Summary of Ch 7: Preparing Alkynes

1) Preparing terminal alkyne:

a. From acetylene:



b. From terminal alkene:



2) Preparing internal alkyne:
a. From acetylene:



b. From internal alkene:



Summary of Ch 7: Alkyne Reactions
Alkyne












Terminal Alkyne















Tetrahaloal kane
X and X added twice
Onium ion intermediate
! 1,2-shift is not possible
Not a regioselective reaction (2
nd
Br
-

attacks the more substituted C of onium
ion)
Not a stereoselective reaction

Dihaloal kane
X and X added
Onium ion intermediate
! 1,2-shift is not possible
Not a regioselective reaction (2
nd
Br
-

attacks the more substituted C of onium
ion)
Stereoselective anti (-X and X will be
trans)

Dihaloal kane-geminal
H and X added twice
Carbocation intermediate
! 1,2-shift is not possible
Regioselective reaction
! Markovnikov`s Rule: H Irom H-
X adds to the C oI CC with the
most H.
! Second X from H-X adds to C
with 1
st
-X group
Not a stereoselective reaction

Vinyl halide
H and X added
Carbocation intermediate
! 1,2-shift is not possible
Regioselective reaction
! Markovnikov`s Rule: H Irom H-
X adds to the C oI CC with the
most H.
Not a stereoselective reaction
Terminal Alkyne





























Keto
H and OH added
Keto-enol Tautomerization
Carbocation intermediate
! 1,2-shift is not possible
Regioselective reaction
! Markovnikov`s Rule: H adds to
the C oI CC with the most H.
Not a stereoselective reaction

Keto
H and OH added
Keto-enol Tautomerization
Onium ion intermediate
! 1,2-shift is not possible
Regioselective reaction
! Markovnikov`s Rule: H Irom H-
OH adds to the C oI CC with
the most H.
Stereoselective reaction: anti, but loss of
stereochemistry during keto-enol
tautomerization

Keto
H and OH added
Keto-enol Tautomerization
Regioselective reaction
! Non-Markovnikov`s Rule: H
from H-OH adds to the C oI CC
with the least H.
Stereoselective reaction: syn, but loss of
stereochemistry during keto-enol
tautomerization






Alkyne





























Al kane
H and H added twice
Not a regioselective reaction
Stereoselective reaction syn addition,
but after the second equivalent of H
2

added, stereochemistry is lost.


cis-Al kene
H and H added
Not a regioselective reaction
Stereoselective reaction syn addition =
cis product.


trans-Al kene
H and H added
Not a regioselective reaction
Stereoselective reaction anti addition =
trans product.