5.
Alkenes: Structure
and Reactivity
Assoc. Prof. Ph. D. Tran Thuong Quang
Department of Organic Chemistry
School of Chemical Technology
HUST
5.1Alkene - Hydrocarbon With
Carbon-Carbon Double Bond
n Includes many naturally occurring
materials
n Flavors, fragrances, vitamins
n Important industrial products
n These are feedstocks for industrial
processes
2
Alkenes
3
5.2 Degree of Unsaturation
độ bất bão hoà
n Relates molecular formula to possible structures
n Degree of unsaturation: number of multiple bonds or rings
n Formula for a saturated acyclic compound is CnH2n+2
n Each ring or multiple bond replaces 2 H's
4
Example: C6H10
n Saturated is C6H14
n Therefore 4 H's are missing
n This has two degrees of unsaturation
n Two double bonds?
n or triple bond?
n or two rings
n or ring and double bond
5
Other Examples of C6H10:
6
Degree of Unsaturation With Other
Elements
n Organohalogens (X: F, Cl, Br, I)
Halogen replaces hydrogen cộng chỉ số của halogen như H
n
n C4H6Br2 and C4H8 have one degree of unsaturation
n Oxygen atoms: these don't affect the total count of H's
C4H8O3 7
Degree of Unsaturation With Other
Elements
8
If C-N Bonds Are Present
n Nitrogen has three bonds
n So if it connects where H was, it adds a connection point, and
there an extra H
n Subtract one H for equivalent degree of unsaturation in
hydrocarbon thay 1H=NH2
-> bỏ 1H thêm 2H
-> có 1N sẽ cần trừ đi 1H
9
Summary - Degree of
Unsaturation
nCount pairs of H's below CnH2n+2
nAdd number of halogens to
number of H's (X equivalent to H)
nDon't count oxygens (oxygen
does not affect the # of H’s)
nSubtract N's - they have three
connections
10
5.3 Naming of Alkenes
n Find longest continuous carbon chain for root of the name
n Number carbons in chain so that double bond carbons have lowest
possible numbers
n Double bond carbons must be numbered consecutively
tìm mạch dài nhất chứa nối đôi
đánh số sao cho nối đôi (nếu nối đi đối xứng thì xét đến vị trí nhóm thế) có số thứ tự nhỏ nhất
11
Alkene Nomenclature: longest
chain must contain the C=C
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Alkene Nomenclature
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Cycloalkene nomenclature
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Cycloalkene nomenclature
1 CH3 CH3 CH3
3 4
2 2 1
1 2
1-methylcyclohexene 3-methylcyclohexene 4-methylcyclohexene
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Problem 5.1 IUPAC
3 methyl 3 hexene
3,4,4 trimethyl 1 pentene
2,5 dimethyl 3,6 octandiene
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Problem 5.2
1,2 dimethyl 1 cyclohexene
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Many Alkenes Are Known by
Common Names
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Alkene Group Names
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5.4 Electronic Structure of Alkenes
n Carbon atoms in a double bond are sp2-
hybridized
n Three equivalent orbitals at 120º separation in
plane
n Fourth orbital is an unhybridized p orbital
n Combination of an electron pair in an orbital
formed by the overlap of two sp2 orbitals of
two atoms forms s bond between them
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sự hình thành của liên kết
pi ngăn cản sự quay
21
5.4 Electronic Structure of Alkenes
Tính chất nối đôi: giàu electron (nucleophiles)
n Additive interaction (overlap) of p orbitals
creates a p bonding orbital
n Subtractiveinteraction creates a p anti-
bonding orbital
n Occupied p orbital prevents rotation about
s-bond
n Rotation prevented by p bond - high barrier,
about 268 kJ/mole in ethylene
22
Rotation of p Bond Is Energetically
Costly
n This prevents
rotation about a
carbon-carbon
double bond (unlike
a carbon-carbon
single bond).
