ORGANIC CHEMISTRY REACTIONS

Organic Halogen Compounds

Preparations of Alkyl Halides

1. Electrophilic Addition of Halogens or Hydrogen Halides to Alkenes

1. R R R R
+ X2 R R
R R X X
Examples:

H3C CH3 H H
+ Cl2 H3C CH3
H H Cl Cl

2. R R R R
+ HX R R
R R H X

Examples:

H3C CH3 H H
+ HCl H3C CH3
H H H Cl

2. Nucleophilic Substitution of Alcohols

General equation:

X = Cl, Br, I (Reagents: HCl, HBr, HI, SOCl 2 , PCl 3 , PBr 3 )

Examples:

OH Cl
+ HCl + H2O

OH + SOCl2 Cl + SO2 + HCl

OH + PBr3 Br + H3PO3
3. Preparation of Aryl Halides

X
FeX3
+ X2 + HX

X = Cl, Br
Example

Cl
FeCl3
+ Cl2 + HCl

Reaction of Alkyl Halides

H H
R X + Nu- R Nu + X-
H H

X = Cl, Br, I

Examples of nucleophiles: OH-, H 2 O, RO-, RCOO-, H 2 S, RSH, NHR 2 , NH 2 R, NH 3 .

1. RX + HO- ROH + X-
alcohol

Br + NaOH OH + NaBr

2. RX + H2O ROH + HX
alcohol
Cl OH
+ H2O + HX

3. RX + RO-Na ROR + X-
ether
Br + O-Na+ O + NaBr

4. RX + RCOO- RCOOR + X-
ester
O
Br + O + NaBr
O-Na+
O
 5. RX + H2S RSH (thiol) + HX

Cl + H2S SH + HCl

6. R'X + RNH2 (excess) RNHR' + HX

CH3CH2NH2 + CH3Br CH3CH2NHCH3 + HBr

(excess)
+ -
7. R'-X (excess)+ RNH2 R-N(R')3X

CH3CH2NH2 + CH3Br CH3CH2N+(CH3)3Br-

(excess)

Reaction Mechanism of Nucleophilic Substitutions

(i) S N 2 Reaction Mechanism

Example: Reaction of OH- with bromomethane (methyl bromide)

(ii) S N 1 Reaction Mechanism

C X C + X

Carbocation

Nu C Nu C Enantiomer A

C Nu C Nu Enantiomer B
 Example:
Reaction of water with (S)-3-bromo-2,3-dimethylpentane

Amines

Preparations of Amines

1. Reduction of Amides

Amides can be reduced to amines by using lithium aluminium hydride (LiAlH 4 ).

O LiAlH4
then H2O
R NH2 R NH2
Amide

Example:

O LiAlH4
then H2O
NH2 NH2
Butanamide

2. Reduction of Nitriles

Nitriles are compounds that contain group. C N Nitriles can be reduced to primary
amines by using hydrogen in the presence of Ni catalyst.

H2/ Ni
R C N R NH2
Nitrile

Example:

H2/ Ni
C N
NH2
3. Reduction of Aromatic Nitro Compounds to Aromatic Amines

Aromatic nitro compounds can be reduced to aromatic amines by using hydrogen/Pt or

Sn/HCl.

H2/ Pt
NO2 or NH2
Sn/ HCl, then NaOH

Reactions of Amines

1. Neutralisation with Acids

As amines are basic, they can react with acids to form salts which are soluble in water.

R-NH 2 + HCl  RNH 3 +Cl-

Amine Alkyl ammonium chloride,

Example:

CH 3 NH 2 + HCl  CH 3 NH 3 +Cl-

2. Reaction of Alkyl Halides

RNH2 (excess) + R'X RNHR' + HX

CH3CH2NH2 + CH3Br CH3CH2NHCH3 + HBr

(excess)
+ -
RNH2 + R'-X (excess) R-N(R')3X

CH3CH2NH2 + CH3Br CH3CH2N+(CH3)3Br-

(excess)

3. Formation and Reaction of Diazonium Salts

Cl
NH2 NaNO2, HCl
N N
0 oC
aniline diazonium salt

The diazonium salt can undergo a coupling reaction with phenols or aromatic amines to
give azodye compounds, which are highly coloured.
 R
Cl
N N + R N
N

diazonium salt R = OH, NH2, NHR, NR2

Azodye

Example:

N
Cl
N N + N N
N

diazonium salt N.N-dimethylaniline

Azodye

Alcohols, Phenols and Ethers

Preparations of Alcohols

1. Hydration of Alkenes

H+
+ H2O

H OH

Example: Hydration of trans-but-2-ene

OH
H+ H
+ H2O
H
H

2. Nucleophilic substitution of alkyl halides

R X + OH- R OH + X-

OH- can be obtained from H 2 O, NaOH, KOH and X = Br, Cl, I

Example:

