Alkenes

Functional Group
Pi bond is the functional group. More reactive than sigma bond. Bond dissociation energies:
C=C BDE C-C BDE Pi bond 146 kcal/mol -83 kcal/mol 63 kcal/mol
=>
2

Orbital Description
Sigma bonds around C are sp2 hybridized. Angles are approximately 120 degrees. No nonbonding electrons. Molecule is planar around the double bond. Pi bond is formed by the sideways overlap of parallel p orbitals perpendicular to the plane of the molecule. =>
3

Bond Lengths and Angles

Hybrid orbitals have more s character. Pi overlap brings carbon atoms closer. Bond angle with pi orbitals increases.
Angle C=C-H is 121.7 Angle H-C-H is 116. 6 =>
4

Pi Bond
Sideways overlap of parallel p orbitals. No rotation is possible without breaking the pi bond (63 kcal/mole). Cis isomer cannot become trans without a chemical reaction occurring.

=>
5

Elements of Unsaturation
A saturated hydrocarbon: CnH2n+2 Each pi bond (and each ring) decreases the number of Hs by two. Each of these is an element of unsaturation. To calculate: find number of Hs if it were saturated, subtract the actual number of Hs, then divide by 2. =>
6

Propose a Structure:
for C5H8
First calculate the number of elements of unsaturation. Remember:
A double bond is one element of unsaturation. A ring is one element of unsaturation. A triple bond is two elements of unsaturation. =>

IUPAC Nomenclature
Parent is longest chain containing the double bond. -ane changes to -ene. (or -diene, -triene) Number the chain so that the double bond has the lowest possible number. In a ring, the double bond is assumed to be between carbon 1 and carbon 2. =>
8

Name These Alkenes

CH2 CH CH2 CH3

1-butene
CHCH2CH3

CH3

C CH CH3 CH3

H3C

2-sec-butyl-1,3-cyclohexadiene

2-methyl-2-butene
CH3

3-methylcyclopentene

3-n-propyl-1-heptene =>
9

Common Names
Usually used for small molecules. Examples:
CH3 CH2 CH2 CH2 CH CH3 propylene CH2 C CH3

=>

ethylene

isobutylene

10

Cis-trans Isomerism
Similar groups on same side of double bond, alkene is cis. Similar groups on opposite sides of double bond, alkene is trans. Cycloalkenes are assumed to be cis. Trans cycloalkenes are not stable unless the ring has at least 8 carbons. =>
11

Name these:
H C C CH3CH2 H
H

CH3

Br C C

Br H

trans-2-pentene

cis-1,2-dibromoethene

=>
12

Commercial Uses: Ethylene

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13

Commercial Uses: Propylene

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14

Other Polymers

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15

Substituent Effects
More substituted alkenes are more stable.
H2C=CH2 < R-CH=CH2 < R-CH=CH-R < R-CH=CR2 < R2C=CR2

unsub. < monosub. < disub.

< trisub. < tetra sub.

Alkyl group stabilizes the double bond.

=>
16

Cycloalkene Stability
Cis isomer more stable than trans. Small rings have additional ring strain. Must have at least 8 carbons to form a stable trans double bond. For cyclodecene (and larger) trans double bond is almost as stable as the cis. =>
17

Physical Properties
Low boiling points, increasing with mass. Branched alkenes have lower boiling points. Less dense than water. Slightly polar
Pi bond is polarizable, so instantaneous dipoledipole interactions occur. Alkyl groups are electron-donating toward the pi bond, so may have a small dipole moment. =>
18

Polarity Examples
H3C C C H H CH3

H C C H3C

CH3 H

cis-2-butene, bp 4 C

trans-2-butene, bp 1 C

= 0.33 D

=0

=>

19

Industrial Methods
Catalytic cracking of petroleum
Long-chain alkane is heated with a catalyst to produce an alkene and shorter alkane. Complex mixtures are produced.

Dehydrogenation of alkanes
Hydrogen (H2) is removed with heat, catalyst. Reaction is endothermic, but entropy-favored.

Neither method is suitable for lab synthesis =>

20

Reactivity of C=C
Electrons in pi bond are loosely held. Electrophiles are attracted to the pi electrons. Carbocation intermediate forms. Nucleophile adds to the carbocation. Net result is addition to the double bond. =>
21

Electrophilic Addition
Step 1: Pi electrons attack the electrophile.
E C C + E
+

C +

Step 2: Nucleophile attacks the carbocation.

