Handout:

Organic Chemistry Reactions

Reactions Organized by Compound Families

Alkanes
1. Combustion
2. Halogenation

Alkenes and Alkynes
1. Additions: hydrogenation, halogenation,
hydrohalogenation, hydration
2. Polymerization

Aromatic Compounds
Substitutions: nitration, halogenation, sulfonation

Alcohols
1. Elimination: dehydration
2. Oxidations

Thiols
Oxidation

Amines
Acid-Base reactions

Aldehydes and Ketones
1. Addition: Acetal/hemiacetal formation by alcohol
addition
(Reverse rxn: Acetal hydrolysis with acid)
2. Oxidation and Reduction for aldehydes
(*Ketones go through reduction only)

Carboxylic Acids
1. Substitutions: esterification, amidation
(Reverse rxns: ester hydrolysis with acid or base, amide hydrolysis with acid or base)
2. Acid-base reactions

Phosphoric acid and Phosphates
Phosphoric acid: Esterification with alcohol
Phosphates: Phosphorylation

H. Kim for Chem 30B 1

 Reactions Organized by Reaction Type

Family Reaction Example

1. ADDITION
Alkenes and Hydrogenation H H Pd catalyst H H
C C + H2
alkynes H H
H C C H
H H
H H
Pd catalyst
H C C H + 2 H2 H C C H
H H
Halogenation H H Cl Cl
C C + Cl2 (or Br2) H C C H
H H
H H
Hydro- H H
H Cl Markonikov’s Rule
halogenation C C + HCl (or HBr) H C C H applies: H adds to C
H CH 3
H CH 3 with more Hs already.
Hydration H H H+ catalyst
H OH
C C + H2O H C C H Markonikov’s Rule
H CH 3
H CH 3 applies.
Aldehydes Addition of O OH
H + catalyst
and ketones alcohol to get H 3C C H(R) + CH 3CH2OH H 3C C H(R) + CH 3CH2OH

hemiacetals or O CH2CH 3

acetals hemiacetal

O CH2CH 3
H + catalyst
H 3C C H(R) + H 2O
O CH2CH 3
acetal




2. SUBSTITUTION
Aromatic Nitration H2SO 4 catalyst NO 2
compounds + HNO3

Halogenation FeCl3 (or FeBr3) catalyst Cl
+ Cl2 (or Br2)

Sulfonation H2SO 4 catalyst SO 3H
+ SO3

Carboxylic Esterification O H+ catalyst O
acids with alcohol H 3C C OH + CH 3CH2OH H 3C C OCH2CH 3 + H 2O

Amidation with O
heat
O
amine H 3C C OH + CH 3NH 2 H 3C C NHCH 3 + H 2O

Phosphoric Phosphoric acid: O O
acid and Esterification HO P OH + CH 3OH HO P OCH3 + H 2O
Phosphates with alcohol OH OH
Phosphates: O O O O O O
O P O P O- + ROH Adenosine O P O P O- +
Phosphorylation Adenosine O P RO P O- + Energy
O- O- O- O- O- O-

H. Kim for Chem 30B 2

3. ELIMINATION
Alcohols Dehydration H OH H2SO 4 catalyst H CH 3
H

H 3C C C CH 3 C C + H 3C C C CH2 + H 2O
H 3C H
H H H H
major minor

Zaitsev’s Rule applies: More highly substituted alkene is major
product.

4. OXIDATION/REDUCTION
Alcohols Oxidation OH
[O] O [O] O
1º R C H R C H R C OH
H aldehyde carboxylic acid

OH O
[O]
2º R C H R C R
R Ketone
OH
[O]
3º R C H No Rxn
R
Thiols Oxidation [O]
[H]
Reverse rxn: R-S-S-R 2 RSH
2 RSH R-S-S-R
Aldehydes Oxidation O [O] O
R C H R C OH
aldehyde carboxylic acid
Reduction O [H] OH
(also addition) R C H R C H
H
Ketones Reduction O
[H] OH
(also addition) R C CH 3 R C CH 3
H

5. ACID-BASE
Amines Rxn with water CH 3CH2NH 2 + H 2O CH 3CH2NH 3+ + OH –

(Basic)
Neutralization CH 3CH2NH 2 + H 3O+ CH 3CH2NH 3+ + H 2O

with strong acid CH 3CH2NH 2 + HCl CH 3CH2NH 3+ Cl –

to get ammonium Reverse rxn: ammonium
CH 3CH2NH 3+ Cl – + NaOH CH 3CH2NH 2 + NaCl + H 2O
ion or salt ion or salt + base

Carboxylic Rxn with water O O
acids H 3C C OH + H 2O
H 3C C O– + H 3O+

(Acidic) Neutralization O
O
with strong base H 3C C OH (aq) + NaOH (aq)
H 3C C O – Na +(aq) + H 2O
to get carboxylic
acid salt
Phenols Neutralization OH O –Na +
(very weakly with strong base + NaOH + H 2O
acidic) to get salt

H. Kim for Chem 30B 3

Other Reaction Types

Family Reaction Example

RADICAL REACTIONS
Alkanes Combustion
(Also heat
oxidation/reduction CH4(g) + 2O2(g) CO2 + 2H2O + Heat

reaction)
Halogenation light or heat
Cl
CH 3CH2CH 3 + Cl2 HCl + CH 3CH2CH2Cl + CH 3CHCH 3

Cl Cl
Cl Cl
Cl Cl
+ CH CH CH + + CH 3CCH 3 + CHCH2CH 3
2 2 2 CH2CHCH 3
Cl Cl
Mixed products
Alkenes Polymerization initiator CH 3 CH 3
CH 3CH CH2 H2 H2
( C C C C )
H H

HYDROLYSIS
Esters Acid hydrolysis to get O
H+ catalyst
O
(Reverse rxns of carboxylic acid and R C O CH 3 + H 2O R C OH + CH 3OH

carboxylic acid alcohol
esterification) Saponification: Base O
O
H2O
hydrolysis to get R C O CH 3 + NaOH (aq)
C O – Na + + CH 3OH
carboxylic acid salt and
R

alcohol
Amides Acid hydrolysis to get O
H H + catalyst
O
(Reverse rxns of amine H 3C C N CH 3 + H 2O H 3C C OH + CH 3NH 2

carboxylic acid Base hydrolysis to get O O
H2O
amidation) amine H 3C C
H
N CH 3 + NaOH (aq) H 3C C OH + CH 3NH 2

Acetals Acid hydrolysis to get H H + catalyst
O
H 3C C O CH2CH 3 + H 2O
(Reverse reaction aldehydes of ketones H 3C C OH + 2 CH 3CH2OH
of acetal formation (reverse of acetal O CH2CH 3
from formation)
aldehydes/ketones)
*Note that organic chemistry reactions can be classified in several different ways.

H. Kim for Chem 30B 4