CH203

Lecture 30
November 14, 2014

Alkene reac:ons

Suomalaisten Kemis:en Seuran vierailu Ateneumin Sibelius -nyBelyyn

keskiviikkona 26.11.2014. klo 15.40 (Kaivokatu 2, Helsinki).

Ohjelma: klo 16.00 Opastus, n. 30 min, koko ryhmlle museon auditoriossa.
Opastuksen jlkeen voi vapaas: tutustua nyBelyyn vapaas: omassa tahdissa.
Museo on keskiviikkoisin auki klo 20.00 as:.

Sisnkyn: museoon on Kaivokadun puoleiselta psisnkynnilt. TarviBaessa
liikkumisesteetn sisnkyn: lytyy museon takaa Ateneuminkujalta.

How to solve synthe:c problems

Step One: Ignore the molecule

HBr, t-butylperoxide

Determine what the reagent(s) above the arrow do and what func:onal groups would
be changed.
5

How to solve synthe:c problems

Step Two: Find that func:onal group in the molecule

HBr, t-butylperoxide

Ignore everything else about the molecule except the func:onal group the reagent
changes.
6

How to solve synthe:c problems

Step Two: Find that func:onal group in the molecule

HBr, t-butylperoxide

Seriously - dont be distracted by parts of the molecule which will not react with the
reagent(s) over the arrow.
7

How to solve synthe:c problems

Step Three: Carry out the transforma:on

H
HBr, t-butylperoxide
Br

Success! Go to next problem.

How to solve synthe:c problems

Step One: Ignore the molecule

Cl2, 350oC

Determine what the reagent(s) above the arrow do and what func:onal groups would
be changed.
9

How to solve synthe:c problems

Step Two: Find that func:onal group in the molecule

Cl2, 350oC
O

Ignore everything else about the molecule except the func:onal group the reagent
changes.
10

How to solve synthe:c problems

Step Three: Carry out the transforma:on

Cl

Cl

Cl2, 350oC
+

Success! Repeat as needed.

11

Addi:on of HOH acid-catalyzed hydra:on

12

Addi:on of HOH acid-catalyzed hydra:on

Step 1: Make a new bond between a nucleophile (pi bond) and an electrophile (H+).
:

C H3 C H = C H 2 + H O H

slow, rate
determining

C H3 C H C H 3

A 2o carbocation
intermediate

:O H
H

Step 2: Make a new bond between a nucleophile (H2O) and an electrophile (a
carboca:on intermediate) to give an oxonium ion (O+).
C H3 C H C H 3 +

:O - H
:

fast

C H3 C H C H 3
:

O+

H
H
H

An oxonium ion

Step 3: Take a proton away from the oxonium (acid-base reac:on).

C H3 C H C H 3 + H O H
:O H
H

O:

O+

fast

C H3 C H C H 3

Addi:on of HOH acid-catalyzed hydra:on

Carboca:on rearrangements 1,2 shibs

Cl

Cl
HCl

17%

Carboca:on rearrangements 1,2 shibs

Cl

CH3

HCl
H3C
H3C

CH3
CH3
17%

Cl
H3C

CH3
CH3
83%

In this rearrangement, a methyl group has migrated to the adjacent carbon.

This is a 1,2-alkyl shib.

Carboca:on rearrangements 1,2 shibs

In an electrophilic addi:on to an alkene, there is the possibility for

rearrangement if a carboca:on is involved.

Carboca:on rearrangements 1,2 shibs

Carboca:on rearrangements 1,2 shibs

H3C

H3C
H3C

H3
C

CH3

2o carbocation

H3C

H3C

CH3

H3C

CH3

H3C

H
CH3

3o carbocation

The driving force is rearrangement of a less stable carboca:on to a

more stable one. Ini:al hyperconjuga:on leads to greater and greater
lling of the empty p orbital of the carboca:on by the electron
density of the C-C sigma bond un:l the system rearranges into the
more stable congura:on of the ter:ary carboca:on.

Carboca:on rearrangements 1,2 shibs

If possible, a carboca:on will always rearrange to gain stability.

Carboca:on rearrangements 1,2 shibs

D
H2O
H2SO4
D

HO

If we prepare [3-2H]3-methyl-1-butene and try to hydrate it with sulfuric acid in

water, we will isolate [3-2H]2-methyl-2-butanol. The deuterium atom has
migrated to the adjacent carbon in a 1,2 rearrangement. This is a 1,2-hydride
shib because the hydrogen has traveled with both of its electrons. H- is called
hydride.

Carboca:on rearrangements 1,2 shibs

H3C
H3C

CH3

2o carbocation

H3C

H3C

CH3

H3C

H3C

H
CH3

3o carbocation

The mechanism is the same as that of the 1,2-alkyl shib.

Alkenes addi:on of Br2 and Cl2

Halogena:on with diatomic halides is run neat (without solvent) or in an inert
solvent such as CH2Cl2.

CH3 CH=CHCH3
2-Butene

Br2

CH 2Cl2

Br Br
CH3CH-CHCH3
2,3-Dibromobutane

Addi:on of bromine or chlorine to a cycloalkene gives the trans
dihalocycloalkane as a racemic mixture.
+

Cyclohexene

Br2

Br
C H2 C l 2

Br
+

Br
Br
trans-1,2-Dibromocyclohexane
(a racemic mixture)

Addi:on occurs with an: stereoselec:vity. The halogen atoms add to the
opposite faces of the double bond.

Alkenes addi:on of Br2 and Cl2

The rst step is the pi electrons ac:ng as the nucleophile to form new bonds
with the bromine electrophile with displacement of bromide. The
intermediate ca:onic three-membered ring containing bromine is called a
bromonium ion.

Alkenes addi:on of Br2 and Cl2

In the second step, a bromide atom acts as a nucleophile and forms a new
bond to one of the carbons of the bromonium ring, breaking it apart and to
leave the 1,2 dibromide. Addi:on of the bromide atom is constrained to
happen from the opposite, or an:, side of the molecule from the bromonium
ring and coplanar with the C-Br bond in the bromonium ring.

Alkenes addi:on of Br2 and Cl2

Br

Br
1

3
Br

Br

An: coplanar addi:on of bromide to the bromonium ion ring.

Alkenes addi:on of Br2 and Cl2

An: coplanar addi:on of bromide to the bromonium ion ring obtained from
reac:on of cyclohexene with bromine gives the trans dibromide as two
enan:omers.