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A Guide to Organic Chemistry Mechanisms

An ochem sampler. Print out these pages. Can you add the curved arrows? Look closely and you will see you can do
all of them whether your class discussed them or not. Print out the next set and repeat those problems.
1.
H2C

C
H

H2C

C
H

H2C

C
H

2. An SN1 solvolysis reaction of (R)-(1-chloroethyl)benzene to give rac-1-phenylethanol.

H

dioxaneH2O
CH3
Cl

CH3

Cl

CH3
O

CH3

H3O

3. An E2 elimination reaction of hydrogen chloride from 1-chlorooctadecane with potassium t-butoxide to give 1-octadecene.
(See Notes.)
H

C15H31

CH3

CH3
CH3

Cl

C15H31

O-t-Bu

86%

Cl

t-Bu

C15H31

14%

4. A synthesis of 3-hexyne from trans-3-hexene by bromination and two elimination reactions. (See Notes.)
NH2

Br2

NH2

Br

H
Chap. 5.13

Br2

Br

NH3 Br

NH3

syn
elimination
slow

Et

Br

Et

Br

Et

Br

Et

Et

Br

H
Br

Et

Br

NH2

5. Addition of hydrogen bromide to propene to give 2-bromopropane. (See Notes.)

H

H3C

Br

Br

CH2

H3C

H
CH3

H3C

Br
CH3

Br

6. Addition of hydrogen bromide to 3-methyl-1-butene to give after rearrangement, 2-bromo-2-methylbutane. (See Notes.)
Br
H
H
H3C

Br

CH2
CH3

H
H3C

Br

H
CH3

CH3

IIo carbocation

H3C

Br

H3C

CH3
CH3

IIIo carbocation

CH3
CH3 55%
Br

CH3

CH3

CH3 45%

Part A - Page 1

Curved Arrow Press

A Guide to Organic Chemistry Mechanisms

7. Bromination of methylcyclohexene to give (1R,2R)- and (1S,2S)-2-bromo-1-methylcyclohexanol.

CH3

Br

Br

CH3

Br

Br

CH3

Br
fast

CH3

Br

H H

CH3
Br

H3O

Step intermediate

8. Acid catalyzed Baeyer-Villiger oxidation of 2,2-dimethylcyclopentanone with peracetic acid.

H
O

O
O
O

cont'd

H2O
O H

cont'd
H

H3O

9. A reverse-forward Diels-Alder reaction between cyclopentadiene and maleic anhydride.

O
heat

O
H

10. Formation of the cyanohydrin (2-hydroxy-2-methylpropanenitrile) from acetone. (See Notes.)

C

O
H3C

O
H3C

CH3

C
C

CH3

H3C

C
C

H
CH3
N

11. Base hydrolysis of octyl isobutyrate to give octanol and isobutyric acid. Step 1, treatment with base. (See Notes.)
O
C

O
O

C8H17

C
O

H
cont'd

C8H17

H
O

C8H17
O

C8H17

12. Oxidation of cyclohexanol to cyclohexanone with sodium hypochlorite (NaOCl, bleach).

H

H
O

Cl

H
O

Cl

H
H2O

Part A - Page 2

H
H3O

H
O

Cl

H
H3O

Curved Arrow Press

A Guide to Organic Chemistry Mechanisms

13. Acid catalyzed bromination of acetophenone to give -bromoacetophenone. (See Notes.)

O

HOAc

H
H

Br

Br

cont'd

Br

Br

Br

Br
H

Br

H BrBr
2

Br

Br

14. Reaction of the ketone with hydrazine under basic conditions to form the hydrazide.
H

H
CH3

HO

CH3 H

CH3 H
N

H
N

OH
cont'd

OH
CH3

OH
H

H
N

OH

H2O

CH3
H

CH3 H

OH

H2O

15. Friedel Crafts acylation of benzene.

Cl
Al Cl

O
H3C

Cl

Cl

H3C

Cl

Cl

H3C

Al Cl

Cl
Cl

O
H3C

Cl

CH3

slow

Al

Cl

Cl

CH3

HCl + AlCl3

arenium ion

16. Nucleophilic aromatic substitution of 1-fluoro-4-nitrobenzene with ammonia to give 4-nitroaniline. (See Notes.)
F

NH3

F
O

H
NH3

NH4

H
N

Part A - Page 3