أساسيات الكيمياء العضوية PDF

.

.

.
-9-

.

.

" "
) -
- - - -
- - -
- - -
- - -
.
- 10 -

.
"
"
.
.
. .

- 11 -
- 13 -
- 14 -

:

) (
:
H Cl H
| | |
H CH Cl C Cl Cl C Cl
| | |
H Cl Cl

) (109.5
.
-2 -1
15

C-H C-C C-Cl )(o1.78 o1.9 o1.54
.
10-
= (A )10) (A

.
:

.

.

:
.

.

H
F : H F :

R O H R O H

16
(H F,R OH) :
:

:

C O C =O

: O C O : O =C =O

. :
H H
|
H
O
H HCH

|
Methane
H H
H H

|
Cl O Cl Cl C Cl
Chloroform |
Cl Cl
17
H H H H

| |
H: O : O :H H C C Cl
Ethane | |
H H H H

.

.
.
): (Chemical bonds
): (Atomic Orbitals

.
.

) ( Schroidenger
.

.
.
18

) (S
:

.
) (2S

P
Px,Py,Pz
S Px Py Pz
19
:

.
) (A
) (B,A ) (B
.
H H H H H : H
A B AB
:

P,S

.
20
.
). (S,P,d,f

. SP, SP2 , SP3
SP3 )(SP3
) (Px , Py , Pz) (P ) (SP2
) (S ). (Py, Px
) (SP ) (S) (Px

:
C 1S 2S 2Px 2Py 2Pz

)(2S
) . (2Pz
.
.
C 1S 2S 2Px 2Py 2Pz

) (109.5 ) (SP3
:
21
) (SP3
)(CH4

) (CH2O ) (SP2
) (P .
)(C2H2
) (SP3
). (NH3
) ( :

) (S
) (SP3
.
22
2e O
O 2e
H
H 105o
H
H
) ( :

- ) (CCl4 ) (1.76
.
1.09 CH 0.75 HH
1.78 C Cl 1.54 CC
1.47 CN 1.34 C=C
1.43 CO 1.20 CC
- :
.
) (97
CH4 CH3. + H . H = 97
:
23

70 CN 104 HH
66 C Br 110 OH
146 C=C 100 CH
199 C=C 93 NH
204 CN 82 SC
174 C=O 84 CC
143 C=N 79 C-C

.

.

.

.
24
:

.

.
.

.
C <N < O < F
I < Br < Cl < F

.

.
25

.
O- = O+ = O-

.
H + H +
O -
:

.
.

) 161.5- (

). (Vanderval

) (Dipole Dipole .
.
26
+ - + -
HF HF
+ -
H F

.
:

.
.
:

.

.
1413 161.5- .
27

.

.

.
:

). (C2H6O

.
.
.
H H H H
| | | |
HCOCH HCCOH
| | | |
H H H H

28

.

.
. ) (C5H12

.
29
H
.

:
109.5o
109.5o

.

:
30
| | | | |
CCCCC
| | | | |
.
) (C5H12 :
H H H H H
| | | | |
H CCCCC H
| | | | |
H H H H H
CH3 CH2 CH2 CH2 CH3
CH3CH2CH2CH2CH3 :
CH3(CH2)3CH3 :

C C
+ + -
-

C C C. C. C C
)(3 )(2 )(1
) 1 ( 3

) (2
) (Free radical ) ( .
31

.

.
CH3
|
CH3CH2CH2CH2OH CH3CH2CH OH
32

) (OH
. Alcohols

.
( ) Alkane
-1 )
(Parafines )(CnH2n +2
-2 )
( ) (Alkene Or Olefines )(CnH2n
-3 )
( ) (Alkene Or Acetylene )(CnH2n - 2
-4 ) ( Aromatic Compounds
.
33
:

.
CH3CH2 Cl CH3CH2 Br

.
(1
(2
(3

( X = F , Cl , Br , I ) CH3X
C18 .
) (dipolar
.
.

.
.
34

)
(
) (4n + 2) (Huckeles law ) (n
.
.
:
(2 (1
(3 )
(
.
(4 .
:
-:
(1

NH2 COOH
| |
(2 ) (Polynuclear
.
35

(3

+ -
2 6
(4

O N S N

H

:
) (R O R
) (Ar O R ) (Ar O R

CH3CH CH CH2 CH3
O
3 2
36
.
.
.

.
.

.
.
) (ROH ) (R
. ) (Ar OH

.
OH
|

) (glycols )(diols

) . (Triols
37
) (Polyhydroxyl

O .
O
O
O

) (Carboxyl ) CO2H COOH
( O = C OH ) ( ArCOOH , RCOOH
.
) (R

.

) (R
.
.
38

.
O O
|| ||
C C
O NR
C C
|| ||
O O

) . ( C = O

.

) (R CO H , Ar CO H

) (R CO R ). (Ar CO R
39
:

:
RNH2 R2NH R3N

R

.
R NH+3 X-

:
CH3Li (C2H5)4 Pb

40
:

. (CH2O)n
CH3 CH COOH
|
NH2

) (20

: R
) ( :
41
.

.

.

.
.
)( :
)(Saturated hydrocarbons

.
) (CnH2n + 2 ) (n = . 54321
42

.

.

.

.
.
.

)( ) (-
.
H H H H H H
| | | | | |
HCH HCCCCCH
| | | | | |
H H H H H H
43
(
.

.
.
) (1 ) (2

.
C C
| |
CCCCC CCCC CCC
|
C
) (2 ) (1 ) (3
44

CH3 # CH4
CH3 CH2 # CH3CH3
CH3CH2CH2 #(' CH3CH2CH3
CH3CH CH3 )#
(CH3)2 CHCH2 ) "!# CH3(CH2)2CH3 "!
CH3CH2CHCH3 "! #*"
(CH3)2 C CH3 "! #,+
CH3(CH2)3 "! #+

. C6H14

.
:

.
.

.
45
H H H
| | |
HCC CCC C CH C CCC
| | | |
H H C C

.
H H R R
C=C C=C
H H R R

C=CC=C .
): (Alkynes

.
46
HCCH RCCR

) (180
)
(
)
. (
): (Nomenclature

.
) (Common name
) (n
) (Iso ). (Neo

.

.
-1
.
-2

.
47

.

)( :

CH4
C2H6
C3H8
C4H10 "!
C5H12 '/
C6H14 01
C7H16 '
C8H18 '
C9H20 *"*
C10H22 1

) (ane

.
CH3 CH2 CH2 CH2 CH3

48
)(CH3

.
CH3 CH CH3
|
CH3

) (neo
.
CH3
|
CH3 C CH3
|
CH3

:

H H H
| | |
CH3 C C C CH3
| |
CH3 CH3

.
49
:

.
7 6 5 4 3 2 1
CH3CHCH2CH2CHCH2CH3
| |
CH3 CH2CH3
1 2 3 4 5 6 7
CH3CHCH2CH2CHCH2CH3
| |
CH3 CH2CH3
:

CH3 CH3
| |
BrCH2CH2CCH2CH3 CH3CH2CHCH2CHCH3
| |
CH3 CH2
|
CH2
-4 -1 -2 |
CH3
-3 -3
:
) (-

-2 : -4
50
:

- ) : ( -
CH3 CH3
| |
CF3 = CH CH2 CH C CH3
| |
Br CH3
-4 111 5 5 2

. .
.

) (18 . C18H38

.

.
51
-1 :

212.8 / :
/ CH4 + O2 CO2 + H2O + 212.8

:
3CH4 + 3O2 2CO + 4H2O
CH4 + O2 C + 2H2O
-2 :

"6R H + Cl2
R Cl + HCl

CH3Cl + HCl
"6CH4 +Cl2

:
CH4 +Cl2 "6
CH3Cl

"6CH3Cl + Cl2 CH2Cl2
52
CH3Cl
"6CH2Cl2 + Cl2
CH3Cl + Cl2 "6

CCl4
)( :

) (CnH2n
.

) ( .
): (SP2
H H

CH2 = CH2 C C
H H

.
H H
C=C
H H
:
53
-1
.
-2 )( )(
.
-3

.
CH3CH2CH2CHCH2CH2CH3 CH3CH = CHCH2CH3
|
CH=CH2
-3 - -1 -2

79 7 CH2 = CH2
79 7 CH3CH = CH2
"!79 7!" -1 CH2= CH CH CH2
"!79 7!" -2 CH3CH = CH-CH3
27!" -2- # (CH3)2 C = CHCH3

.
54
:
) (
.

.
A B
B
.
BrCH2 CH2 - Br CH2 = CH2 + Br2
-21

:
H H
| |
C=C + H2
C C
| |

.

.
55

.
| |
C=C + A B
A C C B
| |

"

" .
56
CH3 CH CH = CH2
|
Cl
CH2 = CH CH = CH2
CH2 CH = CH CH2
| |
Cl Cl
)( ): (Alkynes

) (CnH2n-2
)C
(C
). (SP

) (CnH2 :
HCCH

-:
-1

)( )(
.
57
-2
.
-3
.

'79 7 HC CH
#'79 7 CH3 - C CH
#'79 !" -17 HC C CH2CH3
+;/ #'79 !" -27 CH3C C - CH3
) # #'79 - 4'/ -2- #7 CH3 C C CH -(CH3)2
)
(

) ( .

) ( .
.
58
:
) (RC C H
:
-1 .
-2 .

HC C R

.
.
Br Br
| |
Br2CH CHBr2
CH CH + Br2 CH = CH Br 2
) 21 (
Br Br
C=C
H H
) 21 (
) (

21
59
H H
CH3C C CH3 +
H 2 , Pd
C=C
H H
-2 22

RC C H + Na+ NH2 RC C Na+

..
60
:

.
CH3Cl CH3CH2 Cl CH3CH2CH2 - Cl
-1
Cl
|
CH3 C CH3
|
H
-2

CH3 OH >" +9
CH3CH2 OH >" +9
CH3CH2CH2 OH >" +9
CH3(CH2)2CH2OH >" "!+9
CH3 CHOH >" "! +9*"
|
CH2CH3
(CH3)3 C OH >" "! +9,+

(CH3)2 CH OH >" )"!+9
61

)(
-1 .
-2 ) (- Ol .
-3 .
CH3
|
CH3CH2 OH CH3 C OH
|
CH3
-2 2
CH CH3
CH3CH = CH CH CH3 |
OH
|
OH
:

.
CH3 CH2 O CH3 CH3CH2 O CH2CH3

O O CH3
)(
RO
:
62
CH3 CH CH2 CH3 -2
|
O CH3
:

)(HCOOH
). (CH3COOH

.
). (- One
O O O
|| || ||
CH3CCH3 CH3CCH2CH3 CH3CH2CCH2CH3

O O
|| ||
O C C
) ( ) (

* HCHO "A??
* CH3CHO '??
* CH3CH2CHO "*??
"!* CH3CH2CH2CHO !" -??
63

)(
)(
.
O OH
|| |
CH2 CH CH2 CHO CH3 C CH2 CH CH3
-3 -2 4

) ( ) ( .
)(

.

