Hydrocarbons Class 2

ALKANES
• Preparations-II
 Preparation Of Alkanes (RH)
1. From Alkenes & Alkynes
2. From Alkyl Halides
(a) Reduction (b) Wurtz Reaction
(c) Frankland Reaction (d) Corey House Synthesis
(e) From Grignard Reagent
3. Reduction Of Oxygen Containing Compounds
(a) Aldehydes & Ketones (b) Carboxylic Acids (c) Alcohols
4. From Salts Of Carboxylic Acids
(a) Decarboxylation (b) Kolbe’s Electrolysis
5. From Metal Carbides (Only Methane)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

2() Frankland Reaction: Ease of Rxns: (a); (b) ;(c)
RI > RBU / RC1 X) RF

2RI +
In 2R0 R -
R
-

2nIz
(a symm. alkane)
(d) Corey-House sythesis:
·
used for preparing both
symm. & unsymm alkanes

·
Coney-House synthesis used
organo-metallic reagent;
an

RaCuli:Gilmann's reagent:Dialkyl lithium aprate

1. Prepu. of Gilmann's
reagent:
Li
a. RX RLi +

hiX
Ether
Alkyl dithiom

Rli P2uLi LiI

(h) + CuI +

(Gilmann's reagent)
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 ·
Gilmann's reagent can reactwith same kind ofalkyl halide

(RX) to
give R-R:Symm. alkane or itcan react

with another kind ofa lkyl halide (R'x) to

give an un-

symm.allone:R-R'

* ReCuli +
RX R -
R +R-Cu + lix

a alkane
symm.
R2Culi
* +
R'x R -
R/ + REn + liX

an
on-symm. alkane
condition for
Corey-House Syn: R'i can be
only alkyl halide (8-c43)
20 cycloalkyl
RICuli RIF20
1599:
&
730
even phenyl (Reaction is

(gH5 quite slow)

Note: Ph ->

20CCCUs)i20s3
RX
ₕydᵣₒcₐᵣbₒₙₛ
=

& pan and

· -

C̲ i ̲r ̲c̲l ̲e̲
 How
synthesise Isobutane:
2. to
using Corey-House
(R - R') synthesis?
+
(43 a3
n
-

~ 10- R= c4)
20 R
=

hi
Path:
correct Me Br (e)zch-auhi
cu
-

*
-

2. CuT
(I) Gilmann's
CHzI
↓ sobutane MezCH-CHz
(I)
1. Li
In-correctPath:
*
CU3I (13) Chi
2. Cu F

Cuz -cn -

Mez
a cn -
I

20: alkyl halide:Not taken

Corey. House synthesis.

ₕydᵣₒcₐᵣbₒₙₛ
in

C̲ i ̲r ̲c̲l ̲e̲
 i
Me
⑦ How will Isopropyl cyclopentance
you prepare: 20 C420

Me

R R#
I 20 alkyl
Path:
correct
: cychalky l
Gilmann's
should react
will Gilmann's
1. Li
Mezcy Read.
Br
Mezcu--Culi By
-

2. CuI Answer

2: cycloally) is allowed

① How
will synthesise Cumene?
you
su(Me)2:Isopropyl
benzene
20

Me :20:is notallowed Isopropyl Gilmannis

cn
so
-

reagent

Phenyl:can be reacted with

is
Gilmann's reagent(though Rxx slow) &% yield
ₕydᵣₒcₐᵣbₒₙₛ
is

Lesser C̲ i ̲r ̲c̲l ̲e̲

 yourself:
Try

1.x(CH-Bv) Nay
D.E

Identifypossible structures of
X & Y.

2. How will
you prepare following compounds
using Coney-House Synthesis?
(choose two alkyl halides
keeping in mind
the limitation ofreaction).

i) (ii) (iii)

(iv) (iv)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 5 -

8t

2() Using Grignard Reagent: RMgX iX F +

· Alkyl magnesium halide)

Prepn: ·
An
organo-metallic
Mez0
RX R
t
Mg Mg X
-
-

E=0
other)
(dry

Polar Covalent
R
lonic bond

g
-

<- -
->
+

- x
bond

acts as carbanian

when it
simply pulls a
hydrogen ion
(H+) towards it; itbehaves as
When it shares/ gives its
electron cloud to others;
Brousted Base (Proton Acceptor)
itbehave as
Nucleophile
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
Grignard Reagent as Bronsted base:(As proton acceptor)
↓ (G.R) from
abstracts an
acidic-hydrogen (48)
various
Inorganic &
organic compounds??
· look for a n-atom bonded to most
electronegative atom

in a
compound. Usually
0, N, X are such
electronegative
atoms.... ·
St St

iR- d-0
St
10
+
4 -
X j 1 -

01 -
1 j R -
0 -

Chalogen ands) (water as

(carboxylic (Alcohols)
acid) acids)

