06 Chapter 4

lntroduction to Al kenes.
Structu re and Reactivity

Alkenes are hydrocarbons that contain one or more carbon--carbon double bonds. Alkenes are
sometimes called olefins, particularly in the chemical industry. Ethylene is the simplest alkene.
HH
\/
C:C
/\
HH
r
or
*o r,n",i*tliil""
H,C-CH,
: ethene )
Because compounds containing double or triple bonds have fewer hydrogens than the corresponding alkanes, they are classified as unsaturated hydrocarbons, in contrast to alkanes,
which are classified as saturated hydrocarbons.

This chapter covers the structure, bonding, nomenclature, and physical properties of
alkenes. Then, using a few alkene reactions, some ofthe physical principles are discussed that
are important in understanding the reactivities of organic compounds in general.
4.1
STRUCTURE AND BONDING IN ATKENES

The double-bond geometry of ethylene is typical of that found in other alkenes. Ethylene follows the rules for predicting molecular geometry (Sec. 1.38), which require each carbon of
ethylene to have trigonal planar geometryl that is, all the atoms surrounding each carbon lie in
the same plane with bond angles approximatin g 120" . The experimentally determined structure of ethylene agrees with these expectations and shows further lhat ethylene is a planar
molecule. For alkenes in general, the carbons of a double bond and the atoms directly attached
to them all lie in the same plane.
Models of ethylene are shown in Fig. 4. 1, and a comparison of the geometries of ethylene and
propene with those of ethane and propane is given in Fig. 4.2. Notice that the carbon--carbon
122
4.1
STRUCTURE AND BONDING IN
ALKENES 123
Hi
i
(a)
(b)
Fi8ure4.1 Modelsofethylene.(a)Aball-and-stickmodel.(b)
Aspace-fillingmodel.Ethyleneisaplanarmolecule.
H
H
N\A
c
\
11b.6'
\/
/\
HH
t2t.7" /v
^c
r33oA
vv
H,,,*,,..'"-
l*536A
CHI
10e37
H
ethylene
ethane
CH:
FH,
I11.5" /
7/
IJ THrL
cHz
r54 A
propene
propane
Fi9ure 4.2 Structures of ethylene, ethane, propene, and propane. Compare the trigonal planar geometry of
ethylene (bond angles near 120') with the tetrahedral geometry ofethane (bond angles near .|09.5').All carbon-carbon double bonds are shorter than carbon-carbon single bonds.The carbon-carbon single bond in
propene, moreover, is somewhat shorter than the carbon-carbon bonds of propane.
double bonds of ethylene and propene ( t .:S A) are shorter than the carbon--carbon single bonds
of ethane and propane (1.54 A). This illustrates the relationship of bond length and bond order
(Sec. 1.3B): double bonds are shorter than single bonds between the same atoms.
Another feature of alkene structure is apparent from a comparison of the structures of
propene and propane inFig.4.2.Notice that the carbon--carbon slngle bond of propene (1.50 A)
is shorter than the carbon-carb on single bonds of propane ( I .54 A). fne shortening of all these
bonds is a consequence ofthe particular way that carbon atoms are hybridized in alkenes.
A. Garbon Hybridization in Alkenes

The carbons ofan alkene double bond are hybridized differently from those ofan alkane. In this
hybridization (Fig. 4.3, p. 124), the carbon 2s orbital is mixed, or hybridized, with only two of
the three available 2p orbitals. In Fig. 4.3,we have arbitrarily chosen to hybridize the2p,and
2pn orbitals. Thus, the 2p,orbital is unaffected by the hybridization. Because three orbitals are
mixed, the result is three hybrid orbitals and a "leftover" 2p,orbital. Each hybrid orbital has one
124
CHAPTER
O INTRODUCTION TO ALKENES. STRUCTURE AND REACTIVITY
Ll
2p
2P,
2s
2P
aflcctetJ Lrl' hvh riti izitt
tl
Jn
-f':
rnix 2s,2p.r, and

t,
2p,,
orbitals
z(r?t)
---^
4 ---r-4 lhvbrirl
---T--orbitals
J
-++unarttrctetl bv
ls
-f+(
hrl',r'irlizirtioir
-fF
ls
carbon in ethylene
atomic carbon:
ts)2(2s)'(2p*)(2py)
Figure 4.3 Orbitals of an sp2-hybridized carbon are derived conceptually by mixing one 2s orbital and two 2p
orbitals, in this case the 2p, and 2p, orbitals, shown in red.Three sp2 hybrid orbitals are formed (red) and one 2p,
orbital remains unhybridized (blue).
2p orbital
wave peak
900
\
lltrr.
nodal
,r'
20"
\
I
!p2 orbitals
---s
surface
(a)
(b)
(c)
Figure4.4 (a)Thegeneral shapeofansp2hybridorbital isverysimilartothatofansp'hybridorbital,withalarge

and small lobe of electron density separated by a node. (Compare with Fig. 1 .16a, p.40.) (b) A common stylized
representation of an sp2 orbital. (c) Spatial distribution of orbitals on an sp2-hybridized carbon atom.The axes of
the three sp2 orbitals lie in a common plane (the xy-plane in this case) at angles of 1 20', and the axis of lhe 2pzorbital is perpendicular to this plane.
part s character and two parts p character. These hybrid orbitals are called ,qp' (pronounced "sp-two") orbitals, and the carbon is said to be sp2-hybridized. Thus, an sp2 orbital has 33Vo s
character (in contrast to an sp3 orbital, which has257o s character). A perspective drawing of an
sp2 orbital is shown inFig. 4.4a, and a commonly used stylized representation of an sp' orbital
is shown in Fig. 4.4b.If you compare Fig. 4.4a with Fig. 1.16a (p. 40), you can see that the
shape of an individual sp2 orbital is much like that of an sp3 orbital. The difference between
theie two types of hybrid orbitals is that the electron density within an sp2 orbital is concentrated slightly closer to the nucleus. The reason for this difference is the larger amount ofs character in an sp2 orbital. Electron density in a carbon 2s orbital is concentrated a little closer to the
nucleus than electron density in a carbon 2p orbital. The more s character a hybrid orbital has,
then, the more "s-like" its electrons are, and the closer its electrons are to the nucleus.
Because the2p,and1p, orbitals are used for hybridization, and because the 2s orbital is
spherical (that is, without direction), the axes of the three sp' orbitals lie in the ry-plane (see
4,1
ALKENES 125
2p, orbitals
\
\
,,
{n
=r
t:tlt
c;rrlron-carlrcl n rr
L-ronrl
Fi8ure4.5 Ahybridorbital picturefortheabondsofethylene.A2p.orbitaloneachcarbon(dashedlines)isleft

over after construction of a bonds from hvbrid orbitals.
Fig.4.4c); they
are oriented at the maximum angular separation of 120'. Because the "leftover"
(unhybridized) 2p orbitalis a2p- orbital, its axis is the s-axis, which is perpendicular to the
plane containing the axes ofthe sp2 orbitals.
Conceptually, ethylene can be formed in the hybrid orbital model by the bondin g of two sp2hybridized carbon atoms and four hydrogen atoms (Fig. a.5). An sp2 orbital on one carbon containing one electron overlaps with an sp2 orbital on another to form a two-electron sp2-sp2 C-C
a bond. Each of the two remaining sp2 orbitals, each containing one electron, overlaps with a
hydrogen ls orbital, also containing one electron, to form a two-electron sp2-ls C-H obond.
These orbitals account for the four carbon-hydrogen bonds and one of the two carbon--carbon
bonds of ethylene, which together comprise the sigma-bondframework of ethylene. (We have
not yet accounted for the 2p orbital on each carbon.) Notice carefully that the trigonal planar
geometry of each carbon of ethylene is a direct consequence of the way its sp2 orbitals are directed in space. Once again, we see that hybridization and molecular geometry are related.
(Sec. 1.9). Whenever a main-group atom has trigonal planar geometry, its hybridization is sp2.
Whenever such an atom has tetrahedral geometry, its hybridization is ,qp3.
B. Th zr (Pi) eond
The two Zprorbitals not used in o-bond formation (dashed lines in Fig.4.5) overlap side,toside to form the second bond of the double bond. In the hybrid orbital picture, each2p,orbital
contributes one electron to make an electron-pair bond. A bond formed by the side-to-side
overlap of p orbitals is called a zr bond. (The symbol rr, or pi, is used because z'is the Greek
equivalent of the letter p and because the z'bond originates from the overlap ofp orbitals.T
To visualize electron distribution in a rr bond, we'll use molecular orbital (MO) theory
(Sec. 1.8). MO theory provides a richer description of the z bond, and it also forms the basis
for understanding of ultraviolet spectroscopy (an important tool for molecular analysis; see
Sec. 15.2) as well as a class of reactions called pericyclic reactions (Chapter 27). Notice that
we are treating the o-bond framework with hybrid orbital theory and the z'bond with MO theory. This is justified in MO theory because the z'MOs are, to a good approximation, independent of the other MOs of an alkene molecule. This is another relatively rare situation (as in dihydrogen, Hr; Sec. l.8B) in which molecular orbitals are associated with a particular bond that
we can draw in a Lewis structure.
The interaction of two 2p, orbitals of ethylene by a side-to-side overlap is shown in an

orbital interaction diagram (Fig. 4.6, p. 126). Because two atomic orbitals are used, two molecular orbitals are formed. These are formed by additive and subtractive combinations of the 2p-
126
CHAPTER
4 o INTRODUCTION
TO ALKENES. STRUCTURE AND REACTIVITY
zf
molecular orbital
ANTIBONDING
Pt-
H
-E
(' ----------" \
\ \-'..
\ \'\\
nodal
Pz
planes
engrgy of isolatgd
2P, orbitals
electron
OCCUpanC\/
ttr
ti
Pr
Pz
IT
isolated 2p,
atomic orbital
isoLxed 2p"
atomic orbital
hodal
plane
Pt+
?r
Pz
molecular orbital
BONDING
nuclear position
Figure 4.6 An orbital interaction diagram showing the overlap of 2p orbitals to form bonding and antibonding amolecular orbitals of ethylene.The n' bond is formed when two electrons occupy the bonding z molecular orbital.
Wave peak and wave troughs are shown with different colors.The nodal planes are perpendicular to the page.
orbitals. Remember that subtracting orbitals is the same as reversing the peaks and troughs of
one orbital and then adding.
The bonding molecular orbital that results from additive overlap of the two carbon 2p orbitals is called a er molecular orbital. This molecular orbital, like the p orbitals from which it
is formed, has a nodal plane (shown in Fig. 4.6); this plane coincides with the plane of the ethylene molecule. The antibonding molecular orbital, which results from subtractive overlap of
the two carbon 2p orbitals, is called a zr* molecular orbital. It has two nodes. One of these
nodes is the plane of the molecule, and the other is a plane between the two carbons, perpendicular to the plane of the molecule. The bonding (z') molecular orbital lies at lower energy
than the isolated 2p orbitals, whereas the antibonding (zr*) molecular orbital lies at higher en-
4.1
ALKENES 127
ergy. By the aufbau principle, the two 2p electrons (one from each carbon, with opposite spin)
occupy the molecular orbital of lower energy-the z'molecular orbital. The antibonding molecular orbital is unoccupied.
The filled r rnolecular orbital is the rr bond. Unlike a a bond, a zr bond is not cylindrically
symmetrical about the line connecting the two nuclei. The z'bond has electron density both
above and below the plane of the ethylene molecule, with a wave peak on one side of the molecule, a wave trough on the other, and a node in the plane of the molecule. This electron distribution is particularly evident from an EPM of ethylene, which shows the local negative
charge associated with electron density above and below the molecule.
z'-electron densit\n .rbove and be-lorv

the plane of the rnole,--ule
EPM ofethylene
It is important to understand that the z'bond is one bond with two lobes, just as a2p orbital is
one orbital with two lobes. In this bonding picture, then, there are two types of carbon--carbon
bonds: a o bond, with most of its electron density relatively concentrated between the carbon
atoms, and a zr bond, with most of its electron density concentrated above and below the plane
of the ethylene molecule.
This bonding picture shows why ethylene is planar. If the two CH, groups were twisted
away from coplanarity, the2p orbitals could not overlap to form the zr bond. Thus, the overlap of the 2p orbitals and consequently the very existence of the a' bond require the planarity
of the ethylene molecule.
An important aspect of the z electrons is their relative energy. As Fig. 4.3 suggests, the 2p,
electrons (which become the z'electrons of ethylene) have higher energy than the elecffons in
the hybrid orbitals. Tltts, r electrons generally have higher energy than o electrons,just asp
electrons have higher energy than s electrons. A consequence of this higher energy is that z'
electrons are more easily removed than a electrons. In fact, we'll find that electrophiles react
preferentially with the z'electrons in an alkene because those electrons are most easily donated. Most of the important reactions of alkenes involve the electrons of the r bond, and
many of these reactions iwolve the reaction of electrophiles with the r electrons.
The a, bond is also a weaker bond than typical carbon-+arbon o bonds because z'overlap,
which is "side-to-side," is inherently less effective than o overlap, which is "head-to-head." It
takes about 243H mol-l 158 kcal mol-r) of energy to break a carbon--carbon zbond, whereas
it takes a much greater energy-about 377 kJ mol-1 190 kcal mol-t)-to break the carbon -carbon o bond of ethane.
Return to the structure of propene inFig.4.2, and notice that the carbon-+arbon bond to the
group is shorter by about 0.04 A than the carbon-+arbon bonds of ethane or propane.
-CH,
This small but real difference is general: single bonds to an sp2-hybridized carbon are somewhat shorter than single bonds to an sp3-hybridized carbon. The carbon--carbon single bond of
propene, for example, is derived from the overlap of a carbon sp3 orbital of the
group
-CH,
with a carbon sp2 orbital of the alkene carbon. A carbon--carbon bond of propane
is derived
from the overlap of two carbon sp3 orbitals. Because the electron density of an sp2 orbital is
somewhat closer to the nucleus than the electron density of an spi orbital, a bond involving an
spz orbitaT, such as the one in propene, is shorter than one involving only.qp3 orbitals, such as
128
CHAPTER
4 o INTRODUCTION
the one in propane. In other words, within bonds of a given bond order, bonds with more
character are shorten
t\
H.H
,C-CHI
HrC/
\l
.C:CHz
HrC/
sp3-spz single
spi-spi single bond
bond
(shorter)
(longer
G. oouble-gondStercoisomers
The bonding in alkenes has other interesting consequences, which are illustrated by the fourcarbon alkenes, the butenes. The butenes exist in isomeric forms. First, in the butenes with unbranched carbon chains, the double bond may be located either at the end or in the middle of
the carbon chain.
HzC-CH-CHz-CHr
H:C-CH-CH-CH:
l-butene
2-butene
Isomeric alkenes, such as these, that differ in the position of their double bonds are further examples of constitutional isomers (Sec. 2.4A).
The structure of 2-butene illustrates another important type of isomerism. There are fwo
oC;
the other has a boiling point
separable, distinct 2-butenes. One has a boiling point of 3.7
oC.
In the compound with the higher boiling point, called cis-2-butene or (Q-2-butene,
of 0.88
the methyl groups are on the same side of the double bond. In the other 2-butene, called trans2-butene, or (E")-2-butene, the methyl groups are on opposite sides of the double bond.
H..C
\
H
\/c_c
/\
HrC
CH.
J
c-c
\J-v
CH.
v-v
/\
HH
trans-2-butene
(E)-2-butene
cis-2-butene
(Z)-z-butene
These isomers have identical atomic connectivities (CH, connected to CH, CH doubly bonded
to CH, CH connected to CHr). Despite their identical connectivities, the two compounds dffir
in the way their constituent atoms are arranged in space. Compounds with identical connectivities that differ in the spatial arrangement of their atoms are called stereoisomers. Hence, clsand trans-2-butene are stereoisomers. (The (E) nd (Z) notation has been adopted by the IUPAC
as a general way of naming cis and trans isomers. This notation is discussed in Sec. 4.2B.)
The interconversion of cis- and trans-2-batene requires a 180o internal rotation about the
double bond-that is, a rotation of one carbon while holding the other carbon stationary.
H
C
lg0'
internal rotation
H.C
"\
(v-v
CH:
/\ -(\
H
H
(4.1)
cHr
trans-2-butene
cis-2-butene
(interconversion does not occur at ordinary temperatures)
Because cis- and trans-2-butene do not interconvert, even at relatively high temperatures, it
follows that this internal rotation must be very slow. For such an internal rotation to occur, the
2p orbitals on each carbon must be twisted away from coplanarity; that is, the r bond must be
4.1
bonding
ALKENES 129
zr
molecular orbital
CH:
H
H:C
trans
2p orbitals cannot ornerlap;

therefore n"hrond is trroken
cls
FiBure4.7 Internalrotationaboutthecarbon-carbondoublebondinanalkenerequiresbreakingthen
bond.
This does not occur at ordinary temperatures because too much energy is required.
broken. (Fig.4.7). Because bonding is energetically favorable, lack of it is energetically costly.

