Contents

ALKANES ................................................................................................................................................. 2
ALKENES .................................................................................................................................................. 3
ALKYNES ................................................................................................................................................ 11
AROMATIC COMPOUNDS ...................................................................................................................... 14
ALKYL HALIDES ...................................................................................................................................... 19
POLYHALIDES ........................................................................................................................................ 24
AROMATIC HALIDES .............................................................................................................................. 26
ALCOHOLS ............................................................................................................................................. 27
PHENOLS ............................................................................................................................................... 35
POLYHYDRIC ALCOHOLS ........................................................................................................................ 37
CARBONYL COMPOUNDS ...................................................................................................................... 38
CARBOXYLIC ACIDS ................................................................................................................................ 44
DICARBOXYLIC ACIDS............................................................................................................................. 46
ACID CHLORIDES.................................................................................................................................... 47
ACID AMIDES ......................................................................................................................................... 50
ESTERS .................................................................................................................................................. 52
AMINES ................................................................................................................................................. 55
DIAZONIUM SALTS................................................................................................................................. 59

1
PAUL SSESANGA
 ALKANES
Methods of synthesis

NB: R is an alkyl goup (CH3-) or Hydrogen (H-)

Ni / Heat
1. RCH=CH2 + H2 RCH3CH3

Conc HCl
2. RCH2X + Zn RCH3 + ZnX2 X = Cl, Br, I, F

3. RCH=CHR1 LiAlH4 RCH2CH2R

1

Ether/ Heat
4. 2 RCH2X + 2Na RCH2CH2R + 2NaX X = Cl, Br, I, F

Heat
5. RCOOH + NaOH(s) RH + Na2CO3

Zn (Hg) / HCl/Heat
6. RCHO RCH3 + H2O

7. RCOR1 Zn (Hg) / HCl/Heat

RCH2R1 + H2O

Reactions

1. CH3CH3 + O2(g) 2CO2(g) + 3H2O(l)

U.V
2. CH4 + Cl2 CH3Cl + HCl

Mechanism
.
Cl Cl 2Cl

. .
CH3 + HCl
H3C H Cl

.
CH3 Cl Cl CH3Cl + Cl.

Cl. Cl. Cl2

2
PAUL SSESANGA
 300’C
3. RCH3 + HNO3 RCH2NO2 + H2O

Mechanism
. .
HO + NO2
HO NO2

.
H2 . RCH2 + H2O
R C H HO

. . RCH2NO2
RCH2 NO2

ALKENES
Methods of synthesis

3
PAUL SSESANGA
 ROH/ OH-
1. RCH2CH2X RCH=CH2 + X-
Heat

Mechanism

ROH + OH- RO- + H2O

H H

RCH=CH2 + ROH + X-
R C C X

H H

RO-

NB: R is an alkyl group and X is a halogen. And the above mechanism (Bimolecular elimination)
is for a primary alkyl halide, for a secondary and tertiary alkyl halides, the mechanism is
unimolecular elimination

ROH/ OH-
(CH3)3CX (CH3)2C=CH2 + X-
Heat

Mechanism

ROH + OH- RO- + H2O

CH3 CH3

H3C C + X-
H3 C C X

CH3 CH3

CH3
CH3 H

H3C C CH2 + ROH

H3C C C H

RO-

4
PAUL SSESANGA
 Conc H2SO4
2. RCH2CH2OH RCH=CH2 + H2O
180oC

Mechanisms

H2SO4 H+ + HSO4-

H H H H

R C C OH H+ R C C OH2

H H H H

H H

RCH=CH2 + H2O + H2SO4

R C C OH2

H H

HSO4-

NB: R is an alkyl group and the above mechanism (Bimolecular elimination) is for a primary
alcohol, for a secondary and tertiary acohols, the mechanism is unimolecular elimination

20% Conc H2SO4

(CH3)3COH (CH3)2C=CH2 + H2O
85oC

Mechanism

5
PAUL SSESANGA
 H2SO4 H+ + HSO4-

CH3 CH3

H3C C OH H+ H3C C OH2

CH3 CH3

CH3 CH3

H3C C + H2O
H3C C OH2

CH3 CH3

CH3
CH3 H

H3C C CH2 + H2SO4

H3C C C H

HSO4-

6
PAUL SSESANGA
 Pt
3. RC CH + H2 RCH=CH2
r.t

REACTIONS

CCl4
1. RCH=CH2 + X2 RCHXCH2X (X= Cl, Br, I)