n Creates possible
geometric isomers
(cis/trans)
23
5.5 Cis-Trans Isomerism in Alkenes
n The presence of a carbon-carbon double can create two possible
structures
n cis isomer - two similar groups on same side of the double bond
n trans isomer similar groups on opposite sides
n Each carbon must have two different groups for these isomers to
occur
trong các chất béo các H thường ở trạng thái cis
khi đun nóng, chiên dầu -> các lk đổi bị phá vỡ, 1 số lk đôi tồn tại sẽ chuyển thành đồng phân trans bền hơn
24
-> trans fat là chất béo ở dạng trans # chất béo chuyển hoá -> ko tốt cho sức khoẻ
Cis, Trans Isomers Require That End
Groups Must Differ in Pairs
25
5.6 Sequence Rules: The E,Z
Designation
n Neither compound is
clearly “cis” or “trans”
n Substituents on C1 are
different than those on
C2
n We need to define
“similarity” in a precise
way to distinguish the
two stereoisomers
n Cis, trans nomenclature
only works for
disubstituted double
bonds đồng phân cis, trans chỉ dùng
cho gốc ankin
26
Develop a System for Comparison of
Priority of Substituents
xác định mức độ ưu tiên
cùng hướng: E
ngược hướng: Z
n Assume a valuation
system
n If Br has a higher
“value” than Cl
n If CH3 is higher than H
n Then, in A, the higher
value groups are on
opposite sides
n In B, they are on the same
side
n Requires a universally
accepted “valuation”
27
Ranking Priorities: Cahn-Ingold-
Prelog Rules quy tắc CIP
n Must rank atoms that are connected at
comparison point
n Higher atomic number gets higher priority
In this case,The higher priority
groups are opposite:
(E )-1-bromo-1-chloro-propene
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E,Z Stereochemical Nomenclature
n Priority rules of
Cahn, Ingold, and
Prelog
n Compare where
higher priority group
is with respect to
bond and designate
as prefix
n E -entgegen,
opposite sides
n Z - zusammen,
together on the
same side
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2-chloro-2-butenes
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Extended Comparison
n If atomic numbers are the same, compare at next
connection point at same distance
n Compare until something has higher atomic number
n Do not combine – always compare
32
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Dealing With Multiple Bonds
n Substituent is drawn with connections shown and no double
or triple bonds
n Added atoms are valued with no ligands themselves
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Some Examples:
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Practice problem 5.1
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Solution
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Problem 5.3 E, Z
Z E
E
Z
C,O,O cao hơn C,O
C có CH3 cao hơn C ko có
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Problem 5.4 E or Z?
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5.7 Alkene Stability
n Cis alkenes are usually less stable than trans
alkenes
41
42
5.8 Alkene Stability
n Compare heat given off on hydrogenation:
DHo
n Less stable isomer is higher in energy and
gives off more heat
n tetrasubstituted > trisubstituted >
disubstituted > monosusbtituted
43
Comparing Stabilities of Alkenes
n Evaluate heat given off when C=C is
converted to C-C (catalytic hydrogenation)
n More stable alkene gives off less heat (DH)
44
Heats of hydrogenation of butenes
45
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Equilibration of 2-butenes
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Alkene Stability
n Compare heat given off on hydrogenation:
DHo
n Less stable isomer is higher in energy and
gives off more heat
n tetrasubstituted > trisubstituted >
disubstituted > monosusbtituted
48
49
Alkene Stabilities from DH’s:
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Hyperconjugation
n Electrons in neighboring filled s orbital stabilize vacant
antibonding p orbital – net positive interaction
n Alkyl groups are more stabilizing than H
51
Bond strengths/hybridization effects
n sp3-sp3 bond is weaker than sp3-sp2, sp2-sp2
52
Name each; which is more stable?
Problem 5.5
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5.9 Electrophilic Addition Reactions
of Alkenes
n General reaction mechanism: electrophilic
addition
n Attack of electrophile (such as HBr) on p
bond of alkene produces carbocation and
bromide ion
n Carbocation is itself an electrophile, reacting
with nucleophilic bromide ion
54
Examples:
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Writing Organic Reactions
n No established convention – shorthand
n Can be formal kinetic expression
n Not necessarily balanced
n Reactants can be before or on arrow
n Solvent, temperature, details, on arrow
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For Example:
57
Addition of
HBr to 2-
methylpropene
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Electrophilic Addition Energy Diagram:
59
Electrophilic Addition for Syntheses
n The reaction is successful with HCl and with HI as well as
HBr. Note that HI is generated from KI and phosphoric acid
60
5.10 Orientation of Electrophilic Addition:
Markovnikov’s Rule
n In an unsymmetrical alkene, HX reagents can
add in two different ways, but one way may be
preferred over the other
n If one orientation predominates, the reaction is
regiospecific
n 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)
n This is Markovnikov’s rule
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Example of Markovnikov’s Rule
n Addition of HCl to 2-methylpropene is regiospecific – one
product forms where two are possible
n If both ends have similar substitution, then the reaction is not
regiospecific
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Examples:
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But:
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Practice Problem 5.2
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Solution:
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Practice Problem 5.3 :
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Solution:
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Problem 5.6: Major products?
