GRIGNARD’S REAGENT, REDUCTION & ALKANE

Contents
Topic Page No.

Theory 01 - 13

Exercise - 1 14 - 25

Exercise - 2 26 - 34

Exercise - 3 35 - 38

Exercise - 4 39 - 39

Answer Key 40 - 42

Syllabus
Grignard’s reagent : Nucleophilic substitution reactions, nucleophilic addition reactions (grignard
addition)

Reduction : Reduction of alkenes and alkynes, Carbonyl compounds etc.

Alkane : Preparation, properties and reactions of alkanes. Combustion and halogenation of

alkanes preparation of alkanes by Wurtz reaction and decarboxylation reactions.

Name : ____________________________ Contact No. __________________

GRIGNARD REAGENT, REDUCTION & ALKANES
Introduction of 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 e.g. R-MgX, R2CuLi, R2Zn

(Where C is a carbon atom of an organic molecule and M is a metal atom)

If the metal atom is attached to oxygen, nitrogen. sulphur, etc., then such an organic compound is not
regarded as an organometallic compound. The following structural formula do not belong to the family of
organometallic compounds.

RONa (Sodium alkoxide). CH3COONa (Sodium acetate), CH3COOAg (Silver acetate), RSK (Potassium
mercaptide) RNHK (N-Alkylpotassamide), (CH3COO)4Pb (Lead tetraacetate), etc.

Note : It should be noted that (CH3)4Si (Tetramethylsilane, TMS) is also not an organometallic compound
because silicon is a nonmetal.
Most important examples of organometallic compounds are Grignard's reagents. In Grignard's 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.

(Functional part of a Grignard's reagent molecule)

In organometallic compounds, the metal atom can be bonded to carbon atom 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's reagent
R – MgX (Alkylmagnesium halide)
CH3 – MgI (Methylmagnesium iodide)

2. Unsaturated Aliphatic Grignard's reagent

(i) Alkenyl Grignard's reagent
CH2 = CH – CH2 – MgX (Allylmagnesium halide)
(ii) Alkynyl Grignard's reagent
CH  C – CH2 – MgX (Propargylmagnesium halide)

3. Alicyclic Grignard's reagent

(Cyclohexylmagnesium halide)

4. Aromatic Grignard's reagent

(Phenylmagnesium halide)
C6H5CH2MgCl (Benzylmagnesium halide)

Preparation
Dry and pure
RX + Mg  Ether
  RMgX

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's reagent by completing the octet on
magnesium atom.



Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 1
B.Tech. IIT Delhi M.Sc. IT-BHU
 Process : To an etherial solution of alkyl halide Mg metal is added at very low temp. (0 – 5°C). A vigorous
reaction takes place , and a solution of G.R. is obtained. It cannot be evaporated to get it in solid state. The
reaction will be explosive. It is stable only in solution state.
Reactivity order with respect to X (For preparation of RMgX)
R–X:

Iodides forms organometallic compounds at the fastest rate.

Structural stability of G.R.
If the alkyl part has more stable negative charge, then RMgX is more stable. It will be less reactive
e.g. CH3 – CH2 – MgX ; CH2 = CH – MgX ; CH3C  C – MgX
Reactivity order : 1>2>3
Stability order : 1<2<3

Reactivity order of Grignard's reagent

On having same hydrocarbon radical, the order of reactivity of Grignard's reagents will be as follows :
RMgI > RMgBr > RMgCl

Reactivity order with respect to active H

Acidic H > – CHO > > > >R–X

Except X (halogen) all other functional groups must be absent in the alkyl group otherwise. G.R. will be
destroyed by internal reactions.
[– NO2, – CN must also be absent]

Reduction
Catalytic Hydrogenation :

Catalyst
| |
General Reaction C = C + H2 –C–C–
| |
H H
(syn addition)
Hydrogenation of an alkene is an exothermic reaction (Hº  – 120 kJ mol–1)
Ni
R  CH  CH  R  H2   R  CH2  CH2  R  heat
Partial Reduction
(a) Lindlar's catalyst :
It is a poisoned palladium catalyst (composed of powdered barium sulphate coated with palladium) poisoned
with quinoline or sulphur. Nickel boride Ni2B(P-2 catalyst) (made from sodium acetate and sodium borohidride)
is an excellent alternative catalyst for the conversion of alkyne into alkene. (syn addition)
The partial reduction of alkyne to alkene is heterogeneous hydrogenation with Lindlar's catalyst.
C2H5 CH3
H2 Lindlar's catalyst
CH3 – CH2 – C  C – CH3 C=C (syn addition)
or Ni2B
H H
Acid chloride reduced to aldehyde by using Pd/BaSO4 catalyst is called Rosenmund Reduction.
O
|| H2/Pd-BaSO4
(i) CH3 – C – Cl CH3 – CHO
H2/Pd
(ii) O2N – CH = CH – CH2 – CH3 H2N – CH2 – CH2 – CH2 – CH3

H2/Pd or Pt
(iii) CH = CH2 CH2 – CH3

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 2
B.Tech. IIT Delhi M.Sc. IT-BHU
 (b) Reduction by Dissolving Metals :
The general mechanism of reduction by dissolving metals is based on the fact that the metal acts as a
source of electrons first an electron adds to the substrate causing fission of a single bond into a free radical
and an anion or it can adds to a double bond forming a resonance-stabilized radical ion.
e
A– B A + B: or A: + B
e
A= B : A – B or A + B:

Reduction by Na or Li/NH3 (Birch reduction) :

Mechanism :
Reagents Na(or Li, K) + liq NH3  Na+ + e– (solvated electron)

R R H
Na H – NH2
R–CC–R C=C C=C
R R

Na

R H R H
H2N – H
NaNH2 + C=C 
C=C (anti addition)
Na
H R R
(~ 100%)
(trans alkene)
Typical example of reduction for aromatic system :
(electron releasing group – R, – OR, – NH2)
G G

H
Na/NH3
H H
H
(electron withdrawing group – NO2, COOH, – CHO, – CN)
G
G H

Na/NH3

H H

Reduction by Na/C2H5OH [Bouvealt-Blanc reduction]

Na/C2H5OH
(a) CH3CHO CH3CH2OH
Acetaldehyde Ethanol

Na/C2H5OH H3C
(b) CH3–COCH3 CHOH
H3C
Acetone propane-2-ol

O
|| Na/C2 H5OH
(c) CH3 – C – OC2H5 CH3CH2OH
H3O+

Ethyl acetate Ethanol

Physical & Inorganic By Organic Chemistry By

A-479 Indra vihar, kota
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 3
B.Tech. IIT Delhi M.Sc. IT-BHU
 Reduction by metal hydrides and alkoxides :
LiAlH4(LAH) Lithium aluminium hydride (strong reducing agent) :
NaBH4 Sodium borohydride (Mild reducing agent) :

Mechanism :

O
|| R2C=O
H3Al – H C H3Al – O – CHR2 H2Al (OCHR2)2
R R
R2C = O

H3O –
R2C=O
4 R2CHOH Al (OCHR2)4 HAI (OCHR2)3

DIBAL-H (Diisolbutyl Aluminium Hydride) (ALANE)

Most important alane is diisobutyl aluminium hydride. It runs parallel to LAH (Lithium aluminium hydride) as
a reducing agent but it is more selective.

LiAlH4 – THF
(a) Ph – CH = CH – COOC2H5 Ph – CH2 – CH2 – CH2OH + C2H5OH
H2O

DlBAL-H

Ph – CH = CH – CH2OH + C2H5OH

By DIBAL at ordinary temperature esters are reduced to alcohols but at low temperature esters are reduced
to aldehyde.

