chlorom

charge, making it somewhat electrophilic. A nucleophile can attack this electrophilic carbon, and the halogen atom can leave as a halide ion, taking the bonding pair of electrons
with it. By serving as a leaving group, the halogen can be eliminated from the alkyl halide,
u.e.a. Qumica III
or it can be replaced (substituted for) by a wide variety of functional groups. This versaTarea 1. Halogenuros de alquilo va radicales libres.
tility allows alkyl
halides to serve as intermediates in the synthesis of many other functional
groups.

1.- Clasifique cada compuesto como haluro de alquilo, haluro de vinilo o haluro de arilo,
P R O B L E M 6-1
adems indique si es primario, secundario o terciario.
Classify each compound as an alkyl halide, a vinyl halide, or an aryl halide.
(a) CH3 CHCFCH3
(b) 1CH323 CBr
(c) CH3CCl3
(d)

(e)

(f) Cl

Cl

1-bromocyclohexene

bromocyclohexane

FIGURE 6-1

Cl Cl

Br

Br

EPM of chlo

Cl
a PCB (polychlorinated biphenyl)

Chloromethane and
potential map (EPM
C Cl bond is seen
an electron-rich (red
chlorine and an elec
region around carbo
hydrogen atoms.

6-2

Cl systematic
Cl
There
(g) are two ways of naming
(h)alkyl halides. The
(i) (IUPAC) nomenclature

treats an alkyl halide as an alkane with a halo- substituent: Fluorine is fluoro-, chlo- Nomenclat
is chloro-, bromine is bromo-, and iodine is iodo-. The result is a systematic
rine
Alkyl Halid
haloalkane name, as in 1-chlorobutane or 2-bromopropane. Common or trivial
2.- Provea las estructuras qumicas de los compuestos siguientes.
names are constructed by naming the alkyl group and then the halide, as in isopropyl
bromide.
This is the origin
of the term
Common names are useful only
a) ioduro de metilo

alkyl
halide.
b) tetrabromuro de carbono
for simple alkyl halides, such as the following:
c) 3-bromo-2-metil-pentano


d) iodoformo

e) 2-bromo-3-etil-2-metilhexano Cl

Br
f) bromuro de iso-butilo

CH3CH2 F
CH2CH2CHh) cloruro de tert-butilo
CH3 CH CH3
g) cis-1-fluoro-3-(fluorometil)ciclohexano
2CH3
IUPAC name:

common
name:
8418_06_ch6_p218-284.qxd
11/18/11
3:54

PM

fluoroethane
ethyl
Page fluoride
227

1-chlorobutane
n-butyl chloride

2-bromopropane
isopropyl bromide

I
3.- Para cada par de compuestos, prediga cual tiene el momento dipolar ms grande y
H
CH3
explique de manera concreta su razonamiento.
Cl
H
6-6
Preparation
of Alkyl Halides
227
(a) cloruro de etilo o yoduro de etilo
IUPAC name:

iodocyclohexane

trans-1-chloro-3-methylcyclopentane

that is more reactive than the others. Isobutane has only one tertiary hydrogen atom,
common name:
cyclohexyl iodide
(none)
(b) 1-bromopropano o ciclopropano
and this atom is preferentially abstracted to give a tertiary free radical. In general,
however, we are not inclined to use free-radical halogenation in the laboratory because
CH2 I
it tends to be(c) cis-2,3-dibromobut-2-eno o trans-2,3-dibromobut-2-eno
plagued by mixtures of products.
6-6B

CH2CH2

CH3CH2CH2 CH CH2CH2CH3
(d) cis-1,2-diclorociclobutano o trans-1,3-diclorociclobutano
Allylic
BrominationCH3CH2 CH CH2CH3
3-(iodomethyl)pentane
4-(2-fluoroethyl)heptane
IUPAC name:

Although free-radical halogenation is a poor synthetic method in most cases, free-radical

bromination of alkenes can be carried out in a highly selective manner. An allylic position is a carbon atom next to a carboncarbon double bond. Allylic intermediates
4.- A partir de la informacin siguiente indique porqu los valores de entalpa de disociacin
(cations, radicals,
and anions) are stabilized by resonance with the double bond, allowing the charge
or radical to be delocalized. The following bond dissociation enthalpies
de enlace son diferentes. Provea cuando menos tres razones fisicoqumicas para esta
show that less
energy is required to form a resonance-stabilized primary allylic radical
diferencia.
than a typical secondary radical.
CH3
H 3C

CH3
H3C C H + H
(2 radical)

H
H
H

C
C

H = +397 kJ/mol (95 kcal/mol)

C
C

C
C

H + H

show that less energy is required to form a resonance-stabilized primary allylic radical
than a typical secondary radical.
228
C H A P T E R 6 Alkyl Halides: Nucleophilic Substitution and Elimination
CH3

