Alkenes: Structure and Reactivity Nomenclature of Alkenes

olefins are hydrocarbons containing

Alkenes, also called ______, vinylic carbons
one or more double bonds.

Naming the alkenes: Hex-2-ene

2-Methylhex-3-ene
Rule 1: Find the longest chain containing the double bond and name the
compound by replacing the alkane suffix –ane with –ene. allylic carbons
Rule 2: Number carbons in the chain so that double bond carbons have the
lowest possible numbers; if the double bond is equidistant from two vinyl group
_____
ends, begin at the end nearer the first substituent.
2 Eth l
2-Ethylpent-1-ene
t1 2-Methylbuta-1 3-diene
2-Methylbuta-1,3-diene allyl group
_____ gro p
Cycloalkenes: -diene and -triene

8-1 8-2

Factoids of Alkenes E,Z Nomenclature

cis or trans?
Polarization of Alkenes Sometimes “cis” and “trans” are ambiguous;
in such cases we resort to the more formal Z
E,Z nomenclature.
m.p. -139 oC m.p. -106 oC

b.p. 4 oC b.p. 1 oC
Steps to assign E and Z descriptors
• For each C atom, assign substituent priority
• Z if highest priority substituents on same side of double bond
• E if highest priority substituents on opposite side of double bond

higher higher hi h
higher l
lower

lower lower lower g

higher

Th barrier
The b i to rotation
i iis very large.
l Thi leads
This l d to the
h possibility
ibili off cis
i and
d
isomers stable, separable compounds with different properties.
trans ________,
8-3 8-4
 Stability of Alkenes Heat of Hydrogenation: a Measure of Stability

∆Ho

more hyperconjugation
8-5 8-6

Preparation of Alkenes Reactions of Alkenes: The C=C Double

Elimination Reactions:
Bond as a Nucleophile
follows Zaitsev’s rule
∆

Ap
pi bo
bond
d ca
can do
donate
aee electrons
ec o s
An E2 reaction that generates
the thermodynamically less
favored isomer is said to
follow the Hofmann rule.
rule

Dehydration of Alcohols: This atom has

H+ re-hybridized
____________
from sp2 to sp3

The brackets denote This carbon now has an empty

intermediate along p orbital; its incomplete octet
an ___________
Reactivity in dehydration: (6 electrons) makes it electron
the reaction pathway
1o < 2o < 3o alcohols 8-7 deficient 8-8
 Classifying Reactants HBr as an Electrophile
Many steps in the mechanisms that we will encounter involve charge distribution
nucleophiles
p
bond formation between ___________ p
electrophiles
and ___________. .

donate electrons
Nucleophiles ______ electrons. Identifying nucleophiles The electrophile revealed
• Lone pairs
• (-) charges
• π bonds

An electronegative atom
accept electrons.
Electrophiles ______ Identifying electrophiles
• Empty orbitals (incomplete octet)
H C • (+) charges 9 Identify
Id tif b bonds
d maded and dbbroken
k
H O δ− • Polarized bonds 9 Identify nucleophiles and
H B • Weak σ bonds electrophiles
δ+ Br Br 9 Draw arrows to indicate reaction
H
mechanism
8-9 8-10

The Reaction Coordinate Diagram for Product Distribution in HX Addition to Alkenes

HBr Addition to Alkenes
In the addition of HX to alkene, the H attaches
along the reaction paths are typically high-energy, to the carbon with more H’s and X attaches to
unstable species.
species Unlike TS≠ however,
however they have fully formed th other
the th end d (to
(t the
th one with
ith more alkyl
lk l
bonds and lie in minima on reaction coordinate diagrams. substituents); this is Markovnikov’s rule.
major minor

8-11 8-12
 Product Distribution and Electrophilic Addition: Alkyl Halide Preparation
the Reaction Coordinate Diagram
• The reaction is successful with HCl and with HI as well as HBr
For this step
step, the TS≠ is • HI is generated from KI and phosphoric acid
late. Thus, we ordered
the energies of the TS≠s
according to the energies
of the intermediates.

Predict the relative reactivity of the following alkenes toward

electrophilic addition of HX and give your explanations.

