Chemistry

1. H. Kim for Chem 30B 1
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

2. H. Kim for Chem 30B 2
Reactions Organized by Reaction Type
Family Reaction Example
1. ADDITION
Alkenes and
alkynes
Hydrogenation
Halogenation
Hydro-
halogenation
Markonikov’s Rule
applies: H adds to C
with more Hs already.
Hydration
Markonikov’s Rule
applies.
Aldehydes
and ketones
Addition of
alcohol to get
hemiacetals or
acetals
2. SUBSTITUTION
Aromatic
compounds
Nitration
Halogenation
Sulfonation
Carboxylic
acids
Esterification
with alcohol
Amidation with
amine
Phosphoric
acid and
Phosphates
Phosphoric acid:
Esterification
with alcohol
Phosphates:
Phosphorylation
C C
H
H
H
H
+ H2
Pd catalyst
C C H
H
H
H
H H
C C H
H C C H
H
H
H
H H
+ 2 H2
Pd catalyst
C C
H
H
H
H
+ Cl2 (or Br2) C C H
H
H
H
Cl Cl
H3C C
O
H(R) + CH3CH2OH H3C C
OH
H(R)
O CH2CH3
hemiacetal
H3C C
O
H(R)
O CH2CH3
CH2CH3
acetal
H+ catalyst + CH3CH2OH
H+ catalyst
+ H2O
+ HNO3
H2SO4 catalyst NO2
+ Cl2 (or Br2)
Cl
FeCl3 (or FeBr3) catalyst
+ SO3
H2SO4 catalyst SO3H
H3C C
O
OH + CH3CH2OH
H+ catalyst
H3C C
O
OCH2CH3 + H2O
H3C C
O
OH + CH3NH2
heat
H3C C
O
NHCH3 + H2O
HO P
O
OH + CH3OH
OH
HO P
O
OCH3
OH
+ H2O
O P
O
O + ROH
O-
RO P
O
O-
O-
+ Energy
Adenosine P O P O-
O O
O- O-
O P
O
O
O-
Adenosine P O-
O
O-
+
C C
H
CH3
H
H
+ HCl (or HBr) C C H
CH3
H
H
H Cl
C C
H
CH3
H
H
+ H2O C C H
CH3
H
H
H OH
H+ catalyst

3. H. Kim for Chem 30B 3
3. ELIMINATION
Alcohols Dehydration
Zaitsev’s Rule applies: More highly substituted alkene is major
product.
4. OXIDATION/REDUCTION
Alcohols Oxidation
Thiols Oxidation
Aldehydes Oxidation
Reduction
(also addition)
Ketones Reduction
(also addition)
5. ACID-BASE
Amines
(Basic)
Rxn with water
Neutralization
with strong acid
to get ammonium
ion or salt
Carboxylic
acids
(Acidic)
Rxn with water
Neutralization
with strong base
to get carboxylic
acid salt
Phenols
(very weakly
acidic)
Neutralization
with strong base
to get salt
C
H3C C
OH
CH3
H
H2SO4 catalyst
C C
CH3
H
H
H3C
H
H
+ C
H3C C CH2
H
H
H
major minor
+ H2O
[O]
C
R
H
OH
H C
R
O
H C
R
O
OH
[O]
aldehyde carboxylic acid
1º
[O]
C
R
R
OH
H C
R
O
R
Ketone
2º
[O]
C
R
R
OH
H
3º No Rxn
2 RSH
[O]
R-S-S-R
Reverse rxn: R-S-S-R
[H]
2 RSH
C
R
O
H C
R
O
OH
[O]
aldehyde carboxylic acid
C
R
O
H C
R H
[H] OH
H
C
R
O
CH3
[H]
C
R
OH
CH3
H
CH3CH2NH2 + H2O CH3CH2NH3
+ + OH–
CH3CH2NH2 + H3O+
CH3CH2NH3
+ + H2O
CH3CH2NH2 + HCl CH3CH2NH3
+ Cl–
CH3CH2NH3
+ Cl– + NaOH CH3CH2NH2 + NaCl + H2O
Reverse rxn: ammonium
ion or salt + base
C
H3C
O
OH + H2O
C
H3C
O
O– + H3O+
C
H3C
O
OH (aq) + NaOH (aq)
C
H3C
O
O– Na+(aq) + H2O
OH
+ NaOH
O–Na+
+ H2O

4. H. Kim for Chem 30B 4
Other Reaction Types
*Note that organic chemistry reactions can be classified in several different ways.
Family Reaction Example
RADICAL REACTIONS
Alkanes Combustion
(Also
oxidation/reduction
reaction)
Halogenation
Mixed products
Alkenes Polymerization
HYDROLYSIS
Esters
(Reverse rxns of
carboxylic acid
esterification)
Acid hydrolysis to get
carboxylic acid and
alcohol
Saponification: Base
hydrolysis to get
carboxylic acid salt and
alcohol
Amides
(Reverse rxns of
carboxylic acid
amidation)
Acid hydrolysis to get
amine
Base hydrolysis to get
amine
Acetals
(Reverse reaction
of acetal formation
from
aldehydes/ketones)
Acid hydrolysis to get
aldehydes of ketones
(reverse of acetal
formation)
CH4(g) + 2O2(g)
heat
CO2 + 2H2O + Heat
CH3CH2CH3 + Cl2
light or heat
HCl + CH3CH2CH2Cl + CH3CHCH3
Cl
CH2CH2CH2
Cl
Cl
CH2CHCH3
Cl
CHCH2CH3
CH3CCH3
Cl
Cl
Cl
Cl
Cl
+ + + +
CH3CH CH2
C
H
H2
C C
H
H2
C
CH3 CH3
( )
initiator
C
R
O
O
H+ catalyst
C
R
O
OH
CH3 + H2O + CH3OH
C
R
O
O
C
R
O
O– Na+
CH3 + CH3OH
H2O
+ NaOH (aq)
H+ catalyst
C
H3C
O
OH
+ H2O + CH3NH2
C
H3C
O
H
N CH3
C
H3C
O
C
H3C
O
OH
H
N + NaOH (aq) + CH3NH2
CH3
H2O
H
C
H3C O
H+ catalyst
C
H3C
O
OH
CH2CH3 + H2O + 2 CH3CH2OH
O CH2CH3