HCOOH "A CB C*"B
CH3COOH C'B C*"B
CH3CH2COOH C"*B C*"B
CH3CH2CH2COOH C!" -B "*!" CB
CH3(CH2)3 COOH A CB "*'/ CB
CH3(CH2)4COOH CB C"*01B
64

:

COOH COOH C)B
COOH CH2COOH C"*B
COOH CH2 CH2COOH CB/01
COOH(CH2)3 COOH !"9 CB

R
R NH2 R2NH NR3

R

:
CH3 NH2 (CH3)2 NH (CH3)3 N
65
)( )(
)(

NH2
|
CH3 CH CH2CH3 NH2 CH2CH2CH2 - OH
-2 -3 -1-
NH2 CH2CH2CH2 NH2

31
: Aromatic Hydrocarbones
) (
.
66

.
:

) (C6H6
:
H
C
H C C
H
C C
C
H H
H

)(
)( .
) (

C-C
). ( A1.4
)( )(
C-C
67
1.54 1.34 C-C
.
)( )(
)( )(

)( )( .
)( )(
)( )(

)(
. )(
)( .
)( ) (
)( )(

.
68
36
/

.
= C 6 H5 -

Ar

.
Br Cl NO2 CH2CH2

CH = CH2
|
CH3 CH2Cl
69

| -2
H3C C H
|
CH3

)
( .
OH OH OH
| | |
OH
OH
|
OH

.
NH2
|
Br Br NH2
NH2 Br Cl
| |
Br OH
-5 3 1 -4 -3 -4-2-
:
COOH OH NO2
| | |
O2N NO2
|
CH3
-6 4 2
70

.

80 5
. )
( .

. 50 -
71

.
.
Cl
|
Cl
2 /
AlCl 3
Br
Br
2 /
AlBr3
NO2
|
HNO

3 / H 2 SO 4
CH3
|
CH
3
Br / AlBr3
SO3H
|
-H
2 SO 4
HO2

.
.
72

) (NAD+
.

) (Heam

R N H2 R2 C = N R RC N

O O-
|| |
RCN RN =O

) (Pyrrol ) (Pyridine

.
73

.

) (CH
.

.
.

) (Uracil , Thymine , Cystosine
. .
74
" "
-1 .
-2
.
-3 .
-4 .
-5 .
-6 .
-7
.
-8 .
-9 :
- -
- -
- -
75
77
78

:

:
) ( Intramolecular

" " 2 1 :
X X
| |

AB
A B

). (Intramolecular
X AB + X-A-B
|
AB +
A B ) (
) (X
) . ( Anionotropic
) ( Cationotropic
) . ( Free radical
79
:

:

) : R ( ) ( H
.
) OH (

: SN1 . SN2
SN2
( Y
) ( X ) &&
. SN2
SN1
) ( .
80
X X X
| |
ABY

A B + Y
+
+
AB &&
Y
SN2
X X X
| | |
AB A B
+
A B
| &&
+ Y
Y
SN1

)
X : ( ) ( Y
. .
X X X
| |
AB AB
Z&&
AB

+
| |
Y &
+ Y& Z
) Z :
) ( X

.

81
) ( . ) ( Inversion
) . ( SN2

.

.

O ) ( Br
&& , S &&
&& , N
X: X X
| + |
CC C C + Y C C
&& Z
| |
Y Z
X = RS , R2N , O , Br , C=C
:

.

.
82

) ( X :
X X X
| | |
) (1 ) (2 ) (3
A B A B AB
- 2 2 2
- 2 1 1

) ( . :
Ph Ph Ph
| | |
) (1 ) (2
Ph C CH2 Cl Ph C CH2 Ph C CH2
| | |
Ph Ph Ph
2 2 2
Ph
|
) (3
Ph CH CH2
|
Ph
2 1 1
:

. .
83

) ( X
.
X X X
|
) (1 ) (2 ) (3
A B A B AB AB
2 2 -2

) ( .
:

.
84
) ( NaOBr

:
O
OBr
R NH2 + CO3
--
RC
NH2

.
) ( R ) . ( Ar
:
)(1
)(2
)(3
)(4
85
-N
.
) -N(
.

-N
) ( .

.
SN2 )
( .
.
. .
R
.
.
86

.

.

.
:

.

.
) (15N
) 15N
( 14N
15N
87

.
) 15N
(
) 15N -
( .
OCl
N15
:

.
.
:
CH3 O CH3

H C OBr
H NH2
C 6 H5 NH2 C 6 H5
) - ( + ) ( -
88

.

.
.

.
OH , CH3 , OCH3 .

:
89
G = OCH3 , CH3 , OH

) ( Cl, NO2
.
:
) = R (

:

.
:
90
|
CH3 C O OH + H+
CH3 C = O
| |
CH3 CH3 + PhOH

H
|
H+
R C O O H R C = O + H2 O
|
H H
H
|
H+
R C O O H R C = O + H2 O
|
H R

:
R R R
| | + | +
H+
RCOOH RC O OH2
RC O |
| | |
R R R
+
OH2
+ |
H+
RC O R RCOR
H O 2
R'C=O+ROH
| | |
R R R
91

) ( .

) ( 2 1

) ( 3
) . ( 4

) . ( 5
) ( 3
.
2 1-

) (
) ( :
)(
92
)(

C 6 H5 +
H

2O.H
93

) ( .

.
:
2 1-

2 1- .

.

)
( :
94

.
2 1- .

.
Ag+ . Hg2+
or

). (HNO2
95

:
HONO

) . ( pinacolic deamination

.

.

2 1 2 1 -

:
2 1 2 1
96

2 1 - - 2 , 1 -
) (

:
2 1 2 1

.
2 1 1 1
2 1 1
%88 %12
:
-2 -1 1- 2 1 1
-1
97
SN1
.
) ( Collins 2
1 1 1
14 :

* Ph
2 -1 1 )(2 ) ( 88 %
- 1 )(6
)(1

Ph
)(3
) ( 12 %
)(7

Ph
)(4 ) (
)(8

*Ph
)(5
98
) (
)(9

) * ( Ph ) ( %88
) . ( %12

) (
) . (
:
:
)

. (
:

) * ( Ph
. %88
:

C C 60 . %12
99
:

.
C C 120 .

2 1 1 1
) ( . ) (
) (
) ( ph . %88

) ( Ar )
( %12 ) (
) ( ) ( %94 %6
.

) ( %94

.
)
( ) ( %12
) ( %88
) ( . :
100
) (i
C C
.
) (ii .

C C 60
.
) ( 18
) ( 16
) ( 11
-2 1 1 ) ( 19
1 - ) ( 17 ) ( 6%
) ( 94%
) ( 14
) ( 12
101
) ( 10 ) ( 13 ) ( 15
-2 1 1 ) ( 88% ) ( 12%
1 -
:

)
( SN2 SN1
) ( :
or
R OH HX R X
PX 3

) ( SN2 ) . ( SN1

.
.
R R
| |
ZCR
Z C R
Y
| |
RCX RCY + X
102
| |
R R
SN1 SN2
SN2
.
) ( Z
) ( X

) ( Y
) ( :

3 2 ) (
3 2
) ( )
( ) ( ) ( :
103
-3 -2- ) ( 3 2 ) (
3 -2- ) ( 3 2-

) (
.
.
3 2 )
( 3 2
) ( .

) . ( OH
) ( Br-

) ( :
104
3 2
)(25 ) (
-3- -2
)(24
) (

OCOR COOR OR OH :
) COO ) Br, I ( COOH S O NH2 ( Cl
. NHR NR2 NHCOR SH SR

) ( nonclassical .
3 2 )
( 3
2 2 ) (
) ( .
105
(+) L -3- -3- -2- -
-2- -2 ) (
)(26 )(28 )(27

. ) 2
(
) ( :
CH2CH2Br CH2CH2 OEt
106
" "
) (1 R2CHO-OH RCH2O-OH
.
.
) (2 ) ( %61 ) ( %38
( P.CH3CH4CH2O-
) OH ) .(
) .(
.
) (3 :
2 1 1 : 2 1 HONO
- 2 1 1 - .

2 : 1 2
+
Ag
) (4
.
.
)( 2 1 .
)( 2 2 1 - .
)( 1 2 1 - .
107
)( 1 2 1 - .
)( 1 1 2 2 - 2 1 -
.
)( 2 1 1 2 - 2 1 - .
) (5 1 1 2 1 -
) :( ) . HCl(
.
.
) (6
:
( 1 1 2 1- .
( -1 1 2 1 . HONO
108
109
110

:

.

) (:B ) ( enolate ) ( 1
) ( resonance hydrid
) ( 2 ) ( 3
.
)(1
)(2 )(3
111

.
) (OH

.
112

.
:

. .
| +
|
C C + X2
C C + HX
OH H
X2 = Cl2, Br2, I2
|| | || |
H O X O
:

.
.
CH3COCH3 + Br2 + :B

CH3COCH2Br + Br- + H:B

CH >> CH 2 >> CH 3

113

.
] ] [:B [ = k

.

). (1

: = ] k [ ] [
114
k
.

N .
:

:
CH3CCH3 + Br2
CH3COCH2Br + HBr

.

:
115
)(1 CH3CCH3 + H:B CH3CCH3 +:B
|| ||
O + OH
)(2 CH3CCH3 + :B

CH3C=CH2 + H:B
|| |
+OH OH
)(3
CH3C=CH2 + X2
CH3CCH2X + X-
| ||
OH + OH
X Br I
)(4 CH3CCH2X + :B CH3CCH2X+ H:B

|| ||
+ OH O

.
.
+

+ Br2
H
+ HBr
116
:

. .
:
2

) -3

! (
2
!

$
%
#

2
4
! ( 2 $
%
4
) (
) (

117

.

) (

2 2

.

. ArCOCR3
)
(

.
CH3CHO + OH- ]H2O + [CH2CHO
)( 2
H H
| |
CH3 C=O + [CH2CHO]- CH3 C CH2CHO
|
O
)( 3
H H
| |

CH3C CH2CHO + H2O CH3 C C CH2CHO +OH
| |
O- OH

) ) (2
118
(
) ( ) (3
)(3
.
) (3

.

:
+
O OH OH
|| || |
CH3CH + H+
CH3CH CH3 C H
+
OH OH OH OH
| | | |
CH3 C - H + CH2 = CH
CH3 CHCH2 C H
+ +

OH H OH OH O
| | | | ||
+
H
CH3 CH - CH C H
CH3 CHCH2CH
+

119

.

:

.
:

.

.
120
) -2 (

I
+2 ,

*

$
) 2
( 3 $
%
4 (

.

:

MaOC 2 H 5
3 1 2 1
:

121

.

2
1 .

H 2O
2CH3CHO

OH
CH3CHOHCH2CH
CH3CH=CHCHO

H2, Ni
CH3CH2CH2CH2OH

o
250
2 1

122

) ( NaBH4

:
:
)
(
.
.
-

.
- .
123
-

) ( Acroline

:
O
||
CO 23
CH2OH+CH3CHO HOCH2CH2CHO
CH2=CHC-H
.
/2

) (
.
o
30
o
100
o
20
124
: :

.

. .
:
2CH3COOC2H5 + Na+ -OC2H5

C2H5OH
CH3COCHCOOC2H5-Na+
+ 2C2H5OH
H+

CH3 C OCH2COOC2H5
-

(
) (
.

125

.

.
126

:
:

.
:
127
: :

) (

.

.