E C C+ + _ Nuc: E Nuc C C

22

=>

Types of Additions

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23

Addition of HX (1)
Protonation of double bond yields the most stable carbocation. Positive charge goes to the carbon that was not protonated.
CH3 CH3 CH3 C CH CH3 H Br CH3 C CH CH3 + H

+ Br CH3 CH3 C CH CH3 + H

=>
24

Addition of HX (2)
CH3 CH3 C CH CH3 H Br CH3 CH3 C CH CH3 + H + Br _

CH3 CH3 C CH CH3 + H _ Br

CH3 CH3 C CH CH3 Br H

=>

25

Regiospecificity
Markovnikovs Rule: The proton of an acid adds to the carbon in the double bond that already has the most Hs. Rich get richer. More general Markovnikovs Rule: In an electrophilic addition to an alkene, the electrophile adds in such a way as to form the most stable intermediate. HCl, HBr, and HI add to alkenes to form Markovnikov products. =>
26

Free-Radical Addition of HBr

In the presence of peroxides, HBr adds to an alkene to form the antiMarkovnikov product. Only HBr has the right bond energy. HCl bond is too strong. HI bond tends to break heterolytically to form ions. =>
27

Free Radical Initiation

Peroxide O-O bond breaks easily to form free radicals.
R O O R
heat

R O

O R

Hydrogen is abstracted from HBr.

R O + H Br R O H + Br

=>
Electrophile
28

Propagation Steps
Bromine adds to the double bond.
Br
+

C C

C C Br

Hydrogen is abstracted from HBr.

C C Br + H Br C C Br H + Br

Electrophile =>

29

Anti-Markovnikov ??
CH3 CH3 C CH CH3

CH3 CH3 C CH CH3 + Br

Br

CH3 CH3 C CH CH3 Br

30

Hydration of Alkenes
H C C alkene + H2O
+

H OH C C alcohol

Reverse of dehydration of alcohol Use very dilute solutions of H2SO4 or H3PO4 to drive equilibrium toward hydration. =>
31

Mechanism for Hydration

H H C C + + H O H + C C + H2O

+ C C

H + H O H + H2O C C

H + H O H C C + H2O

H H O C C + H3O +

=>
32

Orientation for Hydration

Markovnikov product is formed.
CH3 H CH3 CH3 C CH CH3 + H2O + H
H2O

CH3 C CH CH3 + H O+ H
CH3 CH3 C CH CH3 +O H H H H2O

CH3 CH3 C CH CH3 H O H

=>
33

Indirect Hydration
Oxymercuration-Demercuration
Markovnikov product formed Anti addition of H-OH No rearrangements

Hydroboration

Anti-Markovnikov product formed Addition of H-OH =>

34

Oxymercuration (1)
Reagent is mercury(II) acetate which dissociates slightly to form +Hg(OAc). +Hg(OAc) is the electrophile that attacks the pi bond.
O CH3 O CH3 O _ C O + Hg O C CH3 O

C O Hg O C CH3

=>
35

Oxymercuration (2)
The intermediate is a cyclic mercurinium ion, a three-membered ring with a positive charge.
OAc C C
+

Hg(OAc)

Hg C C
=>
36

Oxymercuration (3)
Water approaches the mercurinium ion from the side opposite the ring (anti addition). Water adds to the more substituted carbon to form the Markovnikov product.
OAc Hg C C H2O
+

OAc Hg C C H O H2O H
+

OAc Hg C C O H

=>
37

Demercuration
Sodium borohydride, a reducing agent, replaces the mercury with hydrogen.
OAc Hg 4 C C O H _ + NaBH4 + 4 OH H 4 C C O H + NaB(OH) 4 _ + 4 Hg + 4 OAc

=>
38

Predict the Product

Predict the product when the given alkene reacts with aqueous mercuric acetate, followed by reduction with sodium borohydride.
CH3 D (1) Hg(OAc) 2, H 2O (2) NaBH 4
OH CH3 D H

anti addition

=>
39

Alkoxymercuration Demercuration
If the nucleophile is an alcohol, ROH, instead of water, HOH, the product is an ether.
C C (1) Hg(OAc) 2, CH 3OH O Hg(OAc) C C H3C H3C (2) NaBH4 O H C C

=>
40

Hydroboration
Borane, BH3, adds a hydrogen to the most substituted carbon in the double bond. The alkylborane is then oxidized to the alcohol which is the anti-Mark product.
C C (1) BH3 C C H BH2 (2) H2O2, OH
-

C C H OH

=>
41

Borane Reagent
Borane exists as a dimer, B2H6, in equilibrium with its monomer. Borane is a toxic, flammable, explosive gas. Safe when complexed with tetrahydrofuran.
H 2 O
THF

B2H6

O B H H
THF . BH3

=>
42

Mechanism
The electron-deficient borane adds to the least-substituted carbon. The other carbon acquires a positive charge. H adds to adjacent C on same side

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43

Oxidation to Alcohol
Oxidation of the alkyl borane with basic hydrogen peroxide produces the alcohol. Orientation is anti-Markovnikov.
CH3 H CH3 C C H B H CH3 H CH3 C C H OH H

H2O2, NaOH H2O

=>
44

Hydrogenation
Alkene + H2 Alkane Catalyst required, usually Pt, Pd, or Ni. Finely divided metal, heterogeneous Addition

45

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Addition of Carbenes
Insertion of -CH2 group into a double bond produces a cyclopropane ring. Three methods:
Diazomethane Simmons-Smith: methylene iodide and Zn(Cu) Alpha elimination, haloform =>
46

Diazomethane
N N CH2 diazomethane N N CH2

CH2

heat or uv light

H N2 + C H carbene

C C C

H H

C C

H C H

Extremely toxic and explosive.