O
||
DIBAL
(b) C6H5 – C – OCH3 C6H5CH2OH
toluene 25ºC

DIBAL toluene – 78ºC

C6H5CHO

LAH reduce RCN to amine but DIBAL is found to be reduce it to aldehyde.

LiAlH4 – THF
(c) CH3 – C  N CH3 – CH2 – NH2
DIBAL
25ºC

CH3 – CHO

MPV Reduction (by isopropyl alcohol and aluminium isopropoxide)

Al(OCHMe2)3
R – C – R' + CH3 – CH – CH3 R – CH – R' + CH3 – C – CH3
|| | | ||
O OH OH O

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 4
B.Tech. IIT Delhi M.Sc. IT-BHU
 Stephen's Reduction :
When reduction of compounds is carried out with acidified stannous chloride (SnCl2/HCl) at room temperature,
imine hydrochloride is obtained which on subsequent hydrolysis with boiling water gives aldehyde. This
specific type of reduction of nitrile is called stephen's reduction.

LiAlH4 or Na/C2H5OH
R – CH2NH2
(Complete Reduction)
(1º Amine)
R–CN
(i) SnCl2/HCl (ii) H2O
R – CHO
(Partial Reduction) Aldehyde

Clemmensen's Reduction
Used to get alkane from carbonyl compounds :
Zn – Hg/HCl
C=O CH2
2 3
sp sp

Clemmensen reduction is not used for compounds which have acid sensitive group.

Wolff-kishner reduction (NH2NH2/KOH) :

Used to get alkane from carbonyl compounds
NH2 – NH2/KOH
C=O CH2
Using high boiling
2 solvent (ethylene glycol) 3
sp sp
Wolff-kishner reduction is not used for compounds which have base sensitive groups.

By Red P & HI :
All the functional groups reduced into corresponding hydrocarbon.
Red P + HI
(a) R – C – OH R – CH3
|| 
O
Red P + HI
(b) R – C – Cl R – CH3
|| 
O
Red P + HI
(c) R – C –OEt R – CH3
|| 
O
Red P + HI
(d) R–C–R R – CH2 – R
|| 
O
Red P + HI
(e) CH3 – C – OH CH3CH3
|| 
O
Red P + HI
(f) CH3 – C – CH3 CH3CH2CH3
|| 
O

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 5
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 Various functional groups and their products by the use of different reducing agents

t
S. No. Group Product H2 + Catalyst LiAlH4 in ether NaBH4 in EtOH LiAlH(OBu )3
in THF

1 – CHO – CH2OH + + + +

2 C=O CHOH + + + +

3 – CO2 H – CH2OH – + – –

4 – COOR' – CH2OH – + – –

5 – CONH2 – CH2NH2 – + – –

6 – COCl RCH2OH + + + +

7 – epoxide alcohol + + – –

8 – CN – CH2NH2 + + – –

RNO2 RNH2 + + – –
9

10 C=C CH – CH + – – –

(*) double bond can be reduced by LiAlH4/THF only in cinnamic system.

LiAlH4 – THF
For eg. Ph – CH = CH – CHO Ph – CH2 – CH2 – CH2OH
H2O

A L KA NE
INTRODUCTION :
* Saturated hydrocarbons are known as alkanes or paraffins (Less reactive).

* Alkanes with carbon chains that are unbranched are called normal alkanes. Each member of the series differ
from the next higher and next lower member by >CH2 group.

* General formula : CnH2n+2

3
* All the carbon atoms in alkanes are in sp state of hybridization and geometry is tetrahedral.

* All the bond angles are tetrahedral angles i.e., H–C–H or H–C–C bond angle is 109º28'

 Properties
3
C–C
3 3
C–H
(i) Overlapping sp – sp sp – s
(ii) Bond length 1.54 Aº 1.112 Aº
(iii) Bond energy 80 – 85 kcal 98.6 kcal

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 6
B.Tech. IIT Delhi M.Sc. IT-BHU
 METHODS OF PREPARATION :
(i) From Carboxylic acids :
(a) By de-carboxylation :

RCOONa + NaOH/CaO  R–H + Na2CO3
Sodium carboxylate Soda lime Alkane
(n) (n – 1)

[b] Kolbe's electrolytic synthesis :

Electrolys is
2RCOONa + 2H2O     R – R + 2CO2 + H2 + 2NaOH
* Methane cannot be prepared by this method.
2CH3COONa + 2H2O  CH3–CH3 + 2CO2 + 2NaOH + H2

Anode Cathode
Mechanism :
Ionic free radical :
– +
2CH3COONa 2CH3COO + 2Na
At anode :
–  –
2CH3COO 2CH3COO + 2e
2CH3COO





2CH3 + 2CO2 A
CH3 + CH3 C2H6
At cathode :
+ –
2Na + 2e 2Na
2Na + 2H2O 2NaOH + H2 A
(ii) Reduction of Alkyl Halides :
Re duc tan t
R–X   R–H + HX
Alkyl halide Alkane
Reductants : Zn–Cu couple/EtOH, Na–EtOH, Zn–HCl, Pt or Pd or Ni/H2 Al–Hg/EtOH, LiAlH4 etc.

(iii) Wurtz Reaction :


R–Br + 2Na + Br–R   
Dry Ether R–R + 2NaBr
Alkane
* Methane cannot be prepared by this method.
* The alkane produced is higher and symmetrical i.e., it contains double in the number of carbon atoms
present in the alkyl halide taken.
* When the two reacting alkyl halides are different, a mixture of three different alkanes is obtained. So the
Wurtz reaction is not useful for preparing alkanes containing odd no. of C atoms.
C2H5I + CH3I  C2H6 + C3H8 + C4H10
* Mechanism : Wurtz reaction may proceed via the formation of organometallic compound or alkyl free radicals.
[i.e. Both ionic and free radical mechanisms are proposed]
Dry ether
2C2H5Br + 2Na    C2H5–C2H5 + 2NaBr

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 7
B.Tech. IIT Delhi M.Sc. IT-BHU
 (A) Ionic Reaction Mechanism :
+
C2H5Br + 2Na  C2 H5– Na + NaBr
Ethyl sodium
(organo metallic)
+
C2 H5– Na + C2H5Br  C2H5–C2H5 + NaBr
n-Butane
(B) Free radical Reaction Mechanism :

C2H5Br + Na  C2H5 + NaBr
Ethyl free
radical
  Dimerisation
C2H5 + C2H5      C2H5–C2H5
(iv) From Grignard reagent :
Z H
RMgX   RH + Mg(Z)X
Z–H [compound containing active hydrogen]
HOH, NH3, RCCH, C6H5OH, CH3COOH, RNH2, R2NH, Pyrrole, C2H5OH etc.
(v) From Alkenes and Alkynes (Hydrogenation) :
Ni / 200º
R–CH=CH–R' + H2   R–CH2–CH2 R'
Olefin Alkane
Ni / 300º
R–CC–R' + 2H2   R–CH2–CH2–R'
* When the catalyst are Pt or Pd, hydrogenation proceeds smoothly at ordinary temperature and pressure.
* With Nickel catalyst, higher temperature (200º – 300ºC) and pressure are needed. (In this case the reaction
is known as Sabatier Senderen's reaction)
* With Raney Nickel, the reaction takes place at room temperature.
Ni / Al + NaOH  Ni in powdered form (Raney Nickel)
In this reaction following alkanes are not formed from unsaturated hydrocarbons
Alkene / Alkyne  Methane
Alkene / Alkyne  Neopantane
Alkyne  Isobutane
* The reaction is exothermic. The heat released in the reaction is known as heat of hydrogenation.