It takes more energy to break the zr bond than is available under normal conditions; thus, the
zrbond in alkenes remains intact, and internal rotation about the double bond does not occur.
In contrast, internal rotation about the carbon--carbon single bonds of ethane or butane can
occur rapidly (Sec. 2.3) because no chemical bond is broken in the process.
Ci.r- and trans-2-bttene are examples of double-bond stereoisomers. Double-bond

stereoisomers (also called cis-trans stereoisomers or ,E,Z-stereoisomers) are defined as
compounds related by an internal rotation of 180" about the double bond. (We can always
imagine such a rotation even though it does not occur at ordinary temperatures.) Another
equivalent definition is that double-bond stereoisomers are different compounds related by interchange of the two groups at either carbon of a double bond.
H,C
H\
/ \
C:C
/
\*
HCH
H:Q
-\
/,CH,
C:C
/\
interchange colored groups
(4.2)
When an alkene can exist as double-bond stereoisomers, both carbons of the double bond
ate stereocenters. Interchanging two groups at a stereocenter gives stereoisomers. (Other
terms that mean the same thing are stereogenic atom and stereogenic center.)
these carbons
are stereocenters
A
/\/\
H.C I \ CH.
\rC:C\/
/\
HH
therSC
11
rbDOIIS
re stte *nttt'
.entelrS
Lle
H
HI
\r
//\
\C]H
\\/
c=
(
H 3c
C
-( C
H
Because the exchange of the two groups at either carbon of the double bond gives stereoisomers, each of these carbons is a stereocenter.
30
CHAPTER
4.
INTRoDUCTIoN TO ALKENES. STRUCTURE AND REACTIVITY
You'll learn in Chapter 6 that double-bond stereoisomers are not the only type of stereoisomer. In every set of stereoisomers we'll be able to identify one or more stereocenters.
stereocenters.
CH2CH3
HrC
"\
/
C:C
/\
H
CHr
H,C
CHI
-\
/
C:C
/\
H
H:C
SOfUtiOn Apply the definition of double-bond stereoisomers as illusfiated inEq.4.2. That is, in-
two grottps at either carbon of the double bond. This process will
give one of two results: either the resulting molecule will be identical to the original-that is, superimposable on the original atom-for-atom----or it will be different. If it's different , it can only be
a stereoisomer, because its connectivity is the same.
In molecule A, interchanging the two groups at either carbon of the double bond gives different molecules. In the original, the methyl groups are trans; aftsr the interchange, the methyl
terchange the positions of the
gnoups are cis. Hence, A has a double-bond stereoisomer:
-\
CH:
/
H
\*CH.
H.C
CH,
/
t
C:C
interchirnge col0red groups
CH,
H.C
-\
/
C:C
/\
cHrcHl
H
(4.3)
(You should verify that exchanging the two groups at the other carbon ofthe double bond gives
the same result.) The two carbons of the double bond are both stereocenters.
In the case of structure B, interchanging the two groups at either carbon of the double bond
gives back an identical molecule.
H,C
"\
H:C
H.C
CH:
/
C:C t
\*H
interchange colored groups
:::{__ 0
/\
HrC
cH,
rotatclS0o
HrC
"
\
C:C
/\
HrC
CH.]
/
(4.4)
You may have found that the structure you obtained from interchanging the two groups doesn't /ooft
identical to the one on the left" but it is. You can demonstrate their identity by flipping either struc-
ture 180o about a horizontal axis (green daslud lineY-n other words, by tuming it over, as shown
in Eq. 4.4. But if you have diffrculty seeing this, you must buil.d molecular models of both structures
and corwirre yourself that the two ccor be supeimposed atom-for-atom There is no substitute fot
model building when it comes to the spatial aspects of organic chemistry! After a little work with
models on issues like this, you will develop the ability to see these relationships without models.
tt.l
Different Ways to
Draw the same
STUDY SUIDE LINK
strusture
Study Guide Link 4.1 offers more insights about how to achieve facility in relating alkene structures.
Because interchanging two groups lll,Bq.4.4 does not give stereoisomers, this alkene contains
no stereocenters,
4.2
4.1
NOMENCLATURE OF
ALKENES ".31
Which of the following alkenes can exist as double-bond stereo? Identify the stereocenters in
each.
(a)
H2C-CHCH2CH2CH3
(b) CH3CH2CH:CHCH2CH3
l-pentene
(c)
3-hexene
HzC:CH-CH*CH*CHr
l,3-pentadiene
(d)
CH3CH2CH:CCHr
-
J",
{e)
cyclobuten
2-methyl-2-pentene
2-methvl-2-Dentene
(Hint for pan (e): Try to build a model of both stereoisomers, but don't break your models!)
4.2
NOMENCLATURE OF ALKENES
A.
IUPAC Substitutive Nomenclature

The IUPAC substitutive nomenclature of alkenes is derived by modifying alkane nomenclature in a simple way. An unbranched alkene is named by replacing the ane suffix in the name
of the corresponding alkane with the ending ene and specifying the location of the double
bond with a number. The carbons are numbered from one end of the chain to the other so that
the double bond receives the lowest number. The carbons of the double bond are numbered
consecutively.
l4ii(r
H2C:CH-CH2CH2CH2CH3
hexdil- + ene
: hexene
1-hexene
fnritinn ofdouble bond
The IUPAC recognizes an exception to this rule for the name of the simplest alkene,
H2C:CH,, which is usually called ethylene rather than ethene. (Chemical Abstracts
(Sec. 2.4D, p. 66), however, uses the substitutive name ethene.)
The names of alkenes with branched chains are, like those of alkanes, derived from their
principal chains. In an alkene, the principal chain is defined as the carbon chain containing
the greatest number of double bonds, even if this is not the longest chain. If more than one candidate for the principal chain have equal numbers of double bonds, the principal chain is the
longest of these. The principal chain is numbered from the end that results in the lowest numbers for the carbons of the double bonds.
When the alkene contains an alkyl substituent, the position of the double bond, not the position of the branch, determines the numbering of the chain. This is the main difference in the
nomenclature of alkenes and alkanes. However, the position of the double bond is cited in the
name afterthe name of the alkyl group. Study Problem 4.2 shows how these principles are implemented.
Name the following compound using IUPAC substitutive nomenclature.
H2C-C-CH2CHzCHT
I
cH2cH2cH2cHzcHr
132
CHAPTER
4.
INTRODUCTION TO ALKENES. STRUCTURE AND REACTIVITY
The principal chain is the longest continuous carbon chain containing both carbons of
the double bond, as shown in color in the following structure. Note in this case that the principal
chain is zol the longest carbon chain in the molecule. The principal chain is numbered from the
end that gives the double bond the lowest number-in this case, l. The substituent group is a
propyl group. Hence, the name ofthe compound is 2-propyl-l-heptene:
Solution
/'
position of the substituent group

incorrect nurnbering
-----rrF
correctnumbering-r
nosition of the double bond
ll
tt
2-propyl- l-heptene
6
2
HrC-C-CH2CHzCHT
t'
-<-
CH2CH2CH?CH:CH-r
345fiT
:{-r-1
principal chain (longest chain

containing the double bond;
double bond receives the lowest number)
If a compound contains more than one double bond, the ane ending of the corresponding
alkane is replaced by adiene (rf there are two double bonds), atriene (if there are three double
bonds), and so on.
HzC-CHCH2CH2CH:CH:
1,S-hexadiene
Namethefollowingcompound:
CH2-CH:CH2
CH3CH2CH2CHT-C:C.-CFI3
!
C",
Solution
The principal chain (color in the following structure) is the chain containing the
greatest number of double bonds. One possible numbering scheme (red) gives the first-
I and 4, respectively; the other possible numbering scheme (blue) gives the fust-encountered carbons of the double bonds the numbers
2 and5, respectively. We compare the two possible numbering schemes pairwise-that is, (1,4)
versus (2,5). The lowest number at first point of difference (1 versus 2) determines the correct
numbering. The compound is a 1,4-hexadiene, with a butyl branch at carbon-4, and a methyl
encountered carbons of the two double bonds the numbers
branch at carbon-5:
lncltrreL-t numl-lerlng
rr #
-i
l+correctnllmbering v
?.
<-principal
chain
CH: CHr
,l
CH,
cH3cH2cH2cH2-
9: C-CH,
4
l:t
I
CH:
positions of double bonds

positions of substituents
If the name remains ambiguous after determining the correct numbers for the double bonds,
then the principal chain is numbered so that the lowest numbers are given to the branches at the
first point of difference.
4.2
NOMENCLATURE OF
ALKENES 133
Name the following compound:
QH:
trl
\,,,
/-'.,,.cIJt
SOf
utiOn
TWo ways of numbering this compound give the double bond the numbers
CH:
possible
and2.
CHr
names: 1,6-dimethylcyclohexene 2,3-dimethylcyclohexene

(incorrect)
(correct)
In this situation, choose the numbering scheme that gives the lowest number for the methyl
substituents at thc first point of dffirence.In comparing the substituent numbering schemes
(l,6) with (2,3), the first point of difference occurs at the first number (1 versus 2). The (1,6)
numbering scheme is correct because I is lower than 2. Notice that the number 1 for the
double bond is not given explicitly in the name, because this is the only possible number. That is,
when a double bond in a ring receives numerical priority, its carbons must be numbered consecutively with the numbers I and2. That's why the following numbering scheme is incorrect. One
carbon of the double bond has the number 1. but the other is not numbered consecutivelv.
CHr
1,2
(
-dimethylcyclohexene
incorrect because carbons of drtubie bond

are not nLrmbered consecutiveh'')
Substituent groups may also contain double bonds. Some widely occurring groups of this
type have special names that must be learned:
HzC-CH-
HzC-CH-CH2-
vinyl
allyl
HrC-CI
CH:
isopropenyl
Other substituent groups are nulnbered from the point of attachment to the principal chain.
1
3-vinylcyclohexene
- ( z-butenyl)
AI
I
tf
ryclohexene
pcsrtion nf iJoutllt' LronrJ u'itl-lin

the sulrstitue nr
Lrosition of the substituent grollp

on the prinr-ipal chairr
134
cHAprER
4.
INTRoDUCTToN To ALKENES. STRUCTURE AND REACTtvlry
The names of these groups, like the names of ordinary alkyl groups, are constructed from the
name of the parent hydrocarbon by dropping the final e from the name of the corresponding
alkene and replacing it with y/. Thus, the substituent in the second example above is buten/ +
yl : butenyl. Notice the use of parentheses to set off the names of substituents with internal
numbering.
Finally, some alkenes have nonsystematic traditional names that are recognized by the
IUPAC. These can be learned as they are encountered. Two examples are styrene and isoprene:
H2c:c-cH:cHz
Ph-cH:cHr
styrene
CH.
isoprene
(Recall from Sec. 2.98, p.82, that
Ph-
refers to the phenyl group, a singly substituted ben-
zene ring.)
More Recent IUPAC Nomenclature Recommendations

The nomenclature in this text is based on the widely used 1979 IUPAC rules. In 1 993, the IUPAC recommended an alteration in nomenclature that places the number of the double bond just before
the ene suffix ofthe name.Thut in the new system,
-hexene is named hex-l -ene, and 2,4-hexadiene
is named hexa-2,4diene.This new system is being used by some chemists and not by others.While
the system is logical, its general adoption would require chemical indexing systems either to recognize both old and new names or to cross-reference between them. Because Chemicol Abstracts has
not adopted the new system,we won't use it in this text. However,conversion between old and new
names is a simple matter of moving the numerical designation.
4.2
4.3
Give the structure for each of the following:

(a) 4-methyl-1,3-hexadiene (b) 2-methylpropene {c) l-isopropenylcyclopentene
(d) 5 -(3 -pentenyl)- 1, 3,6,8-decatetraene
Name the following compounds.
(a) QH:
(b) CH3CH2CH-CHCH2CH2CH3
CH:
(c)
HrC-CH:CH-CHz-QH-CH:CH-CH2-CH3
I
CH2-CH:CH2
B. Nomenclature of Double-Bond Stereoisomers: The E,Z System

The cis and trans designations for double-bond stereoisomers are unambiguous when each
carbon of a double bond has a single hydrogen, as in cls- and trans-2-butene. However, in
some important situations, the use of the terms cis and trans is ambiguous. For example, is the
following compound, a stereoisomer of 3-methyl-2-pentene, the cls- or the trans-stereoisomer?
gac,
pzHs
\,/
/\,P:q.
CH.
4.2
NOMENCLATURE OF
ALKENES 1 35
One person might decide that this compound is trans, because the two identical groups are on
opposite sides of the double bond. Another might decide that it is cis, because the larger
groups are on the same side of the double bond. Exactly this sort of ambiguity-and the use
of both conventions simultaneously in the chemical literature-brought about the adoption of
an unambiguous system for the nomenclature of stereoisomers. This system, first published in
I 95 1, is part of a general system for the nomenclature of stereoisomers called the Cahn-Ingold-Prelog system after its inventors, Robert S. Cahn (1899-1981), then editor ofthe Journal of the Chemical Society, the most prestigious British chemistry journal; Sir Christopher K.
Ingold (1893-1970), a professor at University College, London, whose work played a very
important part in the development of modern organic chemistry; and Vladimir Prelog
(190G1998), a professor at the Swiss Federal Institute of Technology, who received the 1975
Nobel Prize in Chemistry for his work in organic stereochemistry. When we apply the
Cahn-Ingold-Prelog system to alkene double-bond stereochemistry, we'Il refer to it simply as
the E,Z system for reasons that will be immediately apparent.
The E,Z system involves assignment of relative priorities to the two groups on each carbon
of the double bond according to a set of sequence rules given in the steps to be described below.
We then compare the relative locations of these groups on each alkene carbon. If the groups of
higher priority are on the same side of the double bond, the compound is said to have the Z configuration (Z from the German word zusammen, meaning "together"). If the groups of higher
priority are on opposite sides of the double bond, the compound is said to have the E configuration (E from the German entgegen, meaning "across").
1ligh prrinritr.
prioritl.,
\/
b-d
/\
low priority
low priority
high
(z)
high
trrrioritv
\/
/\U-U
,/\
low priority
11-(-
low priority
high prir rittn
(F)
For a compound with more than one double bond, the configuration of each double bond is
specified separately.
To assign relative priorities, proceed through each of the following steps in order until a decision is reached. Study Problems 4.5 and4.6 illustrate the use of these steps.
Step
Examine the atoms directly attached to a given carbon of the double bond, and then follow the first rule that applies.
Rule
Rule
Step 2
Ia
Ib
Assign higher priority to the group containing the atom of higher atomic number.
Assign higher priority to the group containing the isotope of higher atomic mass.
If the atoms directly attached to the double bond are the same, then, working outward
from the double bond, consider within each group the set of attached atoms. You'll have
two sets-one for each group on the double bond.
RuIe 2 Arrange the attached atoms within each set in descending priority order, and make a
pairwise comparison of the atoms in the two sets. The higher priority is assigned to the atom of
higher atomic number (or atomic mass in the case of isotopes) at the first point of dffirence.
Step 3
If the
sets of attached atoms are identical, moye away from the double bond within each
group to the next atom followingthe path of highest priority, and identify new sets of attached atoms. Then apply rule 2 to these new sets. Keep following this step until a decision is reached. Remember that a priority decision must be made at the first point of dif-
ference.
136
CHAPTER
4I
@WhatistheconflgurationofthefolIowingstereoisomerof3-methyl-2-pentene?(Thenumbers
and letters are for reference in the solution.)
23
||ill
H:c
-\tI t/I cH:
C:C
/\
CH2CH3
H
SolutiOn First,
consider the relative priorities of the groups attached to carbon-2. Applying rule
la, the two atoms directly attached to carbon-2 are C and H. Because C has a higher atomic number (6) than H ( I ), the CH, group is assigned the higher priority. Now consider the groups attached to carbon-3. Step
leads to no decision, because in both groups the atom directly attached
same-a carbon m in the
case of the methyl group, and a carbon e in the

of the ethyl group. Following step 2, represent the atoms attached to these carbons as a set in
descending priority order. For carbon e, the set is (C,H,H); notice that the carbon of the double
bond is not included in the set.For carbon m, the set is (H,H,H). Now make a pairwise comparison of (C,H,H) with (H,H,H). The first point of difference occurs at the comparison of the flrst
atoms of each set, C and H. Because C has higher priority, the group containing this atom-the
ethyl group-also has higher priority. The priority pattern is therefore
to the double bond is the

case
23
higherprioritygroup---ir-H..C.t|,CH:+[tlll.er|rritrritl.qr()Ltp
r L'
|/
atiarbon-2
,lt irrii'rr
\V
C:C
inn,cr pt-iot'itv
irt t-;rrbron
group
--:-----:j>-
/\
CHZCH3
-<--
.i
higher priorifl" groliP

at carbon-3
Because groups of like priority are on opposite sides of the double bond, this alkene is the E iso-
mer; its complete name is (E)-3-methyl-2-pentene.
@Namethefollowingalkene.(Thenumbersandlettersareforreferenceintheso1ution.)
I it/ in,E^2cH2cH3
\v
C:C
H
/
H:C
\i,t
bl
CH2CHCH:
I
CH:
Soluti0n At carbon-2, the methyl group has higher priority, by rule la. At carbon-3, rule 1a
allows no decision, because atoms a1 and bl ue identical-both are carbons. Proceeding to step
al or bl can be represented as (C,H,H); again, no
decision is possible. Step 3 says that we must now consider the next atoms in each chain along the
path of highest priority. We therefore move to the next carbon atom (a2 and b2) rather than the
hydrogen in each chain, because carbon has higher priority than hydrogen. The set of atoms
attached to a2 is (C,H,H); the set attached to b2 is (C,C,H). Notice that carbons al and bI
considered in the previous step are not considered as members ofthese sets, because we always
2, the set of atoms attached to either carbons
work outward, away from the double bond, by step 2. The difference in the second atoms of each
set-{ versus H--dictates a decision. Because the set of atoms at carbon b2 has higher priority,
4.2
the
gpnp containing carbon b2 (tlrc isobutyl group) also
NOMENCLATURE OF
has the higher
ALKENES 137
prisrity. Tlre process used
can be summarized as follows:
(c,H,H)
H
(C,H,H)
.CH2+692-CH2CH3
\/A
c:c
| +o4"tltionismadehere
/\v
HrC
CHr-->6111611r;,
(c,HJr)
(c,gH)
Because the groups of like priority are on the same side of the double bond, this alkene has the
configuration.
group of lower priority
it
caibon-2
grouP of higher priority

at carbon-2
-.---.*
23
I I CUTCHTCUzCHT
\f | /
C:C'
H.
/\
-=-+ HIC
<-
CH2CHCHI
group of lower priority
it caibon-l
group of higher priority

