Chapter Eight

Alkenes and Alkynes I. Addition Reactions

WWU -- Chemistry

Chapter 8, Problem Assignments (up to Sect 8.6)

In Text problems: 1 b, c, d, e ,g 2 a, b, d, e 3 4 b, c, d, f , i, k 5 6 c, d, e 7 a, b, c, e 8, 9, 10, 11 14 End of Chapter problems: 31, 32, 35, 36, 41b 43 c, d

WWU -- Chemistry

Complete set of problems

In Text problems: 1 b, c, d, e ,g 2 a, b, d, e3 4 b, c, d, f , i, k 5 6 c, d, e 7 a, b, c, e 8, 9, 10, 11 14 16 17 a, b 18, 19 21- 28 End of Chapter problems: 31, 32, 35, 36 41 b 43 c, d 45 49, 50, 52, 53 a 55, 56, 58, 70 b, d, e, h, k, m 72 a, b, d, e, h
WWU -- Chemistry

Sect 8.1: Addition Reactions

Y C C + X Y C X C

WWU -- Chemistry

Addition of H-X
H H C H C H H H X H H C C X H H

X H H H X H H
WWU -- Chemistry

Addition of Water
H C H C H H H O H H

H catalyst

H H C C

H H OH

OH O H H H H
WWU -- Chemistry

H+ catalyst

H H

Sect. 8.2: Introduction to Mechanisms

mechanism two step rate determining step (i.e. slow step) energy diagram transition states intermediates

WWU -- Chemistry

MECHANISM
STEP-BY-STEP ACCOUNT OF WHAT HAPPENS

:Xstep 1

X C C E

C C
+

step 2

C C + E

Intermediate

intermediates are formed during a reaction but are not products

WWU -- Chemistry

ENERGY PROFILE
two step reaction TS1 intermediate TS2
-

E N E R G Y

X
C C + E
step 1 step 2

C C E
+

DH product

X C C
E
WWU -- Chemistry

ACTIVATED COMPLEXES
X C C
+ -

correspond to transition states for each step

X C C E

C C + E
intermediate

X C

C C

+E
ACTIVATED COMPLEXES

+ E

show bonds in the process of breaking or forming (bonds are half formed or half broken)
WWU -- Chemistry

Sect 8.3: Electrophilic Addition to a Double Bond

CH2

CH2

CH2 CH2

WWU -- Chemistry

Hyperconjugation
H Empty p-orbital

H C H H C H

WWU -- Chemistry

CARBOCATION STABILITY
HYPERCONJUGATION

..
C C
H H
R
R

R R

electrons in an adjacent

C-H s bond help to stabilize the positive charge of the carbocation by proximity (overlap)

Most stable

C R + R
R

C +

>

R CH R +
secondary

CH +

>

tertiary

R CH2 +
primary

CH2 +

Least stable
WWU -- Chemistry

Can you recognize the following carbocations? 1o, 2o, 3o

+ + +

2o
+

2o

3o

2o

2o
WWU -- Chemistry

Sect 8.4: Addition of Hydrogen Halides: Markovnikovs rule

CH3 Br C H3C CH3 C H3C CH2 CH3 H C H3C Br C H H C H H H

major product

H-Br

minor product

WWU -- Chemistry

Markovnikovs Rule
In the ionic addition of an acid to the carbon-carbon double bond of an alkene, the hydrogen of the acid attaches itself to the carbon atom which already holds the greater number of hydrogens.
Them that has, gets!

The richer get richer!

(V. W. Markovnikov -- 1838 - 1904)
WWU -- Chemistry

Markovnikov
Markovnikov

Not Markovnikov
WWU -- Chemistry

WWU -- Chemistry

MARKOVNIKOV RULE
When adding HX to a double bond the hydrogen of HX goes to the carbon which already has the most hydrogens

CH2 + HCl

CH3 Cl

..... conversely, the anion X adds to the most highly substituted carbon ( the carbon with most alkyl groups attached).
WWU -- Chemistry

REGIOSELECTIVE REACTION
CH3 CH3 C CH2
HCl

CH3 CH3

CH3

C CH3 + CH3 CH CH2

Cl
major minor

Cl

one of the possible products is formed in larger amounts than the other one Compare

