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CHAPTER 3

ALKANES, ALKENES, ALKYNES , AND CYCLOALKANES

ALKANES

3.1 Functional Groups

Functional group collection of atoms at a


site that have a
characteristic behavior in
all molecules where it
occurs

The group reacts in a


typical way, generally
independent of the rest of
the molecule

For example, the double


bonds in simple and
3 complex alkenes react

Functional Groups with Multiple CarbonCarbon


Bonds
Alkenes have a C-C double bond
Alkynes have a C-C triple bond
Arenes have special bonds that are represented
as alternating single and double C-C bonds in a
six-membered ring

Functional Groups with Carbon Singly Bonded


to an Electronegative Atom

Groups with a CarbonOxygen Double Bond


(Carbonyl Groups)

Survey of Functional Groups

Survey of Functional Groups

3.2 Alkanes and Alkane Isomers


Alkanes: Compounds with C-C single bonds and C-H
bonds only (no functional groups)
Connecting carbons can lead to large or small
molecules
The formula for an alkane with no rings in it must be
CnH2n+2 where the number of Cs is n

Alkanes are saturated with hydrogen (no more can be


added
They are also called aliphatic compounds

Alkane Isomers

CH4 = methane, C2H6 = ethane, C3H8= propane

The molecular formula of an alkane with more


than three carbons can give more than one
structure

C4 (butane) = butane and isobutane

C5 (pentane) = pentane, 2-methylbutane, and 2,2dimethylpropane

Alkanes with Cs connected to no more than 2


other Cs are straight-chain or normal alkanes
Alkanes with one or more Cs connected to 3 or 4
Cs are branched-chain alkanes
10

Constitutional Isomers

Isomers that differ in how their atoms are


arranged in chains are called constitutional
isomers
Compounds other than alkanes can be
constitutional isomers of one another
They must have the same molecular formula to be
isomers

11

Condensed Structures of Alkanes

We can represent an alkane in a brief form or in


many types of extended form
A condensed structure does not show bonds but
lists atoms, such as

12

CH3CH2CH2CH3 (butane)
CH3(CH2)2CH3 (butane)

13

3.3 Alkyl Groups

Alkyl group remove one H from an alkane (a


part of a structure)
General abbreviation R (for Radical, an
incomplete species or the rest of the molecule)
Name: replace -ane ending of alkane with -yl
ending
CH3 is methyl (from methane)
CH2CH3 is ethyl from ethane

14

15

Types of Alkyl groups

Classified by the connection site (See Figure 3.3)

16

a carbon at the end of a chain (primary alkyl group)


a carbon in the middle of a chain (secondary alkyl
group)
a carbon with three carbons attached to it (tertiary
alkyl group)

17

3.4 Naming Alkanes

Compounds are given systematic names by a process that


uses

Follows specific rules


Find parent hydrocarbon chain
Carbons in that main chain are numbered in sequence
Substituents are identified numbered
Write compound name is single word
Name a complex substituents as though it were a
compound itself
See specific examples in text

18

3.5 Properties of Alkanes

Called paraffins (low affinity compounds)


because they do not react as most chemicals
They will burn in a flame, producing carbon
dioxide, water, and heat
They react with Cl2 in the presence of light to
replace Hs with Cls (not controlled)

19

Physical Properties

Boiling points and melting points increase as size


of alkane increases
Dispersion forces increase as molecule size
increases, resulting in higher melting and boiling
points

Dispersion forces acted


on the neighbouring
molecules

20

3.6 Conformations of Ethane

Stereochemistry concerned with the 3-D


aspects of molecules
bonds are cylindrically symmetrical
Rotation is possible around C-C bonds in openchain molecules

21

Conformers

Conformation- Different arrangement of


atoms resulting from bond rotation
Conformations can be represented in 2 ways:

22

Torsional Strain

We do not observe perfectly free rotation


There is a barrier to rotation, and some
conformers are more stable than others
Staggered- most stable: all 6 C-H bonds are
as far away as possible
Eclipsed- least stable: all 6 C-H bonds are as
close as possible to each other

23

24

3.7 Conformations of Other Alkanes

The eclipsed conformer of propane has 3


interactions: two ethane-type H-H
interactions, and one H-CH3 interaction

25

Conformations of Other Alkanes

Conformational situation is more complex


for larger alkanes

Not all staggered conformations has same


energy, and not all eclipsed conformations
have same energy

26

Conformations of Butane

Anti conformation- methyl groups are 180 apart


Gauche conformation- methyl groups are 60
apart

Which is the most energetically stable?

