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Chapter 10

Alkenes: Structure and Reactivity


Alkene - Hydrocarbon With Carbon-Carbon Double Bond
 Also called an olefin
 Hydrocarbon that contains a C-C double bond
Includes many naturally occurring materials
Flavors, fragrances, vitamins
Why this Chapter?

 C=C double bonds are present in most organic and


biological molecules

 To examine consequences of alkene stereoisomerism

 To focus on an important alkene reaction: electrophilic


addition
7.1 Industrial Preparation and Use of Alkenes
 Ethylene and propylene are important organic chemicals
produced in order to synthesize other chemicals.
7.2 Calculating Degree of Unsaturation

 Degree of unsaturation: number of multiple bonds or rings


 Formula for a saturated acyclic compound is CnH2n+2
 Alkene formula is CnH2n
 A ring structure also has formula of CnH2n
 Alkyne formula is CnH2n-2

For a formula that has n Carbons,


the degree of unsaturation = ½(2n+2-No. of H in the formula)
Example: C6H10

This has two degrees of unsaturation. What kind of molecule(s) do you


expect is it?

 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)
 treat a halogen as a hydrogen
 C4H6Br2 and C4H8 have one degree of unsaturation
 Organoxygen compounds (C,H,O) – Oxygen forms 2
bonds
 these don't affect the formula of equivalent
hydrocarbons
 May be ignored in calculating degrees of
unsaturation
 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
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 from the number of H - they have two
connections
Calculate the degree of unsaturation for the following, and then draw
as many structures as you can for each:
a) C4H8 b) C4H6 c) C3H4

Calculate the degree of unsaturation for the following:


a) C6H5N b) C6H5NO2 c)C8H9Cl3 d) C9H16Br2
e) C10H12N2O3 f) C20H32CIN

How many H are in C16H?ClN2O if there are three rings, eight double
bonds ?

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7.3 Naming Alkenes

1) Name the parent hydrocarbon (longest, containing the double


bond, -ene)

2) Number the carbons in chain so that (1) double bond


carbons have lowest possible numbers; (2) branches have
lowest possible numbers
Write the full name- Number substituents according to:
1) Position in chain, 2)Alphabetically.
Give the number of the first alkene carbon.

Use suffixes –diene, -triene, and so on for more than one


double bonds
Rings have “cyclo” prefix in front of the parent name. The double bond is
alwasys between C1 and C2.

Make the first substituent have as low a number as possible.

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New IUPAC is recommended in 1993 but not widely accepted. Be aware
of its existance. Both will be counted correct in exams. Please tell the
difference between the old and new names.

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Some common names are accepted by IUPAC
Give IUPAC names for the following:

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Name the following:

1)2-Methyl-1, 5-hexadiene

2)3-Ethyl-2,2-dimethyl-3-heptene

3)2,3,3-Trimethyl-1,4,6-octatriene

4)3,4-Diisopropyl-2,5-dimethyl-3-hexene

5)2,5,5-Trimethyl-2-hexene

6)2,3-Dimehtyl-1,3-cyclohexadiene

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7.4 Cis-Trans Isomerism in Alkenes

What do you remember about pi- ( )bond?

 Occupied  orbital prevents rotation about -bond

Rotation prevented by  bond - high barrier, about 268


kJ/mole in ethylene
Cis-Trans Isomerism in Alkenes
(Continued)

 Rotation of  bond is prohibitive


 This prevents rotation about a carbon-carbon double
bond (unlike a carbon-carbon single bond).
 Creates possible alternative structures
 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
 Cis-Trans Isomerization requires that end groups differ
in pairs

Need E,Z nomenclature system to distinguish cis and trans double bond
E,Z Stereochemical Nomenclature

 Priority rules of
Cahn, Ingold, and
Prelog (?, chapter 5)

Compare where higher


priority groups are with
respect to bond and
designate as prefix

E -entgegen, opposite
sides (enemy)

Z - zusammen, together
on the same side
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
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
RULE 3
 Multiple-bonded atoms are equivalent to the same number of
single-bonded atoms
Assign E or Z for the following:

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Rank the substituents:

a)–CH3, -OH, -H, -Cl

b)-CH3, -CH2CH3, -CH=CH2, -CH2OH

c)-CO2H, -CH2OH, -C≡N, -CH2NH2

d)-CH2CH3, -C ≡ CH, -C ≡ N, -CH2OCH3

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Assign E or Z for the following:

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Assign E or Z. Convert it to skeletal structure (red = O)

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7.6 Stability of Alkenes
Cis alkenes are less stable than trans alkenes
Evaluate heat given off
when C=C is converted to
C-C
More stable alkene gives
off less heat
 trans-Butene
generates 5 kJ less
heat than cis-butene
 Stability order for alkenes:
 tetrasubstituted > trisubstituted > disubstituted >
monosusbtituted
 hyperconjugation stabilizes

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Stability of Alkenes (Continued)
Why that order
1) Hyperconjugation among  bond and adjacent C-
H  bonds.

