REACTIONS OF HYDROCARBONS

REACTIONS OF ALKANES
1. Combustion
3n 1
C n H 2n 2 2
O2 nCO2 (n 1)H 2O

2. Free Radical Halogenation

heat
H + X2 X + H-X
C light C

Where X2 = Cl2, Br2

3. Pyrolysis

REACTIONS OF CYLOALKANES
1. Combustion
3n
C n H 2n 2
O2 nCO2 nH 2O

2. Ring Opening Reactions

Cl2, light
Cl
RT

Cl2, FeCl3
Cl Cl

Cyclopropane HX
H X

H2, Ni at 800C
H H

* Dashed lines are bonds that are broken

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REACTIONS OF ALKENES

A. Electrophilic Addition
General Addition Reaction:

reaction
C C + X-Y
conditions

X Y

1. Hydrogenation

Ni ,Pd +
C C + H2
or Pt

H H
* Syn – Addition

2. Addition of HX

C C + HX

H X
where HX = HCl, HBr or HI
* Addition of HX follows Markovnikov’s Rule

3. Addition of Water or Hydration

H+
C C + H2O

H OH
alcohol
* Addition of Water also follows Markovnikov’s Rule
4. Addition of cold concentrated H2SO4

C C + H2SO4

H OSO3H

5. Addition of Halogen
X
CCl4 / CH2Cl2
C C + X2

X
where X2 = Cl2 or Br2

* Anti-addition (Due to cyclic halonium ion that has a high steric hindrance)

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6. Halohydrin Formation
OH

C C + X2, H2O + HX

X
where X2 = Cl2 or Br2
* Anti-addition (Due to cyclic halonium ion that has a high steric hindrance)

7. Addition of Alkenes: Dimerization

isooctane
800
2

8. Addition of Alkenes: Alkylation

con'c H2SO4/ HF
C C + R-H
0 -10 0C

R H
CH3 CH3
H con'c H2SO4/HF
+ C H
H3C CH3 0- 10 0C C C
CH3 H3C C CH3
CH3
H H

9. Oxymercuration – Demercuration
H
1. H2O, Hg(OAC)2
RCH = CH2 RCH CH2
2. NaBH4
OH
* Markovnikov Orientation
* Anti – addition

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10. Hydroboration – Oxidation
OH
1. BH3, THF
RCH = CH2 RCH CH2
2. H2O2, -OH
H
* Reverse Markovnikov Orientation
* Syn – addition

11. Alkoxymercuration – Demercuration

1. Hg(O2CCF3)2
C C + ROH
2. NaBH4
H OR
ether
* Note: Hg(OAc)2 can be used.
* Produces an ether from an alcohol/ alkoxy group.

12. Hydroxylation or Glycol Formation

C C + KMnO4 + MnO2

HO OH
cis - 1,2- diol
* Syn – addition
* occurs with H2O

Alternative Reaction:

1. OsO4, pyridine
C C
2. NaHSO3, H2O
HO OH
cis - 1,2- diol
* Produces the same product as cold dilute neutral KMnO4

13. Oxidative Cleavage: Ozonolysis

1. O3
C C 2 C O

2. Zn, H30+

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14. Oxidative Cleavage: Hot acidic KMnO4
R R R

hot acidic KMnO4

C C 2 C O

H H HO

R H R

hot acidic KMnO4 + CO2

C C C O

R H R

Notes:
CH2 CO2

C
O C

H
OH

C
O C

15. Epoxidation
O
MCPBA O
C C
C
C C + O C
O +
R OH
epoxide
OH

m- chloroperoxybenzoic acid

* Instead of MCPBA, RCO3H is used as reagent where R is an alkyl group

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16. Carbenes
Generation of carbene
Cl
CHCl3 + KOH + H2O
chloroform C
Cl Cl
trichloromethanide

Cl Cl
KOH C
C C + CHCl3

Note: Stereochemistry is retained. A cis-alkene will result to a cis-

disubstituted cyclopropane.

17. Simmons – Smiths Reaction, Carbenoid

ether
CH2I2 + Zn(Cu) I - CH2 - Zn - I = ":CH2"

Example:
H

ether
+ CH2I2 CH2 + ZnI2
Zn(Cu)

18. Addition of HBr with ROOR, known as Peroxide effect

CH3 CH3
ROOR
+ HBr CH
C
H3C CH2 H3C CH2Br

* Note: not applicable for other Acid Halides such as HCl

* Reverse Markovnikov Orientation
* Free Radical Addition

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REACTIONS OF POLYMERS
1. Free Radical Polymerization
O2, 100 - 250 0C
n CH2 = CH2 CH2CH2
1000 - 300 atm n
or peroxides

2. Allylic Halogenation or Wohl-Ziegler Bromination

O

C H ROOR, CCl4 C H
C C + C C
N Br

Br
NBS
O

* uses NBS, n-bromosuccinimide

* Br is attached to an allylic carbon
* Possible rearrangement can occur due to allylic carbon