27

Steric Strain

Steric strain- repulsive interaction occurring between


atoms that are forced closer together than their atomic radii
allow

28

29

CYCLOALKANES AND THEIR


STEREOCHEMISTRY

Weve discussed open-chained compounds up to this point


Most organic compounds contain rings of carbon atoms
e.g.
Prostaglandins

Steroids

31

Why this chapter?

Because cyclic molecules are commonly


encountered in all classes of biomolecules:

Proteins
Lipids
Carbohydrates
Nucleic acids

32

4.1 Naming Cycloalkanes

Cycloalkanes are saturated cyclic hydrocarbons


Have the general formula (CnH2n)

33

Naming Cycloalkanes
Find the parent. # of carbons in the ring.

1.
1.
2.

34

If the no. of C in the ring is equal or greater than the no. of C in


the substituent chain then name as alkyl-substituted cycloalkane.
If the no. of C in the ring is less then name as cycloalkylsubstituted alkane.

Naming Cycloalkanes
Name the substituent.

2.

Number the substituent as low as possible

Different substituent must be arrange according


to alphabetical order

35

4.2 Cis-Trans Isomerism in Cycloalkanes

Cycloalkanes are less flexible than open-chain


alkanes
Much less conformational freedom in
cycloalkanes

36

Because of their cyclic structure, cycloalkanes have 2 faces


as viewed edge-on
top face
bottom face
Therefore, isomerism is possible in substituted
cycloalkanes
There are two different 1,2-dimethyl-cyclopropane isomers

37

Stereoisomerism

Compounds which have their atoms


connected in the same order but differ in 3-D
orientation

38

4.3 Stability of Cycloalkanes: Ring Strain

Rings larger than 3 atoms are not flat


Cyclic molecules can assume nonplanar
conformations to minimize angle strain and
torsional strain by ring-puckering
Larger rings have many more possible
conformations than smaller rings and are
more difficult to analyze

39

Stability of Cycloalkanes: The Baeyer Strain


Theory

Baeyer (1885): since carbon prefers to have


bond angles of approximately 109, ring sizes
other than five and six may be too strained to
exist
Rings from 3 to 30 Cs do exist but are
strained due to bond bending distortions and
steric interactions

40

Summary: Types of Strain

Angle strain - expansion or compression of bond


angles away from most stable
Torsional strain - eclipsing of bonds on
neighboring atoms
Steric strain - repulsive interactions between
nonbonded atoms in close proximity

41

4.4 Conformations of Cycloalkanes

Cyclopropane
3-membered ring must have planar structure
Symmetrical with CCC bond angles of 60
Requires that sp3 based bonds are bent (and
weakened)
All C-H bonds are eclipsed

42

Bent Bonds of Cyclopropane

In cyclopropane, the C-C bond is displaced


outward from internuclear axis

43

Cyclobutane

Cyclobutane has less angle strain than


cyclopropane but more torsional strain
because of its larger number of ring
hydrogens
Cyclobutane is slightly bent out of plane - one
carbon atom is about 25 above

44

The bend increases angle strain but decreases


torsional strain

Cyclopentane

Planar cyclopentane would have no angle


strain but very high torsional strain
Actual conformations of cyclopentane are
nonplanar, reducing torsional strain
Four carbon atoms are in a plane

45

The fifth carbon atom is above or below the plane


looks like an envelope

4.5 Conformations of Cyclohexane

Substituted cyclohexanes occur widely in


nature
The cyclohexane ring is free of angle strain
and torsional strain
The conformation is has alternating atoms in a
common plane and tetrahedral angles
between all carbons
This is called a chair conformation

46

How to Draw Cyclohexane

47

4.6 Axial and Equatorial Bonds in


Cyclohexane

The chair conformation has two kinds of


positions for substituents on the ring: axial
positions and equatorial positions
Chair cyclohexane has six axial hydrogens
perpendicular to the ring (parallel to the ring
axis) and six equatorial hydrogens near the
plane of the ring