REGIOSPECIFIC
only one of the possible products is formed (100%).
WWU -- Chemistry

Mechanism (Markovnikov)
1) R CH CH2 + + H slow R CH-CH2 H

Electrophile

Secondary C+
fast R CH CH2 H Br

2)

CH-CH2 H +

_ Br

+
Nucleophile

Major product
WWU -- Chemistry

Mechanism (anti-Markovnikov)
1) R CH CH2 + + H slow R

+ CH CH2
H

Primary carbocation
+ CH
2

2)

CH H

_ + Br

fast

CH CH2 Br H

Minor!
WWU -- Chemistry

COMPETING PATHWAYS
rate-determining step
slower faster

higher energy intermediate

lower energy intermediate

1o 2o

rate-determininng (slow) step

WWU -- Chemistry

Markovnikov Addition to an Alkene

CH3 C CH3 CH2 + H X CH3 CH3 C X major product X = Cl, Br, I CH2 H + CH3 CH3 C H minor product CH2 X

WWU -- Chemistry

Mechanism
CH3

1)
CH3

CH2

slow

CH3 CH CH3 CH2

Electrophile

+ 3 o C+
H C CH2

CH3

H C

2)
CH3

_ +
X

fast

CH3

CH2

CH3

Nucleophile

WWU -- Chemistry

SOME ADDITIONAL EXAMPLES

only major product is shown

CH3 + HCl

CH3 Cl

CH2 + HCl

CH3 Cl

CH CH2 + HCl

CH CH3 Cl

WWU -- Chemistry

Sect 8.5 Addition of Sulfuric Acid to an Alkene

R CH CH2 + H2SO4 R CH CH2 H O O S OH an alkyl hydrogen sulfate O (cold, concentrated)

WWU -- Chemistry

ALKYL HYDROGEN SULFATES

-O
SLOW
C C C C + H

O S O H O O SO 3 H C C H
alkyl hydrogen sulfate

O
H O S O H O cold
FOLLOWS MARKOVNIKOFF RULE

OH C C H

water room temp

WWU -- Chemistry

Addition of Water to an Alkene

H2SO4 R CH CH2 H OH an alcohol

CH CH2

H2O

WWU -- Chemistry

Mechanism of Hydration
1) R CH CH2 + H2SO4 slow _ R CH CH2 H +

HSO4

2)

CH CH2 H

H2O

CH CH2 H

+ OH2
_ O R CH CH2 H OH + H O S O OH

3)

CH CH2 H

HSO4

+ OH2

WWU -- Chemistry

Sect 8.6 Addition of Bromine to an Alkene

Br R CH CH R + Br2 CCl4 or CH2Cl2 R CH CH Br R

WWU -- Chemistry

ADDITION OF BROMINE
Br C C
CCl 4

Br
C C Br

SLOW
Br Br

C C + Br

Br

Br

alkene polarizes bromine

WWU -- Chemistry

THE REACTION IS STEREOSPECIFIC

ANTI ADDITION

Br

anti

H Br H

open carbocation would give both cis and trans

Br
Br

syn

syn

anti

H Br H
trans compound ACTUAL PRODUCT
WWU -- Chemistry

H
Br
cis compound

Br

Br

NOT OBSERVED

WHAT WOULD EXPLAIN FORMATION OF ONLY THE trans PRODUCT ?

..... A BRIDGED OR CYCLIC INTERMEDIATE

WWU -- Chemistry

CYCLIC BROMONIUM ION

note size of bromine

+ + Br

WWU -- Chemistry

BRIDGED BROMONIUM ION

Br
H H

Br Br

Br
bridging blocks approach from this side
WWU -- Chemistry

FORMATION OF ENANTIOMERS
Br
symmetric intermediate

H Br H
Addition could also start from the top with bromide attacking the bottom.

H Br H
ENANTIOMERS

Br H Br
WWU -- Chemistry

Br

ADDITION OF BROMINE TO 2-BUTENE

CH3 CH CH CH3 + Br2 CH3

* H *C H C H C 3
Br Br

2n possible stereoisomers
CH3 H CH3 H H CH3

CH3 H

cis-2-butene

trans-2-butene

WILL THESE STEREOISOMERS GIVE THE SAME PRODUCTS?