Mechanism
H
RCH=CH2
R C C X + X-

X X H H

X H
H H2
R C C X
R C C X

H H
-
X

Ni
2. RCH=CH2 + H2 RCH2CH3
o
150 C

3. RCH=CH2 + HX RCHXCH3 (X= Cl, Br, I)

7
PAUL SSESANGA
 Mechanism
H
RCH=CH2
R C C H + X-

H X H H

X H
H
R C CH3
R C C H

H H
X-

ROOR
3. RCH=CH2 + HX RCH2CH2X (X= Cl, Br, I)

Mechanism

.
RO 2RO
OR

. .
X H RO ROH + X

.
RCH=CH2 . RCHCH2X
X

. .
RO H RCHCH2X RCH2CH2X + RO

. .
RO OR ROOR

8
PAUL SSESANGA
 H

4. RCH=CH2 + H2SO4 R C CH3

OSO3H

Mechanism

H2SO4 H+ + -OSO3H

RCH=CH2 RCHCH3

H+

OSO3H
- R CH CH3
RCHCH3 OSO3H

H2O
5. CH2=CH2 + O3 H2C O CH2 2HCHO + ZnO
Zn
O O

MnO4-/OH-
6. RCH=CH2 RCHOHCH2OH

O2 catalyst
7. nCH2=CH2 ( CH2CH2 )
o
High pressure/200 C

9
PAUL SSESANGA
 H
8. RCH=CH2 + Br2 + H2O R C CH2Br
OH

Mechanism

RCH=CH2
RCHCH2Br

Br Br

H H H H
O O

RCHCH2Br
RCHCH2Br

H
H H
R C CH2Br
O
OH
RCHCH2Br

10
PAUL SSESANGA
 ALKYNES
METHODS OF SYNTHESIS
EtOH
1. RCH2CHX2 RC CH + 2HX
OH-

Mechanism

EtOH + OH- EtO- + H2O

H X H

R C C H R C CH + EtOH + X-

H X X

EtO-

EtO-
H

RC CH + EtOH + X-
R C CH

2. CaC2 (s) + 2H2O (l) Ca(OH)2 (s) + CH CH

REACTIONS

CCl4
1. RC CH + 2X2 RCX2CHX2

11
PAUL SSESANGA
 Mechanism

RC CH RC CHX + X-

X X

RC CHX X- RCX CHX

RCX CHX RCX CHX2 + X-

X X

RCX2CHX2
RCX CHX2 X-

2. RC CH + 2HX RCX2CH3

Mechanism

RC CH RC CH2 + X-

H X

RC CH2 X- RCX CH2

RCX CH2 RCX CH3 + X-

H X

RCX2CH3
RCX CH3 X-

12
PAUL SSESANGA
 H2SO4 O
3. RC CH + H2 O R C H
HgSO4, 60oC

H2SO4 O
RC CR + H2 O R C CH2R
HgSO4, 60oC

Ni
4. RC CH + H2 RCH2CH3
Heat

Fe
5. 3 HC CH
Heat

6. HC CH (g) + 2NH3(aq) + 2AgNO3(aq) Ag2C2 (s) + 2NH4NO3 (aq)

13
PAUL SSESANGA
 AROMATIC COMPOUNDS
METHODS OF SYTHESIS

Pt or Pd
1. + H2
heat

Fe
2. 3 HC CH
Heat

COOH
Soda lime
3. + NaOH + Na2CO3
Heat

NH2 1. NaNO2 / HCl / <10oC

4.
2. H3PO2 / H2O

OH
Heat + ZnO
5. + Zn

REACTIONS

Conc HNO3 NO2

1.
Conc H2SO4 / 60oC

14
PAUL SSESANGA
 Mechanism

H2SO4 H+ + HSO4-

HO NO2 + H+ H2O NO2

H2O NO2 H2O + NO2

NO2 NO2

H NO2

NO2 + H+

H+ + HSO4- H2SO4

SO3H
Fumming H2SO4
2.

Mechanism

2 H2SO4 SO3 + HSO4- + H3O+

O H
O
S SO3-

15
PAUL SSESANGA
 H SO3H
H+ shift
SO3-

FeCl3 Cl
+ Cl2 + HCl
3.

Mechanism

Cl + [ FeCl4]-
Cl Cl FeCl3

H Cl

Cl + H+

[FeCl4]- + H+ FeCl3 + HCl

AlCl3 R
+ RX + HX
4.