at carbon-3
CHr
Application of the nomenclature rules completes the name: (Z)-3-isobutyl-2-heptene.
Sometimes the groups to which we must assign priorities themselves contain double bonds.
Double bonds are treated by a special convention, in which the double bond is rewritten as a
single bond and the atoms at each end of the double bond are duplicated:
-CH:CH2
istreatedas
-9H-9H2
CC
and
-CH:O
istreatedas
tl
-CH-O
OC
Notice that the duplicated atoms bear only one bond. (The developers of this scheme prefened to
say that each of these duplicated carbons 'obears three phantom (that is, imaginary) atoms of priority zero.") The treatment of triple bonds requires triplicating the atoms involved:
NC
CL
-C-CH
is treated
as
ll
tl
-C-CH
CC
and
-C-\
is treated
ll
-C-N
ll
NC
as
, including tbe(E,|designation for the double-bond stereochemistry. (Ihe carbon numbers are for rcference in the solution.)
fal
O) (cHr,c{
nfr,
/.n,
H.C
C:C
C==C
(c[ts)z$
,/\
HzC-CH
t?
-\
C:C
/\
\H
SOJUtiOn (a) First, give the name without the stereochemistry. By the.principles discussed previ-
and2
At carbon-4, the methyl group receive* higher pri-
ously, thename is 3-isopropyl-1,3-pentadieno. Now we assign stereocbemistry. Carbons 1

are nol steneocenbrs, but carbons 3 and 4 are.
138
CHAPTER
4o
ority than H. The real issue here is the relative priorities of the groups at carbon-3. We represent
the two groups as follows:
'l{:'" ,
,c(c,c,H)
H.C
-\/ /
\r,
C '(,
\C(H,H,H)
c(o,o,o)
isopropyl group
'H)
H2(--cH- tr> r'T-lH-
CH/o
Hr9-o
(The symbol
*/
,/"((-'(
vinyl group
means "implies.") Notice that the carbons of the double bond are duplicated;
the colors show the relationship of the replicated carbons to the original ones. The (0,0,0) next to
the duplicated carbons represents the "phantom atoms" attached to these carbons-that is, imagi-
nary atoms of priority zero. We compare carbon a of the isopropyl group with carbon a of the
vinyl group. The attached groups are the same: (C,H,H). In the isopropyl group, we proceed outward to either of the methyl groups. In the vinyl group, we could proceed to carbon b or to its duplicated image, carbon D'. We must choose the path of higher priority before we compare the result with the isopropyl group. Choosing the path of higher priority requires going out one more
atom beyond carbons b and b'-in other words, comparing (C,H,H) for C'with (0,0,0) for Cb'.
Because the carbon atom attached to carbon b has a higher priority than a phantom atom on carbon b', carbon b represents the path of higher priority for vinyl. Now we are ready to compare the
vinyl and isopropyl groups again. For isopropyl, carbon b is C(H,H,H), and for vinyl, carbon b is
C(C,H,H). Because C has a higher priority than H, vinyl receives the higher priority. The name is
therefore (E)-3-isopropyl- 1,3-pentadiene.
You should be able to work part (b) using the same tactics. Try it. The name Is (2E,42)-3-isopropyl-2,4-pentadiene. (Notice that the position of the isopropyl group determines the numbering
of the double bonds, which is ambiguous otherwise.) Notice also that when two or more double
bonds require a stereochemical designation, the number of the double bond is included with the
EorZ.
4.4
Name each of the following compounds, including the proper designation of the double-bond
stereochemistry:
(a|
H2c-cHC(z
C:C
/\
(cH3)2cHCH2
STUDY GUIDE LINK 4.2
Drawing Structures
from Names
4.5
fr,
(b) (cH3)2c(r
,/t:t\
cH3cHzcHz
f^'
H
Give the structure of:

tai:j (O-4-allyl- 1 ,5-octadiene (b) (28,7 Z)-5-[(4- 1-propenyl]-2,7 -nonadiene
Be sure to read Study Guide Link 4.2 if you have difficulty with this problem.
4.6 In each case,

ta)
which group receives the higher priority?
CH3CH2 (b)
CH
/\
cH3o \,_
I
\/CH/t: J
/
HO
cl2HC
-
(c)
(CH3)3C\
IC:
/
c
-[
/" J H3c-cH
Hzc-cH
I
ocH3
4.3
4.3
UNSATURATION
NUMBER 139
UNSATURATION NUMBER
An alkene with one double bond has two fewer hydrogens than the alkane with the same carbon skeleton. Likewise, a compound containing a ring also has two fewer hydrogens in its
molecular formula than the corresponding noncyclic compound. (Compare cyclohexane or
l-hexene, C6Hp, with hexane, CuH,o.) As both examples illustrate, the molecular formula of
an organic compound contains
"built-in" information about the number of rings and double
(or triple) bonds.

The presence of rings or double bonds within a molecule is indicated by a quantity called
the unsaturation number, or degree of unsaturati on, U . The unsaturation number of a molecule is equal to the total number of its rings and multiple bonds. The unsaturation number of
a hydrocarbon is readily calculated from its molecular formula as follows. The maximum
number of hydrogens possible in a hydrocarbon with C carbon atoms is 2C + 2. Because each
ring or double bond reduces the number of hydrogens from this maximum by 2, the unsaturation number is equal to half the difference between the maximum number of hydrogens and
the actual number H:
U- 2C+2-H -
number of rings
+ multiple bonds
(4 s)
For example, cyclohexene, CuH,o, has U : t2(6) + 2 - l0l/2: 2. Cyclohexene has two degrees ofunsaturation: one ring and one double bond. A triple bond contributes two degrees of
unsafuration. For example, l-hexyne, HC:C-{H2CH2CH2CH3, has the same formula as
cyclohexene: CuH,o.
How does the presence of other elements affect the unsaturation number calculation? You
can readily convince yourself from common examples (for instance, ethanol, CTHTOH) that
Eq. 4.5 remains valid when oxygen is present in an organic compound. Halogens are counted
as if they were hydrogens, because halogens are monovalent, and each halogen reduces the
number of hydrogens by l. Equation 4.5 remains unchanged as long as we let ,F1 represent the
total number of hydrogens and halogens:
zc
-u
(H :hydrogens plus halogens)
(4.6)
Another common element found in organic compounds is nitrogen. When nitrogen is present,
the number of hydrogens in a saturated compound increases by one for each nitrogen. (For example, the saturated compound methylamine, H3C-NH2 , has 2C * 3 hydrogens.) Therefore,
if N is the number of nitrogens, the formula for the unsaturation number becomes
U- 2C+2C+2+N-H
Remember that the unsaturation number is a valuable source
(4.7)
of structural information
about an unknown compound. This idea is illustrated in Problems 4.9 and 4.10.
4.7
Calculate the unsaturation number for each of the,followitg compoundb:

(a) CrHoClo O) C5HsN2
4.8
Without writing a formula or sffucture, give the unsaturation number of each of the following
compounds:
{a) 2,4,6-octafiiene (b)

4.9
A compound
methylcyclohexane
formula CroHroOr. Certain structuml evidence suggests that

the compound contains two methyl groups and no carbon--carbon double bonds. Give one
has the molecular
140
CHAPTER
gnrchu consistct with ee$e fiodiogo in ryliich atl:qingg a$ rh-mmbrcd" (Many s.tnc,i!
a*gs ge,pgssibl6.F '.' ,
,,
4.10
4.4
Which of the follw,ing cannotbe, w.tcr;t fomrula(r) for an organic cornpound? Explain.
(a) C,otfo[.{r (b)CroHalqOr (c) CtoIIry'.IrOr (d) CroIIrcOz
PHYSICAL PROPERTIES OF ALKENES

Except for their melting points and dipole moments, many alkenes differ little in their physical properties from the corresponding alkanes.
H2C:CH(CH2)3CH3
CH3(CH2)4CH3
l-hexene
63.4"C
- 139.8 'C
0.673 gmrt
negligible
0.46 D
hexane
point
melting point
density
water solubility
dipole moment
boiling
68.7
oC
-95.3 'C
mL-'
0.660 g
negligible
0.085 D
Like alkanes, alkenes are flammable, nonpolar compounds that are less dense than, and insoluble in, water. The alkenes of lower molecular weight alkenes are gases at room temperature.
The dipole moments of some alkenes, though small, are greater than those of the corresponding alkanes.
t't\
/tt'
9:C.
H
H
H3C-CH2-CH2-CH3
P:gD
l, = 0.25 D
How can we account for the dipole moments of alkenes? Remember that the electron density
in sp2 orbitals lies closer to the nucleus than it does in qp3 orbitals (Sec. 4.lA). In other words, an
.qp2 carbon has a greater attraction for electrons. This, in turn, means that an sp2 carbon is somewhat more electronegative than an sp3 carbon. As a result, any spz-sp3 carbon--carbon bond has
a small bond dipole (Sec. 1.2D) in which the qp3 carbon is the positive end and the spz carbon is
the negative end of the dipole.
sD3
'
\,
"]afrt- -/
/t"sp2t
,--
polarrzationof electron density
io*ard trigonal carbon
The dipole moment of cis-2-butene is the vector sum of the H3C-C and H-C bond dipoles.
Although both types of bond dipole are probably oriented toward the alkene carbon, therg is
good evidence (Problem 4.62, p. 176) that the polarization of the H3C-C bond is greater.
This is why cls-2-butene has a net dipole moment.
4.5
RELATIVE STABILITIES OF ALKENE
H,c.x
''t bond
\ c\ /'f^-d)^,..,.r
/
l,u -c- u.t --l
d'/
ISOMERS 141
dipoles
+ \k-
HYH
il'i*'lf1'
In summary: Bonds from alkyl groups to trigonal planar carbon are polarized so that electrons are drawn away from alkyl groups toward the trigonal carbon. This means that a carbon--carbon double bond, when viewed as a substituent group, exerts an electron-withdrawing
polar effect (Sec. 3.6C). The polar effect of a double bond is only about lO-I57o that of a chlorine, but it's significant enough to be measurable. (See Problem 4.12.)
4.ll
Which compound in each set should have the larger dipole moment? Explain.
(a) cis-Z-butene or trans-2-butene (b) propene or 2-methylpropene
4.12 Which of the following two carboxylic
acids
more acidic? Explain.
is,
o
tl
tl
4,5
o
tl
HzC:CH-CHz-C-OH
HrC* CHz*CHz-C-OH
3*butenoic acid
butanoic acid
RELATIVE STABITITIES OF ALKENE ISOMERS
-rl
Further Exploration 4.1
Relationship between
Free Energy and
Enthalpy
When we ask which of two compounds is more stable, we are asking which compound has
lower energy. However, energy can take different forms, and the energy we use to measure relative "stability" depends on the purpose we have in mind. We've learned that AG" for a reaction is the energy quantity related to the equilibrium constant (Sec. 3.5). Measuring the equilibrium constant is a good way to determine AG'. However, if we are interested inthe total energy
change for a reaction, we use the standard enthalpy change for the reaction, AIl". The AIf
for a reaction approximates very closely the total energy difference between reactants and
products, and it reflects the relative stabilities of bonding anangements in reactants and products. The AG" and A.F1' for a reaction are related by the equation AGo = LHo - ZAS', where
AS" is the entropy change for the reaction and Tis the absolute temperature. (For a structural
interpretation of AS', see Further Exploration 4.1 in the Study Guide.) In other words, the AGo
for a reaction differs from the total energy difference between reactants and products by
anamount -ZAS'. In Sec. 4.5A we'll learn the conventions for presenting enthalpy data, and in
Sec. 4.5B we'll use enthalpy data to investigate the relative stabilities of alkenes.
A. Heats of Formation
The relative enthalpies of many organic compounds are available in standard tables as heats
of
formation. The standard heat of formation of a compound, abbreviated L,H], is the heat
chanse that occurs when the comoound is formed from its elements in their natural state at
142
CHAPTER
4.
oC.
Thus, the heat of formation of trans-2-bttene is the A11" of the folatm pressure and 25
lowing reaction:
+ 4C
4H2
-------->
trans-2-butene(CaHs)
(4.8)
The sign conventions used in dealing with heats of reaction are the same as with free energies: the heat of any reaction is the dffirence between the enthalpies of the products and the
reactants.
AI1'(reaction)
H" (products)
H"(reactants)
(4.e)
A reaction in which heat is liberated is said to be an exothermic reaction, and one in which
heat is absorbed is said to be an endothermic reaction. The A11' of an exothermic reaction, by
Eq. 4.9, has a negative sign; the AF1' of an endothermic reaction has a positive sign. The heat
of formation of trans-2-butene (Eq. 4.8) is - I 1.6 kJ mol-t 1-2.72 kcal mol-r): this means that
heat is liberated in the formation of trans-2-butene from carbon and hydrogen, and that the
alkene has lower energy than the 4 moles each of C and H, from which it is formed.
Heats of formation are used to determine the relative enthalpies of molecules-that is,
which of two molecules has lower energy. How this is done is illustrated in Study Problem 4.8.
@Calculatethestandardenthalpydifferencebetweenthecisandtransisomersof2.butene.Specify
which stereoisomer is more stable. The heats of formation are, for the cis isomer, -7.40 kJ mol-r,
and for the trans isomer, - 11.6 kJ mol-t 1-1.77 and -2.72 kcal mol-r, respectively).
Solution
The enthalpy difference requested in the problem corresponds to the
AIf
of the fol-
lowing hypothetical reactionl
LHi
cis-Z-butene
--+
-7.40
1..77
trans-}-butene
- 11.6
(4.10)
kJ mol-t
kcal mol-1
-2.72
To obtain the standard enthalpy difference, apply Eq. 4.9 using the corresponding heats
in plnce of thc
If
values . T\us,
product, tans-2-butene. The
AIf
(-1.0 kcal mol-';. This means
offorwntion
AI1i for the reactant, as-2-butene, is subtracted from that of the

for this reaction, then, is
I1.6
(-7.4O)
= -4.2 kJ mol-r
that trans-2-butene is more stable than cis-2-butene by 4.2 kJ
mol-l
(1.0kcal mol-r).
The procedure used in Study Problem 4.8 is based on the fact that chemical reactions and
their associated energies can be added algebraically.This principle is known as Hess's law
of constant heat surnmation. Hess's law is a direct consequence of the first law of thermodynamics, which requires that the energy difference between two compounds doesn't depend on
the path (or reactions) used to make the measurement. Thus, what we have done in Study
Problem 4.8 is to add the two formation reactions and their associated enthalpies, one in the
forward direction and the other in the reverse direction:
Equations:
+e + #5 ---+ trans'1-butene
*c + 145
cis-Z-butene -+
Sum: cis-2-butene +
trans-Z-butene
LH" (kJ
mol*l): LH" (kcal mol-r):
- 1.6
+l .4
I
-A')
-2.72
(4. I 1a)
T 1.77
(4.1lb)
(4.1lc)
1.0
Because cis- and trans-2-bttene are isomers, the elements from which they are formed are the
same and cancel inthe comparison. This is shown by the diagram in Fig.4.8. Were we to com-
45 RELATIVESTABILITIESOFALKENEISOMERS 143
7.40 kJ
{
1.77
mol
The enthalpy of the elements in their

standard states is the reference point
for enthapies of formation
kral mol
I 1.6 kl mol-t
(1.71 kcal mc-rl-l
cis-2-butene
4.1
(
kl nrol
1.0 kcal mol:r
enthalpy difference between

cis- and trans-2-butene
trans-Z-butene
FiSure 4.8
Use of heats of formation to derive the relative enthalpies of two isomeric compounds. The
enthalpies of both compounds are measured relative to a common reference, the elements from which they are
formed.The difference between the enthalpies of formation is equal to the enthalpy difference between the tlvo
isomers.
j
Further E $loration 4.2
Source of Heats
of Formation
pare the enthalpies of compounds that are not isomers, the two formation equations would
have different quantities ofcarbon and hydrogen, and the sum would contain leftover C and
Hr. This sum would not correspond to the direct comparison desired.
Using heats of formation to calculate the standard enthalpy difference between two compounds
(Study Problem 4.8) is analogous to measuring the relative heights of two objects by comparing their
distances from a common reference, such as the ceiling. If a table top is 5 ft below the ceiling, and an
electrical outlet is 7 ft below the ceiling, then the table top is 2 ft above the outlet. The height of the
ceiling can be taken arbitrarily as zero; its absolute height is irrelevant. When heats of formation are
compared, the enthalpy reference point is the enthalpy of the elements in their "standard states," their
normal states at 25 "C and 1 atm pressure; the enthalpies of formation of the elements in their standard states are arbitrarily taken to be zero.
Heats of formation are not measured directly, because the formation reaction is not a practical reaction. Rather, heats of formation are determined by combining the enthalpies of other, more practical reactions, such as combustion (Sec. 2.7) or catalytic hydrogenation (Sec. 4.9A), using Hess's law
calculations. Heats of formation are the conventional way in which these various sources of enthalpy
data are brought together and tabulated. (See Further Exploration 4.2.)
@4.8(a)Calculatetheenthalpychangeforthehypotheticalreactionl-butene-2-methy1propene. The heats of formation are l-butene, -0.30 kJ

2-methylpropene,-17.3 U mol-r (-4.14 kcal mol-r).
(b) Which butene isomer in part (a) is more stable?
4.14
(a)
mol-t (*0.07 kcal mol*l);
If
the standard enthalpy change for the reaction 2-ethyl- I -butene

I -hexene is + I 5.3
kJ mol-r (+3.66 kcal mol-t). and if Afli for l-hexere is -40.5 kJ mol-r (-9.68 kcal
o)frff;?'#Tll1,^f*ilii-,"fJl;,,li[1"
4.15 The
AI{
of CO, is -393.51 kJ mol-l (-94.05 kcal mol-r), and the AH} of HrO is
kJ
mol-r (-57.80 kcal mol-t). Calculate the Anf of l-heptene from its heat of
-241.83
combustion, -4385.1kJmol-r (-1048.1 kcalmol-1). (SeeFurtherExploration4.l.)
144
CHAPTER
4.
B. Relative Stabilities of nlkene lsomers

