CLASS - 8

ALKYNES
• Introduction
• Preparation
Introduction Of Alkynes
I ackadienes
• M.F.cn/tzn-z ( isomeric to cgdoalkenes )
•
Imp . members :
CzHz(HC=cH) :
Acetylene ( Ethyne)

H ↳ Hs ( Cms CECH
) : Propyne
Cop ) -
- s

C -
C ( bond length ~
120pm)
( BDE = 823 KJ Moe
/ )

sp sp
acidic h atom
8- 8-1 -
Terminal R
•

Alkynes : -
C C-H
⇐
sp( % ST ; EWG ; -
I
effect)
AcetyleneG) HCE.cn ; cuz CECH ; cuzcnzc Ch

n Terminal : R -
c -=c -
R ← Symmetric
( Internal)
'
R CEC R ← on
symmetric
- -
-

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Preparation Of Alkynes
1. From De-hydro-halogenation of Di-halides
2. From De-halogenation of Tri-halides
3. From De-halogenation of Tetra-halides
4. From Lower Alkynes to Higher Alkynes
5. Kolbe’s Electrolysis of unsaturated dicarboxylic acids (only Ethyne)
6. From Metal Carbides ( Ethyne & Propyne only
7. From Graphite (only Ethyne)
IMP
Alkynes : He _=C4 ; cuz CECH
; c4zCHzc=c4
-
.

Phc _=cn
; CECH

Chzc C-
cuz j cuz CEC
_cUzCUz

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

1. From De-hydro-halogenation of Di-halides

-
Germinal Isolated
" Vicinal
R-cnz-c.tt 91 fl
'
Cl
Ic of C c c
- -
-

91 11
R -
C -

cuz a £1 c- c- c- C
di di di
c- c- c- c

d, d,
olé : •
Alkynes are mainly formed from
Germinal & vicinal
mutated
-
However
,
isolated give alkadienes
( £4m
conjugated)
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 É
'

• removal of H & ✗ (halogens : Cl

,
Br ) ; only in germinal
H
Base Base
CEE + BH + X
-

(B) C C

P B-

> (40-607)
mono -
halides

Gem : H ✗ An Alkyne
"

EBI let
-

B-
-
,
→ =L B-
-
c=c -

IT
I 1 Base
7) Base
Bht X
-

H ✗ H 1-
-
Hx fvinylic)
step -1 Step -2

>
( Fester) (slower)
sp
-

SCH )

sp3 -

p( X) spa -
s ( H)

stronger bond
weaker bond spa -

p ( X)
(relatively
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 -

Note : Bases : •
Alc KOH : Oh ale

Nat
-

•
Alkoxide : Ro

•
Nantz : ÑHZ : Amide is strongest
Note :
(NaNHz 1-
liq Ntfs) :
why ?

Nanna → Nta + ÑHZ -4%7 Nhs 1- (-04 aq

is not a

H
" stronger base )
RC4zcÑ
, alc
91C .

R -
c = an
^
\C1 KOY
( nay
-
&, KOH R -
C -=c -
n

(MCI)
Spb fast spa slow yield is poor
ÑaÑHz R -
c- c-4

very strong base

good yield
makes Rxn
easy
by abstracting
vinylic H atom
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 + in effect

É=cn A
Observe :

R -
Cl R -
C-H -
ch =c ?
§
bond
stronger due to partial double character

why ?
St
via + M
effect of Cl
/ Br !!!
8-
R -
Ch Ch Cl

\ partial bond :
stronger
halides)
IMP ! De -

hydro -

halogenation ( in mono or di -

ANTI
follow co -

planar Elimn .

B-

§xx
B-
> ! 1g of - + Bn +

✗ &
HB should be

in opposite plane : ANTI -

Elimn

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Terminal Germinal
"
is ale
CJ
.

c <
43 CU Cnc ,
cuz
- - -
=

Koy
h '
CI

C- HCl )
ft
is a
Chez c = C H
- -

cuz -4 = CH
L,
H d,
M&a : Anti -

coplanar
H & Cl : are coplanar
Base : ÑHZ
Ñhz ⇐ toongev
NO Reaction
cuz -
c - c -
H

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 ok
- Non -
Terminal Germinal :
Kon
cn=c=cn(Minor
H
CI
al" 91
cnz d f- u >
cuz c c

Nativity
- -
-
=

Kon 1
d, in H
C- HCl)
C- not)

⑨
I
Cl
it ate
c) cH3-c=c=HCnAJoR)
d- c- En D=
>
-

>
cuz CUZ c-
cuz
- - -

,
' 1
£1
Kon ✗ I -

H H H H2
B

Ñnz C- HCl)
cuz-0=-0 cuz
-

CI H

CH =D - d -

cuz HzC=c=CH cuz -

I,
I "
Cummulated diene alkyne
up Hp cuz __c=cnc4z
Chinook ( Major
HC -= c-
Chzcttz
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
 2,2 Dichlorobutane
-

IMP
F C' n
ale 91
I É Ésnz
.

