Foundations of Organic Chemistry

 2008

Cover Designer : Ahmed Arafa 0927099651

Interior Designer : Wail G. ParPrasAkys
ISBN 978-9959-1-0309-3
ISBN 978-9959-1-0310-9



9090509 9096379 :
9097073 :
nat_Lib_Libya@hotmail.Com :


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VI

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331
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285
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296

VII







.



.



.

.

.

/ /
.
/ / /
.

VIII

Bonding and Molecular Properties


photosynthesis

" " .


) ( .


Torbern Bergman 1770

1808
J.J.Berzelius
Organisms

.
: Vital force theory

.
Friedrich Wohler 1828
) Urea 254 (
Ammonium Cyanate
H2NCONH2

NH4 CNO

Herman Kolbe
Marcelin Berthelot
.

) ( .

) ( .

)110(

)47(

: Atomic theory 1800

1808 John Dalton
-:
.1 Atom
Element .
.2 .
.3 3:2 , 3:1 , 2:1 , 1:1
.4
.
: Atomic structure Particles 30
Protons
Neutrons Electrons
: Nucleus ) p ( n
) (

) e (
.
) : Atomic number (Z
Z = p = e
) : Atomic weight (A
Mass number A = p + n
F

19

12

16

1-1 :
: = = = 8
= = 8 = 8 16 .

: = 6 = 6 12 .
: = 10 = 9 19 .
: Quantum mechanics 1926
" " Wave mechanics Schrodinger
" " W. Heisenberg
.

Lauis De Broglle 1923



.

: Atomic orbital's


.
: Orbital's shapes
Electron cloud

) ( f , d , p , s

.
: Energy of electrons -:
.1 ] [ .
.2 .
.3 sub orbital
s .
.4 p , s
s p .

10

14

.5 p " "
.6 .
.7 s .
: Electron configuration

-:
: Aufbau principle Building up

-:
4

1
2

1s

n = 1 ....... K

2p

2s

2 ....... L

3d

3p

3s

3 ....... M

4f

4d

4p

4s

4 ....... N

5g

5f

5d

5p

5s

5 ....... O

3
5
6
7
9

: Pauli exclusion principle

: Hund,s rule

.
2-1
6C , 7N , 8O , 9F

2s22p2

1s2 2s22p2

6C

2s22p3

1s2 2s22p3

7N

2s22p4

1s2 2s22p4

8O

2s22p5

1s2 2s22p5

9F

.
: valence electrons
) Outer-Shell ( the valence shell
.
5

: Chemical bonds
.
: Ionic bond
2
.
: Electronegativity

.
4
4

) ( ns2np6 .
Electrostatic attraction
.

H
2.1
F

Be

Li

4.0

3.5

3.0

2.5

2.0

1.6

1.0

Cl

Si

Al

Mg

Na

3.0

2.5

2.1

1.8

1.5

1.2

0.9

Br

Ca

2.8

1.0

0.8

I
2.5

3-1
1

: 1s2 2s22p6 3s1

11Na

: 1s2 2s22p6 3s23p5

17Cl

/ / Cation
/ / Anion

= 2.1 = 0.9 3.0

.
Na 2,8,1 + Cl 2,8,7

Na 2,8 Cl 2,8,8

NaCl

2
: 1s2 2s22p6 3s23p6 4s2

20Ca

/ / .

= 2.0 = 1.0 3.0

Cl 2,8,8
Ca 2,8,8

Ca 2,8,8,2 + 2 Cl 2,8,7

Cl 2,8,8

CaCl2

( ns2np6 ) Octet rule

2 1
) 1 ( .

: Covalent bond
-:
:
.1 : Single bond
Sigma

.2 : Double bond
Pi
.3 : Triple bond

:
.1 : Pure covalent bond
.
.2 : Polar covalent bond
2
partial negative -
partial positive +

.

.
: Ionic character

.
M
C
M = Mg , Li

Y
C

Y = O , N , Cl , Br , I

4-1
1
: 1s2 2s22p3

7N

/ .

: 1s2 2s22p5

9F

/ .

= 1 = 3 4
F

N
F

F N
F

N + 3 F

NF3

2 :
O

O + O

O O

O2

3
N

N + N

N N

N2

: Structural theory Kekule

Couper Butleroff
-:
.1 .
.2 .
:
:
:

O,S

F , Cl , Br ,
I
1

Chemical formulas
: Structural formulas
-:
1 : Line formula Kekule structures
.
2 : Condensed formula
.
3 : Skeletal formula



.
5-1
(CH3)4C

(CH3)2CHCH2CH3 ,

H
H

H
H

H
H
C

H
H

H
H

H
C

CH3(CH2)3CH3

(CH3)2CHCH2CH3

10

H
H

CH3(CH2)3CH3

(CH3)4C

6-1

Line segment
) (4 -:
4

5
CH3 3 = 1 4 = C1 5
H CH2 2 = 2 4 = C2 3 4
CH3CH2CH2CH2CH3

H CH 1 = 3 4 = C1 C2
H CH2 2 = 2 4 = C3 C4 ,

C5

2
1

H2
C
CH2

5
7

2
1

HC
HC

H CH 1 = 3 4 = C1 C3,
C6 ,C5 , C4 C6 , C3 CH3 H
C 0 = 4 4 = C2
CH3
CH3

C
H

CH3
C
H

C
H

C
H

HC

4 : Electron-dot formula Lewis structures

Gilbert N. Lewis .
7-1 7N , 8O :

2px 2py 2pz

11

7N : 1s 2s 2p

2s

: 1s2 2s22p4

2px 2py 2pz

8O

2s

8-1 Na2O , Li3N , CH4 :

H
x

C
x

Li

-3
xN x
x

Li

Li

Na

-2
xO x

Na

5 Three dimension formula

-:
H
C

H
H

) ( : Empirical formula
.
: Molecular formula


Cyclopentane Cyclohexane Ethylene CH2
MgCl2 , KI , AgCl
:
.1 ) Qualitative analysis ( .
.2 ) Quantitative analysis ( .
.3 = / .
.4 .

12

:
.1 .
.2 = x .
.3 = / .
:
.1 .
.2 = / .
.3 = x .
9-1 %92.26
78
= 7.74 = 92.26 100

7.74 x 78 = 6.04
100

92.26 x 78 = 71.91
100

6.04 = 5.99
1.008

71.91 = 5.99
12

C6H6 CH

10-1 C
54.4 4.58 40.9
176 ) ( C=12.01 , H=1.01 , O=16
= 3.41 mol

= 4.53 mol
= 3.41 mol

3.41 = 1
3.41

1 mol
12.01 g
1 mol
1.01 g
1 mol
16.0 g

moles C = 40.9 g X

moles H = 4.58 g X
moles O = 54.4 g X

4.53 = 1.33
3.41

3.41
=1
3.41

3 C3H4O3 :

.
13

176 = 2
88
2 C6H8O6 :

11-1
N2H4

C10H20 ,

NH4SO4
CH2
NH2

(NH4)2S2O8
C10H20
N2H4

(NH4)2S2O8 ,

12-1 %60 .

O

_____
60
16

_____
40
32

3.75

1.25

_____
3.75
1.25

1.25
_____
1.25

SO3 .
Classification of organic compounds

-:
.1 )
( .
.2 ) ( .
.3 ) ( .

14

.4 )

( .
Functional group
.
-:
Function group

Family name

CH3

CH3

-ane

Alkane

CH2

CH2

-ene

Alkene

HC

-yne

Alkyne

OH

CH3

-ol

OH

Alcohol

CH3

ether

Ether

NH2

CH3

-amine

NH2

Amine

Simple example

CH

CH3

O
H

CH3 C
O

CH3

CH3 C
O

OH

CH3 C

Name ending

-al

Aldehyde

C
O

-one

-oic acid

OH

15

Ketone

Carboxylic

acid

VSEPR
The Valence Shell Electron Pair Repulsion Theory

.
.1 : Central atom .
.2
Bonding nonbonding
.3
) ( .
.4 lone pair
bond pair

<

<
.5 .

.6 .
.7
.

.8 .
: Hybridization

.
: Molecular orbital

.
16

.
Methane CH4
1s2 2s22p2 :

6C:

1s1 ,

1H:

2s

2p
2s

3 2s 2p
2s
2p 4
.

sp3

4 sp3
s p

sp3

5
o
bond angles 109.5

sigma
.

17

+ 4H

H
1s

H
1s

sp3

H
1s

H
1s

Energy

6 1s
4
sigma .

2s

Energy

2p

Energy

2
2s 2p
4
.

Energy

1
2s
2p

2p

tetrahedral

90o
) ( p s

Ethene CH2=CH2

pz
sp2

Energy

2s 2p
3
pz
sp2
s p

o
120
-:
-
9 sp2
1s
C-H

Planar triangle
9 sp2
C-C

18

Pi
.

Ethyne HCCH

py pz
sp

Energy

2s 2p

py , pz
.
sp
s p

o
180
-:
-
9 sp
1s

C-H

Geometry
Linear

9 sp
C-C

pz , py CC .

19

:
angstroms
10-10 .
)bond length (Ao

bond

molecule

1.10

Csp3-H1s

methane

1.54

Csp3-Csp3

1.10

Csp3-H1s

1.33

Csp2-Csp2

1.076

Csp2-H1s

1.20

Csp-Csp

1.06

Csp-H1s

ethane

ethene

ethyne

-:
.1 C-C C=C
CC .
.2 C-H C-C
s (%50) sp (%33) sp2 (%25) sp3
s .
C-C
)bond length (Ao

hybrid orbital

1.54

sp3-sp3

1.50

molecule
CH3

CH3

sp -sp

CH3

CH

CH2

1.47

sp2-sp2

CH CH2

CH

CH2

1.46

sp-sp3

1.43

sp-sp2

1.37

sp-sp

CH2

CH

CH3

CH

CH

CH

CH C

C-C s
20

: Acidity H+
HCCH > H2C=CH2 > CH3-CH3 :
sp sp2,sp3
sp sp
HCC -

s Pauling
:
:

Csp

Csp2

Csp3

2.99

2.66

2.48

Ammonia NH3
2s 2p 4
sp3 1s

o107 .

.

Trigonal pyramidal
Water H2O
1s 2p
sp3 o105 .
sp3 1s

.

.

Angular
21

-:

AX 3

120

sp2

AX 4

109.5

sp3

AX3

107

sp3

105

sp3

AX 2

AX2

180

sp

A ) (
X ) ( .
.
13-1
, H3C+ , BF3 , H2CO

A
XF

AX3 sp .

AX3 sp

XH

A
XH

H
H

H3C

HX

X H AX3 sp2
H AX3

sp .

22

VSEPR


.
.1 :

o109.5 .
.2 : sp3
N-H o107
.
.3 :

o105
.
.4
.
H

121.7 o

C
H

H
H

C
H

109.6 o

H
H

C
H

.5 NF3 F-N-F o102

N-F N-H
H.A Bent .
: Bent rule
p
s .
Difluoro methane CH2F2 F-C-F o109.5
s %25 H-C-H o109.5 s %25
23

Polyvalent
)(

CF4 CH3F C-
F .

)molecule C-F (Ao

CH3F
1.39
CH2F2
1.35
CHF3
1.33
CF4
1.32

: p
s
.
2
3
sp > sp > sp >> p -:
C-X
dipole
moment

452
351
293
234

4
3
2.8
2.5

1.39
1.78
1.93
2.14

1.85
1.87
1.81
1.62

H3C-F
H3C-Cl
H3C-Br
H3C-I

C
%p
%s

Bond strength
KJmol-1

electronegativity

)C-X ( Ao

molecule

* 34

p s

14-1 Carbonyl fluoride F2CO

F-C-F sp2
F 126o

1.20Ao

108o

C
126o

1.42A

C=O C-F

F-C-F
F-C-O

24

15-1
H

121.7o

CH2

123o

CH2

117o

125o

Cl

CH2

114o

F
C
F

Cl

110o

.
16-1 (CH3)2C=CH2 o114 CH3-C-CH3
C=C CH3
o114 .
CH3
114o

H
C

repulsion

CH3

CH3
117o

H
C

CH3

C
H

17-1 Trimethyl amine (CH3)3N o108

. CH3
.
18-1 Hydrogen sulfide H2S o92
p
VSEPR

VIA , VA )
( S , P
p
s .

19-1 C-C-C H2C=C=CH2

180o

C CH2

2
sp

sp

H2C
sp 2

.
25

: Molecular bonding

-:
.1 Van der Waals forces
.2 Dipole-dipole forces
.3 Hydrogen bonds
/ ) (


) ( .



.

F < Cl < Br < I
.
20-1

.
/

.
21-1

20

131

10

54

Ne ,

Xe ,

CH 4 , H2 ,

( Xenon ) Xe
.

26

/

) ( N , O , F .


sp3
.

Hydrofluoric HF
) ( .

CH3Cl
.

27

: Resonance
Carbonate ion CO32- :
O

O
O

C-O


Hybrid -:

O
C

.1
.

.2 .
.3 .
.4 .
.5 .
.6 .
.7 .

28

22-1
CH3
1 CH CH2

CH3

C CH CH2

H3C

CH CH2

2 H2C CH CH CH2

CH3
3

CH

H2C

H2 C

CH3

H 3C

H2C CH

CH CH2

H2C CH

H 2C

H2C CH
O

O
CH3

C CH CH2

H 3C

2 H2C CH CH CH2
.
3

CH3
CH

H 2C

H2C

23-1 Hydrazoic acid

H

29

:
.
: Homolytic cleavage
Free radical

A B

A +B

: Heterolytic cleavage
Ion

A- + B+
A+ + B-

A B

: Reactive intermediates
.
.1
Electrophile .
CH4

CH3 + H

.2 : Carbocation Carbonium ion

.
+ X-

.3 : Carbanion
Nucleophile .
+ H+

.4 : Carbene
.
30

X
+ Y+

+ X-

C
Y

delocalized
electron releasing

.
.

H3C+ < RH2C+ < R2HC+ < R3C+

24-1
CH3

CH3

CH3

H3 C CH CH CH3 H3 C C CH2 CH3 CH CH CH CH

2
2
3
CH3
CH2 CH3

CH3

CH3
2o

3o

< CH3 CH CH CH3 < CH3 C

1o

CH2 CH CH2 CH3

: Bond energies -:
1 : Dissociation energy D
.

( Y-Z )g

)Y(g) + Z(g

2 : Bond energy E
CH4 C-H
.
434.8 KJ/mol

CH3 + H

CH4

459.8 KJ/mol

CH2 + H

CH3

434.7 KJ/mol

+ H

CH

CH2

338.6 KJ/ mol

+ H

CH

31

.
Bond / Ao

Energy KJ mol-1

334.7
694.5
284.5
615.1
866.1
452
351
293
234

Energy KJ mol-1

C O 1.43
C O 1.20
C N 1.47
C N 1.30
C N 1.16
C F 1.39
C Cl 1.78
C Br 1.93
C
I 2.14

/ Ao

434.8
409.7
397.1
380.4
414.2
347.3
606.7
803.3

Bond

H 3C H
CH3 CH2
H
(CH3)2 CH H
(CH3)3 C H
C H 1.10
C C 1.54
C C 1.33
C C 1.20

.
.
)24 ( .
.


-:
H

CH3

434.8 kJmol-1

CH3

CH3CH2

409.7 kJmol-1

CH3

367.9 kJmol-1
CH3

CH3

CH3 CH2

355.3 kJmol-1
CH CH2

(CH3)2CH

397.1 kJmol-1

CH3

380.4 kJmol-1

351.1 kJmol-1

CH2

CH

sp3-sp3
301 kJmol-1

kJmol-1

CH2
292.5 kJmol-1

CH2

405.5

CH2
300.1 kJmol-1

32

(CH3 )3C

338.6 kJmol-1

sp2-sp3

CH3

CH3

(CH3)2 CH
CH3

(CH3)3C

: Formal charges -:

Nitromethane CH3NO2
H

H C N
O

4 3 ) ( + 1

) ( - 1
-:
= 5 = 8

= 0
8 - 0 = +1
___ formal charge = 5 -
2

-:
= 6 = 2 = 6
2 - 6 = -1
___ formal charge = 6 -
2

25-1 Dimethyl sulfoxide

O

O
CH3

CH3 H3C

CH3

: 1s 2s 2p 3s 3p

16S

= 6 = 6 = 2
6 - 2 = +1
___ formal charge = 6 -
2

)(1-

33

: Dipole moment

-:
= ) ( x ) (
) = q x d (Ao
Debye Peter J.W. Debye D
1D = 3.33x10-30 Coulomb meters ( C.m ) : SI

26-1 1.6x 10-19 Cm 100Pm

= q x d = 1.6x10-19 C x 100x10-12 m = 1.6x10-29 Cm ,

1Pm = 10-12 m

1.6x10-29 Cm x 1D
________________
= 4.8 D
3.33x10-30 Cm

.
.1 = .
.2 =

.
Nonpolar molecules
BF3

CO2

CCl4

CH4

formula
) (D

CH4 CCl4

Cl
Cl
Cl

Cl

=0
34

CO2

.

O C O
BF3

Polar molecules
NF3

NH3

H2O

SO2

CH3Cl

0.24

1.47

1.85

1.63

1.87

formula
) (D

CH3Cl

Cl
C H
H

H-

C-H
C-Cl .

SO2

CO2
bent
.

H2O

) ( .

NF3 NH3

N
F
F H - HH
,

-N

NF3

35

.

C-C Petro
1958 .
) bond moment ( D

bond

0.68

Csp2

Csp3

Csp

Csp2

CH

CH

Csp3

Csp

CH

CH3

CH

CH2

CH3

1.48

CH2

1.15

molecule

)24 (

OH

R
R

>

OH

CH

>

OH

CH2

>R

OH

CH3

27-1 HCC-CH2-CH3 0.8D

H2C=CH-CH2CH3 0.3D
C-C
Csp-Csp3
Csp2-Csp3
28-1 CH3Cl 1.87D 1.85D, CH3F
.
.
36

Acids and Bases

Arrhenius theory
1887
+
H
) ( OH

strong electrolyts
H3O+ + ClCa++ + 2OH-

HCl + H2O
Ca(OH)2 + H2O

weak electrolyts
HCOO- + H3O+

HCOOH + H2O

NH4+ + OH-

NH3 + H2O

Bronsted-Lowry theory

.
CH3COO-Na+ + H2O

CH3 COOH + NaOH

amphoteric
NH4+ + OH-

H2O + NH3

H3O+ + Cl-

H2O + HCl

Ka

37

/ -:
CH3COO- aq + H3O+ aq

CH3COOH aq + H2O l

CH3 COOH3O+
______________________ = Ka
CH3 COOH

pKa = - log Ka
/ -:
aq

C2 H5O- aq + H3O+

C2H5OH aq + H2O l

] [ C2H5O - ] [H3 O+
______________________ = Kb
] [ C2H5OH

pKb = - log Kb

Ka
.
Lewis theory


.
H Cl
Cl

N Al

AlCl3 + NH3

Lewis
base

H Cl

Lewis
acid

F
F

BF3 + CH3 O CH3

CH3 O

Lewis
base

CH3 F

Lewis
acid

Coordinate covalent bond

38

Solvents in organic chemistry

.
classification of solvents
.1 protic and aprotic
.2

polar and apolar

.3 donor and nondonor

. 1 : protic
aprotic
.
. 2 : polar
apolar .
: dielectric constant
q1 , q2 r
q1 q2
_______ E = k
r

k : .

.
) (

15 15
.

39

polar


.
:
O
C OH
= 1.7 D
= 59

O
H

OH

= 1.6 D
= 6.1

CH3

.3 : donor

nondonor .

.i

:
, CHCl3
4.8
61.2oC

.ii

, CH2Cl2
8.9

Benzene
2.3
80oC

39.8oC

CCl4
2.2

76.8oC

Hexane
= 1.9
bp = 68.7o C

) ( :

]Tetrahydrofuran [THF
O
7.6
66oC

], Ethyl acetate [EtOAc

O
C

O C2H5
6.0
77.1o C

]Diethyl ether [Et2 O

CH3CH2 O CH2CH3

CH3

4.3
34.6oC

40

1,4-Dioxan
O

= 2.2
bp = 101.3o C

.iii

:
]Acetic acid [HOAc
O
CH3 C OH
= 6.1
bp = 117.9oC

.iv

]N,N-Dimethyl formamide[DMF

]Nitromethane[MeNO2

]Acetone[Me2 CO , DMK

O
C

N(CH3)2

O
NO2

CH3

37

21
o

56.3 C

101.2 C

= bp

Formamide

Water

Formic acid

C
111
211o C

]Methanol[MrOH

]Ethanol[EtOH

O
NH2

36

153oC

.v

CH3

CH3

H2O
78
100oC

OH

C
59
100.6oC

41

CH3 OH
33
64.7oC

OH

CH3CH2

25
bp = 78.3oC

Solubility
"
" like dissolves like


.
:


.

.1 .
.2
.

.3 ) (I
HgI2 HgBr2 PbCl2 .

.4 ) (II
.

.5
.

42

29-1
35

Cl

17

32

16

24

Mg

12

35

30-1

, Cl
17

32

40

16

20

Ca ,

31-1 : ,
, , ,
32-1 CH4 , H2O , NH3 :
33-1 %46.38
%5.90 % 27.01 .
155
34-1 -:
C4H8O2 , CaCl2 , HgSO4 , C10H14N2 , C3H8O3 , Fe2O3

35-1 :

CH2O
CHN

180
81

36-1
.

, CH3CCl2CH2CH3 ,
, CH3CH(CH2Cl)CH2CH3

CH3CHOHCH2CH3
CH3COCH2CH(CH3)2

37-1 -:
Cl

OH

38-1
ClO3- , BrO2- , PO4-3

43

39-1 -:
OH

CH3

CH CH2

CH3

O
H

OH

40-1 NH3 , BCl3 , MgCl2 , BeI2 :

41-1 NH4Cl , CH3ONa
42-1 H2O , F2 , HI -:
43-1 -:
, 2- Hydrazoic acid N3-H

1- Nitrate ion NO3

44-1 -:
.1 hydrogen fluoride HF .
.2 CH3OCl .
.3
.
.4 C-C CH2=CH-CH=CH2 C-C
CH3-CH3

.5 .
.6 .
.7 1s22s22p63s13p5 .
.8 .
.9 ammonium cation +NH4 .
.10 nonmetal fluorides hydrides
.11 .
.12 H2S .

44

45-1
methyl amine CH3NH2
46-1 BeH2 , CCl4 , BH3 , BeCl2 -:
47-1 VSEPR
122o

124o
116o

Cl
C

126o

111o

108o

Cl
o

48-1 ( 93) PH3

49-1 VSEPR
ClO2- , SCl2 , POCl3 :
50-1
CH3 -CCH

CH2=CH-CH=CH2

51-1 CH2+
52-1 C=C
F

1.31Ao

1.33A o

C
F

C
H

53-1 allyl cation

H
C
CH2

CH2

H2 C

H
C

HC
CH2

H2C

H2C

54-1
O

H3CO CH2CH2OH
= 17
,

CH2CH3

= 19

CH3

F3C CH2OH
= 26

CH3
O
CH3 S CH3
, = 47

CH2 C CH3
CH3

45

CH3 CH
CH3

=2

CH3 C
N
= 38

Hydrocarbons

.
: Aliphatic hydrocarbons

aleiphas " " fat
: Saturated C-C

.

: Unsaturated

.
: Aromatic hydrocarbons
)129(

/
Alkanes
Paraffin's " " Parum affinis -:
: CnH2n+2 n

.
:
CnH2n

46

: Structural isomerism
.
: Skeletal isomers
C4H10 - :
CH3
CH3 CH2 CH2 CH3

CH3

CH3 CH

1-2 C5H12

. 5 = n
CnH2n+2 = C5H5x2+2 = C5H12
.
CH3
CH3

CH3
CH3

CH3

CH

CH3 CH2 CH2 CH2 CH3

CH3 CH2

CH3

2-2 C5H10
CnH2n+2 = C5H5x2+2 = C5H12 .
CnH2n = C5H5x2 = C5H10
.
CH3
CH2 CH3

CH

CH3

H2C

CH

H2C

CH2

CH

CH2

H2C

CH2

H2C

H2C

CH2

H2C
H2C

CH3

CH

CH3

CH3

H2C
H2C

isomers isos+meros
" "

.
47

75
4,347
366,319
4,111,846,763

C10H22
C15H32
C20H42
C30H62

5
9
18
35

C6H14
C7H16
C8H18
C9H20

3-2 C7H16

CH3 CH2 CH2 CH2 CH2 CH2 CH3

CH3
-:
x
C

4
C

CH3
1
2
C
C

3
C

1
2
3
4
x
CH2 CH2 CH2 CH2 CH3

x
C

x
CH3 CH2

CH3
CH CH2 CH2 CH2 CH3

CH3

CH3 2
CH3
x
x
1
2
3
4
CH3 CH2 CH CH2 CH2 CH3

3
4
CH3
.
C

3
C

2
C

x CH3
x
1
2
3
x
CH3 CH CH2 CH2 CH2 CH3

C
1
C C
CH3
CH3

CH3 C

CH2 CH2 CH3

CH3

48

CH3
X

CH2 CH3

CH

CH3

CH

CH3

CH3

CH3

CH2 CH

CH3

CH

CH3

-:
CH3 CH3
C

CH3

CH3
CH2 CH3

CH3 CH

CH3

CH

CH

CH3

CH3
CH2 CH3

CH3

CH3

CH3 CH2 C

CH2 CH3

CH3

CH

CH

CH3

CH3

-:
CH3

CH2 CH3
x
x
CH2 CH3

CH3 CH2 CH CH2 CH3

x
x
CH3 CH2 C
CH3

4-2 :
: Isotope .
: Isomers .