Mechanism

R + [ AlCl3X]-
R X AlCl3

16
PAUL SSESANGA
 H R

R + H+

[AlCl3X]- + H+ AlCl3 + HX

NB: The above mechanism is for a 1o alkyl halide. For 2o and 3o alkyl halides, the X atom leaves
first to create carbonium ions which are attacked by the Pi-electrons in the Benzene ring

R
CHCH3
H+
5. + RCH=CH2

Mechanism

RCH=CH2 RCHCH3

H+
H
CHCH3
RCHCH3
R

H CHCH3
+ H+
CHCH3 R

R
O C O
AlCl3 + HCl
6. + RCCl

17
PAUL SSESANGA
 Mechanism

H
O
C R + [ AlCl4]-
RC Cl AlCl3
O

H C R
O
C R + H+
O

[AlCl4]- + H+ AlCl3 + HCl

7. C6H6 (l) + 15/2 O2 (g) 6 CO2 (g) + 3H2O (l)

Ni
8. + 3 H2
150oC

Cl
U.V Cl Cl
9. + 3 Cl2
Cl Cl
Cl

NOTE: Ortho-para (2 - 4) directors are -R, -OH, -NH2, -OCH3, -NHC-CH3, -OR, -Cl, -Br, -I.

Meta directors (3) are -COOH, -NO2, -CN, -SO3H. Eg:

CH3 CH3 CH3

Conc HNO3 NO2
+
Conc H2SO4 / 60oC

NO2

18
PAUL SSESANGA
 ALKYL HALIDES
METHODS OF SYNTHESIS

1. RCH=CH2 + HX RCHXCH3 (X= Cl, Br, I)

Mechanism

H
RCH=CH2
R C C H + X-
H H
H X

H X H
R C CH3
R C C H

H H

X-

ROOR
RCH=CH2 + HX RCH2CH2X (X= Cl, Br, I)

Mechanism
.
RO 2RO
OR

. .
X H RO ROH + X

.
RCH=CH2 . RCHCH2X
X

. .
RO H RCHCH2X RCH2CH2X + RO

. .
RO OR ROOR

19
PAUL SSESANGA
2. RCH3 + Cl2 RCH2Cl + HCl
Mechanism

.
Cl Cl 2 Cl

H
.
.
Cl RCH2 + HCl
R C H

. .
RCH2Cl + Cl
RCH2 Cl Cl

. . Cl2
Cl Cl

ZnCl2
3. ROH + HX Heat RX + H2O

4. ROH + PCl5 RCl + POCl3 + HCl

Pyridine
5. ROH + SOCl2 RCl + SO2 + HCl

REACTIONS

Reflux
1. RCH2X + NaOH RCH2OH + NaX

Mechanism
NaOH Na+ + OH-

H H

R C X R C OH + X-

H - H
OH
Na+ + X- NaX

20
PAUL SSESANGA
NB: The above mechanism is Bimolecular Nucleophilic Substitution undergone by 1o alkyl halides. 3o
alkyl halides under go Unimolecular Nucleophilic substitution whereas 2o undergoes both. Below is a
mechanism for 3o alkyl halide for the same reaction.

- Reflux
(CH3)3CBr + OH (CH3)3COH + Br-

Mechanism
CH3
CH3
+ Br
H3C C
H3C C Br

CH3
CH3

CH3 CH3

H3C C H3C C OH

CH3 OH CH3

Heat
2. RCH2X + RCH2O- RCH2-O-CH2R + X-

Mechanism
H H H

-
R C X R C O C R + X

H H H
H

R C O

O
Heat
3. RCH2X + RCOO- RCH2-O-C-R + X-

21
PAUL SSESANGA
 Mechanism
R O H
H
O
C
C + X-
H C X R
C R O
R O H

- Heat
4. RCH2X + CN RCH2CN + X-
Alcohol

Mechanism

R H

H C X R C C N + X-

H H

N C

Heat
RCH2X + AgNO2 RCH2-NO2 + RCH2-O-N=O
5.

6. RCH2X + NH3 RCH2NH2 + HX

RCH2NH2 + RCH2X (RCH2)2NH + HX

(RCH2)2NH + RCH2X (RCH2)3N + HX

(RCH2)3N + RCH2X (RCH2)4N + X -

ROH/ OH-
7. RCH2CH2X RCH=CH2 + X-
Heat

22
PAUL SSESANGA
 Mechanism

ROH + OH- RO- + H2O

H H

RCH=CH2 + ROH + X-
R C C X

H H

RO-

NB: R is an alkyl group or Hydrogen and X is a halogen. And the above mechanism
(Bimolecular elimination) is for a primary alkyl halide, for a secondary and tertiary alkyl
halide, the mechanism is unimolecular elimination

ROH/ OH-
(CH3)3CX (CH3)2C=CH2 + X-
Heat

Mechanism

ROH + OH- RO- + H2O

CH3 CH3

H3C C + X-
H3C C X

CH3 CH3

CH3
CH3 H

H3C C CH2 + ROH

H3C C C H

RO-
Ether
8. 2RCH2X + 2Na RCH2-CH2R + 2NaX
Heat

23
PAUL SSESANGA
 POLYHALIDES
METHODS OF SYNTHESIS

CCl4
1. RCH=CH2 + X2 RCHXCH2X (X= Cl, Br, I)