. :
128

:

.
) ( R-CHCN - N,N

) . ( RCHBrCH = CH-CO2R
.
129

.
. :

$/+

:

. .

.

.
.

.
130
:

" "
ZCHRZ Z-CH2-Z
:
'Z C Z
R C R' + Z CH2 Z'

45
||
|| 'R C R
O
Z Z
SO2OR, SO2R, SOR, NO2, CN, COOR, COR, CHO

-2
.

PhCHO + CH3COOH2COOEt Ph CH=C COOEt
Et N 3
|
COOH3
PhCHO + CH3NO2
Ph CH=CH NO2
NaOH
CHCl3
|
CH3COOH3 + CHCl3
CH3 C CH3
KOH
|
OH
131
:
.

.

.
H R
| |
ArCH+(RCH2CO)2O

RCH2COOK
ArC=CCOO +RCH2COOH
||
O
C6H5CHO + (CH3CO)2O
C6H5CH=CHCOOH
CH COONa 3
132
) (II :

.

.

.

.
CH2(COOC2H5)2 + Na+ - OC2H5 CH(COOC2H5)2-Na++HOC2H5
133

.

.
CH(COOC2H5)2 -Na+ + RX
RCH(COOC2H5)2 + Na X
+ -

.
:
RCH(COOC2H5)2 +Na+ -OC2H5 RC(COOC2H5)2-Na++C2H5OH

RX
RRC(COOC2H5)2 + Na+X-
134
o +
RCH(COOC2H5)2
RCH(COO-)2
H2O, OH , 100 H
RCH(COOH)2
140
RCH2COOH + CO2
H O, OH , o100 H+
RR'C(COOC2H5)2
2

RR'CH(COO-)2 RR'CH(COOH)2
140
RR'CH2COOH + CO2

.
.
) (CH3)2CHCH2CH2CO2H

.
135

) (CH3CH2CH2CHCH3CO2H

.
:

.
.
136

). (CH3COCHRCO2C2H5

CHR

). (CH3COR R CO2C2H5

. CH3COR R , CH3COCH2R
.

) (
137

) (
5 2 "
"
. :
5 2
138

.

CH3COCH2COOC2H5 OC
H
CH2CO CHCOOC2H5
2 5

.

.
.
.
.
:

CH3COCHCOOC2H5
H 2O H +

RX

CH3COCHCOOC2H5
|
R
CH3COCHCOOC2H5

C H2CO C HCOOC2H5
+ R

RX

H 2O H
R-CH2CO C H2COOC2H5

-1
139
-2

.
CO2
. CO2

.
140
-2 :

4 2 2 4
) (1 2
2 - 1 .
2 4 4 2 )(1

.
EtOH
H2SO4
RCH2COOEt
H
H2O.H+
|
R C COOH
|
H
141

2 4 4

.

. :
-1
.
-2 2 .
-3 2 .
142

:

:
.
:

) . ( Enamines
.

) ( iminium ions
.
143

SN2
144
) (
:

. :
-2

145

) ( SN2

.
146

147
" "
-1
.
)( (CH3)3 CCOCH3 )( CH3CH2CHO
)( CH3CH2CH2CN )( CH3COOH
-2
1 2 3 .
-3 ) (D2O

CH3COCH3
CH3COCH2D
D O 3
-4 :
3 4 3 2 )(
)( )(
-5

148
-6
.
-7
.
149
-8
.
.
-9
.
O
||
C6H5CH2CH2CCH3 CH2CH2CO2H
)( )(
HO2CCH2CHCO2H
|
CH3
)(
150
151
152

:
) ( Structural isomers ) ( Stereoisomers
:
) ( Enantiomers ) ( Diastereoisomers
). ( Geometrical isomers
:

:

.
153

) (

154

.
.
:

:
) (i ) (ii
) (iii
) (iv ) (v
.

.

) (+

) ( - .
155
:

10 1 / 3

\ ]=[
LC
] [
= C ) / = L ( 3 )10 1 (
\ =

.

.
.
156

CH3CH- CH3
| CH3CH2 CH2 CH3
CH3 C4H10

CH3OCH3OH CH3OCH3
C2H6O

CH3 H CH3 CH3
C=C C=C
H CH3 H H
2 2

CH3 CH3
HO H H OH
| |
CH2 CH2
| |
CH3 CH3
-2 ) (
2 2
C4H8

) ( Enantiomers
157
) ( Diastereomers

.
:

) (2
-2 1 ) (

.
H H
| |
C2H5 C CH2OH CH3 C COOH
| |
CH3 OH
-2 1
H H
| |
CH2H5 C CH3 C CH3
| |
Cl D

158

.
2

.
CH3
CH3 CH3 CH3
CH2
|
CH3
CH2 CH2
| | CH2
CH3 CH3 |
CH3
159
)(
)( )( )(

-2 ) (2-8
:
CH3 CH3
H OH HO H
| |
CH3 CH3
)( )(
CH3 CH3
H C OH HO H
C
| |
CH3 CH3
-2

180

160

.

- 2
) (
)( )(
161
) (
)
( -2
( .
-2
162

-2
:

-1 2-
) ( 2 .
Ph CH3 O
||
*Ph OH H Cl CH
*
|
NH2 H H Cl CHOH
|
163
*
CH3 CH3 CHOH
|
CH2OH
3 2
* *
CH3CH2 CH CH CH3
| |
Cl Cl

CH3
H CH2Cl
CH2CH3
-1 2
:

)
( .
164
-2
:
-2
) ( - ) ( +
99.5 99.5
0808 0.808
1.397 1.397 )(20
13.52 13.52+

-2 -1-

.
165
) ( +
) ( -
.
:

-2
13.52

) . (13.52

) ) ( ( .
:
D : L
166

) ( + ) ( - :

D L ) ( + ) ( -
) 3 . 2 (
D
L .
167

.

D L
) ( NH2
) ( L
. D
CO2H CO2H
NH2 H H NH2
CH3 CH3
- L D

D L
D/L

.

. R-S
168
:
: S/R
-2
) ( IUPAC
-2

) ( S/R
) ( .
) (
)(R
) ( Rectus = Right
s ) . ( Sinister = left
169
:
) ( -i

` CH CI Br I
I > Br > CI > Hr
) ( .
-ii
)( )
(
( .
) ( ) (
) ( R
) ( S
CH CI Br I
:
:
:
:
I> Br > CI > F NH2 > CH3 > H
170

. T > D > H
H
|
H3C C Br
|
D

:

:
CH2OH > CH2NH2 > CH2CH3 H
CH2CH2OH > CH2CH2CH3 > CH2CH2 H
: ) (

CCl3 > CHCl2 > CH2Cl :
:
:
H H H H
| | | |
171
C C CH3 CCH
| | | |
Cl Cl Cl Cl
:
) (

:
O O H
|| || | N O N
-C-OH -C-H -C-OH -C- N; CN C ; C=O C ; C=N
| N O N
H
X
|
C=X CX ; CXCX
| | | |
X C X C

3 2 .
3 2
* *
CH3CH2 CH CH CH3
172
| |
Cl Cl
3 2

) ( N2 ) (

) . ( 4= 22

) ( :
CH3 CH3
H Cl Cl H
Cl H H Cl
C 2H 5 C 2H 5
CH3 CH3
H Cl Cl H
Cl H H Cl
C 2H 5 C 2H 5
)( )(
173

.
) ( )(
) ( )(
)(

) (.
CH3 CH3
H Cl Cl H
H Cl Cl H
C 2H 5 C 2H 5
CH3 CH3
H Cl Cl H
H Cl Cl H
C 2H 5 C 2H 5
) ( )(
174

) - (
) (
) ( .

) ( ) (

.
:
3 2

:
CH3 CH3 CH3 CH3
CH3 CH3 CH3 CH3
175

) ( ) (

.
) ( ) (
)( 180 ) (
) ( ) (
.
) ( ) (
)
(

:
CH3 CH3
Cl OH
H H
H Cl H OH
CH3 CH3
176

) ( S/R
3 2
:
CH3 CH3 CH3 CH3

HO OH H OH
H H H HO
HO H H OH HO H H OH
CH3 CH3 CH3 CH3
( ) ) (( ) (
) ( )
) ( 2
.

) ( 2 ) ( ) ( 2R 2
R
) ( OH > CHOHCH3 > CH3
) ( 3
. 3R
) ( ) 3 2 ( 3R , 2R
) ( ) 3 2 ( 3S , 2S
) ( ) (
177
) ( 3S,2R ) ) ( 3R,2S R,S
( .
:

.

C3 C2

:

) (
) ( .
) (

178

0.8 / .
) . . (
) (
.
:

) (

) ( Allenes
3 2 ) ( :
CH3 CH3 CH3 CH3

C=C=C C=C=C
H H H H
- 2 2

sp1
) ( .
179

.

6.6
.
:

.
180

:
181
:

) ( Cis ) ( Trans
) ( :

) . ( E- Z

E
Z
E
:
182

-1 -2 1-
) ( Z
) ( E .
183
" "
) (1 :
)( )( )(
)( )( ).( )(
)( ) . (
) .( .
) (2
) ( :
)( -1 )( -2 -2 )( -2
) .( -1 )( -2 )( -3 .
) (3 R S

)( -3 )( 2 1 2
)( 13 ) ( 2 1 3
)( C6H5CH (CH3) NG2 .
)( HOOCCH2CHOH COOH
)( CH3CH(NH2)COOH )( C6H5CHOHCOOH
) (4 :
NH2 , CHO , H , Br ,C2H5, CN, OH ,COOCH3 , C6H5
,CONH2 , CH2OH, CH3 , CH2H
184
) (5 ) E ( Z .
) (6 3 2

) (7 ) -2 ( 2R
NaI
.
) (8
)( ) BrCH2 CG2Cl ( . CH3CH2Br CH2Cl :
) (9
)( .
185
)(
)(
) (10 :
CH3 ( CH2 ) 5CHOH CH2CH = CH(CH2)7COOH
)( .
)( .
186
187
188

:

. CnH2n+1
. R-H
:

:
:
) ( .
CH3CH2CH2CH3 - :
CH3CH2 CH2CH2CH3 -
CH3CH2 CH2 CH2CH2CH3 -
:
.
CH3 CH2 CH2 CH2 CH CH3 3 :
|
CH2
|
CH3
189
3 5 2 .
CH3CHCH2 CH2CH2CH3
|
CH3
3 5
:
.
: .
.
.
:

. :
CH3 CH2 CH CH2 CH CH3
|
CH2 CH3
|
CH3
4 2
:
: :
CH2 CH3 Br
| |
CH3 CH2 CH2 C CH2 CH3 CH3 CH2 C CH3
| |
CH3 Cl
3 3 2 2
190
:

:
CH3 CH CH CH3 CH3 CH CH CH2 CH3

| | | |
CH3 CH3 Cl Cl
3 2 3 2
CH3 CH CH CH2 CH CH3

| | |
CH3 CH3 CH3
5 3 2
:
:
. :
CH (CH3)2
|
CH3 CH2 CH CH2 CH2 CH2 CH CH CH3
| |
CH2 CH3 CH3
7 3 2
:
.
:
CH3 CH CH2 CH CH CH3
| | |
CH3 CH3 CH3
5,3,2
191
Alkyl Groups
" "
.
.

