl alcohol (B) Isoamyl alcohol
(C) tert-Butyl alcohol (D) Isobutyl alcohol
Q.8 The compound formed on hydrolysis of the adduct of methylmagnesium iodide and benzaldehyde
(A) Is a phenol (B) Gives iodoform test
(C) Is a primary alcohol (D) Gives benzophenone on oxidation
ANSWER OF UNSOLVED EXAMPLES
1. D 2. D 3. C 4. C 5. D 6. A 7. A 8. B
Ex. Road map problem
NBS aq. KOH Cu/300º Conc. NaOH NaOH/CaO

A (Major) B C B+F G
H2O CH3MgBr
H2O O3/CCl4
HBr ThO2
H (Major) E D
(1 mole) +
OCH3 CH3OH/H
K J I
+
H3O
HBr Zn/Hg/HCl OH /
P O N M L
(1 mole)
Br OH CHO CH2OH COO

Ans.
NBS aq. KOH Cu/300º Conc. NaOH
+
A B C B F
H2O CH3MgBr
CH3 NaOH/CaO
Br CH=CH2 CH=CH2 CH
OH
HBr ThO2
(1 mole)
H E D G
O
COOCH3 +
CH3O
–
COOCH3 CH3OH/H COOH O3/CCl4
COOCH3 COOH
K J I
+
H
O O O Br
COOH
OH / Zn/Hg/HCl HBr
(1 mole)
L M N O P
Ex. Road map problem
+ +
CH3MgX(excess) CH3Br Hg /H /H2O
H – C CH (A) (B) (C)
– CH4 (excess)
H
aO
I 2/N Mg/Hg/H2O
+
H (G)
F D+E
C2H5OH C2H5O Mg/H2O

F J K L M N H O.
H
+ NaOH
(G) H (H) I2/NaOH ( I + E) J
CaO
Ans. + +
+CH3 Br Hg /H /H2O
Br Mg C CMgBr CH3 – C C – CH3 CH3 – C CH2 – CH3
(A) (B) O (C)
I2/NaOH
+
C2H5OH H
CH3 – CH2 – C – OC2H5 CH3 – CH2 – C – OH CH3 – CH2 – C – O + CHI3
(J) O (F) O (D) O (E)
C 2H 5O
CH3
C2H5 – C – CH – C – OC2H5 C2H5 – C – CH – COOH C2H5 – C – CH2 – CH3
(K) O CH3 O O (L) O (M)
Mg/Hg/H2O
C2H5 O OH OH
C2H5 – C – C – C2H5 H / C2H5 – C – C – C2H5
C2H5 (O) C2H5 C2H5 (N)
Ex. Prepare benzyl alcohol from benzene ? without using organic compound ?
Br MgBr COOH CH2–OH
Br2 Mg/ether CO2 LiAlH4

Ans.
AlCl3(anlyed)
Ex. Prepare acetone from metrane without using any organic compound?
Ans. Cl2/hv Mg/Ether
CH4 CH3Cl CH3–MgBr
KCN CO2
PCl5
CH3CN CH3COOH CH3 – C – Cl
LiAlH4 O
Ca(OH)2
CH3–CH=NH CH3CH2–OH
PCl 5/PCl3/SOCl2 CH3 – C – CH3 +CaCO3

(Acetone)
CH3CH2–Cl O
O
+
Ex. 1 mole CH3MgBr CH3MgBr H /
Cl – C – OC2H5 A B C D
CH3MgBr 1 mole H2O
O O
(A) CH3 – C – OC2H5 (B) CH3 – C – CH3
CH3 CH3
(C) CH3 – C – CH3 (D) CH3 – C = CH2
OH
Ans. C
excess
Ex. 0.7 gm CH3MgBr Volume of CO2 at STP.
0 .7
Ans.  2  22.4  volume of CH4
Mw
Ex. Compare the reactivity of the above derivative with grignard reagent (Nu).
(i) CH 3 – C – Cl (ii) CH3 – C – O – C – CH3 (iii) CH3 – C – OCH3 (iv) CH3 – C – NH2
O O O O O
Ans. All acid derivative gives NSR
a > b > c > d Reason extent of the positive charge at C = O or leaving group.
Cl– > O – C – CH3 > CH3 – O > NH2

poor Base
HCl > CH3COOH > CH3OH > NH3
most ceridic
weaker the conjugate base bast the leaving group.
Reactivity with Nu
CH 3 – C – Cl > CH3 – C – O – C – CH3 > CH3 – C – OCH3 > CH3 – C – NH2
O O O O O

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C – MgX (Functional part of a Grignard reagent molecule)

MgX (Cyclohexylmagnesium halide)

MgX (Phenylmagnesium halide)

C6H5CH2MgCl (Benzylmagnesium halide)

5. Heterocyclic Aromatic Grignard reagent

N MgX (Pyridine-4-magnesium halide)

6. Heterocyclic Nonaromatic Grignard reagent

N MgX (Piperidene-4-magnesium halide)

In a Grignard reagent. X is generally Cl, Br or I (Halogen). Order of reactivity is as follows:

Q.1 Which of the following is not an organometallic compounds?

Ex. Which of the following formula represents Grignard reagent?

Ex. Which of the following is not a Grignard reagent?

Ex. A grignard reagent is formed on reacting magnesium with

Q. 2 Grignard reagent gets stabilised in ether medium, because ether.

1.3 Reactivity of grignard reagents.

(ii) Reactions involving addition on polar -Bond

C = O, C=S, C = N and C  N, – N = O, S=O

R – MgX + C=O  R – C – OMgX

Ex. Zerewinoff's method is used for

(ii) with alkyl halide (coupling)

3. Synthesis of higher alkynes

4. Synthesis of other organometallics

(ii) From Carbonyl compounds

(c) Tertiary or 3ºalcohols

Ex. Compare the reactivity of following compound with RMgX?

Ex. compare the reactivity with RMgX with following compounds.

H2O2/OH or partial Hydrolysis

eg. KCN (not possible due to partial double bond )

* Benzene gives ESR reaction not FSR

(ii) From carboxylic esters (other than formic ester)

9. Synthesis of carboxylic acids

11. Synthesis of mercaptans

12. Synthesis of phenols

Q. 6 Which of the following reactions froms an unsaturated Grignard reagent?

ANSWER OF UNSOLVED EXAMPLES

Ex. Road map problem

NBS aq. KOH Cu/300º Conc. NaOH NaOH/CaO

Br OH CHO CH2OH COO

C2H5OH C2H5O Mg/H2O

Br2 Mg/ether CO2 LiAlH4

PCl 5/PCl3/SOCl2 CH3 – C – CH3 +CaCO3

Cl– > O – C – CH3 > CH3 – O > NH2

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