Preparation

Cacz to calorth CHEH

c
acetylide

mgzz.cz eCHz c cH cHz c cHz

0 3 major Minos
c c psoypym.de
I
2
c c ECandide

Higher alkynes from Ethyne

CHEH Nawaz CH Nat Nitz

Nuo
pka 250

Nat
N
CH Rd Rc cH
U Sna

CA CH NIE CH conat 1 gg
cHzc cH

cHz c Ctb
INawaz
case atz c coa.at
f

Reactions of Alkynes

Nu0 addn to c o

CHS C HEHE cuz co Nta

CH

dntmfc
Isomeric forms of Alkynes

CHz C C CH It CHz CHz Enat

Mechi c c citfnitz tz cHz

atz nzcitz cy.ee cHz
EEy
INitz
CHzcit c ct
N c fo cts NHI
citzCH caz cH c o.az

µNH3

CHz atz c CH
nap ona.io
c
atzcaz c
oCHz cHz c cH oHO
g

CH k 973 CE CHz
CHz cha

EHT
City CH CECH CHz c City CH c EH cHzcH c cHz
qq.lt
HfOH0
CHIEF Hz 0
g
CHz czc c.AE eCHz c C cHz

Nanitzlexcess
Br Enat w
l CH Caz
s
Br
Kottexcess
CHz CEC Utz
s

From Gemolihalides Rcha flat I 6 cheat REICH

pic

Fomtnh.ch
2cHUzt6tg s6tycl CH

CH2Rcc1zt6Ag
B c R
 Kolbe's electrolysis
CH CofE electrolysis at
11 Te 111
CH cook1 CH

structure Bond Dissociation Energies

BA c c C C mot
83kcal

HED a moi
146kcal

soo Kalmott
YI akuma

in is less stable the first ti bond

The second it bond CIC
by about
mot
9kcal

e I I 36.7kcal
8.9kcal
A
zs.sk

Enthalpy of hydrogenationof alkyne to altgene is greater than that of alkene

to allgame

Reectivity
Alkynes are more reactive than alkenes towards hydrogenation

Higher Enthalpyof hydrogenation of alkyne to alkene than alkene b alkane

Adsorption
of alkynes compared to alkenes on metal surface
Reactivity towards electrophilic add
Alkynes are less reactive then alkenes towards Ae

High S character of
Carbons
very difficult to polarise the bond towards electrophiles

Vinyl carbocation are less stable then alkye carbocations

4 at _cuz R CH
Litt LH1

R CH Utz R cHz
Vinylcarbocation
The cyclic Intermediate
like bronronium ion formed by alkynes are less
stable than that of alkenes owing to greater angle strain

B cHcHz BE R CH gHz
Br

K CH BI R c CH
htt

Reectivity towards Nucleophilic addn

A R CH caz
0
R CH_CHz ex
y
Nuo
nu

CERH 0
R R g CH

Nuo
f Nu

A since vinylcarbanions are more stable then alkyelarbanions

C c undergo Nu0 addn

ee
R
R at do dT.ec i
HU
R c atz
I
a

Regio Marko addn

 H Br
HBR HBR 1 I
R CECH 4202
R CH CH Br
R o
1
c H
cis Trans Roz I
it Br

Regio AntiMarko

If del
111

la
Fa

g e r is c c
I I of
major minor
Mx
R c cR Kd c r Hg
Hgdz Hg Mtg
Promotor

R c c R
x HoI R E R

Trans major

Xz1Hz

CHz CECH CHS cHd Gt3

1 qy g c.H.it
mohDcHz
Ho fy gHe
CHz ofI cHf

t
fatty 4
dzat
CHEH 9 fd.it

Hox can oxidisethe aldehydes to acidseasily chat d oh

4 Hydration

Regio Maskonikov addh

a he Reagent Heysoalitzsoq H2O Kudrow's toxin

Hgsog tautomerize
Gt3 CH CH3 74 2 Gt3 citz
i
TEE 41

Hgh
ii CHz CEC Ph atz CH ph atz CHz qft.tn
Ht 420 qy
major

Mechog Hey Cd good electrophiles which will polarize triple bonds

20 OH
qHg2 Slow
CHz C CH CHz CECH 043 d at
ads anti 1
48
OH
11
t OH OH
ctz k c.az cPI
city D CH

fl Hg Ig
qf Gt3
CHS

Le Marko addh

No seam

No carbocation
 it
Hydroboration Oxidation
B
1 SickBlt THE I Desiamylborant
CHz CECH
2 1120218 OH0
CHz CH CHz at it
ga go
is
you
Mechoy at CECH t SiazBlt
is
he citz C
i Cft
4202
CHz cHz qH
OH0 OH
I B sia
Lia
atz CH qH g.az x
on at
Bait It CHz CHz dit ca cha dia
ta
Baton

cityCHz carat

Hydroxylation
Le Baeyer's reagent
di di
B ee r R Effi r r r

I IH I I at
R c c it R
Iff H R R

Baeyer's alto
CH CH goat
reagent law cook

Peony acids
M 13 c c R
c R
B
to Antiaromaturing
Alkynes doesnt give exn with perony acids
 Hot KMnoy alkaline

Ifk pi
KMnog
g c c K R'oooo
alle s R Rwoo
0
R c c H R go H R coo KOI

II
CHICK t
2629

Ozonolysis

D R c r
go
3 Go 95k o

Mechi C c R
of 0
Tdt
R R c c R c R
0 T 4 1
oxo
J
t
G1
ZnO
pp I R Zn
Q C R
I toed
oxidatureozonolysis
i 03,1 R'coat
RC R
H2o R coat