48

Axial and Equatorial Positions

Each carbon atom in cyclohexane has one


axial and one equatorial hydrogen
Each face of the ring has three axial and three
equatorial hydrogens in an alternating
arrangement

49

Drawing the Axial and Equatorial Hydrogens

50

Conformational Mobility of Cyclohexane

Chair conformations readily interconvert,


resulting in the exchange of axial and
equatorial positions by a ring-flip

51

4.7 Conformations of Monosubstituted


Cyclohexanes

Cyclohexane ring
rapidly flips between
chair conformations at
room temp.
Two conformations of
monosubstituted
cyclohexane arent
equally stable.
The equatorial
conformer of methyl
cyclohexane is more
stable than the axial by
7.6 kJ/mol
52

1,3-Diaxial Interactions

Difference between axial and equatorial


conformers is due to steric strain caused by
1,3-diaxial interactions
Hydrogen atoms of the axial methyl group on
C1 are too close to the axial hydrogens three
carbons away on C3 and C5, resulting in 7.6
kJ/mol of steric strain

53

Relationship to Gauche Butane Interactions

Gauche butane is less stable than anti butane


by 3.8 kJ/mol because of steric interference
between hydrogen atoms on the two methyl
groups
The four-carbon fragment of axial
methylcyclohexane and gauche butane have
the same steric interaction
In general, equatorial positions give more
stable isomer

54

4.8 Conformational Analysis of


Disubstituted Cyclohexanes

In disubstituted cyclohexanes the steric effects of both


substituents must be taken into account in both
conformations

There are two isomers of 1,2-dimethylcyclohexane. cis and


trans

In the cis isomer, both methyl groups are on the same face
of the ring, and compound can exist in two chair
conformations

Consider the sum of all interactions

In cis-1,2, both conformations are equal in energy

55

Trans-1,2-Dimethylcyclohexane

Methyl groups are on opposite faces of the ring

One trans conformation has both methyl groups equatorial and


only a gauche butane interaction between methyls (3.8 kJ/mol) and
no 1,3-diaxial interactions

The ring-flipped conformation has both methyl groups axial with


four 1,3-diaxial interactions

Steric strain of 4 3.8 kJ/mol = 15.2 kJ/mol makes the diaxial


conformation 11.4 kJ/mol less favorable than the diequatorial
conformation

trans-1,2-dimethylcyclohexane will exist almost exclusively (>99%)


in the diequatorial conformation

56

4.9 Conformations of Polycyclic Molecules


Decalin consists of two cyclohexane rings
joined to share two carbon atoms (the
bridgehead carbons, C1 and C6) and a
common bond
Two isomeric forms of decalin: trans fused or
cis fused
In cis-decalin hydrogen atoms at the
bridgehead carbons are on the same face of
the rings
In trans-decalin, the bridgehead hydrogens
are on opposite faces
Both compounds can be represented using
57chair cyclohexane conformations

58

ALKENES: STRUCTURE AND REACTIVITY

Alkene - Hydrocarbon With Carbon-Carbon


Double Bond

Also called an olefin but alkene is better


Includes many naturally occurring materials
Flavors, fragrances, vitamins

60

Why this Chapter?

C-C double bonds are present in most


organic and biological molecules

To examine consequences of alkene


stereoisomerism

To focus on general alkene reaction:


electrophilic addition

61

6.1 Industrial Preparation and Use of Alkenes

Ethylene and propylene are the most


important organic chemicals produced

62

Calculating Degree of Unsaturation

Relates molecular formula to possible structures


Degree of unsaturation: number of multiple
bonds or rings
Formula for a saturated acyclic compound is
CnH2n+2
Each ring or multiple bond replaces 2 H's

63

Example: C6H10

Saturated is C6H14

Therefore 4 H's are not


present

This has two


degrees of
unsaturation

64

Two double bonds?


or triple bond?
or two rings
or ring and double bond

Degree of Unsaturation With Other Elements

Organohalogens (X: F, Cl, Br, I)


Halogen replaces hydrogen
C4H6Br2 and C4H8 have one degree of unsaturation
Organoxygen compounds (C,H,O) - if connected by
single bonds
These don't affect the total count of H's