 Electrons in neighboring filled  orbital stabilize


vacant antibonding  orbital – net positive interaction
 Alkyl groups are better than H
2) A bond between an sp2 carbon and an sp3 carbon is somewhat
stronger than a bond between two sp3 carbons.

More substituted alkenes have a higher ratio of sp3-sp2 bond.

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Some alkenes are cis/trans, but others are (E)/(Z), what is the difference?

E-Z and cis-trans are describing the same thing, but E-Z gives more
information

If each of the two C only contains one substituent, both cis/trans and E/Z
apply; if the total substituents on the two alkene C is more than two, only
E/Z applies.

It is safe to use E/Z always. But old nomenclature does exists.

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Name these:

Name the following and tell which


compound in each pair is more
stable:

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7.7 Electrophilic Addition of Alkenes (describe the following “old”
reaction)
Alkenes behave as ________ (Lewis ____)

 General reaction
mechanism of
electrophilic addition
 Attack on electrophile
(such as HBr) by bond of
alkene
 Produces carbocation and
bromide ion
 Carbocation is an
electrophile, reacting with
nucleophilic bromide ion
 Two step process
 First transition state is high energy point
 First step is slower than second
 The reaction is successful with HCl and with HI as well as
HBr
 HI is generated from KI and phosphoric acid
Writing organic reactions (both are correct, with different emphasis)

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In biological processes, only the structures of the primary reactant and
product are shown. The coenzymes, enzymes and by-products are
abbreviated.

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7.8 Orientation of Electrophilic Additions: 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 regioselective
Markovnikov observed in the 19th century that in the addition of HX to
alkene, the H attaches to the carbon with more H’s and X attaches to
the other end (to the one with more alkyl substituents)
 This is Markovnikov’s rule
Example of Markovnikov’s Rule

Regioselective
(or regiospecific)
– one product
forms where two
are possible
If both ends have similar substitution, then not regiospecific, and
a mixture of addition products results.

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Markovnikov’s Rule (restated)
In the addition of HX to an alkene, 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. Why? Will be discussed soon.
What product would you expect for the following reaction?

What reactants would you start with for the following product? (More than
one possibility (P243).

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What product would you expect for the following reaction?

What reactants would you start with for the following product? (More than
one possibility.

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7.9 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
Why does tertiary cations and associated transition states are more
stable than primary cations? At least two reasons

 1) Inductive effects from neighbor atoms.

A positive C can be stablized by neighbors that can bring some electron cloud over.
2) Hyperconjugation

Interaction of paralleled neighboring C-H sigma bonds with the


vacant p orbital stabilizes the cation and lowers its energy.

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Show the structure of the carbocation intermediates you would expect in
the following reactions:

Draw a skeletal structure of the


following carbocation. Identify
the primary, secondary, or
tertiary, and identify the
hydrogen atoms that have the
proper orientation for
hyperconjugation in the
conformation shown.

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Summarization of electrophilic addition reactions:

Electrophilic addition gives the more highly substituted carbocation intermediate

A more highly substituted carbocation forms faster than a less substituted one.

A more highly substituted carbocation is more stable than a less substituted one

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7.10 the Hammond Postulate
Why is the reaction through the more stable one faster?

What does the Hammond Postulate state?

“the structure of a transition state resembles the structure of the


nearest stable species. Transition states for endergonic steps
structurally resemble products, and transition states for
exergonic steps structurally resemble reactants”
 Sequential states on a reaction path that are close in
energy are likely to be close in structure - G. S. Hammond
Competing Reactions and the Hammond Postulate
 Normal Expectation: Faster reaction gives more stable intermediate
 Intermediate resembles transition state
 Which one has higher activation energy?
7.11 Evidence for the Mechanism of Electrophilic
Addition: Carbocation Rearrangments
 Carbocations undergo structural rearrangements
following set patterns
 1,2-H and 1,2-alkyl shifts occur
 Goes to give a most stable carbocation
7.11 Evidence for the Mechanism of Electrophilic
Addition: Carbocation Rearrangments
Hydride shifts in biological molecules
For the addition and rearrangement reaction below, propose a mechanism.

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Let’s Work a Problem
Addition of HCl to 1-isopropylcyclohexene yields a
rearranged product. Propose a mechanism, showing the
structures of the intermediates and using curved arrows
indicate electron flow in each step.

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Thermal Cracking: industrial way to produce
ehylene, propylene and butene.

 Thermal cracking may take place w/o catalyst at very high


temperatures
Why it is KI/H3PO4 rather than HI that is used in alkene addition reaction?
Maybe because (1) HI is a List I chemical of DEA (US drug enforcement admin) that can be
used in producing controlled substance (like drugs)

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2) A bond between an sp2 carbon and an sp3 carbon is somewhat
stronger than a bond between two sp3 carbons.

More substituted alkenes have a higher ratio of sp3-sp2 bond. Why?

S orbitals have no nodes and are spherical, and


thus the electron cloud is able to surround the
nucleus more tightly than p orbitals, which have
a node and are dumbbell shaped. The more s
character, the closer the electrons cloud can get
to the nucleus (on average).

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