Mechanism
H
RCH=CH2
R C C X + X-

X X H H

X H
H H2
R C C X
R C C X

H H
X-

CCl4
2. RC CH + 2X2 RCX2CHX2
Mechanism

RC CH RC CHX + X-

X X

RC CHX X- RCX CHX

RCX CHX RCX CHX2 + X-

X X

RCX2CHX2
RCX CHX2 X-

3. RC CH + 2HX RCX2CH3

24
PAUL SSESANGA
 Mechanism

RC CH RC CH2 + X-

H X

RC CH2 X- RCX CH2

RCX CH2 RCX CH3 + X-

H X

RCX2CH3
RCX CH3 X-

Organic peroxide
4. CH3C CH + 2HBr CH3CH2CHBr2

5. CH3CHO + PCl5 CH3CHCl2 + POCl3

REACTIONS
Heat
1. CH3CHClCH2Cl + 2NaOH CH3CHOHCH2OH + 2NaCl

Alcohol
2. CH2BrCH2Br + 2KCN CH2CNCH2CN + 2KBr
Heat
KOH / Alcohol
3. CH3CH2CHCl2 CH3C CH
Heat

25
PAUL SSESANGA
 AROMATIC HALIDES
METHODS OF SYNTHESIS
FeCl3 Cl
1. + Cl2 + HCl
Mechanism
H
Cl + [ FeCl4]-
Cl Cl FeCl3

H Cl

Cl + H+

[FeCl4]- + H+ FeCl3 + HCl

OH Cl

2. + PCl5 + POCl3 + HCl

REACTIONS
Cl OH

300oC
1. + NaOH
Cu / 200 atm

Cl NH2

Cu2O
2. + 2NH3 + NH4Cl
200oC / Pressure

Cl CH3

+ CH3Br + 2Na + NaCl + NaBr

3.

NB: The halogen atom attached to the benzene ring is an ortho-para director to an incoming
electrophile in electrophilic substitution reactions

26
PAUL SSESANGA
 ALCOHOLS
METHODS OF SYNTHESIS

Reflux
1. RCH2X + NaOH RCH2OH + NaX

Mechanism
NaOH Na+ + OH-

H H

R C X R C OH + X-

H - H
OH
Na+ + X- NaX

NB: The above mechanism is Bimolecular Nucleophilic Substitution undergone by 1o alkyl halides. 3o
alkyl halides under go Unimolecular Nucleophilic substitution whereas 2o undergoes both. Below is a
mechanism for 3o alkyl halide for the same reaction.

- Reflux
(CH3)3CBr + OH (CH3)3COH + Br-

Mechanism
CH3
CH3
+ Br
H3C C
H3C C Br

CH3
CH3

CH3 CH3

H3C C H3C C OH

CH3 OH CH3

OSO3H HO
R CH CH3
+ H2SO4
2. R CH CH3 + H2O

27
PAUL SSESANGA
 Mechanism
H H
OSO3H O
R CH CH3
R C CH3 + -OSO3H

O
H
H

- OH
H H OSO3H
O R C CH3 + H2SO4

R C CH3 H

Al2O3
3. RCH=CH2 + H2O RCHOHCH3

O
Pt
4. RCH2-C-H + H2 RCH2CH2OH

O OH
Pt
R-C-R + H2 RCHR

O
H+
5. CH3-C-O-CH2CH3 + H2O CH3COOH + CH3CH2OH

NaNO2
6. RCH2NH2 RCH2OH + N2
HCl

Enzyme
7. C6H12O6 2C2H5OH + 2CO2

28
PAUL SSESANGA
 REACTIONS

1. 2RCH2OH + 2Na 2RCH2O-Na+ + H2

O
H+
2. RCH2OH + RCOOH R-O-C-R + H2O

Mechanism

OH
O
H+
C
C R OH
R OH

H H OH
OH
H
R C O C R
C
R C OH HO R
H OH
H

H H OH H OH2
+
H shift
R C O C R R C O C R

H OH H OH

H OH2 H O

R C O C R R C O C
R
H O H H

3. RCH2OH + R2SO4 R-O-R + RHSO4

O O
4. ROH + R-C-Cl R-O-C-R + HCl
O O O

5. ROH + R'-C-O-C-R' R-O-C-R' + RCOOH

29
PAUL SSESANGA
 ZnCl2
6. RCH2OH + HX RCH2X + H2O

Mechanism

HX H+ + X-

R R

H C OH H+ H C OH2

H H

R R

H C OH2 H C X + H2O

H
X- H

3o alcohols undergo unimolecular nucleophilic substitution shown below. 2o alcohols undergo