49

: Positional isomerism
.
5-2 C4H9Br

Br
CH3 CH2 CH2 CH2 Br

CH3 CH2 CH CH3

CH3

CH3

CH3 C CH3

CH2 Br

Br

CH3 CH

6-2 C2H3Br2Cl
Br
Cl

CH

Br
CH2

Br

CH

Br

Br
CH2
Cl

Br

CH3

Cl

: Stereochemistry of Alkanes
" " Three-dimensional
.
: Conformations C-C

free rotation

.

50

conformation of ethane
H

Rotate

H
H

Sawhorse representations
C-C
C-H .

C-C
Conformer
) (conformational isomer -:
1 : Eclipsed conformation
C-H .
H H
H
H

Newman

projections Melvin S. Newman
C-C
Circle

2 : Staggered conformation
.
H
H

H
H

Skew conformation

51

: Conformational analysis
.
) CH3-CH2-CH2-CH3 : ( C2-C3

CH3

CH3

CH3
H

H
H

(III) Gauche
CH3

H
H CH3
H
(VI) Eclipsed

CH3

H
H
H
CH3

CH3

H
H

CH3

(II) Eclipsed

(I) Anti

CH3

CH3 CH3

H
H

H
H
(V) Gauche

H
H

H
H

(IV) Eclipsed

: Anti
.
: Gauche
)
( .

: Van der Waals Radii

.
Torsion strain
.
Pitzer strain
Y , X C2 , C1
Dihedral angle " " 0 < < o60
.

52

: Eclipsed
)(IV
.
7-2 2-Methyl butane C2-C3

H CH3
CH3
CH3

H
H

CH3

CH3

:-

CH2 CH3

CH3 CH

CH3

)(II

)(I

H CH3
H
CH3

CH3

CH3

CH3
H

CH3

CH3

H
H

H
)(III

)(IV

) . (I .

-:
: Geometric isomerism C-C

cis
trans
Y

Y
cis isomer

trans isomer

53

Conformation of cycloalkanes
sp3
Angle strain
Baeyer strain Adolf Von Baeyer
C-C-C
.
: o60
.
: o88

.

o25
.
H

H
H

H
H
110 kJ/mol

H
114 kJ/mol

: o108
26 kJ/mol


H

H
H
H H

H
H

54

8-2 cis-1,2-Dimethyl cyclobutane trans

cis-1,3-Dimethyl cyclobutane trans
cis-1,2- , trans-1,3- .
:
: Chair Boat
o109.28 C-C-C .

molecular models C1-C2
H

H3
2

)C(3

H1

H1

)C(6

H
o
trans H-C1-C2-H 180
12 C-H 6 6
6 axial 6 equatorial -:

C4

ring-flip

C1
C4

C1

a
e e

e e
e

ring-flip

a
e

e e
a

a
a

55

-:
ring-flip
trans
cis
trans
cis
1,2a,e or e,a
e,e or a,a
e,a or a,e
a,a or e,e
1,3e,e or a,a
a,e or e,a
a,a or e,e
e,a or a,e
e,a or a,e
a,a or e,e
1,4a,e or e,a
e,e or a,a

Steric strain :
X Y
X Y .

Monosubstituted
Methyl cyclohexane : -:
Steric interference

CH3

H
CH3

2
1

H
5

Ring-flip
6

(II) equatorial

3
5

(I) axial

) (II ) (e ) (I
C5 , C3
1,3-Diaxial
-:

56

1,3-diaxial interaction
kJmol-1

Y
1

2
6

-F
-Cl
-Br
-OH
-CH3
-CH2CH3
-CH(CH3)2
-C(CH3)3
-C6H5
-COOH
-CN

0.5
1.0
1.0
2.1
3.8
4.0
4.6
11.4
6.3
2.9
0.4

9-2 ( Cyano ) CN
CN
Disubstituted
1,2-Dimethyl cyclohexane :
cis trans
X
X
Y
Y
trans, diaxial

trans, diequatorial

X
X

Y
cis , axial Y
equatorial X

cis , equatorial Y
axial X

57

cis
-:
CH3
1

CH3

CH3

CH3

Ring-flip

)(II

)(I

) : (I C2
1,3-diaxial C6 ,C4
) : (II C1
1,3-diaxial C5 , C3
.
(CH3-H : 2 x 3.8 = 7.6 kJ/mol ) + 3.8 = 11.4 kJ/mol
trans -:
H

CH3
H

CH3
Ring-flip

H H

H CH3

H
CH3

H
)(I

)(II

cis )(I

) (3.8kJ/mol .
) (II 1,3-diaxial
4 x 3.8 = 15.2 kJ/mol
:
10-2 cis-1-tert-butyl-4-chloro cyclohexane
:
CH3
H
H
Cl

H3C
Cl

CH3

H
H

Ring-flip

CH3
C
CH3

58

H3C

C(CH3)3
) ( 2 x1.0= 2.0 kJ/mol .
C(CH3)3
) ( 2 x 11.4 = 22.8 kJ/mol
11-2 1,3-Dimethyl cyclohexane
Diaxial diequatorial
H

CH3

CH3

CH3

CH3

CH3
Diequatorial

Axial - equatorial

CH3
H

H
Diaxial

12-2
1,3-diaxial strain
1) trans-1-Chloro-3-methyl cyclohexane
Cl
Cl-H : 2 x 1.0 = 2.0 kJmol-1

H
H

H3C

2) cis-1-Ethyl-2-methyl cyclohexane
2CH3-H : 2 x 3.8 = 7.6 kJmol-1
one gauche interaction + 3.8 kJmol-1
____________

CH3
H

Et 2
1

= 11.4 kJmol-1

3) cis-Bromo-4-ethyl cyclohexane
H

Br
H

2Br-H : 2 x 1.0 = 2.0 kJmol-1

Et

4) cis-1-tert-Butyl-4-ethyl cyclohexane
H

Et

2Et-H : 2 x 4.0 = 8.0 kJmol-1

CH3

H3C
H3C

59

: Boat conformation

C4 , C1 ) flag pole
( 11,4-interaction 4
H

H H
1

4
5

6
2

) rigid ( .
twist-boat
.

106 / .

37.7- 46 kJ/mol .
6.7kJ/mol
22.2kJ/mol .

22.2kJ/mol

37.7-46 kJ/mol

Classical
boat

Twist-

-------------------------------------------Reaction Co-

60

P.E

: Nomenclature of alkanes
.
: Systematic name IUPAC
International Union of Pure and Applied Chemistry
-:

Suffix

......

Parent

......

Prefix

: Homologous series
methylene CH2
Homolog's
-:

non
dec
undecane
dodecane
tridecane
icosane
henicosane
triacontane

9
10
11
12
13
20
21
30

meth
eth
prop
but
pent
hex
hept
oct

61

1
2
3
4
5
6
7
8

.1 straight-chain n
normal ane alkane
.2 branched-chain
.
.3
.
.4
.
.5
: , di , tri , tetra penta .
.6 .
.7
.
.8
.
.9 , tri , di .
.10 .

62

(CH3)2CH-R R
Iso R

.
(CH3)4C Neo
Neopentane

: Alkyl group
R
ane yl .

CnH2n+1
alkyl

-H

-H

-CH3
Methyl Me

Et

CnH2n+2
alkane

-H

-C2H5
Ethyl

C1 : CH4
Methane

C2 : C2H6
Ethane

C3 : C3H8

CH3CH2CH3
n-Propane
-H
CH3

CH3 CH

CH3 CH2 CH2

n-Propyl

Isopropyl

63

C4 :

C4H10

CH3
CH3 CH2 CH2 CH3

CH3 CH CH3
Isobutane

n-Butane
-H

-H
2o

CH3 CH2 CH CH3

1o

CH3

1o

CH3 CH2 CH2 CH2

CH3
CH3

CH3 CH CH2
Isobutyl

3o

sec-Butyl

CH3 C

n-Butyl

tert-Butyl

CH3

CH3
1o

CH2

CH3

-H

CH3

C5H12

CH3

C5 :

CH3
Neopentane

CH3
Neopentyl

CH3
CH2CH3

CH3CH2CH2CH2CH3

CH3 CH

n-Pentane

Isopentane

2o

1O

CH3

CH3

CH2CH2

CH3 CH

Isopentyl
or Isoamyl

CH2CH3

3O

CH3 C

tert-Pentyl
or tert-Amyl

64

1o

CH3CH2CH2CHCH3

CH3CH2CH2CH2CH2

sec-Pentyl

n-Pentyl

) : Secondary ( sec
2o

) : Tertiary ( tert
) ( 3o

Primary 1o Quaternary
4o

.
-:
CH3 CH2 CH2 CH2 CH2 CH2 CH3

CH3 CH2 CH2 CH3

n-Heptane

n-Butane

CH3
5

CH3 CH2 CH CH2 CH2 CH3

3-Methyl hexane

) (

CH3
5

CH2 CH2 CH3

di
) (10

CH3 C

CH3
2,2-Dimethyl pentane

CH3
8

CH2 CH2 CH3

CH

CH3
CH3

CH3 CH2 CH2 CH

3 CH2

2
1

) 4(10

CH3

2,2,5-Trimethyl-4-propyl octane

65

CH2 CH2 CH3

4

) (7

CH3 CH2 CH CH CH3

1

CH3 CH2
4-Ethyl-3-methyl heptane

CH2 CH3
2

CH2 CH3

CH

) (8

CH3 CH2 CH
CH3

3-Ethyl- 4-methyl hexane

C(CH3)3
7

CH2 CH2 CH3

CH3
3

CH2 CH

tert
) (9

CH3 CH

4-tert-Butyl-2-methyl heptane

CH3 CH3 CH3

4

CH3

hexa
.

CH3 C

CH3 CH3 CH3

2,2,3,3,4,4-Hexa methyl pentane
CH3
CH3
1
2
3
CH2 CH CH3

CH3
10

CH3

CH2 CH
8

CH2 CH2 CH
7

CH2 CH2 CH2 CH3

2-methyl propyl

CH

CH3

6-Isobutyl-2,3-dimethyl decane
or 2,3-Dimethyl-6-(2-methyl propyl) decane
2

CH3
1

CH2 CH2 CH3

CH
4

CH3
5

CH3 CH2 CH2 CH

4-Isopropyl heptane
or 4-(1-methyl ethyl) heptane

66

CH3 CH

3-Ethyl pentane
triethyl methane
13-2
CH3
CH3

CH

CH

CH3
CH3

CH

2,4-Dimethyl-3-isopropyl pentane

CH3 CH

CH3
Triisopropyl methane

CH3
CH2 CH3

CH3

CH

3,5-Dimethyl heptane

CH3 CH2 CH CH2

Di-sec-butyl methane
CH2 CH3
CH3 CH2 C

CH2 CH3

3,3-Diethyl pentane

CH2 CH3
tetra-Ethyl methane

14-2
(a) 3,4-Dimethyl nonane
9 = nonane
C

C
9

CH3 CH3
CH2 CH2 CH2 CH2 CH3

CH

CH3 CH2 CH

CH3 CH3

67

(b) 3-Ethyl-4,4-dimethyl heptane

CH3 CH2 CH3
CH2 CH3

CH3 CH2 CH2 C

CH

CH3

(c) 2,2-Dimethyl-4-propyl octane

CH2 CH2 CH3
CH2 CH2 CH2 CH3

CH3
CH3 C

CH2 CH

CH3

(d) 2,2,4-Trimethyl pentane

CH3
CH3

CH3

CH2 CH

CH3 C
CH3

Nomenclature of cycloalkanes
.1 " " Cyclo
.2
.
.3
-:
.i

.ii

68

15-2 IUPAC
CH3
3

CH3

CH CH2 CH3
3

CH2 CH2 CH2 CH3

(1-Methyl propyl) cyclobutane
or sec-Butyl cyclobutane
2

CH2 CH2 CH2 CH3

1-Cyclopropyl butane

CH3

3
4

Methyl cyclohexane

CH3

CH3 C

CH3

CH3
1-n-Butyl-4-tert-butyl cyclohexane

CH2 CH

CH3
3 2

CH3 CH

1-Isobutyl-3-isopropyl cyclopentane

16-2
(a) 1,1-Dimethyl pentane
(b) 3-Methyl-2-propyl hexane
(c) 4,4-Dimethyl-3-ethyl pentane
(d) 5-Ethyl-4-methyl hexane
.
CH3
6

) (a

CH2 CH2 CH2 CH3

CH3 CH

2-Methyl hexane
6

CH3 CH2 CH2 CH3

) (b

CH2 CH2 CH3

CH3 CH

CH

4,5-Dimethyl octane

CH3 CH2 CH3

1

) (c

CH3

CH3 CH2 CH

CH3
3-Ethyl-2,2-dimethyl pentane
1

) (d

CH3 CH2 CH3

CH3

CH

3,4-Dimethyl heptane

69

CH3 CH2 CH2 CH

: Petroleum

.
: Petroleum refining
.
-:
1 : Distillation
500
o200
.
2 : Cracking
-:
: Catalytic cracking
.i
o
12 700-500
5 11 .
.ii

: Thermal cracking

) 110 (
.
H 2 + smaller alkanes + alkenes

400-600oC
with catalysis

alkane

-:
.1 : Natural gas C4 - C1
o20 )196(
.2 : Straight-run gasoline C11 - C5
o200-40 Ligroin
.3 : Kerosene C14 - C11 o325-175
)196(
70

.4 " " : Gas oil C25 - C14 o500-275

diesel engines
.
.5 : Lubricating oils and waxes 20
o400 .
.6 : Asphalt 20
.
Gasoline

.
1 Crude oil 250 3
gasoline engines

.
isomerization

pentane AlCl3 o200
2-Methyl butane : 2,2-Dimethyl propane

" " Knock Octane number
Octane number

n-Heptane 2,2,4-Trimethyl pentane
) 100 Isooctane 108 (
90 %90
%10 .

71

Tetra ethyl lead Pb(C2H5)4 1920

0.6 1/
.
P

(C2H5)4 Pb + 4 NaCl + 3 Pb

4 C2H5Cl + 4 Na/Pb
Alloy

Ethyl chloride

1970
] ) tert-butyl methyl ether [ MTBE 190 (
] ) tricresyl phosphate [ TCP180 (

Diesel fuel Cetane number

) ( Hexadecane 100
) -methyl naphthalene133 ( .
: Synthesis of alkanes
-:
1 : Hydrogenation of alkenes
: Ni
Pd Pt
CH3 CH2 CH3

Ni
25oC

CH3 CH

CH2 + H2

2 : Reduction of alkyl halides

) Zinc (Zn
.
Zn , H+

2 CH3 CH2 CH2 CH3 + ZnBr2

CH3

Br
2-Bromo butane

n-Butane
CH3

CH3
CH3

CH3 CH2 CH2 C

CH2

2 CH3 CH

LiAlH4

CH3

CH3 CH2 CH2 C

Br

72

Zn , HCl
CH3 COOH

CH3 (CH2)14 CH3

CH3 (CH2)14 CH2I

Cetyl iodide

Hexadecane
) ( Cetane

: Grignard reagents Victor Grignard 1900

.
R Mg X

& X = Cl , Br or I

CH3 CH2 CH2 CH3

H2O

CH3

X + Mg

R = 1o, 2o , 3o alkyl , aryl , or alkenyl

+ Mg

CH3 CH2 CH

CH3

CH3 CH2 CH
Br

MgBr

sec-Butyl bromide

sec-Butyl magnesium bromide

3 : Corey and House R2CuLi

Lithium dialkyl copper R\ X
C-C ) ( .
R2CuLi + R`-X

R-R` + RCu + LiX

CH3
CH3 Cu Li

Cu-Li

CH3 Li

Lithium dimethyl copper

2Li

CH3 Br
Methyl bromide

)(R2CuLi called Gilman reagents

Henry Gilman
CH3
CH3 Cu Li + CH3 (CH2)6 CH2I

CH3 (CH2)6 CH2 CH3 + CH3Cu + LiI

n-Octyl iodide

n-Nonane

73

4 Cyclopropane synthesis
-

: Simmons-Smith reaction
diiodo methane CH2I2 )Zn(Cu
CH2
)Zn(Cu

CH3 CH CH2
Methyl cyclopropane

CH3 + ZnI2

CH2 + CH2I2

CH3

CH3

CH2
CH

CH3 CH

CH2 CH

CH3 CH

)Zn(Cu

CH3 + CH2I2

CH

CH2 CH

CH3 CH

1-Isobutyl-2-methyl cyclopropane

CH2
+ ZnI2

Zn
alcohol

CH2 CH2

I
I
1,3-Diiodo propane

Cyclopropane
CH2
+ 2NaBr

CH2

CH2

CH2

2Na

CH2 CH2

Cyclopropane

CH2

CH2

CH2

Br
Br
1,3-Dibromo propane

17-2


.

74

18-2 n-Hexane
, ii) Hexyl bromide

i) Propyl bromide

1
Pr
Cu Li
n-Hexane

Pr

CuLi

CH3 CH2 CH2Li

CH3 CH2 CH2Br Li

+
CH3 CH2 CH2I

2
H 2O

n-Hexane

CH3 (CH2 )4 CH2 MgBr

Mg

CH3 (CH2 )4 CH2 Br

Physical properties
1 Boiling point
.
CH3 CH2 CH3

CH3 CH3

-42oC

-88oC

CH4
b.p -162oC

-:
.i

C5H12
-:
CH3

CH3
CH3

CH3 C

CH3 CH

CH2 CH3

CH3 CH2 CH2 CH2 CH3

CH3
9.5oC

28 C

75

36 C

b.p

.ii

.
: C6H14
CH3
CH2 CH3

CH3 CH3

CH3 C

CH3

CH3 CH

CH

CH3
o

50oC

58 C

CH2 CH2 CH3

60.3oC

.iii

CH2 CH3

CH3 CH

b.p

CH3 CH2 CH
CH3
63.3oC

CH3

bp

.
n-Hexane
Cyclohexane
69oC

81oC

b.p

.iv

.v

cis trans
: C7H14
CH3

CH3

CH3
100oC

118oC

CH3

CH3
92oC

99oC

b.p

2 Melting point

-:
10

-30

-54

-57

-91

-95

-130

-138

-188

-172

-183

76

m.p

.
9
-54
10
-30

7
-91

5
-130

3
-188

8
-57

6
-95

4
-138

1
-183
2
-172

m.p

m.p

-80oC
6.5oC
14oC

Cyclobutane
Cyclohexane
Cyclooctane

-127oC
-94oC
-12oC

Cyclopropane
Cyclopentane
Cycloheptane

.
3 Physical state

C17 - C5 .
4 Solubility

) (

.
5 Density
.

77

Chemical properties
C-C C-H
C-H



.
1 : Combustion reaction
.

.
n CO2 + (n+1) H2O + energy
CO2 + 2 H2O + energy

3n + 1
O2
2

CnH2n+2 +

CH4 + 2 O2

.
2n+1
CnH2n+2 + _____ O2
2

nCO + (n+1)H2O + energy

CO + 2H2O + energy

3 O
__ CH4 +
2
2

)
( Carbon black .

CO
2 )70 (

78

3 : Halogenation reaction

Helium
.
Chain reaction
Ultraviolet UV

.
Iodic acid HIO3

HIO3 + HI I2 + H2O

: Chlorination of methane
CH3Cl + HCl
Chloro methane
CH2Cl2 + HCl
Dichloro methane

CH4 + Cl2 h

CHCl3 + HCl
Trichloro methane
) ( Chloroform

CCl4 + HCl
Tetrachloro methane
) ( Carbon tetrachloride

CH3Cl + Cl2

CH2Cl2 + Cl2

CHCl3 + Cl2

79

Halogenation of higher Alkanes

.

.
Cl
CH3 CH2 CH2 Cl + CH3 CH CH3
45 %
55 %

CH2 CH3

h
light , 25oC

CH2 CH2 CH2 CH3 + CH3 CH

light
25o C

CH3 CH2 CH3 + Cl2

CH3 CH2 CH2 CH3 + Cl2

Cl

Cl
28%

72%

Nonselective
Selectivity
.

C-Br , C-Cl :
) D ( kJ mol-1

) D ( kJ mol-1

bond

bond

285

CH3CH2-Br

338

CH3CH2-Cl

274

(CH3)2CH-Br

339

(CH3)2CH-Cl

263

(CH3)3C-Br

330

(CH3)3C-Cl

-:
Relative reactivity toward chlorination : R3CH > R2CH2 > RCH3
5
3.8
1

80

1o

/ n-Butane

2o

1o

2o

CH3 CH2 CH2 CH3

61 + 43.8 = 6 + 15.2 = 21.2

x 100 = 28.3 %

6
_____ = x 100
21.2

No 1o H x reactivity

x 100 = 71.7 %

15.2
_____ = x 100
21.2

No 2o H x reactivity

_______________ = % 1-Chloro butane

21.2
_______________ = % 2-Chloro butane
21.2

19-2 2-Methyl butane

1o

CH3
1o

2o

CH2 CH3

3o

CH

1o

CH3

9 1 + 2 3.8 + 1 5 = 9 + 7.6 + 5 = 21.6

7.6 x 100 = 35.2 %
_____ = % 2-Chloro-3-methyl butane
21.6
_____
5
x 100 = 23.1 %
21.6

= % 2-Chloro-2-methyl butane

:
_____
9
x 100 = 41.7 %
21.6

:
6 x 41.7 = 27.8 %
_____ = % 1-Chloro-2-methyl butane
9
_____
3
x 41.7 = 13.9 %
9

= % 1-Chloro-3-methyl butane

/ ) ( 3oH > 2oH > 1oH

CH3 CH3

CH3 CH3
CH3 + 2 HBr

CH3 + 2 Br2

CH3

3o

3o

CH3

H
H
2,3-Dimethyl butane

Br
Br
2,3-Dibromo-2,3-dimethyl butane
100 % Yield

81

: Freons
Chloro fluoro carbons CFC
.
CHClF2

HF
SbF5

CHCl2F

Freon-22
-40oC

CClF3
Freon-13
-81.1oC

HF
SbF5

CCl2F2

HF
SbF5

Freon-21
9o C

HF
SbF5

Freon-12
-29.8oC

CHCl3
Cloroform

b.p

HF
SbF 5

CCl3F
Freon-11
23.7oC

CCl4

b.p

12 ( CClF2CClF2 ) 114 12 11
.
CFC
CBrF3 , CBrClF2
22 )111(
F2C=CF2 + 2 HCl
tetra-Fluoro ethylene

600oC

2 CHClF

UV
UV :
UV

O2 + O

O3

UV
.
UV

CF2Cl + Cl

CF2Cl2

ClO + O2

Cl + O3

Cl + O2

ClO + O

.
82

Reactions of cycloalkanes
Halogenation
heat

Cl

+ Cl2

light

Br
heat

+ Br2

light

-:
CH3

CH3

CH2Cl

CH3

CH3

Cl
Cl +

heat
light

+ Cl2

Chloromethyl
cyclopentane

Cl
cis , trans

: Ring-opening
C-C
Br
Br

Br

1,3-Dibromo propane

Br
Bromo cyclopropane

CH2 + CH3 CH2 CH

CH2 CH2 CH2 + CH3 CH

Br

Br

Br

Br

+ Br2

Br

AlBr3
CCl4

+ Br2

CH2
Hydrogenation

CH3

H3C

metal catalyst
80oC

CH3 CH2 CH2OH

+ H2

H2SO 4
H 2O

1-Propanol
CH3 CH2 CH2Cl

83

)HCl(g

CH3 CH

CH2 CH3

)HBr(g

Br

Ph

CH2 CH

CH

Br

Br2
CCl4

Ph

Ph
Ph

Br

1,2-Diphenyl
cyclopropane

1,3-Dibromo-1,3-diphenyl
propane

20-2 Trichloro ethane

a) 1,1-Dichloro ethane , b) 1,2-Dichloro ethane :
Trichloro ethane .
a) 1,1,1-Trichloro ethane & 1,1,2-Trichloro ethane , b) 1,1,2- Trichloro ethane
21-2 -:
.1
.2
.3
.4
.5
.6

vicinal
Geminal dihalide ) ( .
C4H10 ) (-CH2-
C5H12 .
.
C4H9Cl .

CH3

CH3 CH
CH3

Cl

CH3 CH

Br

Cl
1,1-Dichloro ethane

Isobutane

CH3

3.

Cl

2.

CH2 CH2

6.
CH3

Br

1,2-Dibromo ethane

CH3

5.
3-Ethyl pentane

CH3

C
CH3

CH3

84

1.

4.
CH3

22-2
a) Heptane ; 3,3-Dimethyl pentane
b) 2,3-Dimethyl hexane ; 2,4-Dimethyl hexane
c) n-Hexyl bromide ; n-Heptyl bromide
d) n-Hexyl iodide ; n-Heptyl chloride
e) 1,1-Dichloro ethane ; 1,2-Dichloro ethane
f) 1,2-Dichloro propane ; 1,3-Dichloro propane
.a
.b
.c
.d
.e
.f

Heptane .
2,3-Dimethyl hexane .
n-Heptyl bromide .
n-Hexyl iodide .
1,2-Dichloro ethane geminal C-X
1,3-Dichloro propane C-X .

) (

.