(13)
R-NG & RIN-y Amines &
5+ many more.....
(20)

Yg -on-
5 -

St

R-MgX 1 0 1 R H +
+ - - -
·

Brousted base Bronsted Acid alkane

an ·

conjugate
(Proton Accepta) (proton donar) conjugate base
ₕydᵣₒcₐᵣbₒₙₛ
·

acid
(GR) C̲ i ̲r ̲c̲l ̲e̲
(water)
 5 -
St

Mg Xz
R-MgX RA
t uX +

-0 mag.
48
5

MgXxp,
-

2 R'
MgX RH
+

alkoxy
-
+
-

(15,2;3% halide

5 -
t
R1
=

R # 0 -X mag.
MgX Mg
c,
-
-
-

RA
+

- I
carboxy
q
R
- -

hahide

t
* -

R
-
Mg X R'- mag
-x mag.
-
+

RA
+

-
NHR' N- alkyl

navide

5 -

R -

+gX + 0 48+
=

Rn Ng =
+

b -
ph
mag.
Phenoxy
(Phenot) halide
Aromatic
alcohols ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 5 -

St
R -

MgX + D20 D-0-D

= R D
- +

Mg=D
heavy
water

5 -

&t
1 RU 1-CEC
R c y mgX
+

Mg
=

-
X
+ -
c - -

-hybridised Acctylenic GR
C-atom is EWG
Acetylene due to-I effect
5

RI-CEC.MgX
/ S
-

R MgX R c c 1 RH +

- +
- = -

Terminal Alkynes Acetylenic GR

-c =
Note: R
c,ingx +

120 2 -
c =
1 -
1
mg
+

·
Acetylenic GR . an
alkyne
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
other
types ofGrignard Reagent:

MgX MgX ; UzC = CH -

CHzMgX
j

·
Phenyl mag. halide PhCUzMgX
UzC = cn-
MgX
It
non
1: Benzene
Mg Br

5 0D D:Benzene

It
1 -
0 - 45+ H D

?
Note:In
general; D (heavy isotope) forms stronger bonds

than 1 (lighter
isotope) => 0-D > 0-1 bond

ₕydᵣₒcₐᵣbₒₙₛ (strongers C̲ i ̲r ̲c̲l ̲e̲

 Aids
Grignard Reagent
HOHS
as Brousted Base: RU (An alkane)

€€€
R"048 +

RU(k' 19,25,30os)
=

-'
R -

04
RH
% 1gX St
H X
(Base) RH
St
84

RH

⑦+
NHz RH

RN12(10)
/ +

R4
R2N115 (2%)
+

RH
3. Reduction Of Oxygen Containing Compounds
(a) Aldehydes & Ketones (b) Carboxylic Acids (c) Alcohols

(a) Aldehydes & Ketones:

Redy,
2 o
21z 120
+

4(u]
Carbonyl group
methylene group
·

· a

·
common to both

aldehydes & ketones (An alkane)

Redy,
RCno RCHz -4
4(u] alkane(s)
->

R-co-R
RCMz-R

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Reducing Agents:

Red P Red P
(1) >
2 o (12 + 12 420
↓ +

HI HI

[n] P

Iz [n]
+

PI3

(ii) Demmenson's Reduction: 2n -

Hg / nx;
(60)
Amalgam
zn H9
C4300cH]
-

2.g CHzCHzC4>
HC
Acetone ·
Propane
(iii) Wolf-Kishner Reduction: NHz. NUz (NIH):hydrazine
kon
in & glycol (a solvent)
N2H4 (alc)
243C40 koU alc
C4343
(glycol) ₕydᵣₒcₐᵣbₒₙₛ
·
Ethane
C̲ i ̲r ̲c̲l ̲e̲
2) Reduction of Carboxylic Aaids:

Red P
R C001 R F2 420
CH3 t +
-
-

/
nI

· An allaye P
Red P P =
3
nc004 CH4
HI,A
Red P
CH,2004 (1zc43
HI,A
Red P
2004
HI,A
C13 (oluene)
Benzoic Acid

Red P
2004
C73 (Methyl cyclopentance)
HI,A
cyclopropane
Carboxylic acid

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

(2) Reduction of
Alcohols:

Red P
ROY Ru +

Fz 1z0
+

nIj
·
an alkane PpIz
Red P
((43) =24 -
04
nI;*
CHzCUCU3

Red P
or

uI;
#
Me
Red D 1
Mezc -

04 Me 4

ce
-
-

4I; *

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

4. From Salts Of Carboxylic Acids : R-Co0N
↓ a0U
R-CONN
120
(salt)
(a) Decarboxylation (b) Kolbe’s Electrolysis
sod. Carboxylate
Naon/ca
B-A-ONa RH NazC03:sod.carbonate
+

dry mixture

(soda time) ·
alkane NaoU

202

Observe

that producthas Ic
less than reactant
tep down

e.g. ChycoNa
Noon/caO
god. Acetate *
CH4 + NazCO3

onscuicooa~
odalime
CH-CHz NazCOy
+

A
sod. propionate

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Mechanism (visualisation) ofReaction:

18 onTa
-

o
*

d
+
2-
+ ⑦N R -
-
Na
E
↑
NaoU
(Nu-
·

electrophilic
substrate · an Intermediate
· unstable

1 oxta
-

u 0
- - - ↑ 2

sod. (icarbonation)
↳ a carbanian (Imp intermediate
St
-

u 0N 2 0 oNa
p-
a

q
R + 0 1
-

*
-
- - - +

·
Carbanian · An allane
· 1c -
lesser carbonate ion
· Prousted base
NazCos Nat

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 cooNTa Naon/cao

t -

Naon/cao
(CH3) >
Cn -c00Na CHzCHzCUs

Mr
Naon/cao Me
CON

oNa Naon/cao
u M2
p
-
-

-coONTa Naon/cao Me -

me

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

4. From Salts Of Carboxylic Acids
(a) Decarboxylation (b) Kolbe’s Electrolysis

Electrolysis of an

Rcooxia (ag):
·

NaOY
RC00Y aqueous solution ofsod.salt
120 &

Electrolyte
I

S
ofan organic acid
o
switch
↓
whichconducts

electricity wilts
cathode assistance of

ANODECIE EC
ions
> aq.soly of
salt Nat
---

- -
RCoolag; ntaq; Enag;
=
~
. . .

=
. . .

- - -

. . . -

Electrolytic cell conducts

electricity electrolyte]
· When we switch on;then what

happen?) I it' are created

ₕydᵣₒcₐᵣbₒₙₛ ions
· start to Move.....
C̲ i ̲r ̲c̲l ̲e̲
·
the ions (n+Nat) will startmoving towards Cathode
- - >

(election rich)
·
-

ve Terminal
& ve ions (RC05 & on) startmoving

towards Anode (e-deficient) or the Terminal

CATHODE 2f +
+

ze 124 Reduction
-

occurs

Nat: remains around cathode

ANODE zRC00- ze
-
+
2Rcop C024 +2R'

OU remains around anode)

R -
R
oxidation
:

occurs

Note: 0
↳ -
-

+C024
R

↓
R -
R Note:
ₕydᵣₒcₐᵣbₒₙₛ Whenswitch ifofrelation
C̲ i ̲r ̲c̲l ̲e̲
 Anode
a'
·
any-auzoN(q) 124 + CO24
charge cathode
0

R-G-ONa +
cnzcnz
- d - 0
Naolaa

CHz(Hz (nz(3 cyzcuz

-

c0z
+

R-R: (ymm alkane

only
(n-Butane)
Vz + Naon + CO24
Q (C) 2oln) (9]
(aas
cooxia
charge
(Biphenyl)
Diphenyl
-

Q
·
n-coonia (as 12 Naon + CO2
+
1-u
+

1z
=

charge (2) (aa)(a)

NaoU
12 ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
Ca0;Δ
5. From Metal Carbides (Only Methane)

AlqCy 12420 3CH4

+

4(0n)3
Aluminium Carbide (methane)

·
Bez 4420
+
<14 + zBe(0n) =

Beryhirm carbide (Methane)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Problems:
*

⑨ Na
Br Δ
·

x x
-
-
-

↓ D. E

·
Recall:RBU > RCI
(in Wurtz Rxox x
-
↑
-
2/

Na
x -
-
2/ (intermolecular Wark)
D.E
.
0
0.

Na (intramolecular Wurtz)
-
Br
x -

D.E

(inexcess
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 viccinal dihalides (Alkene)
No
·

CHz
-

cUz Cuz
-

cMz CHz =
CHz
D.E
br Br
⑥

Ditramolecular
X (very
rave)
:unstable

tore any in in cz
cUzcn-cu-chs
- -

Cu(H cn
c)
-
=

(2-butene)
Mg D20
* B 212
·

CHzBU E t20 I
42 Na

J.E
D

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Mg
D20B
a
Na
P
·
CHzBU *
E t20 J.E

<HyMgBr
D
CHz
-

2 D >c H D

IMz
-

-
-

stronger CH,c
bond

D B
- Cnz
CH D
<Hz
-
-
-

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Red P
X

chz-n-coon HI;< cuy-au-ch3 lsobutane

1. Naolag
Chz-cn-cooN Y Cuz-cz ·Propane.
Sodalime
any dnz
2.
#
2-

C03
1. Nao
ag z

2. Q (charge)
cuzcn-conta Me

dny yae-qn-kn-Me
1024
+

Me-con Me

·
2,3-Dimethyl butane
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