65

Organonitrogen compounds

Nitrogen has three bonds


So if it connects where H was, it adds a connection
point
Subtract one H for equivalent degree of
unsaturation in hydrocarbon

66

Summary - Degree of Unsaturation

Count pairs of H's below CnH2n+2

Add number of halogens to number of H's (X


equivalent to H)
Ignore oxygens (oxygen links H)
Subtract N's - they have two connections

67

Naming of Alkenes

Name the parent hydrocarbon


Number carbons in chain so that double bond carbons
have lowest possible numbers
Rings have cyclo prefix

68

Many Alkenes Are Known by Common Names

69

Cis-Trans Isomerism in Alkenes

Carbon atoms in a double bond are sp2-hybridized

Combination of electrons in two sp2 orbitals of two


atoms forms bond between them
Additive interaction of p orbitals creates a
bonding orbital

Three equivalent orbitals at 120 separation in


plane
Fourth orbital is atomic p orbital

Subtractive interaction creates a anti-bonding


orbital

Occupied orbital prevents rotation about -bond


Rotation prevented by bond - high barrier, about
268 kJ/mole in ethylene
70

Rotation of Bond Is Prohibitive

This prevents rotation about a carbon-carbon


double bond (unlike a carbon-carbon single bond).
Creates possible alternative structures

71

The presence of a carbon-carbon double bond can create


two possible structures
cis isomer - two similar groups on same side of the
double bond
trans isomer - similar groups on opposite sides
Each carbon must have two different groups for these
isomers to occur

72

Cis, Trans Isomers Require That End Groups


Must Differ in Pairs
180rotation superposes
Bottom pair cannot be superposed

without breaking C=C

73

Sequence Rules: The E,Z Designation

Neither compound is clearly cis or trans


Substituents on C1 are different than those on C2
We need to define similarity in a precise way to
distinguish the two stereoisomers
Cis, trans nomenclature only works for disubstituted
double bonds

74

E,Z Stereochemical Nomenclature

Priority rules of Cahn, Ingold, and Prelog


Compare where higher priority groups are with respect
to bond and designate as prefix
E -entgegen, opposite sides
Z - zusammen, together on the same side

75

Ranking Priorities: Cahn-Ingold-Prelog Rules


RULE 1
Must rank atoms that are connected at comparison
point
Higher atomic number gets higher priority
Br > Cl > S > P > O > N > C > H

76

Extended Comparison
RULE 2
If atomic numbers are the same, compare at next
connection point at same distance
Compare until something has higher atomic number
Do not combine always compare

77

Dealing With Multiple Bonds:


RULE 3
Substituent is drawn with connections shown and no
double or triple bonds
Added atoms are valued with 0 ligands themselves

78

Stability of Alkenes

Cis alkenes are less stable than trans alkenes

Compare heat given off on hydrogenation: Ho

Less stable isomer is higher in energy


And gives off more heat
tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted
hyperconjugation stabilizes

79

Comparing Stabilities of Alkenes

Evaluate heat given off when C=C is converted to C-C


More stable alkene gives off less heat
trans-Butene generates 4 kJ less heat than cisbutene

80

Hyperconjugation

Stabilizing interaction between an unfilled orbital and


a neighbouring filled the C-H bond on a substituent.
More substituents, greater stabilisation.
Alkyl groups are better than H

81

Electrophilic Addition of Alkenes

General reaction
mechanism:
electrophilic addition
Attack of electrophile
(such as HBr) on bond
of alkene
Produces carbocation
and bromide ion
Carbocation is an
electrophile, reacting
with nucleophilic
bromide ion

82

Electrophilic Addition Energy Path

Two step process


First transition state is high energy point

83

Electrophilic Addition for preparations

The reaction is successful with HCl and with HI as well


as HBr
HI is generated from KI and phosphoric acid

84

Orientation of Electrophilic Addition:


Markovnikovs Rule

In an unsymmetrical alkene, HX reagents can add in


two different ways, but one way may be preferred over
the other
If one orientation predominates, the reaction is
regiospecific
Markovnikov observed in the 19th century that in the
addition of HX to alkene, the H attaches to the carbon
with the most Hs and X attaches to the other end (to
the one with the most alkyl substituents)
This is Markovnikovs rule