.
.

n-Pentane
,
1-Fuloro butane
:
CH3 CH2 CH2 CH2 CH3

CH3 CH2 CH2 CH2 CH2 F

b.p 32oC

b.p 36 C

72

76

C-F
C-H
.
R
X

3o

R
Tertiary

R
R

2o

CH

Secondary

85

1o

CH2 X
Primary

CH3 X

Methyl

23-2 -:
1) 2-Methyl-5-(1,2-dimethyl propyl) nonane
2) 2,2-Dimethyl-4-propyl octane
3) 1,3-Dibromo-5-methyl cyclohexane
4) Di-tert-Butyl methane
5) Triisobutyl methane
6) tert-n-Butyl methane
7) 3-Ethyl-6-isopropyl-4-tert-butyl nonane
8) 4-tert-Butyl-2,2,6,6-tetra-methyl heptane
9) 1-Cyclopropyl-4-isopropyl cyclohexane
10) 2-Bromo-4-iodo-2,4-dimethyl hexane
11) 4-(1,1-Dimethyl ethyl ) octane
24-2 %84.2 %15.8 .

144

25-2 -:
1) 2-tert-Butyl-4,5-dimethyl hexane
, 2) Isobutane
3) 5-Methyl-3-ethyl heptane
,
4) 3-Methyl-2-propyl hexane
5) 4,4-Dimethyl-3-ethyl pentane
,
6) 3-Dimethyl pentane
7) 1-Chloro-3-ethyl-4-methyl cyclohexane
26-2 -:
.1
.2
.3
.4
.5

C5H12 .
C5H12 .
C6H14 .
C4H9Br
C5H11Br

27-2 -:
C4H10 , C2H5 , (CH3)3CH , C6H14 , C3H7 , CH3CH2CH2CH3 , C8H18

86

28-2
a) 1,2-Dichloro butane ; 2,2-Dichloro butane
b) 1,4-Dichloro butane ; 2,3-Dichloro butane
c) 1,1-Dichloro propane ; 1,2-Dichloro propane
d) Trichloro methane ; tetrachloro methane
e) 2-Methyl heptane ; Octane
f) 2,3-Dimethyl hexane ; 2,2,3,3-tetramethyl butane
g) Methyl cyclopentane ; Cyclohexane
29-2
CH3
CH2 CH2 CH

CH3

CH
CH2

CH3 CH2 CH2 CH2

CH

CH3

CH3

Cl

CH3

CH3

CH2

CH3
(CH3)3C CH2 CH2 CH
CH2 CH3

Br

CH3

CH3

CH3

CH2 CH
CH3

CH2 CH3

CH
CH3

CH

CH3 CH

CH2 CH3

30-2
i) trans-1,4-dimethyl cyclohexane
ii) trans-1,2-dichloro cyclohexane
iii) cis-1,3-tert-butyl cyclohexane
31-2
i) Propane
ii) Isobutane
iii) 2,2,3-Trimethyl butane
iv) 2,3-Dimethyl butane
87

 : II

/
: Alkenes C=C
Olefins
-:
- CnH2n
-

CnH2n-2

: .
: Functional isomers
.

2 32 C4H8
CnH2n
CH3

CH

CH2

CH3 CH

CH3 CH2 CH

CH3
CH2

CH3 C

CH3

CH2

CH2 CH2

CH2 CH

CH2 CH2

-:
H

CH3

CH3
C

CH3
Trans isomer

CH3
C

Cis isomer

.
88

 : II

The E , Z system of nomenclature Z,E

Priorities
Cahn Ingold Prelog :
Sequence Rules -:
.i

Z E
High

Low
C

High

High

High
C

Low

Low

E-double bond

Low

Z-double bond

Br35 > Cl17 > O8 > N7 > C6 > H1 :

.ii

:
H,H,H Low

CH3

C,H,H High

H3C
C

CH2CH3

.iii

3 .

Multiple-bonded
Y
:

O
C

C,C

C
O

H,O,O

332
) ( Br- , Cl- ) ; ( -NH2 , -OH ) ; ( -CH2OH ; -CH=O
( -CH=O ) :

( -OH ) ,

89

( -Br ) ,

 : II

34-2 : Z,E
-CH2OCH3 , -CCH , -CH2CH3 , -CN 1
-CN , -CH2OH , -COOH -CH2NH2 2
1 CH2OCH3 > -CN > -CCH > -CH2CH3
2 - -COOH > CH2OH > -CN > -CH2NH2

352 Z , E
CH3 Cl

b. CH3OCH=C(CN)CH2NH2

CH2OH ,

a. CH3CH2

-a
CH3

CH2OH Low
C
Cl High

Low

Cl High

Low CH3

CH3 CH2

High

CH2OH Low

)(Z

High CH3 CH2

)(E

-b
CN High
C
CH2 NH2 Low

CN High

Low H

C
)(E

High CH3 O

CH2 NH2 Low

High CH3 O

90

C
Low H

)(Z

 : II

) The index of hydrogen deficiency ( IHD

CnH2n+2

H
CH3

2H

CH3

H
C3H6

C3H8
1C3H6

-2H

C3H8

H2
C
C

-2H

H
H

H2
C

H
H

H
C3H6

2H

= IHD
H

C3H8
C3H6

C3H8

IHD = 1

1

IHD
.

362 IHD C6H6

IHD
= 8 H

C6H6x2+2 = C6H14

IHD = 8/2 = 4
4 3
-:
CH

CH2

C
H

C
H

H2 C

91

 : II

372 C6H10
1:1
C6H14 IHD 2
.
CH2 CH3

, CH3 CH2 C

CH2 CH3 ,

CH

CH

CH

CH2

) ( .
IHD -:
(1
:
C6H14O ] C6H14 [ .
(2
: C6H13Cl
] C6H14 [ .
(3
:
C2H7N ] C2H6 [ .
382 :
C7H13N

C7H7Br ,

C6H6NBr , C4H8O , C2H6S ,

C7H13N

C7H7Br

C2H6S

C4H8O

C6H6NBr

C7H12

C7H8

C2H6

C4H8

C6H6

CnH2n+2

C7H16

C7H16

C2H6

C4H10

C6H14

____
16 -8
=4

____
10 -8 = 1

14 -6
_____
=4
2

IHD

=2

16 - 12
_____
2

92

 : II

degree of unsaturation -:
.i

2C + 2 - H = number of ring + multiple bonds

____________ =U
2

2x2+2-6 =0
____________ =C2H6S: U
2
2x4+2-8 =1
____________ =C4H8O: U
2

.ii

.iii

) 2 C + 2 -( X + H
_________________ =U
2
) 2 x 7 + 2 -( 1 + 7
_________________ =C7H7Br: U
=4
2

) 2 C + 2 + N -( X + H
____________________ =U
2

)2x6+2+1-(1+6
C6H6NBr : U = ______________ = 4
2

93

 : II

Nomenclature of alkenes
/ IUPAC system
.1
ane ene alkene
.2
.
.3
.
.4 di , tri ,.. : .
.5 1 2
.

CH CH CH CH2 CH3
1,3-Hexadiene

CH3 CH CH2
Propene

CH3 CH CH CH3
2-Butene

H2C

CH3
6

CH

CH2 CH3

6
CH3
CH3 1
2
3
CH3 CH CH

2-Methyl-3-hexene
CH3

CH

CH2 C

CH3 CH

CH3
5,5-Dimethyl-2-hexene

CH2

2-Ethyl-1-pentene

H
H
cis-2-Butene

Cl
5

CH3

CH

CH

CH3 CH

4-Chloro-2-pentene

1-Methyl cyclopentene

5
4
1

CH3

CH3

CH3

1,5-Dimethyl cyclopentene

CH3

1
2

1,5-Dimethyl-1,3-cyclopentadiene

94

CH3 CH2 CH2 C

CH3
C

CH3

CH3 CH2

CH3

3
2

5
1

5-Methyl-1,3-cyclohexadiene

 : II

/ Common names
ene ylene

CH3

CH2

CH2

CH CH3
Propylene

Ethylene

CH2

CH3 CH CH
-Butylene

CH3

CH2

CH3 C

Isobutylene

CH2

CH3 CH2 CH
-Butylene

-:
CH3
CH2

CH

CH2

CH2

Isoprene

) ( 2-Methyl-1,3-butadiene

CH3 CH CH CH
Piperylene
) ( 1,3-Pentadiene

CH3

CH C
CH2
Methyl allene
) ( 1,2-butadiene

-:
CH2

CH CH2
Allyl group

CH2
CH
Vinyl group

CH2
Methylene group

Cl
CH2
CH2 Cl

CH

CH2

Allyl chloride
) ( 3-Chloro-1-propene

CH2

CH2 CH

CH

Divinyl methane
) ( 1,4-Pentadiene

CH2

Br

CH

CH2

Vinyl bromide
][Bromo ethene

Cl
Dichloro vinylidene
][1,1-Dichloro ethene

CH2

CH2
Methylene cyclopentane

95

5-Methylene-1,3-cyclohexadiene

 : II

: Stability of alkenes
1-Butene -:
CH2 CH

CH2

CH3

CH3

3
2
sp3-sp3 sp -sp

CH

sp3-sp2

CH3

CH

sp 3-sp2

sp -sp ) sp -sp 31 (

sp3-sp2
sp2
.
R2C
CR2 > R2C
~ CHR
CHR > RHC
CHR > RHC
= R2C CH2 > RHC CH2
trans

cis

trans cis
.
C=C endocyclic
C=C exocyclic
C=C .

>

more stable

Exocyclic double bond

Endocyclic double bond

Exocyclic
ylidene Methylene
CH3
CH
CH3

CH
CH3

2-Methyl-1-ethylidene cyclohexane

Ethylidene cyclohexane

39-2
a. 1-Butene , 2-Methyl propene
b. (Z)-2-Hexene , (E)-2-Hexene
c. 1-Methyl cyclohexene , 3-Methyl cyclohexene
) ( a. 2-Methyl propene . b. (E)-2-hexene . c. 1-Methyl cyclohexene
96

 : II

Synthesis of alkenes
1 Oxidation of alkanes
CH2 + H2

CH2 + H2 + C4H8

CH3 CH

CH

CH

Cr2O3 - Al2O3
high temp

CH3 CH2 CH3

Cr2O3 - Al2O3

CH2

560-600oC

1,3-Butadiene

CH3 CH2 CH2 CH3

n-Butane

2 HX Dehydrohalogenation of alkyl halides

HX
-elimination

-elimination

C
X

C
H

X = Cl , Br , I

alkyl halide

alkene

.
) (
Zaitsev,s Rule
Alexander M. Zaitsev 1875
H

CH3
C

CH3

C
CH3 CH2

CH3
C

+
CH3

H
70o C
CH3CH2OH

C
H

CH2
H

CH2

C
Br

CH

CH3 CH2O + CH3

Hofmann Rule
August W. von Hofmann

97

 : II

CH3
C

CH3

CH3 CH2

CH3

CH3
C
H

CH3

CH3

75oC
(CH3)3COH

+ CH3 CH2 C CH3

CH3 C
CH3

Br

.

)153 (
3 Dehalogenation of vicinal bromides
CH3

CH

Zn
Acetone

CH3 CH

CH3

CH3 CH

CH

Br

Br

4 Dehydration of alcohols
H2SO4 95%
170oC

CH2 CH2

CH3 CH2 OH

5 Reduction of alkynes
CH3

CH

CH3 CH

Pt
H2

CH3

CH3 C

2 40 2-Methyl-2-butene , 2-Methyl butane

o27.9 o38.6

.
CH3

CH3
CH3

CH

Br

Br

CH3

Br2 / 25oC

CH CH3

bp = 72oC

No reaction

CH3
Br2 / 25oC

CH2 CH3

98

CH

CH3

CH3

 : II

-:
CH3

CH3
CH3

CH

Zn

CH3 C

CH3COOH

CH3

CH3 C

CH

Br

Br

Physical properties
1 : Boiling point
cis trans
.
H

R
C

=0 R

R
C

-:

diene

2-alkene

1-alkene

alkane

allene
-34oC

-48oC

propane
-42oC

19oC
-4oC

1,21,3-

cis 4oC
trans 1oC

-6.5oC

butane
0oC

44oC
52oC
26oC

1,21,31,4-

cis
37oC
trans 36oC

30oC

pentane
36oC

C
1,4Isolated

1,3Conjugated

99

1,2Cumulated

 : II

.
) Cumulated (1,2
) Conjugated (1,3 )Isolated (1,4
.
.

conjugated > isolated > cumulated :

2 : Solubility
CCl4 ) Ligroin (

412 C5H8
CH2

CH CH2 CH
1,4-Pentadiene

CH3

CH2
CH3

CH2

C
CH CH2
2-Methyl-1,3-butadiene

100

CH2 CH CH CH
1,3-Pentadiene

 : II

Reactions of alkenes
1 Combustion
CO2 , H2O
.
2 Addition reactions


Exothermic
) ( Lewis acid
) ( Lewis base

422



-:

CH3
CH2OEthoxide ion

CH3
CH2SEthyl mercaptide ion

10-12

10-18

Ka

101

 : II

-:
-
-

Addition of symmetrical reactants

Addition of unsymmetrical reactants

/ : .
.i ) ( Hydrogenation
.
CH3 CH3

.ii

Ni , Pd or Pt
25oC

CH2

CH2

Addition of halogen
C

C + X2

X = Cl , Br

X
X
Vicinal dihalide
CH2 CH3

CH

CH

CH3

CCl4

CH2 CH3 + Br2

CH

CH

CH3

Br
Br
2,3-Dibromo pentane
Cl
CCl4

+ Cl2

Cl
1,2-Dichloro cyclohexane

.iii

Oxidation
.
Potassium permanganate KMnO4
Osmium tetroxide OsO4
Peroxy formic acid HCO2OH
CH2 CH2 CH3

CH2 CH

OH
syn-Hydroxylation

CH2 CH2 CH3 + KMnO4 H2O / OH

Cold

OH

102

CH

CH2

 : II

OH
CH3

CH3
1) OsO4 / Pyridine

OH

2) NaHSO3 / H2O

CH3
syn-Hydroxylation

CH3

OH
CH3

HCO2OH
H2O / H+

CH2 CH

anti-Hydroxylation

CH3

OH

432
CH2 OH

CH2 CH

OH

OH

CH

CH2 CH

CH2 OH

OsO4
pyridine

OH

OH

OH

CH

CH2 CH

CH2

CH

OH

CH

CH2

/ :
.
Markovnikov,s rule
Vladimir V. Markovnikov 1869
:

.
.i

Addition of hydrogen halides

.

R
H

+ HX
HX = HCl , HBr , HI

103

C
H

 : II

Cl

+ HCl

.ii

) Addition of water ( Hydration

CH3

CH

CH3

H+

CH

CH3 + H2O

CH2

OH

Anti-Markovnikov addition
.i

:
.
CH3 CH CH3

no Peroxide

HBr

Br
CH2Br

.ii

CH3 CH2

CH3

CH

CH2

Peroxide

: Hydration of alkene
B-H organoborane
CH2 + BH3

CH3 CH

CH2 + CH3 CH2 CH2 BH2

CH3 CH

CH3 CH2 CH2 BH2

CH3 CH2 CH2 BH
2
CH3 CH2 CH2 B
3

CH2 + CH3 CH2 CH2 BH

2

CH

CH3

.
CH3 CH2 CH2 OH

H2O2 , OH-

non-Markovnikov

CH3 CH2 CH2 B

3

2,3-Dimethyl-2-butene :
monoalkyl borane .
104

 : II

CH3

CH3
C

BH2

CH3

CH3

BH3

CH3
C

C
CH3

CH3

CH3

Thexyl borane

Thexyl tertiary hexyl

3 Halohydrin formation


.
X2 + H2O

XOH + HX
X = Cl , Br , I

Hypohalous acids
+ HCl

CH2 Cl

CH3 CH

Solvent
H2O

CH2 + Cl2

CH3 CH

OH
1-Chloro-2-propanol
][Propylene chloro hydrin
+ HBr

CH2 Br

H2C

H2O

CH2 + Br2

H2C

OH
2-Bromo ethanol
][Ethylene bromo hydrin

4 Alkylation
CH3
CH3

CH3

CH3

CH2 C

CH3 CH

Conc. H2SO4
or HF , 0-10oC

CH3
Isooctane

CH3

CH3
CH2 + H

CH3
tert-Butane

5 ) Addition of Carbenoids74 (
105

CH3 C

2-Methyl propene

 : II

6 Halogenation , Allylic substitution

.
CH2 Cl

CCl4

CH3 CH

Cl2

Cl
CH2

CH2

CH3

CH

600 C

CH2 CH
Cl

) N-Bromo succinimide (NBS

.
O
CCl4

Br

Br

N
O
NBS

3-Bromo cyclohexene

Cyclohexene

NBS ) dimethyl sulfoxide ( DMSO

.
CH2 Br

CH2

CH

CH

NBS

OH

H2 O / CH3CO2H , DMSO

7 Cleavage of alkenes
: Ozonization
Ozonide Zn dimethyl sulfide (CH3)2S
H2O2
.
H3C

H
C

CH3
an Aldehyde

H
1) O3

2) Zn , H2O

H3C
a Ketone

106

H3C

CH3

C
H3C

 : II

OH
C

1) O3

CH3

H3C

a Carboxylic acid

H3C
2) H2O2 , H2O

H3C
C

H3C

CH3

a Ketone
1) O3 / CH2Cl2
2) (CH3)2S

2 (CH3)2C
a ketone

C(CH3)2

(CH3)2C

: Potassium permanganate KMnO4

CH2- CO2
COOH

KMnO4
,OH-

COOH
CH3
O + CO2 + H2O

CH3
1) KMnO4 , OH-, heat

CH3 CH2 C

CH2 2) H+

CH3 CH2 C

: Osmium tetroxide OsO4

Periodate ion IO4 ) ( ) (
Lemeiux-Johnson cleavage
CHO
CHO

OsO4 , ether
NaIO4 , H2O

8 ) ( Dimerization of alkenes
) isobutylene ( C4H8
) Dimer ( C8H16
isooctane

107

 : II

CH3
CH3

C
CH3

CH3

CH3
CH

CH3 + CH3 C

C
CH3

20%

CH3

CH3
CH2

CH2

H2SO4
80oC

CH2

2 CH3

80%

H2/Ni

CH3
CH3

CH3

CH2 C

CH

CH3

CH3
Isooctane

9 Cycloadition reaction
- Otto Diels Kurt Alder

1,3-diene
" "dienophile ""diene lover
h

CH2
C

H2C

H2C

150oC

CH2
CH2

CH2
1,2-Dimethylene cyclobutane

H2C

H2C

Allene

electron-withdrawing group
dienophile .

108

 : II

Y
+
Y = CN , CHO , COR , NO2

Dienophile

1,3-Diene

O
CH3

C
H

C
H

30oC
100 %

CH3
+

CH3

CH3

442
1) (CH3)2CHCH2CH2OH , 2) (CH3)2CHCHOHCH3
CH3

CH3
CH3 CH CH2 CH2 OH

1) (BH3)2
2) H2O2 , OH-

CH2
CH 3

CH3 CH CH

)1

2) (CH 3)2 C

CH

452 C8H16
CH3CH2CH2CH2COOH , CH3CH2COOH :
CH2 CH3

CH3 CH2 CH2 CH2 COOH + HOOC

1) KMnO4 ,OH - , heat

2) H +

C8H16

CH3CH2CH2CH2CH=CHCH2CH3

cis or trans

462
CH3CH2CHO + CH3CHO
CH3 CH2 CHO + CH3 CHO

CH3 Zn3 , H O
2

109

CH

CH3 CH2 CH

 : II

10 : Polymerization
Polymers
monomer .
steel



.


.
:
/ : Addition polymers
.
:
.
CH2

CH2 CH2 n
Polyethylene
polymer

n CH2

Ethylene
monomer

.
initiator
) (
-:

.

.
110

 : II

Disproportional
-:

specification

Trade name

Polythene

Uses

polymer name

monomer

Polyethylene

CH2=CH2

Teflon

Polytetrafluoro
ethylene

CF2=CF2

Koroseal

Polyvinyl
chloride

CH2=CHCl

Orlon

polyacrylonitrile

CH2=CHCN

/ : Condensation polymers
.
: Nylon .
nylon 66 Adipic acid
1,6-Diamino hexane 6 66
O
+ 2n H2O

H
H
C (CH2)4 C N (CH2)6 N

heat

Nylon 66

OH + H2N (CH2 )6 NH2

Hexamethylene diamine

HO C (CH2)4 C
Adipic acid

: ) 6253(
: Dacron terylene Mylar
+2n CH3OH
n

O CH2 CH2 O C

200o C

O
C OCH3+ CH2 CH2

OH OH
Ethylene glycol

Dacron

111

O
CH3O C

Dimethyl terephthalate

 : II

: Terpenes
Polyisoprene
CH3
4

CH2

CH

CH2

2-Methyl-1,3-butadiene
) ( Isoprene

5 :
: 1
head
: 4 tail

-:

.
Terpenoids
.

-:
= 5
5 .
: Monoterpenes 10
: .
OH

OH
Menthol

Geraniol

Myrcene

: Sesquiterpene :

-Cadinene

112

 : II

: Diterpenes 4 )(Vitamine A

OH
Vitamin A

: Triterpene 6 : )(Lanosterol

CH3
H
CH3
CH3
Lanosterol

HO

: Tetraterpenes 8 : )(-Carotene
.

-Carotene

113

 : II

472 Myrcene
:
CH2
2

CH3
4

CH3 C CH CH2 CH2 C CH CH2

7-Methyl-3-methylene-1,6-octadiene

:
O

O
C

CH2

CH

CH3

CH3

CH2
CH2 CH2 C

CH

CH2 CH2 C

H3C

: .

CH3

CH3
CH2 CH3

CH2 CH2 CH2 CH

114

CH

H3C

H3 C

 : II

48-2

a) cis-2-Hexene , trans-2-Hexene
b) 3-Hexene , 2-Hexene
c) 2-Methyl-2-butene , 1-Pentene
d) 2-Methyl-2-butene , 4-Methyl-2-pentene
f) 2-Methyl-2-pentene , 3-Methyl-2-pentene
49-2 ) ( cis trans
a) CH3CH=CH2 , b) (CH3)2C=CHCH3 , c) ClCH=CHCl , d) BrCH=CH2

50-2 % 85.60

51-2 C12H13N
C-C
52-2

a) Methyl cyclohexane , b) 2,4,6-Octatriene , c) C9H9OCl , d) C6H4O2NCl
e) C6H2O6N3Cl , f) C7H5NS , g) C7H7NBr , h) C7H5NS

53-2
a) 4-tert-Butyl-2-methyl heptane
b) 2-Chloro-1,3-butadiene
c) 2,3,3-Trimethyl-1,4,6-octatriene
d) 2-Methyl-1,5-hexadiene
e) trans-2,2,5,5-Tetramethyl-3-hexene
f) (Z)-3-isobutyl-2-heptene
g) (E)-4-allyl-1,5-octadiene
h) 1-(2-butenyl) cyclohexene
i) 3-vinyl cyclohexene
j) 5-(3-pentenyl)-1,3,6,8-decatetraene

115

 : II

54-2 Cyclopentene NBS

55-2
CH2OH
)c

a) (CH3)2CHCH2CH2OH

b) (CH3)2CHCHOHCH3

56-2 H2O2
O

O
C

CH2CH3

HO

57-2
b) 2 equiv CH3CH2CHO

a) (CH3)2C=O + H2C=O

58-2 2,3-dimethyl-1,3-butadiene
a) 1,2-dimethyl cyclohexene
CH3

)b

CH3

Cl

59-2 3,7-dimethyl-1-octene
60-2
CH2 CH2 CH3

CH

CH

CH

CH3 CH

C2H5
C

CH2 CH2 CH3

C(CH3)3

C
H

CH3

CH3
CH2

CH2 CH3

CH
CH2

CH

CH2 CH

CH

CH3 CH

CH3

CH2 CH
CH
CH3

CH2 CH

116

CH3 CH2 CH2 CH2 CH

 : II

61-2

CH3
C CH2 CH3 + HCl

a) CH3 CH2

CH

b) 2,2,4-Trimethyl-3-hexene + HI
NBS , H2O
DMSO

CH3

H+

CH2

CH

c) CH3

)(eq

+KMnO4

CH3COOH

O3 / Zn

)d
CH3

)e
CH3

H2 O
solvent

?
125oC

CF2

CH2 +Br2
200oC

C
CCl2

+ F2C

f ) CH3
f ) 2 F 2C

g ) 1,3-Butadiene
CH3

1) O3

C
CH3

)h

2) Zn , H3 O
1) H2 / Pd

Methylene cyclohexene

2) KOH in alcohol

heat

i) 1,3-Butadiene + Allyl chloride

622
a) 2-Methyl-2-pentene
b) 3,3-Dimethyl cyclopentene
c) 3-Methyl-1-butene
d) 1-Methyl-2-propylidene cyclopentane
63-2
I

)c

CH3CH2CHCH2CH2CH3
Br

117

)b

Br

)a

 : iii

: Alkynes CC
Acetylenes Acetylene

CnH2n-2 .
Nomenclature of alkynes
/
.1 ane yne
.
.2
.
.3 .
.4
.
.5
.
/ : .

