1010 ADDITION TO CARBON–CARBON MULTIPLE BONDS

The free-radical addition mechanism is non-stereospecific, may be

stereoselective, .
 Addition of HBr to
1. 1-bromocyclohexene is regioselective gave only cis-1,2-
dibromocyclohexane and none of the trans isomer (anti addition), and
2. Propyne (at 78 to 60○C) gave only cis-1-bromopropene (anti addition),
making it stereoselective.
 1012 ADDITION TO CARBON–CARBON MULTIPLE BONDS

Addition of HBr to 2- bromo-2-butene under free-radical conditions at 80○C.

Cis isomer gave 92% of the meso product,
Trans isomer gave mostly the dl pair.
This stereospecificity disappeared at room temperature, where both alkenes
gave the same mixture of products ( 78% of the —dl pair and 22% of the meso
compound).
The stereospecificity at low temperatures is probably caused by a stabilization of
the intermediate radical through the formation~of a bridged bromine radical, of the
type mentioned:

Br Br
C C C C

This species is similar to the bromonium ion that is responsible for stereo- specific
anti addition in the electrophilic mechanism
●

Cyclic Mechanisms
Addition reactions where the initial attack at both carbons are attacked
simultaneously.
Some of these are four-center mechanisms:

YW
Y W
C C C C

In others, there is a five- or a six-membered transition state.

In these cases the addition to the double or triple bond must be syn.

The most important reaction of this type is the Diels–Alder reaction (15-60).

Addition to Conjugated Systems

Y
C C
C C

In the case of electrophiles like Br+, which can form cyclic intermediates,
Both 1,2- and 1,4-addition products form intermediate like 18.
Direct nucleophilic attack by W— would give the 1,2-product, while
the 1,4-product could be formed by attack at the 4 position, by an SN20 -type
mechanism.
 CHAPTER 15 MECHANISMS 1013

Intermediates like 19 have been postulated, but ruled out for Br and Cl by the
observation that chlorination or bromination of butadiene gives trans 1,4-products

C C
C C
Br
Br
18 19

If an ion like 19 were the intermediate, the 1,4-products would have to have the cis
configuration.
 1014 ADDITION TO CARBON–CARBON MULTIPLE BONDS

In most cases, more 1,4- than 1,2-addition product is obtained. This may be a
consequence of thermodynamic control of products, as against kinetic.

Butadiene and HCl gave only 20–25% 1,4-adduct, while at high temperatures,
where attainment of equilibrium is more likely, the mixture contained 75% 1,4-
product.
1,2-Addition predominated over 1,4- in the reaction between DCl and 1,3-
pentadiene, where the intermediate was the symmetrical (except for the D label)

ORIENTATION AND REACTIVITY

Reactivity
— —
Reactivity toward electrophilic addition of a group of alkenes increased in the
order CCl3CHCH2 < Cl2CHCH CH2 <ClCH2CHCH2 < CH3CH2CH2.
For nucleophilic addition the situation is reversed.

70
Electron-withdrawing groups,
two of the most common being F2C=CF2 and (NC)2C—C(CN)2

The effect of substituents

 the statement that simple alkenes do not react by the nucleophilic mechanism,
and
 poly- halo or polycyano alkenes do not generally react by the electrophilic
mechanism.
CHAPTER 15 ORIENTATION AND REACTIVITY 1015

TABLE 15.1. Relative Reactivity of Some Alkenes

Toward Bromine in Acetic Acid at 24○C68
Alkene Relative Rate

PhCH—CH2 Very fast

PhCH—CHPh 18
CH2—CHCH2Cl 1.6
CH2—CHCH2Br 1.0
PhCH—CHBr 0.11
CH2—CHBr 0.0011

TABLE 15.2. Relative Reactivity of Some Alkenes

Toward Bromine in Methanol68
Alkene Relative Rate

CH2—CH2 3:0 × 101

CH3CH2CH—CH2 2=9 × 103
cis-CH3CH2CH—CHCH3 1:3 × 105
(CH3)2C—C(CH3)2 2:8 × 107
1016 ADDITION TO CARBON–CARBON MULTIPLE BONDS

In compounds containing both double and triple bonds (nonconjugated), bromine,

an electrophilic reagent, always adds to the double bond.
In fact, all reagents that form bridged intermediates like 2 react faster with double
than with triple bonds.
The presence of electron-withdrawing groups lowers the alkene/alkyne rate ratio.
Styrene PhCH=CH2 was brominated 3000 times faster than PhCCH,
The addition of a second phenyl group (PhCH CHPh versus PhC CPh) lowered the
rate ratio to about 250.
In the case of trans-MeOOCCH=CHCOOMe versus MeOOCC CCOOMe, the
triple bond compound was actually brominated faster.
In general triple bonds are more susceptible to nucleophilic and less to attack on
an electrophilic site than double bonds, in spite of their higher electron density.
—
Where electrophilic addition involves —bridged-ion intermediates, those arising
—
from triple bonds (20) are— more strained than the corresponding 21 and
furthermore are antiaromatic systems (see p. 73), which 21 are not.