o
(vi) Reduction of Alcohols, Aldehydes, Ketones and Acids by Red P and HI (150 C) :
(a) By the reduction of alcohols :
Re d P
R–OH + HI  
 RI + H O
150º C 2


R–I + HI  R–H + I2
*Since iodine is produced during the reaction, it may react with the resulting alkane, so it is removed by
adding red phosphorus.
2P + 3I2  2PI3 (volatile)
(b) By reduction of acid :
Re d P
RCOOH + 6HI  
 RCH + 3I + 2H O
150º C 3 2 2

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 8
B.Tech. IIT Delhi M.Sc. IT-BHU
(viii) From dialkyl zinc :
R' X
R2Zn   R–R' + RZnX
(ix) Corey-House Synthesis :
Ether
R–Br + 2Li   R–Li + LiBr
Alkyl bromide Alkyl lithium
Ether
2R–Li + CuI   LiR2Cu + LiI
Lithium dialkyl
cuprate
R2LiCu + R'–X  R–R' + RCu + LiX
Alkane
* This method is useful for prparation of alkanes containing odd no,. of c-atoms.
Specific methods of preparation of CH4 :
12H O
(i) Al4C3  2 3CH4 + 4Al(OH)3
 4H O
2
Be2C  
 CH4 + 2Be(OH)2

Heat
(ii) CS2 + H2S  CH4
Cu

(iii) Sabatier Senderen's :

Ni, 
CO2 + 4H2  CH4 + 2H2O
Ni, 
CO + 3H2  CH4 + H2O
PHYSICAL PROPERTIES :
(i) Alkanes from C1–C4 are gases.
C5–C17 are liquids, C18 – onwards are waxy, white solids.
Note : Neopentane is a gas.
(ii) Boiling point :

1
 Boiling point  molecular weight (for homologes) 
Branches
(for isomers)

e.g. order of boiling point

n-pentane > isopentane > neopentane

(iii) Melting point : Alkanes containing even no. of carbon atoms have higher melting points than it's next
higher or next lower homologue having odd no. of carbon atoms.It is because of more symmetricity of alkane
molecules with even no. of carbon atoms as compared to alkanes with odd no. of carbon atoms.

C C C C C C

C C C C C
C C

(Both methyl groups are directed in opposite direction) (Both methyl groups are on the same side)

* Alkanes are colourless, odourless and tasteless.

* Alkanes are lighter than water. These are insoluble in water and soluble in organic solvents.

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 9
B.Tech. IIT Delhi M.Sc. IT-BHU
 CHEMICAL REACTIONS
1. Stability
2. Substitution reactions :–
(a) Halogenation (b) Nitration
(c) Sulphonation (d) Chlorosulphonation (Reed reaction)
3. Oxidation :
4. Cracking / Pyrolysis :
5. Isomerisation
6. Aromatization
7. Addition of CH2

1. Stability
Although alkanes are chemically unreactive under ordinary conditions due to the presence of strong C–C and
C–H sigma () bonds, yet they give following reactions under special conditions
.
2. Substitution Reaction
(a) Halogenation :
h
R–H + X2  R–X + HX
* Reactivity order of hydrogen atoms in alkanes is
3ºH > 2ºH > 1ºH
*Reactivity order of halogens is
F2 > > Cl2 > Br2 > I2
Fluorine can react in drak. Cl2 and Br2 require light energy. I2 does not show any reaction at room temperature,
on heating it shows iodination.
 Fluorination –
*Direct-fluorination of alkanes is usually explosive.
CH4 + F2  Carbon black (explosive reaction)
*It is carried out successfully by diluting fluorine with nitrogen (Inert gas).
CH4 + F2  CH3F + HF
 Chlorination –
2 Cl 2 2 Cl Cl
CH4 + Cl2  CH3Cl 
  CH2Cl2 
  CHCl3 
  CCl4

 The monochloro derivative of alkane is obtained as a major product by taking alkane in excess.
h
e.g. CH4 + Cl2 
 CH3Cl + HCl
Methane Methyl chloride
(excess)
* When chlorine is in excess, carbon tetrachloride will be the major product.
h
e.g. CH4 + Cl2 
 CCl4
Methane (excess) (Main)
Chlorination of alkanes takes place in the following conditions.
* No reaction at room temperature in darkness.
* At 300ºC in darkness.
* At 100ºC in the presence of organic peroxides.
* At 150ºC in the presence of Tetra ethyl lead

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 10
B.Tech. IIT Delhi M.Sc. IT-BHU
 Chlorination of methane is based on free radical mechanism and it completes in the following three steps :

(a) Chain initiating (first) step

h  
Cl2 
 Cl Cl

(b) Chain propagating (second) step

 
Cl + CH4 CH3 + HCl

 
CH3 + Cl2 CH3Cl + Cl

(c) Chain terminating (third) step

 
CH3 + Cl H3Cl
 
CH3 + CH3 CH3 – CH3

 
Cl + Cl Cl2

 Bromination : Bromination of alkanes is similar to chlorination but not so vigrous.

 Iodination : Iodination of alkanes is slow and reversible.

CH4 + I2 CH3 – I + HI
* Iodination may be carried out in the presence of an oxidising agent such as HIO3, HNO3, HgO, etc. which
destroys the HI as it is formed and so drives the reaction to the right.
5HI + HIO3  3I2 + 3H2O

(b) Nitration : When a mixture of vapour of alkane nitric acid is heated at high temperature (400°C – 450°C)
a mixture of all possible nitroalkanes is obtained (The reaction involves both C–C and C–H bond cleavage).
high temp .
R – H  HO – NO 2    R– NO2 + H2O

(c) Sulphonation : In this reaction, hydrogen atom of the C–H bond is replaced by –SO3H group.

R – H  HO – SO3H   R–SO3H + H2O

(Fuming) Alkane sulphonic acid

* Fuming H2SO4 = mixture of SO3 + Conc. H2SO4 = H2S2O7 (Oleum)

* Alkanes containing 6or more carbon atom and lower branched alkens (not lower unbranced) can be
sulphonated).

Oxidation
(a) Complete oxidation or combustion : All alkanes readily burn in excess of air or oxygen to form CO2
and H2O.

 3n  1 
CnH2n+2 +   O  nCO + (n + 1) H O + heat
 2  2 2 2

Volume of alkane 2
 Volume of oxygen = 3n  1

Physical & Inorganic By Organic Chemistry By

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NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 11
B.Tech. IIT Delhi M.Sc. IT-BHU
 (b) Catalytic oxidation :

1 Cu
(i) CH4 + O2  CH3OH
2 250º C / 100 atm.

MoO
(ii) CH4 + O2  HCHO
270º C / 100 atm.

O
||
( CH3COO)2 Mn,
(iii) R–CH3      R – C – OH

(5) Isomerisation : Straight chain alkanes are converted into their branched chain isomers when heated in the
presence of AlCl3 + HCl at 300ºC.

CH3
AlCl3 HCl
|
e.g. CH3–CH2–CH2–CH3   
 CH3 – CH – CH3
300 º C

*If we take n-heptane then it converts into highly branched alkane (triptane).

CH3
|
e.g. CH3–(CH2)5–CH3  CH3 – C – – CH – CH3
| |
CH3 CH3

n-heptane Triptane [2,2,3–Trimethyl butane]

*If we take n-octane then it converts into most stable form iso-octane.