The heats of formation of alkenes can be used to determine how various structural features of
alkenes affect their stabilities. We'l1 answer two questions using heats of formation. First,
which is more stable: a cis alkene or its trans isomer? Second, how does the number of alkyl
substituents at the double bond affect the stability of an alkene?
Study Problem 4.8 showed that trans-2-butene has a lower enthalpy of formation than cis2-butene by 4.2k1 mol-r 1l .0 kcal mol-l) (see Eq. 4.1lc). In fact, almost all trans alkenes are
more stable than their cis isomers. The reason is that, in a cis-alkene, the larger groups are
forced to occupy the same plane on the same side of the double bond. For example, a spacefilling model of cis-2-butene (Fig. 4.9) shows that one hydrogen in each of the cis methyl
groups is within a van der Waals radius of the other. Hence, van der Waals repulsions occur
between the methyl groups much like those in gauche-butane (Fig.2.6, p. 55). In contrast, no
such repulsions occur in the trans isomer, in which the methyl groups are far apart. Not only
do the heats of formation suggest the presence of van der Waals repulsions in cis alkenes, but
they give us quantitative information on the magnitude of such repulsions.
Another structural aspect of alkenes that has a considerable effect on stability is the number
of alkyl groups directly attached to the carbons of the double bond. For example, let's compare
the heats of formation of the following two isomers. The first has a single alkyl group directly
attached to the double bond. The second has two alkyl groups attached to the double bond.
H:C-CH-CH({-H1)
r)ne
'
AH
- -27.4 kJ mol
(4.12a)
-6.55 kcal mol-r
alkl'l substituent
at the rlotrlrle bontl
("Hl
I
H:C-C-CHr(,Hl
AH?
tu,o alkl'l sutrstitucnts

at the rlor-rble hotrcl
- -3s.1 kJ mol-r
(4. r2b)
-8.39 kcal mol-l
Because the isomer with the branch at a carbon of the double bond has the more negative heat
of formation, it is more stable. The data in Table 4.1 for other isomeric pairs of alkenes show
virn
c1r-r
\\naals replllsirlns
(a) cis-Z-butene
(b) trans-2-butene
FiSure 4.9 Space-filling models of (a) crs-2-butene and (b) rrans-2-butene. Cis-2-butene has van derWaals repulsions between hydrogen atoms of the two methyl groups (red). In trdns-2-butene, these van der Waals repulsions
are not oresent.
4.5 RELATIVESTABILITIESOFALKENEISOMERS 145
Eileffi or Erancnrng on Ar*ene stabitty

Number of alkyl groups
on the double bond
Alkene structure*
HrC-CH-CH2CH2CH2CH3
H:C
AH;
kJ mol-]
-9.68 kcal mol-1
-40.5
a\
cH2cH3
-55.8
cH2cH3
/\
cH3cl-tz
CH2CH3
kJ mol-1
.4 kcal
mol-l
kJ mol-t
-14.4 kcal mol-1
-60.1
CH(CH:)z
\/C:C
/\
H
mol-l
mol-l
-61.5 kJ mol-l
-14.7 kcal mol-l
H.C
-\ /H
C:C
/\
H
kJ
13.3 kcal
-5.70
H?C
-\ /CH.
C:C
,cH,
-62.7
kJ
mol-l
-2.6 kJ mol-l
-0.6 kcal mol-r
- 15.0 kcal mol-1
CHr
-\/'
\/C:C
/\
H
H:C
-\\/ /CH,
C:C
/\
cH3cH2
H?C
mol-]
-51.1 kJ mol-1
-12.2 kcal mol-1
cH2cH2cH3
H,C:C
10.6 kJ
-2.5 kcal mol-r
C:C
Enthalpy
difference
CH.
-88.4 kJ mol-1
-21.1 kcal mol-]
CH(CHr)z
-90.5 kJ mol-r
-21.6 kcal mol-1
CHr
*ln each comparison, the
wo compounds
-2.1 kJ mol-r
-0.5 kcal mol-l
are equally branched; they differ only in whether the branch is at the double bond.
that this trend continues for increasing numbers of alkyl groups directly attached to the double bond. These data show that an alkene is stabilized by allql substituents on the double
bond. When we compare the stability of alkene isomers, we find that the all<cne with the greatest number of allq,l substituents on the double bond is usually the most stable one.
To a useful approximation, it is the number of alkyl groups on the double bond more than
their identities that governs the stability of an alkene. In other words, a molecule with two
smaller alkyl groups on the double bond is more stable than its isomer with one larger group
on the double bond. The first two entries in Table 4.1 demonstrate this point. The second entry,
(E)-2-hexene, with a methyl and a propyl group on the double bond, is more stable than the
first entry, l-hexene, which has a single butyl group on the double bond.
Why does alkyl substitution at the double bond enhance the stability of alkenes? Essentially, when we compare an alkene that has an atkyl substituent at the double bond with one
that has an alkyl substituent elsewhere, we are really comparing the tradeoff of an spz-sp3 carbon--carbon bond and an sp3-1s carbon-hydrogen bond with an sp3-sp3 carbon-carbon bond
and an sp2-ls carbon-hydrogen bond.
146
CHAPTER
4 o INTRODUCTION
-?r--?l carrbon-carbon brond
-.?n,
Hrc/c\c
/'H
HJC
-
CH-,
-,?-t- 1 s carbon-hrnclro ge-n
b..cl
sP3-.-t7-l
---.l4)-I
(\C _acH-cH:
carbon-carrbon bond
spr-ls cartrclrt-hl'clrogen bond
--fHCH3
H
r^Tu'::;:T:
r^at an sp2-sp3carbon--carbon bond is sffonger than an

The major
"u""r
bond. (The bonds to hydrogen have similar but smaller effects.) Intpt-tpt carbon-carbon
creasing bond strength lowers the heat of formation.
We can go on to ask why an spz-sp3 carbon--carbon bond is stronger than an tpt-tpt
carbon-carbon bond. Bond strength is directly related to the energy of the electrons in the
bond. The lower the energy of the bonding electrons, the stronger is the bond. Because s electrons have lower energy than p electrons, a bond with more s character involves electrons of
lower energy than one with less s character. A bond with more s character, such as an spz-sp3
bond, is therefore stronger than one with less s character, such as an sp3-sp3 bond. Bond
strength increases with the fraction of s character in the component hybrid orbitals.
Heats of formation have given us considerable information about how alkene stabilities
vary with structure. To summarize:
Increasing stability:
RRR
\\\/
R-CH-CH) < R-CH-CH-R = C-CH,
RRR
(4.13a)
/4//\
RRRH
\/\/
C:C
/\/\
HHHR
and
a*;u
@=i.ru
(a)
(4. 13b)
*u the conpounds in oderof
incre#;
stabitltyi
CHr
HrC
4.17
Alkenes can un&rgo the addition of

study this reaction in Sec.4.9A.)
gl
prH
tydrognin
the pqerqnce of certain caralysts. (You
gt
,pa
+ H2
' 'R4
catarYst-
Rr#R-
gz
will
4.7 ADDITION OF HYDROGEN
HALIDES TO
ALKENES 147
ADDITION REAGTIONS OF ATKENES
4.6
The remainder of this chapter considers three reactions of alkenes: the reaction with hydrogen
halides; the reaction with hydrogen, called catalytic hydrogenation; and the reaction with
water, called hydration. These reactions will be used to establish some important principles of
chemical reactivity that are very useful in organic chemistry. We'l1 study other alkene reactions in Chapter 5.
The most characteristic type of alkene reaction is addition at the carbon-carbon double
bond. The addition reaction can be represented generally as follows:
bonds broken
/\
\_/_t
\
C=C + X-Y
unna,
fur-".l )
In an addition reaction, the carbon-rcarbon n'bond of the alkene and the

reagent are broken, and new C-X and C-Y bonds are formed.
4,7.
...1...
(4.r4)
-C-C/l lr
/ X Y\
--+
X-Y
bond of the
ADDITION OF HYDROGEN HATIDES TO ALKENES

H-cl,
H-I
The hydrogen halides H-F,

H-Br, and
undergo addition to carbon-+arbon
double bonds to give products called allqtl halides, compounds in which a halogen is bound to
a saturated carbon atom:
CH3CH-CHCH3 + H-Br
2-butene
(Z or
E)
-->
cH3cH-cHCH3
(4.15)
HBr
2-bromobutane
(an alkyl halide)
Although the addition of HF has been used for making alkyl fluorides, HF is extremely hazardous and is avoided whenever possible. Additions of tIBr and HI are generally preferred to
addition of HCI because additions of HBr and HI are faster.
148
CHAPTER
4.
R. negioselectivity of Hydrogen Halide Addition

When the alkene has an unsymmetrically located double bond, two constitutionally isomeric
products are possible.
HzC-CH(CHr):CH: + HI
H:C-CH(CHz):CH:
OT
l -hexene
cHz-cHr(cHz):cH_r (4. 16)
t-
2-iodohexane
(observed)
1-iodohexane
(not obrserved)
As shown in Eq. 4. 16, onf) one of the two possible products is formed from a I -alkene in significant amount. Generally, the mnin product is that isomer in which the halogen is bonded to
the carbon of the double bond with the greater number of allql substituents, and the hydrogen
is bonded to the carbon with the smaller number of allql substituents.
HzC-CH(CH:)",CH:
H goes
/\
/\
here
I goes here
(Another way to think about this result is to apply the old aphorism, "Them that has, gets."
That is, the carbon with more hydrogens gains yet another hydrogen in the reaction.) When the
products of a reaction could consist of more than one constitutional isomer, and when one of
the possible isomers is formed in excess over the other, the reaction is said to be a regioselec'
tive reaction. Hydrogen halide addition to alkenes is a highly regioselective reaction because
addition of the hydrogen halide across the double bond gives only one of the two possible constitutionally isomeric addition products.
When the two carbons of the alkene double bond have equal numbers of alkyl substituents,
little or no regioselectivity is observed in hydrogen halide addition, even ifthe alkyl groups are
of different size.
strt'tller olktl
HBr
group
larger alkyl group
tl
CH.ICH:CHCH2CHT
2-pentene
-----> CHrCH-CHCH2CH3 + CHrCH-CHCH2CHT @'17)

HBr
BrH
2-bromopentane
3-bromoPentane
(nearly equal amounts)
Markovnikov's Rule
ln his doctoral dissertation of 1869, the Russian chemist Vladimir Markovnikov (1838-1904; also
spelled Markownikoff) proposed a'rule"for regioselective addition of hydrogen halides to alkenes.
This rule, which has since become known as Markovnlkov's rule, was originally stated as follows:
"The halogen of a hydrogen halide attaches itself to the carbon of the alkene bearing the lesser
number of hydrogens and greater number of carbons."
Markovnikov's higher education was in political science, economics, and law. During required organic chemistry courses in the Finance curriculum at the University of Kazan, he became infatuated
with organic chemistry and eventually completed his now-famous doctoral dissertation. He was ap
pointed to thechair of chemistry at the University of Moscow in 1873, where he was known not only
for his chemistry but also for his openness to students. He was forced to resign this position in '1893
because he would not sign an apology demanded of the faculty by a political official who had been
insulted by a student. He was allowed, however, to continue working in the university for the duration of his life.
HALIDES TO
ALKENES 149
@4.l9Usingtheknownregioselectivityofhydrogenhalideadditiontoalkenes'predicttheaddition
product that results from the reaction of:
(a) H-Cl with 2-methylpropene (b) H-Br with l-methylcyclohexene
B. Carbocation tntermediates in Hydrogen Halide Addition

For many years the regioselectivity of hydrogen halide addition had only an empirical
(experimental) basis. By exploring the underlying reasons for this regioselectivity, we'l| set
the stage to develop a broader understanding of not only this reaction but many others as well.
A modern understanding of the regioselectivity of hydrogen halide addition begins with the
fact that the overall reaction actually occurs in two successive steps. Let's consider each of
these in turn.
In the first step, the electron pair in the zrbond of an alkene is donated to the proton ofthe hydrogen halide. The elecffons ofthe z'bond react rather than the electrons of obonds because rr
electrons have the highest energy (Sec. 4.1A). As a result, the carbon-carbon double bondis pro-
tonated on a carbon atom. The other carbon becomes positively charged and electron-deficient:
nn
r-1fr-tl
r/
t-ictrr-iunt tartrolr
r/r'r--/ r'1rp/r i/r:
<+
RT,H-CHR
(4. 18a)
a carDocatlon
The species with a positively charged, electron-deficient carbon is called a carbocation, pronounced CAR-bo-CAT-ion. (The term carbonium ion was used in earlier literature.) The formation of the carbocation from the alkene is an electron-pair displacement reactiorz (Sec.
3.2A) in which the z bond acts as a BrQnsted base (Sec.3.4A) toward the Brqnsted acid
H-Br. The z' bond is a very weak base. Nevertheless, it can be protonated to a small extent
by a strong acid such as HBr.
The resulting carbocation is a powerful electron-deficient Lewis acid and is thus a potent
electrophile. In the second step of hydrogen halide addition, the halide ion, which is a Lewis
base, or nucleophile, reacts with the carbocation at its electron-deficient carbon atom:
0 tluL-l('()phile
/'':nt't-
{"
I
RCH-CH'R ---+
Br:
I
I
RCH-CH2R
(4.18b)
This is a Lewis acid-base association reaction (Sec. 3. 1B).

The carbocations involved in hydrogen halide addition to alkenes are examples of reactive
intermediates or unstable intermediates: species that react so rapidly that they never accumulate in more than very low concentration. Most carbocations are too reactive to be isolated
except under special circumstances. Thus, carbocations cannot be isolated from the reactions
of hydrogen halides and alkenes because they react very quickly with halide ions.
The complete description of a reaction pathway, including any reactive intermediates such
as carbocations, is called the mechanism of the reaction. To summarize the two steps in the
mechanism of hydrogen halide addition to alkenes:
1. A carbon ofthe z'bond is protonated.
2. A halide ion reacts with the resultins carhocation.
150
CHAPTER
4.
Now that we understand the mechanism of hydrogen halide addition to alkenes, let's see
how the mechanism addresses the question of regioselectivity. When the double bond of an
alkene is not located symmetrically within the molecule, protonation of the double bond can
occur in two distinguishable ways to give two different carbocations. For example, protonation of 2-methylpropene can give either the tert-bvtyl cation (Eq. 4.19a) or the isobutyl cation
(Eq.4.19b):
.n
:Br:F{1
")
CHr /
,?n-G;,
..
CH.f
\-l
f=CHz
2-methYlProPene
\s4^,
/
CHr
CHE
)r
il
cH. H
\;/
C-CHI
/
"l
l*
HrC-C-CHz
CHr
(4.re)
CHr
tert-batyl cation
isobutyl cation
(not formed)
(a)
(b)
These two reactions are in competition-that is, one can only happen at the expense of the
other because the two reactions compete for the same starting material. Only the tert-bntyl
cation is formed in this reaction. The tert-buityl cation is formed exclusively because reaction 4.19a is much faster than reaction 4. 19b. Because the tert-butyl cation is the only carbocation formed, it is the only carbocation available to react with the bromide ion. Hence,
the only product of HBr addition to 2-methylpropene is rert-butyl bromide.
YY
/A
r-13\
\+
7:Br:o.
,1.
C-CH: +
/l
Hrc
:B;:
I
HrC-C-CH:
(4.20)
cHr
rert-butyl bromide
Notice that the bromide ion has become attached to the carbon of 2-methylpropene bearing the
greater number of alkyl groups. In other words, the regioselectivity of hydrogen halide addition is due to the formation of only one of two possible carbocations.
To understand why the tert-butyl cation is formed more rapidly than the isobutyl cation in
HBr addition, we need to understand the factors that influence reaction rate. The relative stability of carbocations plays an important role in understanding the rate of HBr addition. A discussion of carbocation stability, then, is an essential prelude to a more general discussion of
reaction rates.
HALIDES TO
ALKENES 151
C. Structure and Stability of Carbocations

Carbocations are classified by the degree of alkyl substitution at their electron-deficient car-
bon atoms.
++
R-CH:
Drlmarv
L1
C-R
R-CH-R
secondary
(4.2r)
tertlary
That is, primary carbocations have one alkyl group bound to the electron-deficient carbon,
secondary carbocations have two, and tertiary carbocations have three. For example, the
isobutyl cation in Eq. 4.I9b is a primary carbocation, and the tert-butyl cation in Eq. 4.19a is
a
tertiary carbocation.
The gas-phase heats of formation of the isomeric butyl carbocations are given inTable 4.2.
The data in this table show that allql substituents at the electron-deficient carbon strongly stabilize carbocations. (A comparison of the first two entries shows that substituents at other carbons have a much smaller effect on stability.) The relative stability of isomeric carbocations is
therefore as follows.
Stability of carboc ations
tertiary
secondary
primary
(4.22)
Remember that "greater stability" means "lower energy."