CH3CH2Br + NaOH CH3CH2OH + NaBr

3. Reduction of Aldehydes and Ketones

(i) Catalytic hydrogenation

O Ni catalyst HO H
+ H2
R R' R R'

Reaction conditions: hydrogen + nickel catalyst

Example:

O Ni catalyst HO H
+ H2

(ii) Reduction by lithium aluminium hydride (LiAlH 4 )

O
LiAlH4 H OH
R' R" then H2O R' R"

Example:
O
H OH
LiAlH4
H H
then H2O

(iii) Synthesis using Grignard reagents

O
then H2O R" OH
+ R"MgX
R' R
R' R
Grignard
reagent

R = alkyl or aryl X = Cl, Br, I

Examples:
O
then H2O CH3 OH
+ CH3MgBr
H H

O CH3 OH
CH3 + CH3MgBr then H2O CH3
Reactions of Alcohols

1. Reaction with Hydrogen Halides

R-OH + HX  R-X + H2O

Alcohol Alkyl halide

Reactivity of R-OH: Tertiary OH > Secondary OH > Primary OH

Example:

H OH H Cl
+ HCl + H2O
H3C CH3 H3C CH3

2. Dehydration to Alkenes

R R R R
R R H2SO4 (concentrated) + H2O
H OH R R
alcohol alkene

Concentrated H2SO4 is a dehydrating reagent

3. Oxidation to Carbonyl Compounds

(i) Oxidation of primary alcohol

H R R
R [O] further [O]
OH O O
H H HO

Primary alcohol Aldehyde Carboxylic acid

Oxidation of primary alcohol with PCC

H H H
PCC
R OH R O
Primary alcohol Aldehyde

Example
H
PCC
OH O
1-Propanol Propanal
Primary alcohol
Aldehyde
Oxidation of primary alcohol with CrO 3

H H H OH
CrO3
R OH R O R O
Primary alcohol Oxidation does Carboxylic
not stop here! acid

Example

O
CrO3
OH
OH

OH OH
CrO3
O

(ii) Oxidation of secondary alcohol

R' R no further
[O] [O]
R
OH O
H R'

Secondary alcohol Ketone

R' H R'
PCC or CrO3
R OH R O

Secondary alcohol Ketone

PCC = Pyridinium chlorochromate

CrO3 = Chromic acid

Example

PCC
OH O
2-Pentanol Pentan-2-one
Secondary alcohol Ketone

(iii) Oxidation of tertiary alcohol

R'
[O]
R no reaction
OH
R''

Tertiary alcohol
Preparation of Phenol
SO3H OH
H2SO4
NaOH
concentrated
300 oC
benzene benzenesulfonic phenol
acid

Reactions of Phenols

1. Neutralisation
OH O-Na+
+ H2O
+ NaOH

phenol sodium
phenoxide

2. Electrophilic Substitution with Halogens

OH
OH
Br Br
+ Br2 (aq)

phenol Br
2,4,6-Tribromophenol

Preparation of Ethers

Ethers can be prepared by Williamson synthesis.

2 ROH + 2 Na  2 RO-Na+ + H 2

RO-Na+ + R’-Br  ROR’ + NaBr

Example:

2 CH 3 OH + 2 Na  2 CH 3 O-Na+ + H 2

CH 3 O-Na+ + CH 3 CH 2 Br  CH 3 OCH 2 CH 3 + NaBr

Aldehydes and Ketones

Preparations of Aldehydes

H H H
PCC
R OH R O
Primary alcohol Aldehyde

Example
H
PCC
OH O
1-Propanol Propanal
Primary alcohol
Aldehyde

Preparations of Ketone

R' H R'
PCC or CrO3
R OH R O

Secondary alcohol Ketone

PCC = Pyridinium chlorochromate

CrO3 = Chromic acid

Example

PCC or CrO3
OH O
2-Pentanol Pentan-2-one
Secondary alcohol Ketone

Reactions of Aldehydes and Ketones

1. Oxidation of Aldehydes to Form Carboxylic Acids

CrO3 or
O Tollen's reagent O

R H R OH

Aldehyde Carboxylic acid

Example:

O O
Tollen's reagent
+ Ag
H OH
 Tollen’s reagent (AgNO 3 + NH 3 (aq) ) is used as a test to distinguish aldehydes from
ketones. Upon treatment with Tollen’s reagent, only aldehydes will give a silver mirror.
No silver mirror is formed for ketones.