CH3

C
C
CH3
2-Butyne
][Dimethyl acetylene

CH
CH
Ethyne
][Acetylene

CH3

C
CH
Propyne
][Methyl acetylene

CH3
9

CH3

CH

CH2 CH2 CH

CH2 CH

CH

CH3

CH

CH

CH

4-Methyl-7-nonen-1-yne

CH2 CH3

CH2 C

CH3 CH

2,4-Octadiene-6-yne

CH3
C

CH3 C

2,5-Octadiyne

CH3

CH

CH3
C

CH3 CH

2,5-Dimethyl-3-hexyne
) ( Diisopropyl acetylene

118

 : iii

.
univalent groups
e yl
CH3

CH2

CH
Vinyl
or Ethenyl

CH2

C
Isopropenyl

CH

C
CH2
Propargyl
)or 1-(2-Propynyl

CH2

CH CH2
Allyl
)or 1-(2-Propenyl

CH2 CH3

HC
C
CH2Cl
3-Chloro propyne
][ Propargyl chloride

CH

C
3

CH2 CH

CH

CH3 CH

CH2 CH CH2
5-(2-Propenyl)-2-nonen-6-yne

CH3

1-Propynyl cyclohexane

Ethynyl cyclohexane

Synthesis of alkynes
1 :
CH

HC

170oC

ZnO
2000oC

CaC2

C + CaO

.
+ 3 H2

CH

steam
1200oC

CH

2 CH4

2 Dehydrohalogenation of alkyl dihalides

CH

CH3 C

NaNH2

Br

CH

CH3 CH

)KOH(alc

CH2
Br

CH

Br

CH3

CH3
CH3 C

CH3 CH

K O-t-Bu
DMSO , 130oC

CH2Br

CH

CH3 C

CH3 Br

CH3

119

 : iii

3 : Geminal dihalides

.
Cl
C

CH2 CH2 CH3

NaNH2

H2O

CH

1-Pentyne

CH2 CH2 CH3

K
E t OH
OH

C
CH2 CH3
2-Pentyne

CH3 C

Cl
2,2-Dichloro pentane

CH3 C

4 ) (
C Li
CH

CH + Li NH2

HC

CH3 CH2 CH2 CH2 C

Li

+ CH3 CH2 CH2 CH2 Br

1-Hexyne

n-Butyl bromide

C Na
CH + NaBr

HC

CH

CH3 CH2 C

Lithum acetylide

CH + NaNH2

CH

C Na

CH

+ CH3 CH2 Br

CH

64-2 1-Butyne
a) 1-Butene , b) 2,2-dibromo butane
C CH2CH3

CH

KOH in EtOH
or NaNH2 in
mineral oil

CH2 CH3

CH

CH2

Br

Br

CCH2CH3

CH

CH2 CH3 + Br2

a) CH2

CH

Br
H2O

CH2 CH3 + NaNH2

b) CH3 C
Br

120

 : iii

Physical properties

) CCl4 (

.
Chemical reactions
1 Reaction as acids

Carbanion .

Strong base
R
H

R
C

25
+ NH3

42

Na

( NH3 )eq

CH + Na

55

pka

Ammonical Silver nitrate

Silver alkynide R-CCAg Cu(NH3)2+
.
+ NH4 + NH3

C Ag

CH3 CH2 C

H + Ag(NH3)2

R C

White precipitate
+ NH4 + NH3

C Cu

CH3 CH2 C

H + Cu(NH3)2

R C

red precipitate

.
121

 : iii

2 : Addition of hydrogen

-:
CH3 CH2 CH2 CH3

CH3

Pt

)C CH3 + H2 (2mol

CH3 C

CH3
C

Lindlar
catalyst

CH3 C

C CH3 + H2

H
H
cis-2-Butene

CH3
C
H

)NH3 (Liq

CH3 + Na

CH3 C

CH3

trans-2-Butene

CH3CH2

H
C
Na

CH2CH2 C

NH3 Liq

Na + Na

C CH2CH2

CH3CH2 C

* acetylide
.
* Pd-CaCO3
Pd-BaSO4
.

122

 : iii

3 Addition of halogens
C

CH3

CH3

1 mol
CCl4

CH3 + Br2

Br
Br
2,3-Dibromo-2-butene

CH3

Br

Br

CH3

CH3

2-Butyne

2 mol
CCl4

+ Br2

CH3

Br
Br
2,2,3,3-Tetrabromo butane

CH3

2-Butyne

4 : Addition of hydrogen halides

.
Cl
CH3

HCl

CH3 C

CH2

CH3 C

HCl

CH

CH3 C

Cl

Cl
Isopropylidene chloride
bp 70oC

Propyne
bp -23oC

Isopropenyl Chloride
bp 24o C

HF symmetric alkynes
geminal

CH2CH3

CH3CH2

HF
Pyridine

CH2CH3

H
F
3,3-Difluoro hexane

CH3CH2

3-Hexyne

75%

*

.
CH

CH2 C

CH + Br2

CH2 CH

Br
Br
4,5-Dibromo-1-pentyne

CH2 C

CH

1-Penten-4-yne

123

CH2

 : iii

5 : Addition of water enol

tautomerization .
O

H
CH2

OH

CH3CH2CH2 C

CH2

CH3CH2CH2 C

a Ketone

H2O / H2SO4
HgSO 4

CH3CH2CH2 C

CH

enol

6 : Organoborane
cis- Alkene :
O
B H
O
Catechol borane

H
C

1) Catechol borane

CH2 CH3

CH2

2) CH3CO2H

CH3

cis-3-Hexene

C CH2 CH3

CH3 CH2 C

3-Hexyne

enol
.

C8H18 C

tautomerization

enoles

1) Catechol borane
2) H2O 2 / OH-

C8H18 C

H
an Aldehyde

7 : Oxidation cleavage
.
CH3CH2CH2 COOH + HOOC CH2CH2 COOH

KMnO4
H3O+

124

C CH2CH2 COOH

CH3CH2CH2 C

 : iii

65-2 : trans-2-Butene
1,2,3-Trichloro propane

Vinylidene chloride

C CH3

CH3 C

Na

CH3I

CH3

CH3I

HC

C Na

CH + Na

HC

HC

CH3
C

)NH3(Liq

CH3

+ Na

C CH3

CH3 C

CCl2

Ca(OH)2
90oC

CH2

Cl

H
CH2 C

Cl2

Cl
Cl
1,1,2-Trichloro ethane

Vinylidene chloride

CHCl

CH2

)HCl(1mol

CH

Vinyl chloride

CH3

CH

H2C

CH3 H2 / Lindlar

catalyst

HC

Cl2
600oC

CH2

CH

H2C

Cl
Allyl chloride
bp 45oC

Cl2 / CCl4

CH2

CH

Cl

Cl
90%

125

H2C
Cl

CH3I

Na

CH

HC

HC

 : iii

66-2 2-Pentyne -:
a) 2H2 , Pt catalyst . b) H2,Lindlar catalyst . c) Br2(mol) in CCl4 .
d) 2HCl . e) i. NaNH2 , ii. CH3I .

CH3 (CH2)3 CH3

Pt
Catalyst

C CH3 + 2H2

a) CH3 CH2 C

cis-Pentene

Lindlar
Catalyst

C CH3 + H2

b) CH3 CH2 C

)C CH 3 + Br2 (1mol

c) CH 3 CH 2 C

C CH3 + 2HCl

d) CH3 CH2 C

2,3-Dibromo-2-pentene

CCl4

2,2,and3,3-Dichloro pentane

e) No reaction

67-2

b) CH3CH2CH2COOH + HOOCCH2CH3
CCH2CH3

b) CH3CH2CH2C

a) Benzoic acid + CO2

CH

68-2 : Ag(NH3)+2OH-
, 3-Hexyne , n-Hexyl acetylene

)a

Isopentyne

isopentyne , n-Hexyl acetylene Terminal

126

 : iii

69-2 1-Butyne
- Br2
NaNH2 - .
70-2 IUPAC
CH3
CH2Cl

HC

CH

CH

CH3

CH3
CH3

CH3 C

C CH3

C CH2 CH2

CH

HC

CH3

71-2
CH3CH2 CH2Br

NaNH2
NH3 aq

Hg2+ , H2O
H3O+

?
H2
Lindlar

C(CH2)2CH3

2) H+

2) CH3(CH2)5C

CH

HBr
excess

1) KMnO4 , OH-

CH

1) HC

C CH 3

3) CH 3 C

4) CH3(CH2)2C

C CH2 CH3

5) CH3 C

CH3
?

LiAlH4

Br

6) CH3 CH2 C
CH3

72-2
a) 1-Butyne from 1-Butene
b) 4,4-Dimethyl-1-pentyne from 4,4-Dimethyl-1-pentene

127

 : iii

73-2
a) cis-3-Hexene from 3-Hexyne
b) trans-3-Hexene from 3-Hexyne
74-2
c) cis-2-Butene

,
,

b) 2-Pentene
e) trans-3-heptene

a) Methyl acetylene
d) trans-2-Butene

75-2
+ CH3CH2COOH

COOH

CH3 CH

1) O3
2) H2 O

1. C7H12

CH3

HOOC (CH2)6 COOH

CH3 (CH2)5 CH3

1) O3
2) H2 O

2H2
Pt

2. C8H12

3. C7H12

76-2 a,b,c C5H8 CCl4

a a,b n-Pentane
c
. C5H10

77-2
a) 5-Methyl-1-hexyne
, b) 1-Chloro-2-butyne
, c) Cycloheptyne
d) 3,3-Dimethyl-1-butyne
, e) 2-Octene-6-yne
,
f) Diethyl acetylene
78-2
a) Propane and Propyne
b) Propene and Propyne
c) 2-Butyne and 1-Butyne
79-2 Ethyne

128

 : iv

Aromatic hydrocarbons
Arenes

.

-:
.1
.2
.3
.4
.5

) ( .
.
.
.
,
" " Huckle s rule

Erich Huckel 1931
4n+2 n
) (,2,1,0 n
.
3
14

2
10

1
6

0
2

=n
4n+2

8 .

6
.

Benzene
Michael Faraday
1825

C6H6
-:
129

 : iv

CH2

CH3

H3C

CH CH2

CH C

H2 C

Kekule
-:

C-C 1.39oA
C-C C=C Kekule
C-C C=C

Resonance
Kekule .

physical properties of benzene

.1 .
.2 80.1oC 5.5oC 0.88 g Cm-3
.3 .
.4 .

130

 : iv

Nomenclature derivatives of benzene

: :
Cl

NO2

Chloro benzene

Nitro benzene

:
OH

mp 43
Phenol

NH2

CH3 CH CH3

152o C
Cumene

184oC
Aniline

CH3

bp 111oC
Toluene

.1
1 .
-:
" : Ortho " o 2,1-
" : Meta " m 3,1-
" : Para " p 4,1-
.2
.
.3
Phenyl Ph C6H5-
C6H5CH2 Benzyl

131

 : iv

CH2

HC

COOH

CH2 Cl

bp 145oC
Vinyl benzene
][Styrene

COOH

bp 179 C

Benzyl chloride

O2N
3-Nitro benzoic acid
] [ m-Nitro benzoic acid

Benzoic acid

NH2
CH3
CH

CH

1,2-Diphenyl ethene
][Stillbene

Diphenyl acetylene
] [ Tolan

2-Methyl aniline
][o-Toluidine
CH3
CH3

Cl

CH3
CH3

CH3

Cl
1,3-Dichloro benzene
or m-Dichloro benzene

1,2-Dimethyl benzene
][o-Xylene

CH3
1,2,4,5-tetra-Methyl benzene
][ Durene

CH3
CH3
5

NO2

CH3

NO2

CH3 CH CH CH2 CH3

CH3

2-Methyl-3-phenyl pentane

CH3

1,3,5-Trimethyl benzene
] [ mesitylene

NO2
2,4,6-Trinitro toluene
][T.N.T

80-2
a) 1-Chloro-2-methyl benzene
b) 1-Hydroxy-4-nitro benzene
c) 3-Amino-1-ethyl benzene
a) o-Chloro toluene , b) p-Nitro phenol , c) m-Ethyl aniline

132

 : iv

81-2 2-Chloro-p-xylene
2-Chloro-1,4-dimethyl benzene
: Benzenoids
.
6
1

2
3
4

7
7

5
4

6
4

10

9
10

Anthracene
216oC

Naphthalene
80o C

Phenanthrene
101o C

= mp

-:

1,2 ortho
, 1,3 meta
,
1,4 para
1,5 ana
, 1,6 epi
, 1,7 kata
1,8 peri
, 2,6 amphi
, 2,7 pros
NH2
CH3
Br

1-Methyl naphthalene
or -Methyl naphthalene

NH2
1,5-Diamino naphthalene
or ana-Diamino naphthalene

133

9-Bromo anthracene

 : iv

:
n-Hexane , n-Heptane , Methyl cyclohexane , 1,3-Dimethyl naphthalene
Fractionated petroleum
Destructive distillation
Benzene + 4 H2

Hydroforming

Toluene + 4 H2

Al2 O3 , Cr2O3
500oC
Al2O3 , Cr2O3

n-Heptane

500o C

Al2O3 , Mo2O3

Toluene + 3 H2

n-Hexane

600oC
Pressure

Benzene + CH4

Methyl cyclohexane

675oC

Toluene + H2
CH3

Hydrodealkylation

Naphthalene + 2 CH4

Al2 O3 / Cr2O3
500oC

+ 2 H2
CH3

Reactions of benzene
-1 : Combustion reaction

.
-2 : Hydrogenation

Hexachloro cyclohexane
)240(
Ni
2 atm , 100oC

134

+ 3 H2

 : iv

-3 Electrophilic substitution reactions

. : Halogenation
FeCl3 : AlCl3
.
Cl
FeCl3

+ HCl

+ Cl2

.
I
25oC

+AgI + HClO4

+ I2 + AgClO4

Fluoro benzene -:
BF4

N2

NH2

F
1) HNO2 / HCl

heat

+ N2

2) HBF4

Fluoro borate

. : Nitration NO2
1:1
NO2+ .
NO2

50-60o C

+ HNO3 + H2SO4

. : Sulphonation SO3H

) SO3 (
SO3H
+ H2SO4

+ H2O
Benzene sulfonic acid

135

 : iv

. : Friedel-Crafts alkylation
Charles Friedel James M. Crafts 1877
AlCl3 .
CH3
+ HCl

CH3

CH

Cl

AlCl3

+ CH3 CH CH3

:
i
.
ii .
iii .
CH3
CH3

CH3

H3C
AlCl3
HCl

CH3
1,2,4-Trimethyl benzene
] [ psi-Cumene

CH3
1,3,5-Trimethyl benzene
] [ Mesitylene

iv
.
CH3
CH2CH2CH2CH3

CH2 CH3

CH
CH3CH2CH2CH2Cl

+
n-Butyl benzene
35%

AlCl3 , 0oC

sec-Butyl benzene
65%

. Acylation
O

+ HCl

CH3

C
AlCl3
o

80 C

136

O
Cl

+ CH3 C

 : iv

82-2
AlCl3

No reaction

No reaction

AlCl3

1 ) Aniline + CH3Cl

2 ) Benzene + Chloro benzene

( 1 .
( 2 Chloro benzene
sp2 C-Cl
.

83-2 1) Cyclohexane , 2) Cyclohexene :

( 1
: .
: .
( 2
: .
: .
: .

84-2 Styrene , Durene :

CH2

CH2CH3

CH
Fe2O3

+ H2

HCl / AlCl3
90oC

650oC

CH3
CH3

CH3

AlCl3
100oC

CH3

137

+ 4 CH3Cl

CH2

+ H2 C

 : iv

Reaction of benzene derivatives

-:
: activate .
: deactivate .
- :
-NHCOCH3 , -R , -OH , -OR , -NH2 -:

-:
-:

-X = F , Cl , Br , I

-SO3H , -NO2 , -CN , -COR , -CHO , -COOH

: .
CH3

CH3

CH3
NO2

HNO3

H2SO4

NO2

Br

Br

Br

Br

NO2
+

HNO3

NO2

acetic acid

NO2
2%

36%

62%

NO2

NO2

Br2 / FeBr3
heat

Br

138

 : iv

COOH

COOH

HNO3
H2SO4

COOH

COOH

O2N
96%

Mesitylene
.
CH3

CH3
CCl4

+ HBr

+ Br2

0-10oC

CH3

CH3

H3C

H3C

Br
80%

OH

OH
Br

Br

Br2
H2O

Br
2,4,6-Tribromo phenol

Phenol

NH2
Br

NH2

Br
Br2
H2O

Br
2,4,6-Tribromo aniline

Aniline

] [
m-Xylene Acyl
.

CH3

O
+ HCl

C
CH3

O
CH3

AlCl3

Cl

80%

139

+ CH3 C

CH3
CH3

 : iv

85-2
a) Benzoic acid m-Iodo benzoic acid
COOH

COOH

COOH
Fe / H+

HNO2
HCl

Cl-

N2

COOH
HNO3
H2SO4

NO2

NH2
KI

COOH

b) Benzene m-Nitro phenol

NO2

NO2

NH2
HNO2
HCl

HNO3
H2SO4

(NH4) 2S

HNO3
H2SO4

NO2

NO2
N2 Cl

OH
H 2O
Cu2O , Cu(NO3)2
excess

NO2

NO2

m-Nitro benzene
diazonium chloride

c) Aniline 1,3,5-Tribromo benzene

ClBr

Br

Br

N2

NH2
Br
NaNO2
HCl

H3PO2

Br

Br
2,4,6-Tribromo benzene
diazonium chloride

140

Br

NH2
Br
Br2
H2O

Br

 : iv

d) 2-Bromo-4-nitro toluene 3-Bromo-4-methyl benzoic acid

CH3

CH3

CH3

Br

Br

Br

Br

NaNO2
HCl

CuCN

H+
H2 O

COOH

CH3

Cl-

CN
3-Bromo-4-methyl
benzonitrile

Fe
HCl

NO2

N2

3-Bromo-4-methyl benzene
diazonium chloride

-:
BF4

Fluoro benzene

KI

Iodo benzene

CuX

Chloro benzene or Bromo benzene

X = Cl , Br

Benzene

Cl

N2

H3PO2

Benzene diazonium
chloride

1 Oxidation of alkyl benzene

.
CH3

COOH
KMnO4
H2O , 95oC

NO2

NO2

CH2CH2CH2CH3

COOH

KMnO4

+ CO2

H2O , 95oC

NO2

NO2

141

 : iv

CH3

COOH
COOH

CH3

KMnO4

H2O ,

C(CH3)3
KMnO4

No reaction

H2O ,

Benzylic carbon t-Butyl
2 Halogenation of alkyl benzene
CBr3
+ 3HBr

CH2Br

CHBr2
+

Benzo
tribromide

CH3
h

Benzal
dibromide

+ Br2
Toluene

Benzyl
bromide

Br
CH2CH2CH3

CHCH2CH3
NBS
CCl4 , acetone

Propyl benzene

(1-Bromo propyl) benzene

NBS
benzylic position
3 ) :97(
HC

CH2

CH2CH2 O CH2CH3

C2H5O- Na+
C2H5OH

+
5%

CH2CH2Br

95%

142

 : iv

86-2
NO2
O
No reaction

AlCl3

Cl

H3C

NO2 acylium ion

Reactions of naphthalene
1 Halogenation
Br
Br2 / Fe

+ HBr
1-Bromo naphthalene

Naphthalene

2 : Sulphonation
1 2
.
SO3H
SO3H
H2SO4 / 80oC

H2SO4 /160oC

3 Nitration
NO2
HNO3
H2 SO4

143

 : iv

4 : Hydrogenation
)
( .
100 atm H2

100-200 atm H2

Ni , 100oC

Cu-Cr2O3 , 200oC

1,2,3,4-Tetrahydro naphthalene
][Tetralin

Decahydro naphthalene
][Decalin

5
:
CH3
CH3

AlCl3

+ CH3I

:
CH2 CH3
+ CH3CH2Br

CH3
CHCH3
+ CH3CH2CH2Br

: 2,6
1,4 .
R
AlCl3

2,6- isomer

amphi-Dialkyl naphthalene

144

+ 2 R-OH

 : iv

R
BF3

+ 2 R-OH

R
1,4- isomer

para-Dialkyl naphthalene

.
NO2

NO2

NO2

NO2
HNO3

H2SO4

NO2

1,8- isomer

1,5- isomer

ana-Dinitro naphthalene

peri-Dinitro naphthalene

OCH3 , -CH3
.
OCH3

OCH3

OCH3

NO2

HNO3

HOAc

NO2
85%

14%

Br
CH3

CH3

Br2
CS2

91%

145

 : iv

NH2

N2 Cl

NO2
Zn

NaNO2 / HCl

H+

-Naphthalene diazonium chloride

-:
-Fluoro naphthalene

HBF4 /

-Cyano naphthalene

CuCN

-Hydroxy naphthalene
-Iodo naphthalene
Naphthalene

Cl-

N2

H2O / H+

KI

- Naphthalene diazonium
chloride

H3PO2

87-2 1-Nitro naphthalene & Nitro benzene

.
Cl

NO2
PCl5

146

 : iv

88-2
, b) Naphthalene

a) 1,3,5-Hexatriene

89-2
a) p-Hydroxy benzoic acid
, b) 2-Phenyl heptane
c) m-Iodo phenol
, d) 4-Chloro-2,3-dinitro toluene
e) p-Iodo nitro benzene
, f ) (3-Methyl butyl) benzene
] g ) 2-Phenyl propene [ -Methyl styrene
] h ) p-Isopropyl toluene [ p-Cymene
90-2
,
,
,
,

b) p-Chloro propyl benzene

d) m-Chloro ethyl benzene
f) Triphenyl methane
h) 1,2,4-Trichloro benzene

a) m-Chloro nitro benzene

c) 2-Phenyl-2-methyl butane
e) tert-Butyl benzene
g) p-Bromo benzoic acid

91-2
,
,

b) m-Nitro benzoic acid

d) p-Bromo benzoic acid

a) o and p Nitro benzoic acid

c) Benzyl chloride
e) 3,5-Dibromo toluene

92-2 m-chloro toluene

2,3-Dichloro toluene , 3,4-Dichloro toluene

2,5-Dichloro toluene

93-2
.i
.ii
.iii
.iv

.
Vinyl chloride .
C6H5NHCOCH3 .
1,3,5-Cycloheptatriene .

147

 : iv

94-2
i- Nitration of Bromo benzene
iii- Chlorination of Phenol

, ii- Bromination of Nitrobenzene

, iv- Bromination of aniline

95-2
,

b) o-Xylene ,
d) p-Bromo benzene sulfonic acid

a) m-Nitro phenol
c) p-Dinitro benzene

96-2
NH2

F
Br

Br

NO2

CH2CH2CH3
CH3

H3C

Cl

NO2
CH3
NO2

H3C
Br

97-2 C7H7Cl
98-2
, b) Toluene

148

a) Benzene

 : iv

99-2
NH2
CuCl

NaNO2

)a

HCl

CH3
KMnO4

)b

NO2

KMnO4

CH3Cl
AlCl3

Br2
FeBr3

)c

CH2CH3
NBS
CCl4

)d

CH3
?

O2N

HNO3 / H2 SO4

)e

120oC

NO2
CH2 CH3
Ni / 175oC

180 atm

+ 3 H2

)f

COOH
?

149

HNO3 / H2SO4

)g

 : )(I

Alcohols , Phenols and Ethers

.

.

.

C-O-C

1 : IUPAC e ane
ol Methane Methanol
.
Carbinol
alcohol
2 : Common name
] [
CH3
2

CH3 CH CH2 OH
2-methyl-1-propanol
][Isobutyl alcohol

CH3 CH2 OH
Ethanol
][Ethyl alcohol

CH3

CH3
1

CH3 C CH2 OH

CH3 C CH3

CH3
2,2-Dimethyl-1-propanol
][Neopentyl alcohol

OH
2-Methyl-2-propanol
][t-Butyl alcohol

150

 : )(I

Methyl alcohol
Methanol Carbinol -:
OH
3

CH3

CH

CH3

2-Propanol = Dimethyl carbinol

1-3 Methyl alcohol

i) 4-Methyl-2-pentanol , ii) Cyclohexyl methanol , iii) 3-Buten-2-ol
OH

OH
CH

CH3

CH

Methyl

CH2

CH3

CH2OH

Vinyl

CH2 CH

Methyl

iii) Methyl vinyl carbinol

CH3
CH3 CH
Isobutyl

i) Isobutyl methyl carbinol

ii) Cyclohexyl methanol

: -:
. 1 : .
: Mono hydroxy alcohols
.
OH

OH

CH2
1

CH3

Phenyl methanol
][Benzyl alcohol

CH

CH2 CH

H2C
CH3 OH
Methanol
][Methyl alcohol

Br
CH3
5-Bromo-2-methyl-5-hexen-3-ol

: Dihydroxy alcohols
glycol .
OH
C CH3

OH
CH3 C

CH3 CH3
2,3-Dimethyl-2,3-butanediol
][tetra-Methyl ethylene glycol
)( Pinacol

CH2 CH2 CH2

CH2

OH
OH
1,3-Propanediol
][Trimethylene glycol

OH

151

CH3 CH
OH

1,2-Propanediol
][Propylene glycol

CH2 CH2
OH

OH

1,2-Ethanediol
][Ethylene glycol

 : )(I

: Trihydroxy alcohols
.
CH2

CH2 CH

OH OH OH
1,2,3-Propanetriol
][Glycerol

. 2 : .
Primary alcohols .
Secondary alcohols
Tertiary alcohols .
3 .
: Aliphatic alcohols .
: Aromatic alcohols .