CH3
|
CH3–(CH2)6–CH3 CH3  C  CH2 – CH – CH3
| |
CH3 CH3

n-Octane iso-octane [2,2,4–Trimethyl pentane]

*Isomerisation of alkanes is of great importance in petroleum industry to increase the octane number of
petrol (gasoline).
(6) Aromatization, hydroforming or catalytic reforming : The conversion of aliphatic compounds into aromatic
compound is referred to as aromatization. Alkanes having six or more carbon atoms are heated at 600ºC in
the presence of a catalyst such as Cr2O3 supported over alumina or Pt, an aromatic hydrocarbon results.

CH3
CH2 CH3 Cr2O3 / Al2O3 or
| | Pt
( catalyst)
 
e.g. (i) CH2 CH2 600ºC

CH2
n-Hexane

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 Cr2O3 / Al2O3 or
Pt ( catalyst)
(ii) CH3(CH2)5 CH3 

600ºC

n-Heptane Toluene
* Aromatization involves cyclization and dehydrogenation.
Dehydrogenation :
Cr O / Al O
CH3–CH2–CH3   2   CH –CH=CH + H
2 3 3
e.g. 600º C 3 2 2

Propane Propene
Special properties of CH4

(i) CH4 + O3  HCHO + O2 + H2O
(ii) CH4 + H2O  CO + 3H2
Synthetic gas
1500 º C
(iii) 3CH4 + O2  
 C2H2 + 5H2 + CO2
acetylene
Electric arch
(iv) CH4 + N2     HCN + H2

Al O
(v) CH4 + NH3 2 
3
 HCN + H2
High temp.

Important points :
*Methan is also called marsh gas or damp fire.
*CNG (Compressed naturel gas)  CH4 + propane + butane + Higher alkane. 84%
*LPG is called as liquified petroleum gas or kitchen gas or domestic gas.(Mixture of liquid propane + liquid
butane and other liquid paraffines)
*The mixture of n-butane and isobutane called calor gas.

Physical & Inorganic By Organic Chemistry By

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 PART - I : OBJECTIVE QUESTIONS
* Marked Questions are having more than one correct option.

Section (A) : Grignard's Reagents

A-1. The best yield of given product can be obtained by using which set of reactants X and Y respectively :

CH3
|
Ether
X + Y  
 CH2 – C – CH3
|
CH3

(A) PhLi + Neopentyl chloride (B) PhMgBr + Neopentyl bromide

(C) t-Bu – MgBr + Benzyl bromide Na
(D) Benzylchloride + t-Butyl chloride 

A-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

A-3. 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

A-4*. Which of the following reacts with Grignard reagent to give alkane?
(A) nitro ethane (B) acetyl acetone (C) acetaldehyde (D) acetone

A-5. 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

A-6. 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

MgBr OH

A-7. +  A

O – Ph

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

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A-8*. 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

D O
A-9. 1
equivalent Mg
   X 2
  Y; Y is
ether

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

A-10. 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

A-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

OH
A-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

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 (i ) Mg
A-13. (R) - 2-Bromooctane  X
(ii ) CO 2
(iii ) H 
X is :

(A) (B)

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

A-14. In which one of the following reaction products are not correctly matched in :
(A) RMgX + CO2   Carboxylic acid
( 2) H

(B) RMgX + C2H5OH  Alkane

(C) RMgX + CH3CH2Cl  Alkene
(D) RMgX + Cl O  Ether

A-15. The number of moles of grignard reagent consumed per mole of the compound
is :

(A) 4 (B) 2 (C) 3 (D) 1

A-16*. 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.
O
||
CH3  C CH3 
A-17. CH3–CH=CH2 Br
2     
Mg
H
 Dry ether NH4 Cl 
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 2 C  CH  CH 2  C  CH 3 (D) H 2C  CH  CH 2  CH  CH 2  OH
| |
CH 3 CH 3

OEt
followed
A-18. MgBr + H – C OEt   product
OEt H3O 
Ethyl ortho formate

O
||
(A) C  CH 3 (B) CH2CH=O (C) CH = O (D) CH  CH 3
|
CH  O

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 Br
A-19.  1
. Mg / ether
    Product (s)

2. CH 3CHCH2 CH 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

O
||
A-20*. C 2 H 5 O  C  OC 2 H 5 2
CH 3MgBr
  A. Product A formed
(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

Section (B) : Reduction

Lindlar Na / NH
B-1. B    R–CC–R  3  A
A and B are geometrical isomers (R–CH=CH–R) :
(A) A is trans, B is cis (B) A and B both are cis
(C) A and B both are trans (D) A is cis, B is trans

B-2. B A

A and B are :

(A) in both cases (B) in both cases

(C) A is I, B is II (D) A is II, B is I

B-3. , P is :

(A) (B) (C) both are correct (D) None

B-4. A, A is :

(A) (B)

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

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B-5. Na / NH3 ( )
    P, the product can be :

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

B-6. Na / NH3 ( )
    P, the product can be :

(A) (B) (C) (D) None

x
B-7.  , X can be

(A) NH2 – NH2/ KOH (B) Zn – Hg/ HCl (C) Red P + HI (D) All

Section (C) : Preparation of alkane

C-1. C6H12 (A) has two types of alkenes that can be reduced to one type of C6H14 (B). B is:

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

C-2. Which of the following reaction is correct ?

(A) + (CH3)2CuLi  + CH3Cu + LiI

(B) ( CH CH ) CuLi

3 + CH3CH2 Cu + LiBr
   22 

O O
( CH3 )2 CuLi
(C) CH3 – CH – C – CH3    CH3 – CH – C – CH3+CH3Cu + LiBr
Br CH3
(D) All of these

C-3. Which of the following alkanes can be synthesized by the Wurtz reaction in good yield ?

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 (A) (CH3)2CH – CH2 – CH (CH3)2 (B) (CH3)2CH – CH2 – CH2 – CH (CH3)2
(C) CH3 – CH2 – C(CH3)2CH2 – CH3 (D) (CH3)3C – CH2 – CH2 – CH3

C-4. The product formed in the reaction

is

(A) (BrCH2)3CCH2CH2C(CH2Br)3 (B)

(C) (D)

C-5. Which of the following reaction produces the same product :

Br / h
Na / ether NaOH electrolysis
I : C3H8 2      II :     

Mg / ether CH Br red P  HI
III : 3
      IV :    

(A) I, & II (B) I, II, III & IV (C) I, III & IV (D) II, III & IV

C-6. Which of the following alkanes can be synthesized by the Wurtz reaction in good yield ?
(A) (CH3)2CH – CH2 – CH (CH3)2 (B) (CH3)2CH – CH2 – CH2 – CH (CH3)2
(C) CH3 – CH2 – C(CH3)2CH2 – CH3 (D) (CH3)3C – CH2 – CH2 – CH3

C-7. x, x is :

(A) Only (R,R) product (B) Only (S,S) product (C) Meso compound (D) Racemic mixture

C-8. The product formed in the reaction

is

(A) (BrCH2)3CCH2CH2C(CH2Br)3 (B)

(C) (D)

C-9. During the preparation of ethane by Kolbe’s electrolytic method using inert electrodes the pH of the electrolyte:
(A) Increases progressively as the reaction proceeds
(B) Decreases progressively as the reaction proceeds

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 (C) Remains constant throughout the reaction
(D) May decrease of the the concentration of the electrolyte is not very high

C-10. BrCH2–CH2–CH2Br reacts with Na in the presence of ether at 100 °C to produce :