" " " "
: :
H H
CH4 - CH3 CH3 CH3 CH3 CH2-

. - CH3
. - CH2 CH3
- . - CH2 CH2 CH3
. - CH (CH3)2
. - - CH2 CH2 CH2 CH3
. - CH CH2 (CH3)2
- CH CH2 CH3
" - " . |
CH3
" - " . - C (CH3)3
192
:

:
. 109.5

. :
CH3CH2CH3 , CH3CH2CH2CH3 , CH3CH2CH2CH2CH3

:
CH3(CH2)3CH3 , CH3(CH2)4CH3

.
193

1 CH4 CH4
1 C2H6 CH3CH3
1 C3H8 CH3CH2CH3
2 C4H10 CH3CH2CH2CH3
3 C5H12 CH3(CH2)3CH3
18 C8H18 CH3(CH2)6CH3
35 C9H20 CH3(CH2)7CH3
75 C0H22 CH3(CH2)8CH3

.
) (

.

) . ( CH2

.
194

( Homologous Series ) :
. ( Homolog ) :
:

.
" " ) ( ) ( Normal
. ) ( Iso
(CH3)2CH-
) ( Neo
(CH3)3C- :
CH3CH2CH2CH3 -
CH3CHCH3
|
CH3
CH3CH2CH2CH2CH3 #$ -
CH3CHCH2CH3 #$
|
CH3
CH3CH2CHCH2CH2CH3 -%
CH3CHCH2CH2CH3 %
|
CH3
195
CH3
|
CH3 CCH 2CH3 %
|
CH3
:

.
.
.
+$ 06 % 5 01 01 +

/-
20 23/ %
-164 -182 1
-88 -183 2
-42 -190 3
0 -138 4
0.626 36 -130 5
0.659 69 -95 6
0.684 98 -95 7
0.703 126 -57 8
0.7118 151 -51 9
0.730 174 -30 10
0.740 196 -26 11
0.749 216 -10 12
0.756 243 -5 13
0.763 253 6 14
0.769 270 10 15
196

.

. :
)( )(
-130 36 -
-160 28 -2
-20 9.5 22
1 /
.

.
.
197
:
-1 :
CH3 CH CH = CH CH3 Ni
H
CH3 CH CH2 CH2 CH3
2
| |
CH3 CH3
-4 2 -2
HC CH + 2H2
Pt
CH3 CH3

-2 :

CO2 :
CH4 + Na2 CO3
CH3 COO Na NaOH
CaO
-3 :

HCl :
+
2RI + Zn
H
2R H + Zn I2
2CH3 CH2 I + Zn
CH3 CH2 CH2 CH3 + Zn I2
:

R X + H2 Pd /C
R H + HX
-
OH
198

:
CH3.CH2 I + HI P CH3 CH3 + I2
-4 :

1RX + Mg
RMg X H
O
R H + Mg ( OH ) X
2
RX
R R + Mg X2
-5 :
) (
:
2R X + 2Na
R R + 2NaX
2 CH3I + 2Na
CH3 CH3 + 2 Na I

:
CH3I + CH3CH2I + 2Na
CH3CH3 + CH3CH2CH2CH3

+ CH3 CH2 CH3

199
-6 :

:
2 CH3COO K + 2 H2O
CH3 CH3 + 2CO2 + 2KOH + H2
-7 :

:
CH3 CH2 OH + HI P CH3 CH3 + I2 + H3O
150
O
||
CH3 CCH3 + HI P CH3 CH2 CH3 + I2 + H2O
<;
CH3 COOH + HI P CH3 CH3 + I2 + H2O

<;
:

.
200

.
-1 :

. :
CH3 Cl + HCl
ACH4 + Cl2
?

.
:
CH3 CH2 Cl + HCl
ACH3 CH3 + CI2

-1 :
-2 . :
A2CH3CH2CH3+CI2
CH3CH2CH2+CH3CH-CH3+2 HCl
| |
Cl Cl
-2 -1

HCl
-1 : -2 . .
201

-:
CH3 Cl CI 2
CH CI3 CI
CH2 Cl2 CI CCl4
2 2
A

) ( CO2
.
CH4 + 2O2
C2 + 2H2O H = -212
5 CO2 + 9H2O H = -833
CH3 (CH2)3 + 8O2
CH4 + 3/2 O2
CO + 2H2O
CH4 + O2 C + 2H2O
:

%80 %10
202
-2

.

.

.

.

.
370
425
.
:
203

# B01
#+ B
$F
C )( %
5 )
-2 >20 C4 C2
P MN
BCA +$ KJ
+<# Q :
# )
TS ( 30 60 C6 C5
U; ) N (0NN% . 0N 60 90 C7 C6
1; ) ( N+ ?0W 85 200 C12 C6

:X$S; #; X;
; )Q( Q JH . 200 300 C15 C12
X YQ )Q +X( . 300 400 C18 C15
-PZ Q . 0 < 400 C24 C16
Q ). (YN H#
/
; C24

%20

.

.
: .

) (
:
204
200
:
C6 H14 + C2 H4
C8 H18 C4 H10 + CH4 + C2 H4 + C
C8 H10 + H2

:
.
:

62 90 :
CI
CH3CH2CH2CH2CH3 AL CH3.CH(CH3) CH2.CH3
3
?
:

:
CH3.CH(CH3)2+H2C=C(CH3)2
HF
CH3.C(CH3)2-CH2CH(CH3)2

205
400

.

.

.

. 4,2,2
) (
) 100 (
.

%95 87

.
-Q % 5
-Q/# %
0N#
/#
0N#
93
2 122
91
#$% 94
75
%% 62 #$
103 ; 25 %
116 -3,2,2\
-19 #
100 -4,2,2\

206
113
;
) X X$; (
-2,1

:
Et4Pb + BrCH2 - CH2Br + 16O2
Pb Br2 + 10CO2 + 12H2O

.
.

. CnH2n

. "
" " " :
207

.

.
:
:
:
) (1 :
CH2 Br
CH2 + 2Na
+ 2Na Br
208
CH2 Br
) (2 :

25 .
) (3 :
CH2 CH2 COO- Ca

|

= O Zn /H

HCl
CH2 CH2 COO- Ca

.

.
) (1 :
209

.
A

A

A

:

Br2
BrCH2 - CH2 - CH2Br
3 1

HI
CH3 - CH2 - CH2 I
-1

N2
CH3 - CH2 - CH3
N1

+
H CH3 - CH2 - CH2 - OH
2O / H
210

.
+ H2
Ni
CH3 CH2 CH2 CH3
100

:
KM
N
O4

CH2 CH2 COOH
OH
CH2 CH2 COOH

211
" "
(1 :
- : -
(2 :
-3,3,2,2 - . -3,2 - .
-5,4,4,3 - .
-4 - -4,3 - .
-1 - 2 -5,2 - .
-2,1 - 2 .
(3 :
a) ( CH3 ) 2 CH CH2 CH2 CH3 b) CH3 CH2 CH3
c) CH3 CH2 C( CH3 ) 2 CH2 CH3
d) (CH3 CH2)2 C( CH3 ) CH2 CH3
e) CH3 CH2 CH ( CH3 ) CH(CH2 CH3) CH2 CH2 CH3
f) (CH3) 3 CCH2 C( CH3 ) 3
g) ( CH3 ) 2 CCl CH( CH3 ) 2
h) CH3 CH2 CH( CH3 ) CH2 CHCH2 CH2 CH3
|
CH( CH3 ) 2
(4 ) (1 )(2
:
- . - .
212
- . - .
- .
(5 :
)( - . )( -3,3 .
)( -2 . )( - .
)( -2 .
(6 :
- + .
- + .
- + .
(7 - :
-2 - . - . -1 - .
- -2 - . -1 - .
- .
213
215
216

C2H4

. CnH2n
:
CH2 = CH2 CH3 CH = CH2 CH3 CH = CH - CH3
-2
:

:
-1

) ( ) ( :
CH2 = CH2 CH3 CH3 CH = CH2

217
-2
.
:
CH2 = CH CH2 CH3 CH3 CH = CH CH2 CH3
1 2
-3
.
CH3 CH2 CH - CH2 CH = CH2 CH3 CH C = CH2

| | |
CH3 CH3 CH2
|
CH3
4 1 2 3 1
-4 ) (
1 2
:
CH3 CH3
CH2
-3 4 1
218
-5
:
CH2 = CH - CH = CH2 CH2 = CH - CH = CH - CH = CH2
3,1 5,3,1
:

. :
"!

#$

25
-104 -169 CH2 = CH2 C 2H 4
-48 -185 CH3 CH = CH2 C 3H 6
-65 -130 CH2 = CH CH2 CH3 C 4H 8 1
CH3
-70 -140 | C 4H 8 -2
CH3 - C = CH2
0.641 30 -138 CH2 = CH CH2 CH2 CH3 C5H10 -1
0.673 64 -141 CH2 = CH (CH2)3 CH3 C6H12 -1
H H
4 -139 | | C 4H 8 2-
C = C
CH3 CH3
CH3 H
1 -106 C =C C 4H 8 2 -
H CH3
1 -104 C6H10
219
:

.

.

.
.
:
) ( C1 C4

220
.
.
-1 :

180 170
:
+
c
CH3 CH2 OH H,180
CH2 = CH2 + H2O

) (

400 250 .
.

180 .
%20 85 .
-2 :
) ( NaNH2

.
221

CH3 CH2X KOH CH2 = CH2 + KX + H2O
./0

1 2
:
CH3 CH=CH2 KOH
CH3CH2CH2I KOH CH3CHICH3

1
Cl
+ KOH
+ KCl + H2O
) ( HX
. 2
:
CH3CHCH2CH3 KOH
CH2=CHCH2CH3 + CH3CH=CH
./0

| |
Br CH3
2

:
R Cl < R Br < R I

.
222
-3 :

:
67
BrCH2 - CH2Br + Zn 93 CH2 = CH2 + ZnBr2
2345
-4 :

:
CH2 COOK
2 CH2 = CH2 + 2CO2 + 2KOH + H2
H 2O
CH2 COOK :05<.
:
:
-1 .
-2
) . ( MnO2
-3 .
223
:
-1 ) ( :

. ) (
:
CH3 CH = CH2 + H2
pt
CH3 CH2 CH3

30 / .
-2 :

:
CCl
CH3 CH = CH - CH3 + Br2 CH3 CH - CH CH3
4
| |
Br Br
2 3.2

.
) ( CCl4 / Br2
) (
.
224
-3 :

.

) ( Carbocation
) ( Carbonium
.
HI , HBr , HCl , HF

.

.