CH3

CH3
3o

OH

OH

CH3 C

1o

2o

CH3 CH

CH3 CH2 OH

CH3
2-Methyl-2-propanol

Ethanol

2-Propanol

OH
CH
CH2 OH

CH

C
CH2 OH
2-Propyn-1-ol
][Propargyl alcohol

Diphenyl methanol
][Benzhydrol

CH

CH2

2-Propen-1-ol
][Allyl alcohol

.
O

OH
- H2 O

152

OH

 : )(I

Preparation of alcohols
1 Hydration of alkenes
)103(
CH3

H+

CH3 CH

CH2 + H2O

CH3 CH

OH

-:
H3PO4

CH3 CH2 OH

200 atm , 300oC

CH2

CH2 + H2O

2 : Nucleophilic substitution

:


)97(

.
CH3

CH3
OH + HBr

H2O

CH3 C

Br

CH3 C
CH3

CH3

tert-Butyl bromide

tert-Butyl alcohol

CH3

CH3
CH3 C

CH2 CH3

H2O

CH2 Br

CH3

OH

CH3

CH3
3o

CH2 CH3

CH3 C

CH3 C

Rearrangement

CH2

CH3 C
CH3

153

 : )(I

CH3
+

CH3 C

CH2 OC2H5

C2H5O Na
ethanol

CH3

CH3
CH2 Br

CH3 C
CH3

CH3
C2H5OH

CH2 CH3

CH3 C

OC2H5

: )
( Solvolysis
.

CH3
+ Alkene
28 %

O CH2CH3
72 %

CH3 C

55oC

CH3

CH3
Br + CH3CH2OH
CH3

+ Alkene
19 %

O CH2CH3
81 %

CH3 C
CH3

154

25oC

CH3 C
CH3

 : )(I

:
.
CH2

CH3CH2 O CH2CH3 + CH2

1%

CH3CH2Oethanol

CH3CH2 Br

99 %

CH3
CH3CH O CH2CH3 + CH3 CH

CH2

78 %

CH3CH2Oethanol

Br

CH3 CH

22 %

CH3

CH3

CH3
CH2

CH3

O CH2CH3 +
CH3

CH3C
CH3

99 %

CH3CH2Oethanol

Br

CH3 C
CH3

1%

Aryl halide Vinyl halide

phenyl allyl halide
benzyl halide

F- << Cl- < Br- < I- :

3 : Oxymercuration-demercuration
THF
NaBH4 .
CH3

CH
OH

CH3

NaBH4

CH2

CH

HgOAc

OH

CH3

155

CH2 + Hg(OAc)2

CH

CH3

 : )(I

4 : Grignard reaction RMgX

.
X

Mg

ether
or THF

, alkyl , aryl , alkenyl

X + Mg
3o

2o

R
1o

=R
,
,
X = Cl , Br , I

O Mg Br
1o

H2 O

CH3CH2CH2 OH

H + CH3CH2MgBr

CH2CH3

OH

O Mg Br

2o

CH3

H2O

CH3 CH

CH3 C

H + CH3MgBr

CH3 C

CH3

OH

O Mg Br

3o

H2O

CH3 C CH3

CH3 C CH3

CH3

CH3 C CH3 + CH3 MgBr

CH3

O Mg Br
O

1o

H2O

CH3CH2CH2 OH

CH2 OH

CH

H3O+

CH3 CH2 CH2

H2C=O

C Mg Br

bp = 117oC

5 )214(
6 )239(
7 )261( )263(

156

+ CH3MgBr

CH

CH3MgBr

CH

CH2 CH2

CH

 : )(I

1 )102(
CH2

H2O / H+

H2C

H2 C

CH2

O
Ethylene oxide

OH OH
Ethylene glycol

Ag
heat ,
pressure

CH2 + O2

H2C

: .
H

H2C

H + Soap

HC

H2C

H2O
NaOH

COR

H2C

COR

HC

COR

H2C

2-3 2-Pentanol 1-Pentyne

OH
CH3

CH3 CH2 CH2 CH

H2O
H+

Lindlar
catalyst

CH + H2

CH3 CH2 CH2 C

3-3 1-Phenyl ethanol

O

OH
CH3

H2O

CH

CH3 C

4-3 2-Methyl-1-butene
, 2-Methyl-1-butanol
CH3
CH3

CH3 CH2 C

MgBr

2-Methyl-2-butanol

CH3
H2O
H+

CH2

CH3 CH2 C

OH
2-Methyl-2-butanol
CH3
CH2 OH

CH3 CH2 CH

2-Methyl-1-butanol

CH3
1) B2H6
2) H2 O2 , OH-

157

CH2

CH3 CH2 C

 : )(I

Physical properties
1 :
.
R
R

O
O

.
Isopropanol
n-Propanol
97oC

n-Heptanol
176oC

82.5oC

n-Pentanol

n-Hexanol

138 C

156.5 C

.
CH3
CH3 C

OH

CH3
OH

CH3

CH3 CH2 CH

CH2 OH

CH3 CH

CH3 CH2 CH2 CH2 OH

CH3
tert-Butyl alcohol
83oC

sec-Butyl alcohol
99.5oC

n-Butanol
118oC

Isobutanol
108o C

.
CH3

CH3

CH3

CH3 CH2 C CH3

CH3 CH2 CH CH2 OH

CH3 CH CH2 CH2 OH

OH
tert-pentyl alcohol
102oC

2-Methyl-1-butanol
128oC

Isopentanol
132oC

158

OH
Cyclopentanol
140o C

 : )(I

2 :
)( :
,
.
CH3
OH

CH3 CH2 CH2 CH2 OH

CH3 C
CH3

n-Butyl alcohol

tert-Butyl alcohol

7.9 g / 100 g H2O

) ( hydrophobic

.
tert-Pentyl alcohol

Cyclohexanol

n-Pentanol

n-Hexanol

12.5 g / 100 g H2O

3.6

2.4

0.6

5-3 ethylene glycol

.

6-3 tert-Pentyl alcohol n-Pentyl alcohol

.

159

 : )(I

Reaction of alcohols
-:
.1 .
.2 .
/ RO-H

.


.
: Oxonium
ROH2+
H
H X

Alkoxide RO-
H + H2O

RO + H3O

RO

Ka ) pKa ( .

.
Ethanol
16.00

Water
15.70

Methanol
15.20
Stronger
acid

Weaker
acid

alkoxide
.

160

 : )(I

: Methanol , Ethanol , tert-Butyl alcohol

.
Tert-Butyl alcohol
18.00

Methanol
15.20

Ethanol
16.00

= pKa

alkoxide pKa .

Ethanol
16

, 2,2,2-Trifluoro ethanol
12.43
CF3

CH3
O

= pKa

H3C

CH3

CF3

18

5.4

tert-Butyl alcohol

F3C

= pKa

nonafluoro t-butyl alcohol

7-3
(CH3)2CH OH

< (CF3)2CH OH

< CH3 OH

(CF3)2CH OH

(CH3)2CH OH

161

< CH

, CH OH
3

HC

CH

HC

 : )(I

: Reaction with alkali metals

Li , Na , K .
1
+ __ H2
2

Na

CH3 CH2 O

Na

CH3 CH2 OH +

Sodium ethoxide

.
CH3 CH2 OH + NaOH

+ H2O

Na

CH3 CH2 O

Sodium hydride Hydride ion H-

.
Na

NaH
DMF

OH
Cyclohexanol

Sodium cyclopentoxide

Ester formation

.
O

O
CH3 + H2O

CH3

CH3 CH2 O

H + HO

CH3 CH2 O

Oxidation
-:

:
.
O
OH

O
R

][O

162

][O

1o

CH2 OH

 : )(I

.
O
CH3 C

Cu
300oC

CH3 CH2 OH

Pyridine-Chromic Collins's reagent PCC

Corey's reagent

ClCrO3

HCl

N H

N
Pyridine

]Pyridinium chloro chromate [PCC

CrO3
Chromium trioxide

CrO3 N
2
Chromium oxide pyridine

.
O
H

CH3

CH3
CH

CH3

PCC
CH2Cl2

1o

CH2 OH

OH

O
H

CH

CH3

CH3 CH2 CH2 CH2 CH2 C

80 %

CrO3 (Pyr)2
CH2Cl2 , 20o C

CH3 CH2 CH2 CH2 CH2 CH2

KMnO4 , Na2Cr2O7 : Jones's reagent

CrO3 .

163

 : )(I

:
R

O
C

][O

OH

CH

O
C

CH3 + H2

OH
CH3

ZnO
380o C

CH3

CH

OH

O
CH3 + H2

CH3

CH3 CH2

NaOCl

CH3

CH

CH3 CH2

(NaOCl) Hypochlorites

: C-C

)190(

: reaction with Phosgene

.
COCl2 + HCl
O
O + 2 HCl

light

CHCl3 + O2
Cl

R
O + 2 ROH

R
O
Alkyl carbonate

Alcohol

164

C
Cl
Phosgene

 : )(I

/ C-O

Dehydration

:
R3COH > R2CHOH > RCH2OH :
CH3

CH3
+

H3O , THF
50oC

OH
1-Methyl cyclopentanol

1-Methyl cyclopentene

CH3
CH3

CH3
CH3 CH2 CH

POCl3
Pyridine ,0o C

CH3

OH
CH3 CH2 CH

CH

POCl3 : Phosphorus oxychloride

:
.
140oC

CH3 CH2 O CH2 CH3 + H2O

H2SO4

CH3 CH2 OH

180oC

CH2 CH2 + H2O

140) o 189 (
o
180
SOCl2 , PBr3 , HX
X + H2O

OH + HX

Hydrogen halides
HX : HI > HBr > HCl

HI

CH3 CH2 I + H2O

165

CH3 CH2 OH

 : )(I

HBraq / H2SO4

CH3 (CH2)4 CH2 Br + H O

2

CH3 (CH2)4CH2 OH
1-Hexanol

1-Bromo hexane

CH3

CH3
1o

CH2 Cl

HClaq / 25 C

CH3

CH2 OH

5 Min

CH3

CH3

CH3
80%

X + H3PO3

3 R OH + PX3

Phosphorus
trihalide
X = Br , I

CH2 CH2 Br + H3PO3

PBr3

CH3

CH2 CH2 OH

CH3

CH3
PBr3

CH3 CH CH2 Br + H3PO3

60 %

Cl + SO2 + HCl

CH3

CH2 OH

OH + SOCl2

3 CH3 CH

Thionyl chloride

SOCl2

CH3 CH2 Cl + SO2 + HCl

CH3 CH2 CH2 CH2 CH2 Cl + HCl + SO2

166

SOCl2

CH3 CH2 OH

CH3 CH2 CH2 CH2 CH2 OH

 : )(I

Reaction of glycols
: Oxidative cleavage of Glycols C-C
Periodic acid
.
O
C

O
CH3 C CH3

CH3

Acetic acid
dilute

+ HIO4

HIO4

2 H2C=O

or Pb(OCOCH3)4
Lead tetra-acetate

OH
OH

OH

OH

CH

CH3

H2C
H2C

:
CH2 CH2
I

PI3

CH2 CH2
OH

OH

:
.
NO2

H2C

NO2 + 3H2O

HC

NO2

H2C

H2SO4

Nitro glycerin
][Glyceryl trinitrate

NO2

HO

H2C

NO2

HO

HC

NO2

HO

H2C

Nitric acid

167

 : )(I

:
-:

2HIO4

2 H2C=O + HCO2H

OH

H2C

OH

HC

OH

H2C

-:
OCH3
+ H2C=O

OCH3

H2C
HC

No reaction

HIO4

HIO4

OH

HC

OH

H2C

OH

H2C

OCH3
OH

168

H2C

HC
H2C

 : )(I

8-3 Methyl alcohol

i) 2-butanol
ii) 3-pentanol
iii) 2-Octanol
iv) 2,6-dimethyl-4-heptanol
9-3 IUPAC
OH

CH2

CH

CH2

CH3

CH

H3C

CH3

CH3

CH

CH2

C6H5

CH

CH3

CH

OH

CH

CH3

OH

OH
OH

CH2 CH2
CH3

OH

CH3 CH
Br

OH

OH

10-3
i) Ethene
ii) propene
iii) 2-methylpropene
iv) 2-methyl-1-butene
11-3
i) 2,4-Hexadiene-1,6-diol
ii) 1,2,4-Cyclopentanetriol
iii) 2-Ethyl-4-isopropyl cyclohexanol
iv) sec-Butyl alcohol
v) Neopentyl alcohol
vi) cis-1,3-Cyclopentanediol
vii) 3-Butyn-1-ol
viii) 1-Phenyl-1-pentanol
ix) o-Chloro benzyl alcohol
] x) 1,4-Butanediol [ tetra-Methylene glycol
169

 : )(I

xi) 2-Butyne-1,4-diol
] xii) 2-Buten-1-ol [ Crotyl alcohol
] xiii) 3-Chloro-1,2-propandiol [ -Chloro hydrin

12-3
) i) Ethanol +( Ph-Mg-Br in ether
ii) Sodium ethoxide in ethanol + H2O
iii) 1-propanol + Na

13-3 POCl3 in Pyridine

i) cis-2-Methyl cyclohexanol
,
ii) trans-2-Methyl cyclohexanol

14-3 2-Hexanol PCC

15-3
H+

?
?

Zn
acetone

CrO3 /

a) 1-Hexanol

PI3

b) CH2 CH2
OH

OH

CH3
?

1) BH3
2) H2O2 / H2O

c) CH3 C

CH2

CH3
?

Br2 / H2O

C
CH3

170

CH3
C
CH3

)d

 : )(I

CH3

CH3
H2O

H2SO4

)e

C
CH3

OsO4

)f

CH3
?

KMnO4

SOCl2

PCC

g) CH3 CH

CH2 OH

h) CH3 CH2 CH2 OH

CH

CH2 CH2

i) CH2

OH
HClaq

ZnCl2 ,

j) CH3 CH2 CH2 CH2

OH

CH3
?

H2SO4

CH3

K) CH3 CH

CH
OH

CH3 COOH

OH +

l) CH3 CH2

16 -3
CH3
, CH CH (CH ) OH
3
2 4

CH3

CH3
CH2 CH2 CH2 OH

, CH CH
3

CH2

CH3 CH

)a

OH
CH3 CH2 CH2 OH

, CH3 CH2 CH2 CH3

CH2 CH2
OH

171

OH

)b

 : )(I

17-3 C5H12O
2o , 1o 3o

18-3 1-Propanol
2) Na then Bromo butane ,
3) KMnO4 , OH- , heat
,

5) Benzene and BF3

1) Na

4) H2SO4 , 140oC

19-3
R-Cl + H 3PO3

i) R-OH + A

R-Cl + HCl + POCl3

ii) R-OH + B

R-Cl + H 3PO 4

iii) R-OH + C

R-Cl + SO2 + HCl

iv) R-OH + D

172

 : )(II

/ Phenols
: )131(

OH
NO2

OH

OH

O2N

OH

CH3

NO2

NO2
2,4,6-Trinitro phenol
] [ Picric acid

2-Methyl phenol
][o-Cresol

Benzenol
Phenol
] [Carbolic acid

2-Nitro phenol
][o-Nitro phenol

: -:
1 : :
OH

OH

OH
NH2

NH2

O2N

NO2
2-Amino-4,6-dinitro phenol
][Picramic acid

HN CH3
4-(N-Methyl amino) phenol
] [ Metol

CH(CH3)2
3

2,4-Diamino phenol
] [ Amidol

OH

OH
2

NH2

CH3

CH3

2-Isopropyl-5-methyl phenol
][Thymol

OH

(CH3)2 CH

5-Isopropyl-2-methyl phenol
][Carvacrol

173

Br
3-Bromo benzenol
m-Bromo phenol

 : )(II

2 : :
OH

OH

OH
OH

OH

OH
Hydroquinone
] [ or Quinol

2-Hydroxy phenol
or 1,2-Benzenediol
][Catechol

][Resorcinol

OH
O2N

NO2

CH3

OH
NO2

OH

2,4,6-Trinitro resorcinol
][Styphnic acid

HO

3,5-Dihydroxy toluene
][Orcinol

3 - :
OH
OH

OH

OH

OH
OH

OH
1,2,3-Trihydroxy benzene
][Pyrogallol

HO

1,3,5-Trihydroxy benzene
][Phloroglucinol

OH
1,2,4-Trihydroxy benzene
][Hydroxyquinol

4 :
OH

OH

1-Hydroxy naphthalene
][ -Naphthol

OH
4-Hydroxy naphthol

174

OH
9-Phenanthrol

 : )(II

Dow process -:
Cl

O Na

OH

NaOH , 360oC
Pressure

HCl

.
OH
OH

CH3

O
CH3

CH3 CH CH3

CH3 C
O2

H3O+

+ H3C

Acetone

Cumene hydroperoxide

Phenol

Cumene

-:
SO3 Na

SO3H
NaOH

Sodium benzene
sulfonate

+ H2SO4

Benzene sulfonic acid

O Na

NaOH , 350oC

OH
HCl

Fusion

Sodium phenoxide
] [ Phenolate ion

)196(

175

 : )(II

2-Methoxy phenol -:
OH

OH
OH
HBr

+ CH3Br

CH3

86 %

Gallic acid o210 CO2

Gallic acid o120 .
OH

OH
OH

OH
Solid

+ CO2

210o C

OH

OH

HOOC

40 %

2,4,6-Trinitro benzoic acid

COOH

COOH
OH

NH2

HO

Sn / HCl

HCl

+ CO2 + 3 NH4Cl

NO2

H2 N

NO2

NH2

OH
53 %

Sodium sulphide Na2S

OH

OH
O2N

NH2

O2N

O2N

NO2
Na2S

NO2

NO2
90 %

Picric acid

Picramic acid

176

 : )(II

Physical properties
1 :


O-H

o182 o161.5 .
2 :

9.3 g/100ml H2O :
45 g/100ml H2O:

20-3 Benzyl alcohol Cresol

OH
OH
CH2 OH

CH3
CH3

CH3
205oC

OH

202o C

201 C

191 C

177

 : )(II

21-3
a) o-Nitro phenol , phenol , o-Cresol
b) p-Ethyl phenol , o-Ethyl phenol , m-Ethyl phenol
OH

OH

OH

CH3

NO2

<
217oC

<

)a
182o C

191oC

OH

OH

OH
CH2CH3

<

<

)b

CH2CH3
CH2CH3
219oC

207 C

217 C

.
/
: Acidity
.
OH

-H

Cyclohexoide ion

OH
-H

Cyclohexanol

178

phenoxide anion

Phenol

 : )(II

.
O

.
Phenol + NaOH

Sodium phenoxide + H2O

pKa = 9.89
Stronger acid

pKa = 15.7
Weaker acid

Sodium phenoxide + H2CO3

Phenol + HCO3
pKa = 9.89
Weaker acid

pKa = 6.37
Stronger acid

]Electron-withdrawing [EWG

] Electron-donating [EDG
pka
pKa

9.89
8.39
8.11
7.17
10.20

pKa

9.89
9.25
9.20
7.15
10.17

pKa

9.89
8.85
8.80
8.28
10.01

179

Phenol
-Br
-Cl
-NO2
-CH3

 : )(II

22-3
a - Phenol , p-Methyl phenol , p-(Trifluoro methyl) phenol
b Benzyl alcohol , Phenol
c p-Bromo phenol , 2,4-Dibromo phenol , 2,4,6-Tri bromo phenol
a p-Methyl phenol < phenol < p-(Trifluoro methyl) phenol
b Benzyl alcohol < phenol
c p-Bromo phenol < 2,4-DiBromo phenol < 2,4,6-Tribromo phenol
Phosphorus oxychloride POCl3
) ( POCl3 TCP
.
OH
O

O P
+ POCl3

+ 3HCl

CH3

CH3

] Tricresyl phosphate [TCP

Iron(III)chloride

Cresol Catechol
.
OH

-3
+ 6H+ + 3Cl-

Fe

+ FeCl3

23-3 p-Cresol and Benzyl alcohol :

.i
.ii

.
.

180

 : )(II

) 189 (
)237(
/
:
%100 .
OH
Br

OH
Br
H2 O

+ 3HBr

+3 Br2

Br

.
OH

OH

OH
Br

+ 2HBr

CHCl3

apolar solvent

+2 Br2

Br

Carbon disulfide CS2
% 82 .
OH

OH
CS2

+ HBr

0o C

Br

181

+ Br2

 : )(II

% 87 .
OH

OH
Br
H2O
HBr

+ 2HBr

+ Br2

Br
2,4-Dibromo phenol

.
OH

OH
Br

Br2 , CH2Cl2
0oC

CH3

CH3

: Nitirc acid
.
OH

OH

OH

NO2

dilute

+ H2O

20oC

+ HNO3

NO2

OH
NO2

OH
O2N
conc.

+ H2O

20oC

NO2

182

+ HNO3

 : )(II

:
.
OH
SO3H

25o C

OH
/ H2SO4
conc

H2SO4
conc.

OH
100oC

SO3H

Friedel-Crafts alkylation
OH
OH
CH3
70% H2SO4

+ H2O

CH3
CH3

80oC

OH

+ CH3

CH3

CH3

80 %

p-tert-Butyl phenol

BHT , BHA
.
OH

OH
C(CH3)3

(H3C)3C

H2SO4

CH2

C
CH3

CH3
]Butylated hydroxy toluene [BHT

183

+ CH3
CH3

 : )(II

OH

OH

OH
C(CH3)3

H2SO4

CH2

+ CH3

CH3

C(CH3)3
OCH3

OCH3

OCH3

]Butylated hydroxy anisol [BHA

: Catalytic hydrogenation of aromatic ring

rhodium .
OH

OH
H2 , ethanol
1 atm , 25oC

C(CH3)3

C(CH3)3

24-3
1) Benzene p-Cresol
CH3

CH3

CH3
1) NaOH / 300oC
2) H3O+

AlCl3

SO3
H2SO4

+ CH3Cl

SO3H

OH 72 %

p-Toluene sulfonic acid

2) 2-Bromo-4-methyl aniline 2-Bromo-4-methyl phenol

OH
Br

92 %

N2 HSO4
H3O+

CH3

NH2
Br

Br
HNO2
H2SO4

CH3

184

CH3

 : )(II

3) Chloro benzene 2,4-Dinitro phenol

Cl

OH
NO2

Cl

NO2
HNO3
H2SO4

1) OH2) H3O+

NO2

NO2

4) 3-Nitro aniline 3-Nitro phenol

OH

NH2

N2 HSO4
NaNO2 , H2SO4

H2O

5oC

NO2

NO2

NO2

5) Phenol 2,4,6-Triisopropyl phenol

OH
CH(CH3)2

OH
(H3C)2HC

CH3
HF

+ 3H2O

CH OH

+ CH3

CH(CH3)2

6) Naphthalene 2-Naphthol

SO3 Na

OH

1) H2SO4 conc.
2) NaOH

1)NaOH , H2O , 300oC

2) H2SO4

185

 : )(II

25-3
OH
OH

Br
C2H5

H3C

OH

C(CH3)3

26-3
a) 4-Methyl phenol , 4-Fluoro phenol
b) 3-Nitro phenol , 3-Ethyl phenol
c) 4-Methyl phenol , Benzyl alcohol
27-3 OH- , C2H5O- , C6H5O-
28-3
a) 4-Chloro phenol , 4-Chloro-1-methyl benzene
b) 2-Hydroxy phenol , Resorcinol
29-3
OH

OH

OH
CH3

C2H5

9.89

7.17

10.20

pKa

30-3
a) 2,6-Dimethyl phenol , 3,5-Dimethyl phenol
b) 2,3-Dimethyl phenol , 3,4-Dimethyl phenol

186

 : ) (III

/ Ethers


Ether

CH3
CH3

CH

CH3

CH3

Isopropyl methyl ether

CH3 CH2

CH3

Ethyl methyl ether

CH3

Dimethyl ether

Methyl ether

Or

Alkoxy
CH3
O
Methyl Oxygen

Alkyl

Oxygen

Alkoxy

Methoxy

1CH 3

OCH3
CH3

OCH3
1,2-Dimethoxy benzene
][Veratrole

1CH3

CH3

CH3
2-Methoxy-2-methyl propane

CH2 CH2 CH3

CH

CH3 CH2 O

2-Ethoxy pentane

-:
1 : :
CH2 CH2

CH3

Cyclopentyl methyl ether

][Methoxy cyclopentane

CH3 CH2
O
CH2 CH3
H3CO
OCH3
1,2-Dimethoxy ethane
Diethyl ether
][DME
][Ethoxy ethane

187

 : ) (III

CH3
CH2

CH2 CH

CH CH2

CH3

CH2

O C

2
1

CH3
4-tert-Butoxy-1-cyclohexene

Diallyl ether

2 : :

O
Pyrylium

Diphenyl ether

3 : :
OH

OCH3

CH2CH3

Ethyl phenyl ether

][Phenetol

o-Hydroxy anisole
][Guaiacol

OCH3

CH3

CH2 CH CH2

Methyl phenyl ether

][Anisole

OCH3

p-allyl anisole
][p-Stragole or Methyl chavicol

CH3 CH CH

p-Methoxy propenyl benzene

][Anethol

4 : :
O
O
1,4-Dioxane

CH2
O
Furan

O
Tetrahydrofuran

188

O
Oxetane

H2C
O

Ethylene oxide
][Oxirane

 : ) (III

Preparation of ethers
1 : o140 .
H2 SO4
140oC

CH3 CH2 O CH2 CH3 + H2 O

2 CH3 CH2

OH

.
CH3CH2 O CH2 CH3 + CH3 O CH3 + CH3 O CH2CH3 + 3H2O

H2SO4

3 CH3 CH2 OH +3 CH3 OH

140oC

tert-Butyl alcohol
%95 -:
CH3
O

CH2CH3 + H2O

CH3 C

CH3
dilute H2SO4

OH + CH3CH2 OH

CH3

CH3 C
CH3

2 Williamson synthesis
Alexander.W.Williamson
Sodium alkoxide Sodium phenoxide
R + NaX

R
o

Unsymmetrical ether

Na

R=1 ,2 ,3

CH3
CH3 + NaBr

+ R

X
o

R
o

R= 1 , 2

CH3
CH3O

CH3

CH3

Na O

CH3
Sodium tert-butoxide

189

CH3Br +

 : ) (III

O Na
NaOH aq

CH2 O

+ NaBr

CH2Br
+
Benzyl bromide

Benzyl phenyl ether

31-3 n-Butane n-Butyl ether

+ HBr

CH3 CH2 CH2 CH2

CH3 CH2 CH2 CH3 + Br2

Br

CH3 CH2 CH2 CH2Br

CH3 CH2 CH2 CH2

OH

(CH3CH2CH2CH2)2O

3 :
-:
CH3
OCH3

CH3

CH3 C

dilute H2SO4

CH2 + CH3OH

C
CH3

CH3
tert-Butyl methyl ether
][MTBE

Alkoxymercuration-reduction -:
CH(CH2)3CH3

CH2

OCH(CH3)2

NaBH4

Hg(OAc)2

Sodium
borohydride

(CH3 )2CHOH
Solvent

2-Isopropoxy hexane
91%

190

CH(CH2)3CH3

CH2

 : ) (III

1
From halohydrin
CH3 CH

CH2

conc.aq OH-

CH2

Cl

CH3

C
CH2 + NaBr + H2O
CH3
2,2-Dimethyl oxirane

CH3 CH
OH

OH
60oC

+ NaOH

CH2 Br

CH3 C
CH3

81 %

:
) 200 o400 ( .
CH2

1
__ CH2 +
O
2 2

H2C

H2C

+ C6H5CO 2H

CO3H

CH2 CH2
O

CH2

CH2

Peroxy benzoic acid

O

CH(CH2)5CH3 +

CO2H
Cl

CH2

Benzene
CO3H 25oC

CH(CH2)5CH3 +

2-Hexyl oxirane

Cl

2
.
O

H2SO4

O
Dioxane
][1,4-Dioxane or Diethyl dioxide

191

2 H2C

CH2
O

1-Octene

CH2

 : ) (III

) Fuming sulphuric acid

( SO3
O

H2SO4
fuming

H2C

CH2

OH OH

OH

OCH3
OH

OCH3

(CH3)2SO4
NaOH

1,2-Dimethoxy benzene
][Veratrole

Catechol

: -:
R-OCH2ph + NaBr

NaH , phCH2Br
DMF

OH

1 :

.
CH3 CH2 CH3

CH3
O
CH3
= 1.31 D
bp = -23.7 oC

0
-42.1oC

.
CH3 (CH2)5 CH3
98oC

CH3 CH2CH2 O CH2CH2CH3

o

90.5 C

192

CH3 O (CH2 )4CH3

o

99 C

= bp

 : ) (III

.
OH

CH3 O CH3
-23.7oC

CH3 CH2
o

78.3 C

= bp

2 :

Dimethyl ether 37
Diethyl ether 1-Butanol
.
CH2 CH3

CH3 CH2

OH

CH3 CH2 CH2 CH2

8 g / 100 g H2 O

Anisole
1.04 g / 100 ml H2O

Diphenyl ether
0.39 g /100 ml H2O

Dibutyl ether
0.03 g / 100 ml H2O

THF
)(
Furan 32-3 THF

Furan

THF

THF
.