85

Example of Markovnikovs Rule

Addition of HCl to 2methylpropene


Regiospecific one
product forms where two
are possible
If both ends have similar
substitution, then not
regiospecific

86

Markovnikovs Rule (restated)

More highly substituted carbocation forms as


intermediate rather than less highly substituted one
Tertiary cations and associated transition states are
more stable than primary cations

87

Carbocation Structure and Stability

Carbocations are planar and the tricoordinate carbon is


surrounded by only 6 electrons in sp2 orbitals
The fourth orbital on carbon is a vacant p-orbital
The stability of the carbocation (measured by energy
needed to form it from R-X) is increased by the
presence of alkyl substituents

88

89

Inductive stabilization of cation species

inductive effect is simply the shifting of


electrons in a bond in response to the
electronegativity of nearby atoms

90

The Hammond Postulate

If carbocation intermediate is more stable than


another, why is the reaction through the more stable
one faster?
The relative stability of the intermediate is related to
an equilibrium constant (G)
The relative stability of the transition state (which
describes the size of the rate constant) is the
activation energy (G)
The transition state is transient and cannot be
examined

91

Transition State Structures

A transition state is the highest energy species in a


reaction step
By definition, its structure is not stable enough to exist
for one vibration
But the structure controls the rate of reaction
So we need to be able to guess about its properties in
an informed way
We classify them in general ways and look for trends in
reactivity the conclusions are in the Hammond
Postulate

92

Examination of the Hammond Postulate

A transition state
should be similar to
an intermediate
that is close in
energy

Sequential states
on a reaction path
that are close in
energy are likely to
be close in
structure - G. S.
Hammond
93

Competing Reactions and the Hammond


Postulate

Normal Expectation: Faster reaction gives more stable


intermediate
Intermediate resembles transition state

94

6.11 Mechanism of Electrophilic Addition:


Rearrangements of Carbocations

Carbocations undergo
structural
rearrangements
following set patterns
1,2-H and 1,2-alkyl shifts
occur
Goes to give more stable
carbocation
Can go through less
stable ions as
intermediates

95

Hydride shifts in biological molecules

96

ALKENES: REACTIONS AND


SYNTHESIS

Diverse Reactions of Alkenes

Alkenes react with many electrophiles to give


useful products by addition (often through
special reagents)

98

Why this chapter?

To begin a systematic description of major


functional groups
Begin to focus on general principles and
patterns of reactivity that tie organic
chemistry

99

7.1 Preparation of Alkenes: A Preview of


Elimination Reactions

Alkenes are
commonly made by

elimination of HX from
alkyl halide
(dehydrohalogenation
)

elimination of H-OH
from an alcohol
(dehydration)

100

Uses heat and KOH

require strong acids


(sulfuric acid, 50 C)

7.2 Addition of Halogens to Alkenes

Bromine and chlorine add to alkenes to give


1,2-dihalides, an industrially important
process

F2 is too reactive and I2 does not add

Cl2 reacts as Cl+ Cl

101

Br2 is similar

Addition of Br2 to Cyclopentene

Addition is exclusively trans

102

Mechanism of Bromine Addition

Br+ adds to an alkene producing a cyclic ion


Bromonium ion, bromine shares charge with
carbon

103

Gives trans addition

Bromonium Ion Mechanism

Electrophilic
addition of
bromine to give a
cation is followed
by cyclization to
give a bromonium
ion
This bromoniun ion
is a reactive
electrophile and
bromide ion is a
good nucleophile

104

The Reality of Bromonium Ions

Bromonium ions were postulated more than


60 years ago to explain the stereochemical
course of the addition (to give the transdibromide from a cyclic alkene
Olah showed that bromonium ions are stable
in liquid SO2 with SbF5 and can be studied
directly

105

Addition of Hypohalous Acids to Alkenes:


Halohydrin Formation

This is formally the addition of HO-X to an


alkene to give a 1,2-halo alcohol, called a
halohydrin
The actual reagent is the dihalogen (Br 2 or Cl2
in water in an organic solvent)