.
HX

: ( X )-
225
CH2 = CH2 + HCl
CH2 CH2
| |
H Cl

) ( HCl
) (
:
CH3 CH = CH2 + HCl

CH3 CH - CH2 + CH3 CH - CH2
| | | |
Cl H H Cl
-2 -1

-2 HI -2
-2 -2- :
CH3 CH3
| |
CH3 C = CH2 + HI CH3 C - CH3
|
I
-2 ) ( -2 -2-

" "

.
226
:

(

)

( HX
)
) (

) ( X-
.
CH3 CH2 CH = CH2 + HBr
Br
CH3 CH2 CH CH2
| |
Br H
-1 -2

.
:
- ) ( HX
.
-

.
227
-2 :

:
CH3CH CH3
CH3CH = CH2 HBr
HBr
CH3 CH - CH2
<#4
| | |
Br H Br
-2 -1
) ( ) (

.
. HBr

.
-3 :

:
+
CH2 = CH2 + H2O
H
CH3 CH2OH

+
CH3 CH = CH2 + H2O
H
CH3 CHCH3
|
OH
2
228
CH3 CH3
| | +
CH3 - C = CH2 + H2O CH3 - C - CH3
H
|
OH
-4 :

:
CH2 = CH2 + H2SO4

CH3 - CH2
|
OSO3H

H 2O
CH3 CH2OH + H2 SO4

.
CH3CH = CH2 CH3CH - CH3 H
H 2SO 4
O
CH3CHCH3 2

| |
OSO3H OH
-5 :

.
CH2 = CH2 + 3O2
2CO2 + CO2 + H2O H = - 322

229

.
.
.
- :

.
3CH3CH=CH2 + 2KMnO4
3CH3CH-CH2 + 2MnO2 + 2KOH
| |
OH OH
2.1

) . ( MnO2
- :

:
+
CH3 CH = CH2 + KMnO4
H
3 CH3 CHO + HCHO

+
2CH3 COO
CH3CH = CHCH3 KMnO 2CH3COOH
-4H

230

CH3
|
+

CH3CH = CCH3 KMnO CH3COOH +CH3COCH3
/H 4
<

. 1
CO2
:
CH3 CH3 O
| | ||
<CH3CH2C=CH2 1)KMnO4 ,OH
CH3CH2C=O + HCH
2) H+ ][O
CO2 + H2O HCOOH

<
- :

:
RCH = CH2 + O2
Ag
RCH CH2
O
CH3CH = CH2 + O2
Ag
CH3 CH CH2
231
O
- :

) ( :
CH3 CH3 O
| | ||
CH3C = CHCH3 + O3
Zn
CH3 C = O + CH3 C H
H 2O

CH3 CH2 CHO , CH3 CHO
2 . CH3 CH2 CH = CH CH3
-6 :
)
( HOX
:
| |
C = C + Br2 H
O
CC
2
| |
Br OH
232

CH3 CH3
| |
CH3 C = CH2 + Br2 H
O
CH3 - C - CH2
2
| |
OH Br
-7 :

.
CH3CH2CH2CH=CH2 Al
( CH3CH2CH=CHCH3
) SO 2 4 3
200 300o
:
.

) ( Monomes
) . ( Polymers
233
" "
(1 :
- 3,2 - 2 .
- 3 - 2 .
4 - . - 2 2 .
- 4,3 3 .
(2 :
3 . - .
3,3 - 1 .
- 5,2 - 3 .
(3 :
- . - .
- . - . - .
(4
) ( HX :
2 - . 1 - .
1 - 2 .
2 - 2 .
3 - 2 .
2 - 4 .
3 - 3,2 .
234
(5 :
. CCl4 / Cl2 - . Ni / H2 -
. H2 SO4 - / HBr - . . HBr -
- . . H / H2 O -
- /. - .
(6 :
2 - . 2 - .
2 - 2 . 2 - 1 .
3.2 - 1 . 3 - 1 .
4,4,2 - 2 .
(7 /
:
4 - . - .
2 - . - .
235
237
238

CnH2n-2
. . HC CH
:
) (1 :

.
:

HC CH
CH3-C CH
1 CH3 CH2 C CH
2 CH3-C CCH3
1 CH3 CH2-CH2 C CH
2 CH3 CH2 C CCH3
CH3
4 2 CH3 C C - C - CH3
H
3 ClCH2 C CH
1 2 CH3 C CCH2Cl
239
) (2 :

) ( ) ( yne

.
.
:

.

3000 2800 :
2 CH CH
/ 4CO2 , H = - 620
5O 2

:
CaCO3
CaO + CO2

CaO + 3C

CaC2 + CO
o
2500
240
HC CH + Ca(OH)2
CaC2 + 2H2O

:
HC = C + 3 H2
o
2CH4
1500
6CH4 + 6O2
2HC CH + 2CO + 10H2
o
600

.
25
300
.

.
. :
HC CH
2C + H2
:
:
-1 :

241

:
R - C CH + NaNH2
R - C C - Na + NH3

:
RC CCH2CH3 + NaBr
RC CNa + CH3CH2Br

.
-2 :

HX .
H H H H
| | | |
RCCR
RC CR
2 NaNH 2
RCCR
NaNH 2
| | | |
X X X X
KOH NaNH2
RCH=CH
CH3CH2C CH
CH3CH2CHCH2
2 NaNH
| |
-2,1 Br Br 1
242
CH3 - CHCl2
HC CH
2 KOH
CH2 - CH2
2 KOH
| |
Cl Cl
-3 :

.
Br Br
| |
RC CR + 2 Zn Br
R - C - C R + 2 Zn
| |
Br Br
- :

:
R COOK R COO-
C C
|| || + 2K+
C C
R COOK R COO-
RC CR + 2CO2 + 2 KOH + H2
:

C5 C18 .
.
243

:

0.618 - 83 - 82 HC CH
0.671 - 23 - 102 CH3 C CH
0.668 9 - 122 CH C - CH2 CH3 1
0.694 24 - 27 CH3 C CCH3 2
0.695 39 - 90 C CCH2 CH2 CH3 1
:

.
:

.
) (1 ) ( :

:
244
CCH
CH3C 3

CH3CH=CHCH3
H 2

CH3CH2CH2 CH3
H 2
Pt Pt
2 2 -

.

.
CH3 C CCH3
H2 Na / NH3
Pd
CH3 CH3 H CH2

C=C C=C
H H CH3 H

:
CH3C C(CH2)2CH = CHCH3 Na
/ NH
3
CH3 CH3 = CH(CH2)2 CH = CH CH3
) (2 :

CCl4 :
245
R Br BrBr
| |
R - C C - R + Br2
C=C
CCl 4
R - C - C - R
Br 2
CCl 2
| |
Br R Br Br
.
CH3 Br
CH3 C C - R + Br2 CCl 4
C=C

Br2
CCl 4
Br H
Br Br
| |
CH3 - C - C - H
| |
Br Br

.

) ( :
CH2 = CH - CH2 C CH Br2
CH2 - CH CH2 C CH
| |
Br Br
) (3 :

) ( HX
:
H H X R
| |
R - C C - R + HX

C=C R - C - C - R

HX
| |
R X H X
HX: HCl, HBr
246

.
) (4 :

) ( HOCl ) ( HOBr
:
OH O
| ||
CH + 2HOCl
HC H O
HC - CHCl2
H - C - CHCl2 2
|
OH

OH O
| ||
CH+2HOBr
CH3C H O
CH2C - CHBr2
CH3CCHBr2 2
|
OH
1.1
) (5 :

) ( .
247
.
.
.
H O-H O
| | ||
+
HC CH + H2O

H
H-C = C-H
CH3C - H
Hg + +
O-H H O
| | ||
+
CH3C CH + H2O

H-C = C-H
H
CH3C - CH3
Hg + +

) (6 :

:
HCCH+ Cu2Cl2 + 2NH4OH
CuCCCu + 2NH4Cl + 2NH3
) (
HCCH+2AgNO3 + 2NH4OH
AgCCAg + 2NH4NO3 + 2H2O
) (

.
2 : ) ( .
248
) (7 :

:
O O O
|| ||
RC CR
RC

O 3
CR
RCCR + H2O2
H O 2
| |
O O
RCOOH + RCOOH
O O
|| ||
HC CH + O3
H - C - C H
H O 2
2HCOOH
H O 2
O O
|| ||
CH+O3
CH3C CH3 C C H
H O 2

H O 2
CH3COOH + HCOOH
) (8 :

:
R - C CH
RCOOH + CO2
] 4[ O
R - C C - R

] 4[ O
RCOOH + R COOH
249
CH3 C CH
CH3 COOH + CO2
] 4[ O
CH CH + 4[O]
(COOH)2
) (9 :

1
2 : ) ( :
CH3 CH2 C CH
CH3 - C C - CH3
KOH
1 2
:

:
HCN,CuCl /NH4Cl CH2 = CHCN

CH3 CH2 OH CH2 = CH-O CH2 CH3
KOH, " ##
HC CH
CH3 COOH CH2 = CH- OCOCH
HgSO4 , 75 & "
CH2 Cl2/ NH4 Cl CH2 = CH- C CH

"(' & (' HCl
)* ' ) ) / ( , -
CH2 = CH - C = CH2
|
Cl
250

:
HC
HC CH
|||

P
HC CH
HC
CH3
3CH3 C CH

P
CH3 CH3
5,3,1
) (

(1

(2
(3

* (4

* (5

* .
251
" "
(1 . C6H10
-
-
. Cu (NH3)2
- ) (
.
(2 :
- . 1 - 2 .
1 - . 2 - .
1.1 - . - .
(3 ) ( 1
/ :
- / .
- / .
- / .
- .
- .
- / .
- .
252
- .
- .
- .
- / / .
(4 .
253
255
256

: :

) F
Cl Br ( I R - X
.

:
H X
| |
RCH2 - X R-C-R R-C-R
| |
X R

= R
.

:
Cl
|
CH3 CH CH3 - CH
| | |
Cl Cl Cl
257

.
:
:

: . CH3 Br
:

.

CH3 Br
CH3 CH2 Cl
2 CH3 CHI CH3
2.1 CH2 Br CH2 Br
2.1 CH3 CH Br CH2 Br
:
:
258
-1 :

400
:
CH4 + Cl2
hv
CH3Cl + CH2Cl2 + CHCl3 + CCl4

.
:
CH3CH2CH2CH3
hv
CH3CH2CHCH + CH3CH2CH2CH2Cl
| |
Cl Cl
2 1
-2 :

) ( HCl , HBr , HI
HBr
.
CH3 CH = CH2 + HI
CH3 CHI CH3
3 (CH3)2 C ClCH2 CH3

(CH3)2C=CHCH3 + HCl
|
Cl
259
CH3 CH = CH2
HBr HBr
CH3 CH2 CH2 Br CH3 CHBr CH3
1 2
-3 :

:
R - OH + HX R - X + H2 O

HX : HI , HBr , HCl / Zn Cl2

HCl

:
CH3 CH2 OH + HI
CH3 CH2 I + H2O

CH3CH2CH2CH2OH + HBr
CH3CH2CH2CH2Br + H2O
1 1
CH3CH2CH2OH2 + HCl/Zn Cl2

CH3CH2Cl + H2O
1 1
(CH3)3 COH + HCl (CH3)3 CCl

o
25
260
:
:
HI > HBr > HCl : HF .
"
"

:
CH3
|
(CH3)3 C - OH + HCl
CH3 - C - CH2 CH3 + H2O
|
Cl
X
2 -2-
CH3
|
CH3 - C - CH2 Cl 1 2- - 2
|
CH3
) (
:
261
CH3 CH3
| |

CH3 - C - CH2 CH3
CH3 CH - CH - CH3 HCl
| |
OH Cl
X
CH3
|
CH3 - C - CH CH3
| |
H Cl ) (
-4 :

:
3 CH3 CH2 OH + PX3
3 CH3 CH2 X + H3 PO3
CH3 CH2 OH + PX5
CH3 CH2 X + POX3 + HX
PX3 = PCl3 , PBr3 , PI3 PX5 = PCl5 , PBr5 , PI5
CH3 CH2 OH + PCl5

CH3 CH2 Cl + POCl3 + H2O

3 CH3 CH2 OH + PBr3

3 CH3 CH2 Br + H3 PO3

.
2 P + 3 Br2
2 PBr3
262
-5 :

:
R - OH + SOCl2
) R - Cl + HCl (g) + CO2 (g
CH3 CH2 OH + SOCl2
CH3 CH2 Cl + HCl + SO2
) (1 :
) (
:
Cl
|
CH3 CHO + PCl5
CH3 - C - H + POCl3
|
Cl
1.1
O Cl
|| |
CH3 - C - CH3 + PCl5
CH3 - C - CH3 + POCl3
|
Cl
2.2
) (2 :

:
263
CH3C CH + HBr
CH3C=CH2 HBr
CH3C(Br)2CH3
|
Br
:
:
) (1 :
CH3 CH - CH2
CH3 CH = CH2 + Br2 CCl 4
| |
Br Br
) (2 :
OH Br
CH2 CH2
| + 2PBr3
| + 2H3 PO3
CH2 CH2
OH Br
:

.