both
ZnCl2
(CH3)3COH + HX (CH3)3CX + H2O
Mechanism

HX H+ + X-
CH3
CH3

H3C C OH2
H3C C OH H+
CH3
CH3
CH3
CH3

H3C C + H2O
H3C C OH2

CH3
CH3
CH3
CH3

X- H3C C X
H3C C

CH3
CH3

30
PAUL SSESANGA
7. 3 RCH2OH + PCl3 3 RCH2Cl + H3PO3

RCH2OH + PCl5 RCH2Cl + POCl3 + HCl

Pyridine
8. RCH2OH + SOCl2 RCH2Cl + SO2 + HCl

0oC
9. RCH2OH + H2SO4 RCH2OSO3H + H2O

Mechanism

H2SO4 H+ + HSO4-

R
R

H+ H C OH2
H C OH

H
H
R R

H C OH2 H C OSO3H + H2O

H H
-
HO3SO

Conc H2SO4
10. 2 RCH2OH RCH2-O-CH2R + H2O
140oC

Mechanism
H2SO4 H+ + HSO4-

R
R

H+ H C OH2
H C OH

H
H

31
PAUL SSESANGA
 R H H H

H C OH2 R C O C R

H H H

OH

R C H

H
-
OSO3H
H H

H H H R C O C R + H2SO4

R C O C R H H

H H

Conc H2SO4
11. RCH2CH2OH RCH=CH2 + H2O
180oC

Mechanisms

H2SO4 H+ + HSO4-

H H H H

R C C OH H+ R C C OH2

H H H H

H H

RCH=CH2 + H2O + H2SO4

R C C OH2

H H

HSO4-

32
PAUL SSESANGA
 NB: R is an alkyl group and the above mechanism (Bimolecular elimination) is for a primary alcohol,
for a tertiary acohols, the mechanism is unimolecular elimination. Secondary alcohol undergoes both
mechanisms at 110oC and 60% conc H2SO4

20% Conc H2SO4

(CH3)3COH (CH3)2C=CH2 + H2O
85oC

Mechanism

H2SO4 H+ + HSO4-

CH3 CH3

H3C C OH H+ H3C C OH2

CH3 CH3

CH3 CH3

H3C C + H2O
H3C C OH2

CH3 CH3

CH3
CH3 H

H3C C CH2 + H2SO4

H3C C C H

HSO4-

Al2O3
12. CH3CH2OH (g) CH2=CH2 + H2O

O
H+/ Cr2O72-
13. RCH2OH R-C-H
Heat

OH O
H+/ Cr2O72-
RCHCH3 R-C-CH3
Heat
33
PAUL SSESANGA
 Ag
14. CH3CH2OH (g) + 1/2 O2 (g) CH3CHO + H2O
500oC

15. CH3CHOHCH2CH3 + 4I2 + 6NaOH CHI3 + CH3CH2COONa + 5NaI + 5H2O

34
PAUL SSESANGA
 PHENOLS
METHODS OF SYNTHESIS
SO3H
OH
1. NaOH / Heat
1.
2. HCl

N2+Cl- OH

HCl
+ H2O + HCl + N2
2. Heat

Cl OH

200 atm
3. + NaOH + NaCl
o
300 C / Cu

REACTIONS

OH O Na

+ 2 Na + H2
1.

OH O Na

+ NaOH (aq) + H2O

2.

OH
Heat + ZnO
3. + Zn
O

OH O C CH3
H+
4. + CH3COOH + H2O

35
PAUL SSESANGA
 O
OH COOH O C
H+
5. + + H2O

O
OH COCl O C
6. + + HCl

O
OH O O C CH3
O
7. + H3C C O C CH3 + CH3COOH

OH O R

8. + RX + HX

OH X
9. + PX5 + POX3 + HX

OH
NH2
10. ZnCl2
+ NH3 + H2 O
200oC

NB: The -OH group is an ortho-para director to the incoming electrophile in electrophilic
substitution reactions
OH OH
Br Br
11. + 3 Br2 + 3 HBr

Br
OH OH

Ni
+ 3 H2
12. 200oC

36
PAUL SSESANGA
 OH

O + 3 HCl
3 + FeCl3
13. Fe
O O

POLYHYDRIC ALCOHOLS
METHODS OF SYNTHESIS

200oC
1. H2C CH2 + H2O HOCH2CH2OH
Pressure
O

MnO4- / H+
2. H2C CH2 HOCH2CH2OH
Heat

REACTIONS

1. HOCH2CH2OH + 2Na Na+O-CH2CH2O-Na+

MnO4- / H+
2. HOCH2CH2OH HOOC-COOH
Heat

37
PAUL SSESANGA
 CARBONYL COMPOUNDS
METHODS OF SYNTHESIS
O
H+/ Cr2O72-
1. RCH2OH R-C-H
Heat
OH O
H+/ Cr2O72-
RCHCH3 R-C-CH3
Heat
O