WWU -- Chemistry

NO ! THEY GIVE DIFFERENT PRODUCTS

CH 3 CH 3 H Br 2 / CCl4 Br CH 3 H Br Br Br H CH 3 Br H CH 3 CH 3 H H

cis
H

trans
CH 3 Br 2 / CCl4 Br H CH 3

H + H CH 3 CH 3

enantiomers

meso

These results can only be explained by stereospecific anti addition.

WWU -- Chemistry

cis
H
H 3C

H
CH 3 Br Br

Br

H H 3C

Br H

CH3

B r+
ADD TO RIGHT

ADD TO LEFT

Br H H 3C

H
CH3 Br

H H3C Br

Br H C H3
ROTATE

ROTATE

Br Br
ENANTIOMERS

Br Br CH3 H H3C H

H H3 C

CH3
WWU -- Chemistry

_
Br CH3 H H3C H Br +
ADD TO RIGHT

trans
CH3 H H 3C Br Br H

Br

ADD TO LEFT

Br H H 3C

CH3 H Br
ROTATE

H H 3C Br

Br CH3 H
ROTATE

Br Br
MESO

Br Br H CH3 H 3C H CH3 H
WWU -- Chemistry

H H3C

IDENTICAL (also meso)

Bromination of an Unsymmetrical Alkene

1) R CH CH2 + Br Br Br slow R CH

+
_ CH2 + Br

2) R CH

Br

+
CH2

Br C R H C

H H Br

. _ : Br: .

anti-addition (stereospecific)
WWU -- Chemistry

Stereochemistry of Bromination of Alkenes

Simple alkenes: Addition of bromine or chlorine goes exclusively anti, with the formation of a bridged ion If a resonance-stabilized open-chain carbocation is possible, there may be a mixture of mechanisms, with some molecules reacting via a bridged ion and some molecules reacting via an openchain carbocation
WWU -- Chemistry

Stereochemistry of Bromination of Alkenes --Part Two

In cases where a resonance-stabilized carbocation is possible, if the solvent is made more polar (acetic acid or nitromethane), the proportion of molecules reacting via an open-chain carbocation increases. For simple alkenes, changing solvents has little or no effect on stereochemistry.
WWU -- Chemistry

Sect 8.7 Halohydrin Formation

OH R-CH=CH-R Br2 H2O R CH CH Br a bromohydrin
Br2 + H2O HO-Br + HBr

+ HBr

WWU -- Chemistry

Mechanism
Br slow R CH CH2 + Br Br R CH CH2 + Br

Br R CH CH2 O H Br R CH O H H H CH2 R CH O H R CH O H

Br CH2

H Br CH2 + H

WWU -- Chemistry

Sect. 8.8: Carbocation Rearrangements

CH3 CH3 C CH3 CH CH2 HCl CH3 C Cl major rearranged!! CH CH3 CH3 H CH2 CH3 + CH3 C CH H CH2

CH3 Cl minor not rearranged!!

WWU -- Chemistry

Sect 8.10 Free Radical Addition of HBr to Alkenes (anti-Markovnikov!)

R CH CH2 ROOR + HBr R CH CH2 Br H

WWU -- Chemistry

ADDITION OF HBr
c onc . HBr CH 2 c onc . HB r CH 2 CH 2 Br CH 3 Br

Markovnikov Addition

Oxygen

Anti-Markovnikov Addition
WWU -- Chemistry

1)

light or R heat

.. O. ..

.. .O ..

2)

.. O. ..

..
+ H Br R O .. H +

.. : Br . ..

hydrogen abstraction

3)

..

: Br . ..

CH2 CH R

slow

Br

CH2 CH R .

4)

Br

CH2 CH R .

Br

Br

CH2 CH R H

.. : Br . . .. .

hydrogen abstraction
WWU -- Chemistry

STABILITY OF CARBON RADICAL INTERMEDIATES

Radicals are electron-deficient just like carbocations and have the same stability order.
R R R < R C H < R CH2 < CH3

lowest energy

highest energy

tertiary

secondary

primary

methyl

and they are stabilized by resonance and / or hyperconjugation.

() () () CH 2

( ) () ()
WWU -- Chemistry

() C H2

etc.