To understand the reasons for this stability order, consider first the geometry and electronic
structure of carbocations, shown in Fig. 4.10 (p. 152) for the tert-butyl cation. The electrondeficient carbon ofthe carbocation has trigonal planar geometry (Sec. 1.3B) and is therefore
sp2-hybridized, like the carbons involved in double bonds (Sec. 4.1A); however, in a carbocation, the 2p orbital on the electron-deficient carbon contains no electrons.
The explanation for the stabilization of carbocations by alkyl substituents is in part the
same as the explanation for the stabilization of alkenes by alkyl substitution (Sec. 4.5B)-the
greater number of sp2-sp3 carbon-carbon bonds in a carbocation with a greater number of
alkyl substituents. However, if you compare the data in Tables a.r @. La5i) and 4.2, you'll notice that each alkyl branch stabilizes an alkene by about 7 kJ mol-r , but each branch stabilizes
a carbocation by nearly 70 kJ mol-r. In other words, the stabilization of carbocations by alkvl
substituents is considerably greater than the stabilization of alkenes.
Heats of Formation of the lsomeric Butyt Cations (Gas phase, 25 "c)

Heat of formation
Cation structure
f
cH3cH2_c:HrcH'
+
(cH3)2cHC
H2
Name
kJ
mol-r
kcal mol-1
Relative energy*
kJ
mol-t
kcal
mol-l
butyl cation
845
202
155
37
isobutyl cation
828
98
138
33
sec-butyl cation
757
181
67
16
fert-butyl cation
69c-
16s
(0)
(0)
cH3c HCH2CH3
+
(cH3)3c
*Energy difference between each carbocation

and the more stable tert-butyl cation
152
CHAPTER
4.
unoccupied 2p orbital
_-----\r_
3\
H:C
20'
/I
CHI-/
g3-sp2 carbon-carbon o bond
Figure 4.10 Hybridization and geometry of the terf-butyl cation. Notice the trigonal planar geometry and the
unoccupied 2p orbital perpendicular to the plane of the three carbons.The C-C bond length, determined in
1995 by X-ray crystallography, is less than the sp2-sp3 C-C bond length in propene because of
hyperconjugation, which is discussed below.
An additional factor that accounts for the stabilization of carbocations by alkyl branching
is a phenomenon called hyperconjugation, which is the overlap of bonding electrons from
the adjacent cr bonds with the unoccupie d 2p orbital of the carbocation.
.rtr.rrl.rp { ltyprrrtoni
r-tgat
ion
unoccupied 2p orbital
carbon-hydrogen 0 bond
CH:
In this diagram, the obond that provides the bonding electrons is a C-H bond. The energetic
advantage of hyperconjugation is that it involves additional bonding. That is, the electrons in
the C-H bonds participate in bonding not only with the C and H, but also with the electrondeficient carbon. Additional bonding is a stabilizing effect. We can show this additional bonding with resonance structures as follows:
H
Y-\
r-'f.
U-U
11
b<il
+/
\
H/l
H -C<H
-H
H/
Further Exploration 4.3
Molecular Orbital
Description of
Hyperconjugation
--,
g+(
{--*
!.-H
C:C
(1.23)
\
H1
H
r'a
H',
\H
-.c-H
The shared electrons are shown in color. (Note that the proton in the right-hand structure hasn't
moved; it's still part of the molecule.) The double-bond character suggested by the resonance
structure on the right is reflected in the lengths of the carbon-<arbon bonds in the rerl-butyl
cation. These bonds are considerably shorter (t.++Z L) than the carbon--carbon single bond in
propene (t.SOt A).
We can draw analogous resonance strucfures for a C-H bond in each methyl group. In
other words, each alkyl branch provides additional hyperconjugation and thus more stabilization. Consequently, alkyl substitution at the electron-deficient carbon stabilizes carbocations.
Let's now bring together what you've learned about carbocation stability and the mechanism ofhydrogen halide addition to alkenes. The addition occurs in two steps. In the first step,
protonation of the alkene double bond occurs at the carbon with the fewer allcyl substituents
HALIDES TO
ALKENES 153
so that the more stable carbocation is formed-thatis, the one with the greater number of allqt
substituents at the electron-deficient carbon.The reaction is completed when the halide ion reacts with the electron-deficient carbon.
An understanding of many organic reactions hinges on an understanding of the reactive intermediates involved. Carbocations are important reactive intermediates that occur not only in
the mechanism of hydrogen halide addition, but in the mechanisms of many other reactions as
well. Hence, your knowledge of carbocations will be put to use often.
George Olah, a Holiday party, and a Nobel prize

Eecause carbocations are in most cases reactive intermediates that are too unstable to isolate,
they
remained hypothetical for many years after their existence was first postulated. However, their importance as reactive intermediates led to repeated, unsuccessful efforts to prepare them. In
1966-67,a team ofresearchers led by ProfessorGeorge A.Olah (b.1912),then at CaseWestern Reserve Universiryfigured out how to prepare'a number of pure carbocation salts in solution and
studied their properties. For example, they formed a solution of essentially pure telt-butyl cation by
protonation of2-methylpropene at -80 "C. As the acid,they used HF in the presence ofthe powerful Lewis acid SbFr, which actually forms the yery strong acid H+ -SbFu.
(cH3)2c
cHz + H+ SbF6
(CH3)3C+
(solve'nt)
2-methylpropene
-SbF6
ferf-butyl cation
hexafl uoroa nti monate
The fluoride ion is so
wards the ferf-butyl
tightly held within the -SbFu complex ion that it can't act
cation.
as a
sa
@.24)
lt
nucleophile to-
The discovery of this method by Olah's group was somewhat serendipitous.In 1966, his group had
only recently discovered HSbF" which they called "magic acidl Following a holiday party, they put a
piece of a holiday candle into magic acid. When they saw that it dissolved, they examined the solution in a nuclear magnetic resonance (NMR) instrument. (You'll learn about NMR as a method for determining structure in Chapter 13.)They saw unmistakable evidence for carbocations.This was the
beginning of a very productive series of investigations in which a numberof carbocations were generated and examined structurally. Subsequently, Olah joined the facuhy df the University of Southern California. He received the 1994 Nobel Prize in Chemistry for his work in carbocation chemistry.
4.20 By writing
the curved-arrow mechanism of the reaction, predict the product of the reaction
of
HBr with 2-methyl- I -pentene.
Give the structure of an alkene that would give 2-bromopentane as the major (or sole) product of
HBr addition. (The numbers are for reference in the solution.)
an
alkene
+ HBr
-1
ll
-------> CH3CH2CH2CHCH:
I
Br
2-bromopentane
H-Br
SOlUtion The bromine of the product comes from the

However, there are many hydrogens in the product! Which ones were there to start with, and which one'came from the H-Br?
154
CHAPTER
4 o INTRODUCTION
First, recognize that the carbon bearing the bromine must have originally been one carbon of the
double bond. It then follows that the other carbon of the double bond must be an adjacent carbon
(because two carbons involved in the same double bond must be adjacent). Use this fact to constract all possible alkenes th^t mightbe starting materials. Do this by "thinking backward": Remove the bromine and a hydrogen from each adjacent carbon in tum.
Remove Br from carbon-2 and H from
carbon-3
CH3CH2CH:CHCHI
2-pentene (cis or trans)
Remove Br from carbon-2 and H from
carbon-l tr> CH3CH2CH2CH:CH2

1-pentene
(The symbol c) means "implies as starting material.") Which of these is correct? Or are they
both correct? You haven't flnished the problem until you've mentally carried out the addition of
lfrlr to each compound. Doing this and applying the known regioselectivity of HBr addition leads
to the conclusion that the desired alkyl halide could be prepared as the major product from l-pentene. However, both carbons of the double bond of 2-pentene bear the same number of alkyl
groups. Eq.4.l7 (p. la8) indicates that from this starting material we should expect not only the
desired product, but also a second product:
CH3CH2CH-CHCHT
HBr
------* cH3cH2cH2cHCH: +
rl
Br
2-pentene
2-bromopentane
CH3CH2CHCHzCH:
Br
3-bromopentane
Furthermore, the two products should be formed in nearly equal amounts. This means the yield of
. the desired compound would be relatively low and it would be difficult to separatb from its isomer, which has almost the same boiling point. Consequently, 1-pentene is the only alkene that will
give the desired alkyl halide as the major product (that is, the one formed almost exclusively).
In solving this type of problem, it isn't enough to identify potential starting materials. You
must also determine whether they really will work, given the known characteristics-in this case,
the regioselectivity----of the reaction.
[email protected]||^eachcase,givetwodifferenta|kenestartingmaterialsthatwouldreactwithH_Brtogive
the compound shown as the major (or only) addition product.
rn) ?", ?", (b)

Hrc-? cH-cH,
Br
.cHr
ot'
D. Carbocation Rearrangement in Hydro8en Halide Addition

In some cases, the addition of a hydrogen halide to an alkene gives an unusual product,
the following example.
as
in
CHt
HALIDES TO
CHr
H:C-q-CH:CHz + HCI ---->

I
CH-
55
CHr
t"
t"
H:C-9 CH-CH: + HrC-C
rlll
cH: cl
CI
(I7o/o of
ALKENES
product)
(83o/o
CH-CH:
(4.2s)
CH:
of product)
The minor product is the result of ordinary regioselective addition of HCI across the double
bond. The origin of the major product, however, is not obvious. Examination of the carbon
skeleton of the major product shows that a rearrangement has occurred. In a rearrangement,
a group from the starting material has moved to a different position in the product. In this case,
a methyl group of the alkene (red) has changed positions. As a result, the carbons of the alkyl
halide product are connected differently from the carbons of the alkene starting material. Although the rearrangement leading to the second product may seem strange at first sight, it is
readily understood by considering the fate of the carbocation intermediate in the reaction.
The reaction begins like a normal addition of HCI-that is, by protonation of the double
bond to yield the carbocation with the greater number of alkyl substituents at the electrondeficient carbon.
9H,
H,c-E-cH5cDH4l, __>
l"
CH:
CH.-*
H:C_C_CH_CH:
(4.26)
CHr
Reaction of this carbocation with Cl- occurs, as expected, to ybtd ttre minorproduct of Eq.4.25.
However, the carbocation can also undergo a second type of reaction: it can rearange.
CH.-*
|
H:c-?-tH-cH:
-+
I-
f"'
HrC-9-CH-CH:
(4.27 a)
CH:
CH.,
In this reaction, the methyl group moves with its pair of bonding electrons from the cnbon adjacent to the electron-deficient carbon. The carbon from which this group departs, as a result,
becomes electron-deficient and positively charged. That is, the rearrangement converts one
carbocation into another. This is essentially a Lewis acid-base reaction in which the electrondeficient carbon is the Lewis acid and the migrating group with its bonding electron pair is the
Lewis base. The reaction forms a new Lewis acid-the electron-deficient carbon of the rearranged carbocation.
The major product of Eq. 4.25 is formed by the Lewis acid-base association reaction of
Cl- with the new
carbocation.
CH.
1..
HrC-C-CH(CH:)z
- +J
CH.
+ iCl:-
-+
HrC-C-CH(CH:)z
(4.27b)
'9J,
Why does reilrangement of the carbocation occur? In the case of reaction 4.27a, a more
stable tertiary carbocation is formed from a less stable secondary one. Therefore, reerrengement is favored by the increased stabiliry of the rearranged ion.
156
CHAPTER
4.
CH,
CH.
H:C-C-CH-CH2 + HCI r
HEC-9-CH-CH:
Cl-
(a secon dury
carbocation)
CH:
CH-,
rearrangement
CH.
(a
tertiary
carbocation)
co
mpeti
tr
g pratl-rrvl\rs
cl-
CHr
I reaction
cl
cHi
tll
(4.28)
CH-CHr
rl
cH: cl
minor product
cl-
I
CH^
t-
HrC-9
cH-.
with
w.ith
CH.
t"l
HrC-g C,
reac-tior-t
----------------
ll
H3C-6-C-CH3
major product
You've now learned two pathways by which carbocations can react. They can (l) react with
a nucleophile and (2) rearrange to more stable carbocations. The outcome of Eq. 4.25 represents a competition between these two pathways. In any particular case, one cannot predict exactly how much of each different product will be obtained. Nevertheless, the reactions of carbocation intermediates show why both products are reasonable.
Carbocation rearrangements are not limited to the migrations of alkyl groups. In the following reaction, the major product is also derived from the rearrangement of a carbocation intermediate. This rearrangement involves a hydride shifl the migration of a hydrogen with its
two bonding electrons.
CH.
CHr
H:C-f-CH:CHz + HBr +
I
CH.
l"
H:C-CH-CH-CHr + H,C-C-CHzCHr
l""l
Br
Br
(about 45o/o of product)
(4.29)
(about 55o/o of product)
The hydride migrates instead of an alkyl group because the rearranged carbocation is tertiary
and thus is more stable than the starting carbocation. Migration of an alkyl group would have
given another secondary carbocation.
Keep in mind the following points about the rearrangement of carbocation intermediates,
all of which are illustrated by the examples in this section.
l.
A rearrangement almost always occrus when
a more stable carbocation can result.

Arearrangement that would give a less stable carbocation generally doesn't occur.
3. The group that migrates in a carbocation rearrangement comes from a carbon directly
attached to the electron-deficient, positively charged carbon of the carbocation.
2.
4.8
REACTION
RATES 157
4. The group that migrates in a rearrangement is typically an alkyl group, aryl group
(p. 82), or
hydrogen.
5. When there is a choice between the migration of
an alkyl group (or aryl group) or a hy-
drogen from a particular carbon, hydride migration typically occurs because it gives the
more stable carbocation.
The First Description of carbocation Rearrangements

The first clearformulation of the involvement of carbocations in molecular rearrangements was pro-
posed by Frank
C.
Whitmore
887-1947) of Pennsylvania State University. (ln fact, such rearrange-
ments were once called "Whitmore shifts.") Whitmore said that carbocation reanangementg,rlesult
when "an atom in an electron-hungry condition seeks its missing electron pair from the next atom
in the molecule."Whitmore's description emphasizes the Lewis acid-base character of the reaction.
Carbocation rearrangements are not just a laboratory curiosity;they occur extensively in living organisms, particularly
in the biological pathways leading to certain cyclic compounds such
as
steroids.
4.22 Whtch
of the following carbocations is likely to rearrange?
If rearrangement occurs, give the
structure of the rearranged carbocation.
.,-<
I
l:t"'
{a)
| |
CH3CH-C-CH3
(b)
(c)
CH3 CH3
r
\./+
4.23
CH.
|
cH3CHcH?C-cH3
f
[",
Draw the curved-arrow mechanism for the reaction in Eq. 4,29 thataccounts for the forma-
tion ofboth products.
4.24
Only one of the following three alkyl halides can be prepared as the nwjorproductof the addition of HBr to an alkene. Which compound can be prepared in this way? Explain why the
other two cannotbeprepared in this way.
Br
I
CH3CH2CH2CH2CH2BT CH3CHCH2CHzCHT
1'
?''
HiC-CH-9-CzHs
CH:
C
4.8
REACTION RATES
Whenever a reaction can give more than one possible product, two or more reactions are in
competition. (You've already seen examples of competing reactions in hydrogen halide addition to alkenes.) One reaction predominates when it occurs more rapidly than other competing
reactions. Understanding why some reactions occur in preference to others, then, is often a
matter of understanding the rates of chemical reactions. The theoretical framework for discussing reaction rates is the subject ofthis section. Although we'll use hydrogen halide addition to alkenes as our example to develop the theory, the general concepts will be used
throushout this text.
158
CHAPTER
4'
A. The Transitlon state

The rate of a chemical reaction can be defined for our purposes as the number of reactant molecules converted into product in a given time. The theory of reaction rates used by many organic chemists postulates that as the reactants change into products, they pass through an unstable state of maximum free energy, called the transition state. The transition state has a
higher energy than either the reactants or products and therefore represents an energy barrier
to their interconversion. This energy barrier is shown graphically in a reaction free-energy
diagram (Fig. a.1 1). This is a diagram of the standard free energy of a reacting system as old
bonds break and new ones form along the reaction pathway. In this diagram the progress ofreactants to products is called the reaction coordinate. That is, the reactants define one end of
the reaction coordinate, the products define the other, and the transition state is at the energy
maximum somewhere in between. The energy barrier AG"+, called the standard free energy
of activation, is equal to the difference between the standard free energies of the transition
state and the reactants. (The double daggeq *, is the symbol used for transition states.) The
size of the energy barrier AG'{ determines the rate of a reaction: the higher the barrier the
smaller the rate.Thus, the reaction shown in Fig. 4.1la is slower than the one in Fig. 4.1 lb because it has a larger energy barrier. In the same sense that relative free energies of reactants
and products determine the equilibrium constant, the relative free energies of the transition
state and the reactants determine the reaction rate.
Notice from Fig. 4.ll that a reaction and its reverse have the same transition state. An
analogy is that if a certain mountain pass is the shortest way to get from one town to another,
then the same mountain pass is the shortest way to make the reverse journey.
If the transition state is of central importance in determining the reaction rate, it would be
nice to have a way of estimating its energy. Because it lies at an energy maximum, a transition
state can't be isolated. However, the energy of a transition state, like the energy of any ordinary molecule, depends on its structure. So, the question is: What does the transition state look
transition state
*'r
t
transition state
+
A G" t
*+
standard free
energy of
t
A
activation
(energy barrier)
GO
I
reactants
standard free
.t"
't'
energy
of
activation
(energy barrier)
reactants
products
reaction coordinate
(a) larger energy barrier, slower reaction
products
reaction coordinate
(b) smaller energy barrier, faster reaction
Figure4.11 Reactionfree-energydiagramsfortwohypotheticalreactions.Thestandardfreeenergyofactivation (AG'+), shown for the forward reaction, is the energy barrier that must be overcome for the reaction to occur.
The reaction in part (a) is intrinsically slower because it has a larger AG'+ than the one in part (b).
4,8
REACTION
RATES 159
like? The power of transition-state theory is that we can visualize the transition state as a
structure. To illustrate, consider the following Brgnsted acid-base reaction.
(CH:)
zC:CHz + H-B;:
<+
(CH:) rt-,CHz
(4.30)
H
You should recognize this as the first step in the addition of HBr to an alkene; see Eq. 4.18a,
p. l49.In the transition state of this reaction, the H-Br bond and the carbon--carbon z'bond
are partially broken, the new C-H bond is partially formed, and the new charges are only
partially established. We can represent this situation using dashed lines for partial bonds and
using 6* and 6- for partial charges, as follows:
r6+
l(CHr)rC-CH,
l'.
Ir
l\
lH
lr
(4.3 1)
t\
t\
|
,d-
:Br:
..
L-
This shows the bonds breaking and forming. If we view this as an event frozen in time, we're
looking at the structure ofthe transition state.
i'ir
tlnninaiogylortheTran$.itiolt stetg ,:., '',r,, ,11:'' r'; 'ti' :'..:: ""lr'r:'l

rSuppose you aJi ro rodt orora high dMng botrd at thelocal pool.vou Flve Oil"o#,.1i
your picture at the height of your jump with a very fast shutter.You can think of that pkture as the
transition state for your dive. lt's the "in-between" stat that defines the polnt of highest potential
energy between )rour starting point on the dMng board and your finish, when your've come to rest
in the water.You're never at the transition state for rnore than an instant, but we dont harre any problem conceptualizing how you would appear at that instant Now imagine rcpeating your dirre an
Avogadro's number of times (you never get tired) and having a picture taken of each dive at the
highest point. Now you average all those pictures. Because each dive is a little different, the "averaged" picture of the trangition state is a bit blurry.This averaged picture of your jump is more like
what we are dealing with when we talk about the transition state for a mole of moleculet but
chances are that the first picture you took is not far from the average. Sq we describe the transition
state wrth a single;tfuctge, ju$t as we
xttrail
d*tribe$urtirge
;n*itq+,and
curvea-rr**
Eqpqi$on*1g*e
reactions. Each reaction-occurs {$ a single step.
(a)CHaCHz-qi, + ;QCU3
----+
rtumber of
suiicM
CH3CH2-dCH3 +
d,-ives
with a single picture.
r"ruf;i
al'.'ilu *"
:i;;
+ (CH3)3d + :Ii;;
4.26 (a)p**,n" q-lttr"ff? *;" reversereactim of F4. 4.3O. Compare it with the transir'.t'' 1';;,r;
' tioil state shown i
lt,lr*o*siu"$**..',.l{
G)mitc""e.ar;hPtr",ltqpnvq;,ma a!p!,,,,,
"ft'
:r.eif?,:ar!3crio_3
O)
(CHr)rC-lii,
r':'r'
60
cHAprER
4 . rNTRoDUcroN To ALKENES.
STRUCTURE
AND REACTtvlry
B. The Energy Barrier