106

Mechanism of Formation of a Bromohydrin

Br2 forms bromonium


ion, then water adds

107

Orientation toward
stable C+ species
Aromatic rings do not
react

An Alternative to Bromine

Bromine is a difficult reagent to use for this


reaction
N-Bromosuccinimide (NBS) produces bromine
in organic solvents and is a safer source

108

Addition of Water to Alkenes:


Oxymercuration

Hydration of an alkene is the addition of H-OH


to to give an alcohol
Acid catalysts are used in high temperature
industrial processes: ethylene is converted to
ethanol

109

Oxymercuration Intermediates

For laboratory-scale hydration of an alkene


Use mercuric acetate in THF followed by
sodium borohydride
Markovnikov orientation

110

via mercurinium ion

Addition of Water to Alkenes: Hydroboration

Herbert Brown (HB) invented hydroboration


(HB)
Borane (BH3) is electron deficient is a Lewis
acid
Borane adds to an alkene to give an
organoborane

111

Non-Markonikov product

Hydroboration-Oxidation Forms an Alcohol


from an Alkene

Addition of H-BH2 (from BH3-THF complex) to


three alkenes gives a trialkylborane
Oxidation with alkaline hydrogen peroxide in
water produces the alcohol derived from the
alkene

112

Orientation in Hydration via Hydroboration

Regiochemistry is opposite to Markovnikov


orientation

OH is added to carbon with most Hs

H and OH add with syn stereochemistry, to


the same face of the alkene (opposite of anti
addition)

113

Mechanism of Hydroboration

Borane is a Lewis acid


Alkene is Lewis base
Transition state involves anionic development on B
The components of BH3 are added across C=C
More stable carbocation is also consistent with steric
preferences

114

Addition of Carbenes to Alkenes

The carbene functional group is half of an


alkene
Carbenes are electrically neutral with six
electrons in the outer shell
They add symmetrically across double bonds
to form cyclopropanes

115

Formation of Dichlorocarbene

Base removes
proton from
chloroform
Stabilized
carbanion remains
Unimolecular
elimination of Clgives electron
deficient species,
dichlorocarbene

116

Reaction of Dichlorocarbene

Addition of dichlorocarbene is stereospecific


cis

117

Simmons-Smith Reaction

Equivalent of addition of CH2:

Reaction of diiodomethane with zinc-copper


alloy produces a carbenoid species
Forms cyclopropanes by cycloaddition

118

Reduction of Alkenes: Hydrogenation

Addition of H-H across C=C


Reduction in general is addition of H 2 or its
equivalent
Requires Pt or Pd as powders on carbon and
H2
Hydrogen is first adsorbed on catalyst
Reaction is heterogeneous (process is not in
solution)

119

Hydrogen Addition- Selectivity

Selective for C=C. No reaction with C=O, C=N


Polyunsaturated liquid oils become solids
If one side is blocked, hydrogen adds to other

120

Sensitive to steric environment

Mechanism of Catalytic Hydrogenation

Heterogeneous
reaction between
phases
Addition of H-H is
syn

121

Oxidation of Alkenes: Epoxidation and


Hydroxylation

Epoxidation results in a cyclic ether with an


oxygen atom
Stereochemistry of addition is syn

122

Osmium Tetroxide Catalyzed Formation of


Diols

Hydroxylation - converts to syn-diol


Osmium tetroxide, then sodium bisulfate
Via cyclic osmate di-ester

123

Oxidation of Alkenes: Cleavage to Carbonyl


Compounds

Ozone, O3, adds to alkenes to form


molozonide
Reduce molozonide to obtain ketones and/or
aldehydes

124

Ozonolysis of Alkenes

Result of ozonolysis : C=C bond cleaved and


oxygen is doubly bonded to each of the
original alkene carbons

125

Permanganate Oxidation of Alkenes

Oxidizing reagents other than ozone also


cleave alkenes
Potassium permanganate (KMnO4) can
produce carboxylic acids and carbon dioxide if
Hs are present on C=C

126

Cleavage of 1,2-diols

Reaction of a 1,2-diol with periodic (per-iodic)


acid, HIO4 , cleaves the diol into two carbonyl
compounds
Sequence of diol formation with OsO4
followed by diol cleavage is a good alternative
to ozonolysis