X X

20 21

Although alkyl groups in general increase the rates of electrophilic addition,

For brominations and other electrophilic additions in which the first step of
the mechanism is rate determining, the rates for substituted alkenes correlate well
with the ionization potentials of the alkenes, which means that steric effects are not
important.

For oxymercuration and hydroboration, where the second step is rate

determining and steric effects are important.
 CHAPTER 15 ORIENTATION AND REACTIVITY 1017

Orientation

Markovnikov’s rule: The positive portion of the reagent goes to the side of the dou-
ble or triple bond that has more hydrogens.

As in the similar case of electrophilic aromatic substitution (p. 658), we invoke the
Hammond postulate and say that the lower energy carbocation is preceded by the
lower energy transition state.
Markovnikov’s rule also applies for halogen substituents because the halogen
stabilizes the carbocation by resonance:

Cl H Cl Y Cl Y Cl H
C C + Y C C H C C H or Y C C

H H H H H H H H
More stable
CHAPTER 15 ORIENTATION AND REACTIVITY 1021

Markovnikov’s rule is also usually followed where bromonium ions or other

three-membered rings are intermediates.
This means that in these cases attack by W must resemble the SN1 rather than
the SN2 mechanism
the overall stereospecific anti addition in these reactions means that the
nucleophilic substitution step is taking place with inversion of configuration.

Y
W Y W
H C C R H C C R
H H H H
1020 ADDITION TO CARBON–CARBON MULTIPLE BONDS

For conjugated dienes, attack by a positive ion, a negative ion, or a free radical
is almost always at the end of the conjugated system, since in each case this gives
an intermediate stabilized by resonance.
In the case of an unsymmetrical diene, the more stable ion is formed.
For example,
 Isoprene (CH2=CMeCH=CH2),+ HCl gives only Me2CClCH=CH2 and
Me2C=CHCH2Cl,
with none of the product arising from attack at the other end.
 PhCH= CHCH =CH2 gives only PhCH= CHCHClCH3
CHAPTER 15 ORIENTATION AND REACTIVITY 1021

ALLENE
When allenes attack electrophilic reagents,
Markovnikov’s rule would predict that the formation of the new bond should be
at the end of the system, since there are no hydrogens in the middle.
Stability of the allylic cation has no effect on the transition state,
1. So, attack on the unsubstituted CH2=C= CH2 is most often at the end
carbon, to give a vinylic cation
2. Alkyl or aryl groups are substituted on the allene carbons, attack at the
middle carbon becomes more favorable because the resulting cation is
stabilized by the alkyl or aryl groups
3. For example,
Allenes of the form RCH=C=CH2 are still attacked most often at the end,
but with
RCH=C=CHR’ center attack is more prevalent.
Tetramethylallene is also attacked predominantly at the center carbon.

Stereochemical Orientation
For cyclic compounds steric orientation must be considered.
1022 ADDITION TO CARBON–CARBON MULTIPLE BONDS
CHAPTER 15 ORIENTATION AND REACTIVITY 1023

Additions of Br2 and HOBr are often anti because of formation of bromonium
ions and that free-radical addition of HBr is also anti.
Additions is a cyclohexene, the addition is not only anti but the initially formed
product is conformationally specific too, being mostly diaxial.
This is so because diaxial opening of the three-membered ring preserves a
maximum coplanarity of the participating centers in the transition state;
 1024 ADDITION TO CARBON–CARBON MULTIPLE BONDS

Addition to Cyclopropane Rings

Cyclopropane rings resemble double bonds.
Cyclopropanes undergo addition reactions analogous to those undergone by
double-bond compounds

+ HBr --CH3CH2CH2Br

For substituted cyclopropanes, these reactions usually follow Markovnikov’s rule,

degree of regioselectivity is often small.

The application of Markovnikov’s rule to these substrates can be illustrated by the

reaction of 1,1,2-trimethylcyclopropane with HX.