(CH
(CH3)32)C=CH
2C=CH2 2> CH
CH33CH=CHCH
CH=CHCH33 > CH3CH=CH2 >CH
CH2=CH
2=CH22
8-13 8-14

Rearrangement of Carbocations Electrophilic Hydration of Alkenes

Alkene hydration and alcohol

dehydration are equilibrium processes.

mechanism

Acid Catalyzed
y Equilibration
q of Alkenes

catalytic
H+

catalytic H+ more stable; major component

in isomeric product mixture
8-15 8-16
Electrophilic Addition of Halogen to Alkenes Stereochemistry Elucidates the Mechanism

Br-

a carbocation would
be trigonal planar

O t t satisfied
Octet ti fi d for
f allll atoms
t

a racemic mixture (±) 8-17 8-18

Bromonium Trapped by Other Nucleophiles Regioselectivity in Halonium Ion Opening

Br2

CH3OH
(±)

(±)

similarly following
Markovnikov rule

δδ+
δ+

8-19 8-20
 Oxymercuration and Demercuration Hydroboration-Oxidation: an Anti-
Markovnikov Hydration
H2O2
RCH=CH
RCH CH2 + BH3 (RCH2CH2)3B 3 RCH2CH2OH

Step 1: oxymercuration Step 2: demercuration Borane is commercially available

iin an ether-tetrahydrofuran
th t t h d f solvent.
l t

In manyy cases, the alcohol from

demercuration is the same as acid-
catalyzed hydration of alkenes; however,
because no carbocation intermediate is
mechanism
involved oxymercuration
involved, oxymercuration-demercuration
demercuration
is not susceptible to rearrangement
of carbocation intermediate. Four-center
8-21 transition state 8-22

Mechanism of Hydroboration-Oxidation Carbene Formation and Cyclopropane Synthesis

mechanism

singlet carbene
Consequences:
q (vs. triplet carbene)
anti-Markovnikov;
syn-addition
Carbene formations and reactions:

8-23 8-24
Carbene and Carbenenoid Reactions Reduction of Alkenes: Catalytic Hydrogenation

syn- addition

bicyclo[4.1.0]heptane cis-diethylcyclopropane

Simmons-Smith reagent: (iodomethyl)zinc iodide

“ b
“carbenoid”
id” (a
( carbene-like
b lik substance)
b t )

diastereoselective

92% 8-25 8-26

Oxidation and Reduction in Organic Epoxide Synthesis

Chemistry
electrophilic
Reduction increase electron density on carbon by:
— forming: C–H
δ+
— or breaking: C–O C–N C–X

oxidation by
peroxycarboxylic acid:

Oxidation decrease electron density on carbon by:

— forming: C–O C–N C–X
— or breaking: C–H
via halohydrin:

an epoxide
8-27 8-28
 Diol Formation: Epoxide Ring-Opening Vicinal Syn Dihydroxylation of Alkenes
cold, dilute Not very useful for
(w/ NaOH) synthesis: easily over-
oxidized into ketones
and/or carboxylic acids.

Use of OsO4:
or NaHSO3

+ OsO3

+ OsO3
vicinal anti
dihydroxylation

OsO4: expensive and toxic a syn vicinal diol

8-29 8-30

Oxidative Cleavage: Ozonolysis More Oxidative Cleavages to Carbonyl

Compounds
KMnO4
H+
(or CH3SCH3)

or NaHSO3

mechanism: HIO4

8-31 8-32
 Anti-Markovnikov Product Formation from Mechanism of Radical Chain Addition
Radical Addition of Alkenes
Some weak bonds have a tendency to fragment initiation
homolytically e.g., peroxides

This provides a
pathway to initiate
radical reactions.
Compare:
O–O
propagation

h t
heat anti-Markovnikov product

termination
< < <
Review stability of
carbon-centered radicals

increasing stability 8-33 8-34

Radical Polymerization of Ethylene Polymerization of Other Alkenes

―CH2(CH2)nCH2CH2―

Polymerization of ethylene
happens
pp via a radical mechanism.

regioselectivity of polyolifens

Initiation:

Propagation:

Termination:
2 BzOCH2CH2y BzOCH2CH2CH2CH2OBz
8-35 8-36