2. Reduction to Alcohols

O
LiAlH4 H OH
R' R" then H2O R' R"

LiAlH4
Aldehydes Primary alcohols
then H2O
Example
O
LiAlH4
OH
H then H2O
1-Butanol
Butanal
primary alcohol
aldehyde

LiAlH4
Ketones Secondary alcohols
then H2O
OH
O
LiAlH4
then H2O
3-Methylpentan-2-ol
3-Methylpentan-2-one
secondary alcohol
ketone

Reaction mechanism of carbonyl compounds with LiAlH 4

O O- H-OH O H
R R R H
R R H
H- R

3. Reaction with Grignard Reagents

R"MgX
Aldehydes Secondary alcohols
then H2O
Example
O OH
then H2O H
+ CH3MgBr
H CH3
Butanal Methyl magnesium Pentan-2-ol
bromide
 R"MgX
Ketones Tertiary alcohols
then H2O
Example
O OH
then H2O CH3
+ CH3MgBr CH3
Pentan-2-one Methyl magnesium 2-Methylpentan-2-ol
bromide

Reaction mechanism of carbonyl compound with Grignard reagent

O OMgX H-OH O H
R R R R'
R R R
R'MgX R

4. Reaction with Amines or Hydrazines

Reaction of aldehydes and ketones with 2,4-dinitrophenylhydrazine

O2N O2N
H3C H3C
O + H2N N NO2 N N NO2 + H2O
H H
H H

O2N O2N
H3C H3C
O + H2N N NO2 N N NO2 + H2O
H3C H3C
H H

Aldehydes and ketones react with 2,4-dinitrophenylhydrazine to produce 2,4-

dinitrophenylhydrazone (orange precipitate). This reaction used as a test for aldehydes
and ketones.

Reaction mechanism of ketones with primary hydrazines:

Proton NHR'
O O- H N
transfer O- - H2O
R R R NH2NHR' R R
R R NHNHR'
R
R'NHNH2 Tetrahedral
intermediate
5. Iodoform Reaction

A chemical test for aldehyde and ketone with a CH 3 CO- group will gives CHI 3
(iodoform), a yellow ppt.

O
warm
H3C R + 3I2 + NaOH CHI3 + RCOO-Na+ + 3HI
yellow ppt

Carboxylic Acids and Their Derivatives

General properties of carboxylic acids

1. Carboxylic acids can react with sodium to form salts and water.

2 RCOOH + 2 Na  2 RCOO-Na+ + H 2

O O
2 OH + 2Na 2 O-Na+ + H2

2. Carboxylic acids can react with inorganic bases to form salts and water.

RCOOH + NaOH  RCOO-Na+ + H 2 O

O O
OH + NaOH O-Na+ + H2O

3. Carboxylic acids can react with carbonate to form salts, carbon dioxide and water.

2 RCOOH + Na 2 CO 3  2 RCOO-Na+ + CO 2 + H 2 O

O O
2 OH + Na2CO3 2 O-Na+ + CO2 + H2O

Preparations of Carboxylic Acids

1. Oxidation of Primary Alcohols

H H H OH
CrO3
R OH R O R O
Primary alcohol Oxidation does Carboxylic
not stop here! acid
 Example:

O
CrO3
OH
OH

OH OH
CrO3
O

2. Oxidation of Alkylbenzenes

R KMnO4 COOH

Alkylbenzene Benzoic acid

Examples:

KMnO4 COOH

Benzoic acid

OH KMnO4 COOH

3. Carboxylation of Grignard Reagents

then H2O
RMgX + CO2 RCOOH

Examples:

then H2O
MgBr + CO2 COOH

MgBr
then H2O COOH
+ CO2

Reactions of Carboxylic Acids

1. Reduction to Form Alcohols

O
LiAlH4, heat
R OH
R OH
then H2O
 Example:

O
LiAlH4, heat
OH OH
then H2O
1-Propanol
Propanoic acid

2. Formation of Acid Chlorides

O SOCl2 O

R OH R Cl

Example:

O SOCl2 O

OH Cl
Propanoic acid Propanoyl chloride

3. Formation of Acid Anhydrides

O O O O
+ + H2O
R OH HO R heat R O R
acid anhydride

4. Formation of Esters

Carboxylic acids can react with alcohols to give esters. This process is called Fishcher
esterification. The esterification is catalysed by dilute sulphuric acid. One water molecule
is also formed: OH from carboxylic acid, H from alcohol.

O
H+ O
+ HO R'
R OH R' + H2O
heat R O
Carboxylic Alcohol
Ester
acid

Example:

O O
+
H
OH + OH O + H2O
heat

Benzoic acid Ethyl benzoate

Acid Chlorides

Preparation of Acid Chlorides

Acid chlorides can be prepared by reacting carboxylic acids with thionyl chloride
(SOCl 2 ).

