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How many H are in C16H?ClN2O if there are three rings, eight double
bonds ?
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7.3 Naming Alkenes
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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
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)
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:
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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.
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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.
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Name these:
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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
A positive C can be stablized by neighbors that can bring some electron cloud over.
2) Hyperconjugation
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Show the structure of the carbocation intermediates you would expect in
the following reactions:
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Summarization of electrophilic addition reactions:
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?
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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.
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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.
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