:
R I > RBr > RCl > RF

.
264

.

:
85 32 56 188 .
.
:

.
:
R R
R C
X CH
X R CH2 X
R R
+ -
CH3 CH2 . Cl

.
265

:
R - X + Nu -
R - Nu + X

.
. RI > R Br > R Cl :
:

.

:

Cl : Cl

-
-

CH2 = CH - Cl : CH2 - CH = Cl

NaOH : NaOCH3
NaCN . NH3
.
266
:
) (1 :

:
-
R - HO + HX
R - X + H2O OH
CH3 CH2- I
CH3 CH2 OH + HI
CH2 Cl + NaOH CH2 OH + HCl

. SN2
: < < .

.
:
CH3 CH Cl2 2 CH3 CH (OH)2

KOH
CH3 CHO
H O 2
O
||
CH3CBr2CH3 2 CH3C(OH)2CH3

KOH
CH3 CCH3
H O 2
267

:
Cl ONa OH
| | |
+
350

o
+ 2NaOH
H

283
Cl OH
| NO2 | NO2
130 + 2NaHCO3
o

Cl OH
| NO2 | NO2
) 100( + 2NaHCO3
o

| |
NO2 NO2
Cl OH
NO2 | NO2 NO2 | NO2
) ( + 2NaHCO3
o
35
| |
NO2 NO2
268
) (2 :

:
R - OH + Na
RONa + H2

2CH3 CH2 OH + 2Na

2CH3 CH2 ONa + H2

O
2CH3 CH2 ONa + CH3 Br
CH3 CH2 CH3 + NaBr

OH ONa O
| |

+ NaOH
+ CH3 Br
CH3
) (3 :

:
R - NH2 + HX
R - X + NH3

269
CH3 CH2 NH2 + HBr
CH3 CH2 Br + NH3

CH3 CH2 NH2 CH
( CH3 CH2 )2 NH CH
CH Br 3 2

CH Br 3 2

+
( CH3 CH2 )4 N Br
CH 3 CH 2 Br
( CH3 CH2 )3 N

) (4 :

:
R - X + NaCN
R - CN + NaX
CH3 CH2 Br + NaCN
CH3 CH2 CN + NaBr

:
H + , H 2O CH3 . CH2 . COOH

CH3 . CH2CN
H2
CH3 . CH2 . CH2 . NH2
270
) (5 :

.
) ( KSH
) ( K2S :
S
CH3CH2I K
CH3CH2SH KHS S CH3CH2 2
CH3CH2

) (6 :
CCH3
CH3 Br + NaC CCH3 + NaBr
CH3 C
2
:
) ( XY
.
:

.
) ( HX :
271
CH3 CH2 Br + KOH
CH2 = CH2 + KBr + H2O

CH3CHBrCH3 + KOH
CH3CH = CH2 + KBr + H2O

CH3CHCH2CH3 KOH CH3CH=CHCH3+CH2=CHCH2CH3

|
Br
! 2 ! 1
) ( %80 ) ( %20
:

LiAIH4
:
CH3 CH2 CH2 I + H2
Ni
CH3 CH2 CH3

4 CH3CH2Br + LiAIH4
4CH3CH3 + LiBr + AlBr3
:

:
272
CH3 CH2 I + Mg
CH3 CH2 Mg I
) (

CO2
.
Cl MgCl
| |
+ Mg

:

:
CH3
|

+ CH3 Cl AlCl 3
CH2 CH3

+ CH3 CH2 Br AlBr 3
273
: :
:

I, Br, Cl, F = X, ArX Ar
- .
:
Cl Br I COOH
Cl
NO2 OH
-

274
:

:

:
ArH + X2
ArX + HX
X2 = Cl2, Br2
= FeCl3, AlCl3, Tl(OAc)3,
275

.

.
.
ClO3F
:
:

.
) . ( I-
276

) (
I- I-3
ArN2+I-3
. ArI
ArN2+BF4- heat
ArN2+X- HBF 4
ArF + BF3 + N2

. HBF4

.
:

.
277

:
H3CO-, Cl-, R-

CH2OCH3, - COOCH3, - COOH
:
CH3 CH3
Tl
( OOCCF 3 )3

Kl

I

COOH COOH
Tl
( OOCCF
3 )3

Kl
I
:

.

.
278
:

.

.

.

) ( sp2
279

) . ( sp3

) ( sp2
) . ( sp2 :
Cl
CH2 = CHCl
CH2Cl
CH2 = CH - CH2 Cl

) 1 ( 2
) ( 5 4 3

:
280
.. .. .. .. ..
: Cl : : Cl : Cl : Cl : Cl :
| | || H || H ||

H

1 2 3 4 5
) ( 6

2 ) ( 7
) . ( 5 4 3
2 1 2 1
H H H H

H : C :: C : Cl : H : C : C :: Cl :

6 7
7 5 4 3

.

). (89
CH2Cl CH2Cl
| |
281
8 9

.

sp3 .
sp2

.

C Cl
1.69 C Cl
1.80 1.77 C Br
1.86 C Br
1.92 1.91 .
:

.

.
Br MgBr

Mg

(

282
2,1

.

.

.
NH2, OH, COOH SO3H
.
)
( CN
NO2
.
:

C N , N H3 , R , H ,

:
283
Cl OH
8
2
%
o

6 NaOH , 350 , 4500 lb / in .
o
350 - 4500 /
Cl OH
%
15
o
NaOH , 160
NO2 NO2

Cl NO2 OH NO2
2

o
Na 2CO 3 , 130
o
.0 130 /
NO2 NO2
4 2 4 2
O2N Cl NO2 OH NO2

34

O2 N
NO2 NO2
-6 4 2 -6 4 2

6 4 2

.
284

OH

)(

) ( )( .
Cl NH2
)(
2
NH
3
, Cu 2O , 200 , 900 lb in .
Cl NO2 NH2 NO2

)(
o
NH
3
, 170
NO2 NO2
O2N Cl NO2 O2N OCH3 NO2

)(
o
NaOCH
3
, 20
NO2 NO2

) COR, - CHO, - COOH, - SO3H, - CN, N+(CH3

.

) ( .
285
" "
(1 :
. BrCH2 CH2 CH2 CH2 Br -.(CH3)3 CH CH2 CH2 Cl -
(2 :
1 - 2 .
4 - 4 2 .
2,1 - 3 .
- . - .
- . - .
(3 ) ( -1
:
- . - .
286
- . - .
- . - . - / .
(4 -1
. 1 - . :
- . - .
(5
.
(6 :
- . . - .
- . - .
(7 :
- .
2 1 .
- 2,1 1 .
- .
- .
- 2,2 .
- ) ( .
(8 :
- . . - .
287
(9 :
a. C6 H5 CH2 Br + NaOCH2 CH3

b. HO - - CH2 OH + HBr

c. CH3 CH2 Cl + CH3 C C Na

d. CH3 CH2 Br + CH3 NH2

e. C6 H5 CH Br CH3 + KOH

Br
f.
+ H2O OH

!g. CH2 = CH - CH3 + HBr 56
h. C6 H5 CH2 OH + SOCl2

i. C6 H5 CH3 + Cl2
hv

j. CH3 CH Cl CH (CH3)2 + KOH

k. (CH3)2 C = CH CH3 + Cl2 CCl 4
l. HC CH + 2Cl2

(10

.
- .
- .
2 - 2 . - .
- . 4 2 - .
- . - .
288
(11
:
- + .
- + ) ( .
- + Br2
.
- K+N(C2H5)2 + .
- + .
(12 4 2
. .
- . - .
- .
(13
.
(14 :
- 6 2
.
-

.
(15

289

.

)
( . .
(16

.
- .
- .
- .
- .
(17
.
-
.
-
.
(18

.
290
4 2 - . - .
- . 4 3 - .
- .
(19 ) ( .
-
340 ) (
:
%51 - %49 +
250
.

-
/ ) (CH3CN
%20 10 %70 m-HOOC C6H4 CH2CN
2 : 1
.
291
293
294

) (

.
) (OH
R - OH :
CH3 CH2 - OH CH3 - OH

:
:
-2 . -1 .
-1 :

:
- .
- .
- : .
295
H H H
| | |
RCR RCR RCR
| | |
OH OH OH

. Sp3

Sp3

.
Sp
.
) (OH Sp3 )(S

105

.

.
.
296
:
OH
|
CH3OH CH3 CH2 OH CH3 CH CH3

" "
)
(

" " " "
.
:

65
.
297

CH3 OH
CH3 CH2 OH
1 CH3 CH2 CH2 OH
2 CH3 CH(OH) CH3
# 1 # CH3 CH2 CH2CH2 OH
CH3 CH2 CH CH3
# 2 # |
OH
2 2 # - (CH3)3 C - OH
2 1 # (CH3)2 CH CH2 OH
2' 1 CH2 = CH - CH2 OH
OH
*) ( *) (
OH Br
2 4)
*) *
Cl
CH2 CH2
2,1 )* )' | |
OH OH
CH2 CH CH2
3,2,1 # ) | | |
OH OH OH
OH
|
CH3 CH2 - CH = CH - C - CH3
3* ' 2
CH2OH OH
3 OH
CH2 = CH - OH 2,1 -*) *

298

.

.

C4 C1
C10 H21 OH
.

:

CH3 CH2 OH + H+
CH3 CH2 O H2

:
2 CH3 CH2 OH + 2 Na
CH3CH2ONa + H2
299
>
= < 6 6 6
*
100/ ): 7
65 -97
78 -114
97 -126 1
82 -88 2
7.9 117 -90 # 1
12.5 99 -114 # 2
82 25 2 2
-108 108 108 2 1
161 136 24 *) (
- 140 *) *
2.4 138 -78 ( 1
0.6 156 -52 1*
197 -16 )* )'
290 18 )
:
:
.
250

:
300
) ( C + H2O
CO + H2
o
1300
300
300 ) (ZnO/CrO3
65 :
C
CH3 OH
ZnO / CrO 3
H 2 / 300 o

) ( 1 : 9
250 :
2CH4 + 2 O2
Cu
2 CH3 OH
,P
) 15 (

.

