CHAPTER 2

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 complex alkenes react
with bromine in the same way

3
Functional Groups with Multiple Carbon–
Carbon 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

4
Functional Groups with Carbon Singly Bonded to an
Electronegative Atom

5
Groups with a Carbon–Oxygen Double Bond
(Carbonyl Groups)

6
Survey of Functional Groups

7
Survey of Functional Groups

8
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 C’s is n
 Alkanes are saturated with hydrogen (no more can be added
 They are also called aliphatic compounds

9
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 2,2-dimethylpropane
 Alkanes with C’s connected to no more than 2 other C’s are
straight-chain or normal alkanes
 Alkanes with one or more C’s connected to 3 or 4 C’s 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
 CH3CH2CH2CH3 (butane)
 CH3(CH2)2CH3 (butane)

12
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)
 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)

16
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 H’s
with Cl’s (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 open-chain
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
 We’ve 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
1. Find the parent. # of carbons in the ring.
1. 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.
2. If the no. of C in the ring is less then name as cycloalkyl-
substituted alkane.

34
Naming Cycloalkanes
2. Name the substituent.
 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 C’s 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 C–C–C 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
 The bend increases angle strain but decreases torsional strain

44
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
 The fifth carbon atom is above or below the plane – looks like
an envelope

45
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 aren’t 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 chair
cyclohexane conformations
 Flips and rotations do not interconvert cis and trans
57
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
 Two double bonds?
 or triple bond?
 or two rings
 or ring and double bond

64
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
 Three equivalent orbitals at 120º separation in plane
 Fourth orbital is atomic p orbital
 Combination of electrons in two sp2 orbitals of two atoms
forms  bond between them
 Additive interaction of p orbitals creates a  bonding 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
 180°rotation 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 cis-butene

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:
Markovnikov’s 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 H’s and
X attaches to the other end (to the one with the most alkyl
substituents)
 This is Markovnikov’s rule

85
Example of Markovnikov’s Rule
 Addition of HCl to 2-
methylpropene
 Regiospecific – one product
forms where two are possible
 If both ends have similar
substitution, then not
regiospecific

86
Markovnikov’s 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 (Gº)
 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)
 Uses heat and KOH
 elimination of H-OH from
an alcohol (dehydration)
 require strong acids (sulfuric
acid, 50 ºC)

100
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-
 Br2 is similar

101
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
 Gives trans addition

103
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 trans-dibromide 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 (Br2 or Cl2 in water in
an organic solvent)

106
Mechanism of Formation of a Bromohydrin
 Br2 forms bromonium ion,
then water adds
 Orientation toward stable
C+ species
 Aromatic rings do not react

107
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
 via mercurinium ion

110
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
 Non-Markonikov product

111
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 H’s
 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 Cl- gives
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 H2 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
 Sensitive to steric environment

120
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 H’s 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 1,2-
dihalidoalkane 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
π bonds.
 The remaining sp orbitals form bonds to other atoms at 180º
to C-C triple bond.
 The bond is shorter and stronger than single or double
 Breaking a π 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
 Mercury (II) catalyzes - Markovnikov oriented addition
 Hydroboration-oxidation - non-Markovnikov product

145
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 non-Markovnikov
 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 ºC
 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 Brønsted 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 1º alkyl bromides and alkyl
iodides
 Acetylide anions can behave as bases as well as nucelophiles
 Reactions with 2º and 3º 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
 Questions related to synthesis can include partial information
about a reaction of series that the student completes

161
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
 Problem: prepare octane from 1-pentyne
 Strategy: use acetylide coupling

162