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Problem 5.7: Which alkene would
you add HX to?
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Stability of Carbocations and
Markovnikov’s Rule
n More stable carbocation forms faster
n Tertiary cations and associated transition states are more stable than
primary cations
71
72
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Mechanistic Source of Regiospecificity in
Addition Reactions
n If addition involves a
carbocation intermediate
n and there are two
possible ways to
add
n the route producing
the more alkyl
substituted cationic
center is lower in
energy
n alkyl groups
stabilize carbocation
74
5.11 Carbocation Structure and
Stability
n Carbocations are planar
n The positively charged carbon is
surrounded by only 6 electrons in
three sp2 orbitals
n The fourth orbital on carbon is a
vacant p-orbital
75
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5.12 Carbocation Structure and
Stability
n The stability of the carbocation
(measured by energy needed to form it
from R-X) is increased by the presence
of alkyl substituents
n Therefore stability of carbocations:
3º > 2º > 1º > +CH3
77
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Heterolytic bond dissociations
energies:
79
Stabilizing Carbocations:
80
Stabilizing Carbocations:
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Problem 5.8 : carbocation structure?
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5.13 The Hammond Postulate
n If one carbocation intermediate is more stable
than another, why is the reaction through the
more stable one faster?
n The relative stability of the intermediate is
related to an equilibrium constant (DGº)
n The relative stability of the transition state
(which describes the size of the rate constant)
is the activation energy (DG‡)
n The transition state is transient and cannot be
examined
83
Transition State Structures
n A transition state is the highest energy species
in a reaction step
n By definition, its structure is not stable enough to
exist for one vibration
n But the structure controls the rate of reaction
n So we need to be able to guess about its
properties in an informed way
n We classify them in general ways and look for
trends in reactivity – the conclusions are in the
Hammond Postulate
84
Statement of the Hammond Postulate
n A transition state should be similar to an intermediate that is
close in energy
n Sequential states on a reaction path that are close in energy
are likely to be close in structure - G. S. Hammond
In a reaction
involving a
carbocation, the
G transition states
carbocation look like the
intermediate 85
Reaction
Competing Reactions and the
Hammond Postulate
n Normal Expectation: Faster reaction gives more stable
intermediate
n Intermediate resembles transition state
86
“Non-Hammond” Behavior
n More stable intermediate from slower reaction
n Conclude: transition state and intermediate must
not be similar in this case – not common
87
Transition State for Alkene
Protonation
n Resembles carbocation intermediate
n Close in energy and adjacent on pathway
n Hammond Postulate says they should be similar in structure
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Transition State resembles cation
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Energy Diagrams for Markovnikov
& Anti-Markovnikov Addition
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5.14 Mechanism of Electrophilic Addition:
Rearrangements of Carbocations
n Carbocations undergo structural
rearrangements following set patterns
n 1,2-H and 1,2-alkyl shifts occur
n Goes to give more stable carbocation
n Can go through less stable ions as
intermediates
91
Carbocation rearrangements:
92
Hydride Shifts
93
Alkyl (methyl) shifts
94
Cholesterol Biosynthesis:
95
Problem 5.9: What will be the
rearranged cations?
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Problem 5.10: mechanism?
97
HBr
H
H-shift
Br-1
Br
98
Problem 5.11: mechanism?
99
Problem 5.12: mechanism?
100
H3C H3C
CH2 CH3
CH3 CH3
CH3
CH3
CH3
CH3
CH3
CH3
Cl
101
Terpenes
102
Terpenes
103
Terpene Biosynthesis
104
105
Limonene biosynthesis
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