Heat
2. (HCOO)2Ca CaCO3 + H C H

Heat
(CH3COO)2Ca + (HCOO)2Ca 2 CaCO3 + 2 CH3CHO

O
Heat
(RCOO)2Ca CaCO3 + R C R

H2O
3. CH2=CH2 + O3 H2C O CH2 2HCHO + ZnO
Zn
O O

H2SO4 O
4. RC CH + H2O R C H
HgSO4, 60oC

H2SO4 O
RC CR + H2O R C CH2R
HgSO4, 60oC

O O

5. R C Cl + H2 R C H + HCl

R
O C O
AlCl3 + HCl
6. + RCCl

38
PAUL SSESANGA
 Mechanism
H
O
C R + [ AlCl4]-
RC Cl AlCl3
O

H C R
O
C R + H+
O

[AlCl4]- + H+ AlCl3 + HCl

REACTIONS

1. RCH2CHO + Br2 RCHBrCHO + HBr

RCHBrCHO + Br2 RCBr2CHO + HBr

O
Ni
2. RCH2-C-H + H2 RCH2CH2OH
Heat
O Ni OH
R-C-R + H2 RCHR
Heat
OH
O
H2SO4
+ KCN R C C N
3. R C R

Mechanism

KCN + H2SO4 HCN + KHSO4

HCN H+ + -
CN

39
PAUL SSESANGA
 OH
O +
H
R C R
R C R

OH
OH

R C C N
R C R

R
C N

OH
O

+ NaHSO4 R C SO3Na
4. R C R

H
Mechanism

NaHSO4 Na+ + HSO4-

O
O O

O R C R
O S C R

O S
OH R

OH
O O O OH
+
H shift
O S C R O S C R

OH R O R

O OH O OH
Na+
O S C R O S C R

O R Na+ O R

5. CH3CHO + PCl5 CH3CHCl2 + POCl3

CH3COCH3 + PCl5 CH3CCl2CH3 + POCl5

40
PAUL SSESANGA
6. Condensation reactions

R H+ R
C O + H2N A C N A + H2O
R R

Mechanism

OH
O +
H
C
C
R R
R R

OH OH H

R C R R C N A

R H
H2N A

OH2
OH H H
H+ shift
R C N
R C N A
A
R
R H

OH2 R
H
C N A + H2O
R C N R
A
R

R can be an alkyl group to make a ketone or one R can be a Hydrogen atom to make an
aldehyde. A can be one of the following group of atoms from the corresponding reagents

41
PAUL SSESANGA
 A From Reagent

NH2 From H2N NH2

OH From H2N OH

NH H2N NH

From

H2N NH
NH

From
O2N NO2
O2N NO2

O O

H From H
N C NH2 H2N N C NH2

Example
O
H
H2N OH C N OH + H2O
H C H +
H
O OH O
-
OH H2
7. 2 H3C C CH3 H3C C C C CH3

CH3

OH O
-
OH H2
2 CH3CHO H3C C C C H
H

42
PAUL SSESANGA
 Mechanism

O
O
H2 H2C C H + H2O
H C C H

HO-
O O H O

H3C C C C H
H3C C H
O
H H

H2C C H

O
H OH H O
H

H3C C C C H
O H O
H H
H3C C C C H

H H

MnO4- / H+
8. RCHO RCOOH
Heat

9. CH3CHO + 2 Ag(NH3)2NO3 + H2O CH3COONH4 + NH3 + 2 NH4NO3 + 2 Ag

10. CH3-C-R + 3 I2 + 4 NaOH CHI3 + RCOONa + 3 NaI + 3 H2O

43
PAUL SSESANGA
 CARBOXYLIC ACIDS
METHODS OF SYNTHESIS

O
H+/ Cr2O72- H+/ Cr2O72-
1. RCH2OH R-C-H RCOOH
Heat Heat
O H2O/Heat
H+
2. R C N + H2O R C NH2 RCOOH + NH3
Heat H+ or -OH
Heat
3. HOOCRCOOH RCOOH + CO2