193

Furan

THF

0.7D
31.4o C

dipole moment : 1.7D

boiling point :
67oC

 : ) (III

Reaction of ethers
HBr , HI , H2SO4
HI , HBr
.
H
Cl

CH3CH2 O CH2CH3

O CH2CH3 + HCl

CH3CH2

Diethyl oxonium chloride

Br

CH3CH2 OH + CH3CH2

CH2CH3 + HBr

CH3CH2

HBr

Br + H2O
OH + CH3CH2CH2CH2I

CH3CH2

CH3 CH

H2O

CH2 CH2 CH2 CH3 + HI Reflux

CH3

CH3 CH
CH3

.

CH3
OH

CH3
CH

CH2

Propene

CF3 COOH
0oC

+
Cyclohexanol

CH3

CH3
Cyclohexyl t-butyl ether

) 178 (

194

 : ) (III

Hydrogenolysis

.
CH3

CH2

OR

+ R-OH

Benzyl radical C-O

) (1o , 2o , 3o .
CH3

CH2

OH
H2 / Pd

+ H2O

C2H5OH , 3 atm H2

O (CH2)4CH3

CH3

CH2

H2 / Pd

+ CH3CH2CH2CH2 CH2

C2H5OH , 3 atm H2

OH

.
H2SO4
dilute

2ROH

R + H2O

:
.
CHCH3
Cl

Cl2

CH3CH

CH2CH3

Cl

Cl2

CH3CH

CH2 CH3

Cl
\

1,1 -Dichloro diethyl ether

.
C2Cl5

C2Cl5

5Cl2
h

195

CH2CH3

CH3CH2

CH3 CH2 O

 : ) (III

Boron tribromide
+ CH3Br

BBr2

BBr3

CH3

good lewis acid

Aryloxy dibromo boron

H2O
excess

2HBr + H3BO4 +

OH

) (
:
Ethylene oxide
:
1 C-O Ethylene glycol
.
CH2

H+

H2C

OH

+ H2O

CH2

H2C
O

OH

Cellosolves
2
2-Methoxy ethanol Jet fuels .
1

H+

CH2CH2 OH

OH

+ CH3CH2

CH2 CH2
O

OCH3
Methyl cellosolve

3 Ethanol amine
.
CH2 CH2 + NH3

CH2CH2 OH

NH2

196

 : ) (III

:
+ HBr

BrCH2CH2CH2CH2OH

: Claisen rearrangement
.
O Na
O CH2 CH

CH2

CH

CH2

+ Br CH2

) o250 -200( .
OH
CH2

CH2 CH

200-250oC

O CH2 CH

CH2

o-Allyl phenol

33-3 2-Butenyl phenyl ether

OH
CH3

CH

CH

CH2

CH3
250oC

o-(1-Methyl allyl) phenol

197

CH

CH

CH2

 : ) (III

34-3 p-Methoxy toluene FeBr3

CH3

CH3
Br2 / FeBr3

Br
OCH3

OCH3

Methoxy
( OR > alkyl > halide ) Methyl

35-3 m-Methoxy toluene

CH3

CH3

CH3
HO3S
H2SO4 /

+
OCH3

OCH3

OCH3

SO3H

CH3
SO3H

OCH3

198

 : ) (III

36-3
1) Anisole 1-Bromo-2-methoxy benzene
OCH3

OCH3

OCH3

OCH3
SO3H

Br
Br2 / FeBr3

H2SO4 /

SO3H

SO3H

Major product

OCH3
Br

H2O
H2SO4 ,

2) Benzene Phenetole
NO2

NH2

HNO3
H2SO4

Sn / HCl

OCH2CH3

OH
1) NaNO2 / HCl

1) NaOH
2)CH3CH2 I

2)H2O

199

 : ) (III

37-3
CH3 CH2 CH2 O CH3

CH2 CH2 CH3

CH3
CH2 CH3

CH3

CH3 CH

CH3

38-3
i) 4-Isopropoxy-1-cyclohexanol
ii) 2-Ethoxy butane
iii) -Naphthol
iv) 2-Vinyl oxirane
] v) Benzyl-(4-hydroxy phenol) ether [ Monobenzone
39-3 C5H12O
40-3
CH3
HBr

SOCl2
Pyridine

CH3

a) CH3 CH

b) CH2

OCH3

OH

H3CO

COOH

c) OH

COOH

OH

OCH3

?
?

H+
H+

2HBr

)d

25oC

e) Ethylene oxide + Phenol

)f

+ CH3CH2OH
O

200

 : ) (III

41-3 Methane , n-Butane

Methyl n-butyl ether

42-3
a) Diethyl ether , Ethanol
b) 2-Methyl phenol , Anisole
43-3

B
Fe2O3 / 650oC

Benzene
BF3

O2 / Ag
200-400 oC
Pressure

Cl2

1,2-Dichloro
ethane

201

H2O / H+

1,2-Ethandiol

Aldehydes and Ketones

.
:
Formyl -CHO
: .
Carbonyl group

.
: sp2
Planar triangle
O

C
C

116 o

1.21Ao

118 o

.
O

/
1 : e
al
.
O
1

CH3
2

CH3 CH CH2 C
3-Methyl butanal

CH3 C
H
Ethanal

202

O
C
H
Methanal

CH2 CH2 CH2 C

Pentandial

OHC CH2 CH2 CH2 CH2 CHO

Hexandial

Carbaldehyde :
CHO

CH3

CHO

CHO

Cyclohexane carbaldehyde

Benzene carbaldehyde
][Benzaldehyde

3-Methyl benzene carbaldehyde

2 :
ic acid aldehyde
)228(
O
H

CH3

CH CH2

CH3 CH2

-Methyl valeraldehyde

CH3

Formic acid

Acetaldehyde

Formaldehyde

/
1 : e one
.
CH3
1

O
H

CH3 CH2 C
CH CH3
2-Methyl-3-pentanone

CH3 CH2
C
CH2 CH3
3-Pentanone
O

O
4

C
CH3
Propanone

CH3 C
CH2 CH2 C
4-Oxopentanal

O
3

O
5

CH2 C CH3
CH2 C
2,4,6-Heptantrione

203

CH3

CH3

2 :
Ketone :
CH3

CH3
C
CH2 CH3
Ethyl methyl ketone

CH3
C
CH CH3
Isopropyl methyl ketone

CH3
C
CH3
Dimethyl ketone

-:
O

O
Ph
C
Benzoyl group

CH3CH2
C
Propionyl group

CH3
C
Acetyl group

H
C
Formyl group

CHO

O
CHO

CH3 C

CO2H
o-Formyl benzoic acid

p-Acetyl benzaldehyde

:
-:
1 : :
O
CH3 CH2
C
H
Propanal
][Propionaldehyde

CH3 CHO
Ethanal
][Acetaldehyde
O

CH3 CH2 CH2 CH2 CHO

Pentanal
][Valeraldehyde

CH3 CH2 CH2

C
Butanal
][Butyraldehyde

2 : .
CHO

CH

CH

3-Phenyl propenal
][Cinnamaldehyde

CHO

CH

CH3 CH

2-Butenal
][Crotonaldehyde

204

CH CHO
2-Propenal
][Acrolein

CH2

3 : phenyl :
CHO
CHO

OH

OCH3
4-Methoxy benzaldehyde
][Anisaldehyde

OH
3,4-Dihydroxy benzaldehyde

CH

Furfural

CHO
CHO

CH3

2-Naphthalene carbaldehyde
][Naphthaldehyde

O
H

2-Methyl benzaldehyde
][o-Tolualdehyde

CH2 C

Phenyl acetaldehyde

: -:
) (

CH3
6

CH2 CH3

CH2 CH

CH3

C
CH2 CH2 CH3
2-Pentanone

4-Methyl-2-hexanone

C
CH3
Propanone
][Acetone

CH3

O
O
1

CH3

O
2

1
5

CH

CH3

CH CH2 C
CH3
4-Hexen-2-one
][2-Butenyl methyl ketone

CH3 CH2 C CH2 C

2,4-Hexanedione
O

CH3

CH3

O
2-Methyl cyclohexanone

Diphenyl ketone
][Benzophenone

205

Methyl phenyl ketone

][Acetophenone

CH3

1 : Formaldehyde
)167( )168( .
CH2O + H2
bp -21oC

Ag

OH

700-600oC

CH3

%40 Formalin
.

2 : Acetaldehyde
)162(
CH3CHO

Cu-Pd

CH2 + O2

100-130oC

CH2

O
H

CH3

CH3CHO

PdCl2

CH2 + O2

CuCl2
][O

OH

CH2

CH3CH2

3 Chloral : Trichloro acetaldehyde

DDT
.
CCl3CHO

CCl3CH(OH)2
Chloral hydrate

CH3CHO + 3Cl2
H2O

CCl3CHO

Cl

CCl3
CH
H+

+ 2 H2O
Cl

DDT

Cl

206

CCl3CH(OH)2 +

Diol
Chloral hydrate .
OH
C OH

Cl3C

H
2,2,2-Trichloro ethandiol
bp 51.7oC

4 : Acetone 2-Propanol
.
Cu-Pd

CH3COCH3

CH2 + O2

O
CH3

CH

CH3

OH
CH3

ZnO / 380oC

CH3

CH

CH3

)175(
5 : Glyoxal
.
CH
O

HC
O

O2
Ag or Cu
300oC

CH2

H2C

OH OH

Triozonide Zn/CH3CO2H
-:
O

HC

HC

2) Zn
CH3CO2H

207

1) 3O3

1 Oxidation of alcohols
) (
Manganese dioxide MnO2 Benzylic and Allylic
.
162

O
H

CH

MnO2
C6H6 , 25oC

CH

CH2 OH

CH

CH

OH

C
CH2 CH2 CH2 OH
CH3

MnO2
acetone,
25oC

CH
CH2 CH2 CH2 OH
CH3

2 )106(
3 )124(
4 )136(
5 )258 (
6 )265(
7 )268(
8 : Cyclohexadienedione
-:
OH

O
CrO3
HOAc

O
Quinone
or p-Benzoquinone

208

OH
Hydroquinone

.
O

OH

OH

Ag2+

Catechol

o-Quinone

1-4
a) 1-Hexene Pentanal
1) O3

CH3(CH2)3CHO + CH2O

a) CH3(CH2)3CH=CH2

2) Zn , H3O+

b) Bromo benzene Acetophenone

O
CH3

OH

CH3
PCC

MgBr

HC

1) CH3CHO

Br
)b

Mg

2) H3O+

CH2CL2

c) 1-Methyl cyclohexene 2-Methyl cyclohexanone

CH3

CH3

CH3

PCC

H2O2

(BH3)2

NaOH

OH

CH3

d) Toluene Benzaldehyde
CHO

CH2 Br

CH2OH
PCC

CH3

NaOH

NBS , CCl4
(Ph-CO) 2
Benzoyl peroxide

Benzyl bromide

209

e) Benzene Acetophenone
Br
CH

CH2

CH3

CH2 CH3

CH

Br 2 / light

C2H5 O-K+

CH3CH2Cl
AlCl3

HO
CH3

CH

CH3

H2O / H+

][O

1 : Boiling point



.
CH3 CH2 OH

78.3oC
1.7D

CH3 CH

CH3
o

82.3 C
1.7D

20.8 C
2.7D

-47.4 C
0.4D

CH3

OH
CH3 CH

CH2

CH3 CH

CH3

CH3

C
o

56.5 C
2.7D

CH2

C
o

-6.9 C
0.5D

bp

CH3
bp

2 : Solubility

.

210

3 : Physical state
.

2-4
a) Pentanal , 1-Pentanol
b) n-Pentane , Pentanal
c) Acetophenone , 2-Phenyl ethanol
) 1-Pentanol (a (
) Pentanal (b (
2-Phenyl ethanol (c

3-4
1-Pentanol (a Pentanal
) Pentanal (b (
Acetophenone (c .

:
-hydroxy carbocation -:
OH

OH
R

-Alkoxy carbocation -:
OR

OR
R

-:
211

OH OH

CH3 O
CH3
70%

H2SO4

CH3

CH3

CH3

CH3 CH3
Pinacol

CH3
Pinacolone

.
1 : Oxidation reaction
C-C
HNO3 : KMnO4 )163(
CH3(CH2)4COOH

Jones, reagent
acetone , 0oC

CH3(CH2)4CHO

85%

: Tollens reagent Silver oxide Ag2O

aqueous ammonia
+
Ag Ag0

Silver mirror test
O

O
OH + Ag

CH C

Ag2O
NH4OH , H2O
ethanol

CH

Silver mirror

CH C

CH

-Hydroxy

CH3 + Ag
Silver mirror

CH3 CH2

OH

Tollens reagent
CH3 CH2
C
CH CH3
2-Hydroxy-3-pentanone
-Hydroxy

212

: Fehling reagent ) ] (I
[CuSO4 ) ] (II [
Complex Cu+ in aqueous tartrate

.
+ Cu2O

COOH

CH3

Benedicts, reagent
Cu2+ in aqueous sodium citrate

NaOH

CH3 CHO + Cu2+

: Iodoform test
-:
O

OH
CH3

CH

CH3

CHI3
O
+ CHI3

O
NaOH

Na O

H + I2

O
CH3+ CHI3

NaOH

Na O

CH3

O
CH3 + I2

CH3

KMnO4

.
O

O
OH + CO2 + H2O

CH3

KMnO4
OH-

COOH

1) KMnO4 , H2O , NaOH

COOH

2)H3O+

213

CH3 C CH3 + O2

2 Reduction reaction
:
-:
) (NaBH4) , (LiAlH4) , (Ni,Pt or Pd ) (NaBH4 or LiAlH4
C-C .
OH

O
Ni

+ H2

Ni

CH3 CH2 CH2 CH2OH

CHO + H2

CH

CH3

CH

CHO

CH2OH
NaBH4
CH3OH

NO2

NO2

.
CH3

OH

OH

CH3 + CH3 CH2 CH2 CH

CH

11%

O
CH

CH3 CH

NaBH4
CH3OH

CH3

CH

CH

CH3

89%

Cerium trichloride CeCl3 .

OH
CH3

CH

O
CH

CH3 CH

100%

NaBH4 , CeCl3
CH3OH

CH3

CH

CH

CH3

CH2-
: Clemmensen reduction
Amalgamated Zinc
HCl .
O
CH2(CH2)4CH3

C
)Zn(Hg

CH2(CH2)3CH3

HCl

n-Pentyl phenyl ketone

n-Hexyl benzene

214

O
)Zn(Hg
HClconc

Tetralone

Tetralin

: Wolff-Kishner reduction
Hydrazine N2H4 .
CHO

CH3
N2H4
KOH

+ N2 + H2O

O
CH3

81%

CH3O
N2H4 , heat
triethylene glycol
KOH

CH3O

CH3O

H
CH3O

) Thiols (
Thioacetals and Thioketals
Methylene CH2-

PCl5

Gem-dichloro
O

Cl
+ POCl3

Cl
+ PCl5

3 : Nucleophilic addition
) (
sp2 sp3

215

:
Hemi acetal
O

OH
C

HCl

CH3

H + CH3OH

dry

CH3

OCH3
Methyl hemiacetal acetaldehyde
][1-Methoxy ethanol

acetal
.
OCH3
+ H2O

OH

HCl

CH3

H + CH3OH

dry

OCH3

CH3

OCH3

Dimethyl acetal acetaldehyde

][1,1-Dimethoxy ethane

: Hemi ketal
ketal
O

OH
CH3

CH3

HCl

+ C2H5OH

dry

CH3

CH3

OC2H5
Ethyl hemiketal acetone
][2-Ethoxy-2-propanol

OCH3
CH3 + H2O

OH
CH3

HCl
dry

OC2H5
Diethyl ketal acetone
][2,2-Diethoxy propane

CH3 + CH3OH

OC2H5

216

CH3

: CHCl3
Chloretone .
O

OH
CH3

CH3

KOH

CH3 + CHCl3

CH3

CCl3

mp 97oC

: Addition of ammonia
Imines Schiff bases
.
O

OH
+ H2O

CH3

NH
Imine

CH3

CH3 C H + NH3

NH2

:
.
: Hydroxyl amine .
H
C
N
OH + H2O
Acetaldoxime

H
CH3

H+

OH

O + H2 N

CH3
C
N
OH + H2O
Acetoneoxime

CH3

CH3
CH3

H+

217

OH

O + H2N

CH3

: Phenyl hydrazine .
H
+ H2O

H
N

H+

H
H2N

O +

Phenyl hydrazine

Benzaldehyde phenyl hydrazone

2,4-Dinitrophenyl hydrazine
CH3

H
NO2 + H2O

CH3

CH3 C

H+

NO2

O + H2N

CH3

NO2

NO2

Semi carbazide

NH2 + H2O

H
N

H3C

H+

NH2

H
O + H2N

H3C C

Semi carbazide

Acetaldehyde semi carbazone

: HCN HCN Cyanohydrin

-:
OH
CN

CHO

CH

Mandelonitrile

218

OH
CH2 NH2

1) LiAlH4 / THF
2) H2O

CH

OH

2-Amino-1-phenyl ethanol

CH CN

OH
CH COOH
H3O+

: .
OH
CH3 + Mg(HO)Br

OMgBr
CH3

H2O

CH3

CH3

CH3 + CH3MgBr

CH3

CH3

CH3

: Cannizaro reaction


-:
CHO
COOH

CH2 OH

1) OH- / H2O
2) H3O+

CH3 O
OH

CH2 OH + CH3 C
CH3

CH3

CH3 O

CH3 C
CH3

Ca(OH)2

2 CH3 C
CH3

-Proton
.

219

B
H

+ HBr

keto form ) Enol form124 (
H
C

HO

O
C

Keto form

Enol form

4 :
-:
O

O
C

CH3CBr2

NaOH

+ Br2

O
H + 3 HCl

Cl3C

H + 3 Cl2 acetic acid

CCl3 + 3 H2 O

CH3
O

O
C

CH3CH2

Cl3 C

CH3CO 2H

220

CH3 + 3Cl2

CH3 C

.
O
H + Ca(OH)2

2 CHCl3 + (HCOO)2Ca

Cl3C

5 : Aldol condensation 1872

Charles Wurtz 3-hydroxy butanal
.
O

OH

CH3 CH

CH2 C

H3 O +

CH2 C

CH3 CH

aldehyde , alcohol Aldol

-Hydroxy aldehyde

-hydrogen
-:
O

OH

CH2 C

CH

NaOH

Ph

CH + H

CH2 C

Ph

excess

--unsaturated carbonyl
O

O
H + H2O

CH

CH

Ph

or

H+

H
CH

OH
CH

Ph

Methyl ketone
Sodium bisulfate NaHSO3
.

221

O
CH3

OH

CH2 C

CH3 C

1) NaHSO 3
2) H3O+

CH2 C

CH3

H
CH3 C

CH3
CH3

-hydrogen
Crossed aldol reaction NaOHaq .
CH3 O

OH

CH

CH

OH

CH CH2

O
-

H + CH3 CH2

3-Hydroxy-2-methyl pentanal

OH

CH CH2

CH3

3-Hydroxy butanal

H + CH3 CH2

3-Hydroxy pentanal

OH
H2O

CH3 O

OH

CH

CH

H + CH3 CH2

Propanal

CH3

Acetaldehyde

+ CH3

3-Hydroxy-2-methyl butanal

: Claisen-Schmidt
-hydrogen -hydrogen
.
O

O
H

C
+ H2O

Ph
H

95%

H2SO4
CH3CO2H

C
C

Ph
H

Ph

Benzalacetophenone
][Chalcone

222

C
H

Ph

Mesitylene
Protonation .
CH3
O
H2SO4

+ 3 H2O
CH3

CH3

CH3

3 CH3 C

4-4
a) Acetone , b) Acetophenone , c) Pentanal , d) 2-Pentanone , e) 3-Pentanone
a , b , d

5-4
a) Benzaldehyde , Benzyl alcohol
b) 2-Hexanone , 3-Hexanone
c) 2-Butanone , 2-Butanol
d) Benzladehyde , Cyclohexanone
( a .
( b .
( c .
( d .

6-4
O
CH2

CH

CH3

CH2OH

223

CH3

a) CH

CHO
?

)b

OH
CH3

CH3 CH

CH3 CH2 CHO

)c

O
?
(CH2)4

)d

a) LiAlH4 , H2SO4 , heat , b) LiAlH4

c) LiAlH4 , H2SO4 , heat , H2O , H+ , d) LiAlH4 , H2SO4 , heat , O3,Zn

7-4


.
O

C
H

O
C

8-4

.
.

C
R

224

9-4
]a) 1,3-Diphenyl-2-propen-1-one , [Benzal acetophenone
b) 3-tert-Butyl cyclohexane carbaldehyde
c) 2-(1-Chloro ethyl)-5-methyl heptanal
d) 2,6-Dimethyl-2,5-heptadiene-4-one
]e) 3-Penten-2-one , [Mesityl oxide
]f) 3,5,5-Trimethyl cyclohex-2-en-1-one , [Isophorone
]g) Phenyl n-Propyl ketone , [Butyrophenone
]h) o-Hydroxy benzene carbaldehyde , [Salicylaldehyde
]i) Butane-2,3-dione [Biacetyl
10-4
a) 1-Pentanol Pentanal
b) 3-Hexyne 3-Hexanone
c) Benzene m-Bromo acetophenone
11-4 p-Bromo acetophenone
, b) LiAlH4 / ether , c) K2Cr2O7 / H2SO4

a) NaOH / I2

12-4 Butanal
c) CH3MgI / hydrolysis ,

b) LiAlH4 / ether

a) Ag(NH3)2+ ,
d) Phenylhydrazene

13-4
a) Hexanal , 2-Hexanone
b) 1-Phenyl ethanol , 2-Phenyl ethanol
c) Pentanal , Diethyl ether
14-4
a) 1-Phenyl ethanol , b) 2-Phenyl ethanol , c) 2-Butanol ,
d) 3-Pentanol

225

15-4
OH

CH

C
CH3

CH3

AlCl3

)a

)b

+ CH3COCl
CHO
Fe

+ Br2

O
NaBH4

CH3CH2OH

)c

CH3

CH3
d) CH3 C

CH
O
C

+ 3I2 + 3NaOH

CH3

)e

CH3
H2O

Ca(OH)2

+ 2Cl2

)f
O

CH2 CH3
N2H4

)g

KOH

CH3COCCl3 + 3 HCl

? + (CH3COO)2Ca

h) ? + 3Cl2

Ca(OH)2

O
?

equeous
NaOH

CH CHO + H2O
Acrolein

226

CH3

CH2

+ CH
3
Cu2O
370oC

)i

+ O2

Ph

)j

Carboxylic acids
.
Carboxylic group

-:
Carbonyl

Hydroxyl
Carboxyl

sp2
C=O C-O O-H
1.36

1.21

2
1.5

110.6 o

/ Systematic nomenclature
e oic
acid
.