O SOCl2 O

R OH R Cl

Example:

O SOCl2 O

OH Cl
Propanoic acid Propanoyl chloride

Reactions of Acid Chlorides

1. Acid chlorides can react with water to form carboxylic acids. This reaction with water is
called hydrolysis of acid chlorides.

O H2O O

R Cl R OH
Acid chloride Carboxylic Acid

Example:

O O
H2O
Cl OH
Propanoyl Propanoic
chloride acid

2. Acid chlorides can also react with alcohols to form esters.

O O
+ R'OH
R Cl R OR'
Acid chloride Alcohol Ester

Example:
 O
O
Cl + OH
O

3. Acid chlorides can react with ammonia/amines to form amides.

O O
+ 2 NH3 + -
H + NH4 Cl
R Cl R N
Ammonia
Acid chloride H
Primary amide

O O
+ 2 R'NH2 R' + R'NH +Cl-
R Cl R N 3
Primary H
Acid chloride amine
Secondary amide

O O
+ 2 R'NHR" R' + R'NR"H +Cl-
R Cl R N 2
Secondary R"
Acid chloride amine
Tertiary amide

Examples:

O O
+ NH3 H + NH4+Cl-
Cl N
H

O O
+ CH3NH2 CH3
+ CH3NH3 Cl-
+
Cl N
H

Acid Anhydrides

Preparation of Acid Anhydrides

The most general method for preparing acid anhydrides is by reacting sodium salt of
carboxylic acids (sodium alkanoates) with acid chlorides.

O O O O
+
- +
R O Na R' Cl R O R'
Sodium Acid Acid anhydride
alkanoate chloride

Example:
 O O O O
- +
+
O Na Cl O
Sodium ethanoate Ethanoyl chloride Acetic anhydride
(sodium acetate) (acetyl chloride)

Reactions of Acid Anhydrides

1. Acid anhydrides can be hydrolysed by water to form carboxylic acid.

O O
H2O O O
R O R' +
R OH R' OH
Acid anhydride

Example:

O O O
H2O O
O +
OH OH

2. Acid anhydrides can also react with alcohols to form esters. This reaction requires a
base (eg. pyridine)
O O O
pyridine
+ R'OH
R O R R OR'
Acid anhydride Ester

Example:

O O O
pyridine
O + OH O

3. Acid anhydrides can react with ammonia/amines to form amides.

 O O O O
+ 2 NH3 H +
R O R' Ammonia R N R' O-NH4+
H
Primary amide

O O O O
+ 2R''NH2 R'' +
R N +
R O R' R' O-N
Primary H
amine R''
Secondary amide

O O O O
+ 2R''NHR"' R'' + +
R O R' R N R' O-NH2 R'''
Secondary R"'
amine R''
Tertiary amide

Examples:

O O O O
H O-NH4+
O + 2NH3 N
+
H

O O O O
+ 2CH3NH2 CH3 + +
O N O-NH3CH3
H

Esters

Preparations of Esters

1. Fishcher esterification

O O
H+
+ HO R'
R OH heat R' + H2O
R O
Carboxylic Alcohol
Ester
acid

Example:

O O
+
H
OH + OH O + H2O
heat

Benzoic acid Ethyl benzoate

2. Esters can also be synthesized from acid chlorides and alcohols. Pyridine is used as a
base to remove HCl that is formed during the reaction

O pyridine O
+ R'OH
R Cl R OR'
Alcohol
Acid chloride Ester

Reactions of Esters

1. Esters can be hydrolysed by water under acidic condition to form carboxylic acid and
alcohols.

O O
H+
R' + H2O + R'OH
R O R OH
Ester Carboxylic Alcohol
acid

Example:

O O
H+
O + H2O + CH3OH
OH

Methyl benzoate

2. Esters can also react with base (NaOH) to carboxylic acid salts and alcohols. The basic
hydrolysis is called saponification.

O O
R' + NaOH + R'OH
R O R O-Na+
Alcohol
Ester Carboxylic
salt

Example:

O O
+ NaOH
O O-Na+ + CH3OH

Methyl benzoate Sodium benzoate

3. Esters can react with ammonia/amines to form amide and alcohols.

 O O
R' + NH3 H + R'OH
R O R N
H
O O
R' + R"NH2 R" + R'OH
R O R N
H

Examples:

O O
+ NH3 H
O N + OH
H

O O
+ CH3NH2 CH3 + OH
O N
H

4. Esters can be reduced with lithium aluminium hydrides (LiAlH 4 ) to form alcohol.

O
LiAlH4
R' R OH + R'OH
R O then H2O
Alcohol Alcohol
Ester

Example:

O LiAlH4 OH + CH3OH
then H2O Methanol
Methyl benzoate Benzyl
alcohol