CH3 MnO4- / H+ COOH

4.
Heat

REACTIONS
O
H+
1. RCH2OH + RCOOH R-O-C-R + H2O

Mechanism

OH
O +
H
C
C R OH
R OH
H H OH
OH
H
R C O C R
C
R C OH HO R
H OH
H
H H OH H OH2
H+ shift
R C O C R R C O C R

H OH H OH

H OH2 H O

R C O C R R C O C
R
H O H H

44
PAUL SSESANGA
 O O

2. 3 R C OH + PCl3 3 R C Cl + H3PO3

O O

R C OH + PCl5 R C Cl + POCl3 + HCl

O O

R C OH + SOCl2 R C Cl + SO2 + HCl

3. RCOOH + Na RCOONa + H2

2 RCOOH + ZnO (RCOO)2Zn + H2O

2 RCOOH + Na2CO3 2 RCOONa + CO2 + H2O

RCOOH + NaOH RCOONa + H2O

RCOOH + NH4OH RCOONH4 + H2O

LiAlH4 / Ether
4. RCOOH RCH2OH

Soda lime
5. RCOOH + NaOH R-H + Na2CO3
Heat
O

Heat
6. (HCOO)2Ca CaCO3 + H C H

Heat
(CH3COO)2Ca + (HCOO)2Ca 2 CaCO3 + 2 CH3CHO

O
Heat
(RCOO)2Ca CaCO3 + R C R

45
PAUL SSESANGA
 DICARBOXYLIC ACIDS
METHODS OF SYNTHESIS

O O O O
H2 H2 H+/Cr2O72- H+/Cr2O72-
1. HO C C OH HC CH HO C C OH
Heat Heat
O
H2C C N H+ / Heat H2C C OH
2.
H2C C N H2O H2C C OH