>
cuz cuz e = c-
cuz
- - - -

I
di te Kon ✗

Hp tip -42
C- not)
ÑHZ cuz-0=-0
-

cuz
less Imp
HzC=c=CH cuz I
Ñ"2
-

cummulated diene alkyne

c' 4
Canopy ( Major
Cy =D - d -

cuz
I '
ÑK
n
p
n
p cuz __e=cncnz(Minor)

Ñnz he _= c-
Chzcttz

Cmp .
Minor )
ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲
Vicinal dihalides :

T T ak
H

cuz
-
c -
c -

cuz
'

cuz -
C = d- cuz
I 1 KOH
CI CI £1
-
HCl -

n,
a / c. KOH
2.
eq #-) NaN H2

> Ch
Hzc Ch Ch =cHz 2. CHz c - c -

oeq
-

= -

(conjugated diene
)
( MD)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

2. From De-halogenation of Tri-halides ( Gemina / Type)

✗
✗
R -
C ✗ + GAG + * c- R R -
C C -
R
✗ (powder) ×
-

6AgX internal

✗ : Cl
,
Br, I alkynes .

Note : R +
Ag Agx + Ro
le
-

6^-9 Agx
* 2.
CHXZ HC _=C4 1- 6

(Haloform)
6Ag CEC
Zphcclz
-

Benzo - trichloride 0hc=c-Ph

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

3. From De-halogenation of Tetra-halides :

✗ ×

-
d- d- 22h
- CIC -

I 1
✗ ✗ - 22h ✗
z an
alkyne
- a tetra -
halide

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

4. From Lower Alkynes to Higher Alkynes
idea ? He - CH R -
CECH

step -1 : Prepn . of Alkynide ion

'
2- c=c -
R
8- St N+aÑnz Ña
R -
CEC -
H R -
C c- -

Terminal
alkynes (bases) p
sod .
alkynide ion

t, I
A Base
A- Nu
-

step -2 :
'
R c - c-
-
Nta + R' × R -
⇐ c- R
Ca higher alkyne)
-
Na"

④ )
u
(substrate )
Electrophilic SN
Nucleophilic substitution

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 Na+ÑHz
step -1 : R -
c -= c- not
Noise
-

Ro
-

NE R- CEE

ALKynideion@lkoxide3.As
ROH

Naor
-

RMg× .
As Base ??

Step -2 :

R -
c- E + Rt -
✗ R -
c - c -

R
'

(Nii) SN

Rxn :
R' I > R' Br > Rt a >> R' f
of
- - -

Ease
Note :

@ -1-30 → E is Major)

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Ote : Ease of Rxn :
1°
~1°
✗ > cuz cuz ✗ > cuz
2°
✗ 3)
30 3- ✗
cuz gn cuz
- - - -

I
v10
[
M3
Caz
CHzBr
R -
C - c- Nta R -
C c- cuz
i
c4zCHzBV

R-CEC-czltscnzcnzcnzBVR-c.EC -
n -
Pr

Garden -
BV
2- CEC -
isopr
•
Slow Rxrg
(SN ) .

yield
-

low

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 as base
✓✓ H -

cuz cuz
I
R -
C C- Nat +
cuz
-
✗
c- Br
11
cuz -q (E product)
301 I

?? CUZ CUZ

alkynide ion as
Nut R -
CEGH

* Elimination product
* 3° Halides prefer Elimination dominates over

0mV Substitution .
SN product
* 3° Halides are
sterically hindered
around 2 -
C & hence a Nui Fails to approach
or attack 302 -
C to
give SN Product .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

Note :

R C
-
= c- Nat + HzC=cnۃ1 No Rxn
(vinylic)

+ 9€ →
No Rxn
(aryl)
CI bond becomes
Because of + IN
effect of C1 ; C

partial double bond

( Resonance)
& hence it becomes

stronger
As a result , it does not

give any SN Reaction .

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 HCE.cn R -
c=c→ How ?

* Ñ-c=c not -
+ ÑaÑnz NÉE c- Nta
2.
oeq • Di -

acetylide
'

has Nucleophilic
'
• 2

NÉE c- Nta + 2 R' ✗ ends .

'
pi -
c c-R

symm
. internal alkyne
* H C
-
c- Ñ+ + N+aÑuz
1-
Oeq
H C-
C- Nat

H -
c=ENa+ + Rx 4- CEC -

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

 " "
Kolbe's
Electrolysis of Unsaturated Dicarboxylic Acids

H C Coon h cool
g
- -
- -

11 &
H -
C -

COOH
400C - C -
n

Trans : fumaric acid Cis : Maleic acid

1. NaOH

cathode : Hz + Nat 2-
Hzo

0
3 . Q :
charge .

Anode :
E -0-1-8-0
-

o
H
-

c
-
-

+ H
-

ee
11
202
n
g
c
-

o -0
- -
-

n
+
( )
cis
" H
fi
-

TT
Try with trans ₕydᵣₒcₐᵣbₒₙₛ H -
C
←
neo
C̲ i ̲r ̲c̲l ̲e̲
From Metal Carbides : ( HC=cn ; CUZCECU)

* Cacz 1- H2O Cztlz t Ca( 04) ,

[cast -1 c- c-
]
Cacz + Dzo D-CEC -
D 1- Ca(0D) ,

*
MgyCz 1- 420 cuz -c=cn + cuz __c=cnz

Mag .
Carbide (Major) (Minor
+ Mg(OH)z

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲

From Graphite :

Electric Ave
2C ( Hz HCE.CH
graphite +
1000°C

only Acetylene
is
formed

ₕydᵣₒcₐᵣbₒₙₛ C̲ i ̲r ̲c̲l ̲e̲