REACTIONS OF DIENES OR ALKADIENES

1. Electrophilic Addition of Dienes
Y
H H X-Y
C C H
CH X CH C
H2C CH2
C CH CH2
H2
H
H
X-Y

Y X

X CH CH Y
C CH C
H2 H2

* Reacts like normal alkenes

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 H
H
X-Y X
C CH2
C CH2
H2C C
H2C C

H
Y H
X-Y 1,2 addition product

H Y

C CH2
H2C C

X H
1,4 addition product
2. Diels – Alder Cycloaddition Reaction

benzene,
+

3. Free Radical Polymerization of Dienes

n (CH2 = CH - CH = CH2) ( CH2 - CH = CH - CH2 )n
* Results in a 1, 4- addition

NOTES:

Stability of Free Radicals:

Allylic, Benzyllic > 3o > 2 o > 1 o > •CH3 > Vinyl

Stability of Carbocations:
Subsituted Allylic and Benzyllic > 3o > Allylic, Benzyllic > 2 o > 1 o > Vinyl > CH3+

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REACTIONS OF ALKYNES
1. Hydrogenation

H H
2H2
C C
Ni, Pt or Pd C C

H H
H
Na or Li
C C
liquid NH3 C C

H
* Trans- alkene, Anti – addition

H2
C C
Lindlar Catalyst C C

H H
* Cis – alkene, Syn – addition

2. Electrophilic Addition
X X
2X2
C C
CCl4 C C

X X

Br H
2HBr
C C
C C

Br H
3. Hydration
OH H O
H2SO4
C C + H2O C C C C
HgSO4
H H
enol ketone
Over-all Reaction:
H O
H2SO4
R C C H + H2O R C C
HgSO4
H CH3
* Follows a Markovnikov orientation

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4. Hydroboration – Oxidation of Terminal Alkynes
R H H O
1. B2H6
R C C H C C R C C
2. NaOH, H2O2
H OH H H
enol ketone
* Follows a reverse Markovnikov orientation

5. Acidity of Terminal Alkynes

Na
R C C Na

NaNH2
R C C H R C C Na + NH3

alcoholic AgNO3
R C C Ag
6. Ozonolysis
a. Internal Alkyne
O O
1. O3
R C C R' +
2. Zn, H3 O+ R C OH R' C OH
b. Terminal Alkyne
O
1. O3 + O
R C C H C O
2. Zn, H3 O+ R C OH

7. Alkylation of Acetylide Anions

SN2
RCH2 - X + R C C R H2C C C R

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REACTIONS OF ALKYL HALIDES
1. SN1, Unimolecular Nucleophilic Substitution
R R
1.
slow + X
C C
R X R

R R

R R

2.
fast
C Nu C
R R Nu

R R
2. SN2, Bimolecular Nucleophilic Substitution

slow Nu X fast
Nu C X C C +X
Nu

Transition State

3. E1, Unimolecular Elimination Reaction

X
X
slow fast
C C C C C C +HB + X

H H
B
Base

4. E2, Bimolecular Elimination Reaction

R R
1.
slow + X
C C
R X R

R R

R
2. fast
C C C C + BH

H R
Base

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REACTIONS WITH ORGANOMETALLIC COMPOUNDS

1. Grignard Reagents

dry ether
X + Mg Mg X or Ar - MgX
C C
R R

2. Organometallic Coupling Reactions

a. Alkyllithium Reagent
2Li
CH3CH2CH2CH2Br CH3CH2CH2CH2Li + LiBr
pentane

b. Gilman Reagent
ether
3CH3Li + CuI (CH3)2Cu-Li+ + LiI

c. Organometallic Coupling
(CH3)2CuLi + CH3(CH2)2CH2I CH3(CH2)2CH2CH3 + LiI + CH3Cu

Example:
I CH3

+ (CH3)2CuLi + CH3Cu + LiI

REACTIONS WITH AROMATIC HYDROCARBONS

Electrophilic Aromatic Substitution (EAS)

1. Nitration
H NO2

H2SO4
+ HNO3 + H2O

nitrobenzene

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2. Halogenation
H X
Fe or FeX3
+ X2 + HX

where X2 = Cl2 or Br2 halobenzene

3. Sulfonation
H SO3H
fuming H2SO4
+ SO3 + H2O

benzenesulfonic acid

4. Friedel-Crafts Alklyation
H R

AlCl3
+ R - Cl + HCl
alkyl chloride

alkylbenzene

5. Friedel-Crafts Acylation
O

C
H O
R
AlCl3
+ C Cl
+ HCl
R
acid chloride aromatic ketone

6. Oxidation of Alkyl Side Chains

R COOH

hot acidic KMnO4

where R contains a benzylic hydrogen

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Nucleophilic Aromatic Substitution (NAS)

1. Bimolecular Displacement or Addition – Elimination, SNAr

X Z

+ Z: + X:

Mechanism:

X X Z X Z X Z

1.
slow
+ Z:

Meisenheimer Complex
2.
Z
X Z

+ X:

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2. Elimination – Addition or Benzyne Mechanism

X NH2
- NH2
NH3

Mechanism

1.
X X

NH2 + NH3

2. X
+X

benzyne
3.
NH2
NH2

4.

NH2 NH2

H NH2 + NH2

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