127

Addition of Radicals to Alkenes: Polymers

A polymer is a very
large molecule
consisting of repeating
units of simpler
molecules, formed by
polymerization
Alkenes react with
radical catalysts to
undergo radical
polymerization
Ethylene is
polymerized to
poyethylene, for
example
128

Free Radical Polymerization: Initiation

Initiation - a few radicals are generated by


the reaction of a molecule that readily forms
radicals from a nonradical molecule
A bond is broken homolytically

129

Polymerization: Propagation

Radical from initiation adds to alkene to


generate alkene derived radical
This radical adds to another alkene, and so on
many times

130

Polymerization: Termination

Chain propagation ends when two radical


chains combine
Not controlled specifically but affected by
reactivity and concentration

131

Other Polymers

Other alkenes give other common polymers

132

Biological Additions of Radicals to Alkenes

Severe limitations to the usefulness of radical


addition reactions in the lab
In contrast to electrophilic additions, reactive
intermediate is not quenched so it reacts
again and again uncontrollably

133

Biological Reactions

Biological reactions different than in the


laboratory
One substrate molecule at a time is present in
the active site of an enzyme
Biological reactions are more controlled, more
specific than other reactions

134

135

ALKYNES

Alkynes

Hydrocarbons that contain carbon-carbon


triple bonds
Acetylene, the simplest alkyne is produced
industrially from methane and steam at high
temperature
Our study of alkynes provides an introduction
to organic synthesis, the preparation of
organic molecules from simpler organic
molecules

137

Why this chapter?

We will use alkyne chemistry to begin looking


at general strategies used in organic synthesis

138

Naming Alkynes

General hydrocarbon rules apply with -yne


as a suffix indicating an alkyne
Numbering of chain with triple bond is set so
that the smallest number possible for the first
carbon of the triple bond

139

Preparation of Alkynes: Elimination Reactions


of Dihalides

Treatment of a 1,2dihalidoalkane with


KOH or NaOH
produces a two-fold
elimination of HX
Vicinal dihalides are
available from
addition of bromine
or chlorine to an
alkene
Intermediate is a
vinyl halide

140

Reactions of Alkynes: Addition of HX and X2

Addition reactions of alkynes are similar to


those of alkenes
Intermediate alkene reacts further with excess
reagent
Regiospecificity according to Markovnikov

141

Electronic Structure of Alkynes

Carbon-carbon triple bond results from sp orbital


on each C forming a bond and unhybridized pX
and py orbitals forming bonds.
The remaining sp orbitals form bonds to other
atoms at 180 to C-C triple bond.
The bond is shorter and stronger than single or
double
Breaking a bond in acetylene (HCCH) requires
318 kJ/mole (in ethylene it is 268 kJ/mole)

142

Addition of Bromine and Chlorine

Initial addition gives trans intermediate


Product with excess reagent is tetrahalide

143

Addition of HX to Alkynes Involves Vinylic


Carbocations

Addition of H-X to alkyne


should produce a vinylic
carbocation intermediate
Secondary vinyl
carbocations form about
as readily than primary
alkyl carbocations
Primary vinyl
carbocations probably do
not form at all
Nonethelss, H-Br can add to
an alkyne to give a vinyl
bromide if the Br is not on a
primary carbon

144

8.4 Hydration of Alkynes

Addition of H-OH as in alkenes

145

Mercury (II) catalyzes - Markovnikov oriented


addition
Hydroboration-oxidation - non-Markovnikov product

Mercury(II)-Catalyzed Hydration of Alkynes

Alkynes do not react with aqueous protic acids


Mercuric ion (as the sulfate) is a Lewis acid
catalyst that promotes addition of water in
Markovnikov orientation
The immediate product is a vinylic alcohol, or
enol, which spontaneously transforms to a
ketone

146

Mechanism of Mercury(II)-Catalyzed Hydration


of Alkynes

Addition of Hg(II) to
alkyne gives a vinylic
cation
Water adds and loses a
proton
A proton from aqueous
acid replaces Hg(II)

147

Keto-enol Tautomerism

Isomeric compounds that can rapidily interconvert


by the movement of a proton are called
tautomers and the phenomenon is called
tautomerism
Enols rearrange to the isomeric ketone by the
rapid transfer of a proton from the hydroxyl to the
alkene carbon
The keto form is usually so stable compared to the
enol that only the keto form can be observed