(A) BrCH2–CH=CH2 (B) CH2=C=CH2 (C) (D) All of these

Section (D) : Reactions of Alkane

D-1. Which statement is incorrect about free radical halogenation of alkanes –
(A) The number of product molecules formed by one photon is very high
(B) If O2 is added, initially the rate of reaction decreases, then it increases
(C) Inhibitors combine with free radical and terminate the chain reaction
(D) presence of C 6H5  CO  OC  C6H5 inhibits the free radical reaction.
|| ||
O O

D-2. The number of possible enantiomer pairs that can be produced during monochlorination of 2-methylbutane
is :
(A) 2 (B) 3 (C) 4 (D) 1

D-3. For the given reaction how many products are optically active (all isomers) :
CH3 CH3
| |
Br2 / h
CH3  C  CH2  CH  CH3  
|
CH3
(A) 1 (B) 2 (C) 3 (D) 4

D-4. Which statement is correct about photochemical bromination of Butane

Br2 , h
CH3 – CH2 – CH2 – CH3  
(A) 1-Bromobutane and 2-Bromobutanes are formed in equal amounts.
(B) 2-Bromobutane is formed with faster rate than 2-chlorobutane in the other experiment of chlorination.
(C) The major product is an equimolar mixture of two compounds
(D) Homolysis of C – H bond has lower activation energy than homolysis of Br – Br bond.

D-5. Write correct reactivity order towards photochemical chlorination.

CH3
|
(X) CH3 – CH2 – CH2 – CH2 – CH3 (Y) CH3  CH  CH2  CH3

CH3
|
(Z) CH3  C  CH3 (W) CH3 – CH3
|
CH3

(A) X > Y > Z > W (B) Y > X > Z > W (C) X > Z > W > Y (D) Z > W > Y > X

D-6. Formation of free radical takes place with absorption of minimum energy in the case of :
(A) CH3 – (CH2)2 – CH2Br (B) (CH3)2CHCH2Br

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 (C) CH3  CH  CH2CH3 (D) (CH3)3CBr
|
Br

D-7. What is the chief product obtained when n-butane is treated with Br2 in the presence of light at 130°C ?
(A) CH3 – CH2 – CHBr – CH3 (B) (CH3)2CHCH2Br
(C) (CH3)3CBr (D) CH3 – CH2 – CH2 – CH2 – Br

D-8. Br / h
2  Product, major product will be

(A) (B) (C) Both A and B (D) none of above

D-9. Br / h
2  Product (major)

Identify the major product.

CH3 CH3
| |
(A) CH3  C  CH2  Br (B) CH3  C  CH3 (C) CH3 – CH2 – CH2 – Br (D) CH3  CH  CH3
| | |
H Br Br

CH3
|
D-10*. Ph  CH2  CH  CH3
Which statements is/are correct about photochemical chlorination of the above compound
(A) The major product will have chiral carbon atom but is optically inactive.
(B) The intermediate free radical of the major product is resonance stabilised.
(C) The intermediate free radical is tertiary for major product.
(D) The intermediate free radical is planar, and stabilised by only hyperconjugation.

PART - II : MISLLANEOUS QUESTIONS

COMPREHENSION
Comprehension # 1
Consider the given reaction and answer the following questions.

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 COOCH3

MeMgBr
 Productss
O OCH3 (excess)
O SH
||
O

1. Number of RMgX consumed in the reaction is :

(A) 4 (B) 5 (C) 6 (D) 7

2. How many product will be formed in given reaction (excluding stereo) :

(A) 2 (B) 3 (C) 4 (D) 5

3. 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 

Comprehension-2
The addition of hydrogen to an alkene is an exothermic
reaction & the enthalpy change is called the heat of
hydrogenation. More branched alkenes are more stable
and have less potential energy. The alkene having higher
potential energy releases more heat on hydrogenation.
In the figure the enthalpy changes of three isomeric
alkenes has been shown.

4. From the above statement & graph identify P if P, Q & R are the isomers of butene.

(A) (B) CH3 – CH2 – CH = CH2

(C) (D)

5. Which of the following can be R if P, Q and R are isomeric pentenes ?

C H3 C H3
| |
(A) CH3  CH  CH  CH2 (B) CH3  C  CH  CH3

C H3
|
(C) CH2  C  CH2  CH3 (D) Both A and C

Match the column

6. Match the reactants given in Column-I with the reagent given in Column-II of reagent in the preparation of
cyclobutane
Column-I Column-II
COOH O
(A) (p) , NH2 – NH2 /KOH
COOH

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 COOH

(B) (q) Na/ ether

O

COOH

(C) (r) NaOH/CaO/, Zn-Hg/HCl

COOH
(D) Cl – CH2 – (CH2)2 – CH2 – Cl (s) Electrolysis, H2/ Ni

7. Match the column

Column I Column II

(A)  (P) Birch reduction

(B)  (Q)Stephen’s reduction

(C)  (R) Wolf-Kishner reduction

(D)  (S) Clemmensen reduction

8. Match the column

Column I Column II

electrolys is
(A) RCOONa   
 R–R (P) Correy-House reaction

Soda lim e
(B) R–CH2–COOH   R–CH3 (Q) Kolbe electrolysis


3 ( i ) AgNO
(C) RCOOH     R–Cl (R) Oakwood degradation
( ii ) Cl 2 / 

(D) R’–X + R2CuLi  R–R’ (S) Hunsdiecker reaction

Assertion / Reasoning
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
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9. Statement-1: In the bromination of propane and 2-Methyl propane. 2-Methyl propane gives more stable
transition state.
Statement-2: 3° C–H bond is weaker than 2° C – H bond.

10. Statement-1 : In the free radical reaction, reaction slow down for the peroid of time during which inhibitor
exists and after which the reaction proceed normally.
Statement-2 :Oxygen as inhibitor slow down the reaction for some times.

11. Statement-1 : The melting point of neopentane is higher than n-pentane but boiling point of neopentane is
lower than n-pentane
Statement- 2 : Melting point depends upon packing of molecules whereas boiling point depends upon
surface area. Neopentane fits into crystal lattice readily but has minimum surface area.

 
12. Statement-1 : Cl + CH4 CH3 + H – Cl step (1)
 
CH3 + Cl2 CH3 – Cl + Cl step (2)
Step (1) is more difficult than step (2)
Statement-2 : Once formed, methyl radicals react easily with any of the halogen; it is how fast methyl
radicals are formed that limit the rate of overall reaction.

13. Statement-1 : Grignard reagent can be prepared in all nonpolar solvent.

Statement-2 : Diethyl ether solvates the Grignard reagent.

14. Statement-1: In the bromination of propane and 2-Methyl propane. 2-Methyl propane gives more stable
transition state.
Statement-2: 3° C–H bond is weaker than 2° C – H bond.

15. Statement-1 : The preparation of G.R. occurs in solution phase.

Statement-2 : The reaction will be explosive in solid phase. G.R. is stable only in solution phase.

16. Statement-1 : n-butane on heating in presence of AlCl3 gives Isobutane

Statement-2 : n-butane and isobutane are isomers.

17. Statement-1 : Alkanes undergo free radicals substitution reaction

Statement-2 : Alkanes undergo homolytic fission.

18. Statement-1 : CH3MgBr is prepared in cold aqueous solution.

Statement-2 : Water molecule stablise grignard molecule by H–Bonding.

TRUE I FALSE

19. The product of reaction

COONa COONa
NaOH Electrolysis
 
 Will be an alkene while COONa   will be an alkane.
COONa CaO in H 2O

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20. can be reduced by, NaBH4/THF..