CH3

u.e.a. Qumica III

MECHANISMTarea 1. Halogenuros de alquilo va radicales libres.
6-1 Allylic Bromination
=+
H3C C H + H
(2 radical)
Initiation Step: Bromine
H absorbs light, causing formation of radicals.
H 3C

H
11/18/11

_06_ch6_p218-284.qxd

H
Page
228
Br

3:54 PM

Hh

Br

H + H

C
C
C
C
First Propagation
Step: A bromine
radical
abstracts anC allylicC hydrogen.

qxd

(1 allylic radical)

228

397 kJ/mol (95 kcal/mol)

2 Br

H = +364 kJ/mol (87 kcal/mol)

5.- a) Acomode las etapas de reaccin mostradas a continuacin de acuerdo a las prioridades
CHAPTER
6 Alkyl Halides: Nucleophilic
Substitution
and
Elimination
+ H Br
H + Bris highly
Recall from SectionC4-13C that
selective,
only
Cwith
C
C bromination
C the most stable C
68418_06_ch6_p218-284.qxd
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3:54
PM
Page
229
de reaccin siguientes: 1) iniciacin, 2) propagacin 1, 3) propagacin 2. b) de acuerdo a lo
radical being formed. If there is an allylic hydrogen, the allylic radical is usually the
anterior proponga la etapa de terminacin de la reaccin. c) Finalmente escriba la reaccin
Allylic Bromination
MECHANISM
6-1
completa.
Initiation Step: Bromine absorbs light, causing formation of radicals.
most stable of the radicals that might be formed. For example, consider the
free-radical
allylic
radical
bromination of cyclohexene. Under the right conditions, free-radical bromination of
cyclohexene
can give a Step:
good yield
of 3-bromocyclohexene,
has substiSecond
Propagation
Either
radical carbon canwhere
react bromine
with bromine.
tuted for an allylic hydrogen on the carbon atom next to the double bond.

11/18/11

3:54
PMpositions
Page 228
allylic

allylic hydrogens

HC H

C
C

Br + BrBr

Br H

Br2

Br

C
C

or

+ HBr
+ Br2
P R O B Step:
L E M 6-8
First Propagation
A bromine radical abstracts
an allylic hydrogen.
h

Br

C 6-6
C

Preparation
of Alkyl
+ Br

Br

allylic shift

3-bromocyclohexene
(a)cyclohexene
Propose a mechanism forHtheH following reaction:
(80%)
" H C CH CH Br + HBr
H2 C CH CH3 + Br2
2 hv
2
The mechanism
AC
bromine radical abstracts
C is similar to other free-radical
C C halogenations.
+
Br
C C C + HBr
2
an allylic hydrogen atom
to give
allylic radical. This radical
+H
Bra resonance-stabilized
(b)
Use the bond-dissociation
enthalpies
given
Table
4-2 (page 143)
Allylic Bromination
C Cto calculate
C in
C
C H +a bromine
C reaction.
reactsCwith Br2, regenerating
radical
the chain
C that continues
the value of H for each step shown in your mechanism. (The BDE for
p: Bromine absorbs light,
causing formation of radicals.
Br the overall
allylic
radical
abstraction
of allylic
H 2 Br is about H
CH2
280 kJ> mol, or 67 kcal
> mol.)
Calculate
CHCH
an allylic hydrogen
an allylic bromide
value of H for the reaction.
AreH these values consistent
with a rapid free-radical
h
H
H Br
H H
2
Br
Br
Br
Second Propagation
Step:
Either
radical
carbon
can
react
with
bromine.
chain reaction?
H
H

ER 6

Overall reactionand Elimination

Alkyl Halides: Nucleophilic Substitution
hn

SM 6-1

Br

Br

Br

Br

+ The general mechanism for allylic bromination shows

+ that
Br either end of the
ation Step: A bromine
radical abstracts an allylic hydrogen.

H
H
H
resonance-stabilized allylic radical can react with bromine to give products. In one of
C
C
+ atom
C
or
C
Br
the products,
bromine
where the hydrogen
+ Br theallylic
cyclohexene
radicalatom appears in the same position
allylic bromide
Br
6.- La reaccin iniciada por luz a partir del 2,3-dimetilbut-2-eno con N-bromosuccinimida
C
C
C
C
was
abstracted.
The
other
product
results
from
reaction
at
the
carbon
atom
that
bears
The
light-initiated
reaction
of
2,3-dimethylbut-2-ene
with
N-bromosuccinimide
(NBS)
gives
C
C
C
C
(NBS) da como resultado dos productos.
C
C resonance form of the allylic
C the radical in the second
two products:
Br This second compound
Br radical.
is said to be the product of an allylic
shift.
Br
H
+
+
H
Br
C
C
C
C
C
C For efficient allylic
allylic shift
bromination, a large concentration
must be avoided
CH3 of bromine
H3C
CH3
H
C
CH
Br
CHN-Bromosuccinimide
3
2
because bromine
can also add 2to the double bond (Chapter 8).
h
allylic
radical
Overall reaction NBS,
(NBS)
is often
used
because it comBr C brominations
C C
C as the
C bromine source+in free-radical
C
bines with the HBr side product to regenerate a constant low concentration of bromine.
H3C carbon can
CH
CH3react with
Cbromine ishvneeded
CH3 because most samples
agation Step: Either radical
Nobromine.
additional
of NBS
CH+
C C
+ H3Br
C C
HBr3contain traces of Br2
3
2
to
initiate
the
reaction.
2,3-dimethylbut-2-ene