Carboxylic acid

O
OH

O
CH3CH2

Propanoic acid

OH

CH3

Ethanoic acid

OH

+ oic acid = Methanoic acid

227

Methane

COOH

COOH

2-Cyclopentene carboxylic acid

CH3

CH3CH
C
OH
2-Methyl propanoic acid

Cyclopentane carboxylic acid

CH3
COOH
CO2H

H3CO

CH3

CH3
2,2-Dimethyl propanoic acid
][Pivalic acid

p-Methoxy benzene carboxylic acid

][p-Anisic acid

/ Common nomenclature


Methanoic Formic acid
Ethanoic Acetic acid
, ,
.
derivation of name

Common name

structure

Formica

Formic acid

HCO2H

Acetum

Acetic acid

CH3CO2H

(Gr) . Proto

Propionic acid

CH3CH2CO2H

Butyrum

Butyric acid

CH3(CH2)2CO2H

Valere

Valeric acid

CH3(CH2)3CO2H

Caper

Caproic acid

CH3(CH2)4CO2H

-:
NH2

CH3

CH3

O
C

CH

COOH
2-Amino benzene carboxylic acid
][o-Amino benzoic acid
][Anthranilic acid

COOH
m-Methyl benzoic acid
][m-Toluic acid

228

OH
2-Phenyl propanoic acid
][-Phenyl propionic acid
or Hydratropic acid

Classification
-:
1 :
-
-
-

: Monocarboxylic acid
.
: Dicarboxylic acid
.
: Tricarboxylic acid
.

OH

OH

HOOC
CH CH COOH
2,3-Dihydroxy butanedioic acid
][Tartaric acid

HOOC
COOH
Ethanedioic acid
][Oxalic acid

CH3 CH2 CH2 CH2 COOH

Pentanoic acid
][Valeric acid

OH
CH2 COOH

CH2

HOOC

COOH
Citric acid

HOOC (CH2)2 COOH

HOOC CH2 COOH

Succinic acid

Malonic acid

2 :
- ) (
- .

Br
COOH

CH

CH

3-Phenyl propenoic acid

][Cinnamic acid

CH CH COOH
Maleic acid

HOOC

CH3 CH CH2 COOH

3-Bromo butanoic acid
][-Bromo butyric acid

COOH

COOH

COOH
COOH

COOH
Terephthalic acid
][Benzene-1,4-dicarboxylic acid

COOH
Isophthalic acid

229

Phthalic acid

3 :
.

CH2 CH2 CH2 CO2H

- Amino butyric acid

H2N

OH

CH3
C
COOH
- Pyruvic acid

CH3
CH COOH
-Lactic acid

.
CH3 (CH2)16 COOH CH3 (CH2)7 CH
CH (CH2)7 COOH
Oleic acid
Stearic acid

CH3 (CH2)14 COOH

Palmitic acid

1 Methanoic acid
: .
: .

H COOH + CO 2

COOH

HOOC

Catalytic hydration
.
HCOO Na
2HCOOH + Na2SO4

CO + NaOH
2HCOO Na + H2SO4

2 Ethanoic acid
:
- .
- :
.
CH3COOH + H2O

230

CH3CH2OH + O2

:

Herbicide 2,4-D
O
OH

CH2 C

Cl2

OH

Light

CH3 C

Cl

CH2 CO2H

O Na

O
Cl

Cl

OH

CH2 C
Cl

Cl

Cl
2,4-Dichloro phenoxy acetic acid
][2,4-D

%100 Glacial acetic acid

.

1 )162(
2 )106(
3 )141(
4 Carbonation of Grignard reagent
O
CO2H

O Mg Br

MgBr

C
CO2

HBr

+ MgBr

5 Hydrolysis of nitriles
O

O
OH

CH3

H3O+

NH2

CH3

+
N H2O / H

CH3

Aceto nitrile

6 )256(
231

7 :
KMnO4 H2CrO4
-:
O

O
CH3

OH + HO

CH3 CH2 CH2

O
CrO3

+
O

O
CH2 CH3

CH2 CH3

OH + HO

C
1

CH3 CH2

CH3 CH2 CH2

2

alkyl aryl ketone -hydrogen

.
O

C
KO

OK

KMnO4

CH2 R

KOH

Hypochlorites
.
O
OH + CHCl3

CH3 CH2 C

O
OH-

H2O /

CCl3

O
NaOCl

CH3 CH2 C

CH3

CH3 CH2 C

1-5
Pt

a) 4-Pentenoic acid + H2
B

KMnO4 / OH0-10oC

O
C
D

NaBH4
H3 O+

CO2H
CO2

CH2 CH2 C
Mg
Et2 O

232

CH

b) CH2

c) 5-Chloro-1-pentene

C7H5BrO

Na2Cr2O7

H3O+ , heat

C7H7Br

Br2

d) Toluene

Fe

C7H6O2

Na2Cr2O7
H3O+ , heat

a) A = Pentanoic acid
,
B = 4,5-Dihydroxy pentanoic acid
b) C = 2-Hydroxy-5-hexenoic acid
, c) D = 5-Hexenoic acid
d) E = o,p-Bromo toluene , F = o,p-Bromo benzoic acid , G = Benzoic acid
2-5 Phenyl acetic acid Benzyl bromide
CH2COOH

CH2Br

CH2MgBr
H3O+

CO2

Mg
ether

1 : Physical state

.
2 :

dimer
.
O
C

Hydrogen bond

C
O

Carboxylic acid dimer

3 : Solubility

.

233

1 : Acidity
O

O
+ H3O+

+ H2O

O-H

.
-: Ka
Ka

Structure

0.23

Cl3CCOOH

3.310-2

Cl2CHCOOH

1.710-4

HCOOH

1.710-5

CH3COOH

1.310-5

CH3CH2COOH

6.410-5

C6H5COOH

Cl

O
C

O
Cl

O
Cl
Stabilization of anion

Cl

O
H
Cl
Strong electron withdrawing

Cl

O
C

O
H
H
Weak electronic release

O
H
Small stabilization of anion

234

.
CH3OH
15.2

HCl HCOOH
4.75

pKa

= -7

-:
1
O

O
+ H+
Ka = 1.8 X 10-4

H
H

.
O -

O
C

O -

O
Formate ion

O
C
H

O
C

H
H

H
H

Formic acid

2

.
+H +

CH3 O

235

CH3 O

.
Cl

Cl

CH3CH2CH COOH
2.86

Cl
CH2CH2CH2 COOH

CH3CHCH2 COOH

4.52

4.05

CH3CH2CH2 COOH
4.82

= pKa

ic acid
ate .
O
O Na

CH3

Acetic acid + ate

Sodium acetate

3-5
ClCH2COOH , Cl2CHCOOH , CH3CO2H , Cl3CCO2H
CH3CO2H < ClCH2CO2H < Cl2CHCO2H < Cl3CCO2H

2 : Salt formation
.
CH3COO- Na+ + H2O

CH3COOH + NaOH

CH3COO- Na+ + CO2 + H2O

CH3COOH + NaHCO3

)
( Nitrophenol
.

236

3 Substitution reactions


Thionyl chloride SOCl2
O

O
Cl + HCl + SO2

OH + SOCl2

Phosphorus trichloride PCl3

O

O
Cl + H3PO3

OH + PCl3

3R

Phosphorus pentachloride PCl5

O

O
Cl + HCl + POCl3
Phosphprus oxochloride

OH + PCl5

Dehydration of carboxylic acids
O
R

O
C CH3

heat
-H2O

OH

O
O

2 R

CH3 C

OH

2 CH3 C

:
O
OR

+ H2O

O
OH + R-OH

O
O CH3

H2SO4

237

OH + CH3 OH

.

Reaction with Ammonia or Amines
O
+ H2O

NHR

O
R

heat

OH3NR

Neutralization

OH + R-NH2

: Hell Volhard Zelinski

HVZ reaction
PBr3 Br2
PBr3
H

H
COOH

X2
P

COOH

X = Cl , Br

-Halo acid

CH COOH

CH3

Br2 / P

CH3 CH2 COOH

Br
Cl
C COOH

Cl

Cl2 / P

Cl CH COOH

Cl

Cl2 / P

CH2 COOH

Cl

Cl2 / P

CH3 COOH

Cl

.
COOH + NH4Br

CH

COOH + 2 NH3

CH3

CH
Br

NH2

COOH

CH

CH3

CH3

1) K2CO3 , H2O , 100oC

2) H+

OH

COOH

CH
Br

238

CH3

4 : Decarboxylation
-:
-Keto acids
.i
.
O

O
+ CO2

CH2 H

H3O+
25oC

CH3

CO2H

CH2

CH3

Acetone

.ii

: Malonic acid and derivatives

.
O
CH2 H + CO2

CH2 C

H3O+
135oC

HO

CH2

CO2H

CH2 C

HO

Propanoic acid

.iii

: Carbonic acid and derivatives

.
O
H2 O + CO 2

H3O+

OH

HO

C
O

OH + CO2

CH3

H3O+

OH

H3CO

Methyl carbonate

.
5
: LiAlH4
NaBH4 LiAlH4 Al-H
B-H
CH(CH2)4CH2OH

H2C

1) LiAlH , Et2O

CH(CH2)4COOH 2) H O+4
3
6-Heptenoic acid

6-Hepten-1-ol
83%

239

H2C

: Birch reduction
1,4-Cyclohexandiene -:
)Na , NH3 (l
t-Butyl alcohol

Benzene

1,4-Cyclohexanediene

3-Substituted-1,4-cyclohexanediene -:
COOH

COOH
)Na , NH3 (l
t-Butyl alcohol

1-Substituted-1,4-cyclohexanediene
.
OCH3

OCH3
)Na , NH3 (l
t-Butyl alcohol

4-5
a) Benzene p-Nitro benzoic acid
COOH

CH3
H2SO4
HNO3

KMnO4
OH-

NO2

CH3

NO2

240

CH3Cl
AlCl3

b) Toluene o-Bromo benzoic acid

COOH

Br

Br

Br

CH3

CH3

CH3

CH3

H2O/H+

KMnO4
OH-

H2SO4

Br2
FeBr3

SO3H

SO3H

C) 2-Methyl-1-butene 2-Methyl butanoic acid

CH3

CH3
COOH

CH3 CH2 CH

KMnO4
OH-

CH2 OH

CH3
B2H6
H2O2 , OH-

CH3 CH2 CH

CH2

CH3 CH2 C

d) Ethanoic acid Malonic acid

CH2 COO Na

HCN

NaOH

CH2 COO Na

CH2 COOH
Br

Br

CN

Br2
PBr3

COOH

CH3

H2O / H+

CH2 COOH
COOH

5-5
H3O+

Et2O

H3O

H3O+

1) 4-Pentenoic acid + LiAlH4

LiAlH
Et2O

LiAlH
Et2O

2) 4-Chloro butanoic acid

Br2
AlBr3

3) Benzoic acid
SOCl2

4) D

A = 4-Penten-1-ol , B = 4-Chloro-1-butanol , C = m-Bromo benzoic acid ,

D = m-Bromo benzyl alcohol , E = m-Bromo benzyl chloride

241

6-5
4-Methyl cyclohexanol , p-Methyl phenol , Benzoic acid

COOH

COO Na

+ H2O

+ CO2

H2O

+ NaHCO3

OH

No reaction

H2O

+ NaHCO3

CH3

OH

No reaction

H2O

+ NaHCO3

CH3

HBr NaOH

242

7-5
Cl
COOH
COOH

CH3 CH

c-

a - (CH3)3CCO2H ,

b - BrCH2CHBrCH2CH2COOH ,

COOH

e - Cl3CCOOH

f - CH3 CH CH2 CH2 CH CH3

d - HOOC

COOH

8-5
a- Heptanedioic acid ,
b- Triphenyl acetic acid ,
c- 2-Hexen-4-ynoic acid
d- 4-Ethyl-2-propyl octanoic acid ,
e- 3-Chloro phthalic acid ,
f- Hexanedioic acid [Adipic acid] ,
]g- Pentanedioic acid [Glutaric acid
h- 3-Methyl benzoic acid [m-Toluic acid] ,
]i- 2-Hydroxy benzene carboxylic acid [Salicylic acid
]k- 2,5-Dihydroxy benzoic acid [Gentisic acid
9-5 C5H10O2

10-5
CH2 COOH

CH2 COOH

CH2 COOH

Br

COOH

COOH

OH

COOH

CH3 COOH

a ) CH2 COOH
Cl

COOH

COOH

NO2

CH3

COOH

COOH

CH3
CH3
CH3

243

)b

)c

COOH

COOH

COOH

COOH

)d

Cl
Cl
Cl

11-5 O-H
O
H

CH3 C

CH3 CH2 O
O

12-5
13-5
a) Benzene m-Nitro benzene carboxylic acid
b) p-Chloro toluene p-Chloro phenyl acetic acid
c) Pentanoic acid Pentanol
d) Pentanoic acid Hexanone
e) Butanoic acid Butanal
14-5
Acetic acid , Ethanol , Diethyl ether
15-5
COOH
?

)a

+ SOCl2

CH3
?

1) CO2

2) H3O+

Mg
Et2 O

Cl

b) CH3 C
CH3

244

KMnO4 / OH-

CH2

c) CH3 CH

CH3

CH3
CH2 OH

CH3 C

COOH

CH3

CH3

92%

d) CH3 C

COOH
KMnO4 / OH-

)e

COOH
H3O+

+ CO2

f) CH3 MgBr

CH3 O
Br2 / P

?
H 3O +

OH

NaCN

h ) CH3 CH 2CH 2Br

CH3 O
KOH in alc

Br2 / P

OH

g) CH CH
3

CH

CH3
CH

)i

CH3

CH2 CH2 COOH

H+

+ C2H5OH

KMnO4 , OH0-10 oC

)j

CH (CH2)7COOH

k) CH3(CH2)7 CH

Oleic acid

Glycol formation

KMnO4 , OH-

Oxidative cleavage

245

CaO

l) Sodium benzoate + NaOH

Carboxylic acid derivatives

hydrolysis
-:
-X

-OR , -NH2 , -O-COR ,

O
C

O
C

O
C

C
C

NH2
Amide

\OR
Ester

O
Anhydride

X
X = F, Cl , Br , I

Acid halide

1 : ic acid
oyl chloride

O
C

Cl

O
CH

CH3 CH

2-Butenoyl chloride
][Crotonyl chloride

Cl

CH3 CH2 CH2 C

Butanoyl chloride
][Butyryl chloride

CH2

CH3 C

3-Pentynoyl bromide

Cl
Benzene carbonyl chloride
][Benzoyl chloride

246

O
C

C
Br

Cl
Methanoyl chloride
][Formyl chloride

Cl

C
Cl

Ethanedioyl chloride
][Oxalyl chloride

2 : acid
anhydride

anhydride

F3C C
O
C CF3
Trifluoro acetic anhydride

CH3 C
O
C CH3
Acetic anhydride

C CH2CH3

CH3 C

Acetic propionic anhydride

C CH3

O
C

O
Maleic anhydride

O
Phthalic anhydride

CH2

Benzyl acetic anhydride

3 : ic acid
ate .

O
CH2 CH3

H3C

CH2 CH3

O CH3

O
1

CH2

Ethyl formate

Ethyl acetate

CH3 CH2 CH2 C

Methyl-3-oxo hexanoate

Ph

Phenyl cyclohexane carboxylate

4 :
oic acid amide ic acid
amide

247

NH2

CH3 CH2 CH2

CH3
C
NH2
Ethanamide
][Acetamide

Butan amide
][n-Butyramide

H C N(CH3)2
N,N-Dimethyl formamide
][DMF

NH2

Benzamide

ylic acid
amide
O

NH2

C
N(CH2CH3)2

Cyclohexane carboxylic acid

N,N-Diethyl cyclohexane carboxamide

Cyclohexane carboxamide

Lactones

.
O

O
C

O
CH

H+
-H2O

CH2 CH2 C

CH

OH

O
H

R
-Lactone

O
O

H+
-H2O

OH

CH2 CH2 CH2 C

CH
O

R
-Lactone

248

CH3
-Butyrolactone
O

-Pentyrolactone

-Butyrolactone
CH2 CH

O
OH

OH

OH

HO

Coumarin
][ -Lactone

Ascorbic acid
][ -Lactone

: Ortho-Esters

R-C(OR\)3
R-C(OH)3 Orthoformic
)263(
CH3Cl + 3 CH3O- Na+

HC(OCH3)3 + 3 NaCl
Trimethyl orthoformate
][Trimethoxy methane

Lactams

.
O

O
NH

NH

R
-Lactam

-Lactam
O
NH

NH

C2H5

-Lactam

C6H5
NH

NH

O
Phenobarbital

Caprolactam

249

NH

-Butyrolactam

/ : -:
O

O
Cl

SOCl2
or PCl5
or Cl C

R
Cl

OH

: Oxalyl chloride
Oxalic acid -:
O

Cl

HO
C

C
+ 2POCl3 + 2HCl

+ PCl5

C
O

C
O

Cl

HO

55%

/
: Acetic anhydride
Ketene -:
CH2
+ H2O

C
O
Ketene

700-750oC
dehydration catalyst

H2C

C
HO

bp = -56oC

Ketene C=C
)103( .
O
C

CH3
rapid

O
C

+ CH3CO2 H

CH3

O
Acetic anhydride

250

H2 C

: Succinic anhydride .
O
O

+ H2 O

C
150oC

OH

H2C

OH

H2C

C
O

95%

: Maleic anhydride
O
O

O2 / V2O5
400oC

Formic anhydride Formyl chloride

HCl + CO

PCl5

O
OH

H2O + CO

H2SO4

/
: Peracetic -:
O

O
CH3

+ CF3 CO3H

CH3

Peroxy trifluoro acetic acid

][Peracetic
O

O
CH3

+ CF3CO3H

H3C

Methyl acetate

CH3

C
Acetone

251

H3C

: Aspirin
Rheumatic
O
CH3

OH

COOH

COOH
(CH3CO)2O

Acetyl salicylic acid

][Aspirin

: Oil of Wintergreen
.
O

OH

OH

COOH
CH3OH / H+

OCH3
Methyl salicylate
][Oil of Wintergreen

Diethyl adipate
COCH2CH3
+ H2O

(CH2)4

COOH
H2SO4

+ CH3CH2OH

(CH2)4
COOH

COCH2CH3

Adipic acid

97%

: -:
O

O
CH3CO3H

85%

/
Acetamide
O

O
NH2 + NH4Cl

Cl + 2 NH3

CH3 C

252

CH3 C

Caprolactam

O

NOH HCl
h
NOCl

H2SO4

NH

: Cyclohexanone NH2OH
Beckmann rearrangement
Nylon 6
HO
N

H2SO4

NH

NH2OH

O
n H2N (CH2)5 COOH

H2O / H+

NH

6-Amino hexanoic acid

O
+ H2O

NH (CH2)5 C

n H2N (CH2)5 COOH

6-Amino hexanoic acid

Nylon 6

: Phenobarbital .

O
NH
O

C
C

C
NH

NH

C2H5

C6H5

heat
NaOC2H5

OC2H5
O

253

C
OC2H5

NH
O

C2H5

C
O

C6H5

: Urea

-:
O
+ H2O

NH2

150-200o C
Pressure

H2N

Urea + NH4Cl

CO2 + 2NH3

COCl2 + NH3
Phosgene

CO(OC2H5)2 + NH3
Diethyl carbonate

Urea + C2 H5OH

Zwitterions
NH2

NH2

NH2
C

NH2

NH2
C

O
NH2

NH2

NH2

Zwitterions

diethyl malonate N-Acylurea

Ureides Barbituric acid
O
NH
O

C
NH

O
H

C
C

NH
NaOEt / EtOH
110oC

H
+

C
NH

OEt

OEt

C
O

O
Barbituric acid
][Malonyl urea

Nitrous acid .
Urea + HNO2

CO2 + H2O + N2

254

H2C

1 :
.
O

O
C

CH2 CH2 CH3

75oC

CH2 CH3

CH3 C

CH2 CH2 CH2CH3

CH2 CH2CH3

104oC

CH3 C

OCH2CH3

102oC
O
C

CH2CH2CH3

O
CH3CH2

Cl

80o C

(CH2 )4CH3

155o C

CH3CH2

124oC

CH3 C

77o C

131o C

(CH2 )5CH3

CH3 C
OCH3
56oC

80o C

(CH2)4 CH3

CH3 C

CH3 CH2 CH2 C

Cl

102 C

151 C

.
O
CH3

O
C

CH2

CH3

CH3

139o C

CH3
CH3

CH

O
C CH2
168o C

O
O

CH3

140oC

CH3
CH CH2

CH2CH3

CH3

O
O

CH3CH2

168oC

.
H

H
N

255

C
R

Chemical reaction
/
: Hydrolysis .
O
RCOOH + HCl

Cl + H2O

CH3COOH + HCl

Cl + H2O

C
O

CH3

: .
O
OH

O
1) NaOH , H2O

CH3 CH2 CH2 C

2 ) H3O+

CH3 CH2 CH2 C

Cl

: .
O
R\ + HCl

O
O

R\ + NaCl

O
C CH3 + HCl

OH

O
C

O
O

\Cl + R

\R

OH

CH3 C

O
O

Na O

Cl +

Cl + CH3 C

CH3 C

:
3o , 2o , 1o
-:
O
OR\ + HCl

O
\
Cl + R OH

256

CH3
CH3 + HCl

CH3

O
O

quinoline

CH3

+ HO
Cl

CH3

CH3
tert-Butyl benzoate

75%

Steric bulk .
O

O
CH2

1o

CH2

C
Cl

OH

2o

HO

HO

:
Schotten-Baumann
CH3

O
CH3 + HCl

CH3

O
ether / pyridine

CH3

OH + Cl

CH3
3,5-Dimethyl phenyl acetate

CH3

75%

: Aminolysis .
O
NH2 + HCl

O
R

Cl + NH3

O
NH2 + NH4Cl

Cl + 2NH2-H

Cyclopropane carboxamide
90%

257

Cyclopropane carboxylic acid

chloride

: .
O

O
CH3 + CuCH3 + LiCl

Cl + (CH3)2 Cu Li

CH3 CH2 C

CH3 CH2 C

: -:
LiAlH4 .
Cl

OH

O
C

CH2
1) LiAlH4 , ether
2) H3O+
96%

-:
CH3

CH3
3o

CH3

HO

Cl
C

1) CH3MgBr

CH3MgBr
ether

2) H3O+

LiAlH4
CH3OH

CH3

2o

HO

CH

.
O

O
H + HCl

BaSO4

CH3

258

Cl + H2

CH3

1-6 Acetyl chloride

b) Dimethyl amine
d) Sodium acetate

a) Methanol
c) 2,3-Dimethyl-1-octanol

,
,

O
N(CH3)2

O
CH3

)b

OCH3

CH3

O
CH3

O
O

CH (CH2)4 CH3

CH3

)d

CH3

)a

CH2 CH

CH3

)c

CH3

/
: .
O
2 CH3CO2H

CH3 + H2O

O
O

CH3

O
CO2H

CO2H

+ H2O

Hydrogen chloride HCl

-:
O

O
\R or R

C
Cl

C
OH

C
Cl

O
+ HCl

C
OH

R or R

CH3

+ HCl
\

CH3

259

O
C

C
CH3

CH3

: .
O
C CH3

O
N(C2H5)2 + HO

C CH3 + (C2H5)2NH

CH3 C

O
O

CH3 C

: .
O

O
OCH2CH2CH3 + HO

C CH3

C CH3 + CH3CH2CH2OH

CH3 C

CH3 C

: .
O

O
CH2 OH

][H

2R

][H

2 R

2-6 Acetic anhydride

b) Acetic acid
O

O
OH

O
C

a) 3-Pentanol
O

OH

(CH3 CH2)2CH O C CH3 + CH3 C

)a

CH3 C O C CH3+ CH3 CH2 CH CH2 CH3

b) No reaction
3-6 Succinic anhydride
a) 4-Phenyl butanoyl chloride , b) Tetralone
)a
O

CH2CH2CO2H

AlCl3

-Benzoyl propionic acid

Zn , H+

CH2CH2CO2H

O +

CH2CH2CH2COCl

CH2
PCl5

260

H2C
H2C

)b
O
CH2 CH2CH2CO2 H
Polyphosphoric acid
or H2SO4

/
.
:

-:
:
.
O

C
+ C2H5OH

H2O / H+

OH

OC2H5

) ( :
carboxylate
.
O

C
+ C2H5OH

H2O

O Na

OC2H5

NaOH

: Saponification
NaOH )( .
:
.

261

: Saponification number KOH

.