21. Reactivity order of different grignard reagent is CH3MgI > CH3MgBr > CH3MgCl.

22. Cis alkenes are formed by the reduction of alkyne by use of lindlar’s catalyst.

23. H– attacks on carbon of during reduction by LiAlH4/ H2O.

FILL IN THE BLANKS

24. R2CuLi is formed in ...................

25. Reaction of >C=O and grignard reagent is ................... addition reaction.

26. Ni2B is called ............... catalyst.

27. Reaction of H2 with Ni/Pd/Pt on alkene is ..................

28. Paraffin wax is mixture of ..................

29. In Bouvealt Blanc reduction reducing species is an ...............

PART - I : MIXED OBJECTIVE

Single Correct Answer Type

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1. 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

2. 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) I > II > III > IV (C) III > II > IV > I (D) II > IV > I > III

CH3MgX
3. O NH4Cl Product is

(A) Enantiomer (B) Diastereomers (C) Meso (D) Achiral

CH MgBr
4. CH 3CCH 2CH 2CH 2Cl 3 A, A is

||
O
CH 3
|
(A) CH 3CCH 2 CH 2 CH 2 Cl (B) CH 3CCH 2 CH 2 CH 2 CH 3
| ||
OH O

(C) (D)

O O
|| ||
. CH 3CCH 2 CH 2 COCH 2 CH 3 (
i ) CH 3MgBr ( one mol )
     A, A formed in this reaction is
( ii ) H 3O 

OH O O O
| || || ||
(A) CH 3CCH 2CH 2COCH 2CH 3 (B) CH 3CCH 2CH 2CCH 3
|
CH 3

CH 3 CH 3
| |
(C) (D) CH 3CCH 2 CH 2 CCH 3
| |
OH OH

6. 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

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 O O
|| ||
(C) CH 3  C  O NO2 < CH 3  C  O

O O
|| ||
(D) R  C  OR > R  C  NR 2

7. 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) ,

(2)
O OH
C
8. O (3)
RMgX
( 2 moles)
 
H
H
(1)
S
C


CH
(4)

Deprotonation will occur from the following positions :

(A) 1,2 (B) 1,3 (C) any two positions (D) 1,4

Br
14
9. Mg
 (A) ( i ) CO 2
 (B) NaHCO
 3 
(C) gas
( ii ) H  / H 2O
Product C is :
(A) CO (B) 14CO2
(C) CO2 (D) A mixture of 14CO and CO2
2

10. Which of the following is incorrect.

O
O
C ||
CH3MgX
(A) Cl OC2H5 (1  CH 3  C  OC2 H 5
eq )

Physical & Inorganic By Organic Chemistry By

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 O
OC2H5 ||
C 2 H5MgX
(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
|| ||
H3O 
(D) CH3MgX + C = O   CH 3  C  OH

11. Which reaction gives 1° aromatic amine as major product.

Mg
 /
ether
Mg
 /
ether
(A)  NH
3  (B)  NH
3 

(C) Mg
 /
ether
 NH
3  (D) Ph Hg
(OAc ) 2

NH3 / NaBH 4

O
||
H3O 
12. CH3MgBr + CH2=CH  C  H   Product (1, 4 addition). It is %
OH
|
(A) CH 2  CH  C  H (B) CH 2 CH  CH  CH 3
| |
CH 3 OH
(C) CH3CH2CH2CHO (D) none

CH MgBr (1 eq .)
13. 3   ?

The product is :

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

(i ) CH CN RMgX
14. RMgX  3  (A)   (B) will be %
(ii ) NH 4Cl NH 4Cl
(A) 1° ROH (B) 2° ROH (C) 3° ROH (D) Alkene

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15. CH3—CH—CH2 CH
3MgCl

H 2O
O
(A) CH 3  CH  CH 2 OH (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

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) CH O C—CH3
3

CH3
r1
17. (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

18. 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

19. 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

O (i) CH3MgBr
|| + P
(ii) H3O
20. CH3CH = CH  C  CH 3
(i) CuI,CH3MgBr
+ Q
(ii) H3O

P & Q are respectively :

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 OH O
| ||
(A) P is CH3CH = CH  C  Me Q is CH 3CH  CH 2  C  CH 3
| |
Me CH 3

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 2 C  CH 3

| ||
OH O

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

|| |
O OH

H / Pt
21. B 2 
 A

A and B are respectively :

(A) ,

(B) ,

(C) in both case

(D) in both case

22. Which reducing agent, would you use to carry out the following transformation.



(A) LiAlH4 (B) NaBH4 (C) Na/NH3 (D) B2H6/THF

23. Which of the following is correct potential energy diagram for the given chain propagating step.
 
CH3 – H  F  C H3  H – F Ho  –134 kJ / mol
B.E.  435 B.E.  569

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 (A) (B)

(C) (D)

24. An isomer of C5H12 gives total six isomeric products on monochlorination. Calculate the percentage yield of
the primary monochloride which is chiral. Consider the following relative reactivity of C – H bonds for
chlorination.

Degree of C – H 1° C – H 2° C – H 3° C – H

Relative reactivity
1 3 5
for chlorination (RR)

(A) 26.8% (B) 25% (C) 30% (D) 50%

More than one choice type

O

25. (
i ) PhMgBr
  Product.
(ii ) NH 4Cl

Me
Products in this reaction will be
(A) Stereoisomers (B) Enantiomer (C) Diastereomers (D) Geometrical isomers

3 ( i ) CH ONH
26. 2CH3MgBr    2 

(ii ) H
(A) CH3–O–NH–CH3 (B) CH3–NH–CH3 (C) CH3–NH2 (D) CH3–OH

Cl 3 Mg CH CHO
27. PhCH3 
2
 (B)  
 (A)   (C)
h ether NH4 Cl

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 CH3
OH
| OH CH3 OH
CH2 – CH – CH3 CH3 |
CH – CH3 C – CH3
(A) (B) (C) (D)
CH CH3
HO CH3

28. Nucleophilic addition of Grignard reagent cannot occur in :

O O O O
|| || || ||
(A) CH  C  C  CH (B) CH 3  C  CH 2  C  CH 3
3 3

O O
|| || O
(C) CH 3  C  CH 2  CH 2  C  CH 3 (D)
O

O OH

29. (
i ) CH 3MgBr
  (A)
( ii ) H  / H 2 O

CH3
(A) The product is optically active (B) The product contains plane of symmetry
(C) The product shows geometrical isomerism. (D) The product shows optical isomerism.