.

.
:

301

% 15 12 : CO2

C6 H12 O6 2CH3 CH2 OH + 2CO2
I

.
:

CH2 = CH2
CH3 - CH2 - OSO3 H
H 2SO 4
3
H2 O
H2SO4 + CH3 CH2 OH
302
:
% 95 % 5

) ( % 99 95

:
CH3CH2OH + H2O + CaO

CH3CH2OH + Ca (OH)2

:

:
-1 :

.
CH3.Cl + NaOH

CH3.OH + NaCl
-2 :

) . ( THF )
303
( ) (

:
CH3 CH2 CH = CH2 + CH3 - CH2 CH CH2 +

) Hg ( AcO 2
THF H O 2
| |
1 OH HgAcO
NaBH4 / OH
CH3 CH2CH CH3

|
2 OH
-3 :
-4 :
)
( ) ( LiAlH4 ) ( NaBH4
:
CH3 CHO + H2
Ni
CH3 CH2 OH

CH3 COCH3 + H CH3 CH CH3Ni

|
OH
304

.
NaBH4 CH3.CH = CH - CH2.OH
CH3.CH = CH - CHO
H2 / Ni CH3.CH2.CH2 CH2 - OH
-5 :

) (
:
O O- MgX OH
| | | +
R - C H + RMgX

R - C - R
R - C - H

H
| |
R H
+ Mg (OH) X

:
OH
|
HCHO + RMgX

H - C - H
H O 2
+
H
|
R
305
OH
|
CH3 CHO + RMgX

CH3 - C - H
H O 2
+
H
|
R
O OH
|| |
CH3 - C - CH3 + RMgX

CH3 - C - CH3
H O2
+
H
|
R
-6 :
) ( NaNO2 + HCl
:
N
RCH2N=NOH
RCH2NH2 + HONO
RCH2NOH
o
OC 2
R R
| |
R - CH NH2 + HONO
R - CH OH
R3 C NH2 + HONO
R3 C - OH
-7 :

) ( RONa
) ( LiAlH4 ) ( NaBH4
:
306
O
||
R - C - Cl
RCH2OH + HCl
4H
O O
|| ||
R-C-O-C-R
2RCH2OH + H2O
8H
O
||
R - C - OR
RCH2OH + R OH
4H
O
||
R C H
LiAlH
4
RCH2OH

O
R-C-R
NaBH

4
R - CH - R
|
OH
:
:
-1 .
-2 .
-1 :
- :

:
307
2R - OH + 2 Na
2RONa + H2
2CH3 CH2 OH + 2 Na
2CH3 CH2 ONa + H2

. .

) ( +I

.
- :
)
( :
O O
|| ||
R- OH + R - C - Cl
R - C - OR+ HCl

308
O O
|| ||
C - Cl C- OCH2 CH3
CH3 CH2 OH + L'

O O O
|| || ||
CH3CH2OH+CH3C-O-CCH
CH3COCH2CH3+CH3COOH

-2 :

180 170
:
CH3 CH2 OH + H2 SO4
CH2 = CH2 + H2O
o
180
CH3CH2CH2CH+H2SO4
CH3CH=CHCH3+CH2=CHCH2CH3
|
OH
-1
OH

+ 85 % H3PO4 + H2 O
- :
:
R - OH + HX
R - X + H2 O
309
- :
R - OH + PBr3
R - Br + P (OH)3
R - OH + SOCl3
R - Cl + SO2 + HCl
- :

HCl
:
O
H+ ||
R - OH + R COOH RC - OR + H2O
O
H + ||
CH3 CH2 OH + CH3 COOH CH3 C OCH2 CH3 + H2O

:

:
O
||
] [O
RCH2 OH
R C H
Na Cr O 2 2

7
R COOH
H+
310

O
||
] [O ] [O
CH3 CH2 OH
CH3 CH
CH3 COOH

.

.
:

.

.
O
||
] [O
CH3 - CH - CH3
CH3 - C - CH3
|
OH

:
.

.
311
:

) 300 (
:
O
||
CH3 CH2 OH

Cu
o
CH3 CH + H2
300

O
||
CH3 C CH3

Cu
CH3 C CH3 + H2

|
OH

CH3 CH3
| |
CH3 - C - CH3

Cu
CH3 - C = CH2 + H2

|
OH

:
- :

) 2.1
( :
312
CH2 - CH2
| |
OH OH

) 197 (

.

. ) ( %50
34 .
.

.
:
+

CH2 = CH2

O2
CH2 - CH2

CH2 - CH2
H
Ag H 2O
| |
O OH OH
- :

:
CH2 - CH - CH2
| | |
OH OH OH

290 .
313

.
:
O
||
CH2 O - C - R CH2 - OH
O
||
CH O - C - R

3 NaOH
CH2 - OH + 3RCOO Na+
H 2O

CH2 O - C - R CH2 OH
||
O

:
o
CH3 - CH = CH2 + Cl2

600
CH2 - CH = CH2
|
Cl
NaOH
+
CH2 CH CH2

HO Cl
CH - CH = CH2
| | | |
HO OH Cl OH

NaOH CH2 - CH - CH2

| | |
314
OH OH OH

.
:
CH2 - OH CH2 - ONO2

| +
|
CH - OH + 3HNO3

H
CH - ONO2
| |
CH2 - OH CH2 - ONO2

.
.

.
.
.
315
:

) ( :
316
:

) 25 ( )
HCl (

(

)

:
( CH3 )3 C - OH + ZnCl2 / HCl2

( CH3 )3 C - Cl

( CH3 )2 CH - OH + ZnCl2 / HCl2

( CH3 )2 CH - Cl

:
H
|
R - C - CH3
|
OH

:
H
|
R - C - CH3
RCOONa + CHI3
NaOI
317
|
OH
:
O
||
1) R - CH - CH3
R - C - CH3
NaOI
:
|
OH
O O
|| ||
2) R - C - CH3 + 3NaOI
R - C - Cl3 :
O
||
3) R - C - CI3 + NaOH
RCOONa + CHI3 :
O
||
R - C CH3
.
:
:
) (1 .
C H2Cl + NaOH

CH2OH + NaCl

318
) (2 .
Br MgBr CH2OH
+ Mg

1 ) HCHO
+

2) H
) (3 :
Br
|| CH2OH
C-H

][H
O OH
|| |
C CH3 C CH3

][H
|
H
-1
319
) ( :

) ( -OH ROH

. ArOH
:
ArOH
Ar-

:
OH OH OH COOH
Cl
NO2 OH
-

320
-
- 6 4 2
:

.

) 9.3 100 / (
.
321

26 43
161 181
3.6 9.3 100 /

18- 10-
10 10 10 Ka
322

:
) (
323
:

.

.

:
A HA

HA H+ + A -
324

:

.
.
) . ( H2CO3
.

:
CO2 + H2O H2CO3 + ArO- Na+
ArOH + Na HCO3
+ -
325

NO2
CH3 .
-1 :

) (

.

:
SO3H
326
1) NaOH
2 )H+

H 2SO 4

OH
Cl2
FeCl3
Cl

NaOH ,
O- Na+

.
.
327
-2 :
- :

N2 OH

OH :
NH2 N2+HSO4- OH
+
H
2SO 4 , NaNO 2

H 2O , H
+ N2
Cl Cl Cl
-

- :

Tl(OOCCF3)3

. Ph3P

.
.
Tl(OOCCF3)2 OOCCF3
328

H 2O , OH

Pb ( OAr )4
Ph 3 P
O OH
+

H

.

.
- :

.
) ( -OH

.
329

:
OH
OH
.
Sp2
Sp3 C-O .

SN2 , SN1
) O-H (
.
: :

] [(CH3)2 SO4
:
RX
330
Ar O R + X-
ArOH
ArO-
OH
(CH3)2 SO4
Ar O CH3 + CH3OSO3-

.

:
331

:
O- + CH3CH2Br

S 2
CH3CH2O
N
+ Br -
CH3CH2O- + Br

:
Cl OCH3
NO2 NO2
+ Na+ -OCH3

NO2 NO2
4 2 4 2
: :

. :
OH COCl

NaOH
OC
||
O

332
O2 N OH + (CH3CO)2O

CH COONa
O2 N 3
OC CH3
||
O

) ( ArCOCl
) ( RCOCl

. Schotten - Baumann

.
.

(

)

) ( .

.

.
O
333
|| O
OH OCC2H5 || OH OH
CC2H5

C 2 H 5COCl

AlCl 3
+
LMN CS 2
CC2H5
||
O

) ( Acylium ion RCO+
.
:

.

)( )( :
334
)( )(
) (

.

) ( )( )( :
)( )(
OH O-

.

. :
OH OH
CH3 Br CH3
+ 2Br2
+ 2HBr
> < Br
6 4 -
2
335
OH OH
Br Br
+ 3Br2
+ 3HBr + H2SO4
> < SO3H Br
6 4 2

:
OH OH OH
Br
Br2 , CS 2 , 0o

+
Br

.

. -
) 100 (

:
336

.

:
OH OH
O2 N NO2

HNO 3
NO2
6 4 2 ) (
OH OH OH
NO2
HNO 3 , 20o

NO2
13% 40%

337

:
OH OH
NaNO

2 , H 2SO 4
o
8 7
NO
% 80
: :

.

-COOH

) 150 ( .
.
338
" "
-1 :
( . ( 4 2 .
( . ( .
( . ( .
( 2 . ( .
-2
:

-3 1000 .

.
4 2
) D 4 2

-4
( .
-5

.
( 3 4 . ( .
( 2 - 4 .
339
( 5 - 2 .
( 4 2 .( .
( . ( .
-6
:
- . - .
- HNO3 . -
- 150 / . - .
125 NaOH, CO2 - 5 .
CHCl3 - 70 .
- H2O, NaOH - . H2SO4
- . H2O, NaOH6
200 Ni , H2 - 20 .
-7
) (C6H5O2N
.
.
-8 C7H8O HCl

.
340

C7H5OBr3
.
-9

:
( 4 2 .
( .
( 4 2 1 .
( 5 3 1 .
-10 :

-1 NaOH + C2H5Br +
HCl + Sn +
. C8H11ON
+ HCl + NaNO2 +
. H14O2N2
.
+ NaOH +
. C8H11ON
SnCl2 +
+
)
( .
-2 NaOH + ClCH2CO2H+
C8H8O3
HCl
). (C8H7O2Cl
SOCl2 +
3 ). (C8H6O2
AlCl3 +
341
343
344

:
O O
|| ||
R-C-H R-C-R

.

.

.
.
345

.
:
:

.

.

.

.
.

.
.

.
346
:

.
) (

1 :

HCHO
CH3 CHO
CH3 CH2 CHO
CH3 CH2 CH2 CHO
) ( Ph CHO
CH3
|
CH3(CH2)2-CH-CH-CHCH2CHO CH3CH-CH2CHO
| | |
Br Cl CH3
5 3 4 3
CHO CHO
CHO | |
OH | |
NO2 OCH3

347
:
" "

) ( R

) ( .