We've learned that the standard free energy of the transition state (relative to the standard free
energy of reactants and products) defines the free-energy banier AGo+ for the reaction. Let's
learn a little more about the relationship between the size of this energy barrier and rate.
The relationship between rate and standard free energy of activation is an exponential one.
rate d
g-ac"*,/47
= Ig:at'+'l.3Rr
(4.32)
(The sign d means "is proportional to.") The negative sign in the exponent means that large
values of AGo+-that is, large energy barriers-result in a smaller rate, as shown in Fig. 4. 1 1.
It follows that, if two reactions A and B have standard free energies of activation Aci{and AGfil
respectively, then, under standard conditions (all reactants I M concentration), the relative rates
of the two reactions are
rateA
rateB
1g(ac'd
.losllrareorll-\
-\rateu
- acil/
2.3Rr
AG;+- AGf
2.3RT
(4.33a)
(4.33b)
These equations show that the rates of two reactions differ by a factor of 10 (that is, one log
unit) for every increment of 2.3RT (5.7 kJ mol-1 or 1 .4 kcal mol-r at 298 K) difference in their
standard free energies of activation. A factor of 10 in rate is about the difference in rate between a reaction that takes an hour and one that takes a day. This means that reaction rates are
very sensitive to their standard free energies of activation.
j
Further Exploratio n 4.4
Activation Energy
You may have leamed about energy barriers if you studied reaction rates in general chemistry, and
there you may have referred to the energy barrier by the name activation energy and the abbreviation
Eu",.
activation energy is very close to the AIlo+ of the reaction (the standard enthalpy dffirence)
fr"
rather than the standard free-energy difference between the transition state and starting materials. It
is possible mathematically to relate transition-state theory to the theory of activation energy. (See
Further Exploration 4.4.) However, for our discussion, the difference between the two theories is not
conceptually important.
Where do molecules get enough energy to overcome the energy barrier? In general, molecules obtain this energy from thermal motions. The energy of a collection of molecules is
characterized by a distribution (Fig. 4.12a), which is termed a Maxwell-Boltzmann distribution. An analogy is the results of an exam by a distribution of grades (Fig. 4.12b). The rate
of a reaction is directly related to the fraction of molecules that has enough energy to cross the
energy barrier. This fraction is shown inFig. 4.12a as a hatched area. The smaller the banier,
the larger will be the hatched area and the greater will be the reaction rate. Analogously, the
fraction of students who receive an 'A" on an exam depends on the "cutof imposed by the
instructor; the lower is the "cutoff' grade, the more students receive an '4."
For a given reaction under a given set of conditions, we cannot control the size of the energy barrier; it is an intrinsic property of the reaction. Some reactions are intrinsically slow,
and others are intrinsically fast. However, we can sometimes control the fraction of molecules
with enough energy to cross the barrier. We can increase this fraction by raising the temperature. As shown in Fig. 4.12a, the Maxwell-Boltzmann distribution is skewed to higher energies at higher temperature, and, as a result, a greater fraction of molecules have the energy required to cross the barrier. In other words, reactions are faster at higher temperatures.
Different reactions respond differently to temperature, although a very rough rule of thumb is
that a reaction rate doubles for each l0 'C (or 10 K) increase in temperature.
4.8
;it
temperature
distrilrution
iow'er
energy
REACTION
RATES 151
cutoff for
(cA)'
barrier
grade
(a
o
a.)
d.J
(+r
rr
rn
l+,i
distribr"rtion at
higher
tempe
rilture
.F
,F
kinetic energy
exam grades
(a)
(b)
Fi$ure4.12
(a)
AMaxwell-Boltzmannkineticenergydistributionattwodifferenttemperatures.(Therightside
of the distributions extend indefinitely and are cut off in the figure.) This is a plot of the number of molecules as a
function of kinetic energy.The purple dashed line is the energy barrier.The fraction of molecules with enough energy to cross the barrier is given by the hatched areas. At higher temperature, the Maxwell-Boltzmann distribution is skewed to higher energy, and the fraction of molecules with enough energy to cross the barrier is greater
(red hatched area). (b) Results of an exam can also be characterized by a distribution, which is a plot of the number
of students as a function of exam grade.The'tutoff" (purple dashed /ine) defines the part of the distribution that
receives an "A"grade.The fraction of students receiving an'?" is equal to the hatched area under the curve.
Let's summarize. Two factors that govern the intrinsic reaction rate are
1. the size of the energy barrier, or standard free energy of activation AGo*: reactions with
2.
smaller AG"+ are faster.

the temperature: reactions are faster at higher temperatures.
An Analogy for Energy Barriers

An analogy that can help in visualizing these concepts is shown in Fig.4.1 3. Water in the cup would
flow into the pan below if it could somehow gain enough kinetic energy to surmount the wall of the
cup,The wall of the cup is a potential-energy barrier to the downhill flow of water. Likewise, molecules have to achieve a transient state of high energy-the transition state-to break stable chemical bonds and undergo reaction.An analogyto thermal motion is what happens if we shake the cup.
lf the cup is shallow (low energy barrier), the likelihood is good that the shaking will cause water to
slosh over the sides of the cup and drop into the pan.This will occur at some characteristic ratesome number of milliliters per second.lf the cup is very deep (high barrier),water is less llkelyto flow
from cup to pan. Consequently, the rate at which water collects in the pan is lower. Shaking the cup
more vigorously provides an analogy to the effect of increasing temperature. As the "sloshing" becomes more violent, the water acquires more kinetic energy, and water accumulates in the pan at
higher rate. Likewisg high temperature increases the rate of a chemical reaction by increasing the
energy of the reacting molecules.
162
CHAPTER
4 o INTRODUCTION
0.,,,{
height
Fltufe4.l3 Adifferenceofpotentialenergyisnotenoughtocausethewaterinthecuptodroptothebowl
below.The water must first overcome the barrier imposed by the walls of the cup.
It is very important to understand that the equilibrium constant for a reaction tells us
absolutely nothing about its rate. Some reactions with very large equilibrium constants are
slow. For example, the equilibrium constant for the combustion of alkanes is very large; yet
a container of gasoline (alkanes) can be handled in the open air because the reaction of gasoline with oxygen, in the absence of heat, is immeasurably slow. On the other hand, some unfavorable reactions come to equilibrium almost instantaneously. For example, the reaction of
ammonia with water to give ammonium hydroxide has a very unfavorable equilibrium constant; but the small extent ofreaction that does occur takes place very rapidly.
+ft
t"l
* r*rO fie" qgy activatim of ore reaction A is S0 U mt-t (21.5 kcal mol- r).
Tb cdtrd froe encrgy"fof activuim of another rcrctim B is 75 kJ mot-t (l7J kcal
ml-l).
(b)
Which region fu faser and by wh* frctor? Asnrme a tmpraftr of 298 K.

how mrad yor would narc to ircrcaee te tempemrc sf tbe slowcr nraction so
that it srould hd\rc r rate 6qud to tkof &o facEr rcactim-
It*-sF
4.28 The ftandffd ftrc wgr of actimtim of a reaction A is 90 kJ Eol-t (21.5 kcal mol-t) at
29E K" Rcmim B is onc millim timcs frster thm rcacion.{ at th sare tcmperanue. The
tro@cts 0f edi rcr4im src l0 kJ pot-t (2.+ kcal mol-r) more rtable tban the rqctaffs.
C)
ip
6, etuM
(b) Draw reaction

Go
fiee energy of actiration of reaction
f?
tsecmgy drya@ fq tre tc,o ractions *owing
tbe two rnlues of
Ad+
ccale.
.. (c),Whatis,n""*&iUg*g tf'*gA,t*ofthreverseregctionio#"df ':'
c. Multlstep
Reactlons and the Rate-timltlng step
Many chemical reactions take place with the formation of reactive intermediates. Such reactions are called multistep reactions. We use this terminology because, when intermediates
exist in a chemical reaction, then what we commonly express as one reaction is really a sequence of two or more reactions. For example, you've already learned that the addition of hydrogen halides to alkenes involves a carbocation intermediate. This means, for example, that
the addition of HBr to 2-methylpropene
4.8
(CH:)ZC:CH'
* HBr --+
REACTION
(CH3)rC-Br
RATES 163
(4.34)
is a multistep reaction involving the following two steps:
(CHr)'C:CH, * HBr
(4.35a)
(CHr)rC**Br-
(CH3)3C-Br
(4.35b)
Each step of a multistep reaction has its own characteristic rate and therefore its own transition state. The energy changes in such a reaction can also be depicted in a reaction free-energy
diagram. Such a diagram for the addition of HBr to 2-methylpropene is shown inFig. 4.14.
Each free-energy maximum between reactants and products represents a transition state, and
the minimum represents the carbocation intermediate.
Generally, the rate of a multistep reaction depends in detail on the rates of its various steps.
However, it often happens that one step of a multistep reaction is considerably slower than any
of the others. This slowest step in a multistep chemical reaction is called the rate-limiting step
or rate-determining step of the reaction. In such a case, the rate of the overall reaction is equal
to the rate of the rate-limiting step.In terms of the reaction free-energy diagram in Fig. 4.14,
the rate-limiting step is the step withthe transition state of highestfree energy. This diagram indicates that in the addition of HBr to 2-methylpropene, the rate-limiting step is the first step of
the reaction-the protonation of the alkene to give the carbocation. The overall rate of addition
of HBr to 2-methylpropene is equal simply to the rate of this first step.
The rate-limiting step of a reaction has a special importance. Anything that increases the
rate of this step increases the overall reaction rate. Conversely, if a change in the reaction conditions (for example, a change in temperature) affects the rate of the reaction, it is the effect on
the ratelimiting step that is being observed. Because the rate-limiting step of a reaction has
special importance, its identification receives particular emphasis when we attempt to understand the mechanism of a reaction.
transition state of
highest free energy
(cH3)3c+
Br.t.
(CH3)2C:CHz
HBr
(CH3)3C-Br
reaction coordinate
FiSUre 4.14 Reaction free-energy diagram for a multistep reaction.The ratelimiting step of a multistep reaction
is the step with the transition state of highest standard free energy. In the addition of HBr to 2-methylpropene, the
rate-limiting step is protonation of the double bond to give the carbocation intermediate.
164
CHAPTER
An Analory for the Rate-Limiting Step

A rate-limiting step can be illustrated by a toll station on a freeway at rush hour.We can think of the
passage ofcars through a toll booth as a multistep process: (1) entry ofthe cars into the toll area; (2)
taking ofthe toll by the collector; and (3) exit ofthe cars from the toll area.Typically, paying the toll
to the collector is the rate-limiting step in the passage of cars through the toll plaza. ln other words,
the rate of passage of cars through the toll plaza is the rate at which they pay their tolls. Cars can arrive more or less frequently, but as long as there is a line of cars, the rate of passage through the toll
plaza is the same,
Installing automated change collectors generally increases the rate at which cars pass through a
toll plaza.This strategy works because it increases the rate of the rate-limiting step. Increasing the
speed limit at which cars can approach the toll plaza,on the other hand,would not increase the rate
of passage through the toll plaza, because this change has no effect on the rate.limiting step.
Installing "E-Z Past"an electronic toll permit reader, increases the rate of toll payment even more.
In fact itt possible that with "E-Z Pass," toll payment is no longer the rate-limiting step. In this case
the rate of passage through the toll plaza is limited by the first step, which is the rate at which cars
enter the plaza. In this scenario, raising the speed limit of the approach would increase the rate, but
increasing the speed ofthe"E-Z pass"monitorwould have no effect.
4.29
Draw a reaction free-energy diagram for a reaction A +

B+
C that meets the following criteria: The standard free energies me in the order C < A < B, and the rateJimiting step
of the reaction is B::
C.
4.30 Repeat Problem 4.29 for a case in which the standard free energies are in the order
A < C < B, and the rate-limiting step of the reaction
isA:*8.
D. Hammond's Postulate
We've already learned that transition states can be visualized as structures. Recall (Eq. 4.31,p.
159) that, in the addition of HBr to an alkene, the transition state of the first step is visualized
as a structure along the reaction pathway somewhere between the structures of the starting materials, the alkene and HBr, and the products of this step, the carbocation and a bromide ion:
(CH3)2C:CH2
.. f,.",),.-cr,i l-+
l+llH
+ H-Br: --
.._
(CHr)rC-lH, :f.r:
(4.36)
transition state
What makes this transition state so unstable? First, the bonds undergoing transition are neither
fully broken nor fully formed. The unstable bonding situation is why the transition state lies at
an energy maximum. But additionally, a significant contribution to the high energy of the transition state comes from the same factors that account for the high energy of the carbocation.
One factor is that the carbocation has one bond fewer than HBr and the alkene. Because bonding releases energy, this fact alone means that the carbocation has a considerably higher energy than starting materials (or products). The other factor is the separation of positive and
4.8
REACTION
RATES 165
negative charge. The electrostatic law (Eq.3.40, p. 113) tells us that separation of opposite
charges requires energy.
So, we've concluded that the energies of the transition state and the carbocation intermediate are very similar, and that the structural elements that account for the high energy of the carbocation also account for most of the transition-state energy. In view of these similarities, the
following approximation seems justified: The structure and energy of the transition state in Eq.
4.36 can be approximated by the structure and energy of the carbocation intermediafe. This approximation can be generalized in an important statement called Hqmmond's postulate:
Hammondts Postulate: For a reaction in which an intermediate of relatively high energy is either
formed from reactants of much lower energy or converted into products of much lower energy, the
structure end energy of the transition state can be approximated by the structure and energy of the intermediate itself.
This postulate is named for George S. Hammond (1921-2005), who first stated it and applied it to organic reactions in 1955 while he was a professor of chemistry at Iowa State University. (This is not Hammond's exact statement of his posfulate, but it will prove to be the
most useful version of it for us.)
The utility of Hammond's postulate in dealing with reaction rates can be demonstrated by
showing how we could have used it along with a knowledge of carbocation stability to predict
the regioselectivity of HBr addition to 2-methylpropene. Recall (Sec. 4.8C) that the rate-limiting step in this reaction is the first step: protonation of the alkene by HBr to give a carbocation. As shown in Eqs. 4. 19a and 4. 19b, p. 150, this protonation could occur in two different
and competing ways. Protonation of the double bond at one carbon gives the tert-butyI cation
as the unstable intermediate; protonation of the double bond at the other carbon gives the
isobutyl cation. We apply Hammond's postulate by assuming that the structures and energies
of the transition states are approximated by the structures and energies of the unstable interme diate s-the c arb oc ations-thems e lv e s.
H:C
c-cH,
+ H-Br
H rC
/
similar structures
[+
and energies
transiti on statm f +]
similar structures
and energies
CH:
HrC
\*
C-CH:
Br-
l*
H:C-C-CHz
Br-
(4.37)
f
t
H:C
tert-butyl cation
(tertiary, more stable)
H
isobutyl cation
(primar|, much
less stable)
Because the tertiary carbocation is more stable, the ffansition state leading to the tertiary carbocation should also be the one of lower energy. As a result, protonation of 2-methylpropene
to give the tertiary carbocation has the transition state with the smaller free energy and is thus
the faster of the two competing reactions (Fig. 4.15, p. 166). Addition of FIBr to alkenes is regioselective because protonation of a double bond to give a tertiary carbocation has a transition
156
cHAprER
4.
TNTRoDUCTToN To ALKENES. STRUCTURE AND REACTrvrry
higher-energy
transition state
(cH3)2CHCH2
Br-
(cH:hc+
Br(CH3)2C:CHz
+ HBr
(CH3)2C:CHz
(CH3)2CHCH2-Br
slower reac-tion
reaction coordinate
HBr
(CH3)3C-Br
faster reaction
reaction coordinate
Figure 4.15 A reaction free-energy diagram for the two possible modes of HBr addition to 2-methylpropene.
Hammond's postulate states that the energy of each transition state is approximated by the energy of the corresponding carbocation. The formation of tert-butyl bromide (right panel) is faster than the formation of isobutyl
bromide (left panel\ because it involves the more stable carbocation intermediate and therefore the transition
state of lower energy.
state of lower energy than the transition state for protonation to give a primary carbocation. The
stabilities of the carbocations themselves do not determine which reaction is faster; the relative
free energies of the transition states for carbocation formation determine the relative rates of
the two processes. Only the validity of Hammond's postulate allows us to make the connection
between carbocation energy and transition-state energy.