30. The end product of following reaction is :

2 4 H / Pd / BaSO / Quinoline D / Ni
Ph – C  C – Ph     
(1)
 2(2
  
)


Ph
D Ph

(A) Ph – CH2 – CD2 – Ph (B)

D H
H

H Ph
Ph D
Ph
H H
(C) D (D)
D D Ph
H

31. Na /(Dry ether )

      

Products obtained in above Wurtz reaction is :

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 (A) (B)

(C) (D)

32. X


X is / are ?
(A) NaBH4/EtOH (B) LiAlH4/THF (C) (D) Red P + HI

33. Photochemical fluorination is explosive while iodination is too slow to occur. The reason for this is
(A) Bond dissociation energy of I2 is minimum
(B) Formation of CH3 – F is most exothermic
(C) Formation of H – F is most exothermic while formation of H – I is endothermic
(D) F2 has lower bond dissociation energy than Cl2 or Br2

PART - II : SUBJECTIVE QUESTIONS

1. How do you account for formation of ethane during chlorination of methane.

2. How many alkanes of molecular weight 100 are chiral ?

3. Sodium salt of which acid will be needed for preparation of propane ? Write chemical equation for the
reaction.

4. Prepare butane from chloroethane using the Corey-House synthesis.

NaOH
5.   [X] :
Electrolysis

6. Write the major product of following reactions.

(i)

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 (ii)

(iii) Ph–Br + CH3–Br (report mixture)

7. Sodium salt of which acid will be needed for preparation of propane ? Write chemical equation for the
reaction.

8. Prepare butane from chloroethane using the Corey-House synthesis.

9. How is the following conversion carried out ?

Propanoic acid to 1-propanol

10. How will you convert

(i) Benzoyl chloride to benzaldehyde
(ii) Propanone to 2-propanol

11. Complete the following reactions :

(i) Na / NH (  )
 3 


(i) Na / NH (l)
(ii) CH3–CH2–CC–CH2–(CH2)6–CH2OH    3 
(ii) H2O

12. Give reaction conditions (reagents and/or catalyst) for effecting the following conversions :

(i) CH3–(CH2)7–CC–(CH2)7–CH3  C=C

(ii) 

13. An organic compound (A) which have molecular formula C2H4O and reduced by Zn-Hg / HCl to give an
hydrocarbon (B) C2H6. Identify (A) and (B).

14. Identify a to c, in the following reaction :

15. A , A is ?

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 PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)
* Marked Questions are more than one correct options.
1. What would be the major product in the following reaction ? [JEE-2000, 1/100]

H
 2
Lindlar catalyst

2. The appropriate reagent for the following transformation: [JEE-2000, 1/100]

(A) Zn (Hg), HCI (B) NH2NH2, OH– (C) H2/Ni (D) NaBH4

3. Identify X and Y in the following synthetic scheme and write their structures. Explain the formation of
* ) as one of the products when compound (Z) is treated with HBr and
labelled formaldehyde ( H2CO
subsequently ozonolysed. Mark the radioactive carbon in the entire scheme. X is obtained by heating of
*
Ba C O3 with H2SO4.

(i)Mg / ether LiAlH 4

CH2 = CH — Br       Y    Z [JEE-2001, 5/100]
(ii) X
(iii) H3O

CH3MgBr
4. Ethylester     P. The product P will be [JEE-2003, 3/84]
excess

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

5. The number of chiral compounds produced upon monochlorination of 2-methylbutane is :

[JEE-2004, 3/84]
(A) 2 (B) 4 (C) 6 (D) 8

6. The order or reactivity of phenyl magnesium bromide with the following compounds is : [JEE-2004, 3/84]

(A) (II) > (III) > (I) (B) (I) > (III) > (II) (C) (II) > (I) > (III) (D) all react with the same rate

7. 1-Bromo-3-chlorocyclobutane will react with two moles of Na in ether producing [JEE-2005, 3/60]

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

8. Phenyl magnesium bromide reacting with t-Butyl alcohol gives [JEE-2005, 3/60]

(A) Ph – OH (B) Ph – H (C) (D)

Cl / h Fractional
9. (CH3)2CH – CH2CH3 2 [N]     [P] [JEE-2006, 5/184]
distillati on
The number of possible isomers [N] and number of fractions [P] are
(A) (6, 6) (B) (6, 4) (C) (4, 4) (D) (3, 3)

Comprehension -1
In the following reaction sequence, product I, J and L are formed. K represents a reagent.

Hex-3-ynal I J L

10. The structure of the product I is ; [JEE-2008, 4/163]

(A) (B)

(C) (D)

11. The structures of compound J and K, respectively, are : [JEE-2008, 4/163]

(A) and SOCl2 (B) and SOCl2

(C) (D) and CH3SO2Cl

12. The structure of product L is : [JEE-2008, 4/163]

(A) (B)

(C) (D)

13. Match each of the compounds in Column I with its characteristic reaction(s) in Column II.
[JEE-2009, 8/160]
Column I Column II

(A) CH3CH2CH2CN (p) Reduction with Pd-C/H2

(B) CH3CH2OCOCH3 (q) Reduction with SnCl2/HCl

(C) CH3–CH=CH–CH2OH (r) Development of foul smell on treatment with

chloroform and alcoholic KOH.

(D) CH3CH2CH2CH2NH2 (s) Reduction with diisobutylaluminium hydride (DIBAL-H)

(t) Alkaline hydrolysis

Paragraph for Question Nos. 14 to 15

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 P and Q are isomers of dicarboxylic acid C4H4O4. Both decolorize Br2/H2O. On heating, P forms the cyclic
anhydride.
Upon treatment with dilute alkaline KMnO4, P as well as Q could produce one or more than one from S, T
and U.

S T U

14. In the following reaction sequences V and W are, respectively : [JEE Advanced_2013]
H2 /Ni
Q 

 V

(A) and

V W

(B) and

V W

(C) and v kS
j

V W

(D) and

V W

15. Compounds formed from P and Q are, respectively : [JEE Advanced_2013]

(A) Optically active S and optically active pair (T, U)
(B) Optically inactive S and optically inactive pair (T, U)
(C) Optically active pair (T, U) and optically active S
(D) Optically inactive pair (T, U) and optically inactive S

16. Match the chemical conversions in List I with the appropriate reagents in List II and select the correct

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 answer using the code given below the lists : [JEE Advanced_2013]

P. 1. (i) Hg(OAc)2 ; (ii) NaBH4

Q. 2. NaOEt

R. 3. Et-Br

S. 4. (i) BH3; (ii) H2O2/NaOH

Codes :
P Q R S
(A) 2 3 1 4
(B) 3 2 1 4
(C) 2 3 4 1
(D) 3 2 4 1

PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)

1. CH3MgI is an organometallic compound due to : [AIEEE-2002]

(1) Mg – I bond (2) C – I bond (3) C – Mg bond(4) C – H bond

2. But-1-ene may be converted to butane by reaction with : [AIEEE-2003]

(1) Zn – HCl (2) Sn – HCl (3) Zn – Hg (4) Pd / H2

3. Which one of the following is reduced with Zn/Hg and hydrochloric acid to give the corresponding hydrocarbon
[AIEEE-2004]
(1) Ethyl acetate (2) Acetic acid (3) Acetamide (4) Butanone

4. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly [AIEEE-2005]
(1) 1-Bromo-3-methylbutane (2) 1-Bromo-2-methylbutane
(3) 2-Bromo-3-methylbutane (4) 2-Bromo-2-methylbutane

5. The treatment of CH3MgX with CH3CC–H produces [AIEEE-2008]

(1) CH3CC–CH3 (2) (3) CH 4

(4) CH3–CH=CH2

6. 2-Hexyne gives trans - 2 - Hexene on treatment with : [AIEEE-2012, 4/120]

(1) Pt/H2 (2) Li/NH3 (3) Pd/BaSO4 (4) LiAlH4

7. In the given transformation, which of the following is the most appropriate reagent ? [AIEEE-2012, 4/120]

(1) NH2 NH2, (2) Zn – Hg/HCl (3) Na, Liq. HCl (4) NaBH4

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 NCERT QUESTIONS

1. Sodium salt of which acid will be needed for the preparation of propane ? Write chemical equation for the
reaction.

2. How will you convert ethanoic acid into benzene?

3. Write chemical equations for combustion reaction of the following hydrocarbons :

(i) Butane

(ii) Pentene

(iii) Hexyne

(iv) Toluene

4. In the alkane H3C – CH2 – C(CH3)2 – CH2 – CH(CH3)2, identify 1º,2º,3º carbon atoms and give the number
of H atoms bonded to each one of these.

