Alkenes, Alkynes & EA Reaction

Department of Biochemistry Faculty of Pharmacy University of Santo Tomas

Alkenes CnH2n

Alkynes

Alkenes

Cycloalkenes

Alkynes

Alkenes

Physical Properties
Alkenes & alkynes are nonpolar Physical properties are similar to those of alkanes with same C skeletons Those that are liquid at RT have densities <1.0g/mL

Physical Property: Boiling point

Alkenes have diffuse e- cloud; alkanes have stronger interaction; & alkynes e- cloud is tighter than alkenes

ISOMERISM

STRUCTURE OF ALKENES

Alkenes: cis & trans isomerism

cis

trans

H R

H R

R H

H R

All substituents are on one side of bond

All substituents are on different sides of bond

Alkenes: cis & trans isomerism

Alkenes: cis & trans isomerism

Alkenes: cis & trans isomerism

Cis/trans Isomerism in Cycloalkenes

For cycloalkenes with 7 or fewer C atoms, the cis configuration is preferred

Cis/trans Isomerism in Di-, Tri-, & Polyenes

Total # of cis-trans isomers possible = 2n n = # of double bond

Double bond

C2 C3

C4 C5

2,4-heptadiene

trans trans cis cis

trans cis trans cis

What is the correct systematic name for the following?

Br

1. 2. 3. 4. 5.

1-bromo-2-hexene 6-bromo-4-hexene cis-1-bromo-2-hexene trans-1-bromo-2-hexene trans-6-bromo-4-hexene

Alkenes: E/Z System

For more than two substituents the cis/trans, the E/Z system is used.

Alkenes: E/Z System

I H3C H F
H C O H H C C H
path goes to C, not H comparison stops here

H3C H

CH2 OH CH2 CH3

path goes to O, not H

(E)-3-fluoro-2-iodo-2-propene

Alkenes: E/Z System

C H

H H3C

CH CH2 CH2 CH3

CH CH2

C C C H H

H H CH2 CH3 C C H H H

Which is the correct structure for E-3-bromo-2-chloro-2-pentene?

CH3

CH2CH 3 C C Br

CH3

Br C C CH2CH 3

1.
Cl

2.
Cl

CH3

CH2CH 3 C C Cl

CH3

Cl C C CH2CH 3

3.
Br

4.
Br

Alkenes: Stability
The stability of alkenes depends upon number of substituents

Stability of Disubstituted Alkenes

H3C H3C H > H H3C CH3 H H > H CH3 H3C H

ELECTROPHILIC ADDITION & OXIDATION

REACTION OF ALKENES

Reactive Sites of Alkenes & Alkynes

CH3 H3C C H3C CH

Alkenes: Electrophilic Addition

electrophile

R R

R R

R + Y + + Znucleophile

R Y

Z R

Electrophilic addition to the double bond is a two-step process

Alkenes: Electrophilic Addition

Alkenes: Electrophilic Addition

Alkenes: AE - Hydrogenation
CH3 + H2 Pt/C CH3 H H

With the help of metal catalysts, H2 adds to the double bond. (Catalytic Reduction)

Alkenes: AE - Hydrogenation

Alkenes: AE - Hydrogenation

Alkenes: AE - Halogenation

Alkenes: AE - Halogenation

Alkenes: AE - Hydrohalogenation

Electrophilic reagents we can use are hydrogen halides: HF, HCl, HBr, HI

Alkenes: AE - Hydrohalogenation

Alkenes: AE - Hydration

H
HCl, trace CH2 CH2 CH2 CH2 H3C + H2O H3C CH CH
1-butene 2-butanol

OH

Alkenes: AE - Hydration

AE Markovnikovs Rule
HI

I +
H

H
I
2-iodo-1-methylcyclohexane

1-methylcycohexene

1-iodo-1-methylcyclohexane

Major product

Minor product

We obtain both products; however, one is the major product. We have a regioselective reaction.

AE Markovnikovs Rule

In the addition of HX or H2O to an alkene, H adds to the C of the double bond having the greater number of hydrogens.

AE Markovnikovs Rule

AE Markovnikovs Rule

Carbocation Stability

Carbocation Stability

AE Markovnikovs Rule

AE Markovnikovs Rule
HBr

Br H

Br

1-bromo-1-methylcyclopentane

1-bromomethylcyclopentane

AE Markovnikovs Rule

Alkenes: AE Addition of Alcohols

Alcohols react the same way as water
H3C
H3C H3C CH3 CH3 O H2C CH3
ethanol

H
C CH2 + CH3CH2OH

2-methylpropene

tert-butyl-ethyl ether

Note: the reaction works only in the presence of acid.

Alkenes: AE Addition of Alcohols

Alkenes: Oxidation
Cold, alkaline KMnO4

acidic KMnO4

Alkenes: Oxidation
Ozonolysis

Dihydroxylation with OsO4

Alkenes: Oxidation
Hydroboration oxidation

Polymerization of Alkenes
Polymers are large molecules that contain a large number of repeating units of a small molecule (monomer). Biopolymers are typically synthesized by organisms. Synthetic Polymers are made in organic laboratories.

Polymerization of Alkenes
Alkenes can be used as a monomeric unit to form chain-growth polymers

styrene

polystyrene n

Polymerization of Alkenes

Polymerization of Alkenes
For the polymerization, electrophilic addition reactions can be used. BF3

F3 B

In the initiation step an electrophile (BF3) adds to the alkene to form a carbocation intermediate.

Polymerization of Alkenes
Subsequent propagation steps grow the polymer until all monomers are consumed.

F3B

F3B

Polymerization of Alkenes
Termination can also be accomplished by adding a nucleophile.

Nu F3B n

Nu
F3B n

Polymerization of Alkenes
An alternative way to initiate polymerization is starting with a radical initiator. RO OR D (hn) 2 RO
radicals

The radical adds onto the alkene to form a new radical. Propagation is accomplished via subsequent radical additions.
R RO R

R RO

-ELIMINATION REACTION

PREPARATION OF ALKENES

Preparation of Alkenes
-Elimination Reactions Dehydrogenation of alkanes Dehydration of alcohols Dehydrohalogenation of alkyl halides

Dehydrogenation of Alkanes

Dehydration of Alcohols

Zaitsevs Rule

Dehydrohalogenation of RX

ADDITION & DIELS-ALDER REACTIONS

CONJUGATED DIENES

Reaction of Conjugated Dienes

undergo two-step electrophilic addition reactios just as do simple alkenes 1,2 & 1,4-addition

Reaction of Conjugated Dienes

CH2 CH CH CH3
Less Substituted Double Bond (Secondary carbocation)

CH2 CH CH CH3
More Substituted Double Bond (Primary carbocation)

Diels-Alder Reaction: Cycloaddition

+

ADDITION, OXYDATION, & ACIDITY OF TERMINAL ALKYNES

REACTION OF ALKYNES

Reactivity of Alkynes

Hydrohalogenation

Hydrohalogenation

Halogenation

Hydration

Hydration of Alkyne & Tautomerism

Draw the ENOL tautomers of the following ketones:

Catalytic Reduction

Oxidation

Acidity of Terminal Alkynes

HC CH + NH2 HC C + H3N

Acidity of Terminal Alkynes

-FIN-