We need Hammond's postulate because the structures of transition states are uncertain,
whereas the structures of reactants, products, and reactive intermediates are known. Therefore, knowing that a transition state resembles a particular species (for example, a carbocation) helps us to make a good guess about the transition-state structure. In this text, we'11 fre-
quently analyze or predict reaction rates by considering the structures and stabilities of
reactive intermediates such as carbocations. When we do this, we are assuming that the transition states and the corresponding reactive intermediates have similar structures and energies;
in other words, we are invoking Hammond's postulate.
@4.3lApplyHammond,sposfulatetodecidewhichreactionisfaster:additionofHBrto2-methylpropene or addition of HBr to trans-2-butene. Assume that the energy difference between the
starting alkenes can be ignored. Why is this assumption necessary?
4.9
CATALYSIS
Some reactions take place much more rapidly in the presence of certain substances that are
themselves left unchanged by the reaction. A substance that increases the rate of a reaction
without being consumed is called a catalyst. A practical example of a catalyst is platinum in
the catalytic converter on the modern automobile. The platinum catalyst in the converter
4.9 CATALYSIS 167
no cilta[YSt
a catalyst increases the

rate (decreases AGo*)
catalyst
reactants
products
reaction coordinate
FiSure 4,1 6 A reaction free-energy diagram comparing a hypothetical catalyzed reaction (red curve) to the uncatalyzed reaction (bl ue
cu rve).
brings about the rapid oxidation (combustion) of hydrocarbon exhaust emissions. This reaction would not occur were it not for the catalyst; yet the catalyst is left unchanged by the combustion reaction. The catalyst increases the rate of the combustion reaction by many orders of
magnitude.
Here are some important points about catalysts.
1. A catalyst increases the reaction rate. This means that it lowers the standard free energy
of activation for a reaction (Fig. 4. 1 6).
2. A catalyst is not consumed. It may be consumed in one step of a catalyzed reaction, but
if so, it is regenerated in a subsequent step.
An implication of points 1 and 2 is that a catalyst that strongly accelerates a reaction
can be used in very small amounts. Many expensive catalysts are practical for this reason.
3. A catalyst
does not affect the energies ofreactants and products. In other words, aaatalyst does not affect the AG" of a reaction and consequently also does not affect the equilibrium constant (Fig. 4.16).
4. A catalyst accelerates both the forward and reverse of a reaction by the same factor.
The last point follows from the fact that, at equilibrium, the rates of a reaction and its reIf a catalyst does not affect the equilibrium constant (point 3) but increases the
reaction rate in one direction, equality of rates at equilibrium requires that the rate of the reverse reaction must be increased by the same factor.
When a catalyst and the reactants exist in separate phases, the catalyst is called a
heterogeneous catalyst. The catalyst in the catalytic converter of an automobile is a heterogeneous catalyst because it is a solid and the reactants are gases. In other cases, a reaction in
solution may be catalyzed by a soluble catalyst. A catalyst that is soluble in a reaction solution
is called a homogeneous catalyst.
verse are equal.
168
CHAPTER
4.
A large number of organic reactions are catalyzed. In this section, we'll inffoduce the idea
of catalysis by considering three examples of catalyzed alkene reactions. The first example,
catalytic hydrogenation, is a very important example ofheterogeneous catalysis. The second
example, hydration, is an example of homogeneous catalysis. The last example involves catalysis of a biological reaction by an enzyme.
catalyst Poisons
Although in theory catab6ts should function indefinitely, in practice many catalysttparticularly heterogeneous catalysts, slowly become less effective.lt is as if they'wear out."One reason for this behavior is that they slowly absorb impurities,called catalyst poisons,from the surroundings;these impurities impede the functioning of the catalyst. An example of this phenomenon also occurs with
the catalytic converter.Lead is a potent poison ofthe catalyst in a catalytic converter.Thisfact,aswell
as
the desire to eliminate atmospheric lead pollution, are the major reasons why leaded gasoline is
no longer used in automotive engines in the United States.
A. Catalytic Hydrogenation of Alkenes

When a solution of an alkene is stirred under an atmosphere of hydrogen, nothing happens.
But if the same solution is stined under hydrogen in the presence of a metal catalyst, the hydrogen is rapidly absorbed by the solution. The hydrogen is consumed because it undergoes
an addition to the alkene double bond.
./>'H
t tT + Hr
\
Ptic>
H
cyclohexane
ryclohexene
CH:(CHz)5CH:CHz +
l-octene
(4.38)
Hr
Pt/c
CHr(CHz)sCHz-CHr
(4.3e)
octane
These reactions are examples of catalytic hydrogenation, an addition of hydrogen to an

alkene in the presence of a catalyst. Catalytic hydrogenation is one of the best ways to convert
alkenes into alkanes. Catalytic hydrogenation is an important reaction in both industry and the
laboratory. The inconvenience of using a special apparatus for the handling of a flammable gas
(dihydrogen) is more than offset by the great utility of the reaction.
In the preceding reactions, the catalyst is written over the reaction :urows. Pt/C is read as
"Platinum supported on carbon" or simply "Platinum on carbon." This catalyst is a finely divided platinum metal that has been precipitated, or "supported," on activated charcoal. A number of noble metals, such as platinum, palladium, and nickel, are useful as hydrogenation catalysts, and they are often used in conjunction with solid support materials such as alumina
(Al2O3), barium sulfate (BaSO.), or, as in the previous examples, activated carbon. Hydrogenation can be carried out at room temperature and pressure or, for especially difficult cases,
at higher temperature and pressure in a "bomb" (a closed vessel designed to withstand high
pressures).
Because hydrogenation catalysts are insoluble in the reaction solution, they are examples
of heterogeneous catalysts. (Soluble hydrogenation catalysts are also known and, although
important, are not so widely used; Sec. 18.6D.) Even though they involve relatively expensive
noble metals, heterogeneous hydrogenation catalysts are very practical because they can
4.9 CATALYS|S 169

be filtered off and reused. Furthermore, because they are exceedingly effective, they can be
used in very small amounts. For example, typical catalytic hydrogenation reactions can be run
with reactant-to-catalyst ratios of 100 or more.
How do hydrogenation catalysts work? Research has shown that both the hydrogen and the
alkene must be adsorbed on the surface of the catalyst for a reaction to occur. The catalyst is
believed to form reactive metal--carbon and metal-hydrogen bonds that ultimately are broken
to form the products and to regenerate the catalyst sites. Beyond this, the chemical details of
catalytic hydrogenation are poorly understood. This is not a reaction for which a simple
curved-urow mechanism can be written. The mechanism of noble-metal catalysis is an active
area of research in many branches of chemistry.
The benzene ring is inert to conditions under which normal double bonds react readily:
+ H2
GcH:cHz
Pt/c.
stwene
GcHz-cHr
(4.40)
ethvlbenzene
(Benzene rings can be hydrogenated, however, with certain catalysts under conditions
of high temperature and pressure.) You will learn that many other alkene reactions do not
affect the "double bonds" of a benzene ring. The relative inertness of benzene rings toward
the conditions of alkene reactions was one of the great puzzles of organic chemistry that was
ultimately explained by the theory of aromaticity, which is introduced in Chapter 15.
!E@
+.lo oive tnepnrduct fonned when each of the following alkenes reacts with a large exoess of hydrogen in the presence of Pd/C.
(a) l-pentene (b) (E)-1,3-hexadiene
4.33
(a) Give the structures of five alkenes, each with the formula C6Hr2, that would give hexane
as the product of catalytic hydrogenation.
(b) How many alkenes containing one double bond can react with H, over a Pt/C catalyst to
grve methylcyelopentane? Give their structures. (Hint: See Study Pfoblggl 49; p. 1,53i)
B. Hydration
of Alkenes
The alkene double bond undergoes reversible addition of water in the presence of moderately
concentrated strong acids such as H2SO4, HCIO4, and HNOr.
CH.
H.C
-\
C-CHz
H:C
2-methylpropene
I MHNOr
H-oH
(in
excess;
H:C-C-CHr
I
(4.4r)
OH
solvent)
2-methyl-2-propanol
(tert-buryl alcohol)
The addition of the elements of water is in general called hydration. Hence, the addition of
water to the alkene double bond is called alkene hydration.
Hydration does not occur at a measurable rate in the absence of an acid, and the acid is not
consumed in the reaction. Hence, alkene hydration is an acid-catalyzed reaction Because the
catalyzing acid is soluble in the reaction solution, itis ahomogeneous catalyst.
170
CHAPTER
4 o INTRODUCTION
Notice that this reaction, like the addition of HBr, is regioselective. As in the addition of
HBr, the hydrogen adds to the carbon of the double bond with the smaller number of alkyl substituents. The more electronegative partner of the H-OH bond, the OH group, like the Br in
HBr addition, adds to the carbon of the double bond with the greater number of alkyl substituents.
In this reaction, the manner in which the catalyst functions can be understood by considering the mechanism of the reaction, which is very similar to that of HBr addition. In the flrst
step of the reaction, which is the rate-limiting step, the double bond is protonated so as to give
the more stable carbocation. Because water is present, the actual acid is the hydrated proton
(Hro*).
H.C
'\
H:C
C,CH:
/(
H,c
il4n,
\*
utQ
(4.42a)
H:C
This is a Brpnsted acid-base reaction. Because this is the rate-limiting step, the rate of the hydration reaction increases when the rate of this step increases. The strong ac'id HrO+ is more
effective than the considerably weaker acid water in protonating a weak base (the alkene). If a
strong acid is not present, the reaction does not occur because water alone is too weak an acid
to protonate the alkene.
In the next step of the hydration reaction, the Lewis base water combines with the carbocation in a Lewis acid-base association reaction:
(cH:)3c+
lctu, z-
(cH:)rc-i-)Fr,
(4.42b)
Finally, a proton is lost to solvent in another Bronsted acid-base reaction to give the alcohol
product and regenerate the catalyzing acid H,O+:
1-
(cH.).c--cjr-r
\
Jl J
ri
r'
,.ry
H:o"-)
(cH:)3c-L)H + Hro*
(4.42c)
Notice three things about this mechanism. First, it consists entirely of Lewis acid-base and
Br6nsted acid-base reactions. Second, although the proton consumed inEq. 4.42a is not the
same as the one produced inBq.4.42c, there is no nelconsumption of protons. Finally, the
base is F;q.4.42c is water. Some students are tempted to use hydroxide ion in a situation like
this because it is a stronger base. However, there is essentially no hydroxide in a I M nitic
acid or sulfuric acid solution. Nor is hydroxide needed, because the acid on the left of Eq.
4.42cis a strong acid.WheneverHrO* acts as an acid, its conjugate baseHrO acts as the base.
(Read again about amphoteric compounds on p. 97 it this isn't clear.) More generalTy, acids
and their conjugate bases always act in tandem in acid-base catalysis.
Because the hydration reaction involves carbocation intermediates, some alkenes give rearranged hydration products.
L]H
HrC-C-CH:CHz + HrO
I
H:o+
H:C-C-CH|-CH:
-l
I
CH:
CH:
(4.43)
4.9 CATALYSIS 171
{34
Give the mechanism for the reaction in E q. 4.43.Show each step of the mechanism separately
with careful use of the curved-arrow riotation. Explain why"the rehrrangement takes place.
4.35 The alkene 3,3-dimethyl-1-butene
undergoes acid-catalyzed hydration with rearrangement.

Use the mechanism of hydration and rearangement to predict the structure of the hydration
product of this alkene.
4.36 ta) Unlike the alcohol product Eq. 4.41,the product
inEq.4.43 does notcome to equilibrium

with the starting alkene. However, it does come to equilibrium with t'wo other alkenes.
What are their structures?

(b) Why isn't the alkene starting material inEq.4.43 part of the equilibriurn mixture?
The equilibrium constants for many alkene hydrations are close enough to unity that the
hydration reaction can be run in reverse. The reverse of alkene hydratioqis called alcohol dehydration, The direction in which the reaction is run depends on the application of Le ChAtelier's principle, which states that if an equilibrium is disturbed, it will react so as to offset the
disturbance. For example, if the alkene is a gas (as in Eq. 4.41),thereaction vessel can be pressurized with the alkene. The equilibrium reacts to the excess of alkene by forming more alcohol. Neutralization of the acid catalyst stops the reaction and permits isolation of the alcohol.
This strategy is used particularly in industrial applications. One such application ofalkene hydration is the commercial preparation of ethyl alcohol (ethanol) from ethylene:
(.b*'i?i."
H:C-CH' + lrtl
tr
ethvlene
solid suPport)
3oo"c
>
H:C-CHz-[)H
(4.44)
ethanol
A high temperature is required bepause the hydration of ethylene is very slow at ordinary temperatures (see Problem 4.37). Recall (Sec. 4.8B) that increasing the temperature accelerates a
reaction. This reaction was at one time a major source of industrial ethanol. Although it is still
used, its importance has decreased as the fermentation of sugars from biomass (for example,
corn) has become more prevalent.
To run the hydration reaction in the reverse (dehydration) direction, the alkene is removed
as it is formed, typically by distillation. (Alkenes have signi{icantly lower boiling points than
alcohols, as we'll further discuss in Sec. 8.38.) The equilibrium responds by forming more
alkene. Alcohol dehydration is more widely used than alkene hydration in the laboratory.
We'll consider this reaction in Sec. 10.1.
Alkene hydration and alcohol dehydration illustrate two important points. First is one of
the key points about catalysis: a catalyst accelerates the forward and reverse reactions of an
equilibrium by the same factor. For example, because alkene hydration is acid-catalyzed, alcohol dehydration is acid-catalyzed as well. A second point is that alkene hydration and alcohol dehydration occur by the forward and reverse of the same mechanism. Generally, if a re,
action occurs by a cenain mechanism, the reverse reaction under the same conditions occurs
by the exact reverse of that mechanism. This statement is called the principle of microscopic
reversibility. Microscopic reversibility requires, for example, that if you know the mechanism
of alkene hydration, then you know the mechanism of alcohol dehydration as well. A consequence of microscopic reversibility is that the rate-limiting transition states of a reaction and
its reverse are the same. For example, if the rate-limiting step of alkene hydration is protonation of the double bond to form the carbocation intermediate (Eq. 4.42a), thert the rate-limiting step of alcohol dehydration is the reverse of the same equation-deprotonation of the carbocation to sive the alkene.
172
CHAPTER
4.
@437Exp1ainwhythehydrationofethyleneisaveryslowreaction.(Hint:T1tinkaboutthestruc.
ture of the reactive intermediate and apply Hammond's postulate.)
4.38
Isopropyl alcohol is produced commercially by the hydration ofpropene. Show the mechanistic steps of this process. If you do not know the structure of isopropyl alcohol, try to deduce it by analogy from the structure of propene and the mechanism of alkene hydration.
C. Enzyme Catalysis
Catalysis is not limited to the laboratory or chemical industry. The biological processes of nature involve thousands of chemical reactions, most of which have their own unique naturally
occurring catalysts. These biological catalysts are called enzymes. (The structures of enzymes
are discussed in Sec. 26.10.) Under physiological conditions, most important biological reactions would be too slow to be useful in the absence of their enzyme catalysts. Enzyme catalysts are important not only in nature; they are finding increasing use both in industry and in
the laboratory.
Many of the best characteized enzymes are soluble in aqueous solution and hence are homogeneous catalysts. However, other enzymes are immobilized within biological substructures such as membranes and can be viewed as heterogeneous catalysts.
An example of an important enzyme-catalyzed addition to an alkene is the hydration of fumarate ion to malate ion.
ooHo
il
H
C-O_
fumar;rse
(an enztrme
\/
+H_Cl _
C:C
/\
_O-C
H
lltll
-o-c-cH-cFr
?-c-o-
(4.45)
malate
ll
o
fumarate
This reaction is catalyzed by the enzymefumarase.lt is one reaction in the Krebs cycle, or citric acid cycle, a series ofreactions that plays a central role in the generation of energy in biological systems. Fumarase catalyzes only this reaction. The effectiveness of fumarase catalysis can be appreciated by the following comparison: At physiological pH and temperature
(pH : 7, 3'7 "C),the enzyme-catalyzedreaction is about 1010 times faster than the same reaction in the absence of enzyme.
t
I
Alkenes are compounds containing carbon-carbon

double bonds. Alkene carbon atoms, as well as other
trigonal planar atoms, are sp2-hybridized.
The carbon-carbon double bond consists of a o bond
and a n bond.The fr electrons are more reactive than
the
cr
electrons and can be donated to Bronsted or
Lewis acids.
In the IUPAC substitutive nomenclature of alkenes,
the principal chain, which is the carbon chain containing the greatest number of double bonds, is
KEY IDEAS IN CHAPTER
numbered so that the double bonds receive the low-
The unsaturation number of a compound, which is

equal to the number of rings plus double bonds in the
compound, can be calculated from the molecular formula by Eq. 4.7 on p. 139.
Heats of formation (enthalpies of formation) can be

used to determine the relative stabilities of various
bonding arrangements. Heats of formation reveal that
alkenes with more alkyl groups at their double bonds
are more stable than isomers with fewer alkyl groups
and that, in most cases, trans alkenes are more stable
than their cis isomers.
Reactants are converted into products through unstable species called transition states. A transition state
of a reaction step can be approximated as a structure
A reaction rate is determined by the standard free en-
The rates of reactions increase with
increasing
The rates of multistep reactions are determined by

the rate of the slowest step, called the rate-limiting
step.This step is the one with the transition state of
Dipolar molecules such as H-Br and
H-OH
add to
alkenes in a regioselective manner so that the hydrogen adds to the carbon of the double bond with the
most hydrogens, and the electronegative group to
l1
REACTION
/'
ii.
L#
REVIEW
Catalysts are of two types: heterogeneous and homo-
geneous. Catalytic hydrogenation of alkenes is an important example of heterogeneous catalysis; acid-catalyzed hydration of alkenes involves homogeneous
highest standard free energy.
A catalyst increases the rate of a reaction without

being consumed in the reaction. A catalyst does not
affect the equilibrium constant for a chemical equilibrium. Catalysts accelerate the forward and reverse reactions of an equilibrium equally.
tem peratu re.
Reactions involving carbocation intermediates, such

as hydrogen halide addition and hydration, show rearrangements in some cases. unstable carbocations
rearrange to more stable ones by a shift of an alkyl
group, dryl group, or hydrogen to the electron-deficient carbon from an adjacent carbon.The group that
moves brings along its bonding electron pair. As a result, the adjacent carbon becomes electron-deficient.
cha rges.
The regioselectivity observed in the addition reactions of hydrogen halides or water to alkenes is a consequence of two facts: (1) the rate-limiting transition
states of the two competing reactions resemble carbocations; and (2) the relative stability of carbocations
is in the order tertiary > secondary > primary. Application of Hammond's postulate leads to the conclusion that the reaction involving the more stable carbocation is faster.
intermediate between reactants and products, and it
ergy of activation AGo+, which is the standard free energy difference between the transition state and the
reactants. Reactions with smaller standard free energies of activation are faster.
According to Hammond's postulate, the structures

and energies of transition states for reactions involving unstable intermediates (such as carbocations) resemble the structures and energies of the unstable intermed iates them selves.
can be drawn by using dashed bonds and partial
173
the carbon of the double bond with the greater number of alkyl groups. Addition of water requires acid
catalysis because water itself is too weak an acid to
protonate the zr bond.
est numbers.
Because rotation about the alkene double bond does
not occur under normal conditions, some alkenes can
exist as double-bond sterioisomers.These are named
using the E,Z priority system.
catalysis.
Enzymes are biological catalysts that accelerate biological reactions by many orders of magnitude..
For a sammery of reactions discusserl in this chapten see Sectior? R, Chapter 4, in the Study
Guide and Solutions Manual.
174
4.39
4.40
CHAPTER
4.
Give the structures and IUPAC substitutive names of

the isomeric alkenes with molecular formula CuHl2 containing five carbons in their principal chains.
Give the structures and the IUPAC substitutive names
of the isomeric alkenes with the molecular formula
a structure,
in some cases the name is incorrect. Correct
the names that are wrong.
\tr) trans-I-tert-butylpropene (b) 3-butene