5. Why is Wurtz reaction not preferred for the preparation of alkanes containing odd number of carbon atoms?
Illustrate your answer by taking one example.

Physical & Inorganic By Organic Chemistry By

A-479 Indra vihar, kota
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 39
B.Tech. IIT Delhi M.Sc. IT-BHU
 Exercise # 1
PART - I
A-1. (C) A-2. (A) A-3. (C) A-4*. (AB) A-5. (C) A-6. (C) A-7. (A)
A-8*. (BCD) A-9. (D) A-10. (A) A-11. (A) A-12*. (ABC) A-13. (C) A-14. (C)
A-15. (A) A-16*. (ACD) A-17. (B) A-18. (C) A-19. (C) A-20*. (CD) B-1. (A)
B-2. (D) B-3. (A) B-4. (B) B-5. (B) B-6. (A) B-7. (D) B-8. (A)
B-9. (A) C-1. (B) C-2. (D) C-3. (B) C-4. (D) C-5. (B) C-6. (B)
C-7. (D) C-8. (D) C-9. (A) C-10. (C) D-1. (D) D-2. (A) D-3. (D)
D-4. (C) D-5. (B) D-6. (D) D-7. (A) D-8. (C) D-9. (B) D-10*. (AB)

PART - II
1. (C) 2. (C) 3. (C) 4. (B) 5. (B)
6. (A) - (p, r) ; (B) - (r) ; (C) - (r) ; (D) - (q)
7. (A) S; (B) R; (C) P; (D) R,S
8. (A) Q, (B) R, (C) S, (D) P
9. (A) 10. (B) 11. (A) 12. (A) 13. (D) 14. (A) 15. (A)
16. (B) 17. (B) 18. (E) 19. F 20. F 21. T 22. T
23. T 24. corey house alkane synthesis 25. nucleophilic 26. P-2 catalyst
27. syn addition. 28. hydrocarbons 29. electron

Exercise # 2
PART - I
1. (A) 2. (C) 3. (A) 4. (C) 5. (C) 6. (B) 7. (B)
8. (A) 9. (C) 10. (B) 11. (B) 12. (C) 13. (D) 14. (C)
15. (B) 16. (A) 17. (B) 18. (A) 19. (D) 20. (C) 21. (B)
22. (B) 23. (C) 24. (C) 25. (ACD) 26. (CD) 27. (ABC) 28. (BD)
29. (BC) 30. (BC) 31. (AB) 32. (ABC) 33. (BC)
PART - II

1. Chlorination of methane is a free radical reaction which occurs by the following mechanism
Homolytic Fission
Initiation      2

Propagation  + HCl

 CH3 – Cl +

Termination  CH3 – CH3

 CH3 – Cl

 Cl – Cl

2. 4

CaO
3. CH3CH2CH2 – COONa + NaOH  CH3CH2CH3 + Na2CO3
630K
CaO
+ NaOH 630
 CH – CH – CH + Na CO
K 3 2 3 2 3

Ether
4. (i) CH3 CH2 Cl + 2Li   CH3CH2Li + LiCl

(ii) 2CH3 CH2 Li + CuI  (CH3CH2)2 Li Cu + LiI
Lithium diethyl cuprate
(iii) Li (CH3CH2)2 Cu + CH3 CH2 Cl  CH3 CH2 CH2 CH3 + CH3 CH2 Cu + LiCl

Physical & Inorganic By Organic Chemistry By

A-479 Indra vihar, kota
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 40
B.Tech. IIT Delhi M.Sc. IT-BHU
 Butane

5. X is

6. (i) (ii) (iii) Ph–Ph + CH3–CH3 + Ph–CH3

CaO
7. CH3CH2CH2 – COONa + NaOH  CH3CH2CH3 + Na2CO3
630K
CaO
+ NaOH 630
 CH – CH – CH + Na CO
K 3 2 3 2 3

Ether
8. (i) CH3 CH2 Cl + 2Li   CH3CH2Li + LiCl

(ii) 2CH3 CH2 Li + CuI  (CH3CH2)2 Li Cu + LiI
Lithium diethyl cuprate
(iii) Li (CH3CH2)2 Cu + CH3 CH2 Cl  CH3 CH2 CH2 CH3 + CH3 CH2 Cu + LiCl
Butane

LiAlH 4 / THF
9. CH3CH2COOH      CH CH CH OH
3 2 2
H2O

10. (i) H2/Pd/BaSO4 (ii) LiAlH4

11. (i) (ii) CH3–CH2– CH  CH –(CH2)7–CH2–OH

trans

12. (i) H2/Pd-BaSO4-CaCO3

(ii) In this conversion –CO– converts into –CH2– which can be achieved by any one of the following reagents:
(a) NH2–NH2/KOH/ (b) Zn/Hg/Conc HCl/

ZnHg / HCl
13. CH3CHO     CH3–CH3
(A) (B)

14. a: , b: , c:

15.

Exercise # 3
PART - I
1. In presence of lindlar’s catalyst (Pd and CaCO3) in quinoline) partial hydrogenation takes place and give
cis-isomer.

H
 2
Lindlar catalyst

2. (B)

Physical & Inorganic By Organic Chemistry By

A-479 Indra vihar, kota
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 41
B.Tech. IIT Delhi M.Sc. IT-BHU
 
( i) Mg / ether (ii) C O 2
3. CH2 = CH – Br    CH2 = CH – Mg – Br  

( iii) H O  LiAlH
 3   
4

–Mg( OH)Br

4. (A) 5. (B) 6. (C) 7. (A) 8. (B) 9. (B)

10. (D) 11. (A) 12. (C) 13. (A) – p, q, s, t ; (B) – s, t ; (C) – p ; (D) – r

PART - II
1. (3) 2. (4) 3. (4) 4. (4) 5. (3) 6. (2) 7. (1)

Exercise # 4
1. Butanoic acid,
– + CaO
CH3CH2CH2COO Na + NaOH CH3CH2CH3 + Na2CO3

NaOH(aq.) Soda lime

2. CH3COOH CH3COONa CH4

Cl2 h

Cl2 Na/dry ether

C2H5Cl C2H6 CH3Cl
Wurtz reaction
alc.KOH

Br2 CH2Br alc.KOH

CH2 = CH2 | CH2 = CHBr
CH2Br
NaNH2

Red hot tron tube

CH = CH
873 K


3. (i) C4H10 (g)  13 / 2O2 (g)   4CO 2 (g)  5H2O(g)

(ii) C5H10 (g)  15 / 2O 2 (g)   5CO2 (g)  5H2O(g)

(iii) C6H10 (g)  17 / 2O 2 (g)   6CO 2 (g)  5H2O(g)

(iv) C7H8 (g)  9 O2 (g)   7CO 2 (g)  4H2 O(g)

H H CH3 H H
|1º |2º |4º |3º |1º
4. H – C – C – C – C – C – CH3
| | | | |
H H CH3 H CH3
1º 1º
15 H attached to 1º carbons
4 H attached to 2º carbons
1 H attached to 3º carbons

5. Due to the formation of side products. For example, by starting with 1-bromopropane and 1-bromobutane,
hexane and octane are the side products besides heptane.

Physical & Inorganic By Organic Chemistry By

A-479 Indra vihar, kota
NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir G.R., Reduction & Alkane_Advanced # 42
B.Tech. IIT Delhi M.Sc. IT-BHU