=>
47

Simmons-Smith
Best method for preparing cyclopropanes.
CH2I2 + Zn(Cu) ICH2ZnI a carbenoid

CH2I2 Zn, CuCl

=>

48

Alpha Elimination
Haloform reacts with base. H and X taken from same carbon
CHCl3 + KOH K CCl3 + H2O
+-

Cl

C Cl Cl

Cl + Cl

Cl

CHCl3 KOH, H2O

Cl Cl

=>
49

Stereospecificity
Cis-trans isomerism maintained around carbons that were in the double bond.
H C C H3C H CH3 CHBr3 NaOH, H2O H C C H3C Br H

CH3 Br

=>
50

Addition of Halogens
Cl2, Br2, and sometimes I2 add to a double bond to form a vicinal dibromide. Anti addition, so reaction is stereospecific.
Br C C + Br2 C C Br

=>

51

Mechanism for Halogenation

Pi electrons attack the bromine molecule. A bromide ion splits off. Intermediate is a cyclic bromonium ion.
C C + Br Br Br C C + Br

=>

52

Mechanism (2)
Halide ion approaches from side opposite the three-membered ring.
Br Br C C C C Br Br

=>
53

Examples of Stereospecificity

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54

Test for Unsaturation

Add Br2 in CCl4 (dark, red-brown color) to an alkene in the presence of light. The color quickly disappears as the bromine adds to the double bond. Decolorizing bromine is the chemical test for the presence of a double bond.
=>
55

Formation of Halohydrin
If a halogen is added in the presence of water, a halohydrin is formed. Water is the nucleophile, instead of halide. Product is Markovnikov and anti.
Br C C H2O Br C C H O H

Br C C H H2O
56

+ H3O

=>

Epoxidation
Alkene reacts with a peroxyacid to form an epoxide (also called oxirane). Usual reagent is peroxybenzoic acid.
O C C + R C O O H O C C O + R C O H

=>
57

Mechanism
One-step concerted reaction. Several bonds break and form simultaneously.
C

O O

C O C +

O
H

C O

H O

=>
58

Epoxide Stereochemistry
Since there is no opportunity for rotation around the double-bonded carbons, cis or trans stereochemistry is maintained.
O H CH3 C C H CH3 Ph C O O H H CH3 O C C H CH3

=>

59

Opening the Epoxide Ring

Acid catalyzed. Water attacks the protonated epoxide. Trans diol is formed. OH
C C
H3O O C C
+

H O C C

OH C C O H H
H2O

H2O

=>
60

One-Step Reaction
To synthesize the glycol without isolating the epoxide, use aqueous peroxyacetic acid or peroxyformic acid. The reaction is stereospecific.
O CH3COOH H OH H OH

=>
61

Hydroxylation of Alkenes
Alkene is converted to a cis-1,2-diol, Two reagents:
Osmium tetroxide (expensive!), followed by hydrogen peroxide or Cold, dilute aqueous potassium permanganate, followed by hydrolysis with base =>
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Mechanism with OsO4

Concerted syn addition of two oxygens to form a cyclic ester.
O C C O O
H2O2

O Os C C

O Os O

C OH C OH + OsO4

=>
63

Stereospecificity
If a chiral carbon is formed, only one stereoisomer will be produced (or a pair of enantiomers).
H C C H CH2CH3 cis-3-hexene (2) H2O2 CH2CH3 (1) OsO4 CH2CH3 H H C C OH OH

=>

CH2CH3 m eso-3,4-hexanediol
64

Oxidative Cleavage
Both the pi and sigma bonds break. C=C becomes C=O. Two methods:
Warm or concentrated or acidic KMnO4. Ozonolysis

Used to determine the position of a double bond in an unknown. =>

65

Cleavage with MnO4 Permanganate is a strong oxidizing agent. Glycol initially formed is further oxidized. Disubstituted carbons become ketones. Monosubstituted carbons become carboxylic acids. Terminal =CH2 becomes CO2. =>
66

Example
H CH3 C C CH3 CH3 KMnO4 (warm, conc.) H CH3 H3C C C CH3 OH OH
H H3C C O + CH3 C CH3 O

H3C C O

OH

=>
67

Ozonolysis
Reaction with ozone forms an ozonide. Ozonides are not isolated, but are treated with a mild reducing agent like Zn or dimethyl sulfide. Milder oxidation than permanganate. Products formed are ketones or aldehydes. =>
68

Ozonolysis Example
H CH3 C C CH3 CH3 O3 H C H3C O O O C CH3 CH3

Ozonide
(CH3)2S H C O H3C O C CH3 + CH3 CH3 O S CH3

=>

DMSO
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