148

Hydration of Unsymmetrical Alkynes

If the alkyl groups at either end of the C-C triple


bond are not the same, both products can form
and this is not normally useful
If the triple bond is at the first carbon of the chain
(then H is what is attached to one side) this is
called a terminal alkyne
Hydration of a terminal always gives the methyl
ketone, which is useful

149

Hydroboration/Oxidation of Alkynes

BH3 (borane) adds to alkynes to give a vinylic


borane
Oxidation with H2O2 produces an enol that
converts to the ketone or aldehyde
Process converts alkyne to ketone or aldehyde
with orientation opposite to mercuric ion
catalyzed hydration

150

Comparison of Hydration of Terminal Alkynes

Hydroboration/oxidation
converts terminal alkynes
to aldehydes because
addition of water is nonMarkovnikov
The product from the
mercury(II) catalyzed
hydration converts terminal
alkynes to methyl ketones
151

8.5 Reduction of Alkynes

Addition of H2 over a metal catalyst (such as


palladium on carbon, Pd/C) converts alkynes to
alkanes (complete reduction)
The addition of the first equivalent of H2 produces
an alkene, which is more reactive than the alkyne
so the alkene is not observed

152

Conversion of Alkynes to cis-Alkenes

Addition of H2 using chemically deactivated


palladium on calcium carbonate as a catalyst
(the Lindlar catalyst) produces a cis alkene
The two hydrogens add syn (from the same
side of the triple bond)

153

Conversion of Alkynes to trans-Alkenes

Anhydrous ammonia (NH3) is a liquid below -33


C

Alkali metals dissolve in liquid ammonia and function


as reducing agents

Alkynes are reduced to trans alkenes with sodium


or lithium in liquid ammonia
The reaction involves a radical anion intermediate

154

155

8.6 Oxidative Cleavage of Alkynes

Strong oxidizing reagents (O3 or KMnO4) cleave internal


alkynes, producing two carboxylic acids
Terminal alkynes are oxidized to a carboxylic acid and
carbon dioxide
Neither process is useful in modern synthesis were
used to elucidate structures because the products
indicate the structure of the alkyne precursor

156

8.7 Alkyne Acidity: Formation of Acetylide


Anions

Terminal alkynes are weak Brnsted acids


(alkenes and alkanes are much less acidic (pKa ~
25. See Table 8.1 for comparisons))
Reaction of strong anhydrous bases with a
terminal acetylene produces an acetylide ion
The sp-hydbridization at carbon holds negative
charge relatively close to the positive nucleus
(Figure 8.5 in text)

157

8.8 Alkylation of Acetylide Anions

Acetylide ions can react as nucleophiles as well as


bases (see Figure 8-6 for mechanism)

Reaction with a primary alkyl halide produces a


hydrocarbon that contains carbons from both
partners, providing a general route to larger
alkynes

158

Limitations of Alkyation of Acetylide Ions

Reactions only are efficient with 1 alkyl bromides


and alkyl iodides
Acetylide anions can behave as bases as well as
nucelophiles
Reactions with 2 and 3 alkyl halides gives
dehydrohalogenation, converting alkyl halide to
alkene

159

8.9 An Introduction to Organic Synthesis

Organic synthesis creates molecules by design


Synthesis can produce new molecules that are
needed as drugs or materials
Syntheses can be designed and tested to improve
efficiency and safety for making known molecules
Highly advanced synthesis is used to test ideas
and methods, answering challenges
Chemists who engage in synthesis may see some
work as elegant or beautiful when it uses novel
ideas or combinations of steps this is very
subjective and not part of an introductory course

160

Synthesis as a Tool for Learning Organic


Chemistry

In order to propose a synthesis you must be


familiar with reactions

What they begin with


What they lead to
How they are accomplished
What the limitations are

A synthesis combines a series of proposed steps


to go from a defined set of reactants to a specified
product

161

Questions related to synthesis can include partial


information about a reaction of series that the
student completes

Strategies for Synthesis

Compare the target and the starting material


Consider reactions that efficiently produce the
outcome. Look at the product and think of what
can lead to it (Read the practice problems in the
text)
Example

162

Problem: prepare octane from 1-pentyne


Strategy: use acetylide coupling

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