From ozonide
R R
R F F R
q yg a
o

Hao

R E OH R'coat

H c CH
1 03lb
H o Il H 2 Hunt
2 H2o
 Ph c cH 2
Dms
e Ph I I it Dmso

1 03,1
phooey t HCooH
2 H2o

1
Pharon
2 H2O ICD
3 00A

Totten's reagent or KMnoglattls

t
Agnos NHgoH AgRN5h
1
R at
R coat cozP
IDH2o Mycnn.gg

R cito Totten'sreagent RCoo0 Agt silvermirror

Nucleophilic Addhi

CHICH
A Meo CH EH Meo at CHz
to
off
Me
Methylivinylethee

2 HUH BaccnDz
Baccnk
CH CH Hcm CHz CH CN acrylonitrile
a
car0 fPolymerises
feltz g't PolyAcrylonitrile Pant
oelone
Test for terminal Alkynes

Na metal RC CH Na R c Nat 29
1211

with Totten's
reagent

f CECH AgNada R c EAgf

whiteppt

Hc CH t do Ag 8 8 Agt
white
ppt

with Ammonicalcuprous chloride

OH
B CEH Rc aid
Redppl7

Polymerisation

hoo ooo
3 CH CH
T
RH
3 CH ICH µ

3 CHz C ICH mesitylene

CH CH t
cot

Dimerisation
cud
2CHECH HC IC CH_CHz
NHuct
fringeacetylene
 HU
HC C CH cHz
Aecl Polymensicitz
c CH cHz
1
Nance
a
futz c
1
c Hz n
chloroprene A
Neoprene
synthetic rubber

Meck CHECHNCHECH H
cHz cH It
H
N'Hz
f
CHz cH CECH

H cc
TH CH
cH cH HC C
y H
NHS H
CHI CE't
la 5MCts
Elf
CHz CH CHz chloroprene
GH
ee

Hd 1Er Hgaz CHECt

Polymerises
Hc CH Hz
a fatty
Promoter
vinylchloride p.u.ci

Polymouses
Hc CH t CHzwort cHz gH
futz qo
o CH3 n
qf
Vinylacetate
PVA

adz Chaz 9142

Hc CH c I o solvent
fordrycleaning
Cd4 city CHU
Weston Westwood
 d
CH CH TT Lewisite blisters
AEI US CH Asda

game
2CHz cHz cuzcuz s cuzcuz a
mustard gas

a 2CHECH I
Thiophene

7 CH CH
6 CHECK
pity
ftp.n I
 nes

tentated.de conjugated dienes

xx
m
Alkynes

CHz C C CHICH3

stability 2 I 4 3

Note
Most lotteries are less stable than their isomeric alkynes
i ft CHz C CH Allene itself less stable
by 6.7KSmot
then its isomeric alkyne propyne

ii 1,2 butdiene is less stable 16.7 Ksmoi than that of

by
isomeric 2 butyne

cHz c atz CH3CECH SH 6.7Ks

cHz c CHCHz CHz c CHz SH 167Ks

Dehydrohalagination to get Alkynes Allenes are always minor products

D hydrogenation 3 4 I 2

ASHcombustion 37 4 7 I 2
 dienes alkynes
Preparation of

B
Wurtztoxin
dryether

2
pg
Br
ME
Br
B My
cHz c cHz

Br Caz CE cha Br cHz c c cHz

Med
fc cHz
ypg
In
kt
Mott o
M

I cacti Rr c c cI
0
o_0 H CBG fort 1 CB

COBB CBE
Tfo
dihalocarbene
Rzc CRz Br Br
X
c.nl r il me
pc a
r I ER

f
R R
C c c
r R
Reactions
of conjugated dienes
1 zaddn 1 uaddn

Ni n
na
Ee w ma
Br

1 Br por
c ge Br

cHz cH at cHz CHz at_cHz I CHz age at1112 1,2add's

LH ee I
U a
CHz CH CH cuz I CHz CH CH c'Hz 1,4addh

kinetic Us Thermodynamic controlled

Br
N t HBR 2 Br

iz kn

kinetic Thermodynamically

800 so 204

400 20
soy
Diets Alder reaction
Pericyclic error 4 2 cyclo add inn Cisoid form only

x d

KL a
diene dienophile
Nuo Et
mas

T
D f XIN T
Cisoidform

3
it b
it

D H
ER
EE
E

D t
he
6
more reactive
 H
T I
H
4
11 s x
s Trans

Reactivity
EDG groups increase reactivity of dienesNuo
increase
Ewg groups reactivity of dienophile

L EDG Y EWG

TD
Lefty
S St
f Yongin

LIK II cannons

Eti ish
Z

EIJI II mine
 Gif 3 St

so no

E Eino
stereochemistry

Ei Es
Syn1 Cis Erythro meso

E EE aims
syn1 Trans Threes Racemic mix

it as

ftp.YI morph

syn Trans

and
E I Y
t t
X x x
 Dienophiles I It
HA or

to
w Ph
11
N
CHS

Reactions on Cumulenes

cHz c cHz CHIC CH3 cHz

I
CHEE CH
Vinylcarbocation

Hz CH
I
Allylcarbocation
H
I C If CI
B Two pi bonds are 1 to each
gc H
H
f If Nd other Hence no resonance seen

H
Fitz
CHEF44,3g CHIC
s

Ph CH c cHz Ph CH CHz

me
c c cHz Mme cH oHz
me qa