+ 3RCOO-Na+

Soap

OH

H2C

OH

HC

OH

H2C

COR

H2C

COR + 3 NaOH

HC

COR

H2C

Glyceride

Glycerol

4-6 Palmitodistearin
862
glycerol
+
K-palmitate
+
2K-stearate

(CH2 )14 CH3

CO

H2 C

(CH2 )16 CH3 + 3KOH

CO

HC

(CH2 )16 CH3

CO

H2 C

MW of KOH = 56
356=168 g of KOH

168 862 .
= 194.9 mg KOH / g triglyceride

168x103 mg KOH
862 g triglyceride

= Saponification number

5-6 250 47.5

47.5x10-3 g
= 2.827x10-4 moles
3x56 g / mol

= 884 g / mol

-3
MW = 250x10 g
2.827x10-4

: Iodine Number 100

.

262

6-6 680 578 .

884
.
Wt g I2
884 g Oil

0.578 g I2
0.680 g Oil

751.4 g / mol
= 253.8 = 126.9 2
=

751.4 g
= 2.96 moles I2 / mole of Oil
253.8 g / mol

.
:
Iodine number = 751.4
884

x 100 = 85

:
.

O
OCH3 + 2 CH3OH

H+

CH(OCH3)3 + H2O

: Claisen condensation Carbanion

-Keto ester -hydrogen
Ethyl acetate Ethyl-3-oxo-butanoate -:
O

CH2CH3 + CH3CH2OH

CH2CH3

CH2 C

CH3 C

NaOEt

ethanol

CH2CH3

263

CH2 C

CH3 C

-hydrogen C-H
.

-hydrogen

OCH2 CH3

CH2 C

O
O CH2 CH3 + CH2 C O CH2CH3 1) LDA/THF
2) H O+

+ CH3 CH2OH

Claisen condensation
of two different esters

O
4

CH3 + CH3 CH2OH

O
2

CH2

Ph

1) LDA / THF
H3O+

1-Phenyl butane-1,3-dione

)2

CH3

OCH2CH3 + CH2 C

Ph

H
Claisen condensation
of a ketone with an esters

LDA Lithium diisopropyl amide

: diester
Dieckmann cyclization
O
O

CH2CH3

CH2

C
+ H2O

CH2CH3

CH

H2C

CH2

H2C

CH2

1) NaOEt , ethanol
2) H3O+

CH2
CH2CH3

CH2

264

-:
O

O
C

C
CH2

H2 C

CH2

H2 C

H3O+ ,

CH2CH3

CH

H2C

CH2

H2C

: .
O

C
NH2

+ CH3OH

NH3
ether

OCH3

: LiAlH4 LAH

-:
O

OH
CH CH2 + HOCH2CH3

CH3CH2CH

1) LiAlH4 / ether
2) H3O+

CH C

OCH2CH3

CH3CH2CH

DIBAH = Diisobutyl aluminum hydride

-:
O

O
CH3CH2CH2 CH2 C H + HOCH2CH3

1) DIBHA / Toluene
2) H3O+

CH3CH2CH2 CH2 C

OCH2CH3

-:
OH
C

O
MgBr

1) 2 Ph
2) H3 O+

96%

265

OCH3

C O CH2 CH2 + 3CH3OH

CH2

CH2 CH2 O C

OH

CH2 OH
CH2 OH

H 2C

OH OH

C OCH3

OH
O

C O CH2 CH2 O

H3CO C

Dimethyl terephthalate
O

Sb2O3

O
CH2 CH2 O C

C O CH2 CH2
OH

OH

Poly(ethylene)terephthalate
][PETE

:
alkoxide
Transesterification
O
+ CH3OH

\OR

O
R

H+

OH

\+ R

OCH3

O
OCH2CH2CH2CH3 + CH3OH
Methanol

O
Ph

H+

OCH3 + CH3CH2CH2CH2OH

Butyl benzoate

1-Butanol

72%

)(excess

Ph

Methyl benzoate

Triphosphate pH 07
.
O

O
CH3

OH

CH3

O
CH3
Trimethyl phosphate

O
O

O
Acetyl phosphate

266

CH3

]



.
7-6 LiAlH4
O
b) Phenyl benzoate

OCH3 ,

a) CH3 CH2 CH2 CH

CH3
O
CH2 OH + CH3OH

CH3 CH2 CH2 CH

1) LiAlH4 , ether

OCH3

2) H3O+

CH3

CH3

CH2 OH

HO

a) CH3 CH2 CH2 CH

1) LiAlH4 , ether

2) H3O+

)b

/
:
.

O

O
OH + NH4+

CH3(CH2)5

H3O+

NH2

CH3(CH2)5

Caproic acid

O
CH3COO- + H2 N(CH2)4CH3

267

H 2O
OH-

NH(CH2)4CH3

CH3

O
NH(CH2 )4CH3

1) LiAlH4 / ether

CH3 CH2

NH(CH2 )4CH3

2) H2O

95%

CH3

: Dehydration nitriles
-:
Phosphorus pentoxide (P2O5) ,
Acetic anhydride

)Thionyl chloride (SOCl2

)Phosphoryl trichloride (POCl3

H
N + H2O

dehydration of
primary amides

CH3 C

CH3 C

Nitriles
Acetonitrile CH3-CN
38 )39(
H2O / NaOH

NH2

O
C
\OR
Ester

H2O

C
\OR
Imino-ester

R\OH / H+

H2SO4 / 4H2O

+
NH2 H2O / H R
C
OH
Amide
Carboxylic acid

NH3 + RCO2 Na

(NH4)2SO4 + 2 RCO2H

H2O / HCl
1) CH3Mg
or CH3Li
2) H3O+

O
C
CH3
Ketone

:
O
NH2

(CH3)3C CH2
99%

NaOH , Br2
H2O ,

268

NH2

(CH3)3C CH2

8-6
BenzeneN-(p-Bromo phenyl)acetamide
O
CH3

NO2

NH2
HN

CH3COCl

CH3

HNO3
H2SO4 . Conc

Sn/HCl

Br2 / FeBr 3

Br

BenzeneEthyl benzoate
O
OCH2CH3

CH3

COOH

CH3Cl
AlCl3

KMnO4

CH3CH2 OH
H+

Propanoic acidMethyl-2-bromo propanoate

O
Cl

Br
CH3 CH

Br2 / P

Cl
O

CH3OH

OCH3

CH3 CH2 C
Br
CH3 CH

269

O
SOCl2

OH

CH3 CH2 C

Isopropyl bromide 2-Methyl propanoyl chloride

CH3

CH3 O
OH

CH3

CH3 CH

KMnO4

CH3 CH

CH2 OH

1) Mg

Br

2) CH2O

CH3 CH

CH3 O
PCl5

Cl

CH3 CH

Butanoic acid 2-Chloro butanoyl chloride

O

O
Cl

CH3 CH2 CH

NCS
N-Chloro
succinimide

CH3 CH2 CH2 C

Cl

SOCl2

OH

CH3 CH2 CH2 C

Cl

Ethanoyl chloride Acetone

O

O
C

NH2 + NH4Cl

Cl + 2 NH3

CH3

SOCl2

N + SO2 + 2 HCl

CH3

O
CH3

1) CH3MgI
2) H3O+

270

CH3

CH3

9-6
,
,
,

b) 2,2-Dimethyl hexanamide
d) o-Hydroxy benzamide
f) m-Chloro benzoyl chloride

a) p-Bromo phenyl acetamide

c) Ethyl-p-amino benzoate
e) N,N-Dimethyl methanamide
g) Butanoic anhydride

10-6
O
CH3

O
O

CH3
CH3CH2

CH3

CH

O
C

N(CH3)2

CH3CH2

CH2CH3

O
OCH3

CH3

CH3CH2

CH3CH2

O2N

Cl

O
Cl

Cl

CH

CH3CH

Cl

CH3 C CH2CH2 C

11-6 Oleic acid

) ( 90

12-6 230

) ( 730.4
13-6 68 210

) (
14-6 N-Ethyl benzamide
b) Benzyl alcohol , c) PhCH2NHCH2CH3

a) Benzoic acid

15-6 Phthalic anhydride

271

16-6
i) H

CO2H
+ H2O

150oC

90%

CO2H
Maleic acid

ii) (CH3CO)2O + (CH3)3C-OH

COOCH3
NaOH

? + CH3OH

+ OHNO2

HCl

)iii

CONH2
)iv

KOH , Br

87%

H2 O ,

Br

N
?

CH3CH2OH

Cl

CH2 CH

CH2 C
)v

H2O ,HCl
40oC

OH

vi) CH2 CH

O
OH

NaOH

COCl

aqueous

)vi

O
?

HA

94%

272

OCH3 + 1-Butanol

CH

vii) CH2

CO2H

H3O+ ,

1) NaOH , EtOH

H3O+

viii) (CH2)5

)2

CO2H
O
?

CH3 + 2 CH3 NH2

O
O

ix) CH3

O
1) LiAlH4

OCH3

2) H3O+

CH2 C

Ph

)x

CH3 O
SOCl2

NH2

CH2 CH

xi) CH3

O
?

SOCl2
I2

OH

CH2 CH2 C

xii) Ph

1) NaOEt , EtOH

OEt
xiii) EtO

2) H3O+

O
?

xiv) CHCl3 + 3 CH3CH2O- Na+

17-6
a) 2-Phenyl-2-propanol , b) 1,1-Diphenyl ethanol , c) 3-Ethyl-3-heptanol

273

Amines and Amine Derivatives

.

amine
amine
tri , di

amino

1 -:
: Primary amines R-NH2
.
:
CH3
1o

NH2

1o

H2N CH2 CH2 OH

Ethanol amine
][2-Amino ethanol

CH3 C
1o

CH3CH2 NH2
Ethyl amine

CH3
tert-Butyl amine

1o

1o

H2N CH2 CH2 CH2 CH2 NH2

1,4-Butanediamine

274

CH2 NH2

CH

2-Propenamine
][Allyl amine

CH2

: Secondary amines R2-NH

.
:
CH3

NH CH(CH3)2
(CH3)2HC
Diisopropyl amine

2o

NH

CH3CH2

Ethyl methyl amine

2o

(CH3)2NH
Dimethyl amine

: Tertiary amines R3N

.

CH2CH3

CH3
CH3
CH2CH2CH3

N-Ethyl-N-methyl cyclohexane amine

CH3
N,N-Dimethyl propyl amine

.
CH2CH3

N(CH3)2
1

CH2 COOH

CH3
N
CH2CH2CH3
Ethyl methyl propylamine
][N-ethyl-N-methyl-1-propanamine

CH3 CH

3-(N,N-Dimethyl amino) butanoic acid

2 -:
: .
: .
NH2

N(C2H5)2

NH

Diphenyl aniline

N,N-Diethyl aniline

275

Amino benzene
][Aniline

Aniline
CH3

CH3

CH3

CH3 Cl

NH

CH3
N,N,N-Trimethyl anilinium chloride

NH2

N-Methyl aniline
][N-Methyl benzene amine

m-Toluidine

3 : Heterocyclic amines
.
-

H
Piperidine

Pyrrolidine
Pyrroline .

Pyrrolidine

N
Pyrrole

N
Pyridine

Pyridine
B NAD+

N
Quinoline

Isoquinoline

bp 238oC

bp 243oC

NH
Indole

276

Indole
.

:
N
N
Pyrazine

HN

N
N
Pyrimidine

Imidazole

Pyrimidine B

Imidazole

mp 22oC

mp 90oC

:
N

Purine
, Pyrimidine

.

NH
N
Purine

NH

Tetrazole

Alkaloids
Nicotine , Caffeine :

.
O

N
O

Nicotine

Caffeine

: Quaternary ammonium salts

.
R
X

N R
R

R= R , Ar , H

277

R4N+X-
ammonium .

CH3

CH3
CH3 N CH3 OH

H NO3

CH3

CH3 N

CH3
Trimethyl ammonium nitrate

Tetramethyl ammonium hydroxide

1 :

.
CH3 CH2 CH2 NH2 + (CH3CH2CH2)2NH
43%

CH3 CH2 CH2 Br + NH3

45%

+
(CH3CH2CH2)3N
Trace
CH3CH2CH2 N Br
4

dihaloalkane
.
CH3
+ 2 HBr

CH2
CH2

H2C

NH2

H2C

CH3

CH2 CH2 CH2 CH2

Br

278

Br

2 : Azide synthesis azide ion N3-

alkylazide RN3 .
N

CH2 CH2 N

CH2 CH2 Br
NaN3
ethanol

2-Phenyl ethyl azide

CH2 CH2 NH2

1) LiAlH4 /ethanol
2) H2O

2-Phenyl ethyl amine

98%

3 Hofmann and Curtius

O
NaOH , Br2

R-NH2 + CO2

H2O

NH2

Hofmann rearrangement :

O
NH2 + CO2

CH3

NaOH , Br2
H2O

NH2

CH3

O
R-NH2 + CO2 + N2

H2O

Curtius rearrangement :

4 : Phthalimide alkylation
Gabriel amine synthesis .
O
CH2 NH2

1) DMF
2) OH- / H2O

N K

81%

CH2 Br +

O
Potassium phthalimide

279

5 Reduction of Nitriles and Amides

RCN
1) LiAlH4 /ethanol

RCH2NH2

2) H2O

1o Amines

NH2

LAH
.
CH2 NH2

][H

CN-

CN

OH

OH

CH2 NH2
3) OH-

HCN
CN-

1) LiAlH4
2) HCl , H2O

: Michael ,
cyanohydrins LAH
-Hydroxy , -Hydroxy amine -:
O

O
CH3

CH2 C

CH2

3) OH-

1) LiAlH4
+

2) H3O

CH3

CH2 C

CH2

CH3 CN

CH

CH
2

CN

NH2

6 :
Imines
Reductive amination -:

280

NH3

1o Amine

H2 / cat.

O
RNH2

2o Amine

H2 / cat.

Z = R or H

R2NH

3o Amine

H2 / cat.

NH2

CH2 CH CH3

CH3

NH3

CH2 C

H2 / Ni

Phenyl-2-propanone

Amphetamine

CH3

CH3

NaBH3CN
85%

CH3OH

+ NH(CH3)2

N,N-Dimethyl cyclohexane amine

7 Reduction of Nitro compounds

NO2

NH2
H2 , Pt
or SnCl2 , HCl

CH3

CH3

NO2

NH2
HCl / ethanol

+ Fe
NO2

NH2

281

.
NO2

NH2
H2S
NH3 / ethanol

NO2

NO2

1-7
, b) N-Methyl cyclopentyl amine
a) CH3 CH2 NH CH(CH3)2
From aldehyde :
CH3

O
CH(CH3)2

CH3 CH2 NH

CH(CH3)2

CH3 CH2 NH

H2 / Ni

)a

NH2 + CH3

CH3 CH

From ketone :
O
H2 / Ni

CH3 CH2 NH2 + CH3

From ketone
CH3

NH

CH3

NH

O
H2 / Ni

CH3 NH2

From aldehyde
NH2
O
H2 / Ni

282

)b

2-7

NH2

b) H3C

a) (CH3 )3C-CH2 -CH2-NH2

4,4-Dimethyl pentanoyl azide

p-Methyl benzoyl azide

a) 4,4-Dimethyl pentanamide
b) p-Methyl benzamide

or
or

3-7
1) m-Nitro acetophenone m-Ethyl aniline
2) p-Nitro-tert-butyl benzene 3-Chloro-4-tert-butyl aniline
3)Benzyl chloride (2-Phenyl ethyl) amine
)1

O
CH3

CH2 CH3

H2 , Pd
ethanol

NO2

NH2

C(CH3)3
Cl

Cl2 / Fe

Sn / HCl

NH2

CH2 CH2 NH2

C(CH3)3

C(CH3)3

Cl

)2

NO2

1) LAH
ether
H3O+

)2

CH2

Benzyl cyanide
][Phenyl acetonitrile

283

NO2

)3
Cl + Na CN

CH2

Physical properties
1 :

.
CH3
CH3 CH2 CH CH3

CH3 CH2 N(CH3)2

27.8oC
0D

(C2H5)2NH

37.5 C
0.6 D

CH3(CH2)3CH3
36oC
0D

CH3 CH2 CH2 CH2 NH2

o

56.3 C
1.2-1.3 D

(CH3CH2)2O

77.8 C
1.4 D

boiling point :
dipole moment :

(CH3CH2)2NH
o

56.3 C
1.2-1.3 D

37.5 C
1.18 D

boiling point :
dipole moment :

.
CH3CH2CH2 CH2 NH2

CH3 CH2 CH2CH2OH

117.3oC
1.63 D

77.8o C
1.40 D

boiling point :
dipole moment :

2 :
.

284

Chemical properties
/ Basicity


basicity constant Kb
-:
R-NH3+ + OH-

R-NH2 + H2O

][R-NH3+] [OH-
][R-NH2

=Kb

pKb= - log Kb
) Kb ( pKb .
Kb pKb ammonium ion RNH3+ -:
RNH3+ + H2O

RNH2 + H3O+

][R-NH2] [H3 O+
][R-NH3 +

= Ka

][RNH3+][OH-

][R-NH2] [H3O+

][RNH2

][R-NH3+

=Ka.Kb

Ka.Kb= [H3O+] [OH-] = Kw = 1x10-14

Kw
Ka

= Kb

Kw
Kb

= Ka

285

pKa + pKb = 14

:
.i
.ii

Ka .
Ka ) pKa ( .

.

.
O

H
N

H
R

C
N

Resonance stabilization

.
O
C
NH3

Internal strain I-strain
s .
O

CH3
N

>

286

CH3

>

CH3

s ) 24 (
.
1 -:
-

Methyl amines -:
NH3 < CH3NH2 < (CH3)2NH < (CH3)3N

Front
strain F-strain
) pKa (
3o

> (CH3)3N
9.7

3o

1o
CH3NH2

2o

> (CH3)2NH

10.64

1o

10.72

PKa

2o

~ (CH3CH2)2NH > CH3CH2NH2

= (CH3CH2)3N
10.76

3o

10.98

10.75
1o

PKa

2o

(CH3CH2CH2)2NH > CH3CH2CH2NH2 > (CH3CH2CH2)3N

10.64
3o

10.67
1o

10.98

PKa

2o

(CH3CH2CH2CH2)2NH > CH3CH2CH2CH2NH2 > (CH3CH2CH2CH2)3N

10.45

10.56

10.61

PKa

Back-strain B-strain
s
p .

287

CH3
CH2 N
3

CH3 CH

(CH3CH2CH2)3N

10.42

10.64

(CH3CH2)3N

10.76

R
N
R

PKa

R
R

-:
.i

) ( 1

.ii

) ( 2 .

.iii

p+sp2
.

2 :
aniline cyclohexyl amine Aniline
.
NH2

NH2

10.64

NH2

NH2

4.62

NH2

288

pKa

NH2

NH2

Aniline
.

N(CH3)2

NH2

NHCH3

NH2

NH2

NH2

NH2
Cl

CH3
o- 4.38
m- 4.67

4.85

5.06

Cl
3.81

4.62

Cl
2.62

3.32

pKa

pKa Anilinium
NH3

-CN
1.74

-NO2
1.0

-Br
3.86

-Cl
3.81

-H
4.62

-CH3
5.07

-NH2
6.15

-OCH3
5.34

X
pKa

3
s
.

sp2

~
= Zero

N
H
11.27

sp3

pKa

5.25

H
11.30

pKa

4-7
1) CH3CH2NH2 , CH3CH2CONH2
2) NaOH , CH3NH2
3) CH3NHCH3 , CH3OCH3
1) CH3CH2NH2 , 2) NaOH , 3) CH3NHCH3

289

5-7

.
H
+ OH-

+ OH-

R + H2 O

H
NH

R + H2 O

NH

6-7 pKa Benzyl ammonium 9.33 pkb

Benzyl amine
pKa + pKb = 14 pKb = 14 pKa = 14 9.33 = 4.67

7-7 NF3 , NH3

NH3
NF3 .

8-7 Nitroaniline Ka
NH2

NH2

NH2
NO2

NO2

NO2
0.10

-3

3.4 x 10

1.67

= Ka

< <
) 288 (

290

: Salt formation .
I

(C2H5)3N + HI

(C2H5)3NH

Triethyl ammonium iodide

CH3NH2 + CH3CO2H

CH3NH3 CH3COO
Methyl ammonium acetate

.
NH2

NH3 Cl

+ NaOH

+ NaOH + H2O

Phenyl ammonium chloride

Aniline

H2SO4 , HI , HBr , HCl

.

.
Ag2O
-:
CH3(CH2)5N(CH3)3 I

CH3I
excess

CH3(CH2)5NH2

Hexyl trimethyl ammonium iodide

Ag2O
H2O ,

CH2

CH

CH2

N(CH3)3 + CH3 CH2 CH2

)97(

291

: Acyl ) (
.
O

O
CH3 + CH3CH2NH3 Cl

Cl

CH3CH2 NH

2 CH3CH2NH2 + H3C

N-Ethyl acetamide

: .
O
OH

CH3 C

CH3
+

CH3

CH3

O
O

CH3
NH + CH3
CH3

CH3

: dimethyl dioxirane
-:
CH3

CH3

O
HSO5-

CH3

CH3

.
NO2

CH3
O

CH3

NH2

95%

COOH

CH3
O

CH3

COOH

NH2

NO2
95%

292

hydroxyl amine -:
OH

CH3
CH
CH3

CH3

CH3

CH3

CH

CH3

CH

CH

CH3

CH3

97%

CH3

CH3

-:
O
H

OH-

CH3 C

KMnO4 /

CH3 CH2 NH2

O
CH3

NH2

KMnO4 / OH-

CH3

CH3

CH3
NO2

CH3

CH

CH3
CH3

KMnO4

NH2

CH3

CH3

C
CH3

tert-alkyl hydrazine
amine oxides H2O2 -:
CH3

CH3
N

CH3
KMnO4 / OH-

N
CH3

CH3
CH3
tetra-Methyl hydrazine
CH3

CH3
O

H2O2

CH3

CH3
CH3

CH3
Trimethyl amine-N-oxide

293

9-7
tert-Butyl amine
CH3
NO2

tert-Butyl alcohol

CH3

KMnO4

CH3

NH2

CH3

CH3

CH3
CH3

No reaction

KMnO4

OH

CH3

C
CH3

: Isocyanate .
O
R

NH

NH

R\NH

-:
HN CH3

CH3 N CH3
CH3I

NH2
CH3I

C6H5

HN
C6H5Br + Cu
150oC

MnO2 Azobenzene -:
NH2
N

MnO2

294

Diazotization
-:

Called the
Sandmeyer
reaction

NH2

H3O+

OH

Ph

Ph

Ph

1)HBF4
2) heat

Ph

H3PO2

CN

Ph

NH

Ph

Ph

KI

CuCN

Diazonium salt

Na2 SO3
KX,Cu2X2
X= Cl , Br , CN

) ( :

) ( -NH3+ )138( -:
CH3
)+ (2% o-Isomer

NH2
HNO3

H2SO4 , 20oC

NO2
NO2
47%

NH2

51%
98%

295

+ Fe

: Hinsberg,s test
) sulfonyl chloride (-SO2Cl sulfonamides


.
SO 2Ph + HCl

NH

SO2Cl

Ph

NH2 + Ph

Ph
N Na
SO2Ph

R2NSO2Ph

NaOH

SO2Ph

H3O+

NaOH

SO2Cl

296

NH

Ph

R2NH + Ph

Ph

10-7
Aniline p-Bromo aniline
O
NH2

C CH3

O
C CH3

HN

OH-

HN

Br2/FeBr3

NH2
(CH3 CO)2 O

H2O ,

Br

Br

Benzene m-Bromo iodo benzene

NO2

NH2

NO2
Br2 / Fe

Fe / HCl
Reduction

Br

HNO3
H2SO4

Bromination

Br

Nitration

N2 Cl

NaNO2
HCl , 0oC

KI , heat

Diazotization

Replacement

Br

Br

m-Aminobenzoic acid 2,4,6-Tribromo benzoic acid

COOH

COOH
Br

COOH

Br

Br

Br

NaNO2 , HCl
5 oC

Br2 , HCl
H2O ,

NH2

NH2

N2 Cl

Br

Br
COOH
Br

Br
H3PO2

Br 75%

297

11-7
a) Triethyl amine
,
b) Triallyl amine
,
c) N-Methyl aniline
d) N-Ethyl pyrrol
,
e) N-Isopropyl-N-methyl cyclohexyl amine
f) 4,4-Dimethyl cyclohexanamine
g) 1,5-Pentanedi amine
h) N-Ethyl-N\-methyl-1,3-propanediamine
12-7
-

CH2N(CH3)3 I

N(CH3)2

)c

)e

)b

NH2

)a

d) [(CH3)2CH]2NH

13-7
a) CH3CH2NH2 , CH3CH2CONH2
b) NaOH , CH3NH2
c) CH3NHCH3 , CH3OCH3
14-7
(iv) CH3CONH2

(iii) C2H5NH2

O2N

NH2

), (vi

(ii) (CH3)3CNH2

NH2

(i) NH3

CH3

)(v

15-7
i) m-Nitro aniline m-Nitrophenol
ii) Nitrobenzene Benzene
iii) m-Aminobenzoic acid 2,4,6-Tribromo benzoic acid
iv) 2-Methoxy aniline 1-Bromo-2-methoxy benzene
v) p-Methyl aniline Chloro toluene

298

16-7

NO2

Sn , HCl

)i
N2 Cl

? + N2 + KCl

)ii

+ KI
O
O

iii) CH3CH2CH2NH2
Br

NH2
?

NaN3
C2H5OH

)iv

CH3

CH3
?

NaNO2 , H2SO4
< 5oC

)v
Br

Br

NH2

OH
?

NaNO2 , HCl
< 5 oC

Cl
CHO

)vi

CH3

Cu2(CN)2
NaCN

CN

Cl
?

NaOEt
ethanol

)viii
N

299

)vii

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