O
REACTIONS

1. HOOC-COOH + 2 NaOH NaOOC-COONa + H2O

Heat
2. HOOC-COOH HCOOH + CO2

SUBSTITUTED CARBOXYLIC ACIDS

Chloro ethanoic acid

U.V
CH3COOH + Cl2 ClCH2COOH + HCl

ClCH2COOH + 2 NaOH HOCH2COONa + NaCl

ClCH2COOH + 2NH3 H2NCH2COOH + NH4Cl

Hydroxy ethanoic acid

ClCH2COOH + NaOH HOCH2COOH + NaCl

HOCH2COOH + HCl ClCH2COOH + H2O

H+ / Cr2O72-
HOCH2COOH HOOC-COOH

46
PAUL SSESANGA
 ACID CHLORIDES
METHODS OF SYNTHESIS

O O

1. 3 R C OH + PCl3 3 R C Cl + H3PO3

O O

R C OH + PCl5 R C Cl + POCl3 + HCl

O O

R C OH + SOCl2 R C Cl + SO2 + HCl

REACTIONS
O O

1. R C Cl + H2O R C OH + HCl

Mechanism
O
O H
R C Cl + Cl-
R C O
H

H H
O
O H
R C OH + H+
R C O
H

H+ + Cl- HCl

O O

2. ROH + R-C-Cl R-O-C-R + HCl

47
PAUL SSESANGA
 Mechanism

O O H

R C Cl R C O R + Cl-

HO R
O
O H

R C O R + H+
R C O R

H+ + Cl- HCl

O O H
Heat
3. R C Cl + RNH2 R C N R + HCl

O O
Heat
R C Cl + NH3 R C NH2 + HCl

Mechanism

O O H

R C Cl R C N H + Cl-

NH3

O H O H

R C N H R C N H + H+

H+ + Cl- HCl

48
PAUL SSESANGA
 R
O C O
AlCl3 + HCl
4. + RCCl

Mechanism
H
O
C R + [ AlCl4]-
RC Cl AlCl3
O

H C R
O
C R + H+
O

[AlCl4]- + H+ AlCl3 + HCl

49
PAUL SSESANGA
 ACID AMIDES
METHODS OF SYNTHESIS
O O
Heat
1. R C Cl + NH3 R C NH2 + HCl

O O
O O

+ NH3 R C NH2 + R C OH
2. R C O C R

O O

+ NH3 R C NH2 + ROH

3. R C O R

Mechanism

O O

R C O R R C NH3

NH3 O R

O O
+
H shift
R C NH3 R C NH2

O R HO R

O
O

R C NH2 + ROH
R C NH2

HO R

We can use concentrated NH3 or Amines in the above reactions

REACTIONS
O H O
H+
1. R C N R + H2O R C OH + R NH2
Heat

50
PAUL SSESANGA
 O
Heat
2. R C NH2 + H2O RCOOH + NH3
H+

Mechanism

O H+ OH

R C NH2 R C NH2

OH OH

R C NH2 R C NH2

OH2
H2O

OH OH
H+ shift
R C NH2 R C NH3

OH2 OH

H
O
O

R C OH + NH3
R C NH3

OH

O
LiAlH4
3. R C NH2 RCH2NH2 + H2O
Ether

O
Heat
4. R C NH2 + Br2 + 4 KOH RNH2 + 2KBr + K2CO3 + 2H2O

O
KOH / Br2 NH2
C NH2
Heat

51
PAUL SSESANGA
 ESTERS
METHODS OF SYNTHESIS
O
H+
1. RCH2OH + RCOOH R-O-C-R + H2O
Mechanism

OH
O +
H
C
C R OH
R OH
H H OH
OH
H
R C O C R
C
R C OH HO R
H OH
H
H H OH H OH2
H+ shift
R C O C R R C O C R

H OH H OH

H OH2 H O

R C O C R R C O C
R
H O H H

O O

2. ROH + R-C-Cl R-O-C-R + HCl

Mechanism
O O H

R C Cl R C O R + Cl-

HO R
O
O H
R C O R + H+
R C O R

H+ + Cl- HCl

52
PAUL SSESANGA
 O O O

3. ROH + R'-C-O-C-R' R-O-C-R' + RCOOH

REACTIONS
O O
-
OH
R C O R + H2O R C OH + R OH
1.

Mechanism

O O

R C O R R C O R

OH

OH
O O H
O H H
R C O R + -OH
R C O R
OH
OH

O H O

R C O R R C OH + R OH

OH

O O
LiAlH4
R C O R R C OH + R OH
2.

O O

+ NH3 R C NH2 + ROH

3. R C O R

53
PAUL SSESANGA
 Mechanism

O O

R C O R R C NH3

NH3 O R

O O
+
H shift
R C NH3 R C NH2

O R HO R

O O

R C NH2 + ROH
R C NH2

HO R

54
PAUL SSESANGA
 AMINES

METHODS OF SYNTHESIS

1. RCH2X + NH3 RCH2NH2 + HX

RCH2NH2 + RCH2X (RCH2)2NH + HX

(RCH2)2NH + RCH2X (RCH2)3N + HX

(RCH2)3N + RCH2X (RCH2)4N + X -

Mechanism
H
H

R C NH3 + X-
R C X

H
H
NH3

H H H

R C N H R C NH2

H H H

LiAlH4 or H2
2. R C N R C NH2
Na / Ethanol
O
LiAlH4
3. R C NH2 RCH2NH2 + H2O
Ether
O
Heat
4. R C NH2 + Br2 + 4 KOH RNH2 + 2KBr + K2CO3 + 2H2O

NO2 NH2
Sn / Conc HCl
5.

Sn / Conc HCl
RNO2 RNH2

55
PAUL SSESANGA
 O H O
+
H
6. R C N R + H2O R C OH + R NH2
Heat
Mechanism

O H H+ OH H

R C N R R C N R

OH H OH R

R C N R R C N H

H2O OH2

OH H OH
H+ shift
R C N R R C NH2 R

OH2 OH

H
O H O

R C N R R C OH + R NH2

OH H

O H O
-
OH
R C N R + H2O R C OH + R NH2
Heat

Mechanism

O H O H

R C N R R C N R

OH OH

56
PAUL SSESANGA
 O H O

R C N R R C OH + R NH

OH

R NH + H2O R NH2 + OH

REACTIONS

1. R NH2 + H2O R NH3 + OH

> 10oC
2. R NH2 + HNO2 ROH + N2 + H2O

NH2
OH
NaNO2
+ N2 + H2O
HCl > 10oC

H R
3. R N R + HNO2 N N O + H2O
R
R

R N R + HNO2 R3 NH NO2
4.

Heat
R3 NH NO2 R2-N-N=O + R-OH

NH2 N2Cl
NaNO2
5.
HCl < 10oC

Mechanism

57
PAUL SSESANGA
 NaNO2 + HCl HNO2 + NaCl

HNO2 HO- + +
NO

NH2 +
N=O H2N N O

HN N OH
H2N N O +
H shift

N N OH2
N N OH

H+ shift

N N
N N OH2

+ H2O

O O H
Heat / Pyridine
6. R C Cl + RNH2 R C N R + HCl

O O O H O

R NH2 + R' C O C R' R' C N R + R' C OH

7. RNH2 + Na RNHNa + H2

R2NH + Na R2NNa + H2

8. RNH2 + R'X RNHR' + HX

58
PAUL SSESANGA
 DIAZONIUM SALTS
METHODS OF SYNTHESIS

NH2 N2Cl
NaNO2
1.
HCl < 10oC

REACTIONS

N2Cl

NaOH
1. +

N2Cl

2. + H3PO2

N2Cl OH

H+ / H2O
3.
O
N2Cl CN C NH2

CuCN H+ / H2O
4.

N2Cl Cl

CuCl / HCl
5.

59
PAUL SSESANGA
 N2 OH

6. + N N OH

Mechanism

H
OH
N N OH N N

H
OH N N OH

N N

N2 NH2

7. + N N NH2

N2 N
OH N
OH
8. +

60
PAUL SSESANGA