Sect. 8.11 and 8.12: Hydrogenation of Alkenes and alkynes

Pt, Pd, R CH CH R + H2 or Ni R CH CH R H H

syn-addition R R C C R H2 lindlar catalyst H H

WWU -- Chemistry

(stereospecific) R

Hydrogenation of Alkenes
Pt, Pd, R CH CH R + H2 or Ni R CH CH R H H

syn-addition (stereospecific)

Also PtO2 -- sometimes Ru, Rh, or Re

WWU -- Chemistry

HYDROGEN ADSORBS ON THE SURFACE OF THE CATALYST

n H2 +
finely-divided particles dispersed in solution

Pt
H.

Pt(H .)2n
H.

H.

Hydrogen Adsorbed on Catalyst Surface

. H
Pt Pt Pt

. H
Pt Pt

. H
Pt

Pt

Pt

Pt

Pt

Pt
WWU -- Chemistry

MECHANISM OF HYDROGENATION

. H
. H

. H

. H

. H

. H
CATALYST

. H
WWU -- Chemistry

MECHANISM OF HYDROGENATION

. . H H . . H H

. H
. H . H . H

. H
HYDROGEN ADSORBS

WWU -- Chemistry

MECHANISM OF HYDROGENATION
R R
R

. . H . H

. . H H . . H H

. H

. H . H
ALKENE APPROACHES

WWU -- Chemistry

MECHANISM OF HYDROGENATION

. . . H H . . H H

. H

. . H . H

. H

ALKENE PICKS UP TWO HYDROGENS

. H
WWU -- Chemistry

MECHANISM OF HYDROGENATION
R R R R
ALKANE IS FORMED

. . . H

. H

. H
. H

. H

. H

. H

. H
WWU -- Chemistry

BOTH HYDROGENS ADD TO THE SAME SIDE OF THE DOUBLE BOND CH3 not H observed anti addition

CH3 CH3

CH3 CH3
CH3 H H syn addition
WWU -- Chemistry

EXAMPLES
CH3 + H2 Pt CH3

CH3 CH CH CH3 + H2 CH2 + H2 Pt

Pt

CH3 CH2 CH2 CH3 CH3

WWU -- Chemistry

Sect. 8.12: Addition to Alkynes

R H-X C C-H R C X anti addition C H X H H-X R C X C H H H

Br2 C C-H

R C Br C

Br Br2 H R

Br C Br

Br C Br H

anti addition

WWU -- Chemistry

Hydration of an Alkyne
O R C C-H + H2O H2SO4 HgSO4 H R C H C H

WWU -- Chemistry

Hg 2+ R C C H slow R

C 2+ Hg

H O H H

Mechanism of Alkyne Hydration

R C O H C H Hg + - H+ H

R C O H C

Hg+

acid hydrolysis

H C C H H ENOL

R C O

H C H H

Hg2+
O

KETO

WWU -- Chemistry

Keto-Enol Tautomerism
Tautomers: Two compounds with different structures but which exist in equilibrium. Most often, the two structures differ by the position of a proton. NOTE CAREFULLY: This is equilibrium, not resonance!
R C H O: . C H ENOL :O .. H R C H C H KETO
WWU -- Chemistry

Sect. 8.13: Addition of HCN and acetic acid to an alkyne

O R R C C H + CH3 OH O C CH3 R N C N C C H H O C C H H

H-C

WWU -- Chemistry

Sect. 8.14: Addition Polymers

H C H ethylene C H H H polyethylene H H catalyst C H C

a macromolecule with very high molecular weight

WWU -- Chemistry

Polymerization of propene
CH3 C H C H CH3 CH3 isotactic H catalyst three different forms syndiotactic, isotactic and atactic

CH3

CH3

CH3

CH3

CH3

CH3 syndiotactic

WWU -- Chemistry

Polymer Problems
Be sure to look at the mechanism of free radical polymerization of styrene (p. 733735). In-Text Problems 8-27, 8-28, and 8-29 End of chapter problems: 59, 60, and 62

WWU -- Chemistry

Highlights of Chapter 8
HX addition to alkenes/ Markovnikovs Rule Addition of water to alkenes, H+ catalyst Addition of halogens to alkenes/ stereochem. Addition of X2 / H2O to alkenes Carbocation rearrangements Free-radical addition of HBr (Anti-Mark.) Hydrogenation Additions to alkynes Addition polymers
WWU -- Chemistry