Br

P R O B L E M 6-9

C
C
a) Escriba un mecanismo para esta reaccin donde se muestre como ambos productos
(a) Give a mechanism for this reaction, showing
how
the
two
products
arise
as a conseC
provienen como consecuencia de la generacin de un intermediario reactivo estabilizado
O C
C quence of+the Br
or
Br +O Br
resonance-stabilized
intermediate.
Br H
C
C
C
C
C bromination
Cpor resonancia.
an allylic
hydrogen
an allylic
(b) The
of cyclohexene
using NBS gives only one
major bromide
product, as shown on
N Br + BrHBr Br
N H + Br2
page 227. Explain why there is no second
product from an allylic shift.
b) De acuerdo a lo visto en clase provea valores aproximados de rendimiento para esta
allylic shift
reaccin.
O
O
regenerates
a lowshows
concentration
Br2
N-bromosuccinimide
(NBS)
Overall reaction
The
general
mechanism
for
allylic
bromination
thatofeither
end of th
P R O B L E M 6-10
resonance-stabilized
allylic
radical can
with compounds.
bromine to In
give products. In one o
Show how free-radical halogenation
might be used
to synthesize
thereact
following
hv
NBS
also
works
well
for
brominating
benzylic
positions,
next
to
an aromatic
ring
C7.- Muestre como la halogenacin va radicales libres se podra emplear para sintetizar los
C
+
Br
C
C
+
H
Br
the
products,
the
bromine
atom
appears
in
the
same
position
where
the hydrogen
atom
each case, explain why2we expect to get a single major product.
(see
Problem
6-10).
Allylic
and
benzylic
halogenations
are
discussed
in
more
detail
was abstracted.
The otherCproduct results from reaction at the carbon atom that bea
compuestos siguientes. En cada caso explique porqu es esperado solo un producto
(a) 1-chloro-2,2-dimethylpropane
(neopentyl
C
in Chapter
15. chloride)
the
radical
in
the
second resonance form of the allylic radical. This second compoun
mayoritario.
(b) 2-bromo-2-methylbutane
H
is said to be the product ofBran allylic shift.
Br
Br b) 2-bromo-2-metilbutano
a) 1-cloro-2,2-dimetilpropano (cloruro de neopentilo)
an allylic
hydrogen
an allylic
For efficient
allylicbromide
bromination,
a large concentration of bromine must be avoide
CH CH
(c)
(d)
because
can also add to the double bond (Chapter 8). N-Bromosuccinimid
2CH2CHbromine
3
(NBS) is often used as the bromine source in free-radical brominations because it com
1-bromo-1-phenylbutane
bines with the HBr side product to regenerate a constant low concentration of bromin
The general mechanism for allylic bromination shows that either end of the
additional
needed
because
mostproducts.
samples In
ofone
NBS
resonance-stabilizedNo
allylic
radicalbromine
can reactiswith
bromine
to give
ofcontain traces of B
Following is a brief
summary
the most important methods of making alkyl
to initiate
theof
reaction.

Show how free-radical halogenation might be used to synthesize the following compounds. In
each case, explain why we expect to get a single major product.
(a) 1-chloro-2,2-dimethylpropaneu.e.a. Qumica III
(neopentyl chloride)
Tarea 1. Halogenuros de alquilo va radicales libres.
(b) 2-bromo-2-methylbutane
Br
Br
(c)

CH

(d)

CH2CH2CH3

1-bromo-1-phenylbutane

Following is a brief summary of the most important methods of making alkyl

8.- Los tomos de hidrgeno terciarios reaccionan con Cl cerca de 5.5 veces ms rpido que
halides.
Many of them are more general and more useful than free-radical halogenation.
con los tomos de hidrgeno primarios. Prediga las proporciones de los productos de
Several of these methods are not discussed until later in the text (note the appropriate
cloracin del isobutano y provea las estructuras.
section references). They are listed here so that you can use this summary for reference
throughout
the course.

SUMMARY

Methods for Preparing Alkyl Halides

1. From alkanes: free-radical halogenation (synthetically useful only in certain cases) (Sections 4-13 and

X2

heat or light

Example

CH3

CH3
CH3

CH3

Br2
heat or light

CH3

CH3

Br

isobutane

tert-butyl bromide