Bruice_SC_v4.

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4.

5.

6.

= axial bond
= equatorial bond

Chapter 3
Alkenes: An Introduction to
Reactivity. Thermodynamics and
Kinetic

1. Alkenes are hydrocarbons with a double

bond. The total number of p bonds and
rings is the degree of unsaturation. The
general molecular formula for a
hydrocarbon is CnH 2n + 2 minus 2
hydrogens for each degree of
unsaturation. The parent hydrocabon is
the longest carbon chain that contains the
double bond, numbered so that the start
of the double bond is given the lowest
possible number. Alkadiene is used for
two double bonds. Vinylic carbons are
double-bonded carbons; allylic carbons
are adjacent to vinylic carbons (3.13.2).
Br
CH3CHCH2CH
CH3

CH2CH3

+ H

Br

slow

C
+

Br

fast

the electrophile
adds to an sp2
carbon of the
alkene

a carbocation
intermediate

Br H

H
the nucleophile
adds to the
carbocation

4. Energy changes are shown by a reaction

coordinate diagram. A transition state
has partially broken and partially formed
bonds; an intermediate has fully formed
bonds. The more stable the species, the
lower its energy. The change in Gibbs free
energy 1G2 is exergonic 1-2 when
forming a more stable species, and
endergonic 1+2 when forming a less
stable species. G is related to the
equilibrium constant by -RT ln Keq.
The formation of products with stronger
bonds and greater freedom of movement
causes G to be negative;
G = H - TS. If a system at
equilibrium is disturbed, it will adjust to
offset the disturbance (Le Chatleliers
principle). The free energy of activation
( G) is the difference between the free
energy of the transition state and the free
energy of the reactants. The greater G,
the slower the reaction. The ratedetermining step has its transition state at
the highest point on the reaction
coordinate. The rate of a reaction is
directly proportional to a rate constant, k;
the smaller the rate constant, the slower
the reaction. The Arrhenius equation
relates the rate constant to the activation
energy 1Ea2 (3.73.8).
intermediate

CH3CHCH2CH3
+

Br

Cl

CCH2CHCH3

2-bromo-4-ethyl-7-methyl-4-octene
not
7-bromo-5-ethyl-2-methyl-4-octene
because 4 < 5

2. The sp2 carbons of an alkene and the four

atoms attached to them are in a plane. Cis
isomers have the hydrogens on the same
side of the double bond; in trans isomers
they are on opposite sides. The E isomer
has the high priority groups (based on
atomic numbers) on opposite sides of the
double bond; the Z isomer has them on
the same side. Proceeding down a
substituent breaks a tie (3.5).
3. The double bond of an alkene is its
functional group (the center of
reactivity). Curved arrows show the
mechanism for this electrophilic
addition reaction (H + is an electrophile
and the p bond is a nucleophile; the
carbocation is an electrophile and Br - is a
nucleophile) (3.6).

Free energy

3.

chain numbered so the substituent gets

the lower number (2.42.7).
Alkyl halides and alcohols are 1, 2, or 3
depending on whether the X or OH is on
a 1, 2, or 3 carbon. Amines are 1, 2, or
3 depending on how many alkyl groups
are bonded to N (2.4, 2.6, 2.7).
The stronger the intramolecular forces
holding molecules together, the higher
the boiling point: hydrogen bonds are
stronger than dipole-dipole interactions,
which are stronger than van der Waals
forces, which increase with molecular
weight and decrease with branching (2.9).
Polar compounds dissolve in polar
solvents; nonpolar compounds dissolve
in nonpolar solvents. An oxygen can drag
about 3 carbons into water (2.9).
Organic compounds exist in various
conformations due to bond rotation.
Newman projections depict staggered
(anti and gauche) and higher energy
eclipsed conformations. Cyclopropane
and cyclobutane have significant angle
strain; cyclopentane and cyclohexane are
nearly strain free. Cyclohexane adopts a
chair conformation with an axial and
equatorial bond on each carbon. Ring-flip
causes one chair conformer to convert into
another chair conformer; bonds that are
axial in one are equatorial in the other. A
substituent is more stable in an equatorial
position. A cis isomer has substituents on
the same side of the ring; a trans isomer
has them on opposite sides (2.102.14).

CH3CH

Br

CH3

6-bromo-3-chloro-4-methylcyclohexene
not
3-bromo-6-chloro-5-methylcyclohexene
because 4 < 5

CHCH3
HBr

CH3CHCH2CH3
Br

Progress of the reaction

Chapter 4
The Reactions of Alkenes

1. Hydrogen halides add to alkenes to form

alkyl halides. Carbocations are stabilized
by hyperconjugation (e - delocalization
by overlap of adjacent s bond orbitals
with the empty p orbital); relative
stabilities: 3 7 2 7 1. The Hammond
postulate states that the transition state is
more similar in structure to the species to
which it is more similar in energy (4.14.3).
2. Electrophilic addition reactions are
regioselective; the electrophile adds to
the sp2 carbon bonded to the greater
number of hydrogens in order to form
the more stable carbocation (4.4).
3. The addition of water or an alcohol to an
alkene requires an acid catalyst. Addition
of water forms an alcohol; addition of an
alcohol forms an ether (4.5).
4. A carbocation can rearrange to a more
stable carbocation via a 1,2-hydride or 1,2methyl shift, or by ring expansion (4.6).
5. Halogens (Cl2 and Br2) add to alkenes to
form vicinal dihalides via a cyclic
bromonium ion intermediate. If the
reaction is carried out in water, a
halohydrin is formed with water adding
to the more substituted sp2 carbon. Since
the intermediate in these reactions is not a
carbocation, carbocation rearrangements
cannot occur (4.7).
6. Alkenes undergo oxymercurationreduction and alkoxymercurationreduction to form alcohols and ethers,
respectively. Carbocations are not formed
as intermediates, so carbocation
rearrangements do not occur (4.8).
7. Alkenes react with peroxyacids
1RCO3H2 to form epoxides. The reaction
is concerted (it does not have an
intermediate) (4.9).
8. Hydroboration-oxidation of an alkene
involves the concerted addition of borane
1BH 32 to form a trialkylborane that is
treated with H 2O2 and HO - to form an
alcohol. Borane is the electrophile that
adds to the less substituted sp2 carbon;
H - is the nucleophile that adds to the
other sp2 carbon (4.10).
CH3
CH3CHCH

CH3
CH2

3-methyl-1-butene

1. BH3/THF
2. HO, H2O2, H2O

CH3CHCH2CH2OH
3-methyl-1-butanol

9. Alkenes undergo catalytic (Pd/C, Pt/C,

Ni) hydrogenation to form alkanes. The
most stable alkene has the smallest heat of
hydrogenation. The greater the number
of alkyl substituents attached to the sp2
carbons, the more stable the alkene (4.11).

Chapter 5
Stereochemistry

1. Constitutional isomers differ in the way

their atoms are connected. Stereoisomers
(cis-trans isomers and isomers with