(r') (Z)-2-hexene (d) 6-methylcycloheptene
4.46
CuH,, containing four carbons in their principal chain.
Specify the configuration (E or Z) of each of the fol2H, the isolowing alkenes. Note that D is deuterium, or
tope of hydrogen with atomic mass
tal
4.41 Which alkenes
in (ar) Problem 4.39 and (b) Problem

4,40 give predominantly a single constitutional isomer
when treated with HBr, and which give a mixture of
4.43
t t) styrene
t
4.44
lH
|l-- !-1
-/ - \r,.,
4.47
(d) isoprene
e) 5,5-dimethyl- 1,3-cycloheptadiene
(n
l -vinylcyclohexene
(b)
(d)
H:C:CH(CH:)rCF
t",
CzHs
(d) CH3CH2CHzCHz
\-C-CH,
,-rffi
n
C
,_J -c
[j
{.4.3
cH,
CzHs
(>
\-J
I
and
H:Q
-\
/9H.
C:C
HzC:CHCH2CH3 and
/\
HH
H
c:c /
/\ CHZCHzCH:
H
2.
Br
(e)
H.C
"\
(1-(1
v-v
H:C
(d)
CrHs
/FH,
Br
Classify the compounds within each of the following

pairs as either identical molecules (I), constitutional isomers (C), stereoisomers (S), or none of the above (N).
tu) cyclohexane and l-hexene
(b) cyclopentane and cyclopentene
tr:!
Give an IUPAC substitutive name for each of the following compounds. Include the E,Z designations where
approprlate.
\/C-C
/\/\
Arrange the alkenes in ta) Problem 4.39 and (b) Problem 4.40 in order of increasing heats of formation.
(Some may be classified as "about the same.")
Give a structure for each of the following compounds.
( ul cyclobutene (b) 3-methyl- 1-octene
\1
C-C
CD. ft) ct
CH:
H
(c) CH:
isomers? Explain.
4.42
and
CH.CH,CH, CH.
\-C:C /
/\
HH
Use the principles of Sec. 1.38 to predict the geometry
of BF.. What hybridization of boron is suggested by

this geometry? Draw an orbital diagram for hybridized
boron similar to that for the carbons in ethylene shown
in Fig. 4.3, and provide a hybrid orbital description of
(0
the bonding in BF,.
4.49
4.45 A confused
chemist Al Keane used the following names

in a paper about alkenes. Although each name specifies
Classify each of the labeled bonds in the following

structure in terms of the bond type (a or zr) and the
component orbitals that overlap to form the bond. (For
example, the carbon--carbon bond in ethane is an
sp3-sp3 a bond.)
ADDITIONAL
HH
|
H-C-CH_CH-CH_C
(c)
(a)
(b)
|
a* D has the reaction

free-energy diagram shown in Fig. P4.55.
(a) Which compound is present in greatest amount
when the reaction comes to equilibrium? In least
4.55 A reaction A -.--+
(u)/
(d)
PROBLEMS 17 5
amount?
4.50 {a } The following
(b) What is the rate-limiting step of the reaction?

(c) Using a vertical arrow, label the standard free energy
of activation for the overall A --> D reaction.
(d) Which reaction of compound C is faster: C -+ B or
C + D? How do vou know?
compound can be prepared by the addition of HBr to either of two alkenes, give their
structures.
n\ .cH:
\/
\-J
l,
{.5{r
(b) Staning with the same two alkenes, would the products be different if DBr were used? Explain. (See
note about deuterium in Problem 4.46.)
Invoking Hammond's postulate, draw the structure of

the reactive intermediate that should most closely resemble the transition state of the rate-limiting step for
of l-methylcyclohexene. (The first step in

the mechanism, protonation of the double bond, is ratethe hydration
4.51 An
alkene X with molecular formula CrH,, adds HBr to

give a single alkyl halide I with molecular formula
CTHr3Br and undergoes catalytic hydrogenation to give
1,1-dimethylcyclopentane. Draw the structures of X and

I'. (See Study Guide Link 4.3.)
limiting.)
4.51 (al Give the product X expected when methylenecyclobutane undergoes acid-catalyzed hydration.
(,A-tscH, + H:O
l MHNO3
\./
methylenecyclobutane
gruDY GUIDE LIf{K 4,3
Solving Structure
Problems
4.52
Give the structures of the two stereoisomeric alkenes

with the molecular formula CoH,, that react with HI to
give the same single product and undergo catalytic hydrogenation to give hexane.
;1.5J You have been called in as a consultant for the firm
-i>
(b) The rate-limiting step is protonation of the double

bond; use H,O* as the acid catalyst. Draw the structure of the reactive intermediate formed in the rate-
limiting
step.
{r'} Draw the transition state for the rate-limiting step.

td I What is the rate-limiting step for dehydration of X
(the reverse of the reaction shown above)?
A1-
cohols Unlimited, which wants to build a plant to produce 3-methyl-l-butanol, (CH3)2CHCH2CH2OH. The
Al Keyhall, has proposed that acidcatalyzed hydration of 3-methyl- 1-butene be used to

prepare this compound. The company president, O. H.
Gruppa, has asked you to evaluate this suggestion. Millions of dollars are on the line. What is your answer?
Can 3-methyl- 1-butanol be prepared in this way? Explain your answer.
research director,
"l.5"l A certain compound A is converted into a compound B

in a reaction without intermediates. The reaction has an
equilibrium constant K-u : lBl/[A] : 150 ancl, with the
free energy of A as a reference point, a standard free energy of activation of 96 kJ mol-t (23 kcal mol-t).
(a) Draw a reaction free-energy diagram for this
process, showing the relative free energies of A, 8,,
and the transition state for the reaction.
(b) What is the standard free energy of activation for the
reverse reaction fi -> A? How do you know?
reaction coordinate
Figure
Pd.. 5 S
176
CHAPTER
4 o INTRODUCTION
4.58 The he4t of formation of (E)-1,3-pentadiene is 75.8

mol-t (t8.1 kcal mol-r), and that of I ,4-pentadiene
106.3 kJ mol-t (25.4 kcal mol-r).
(a) Which alkene has the more stable atrangement
4.62
kJ
Consider the following compounds and their dipole moments:
is
CI
\/C:C
/\
HrC
of
bonds?
(b) Calculate the heat liberated when one mole of 1,3peqtadiene is burned. The heat of combustion of carbon is
mol-t (- 94.05 kcal mol-r), and

241.8 kJ mol-t (-57.80 kcal mol-r).
393.5 kJ
that of H, is
Assume
CI CI
\/(-_(/\
HH
CI
U-U
CHr
1.9 D
2.4D
that the C-Cl bond dipole is oriented as fol-
lows in each of these compounds.
4.59 When 3-methyl- I -butene
\H
is burned to COr and HtO,
3149.3 kJ/mol (752.7 kcaUmol) of heat is produced.
-C-CI
/
How much heat is liberated when 2-methyl-l-butene is

burne4? Heats of formation are: 3-methyl-1-butene,
(a) According to the preceding dipole moments, which
mol-l (-6.55 kcal mol-r;; 2-methyl-1-27.40

butene, -35.1 kJ mol-r (-8.39 kcal mol-t). The heats
rs more electron-donating toward a double bond,
kJ
methyl or hydrogen? Explain.

(b) Which of the following compounds should have the
greater dipole moment? Explain.
of conlbustion of carbon and hydrogen are not

necessary to work this problem. (Hint: Write a balanced
equatipn for each combustion reaction. Then draw a diagrarrl of the energy relationships among the two hydrocarbons, 5 C + 5 Hr, and 5 CO2 + 5 H2O.)
CI
CI
\/\/
C:C
/\/\
HCH:HH
CH.
C:C
4.60 Make
a model of cycloheptene with the trans (or E)

configuration at the double bond. Now make a model of
cis-cycloheptene. By examining your models, determine which compound should have the greater heat of
4.63 The curved-arrow
notation can be used to understand

seemingly new reactions as simple extensions of what
you already know. This is the first step in developing
an ability to use the notation to predict new reactions.
formation. Explain.
4.61 Which of the following two reactions should
Provide a curved-arrow mechanism for the following
have the
reaction.
greatest LH" change? Why? (Hint: Examine a model of

the two cis alkenes.)
(1)
(cH3)3c c(cH3)r (cHr):c,

C:C
C:C
--->
/\/\
\
J'J
H.c
Hrc
CH.
C:C
/\/\
HHHCHI
/
--->
HrC
C:C
aqueous _
H.C
--J-V
#diluteH2SOa
nrd
l.
2.
groups in the starting material. In this case, focus on

the double bond. Is this transformation similar in
H-OSOTH
HrC,
CHI
I
C-C-H
/l
H:C CH:
Figure F4.64
<+
Examine the reactants and products and label corresponding atoms. If you're not sure, make a guess.
Describe what has happened to the functional
any way to a reaction you have seen before?
H,C
^^r\
-9'
^...,/
To do this, follow these steps:
c(cH3)3
.\
..,
,
C-CHCH2CH2On
L
Leo
(2)
J'
-\\
H.C
I
\+ ?n,
C_C_H
H,/
1",
..
-:OSOTH
:A+
HrC
\/b:C
/\"
H:C
9H,
+ H-OSOTH
CH:
ADDITIONAL
3.
Make the connections you deduced in (l) with a

curved-arrow mechanism, trying to use steps that
are similar to mechanistic steps you've seen in other
reactions. use separate structures for each step of
HzC. 9H,
|
the mechanism; that is, don't try to write several
4.
mechanistic steps using the same structure.

use a Lewis acid-base or Bronsted acid-base reac-
(b)
Supply the curved-arrow notation for the acid-catalvzed

isomerizatron shown in Fig. P1.64.
CH,
CH:
75.9 kl mol-t
18.1 kcal mol-l
free energies of formation
mol-'1 less than rhat for the hydration

1-butene. Which hydration reaction is faster?
of
(c) Draw reaction free-energy diagrams on the same

scale for the hydration reactions of these two alkenes,
:OCH:
showing the relative free energies of both starting materials and rate-determining transition states.
This ether is used commercially as an antiknock gasoline additive. using the curved-arrow notation, propose
a mechanism for this reaction.
(d) what is the difference in the standard free energies

of the transiti.on states for the two hydration reactions? Which transition state has lower energy?
IJsing the mechanism of the reaction, suggest why it
is more stable.
the curved-arrow notation, suggest a mechanism
for the reaction shown in Fig. P4.66.

(Hints: (1) Follow the problem-solving suggesrions in
Problem 1.63.(2) use Hammond's postulare to decide
which double bond should protonate first.)
C-C
H:C
(5.5 kcal
H:c-g-cH:
methyl tert-butyl ether
4.66 Using
r-
of AGr?.)
(a) Which compound is more stable? Why?
(b) The standard free energy of activation for the
hydration of 2-methylpropene is 22.8 kJ mol-r
in the following equation.
Hzso+t
for l-butene and 2-methylpropene is 13.4 lcl mol-t (3.2

kcal mol-t). (see the previous problem for a definition
synthesis of methyl tert-butyl ether involves treatment of 2-methylpropene with methanol

(CH3OH) in the presence of an acid catalyst, as shown
\b-cH: +
cH3o-H
/
H:C
79.0 kl rnol-t
l8'9 kcal mol-r
4.68 The difference in the standard
4.65 The industrial
HrC
AGi
,CH:
--'\
what does the equilibrium constant tell us about the

rate at which this interconversion takes place?
tion for each step.
4.64
Hre
-\
C-C-H
/l/\
HsC CH.
PROBLEMS 177
4.69 The standard free
energy of activation (AG"+) for hydration of 2-methylpropene to 2-methyl-2-propanol (Eq.

4.41, p. 169) is 91.3 kJ mol-t (Zt 8 kcal mol-l;. The
standard free energy AG" for hydration of 2-methyl-
4.67 The standard
free energy of formation, AGi, is the freeenergy change for the formation of a substance at 25 "C
and I atm pressure from its elements in their natural
propene is -5.56 kJ mol-t (- 1.33 kcal mol-1;. The

rate of hydration of methylenecyclobutane to give an al-
cohol (compound X in Problem 4.57) is 0.6 times the

rate of hydration of 2-methylpropene. The equilibrium
constant for the hydration of methylenecyclobutane is
states under the same conditions.
(a) Calculate the equilibrium constant for the interconversion of the following alkenes, given the standard
about 250 times greater (in favor of hydration) than the

equilibrium constant for the hydration of 2-methylpropene. Which alcohol, X or 2-methyl-2-propanol, under-
free energy of formation of each. Indicate which

compound is favored at equilibrium.
goes dehydration faster, and how much faster? Explain.
-\
H,C
/
H:C
c-CHCHZCH2CH-CH2 +
Figure P4.66
Hro,
H:soq
H:C
H:C

06 Chapter 4

Uploaded by

Copyright:

Available Formats

06 Chapter 4

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

06 Chapter 4

Uploaded by

Copyright:

Available Formats

lntroduction to Al kenes.

Structu re and Reactivity

which are classified as saturated hydrocarbons.

STRUCTURE AND BONDING IN ATKENES

STRUCTURE AND BONDING IN

A. Garbon Hybridization in Alkenes

O INTRODUCTION TO ALKENES. STRUCTURE AND REACTIVITY

aflcctetJ Lrl' hvh riti izitt

rnix 2s,2p.r, and

Figure4.4 (a)Thegeneral shapeofansp2hybridorbital isverysimilartothatofansp'hybridorbital,withalarge

STRUCTURE AND BONDING IN

Fi8ure4.5 Ahybridorbital picturefortheabondsofethylene.A2p.orbitaloneachcarbon(dashedlines)isleft

The interaction of two 2p, orbitals of ethylene by a side-to-side overlap is shown in an

TO ALKENES. STRUCTURE AND REACTIVITY

STRUCTURE AND BONDING IN

z'-electron densit\n .rbove and be-lorv

TO ALKENES. STRUCTURE AND REACTIVITY

spi-spi single bond

STRUCTURE AND BONDING IN

2p orbitals cannot ornerlap;

broken. (Fig.4.7). Because bonding is energetically favorable, lack of it is energetically costly.

Ci.r- and trans-2-bttene are examples of double-bond stereoisomers. Double-bond

interchange colored groups

INTRoDUCTIoN TO ALKENES. STRUCTURE AND REACTIVITY

gnoups are cis. Hence, A has a double-bond stereoisomer:

interchirnge col0red groups

interchange colored groups

STUDY SUIDE LINK

IUPAC Substitutive Nomenclature

fnritinn ofdouble bond

Name the following compound using IUPAC substitutive nomenclature.

INTRODUCTION TO ALKENES. STRUCTURE AND REACTIVITY

position of the substituent group

nosition of the double bond

principal chain (longest chain

positions of double bonds

Name the following compound:

names: 1,6-dimethylcyclohexene 2,3-dimethylcyclohexene

incorrect because carbons of drtubie bond

pcsrtion nf iJoutllt' LronrJ u'itl-lin

Lrosition of the substituent grollp

INTRoDUCTToN To ALKENES. STRUCTURE AND REACTtvlry

(Recall from Sec. 2.98, p.82, that

refers to the phenyl group, a singly substituted ben-

More Recent IUPAC Nomenclature Recommendations

-hexene is named hex-l -ene, and 2,4-hexadiene

Give the structure for each of the following:

B. Nomenclature of Double-Bond Stereoisomers: The E,Z System

high prir rittn

INTRODUCTION TO ALKENES. STRUCTURE AND REACTIVITY

leads to no decision, because in both groups the atom directly attached

same-a carbon m in the

case of the methyl group, and a carbon e in the

to the double bond is the

higher priorifl" groliP

mer; its complete name is (E)-3-methyl-2-pentene.

gpnp containing carbon b2 (tlrc isobutyl group) also

has the higher

prisrity. Tlre process used

mol-t (0.07 kcal moll);