CH3 COCH3
O
||
CH3 C CH2 CH3
O
2 ||
CH3C ( CH2 )2 CH3
O
3 ||
CH3 CH2 CCH2 CH3
PhCOCH3
PhCC h
C6 H10 O
CH3 O
O | ||
|| CH3CH - C - CH2 - CH CH CH3
CH3(CH2)3CCH3 | |
2 Cl Ph
5 2 6 3
348
:
:
-1 :
:
] [O
CH3 CH2 OH
CH3 CHO
) (

K2 Cr2 O7
KMnO4
. CrO / AcOH

.
:
OH O
| ||
] [O
CH3 - CH - CH3
CH3 CCH3

-2 :

300 .
349

o
CH3 CH2 OH + Ag 250
CH3 CHO

O
||

o
300
CH3 CH CH3 + Cu CH3 CCH3
|
OH
CH3 OH + Cu
o

O2
HCHO + H2O
500 600
: -3
OH
+
|++
HC CH + H2O
CH = CH
H , Hg

CH3 CHO
|
H

O
+ ++
||
CH3C CH + H2O

H , Hg

CH3 CCH3

O
+ ++
||
CH + H2O
Ph C
H , Hg

Ph C - CH3
-
: -4
CH3 CH = CH CH3
2CH3 CHO + H2 O2
1) O3
2 ) Zn / H 2O

350
O
||
( CH3 )2C = C(CH3 )2

1) O3
2CH3 C CH3 + H2 O2
2 ) Zn / H 2O

O O
|| ||

1) O3
H - C - ( CH2 )4- C H
2 ) Zn / H 2O

:
-1 :

.
:
O
||
C - Cl CHO
+ H2

Pd / Ba SO 4
+ HCl

-2 :
OH OH
NaOH / H +
+ CHCl3

70o
CHO

351
-3 :
CH3 CH(OCOCH3)2 OH

Ac 2O

H 2O
CH
CrO 3
OH
- H 2O
PhCHO

:
-1 :

O
: ||
R C
O
O ||
|| C CH3
+ CH3 C - Cl

AlCl 3

.
:
O O
|| ||
C CH3 C
+

AlCl 3
352
-2 :
) (
:
O O
|| +
||
R C O R + R Mg X R - C - R + R OH

H
O O
|| ||
+
R - C - R + MgXCl
R - C - Cl + R Mg

H
-3 :
.

:
O
||
++
[ CH3CO O ]2 Ca
2CH3COOH + CaO CH3CCH3
o
300
+ CaCO3

.
:
COO
Ba++

o
300
( CH )4 = O + BaO
COO
+ CO2
353
:

. :
-3 . -2 . -1 .
-5 . -4 .
-7 . -6 .

.

.
O
||
] [O
CH3 C H
CH3 COOH

CHO COOH
] [O

354

.

) ( Ag+ ) ( Cu++
.

Ag (NH3)2+
.

) ( .
+
RCHO + 2Ag(NH3)2++2OH
RCOO H 4 + 2Ag + H2O+ 3NH3

) ( Cu++

:
355
+
RCHO + 2 Cu (OH)2 + OH
RCO O N a + Cu2 O + 3H2O

.
++
CH2(CHOH)4CHO + Cu

CH2(CHOH)4COO+Cu2 O
OH
| |
OH OH
:
.

:
O
||
CH3CH2CH2 - C CH2CH3
CH3-COOHCH3-CH2-COOH CH3-CH2-CH2-COOH

) (O

O
||
+

HNO 3
HOOC ( CH2 )4COOH

) ) ( RCOCH3 (
) ( RCH CH3 ) (
356
OH ) ( CHX3
:
RCOONa++ CHI3 + 3NaI + 3H2O
RCOCH3 + 3I2
4 NaOH
) (

:
CH3 CHO + H2

Ni
CH3 CH2 OH

CH3COCH3 + H2

Ni
CH3 CH - CH3
|
OH
2

LiAlH4 : NaBH4 .
O
||
CH3 CH = CH - C H
1) NaBH4 H2 / Ni
2) H2O
CH3CH = CH - CH2OH CH3CH2CH2CH2OH

-2 1- -1
) ( ) (
357
) ( C = O
) ( CH2 :
- . HCl
-
:
O
||
C CH2 CH2 CH3
NH2NH2 / OH Zn ( Hg ) HCl
CH2 CH2 CH2 CH3

) (
:
O O- OH
|| | |
R - C R - C - Z
: Z R - C Z
H O 2
| | |
R R R
358

:
O + OH OH
|| || ||
R - C - R+ H
R - C - R
R - C - R

ZH
OH OH
| +
|
R - C - R H

R - C - R
| +
|
Z ZH

.
Sp2 Sp3

.
-1 :

:
OH
|
CH3 CHO + H2O
CH3 C - H
|
OH

:
Cl3 CCHO + H2O
Cl3 C CH (OH)2
359
-2 :

) (NaHSO3 :
OH
|
CH3 CHO + NaHSO3 CH3 C - H
|
SO3- Na +
OH
|
CH3 CO CH3 + NaHSO3 CH3 C - H
|
SO3- Na +

.
.
-3 :
)
(
:
OH
| +
H O/
CH3CHO + HCN
CH3 C - H
CH3CHCOOH 2
| |
CN OH

OH OH
| | +
H O/
CH3CHO + HCN
CH3CCH3
CH3-CHCOOH 2
| |
CN CH3
360
) (

.
-4 :
)
(
:
RC CH + NaNH2 RC CNa

CH3
|
RC CNa + CH3 COCH3 RC C C - CH3

|
OH
-5 :
HCl

:
OH OR
+
H | ROH
|
RCHO + ROH
RCH RCH
| |
OR OR

361
O OH OR
+
|| H | ROH
|
R C R + R OH RCH RCH
| |
OR OR

-6 :

:
O OH
| +
|
R C R + RMg X

R C R
|
R
:

" " ) (
:
OH
| -H O 2
CH3CH2CHO+NH3 CH3CH2CNH2 CH3CH2CH=NH

|
362
H

.
:

)
( :
OH
|

2CH3 CHO
CH3-CH CH2 CHO

O
||

CH3 CH CH2 CHO
CH3CH = CH C - H
2
|
OH -2
) (
:
) (

) (
:
363

) ( :
O
||

Ph CHO + CH3 CHO PhCH = CH C H + H2O

60 %

2 Ph CHO
Ph CH2 OH + Ph COOK+

) (

.

:
364
O
||

ArCHO + H CH
ArCH2OH + HCOO Na +

%37
)(HO CH2 OH

CH2
O O
3 HCH O
| |
CH2 CH2
O

:
:
n HO CH2 OH
HO CH2 O -- CH2O -- OCH2OH

= n 10 100

.

:
365
CH3
|
CH
O O
3 CH3CH O
| |
CH CH
O
CH3 CH3

) (
) ( :

CH3 CHO + 2Cl2
CCl3CHO
OH
O O
|| ||
CH3 C CH2Br + HBr
CH3 C CH3 + Br2
OH
:

:
Cl
|
CH3 CHO + PCl 5
CH3 C H + POCl3
|
Cl
O Cl
|| |
CH3 C CH + PCl 5
CH3 C CH3 + POCl3
|
Cl
366
" "
(1
( ( (
( ( 4 (
( -3 -2 ( -2
(
( 3 ( -4 -3 -2- .
(
(2
. - .
- .
- .
- . - / .
- . - .
- / . HCl - .
(3
:
- . - 1 - .
- . 1 - -1 .
-2 - - 3- . - .
(4 :
367
1) (CH3)2 C = CH CH2 CH3 + O3

Zn
H 2O
2) CH3 CH2 C (Cl)2 CH3 + KOHaq

3) C6 H6 + CH3 CH2 COCl

AlCl 3
+
2 /
4) C6 H5 CHO + HCN

5) CH3 CH2 CO C6 H5 + CH3 OH

+

6) C6 H5 CHO + CH3 Mg Br

+

7) C6 H5 CO C6 H5 + CH3 CH2 Mg Br

8) C6 H5 CH2 CHO + Cl2

9) CH3 CH2 CHO + NH2 NH2

)10 =O + NaBH4

H 2O
H+
11) CH3 CHO + 2 CH3 CH2 OH
+

)12 =O + H2O

) 13 =O NH2 CH (CH3)2

(5
:
( . ( .
( . ( .
( -2 . ( .
( . ( -1 1 .
( -1 . ( .
(1.1 . ( -11 .
368
(6
:
( -1 1 ) ( .
) ( . ( -2
( -2 2 ) ( .
( 2 . ( 1 .
( . ( -2 .
( 2 2 .
369
371
372

.

.

. R COOH
:
Monocarboxylic Acids -1
Dicarboxylic Acids -2
Tricarboxylic Acids -3

" "
.
373
) (
2 . :
O
| | | | |
C C C C C OH
| | | | |
5 4 3 2 1

" " :

. :
COOH COOH COOH
OH |
NO2

-2

:

.
374

. .

.
CH3 CH COOH
|
OH
) (
:

.

.
+
HCOONa HCOOH
o
CO2 + Na OH 150 H
P
375
.
.
HCOOH + Ag2O
H2 O + CO2 + 2 Ag

CO2 .
+
+ H2
o
CO 50
HCOOH
H
H2O + CO

:
O
||
HCOOH H C Cl
PCl 3
HCl + CO
:

.
RCOOH + NaOH
RCOONa + H2 O
RCOOH + NaHCO3
RCOONa + H2O + CO2
376

.
O ---- H+
H
O----------- H+ ---- O
CH3 ----C H
O-----H+------------ O-
H
H+
O

) (

.
:
:
RCOOH + H2O RCOO + H 3 O+
. 10-5

:
CH3 CH2 OH CH3 CH2O + H+
377

.

.

x 10-5
) ( ) (
17.7 160 8 HCOOH
1.76 118 16 CH3COOH
1.34 141 -21 CH3CH2COOH
1.54 164 -6 CH3(CH2)2COOH
1.52 5 187 -34
1.31 1 205 -3 CH3(CH2)4COOH
378
6.45 0.3 250 122 C6H5COOH
4.30 0.03 275 180 P-CH3C6COOH

.
COONa
(CH3 CH2 COO-)2Ca+ +
HOOC CH (CH2)2COONa

NH2

.
[CH3 (CH2)9COO]2 Zn+ +

:
-:
-1 :
379
] [O ] [O
CH3 CH2 OH CH3 CHO CH3 COOH

-2 :
CH3 COOH CH(CH3)2

] [O ] [O

][
CH2CH2CH2CH3

66
" " :
] [O
OH HOOC ( CH2 )4 COOH
HNO 3

) (
] [O
CH3 CH3 HOOC COOH
-3 :
380

:
] [O
CH3 CH = CHCH3 2CH3 COOH
2
-2-
:
] [O
(CH3)2 C=CHCH2CH3 CH3COCH3+CH3CH2COOH
COOH
H+

=
+ Cr2 O7 + Cr+++
COOH

-4 :
2CH3 COONa HSO

2CH3 COOH + Na2SO4
2 4
-5 :
381

.
H2 O / H +
RCOOH + NH+4
RCN
NaCN H2 O / H
RCOO Na+ + NH3
RX

. HCl

.

CH2 OH HCl
CH2 Cl NaCN CH2 CN
CH2COOH H 2 O / H+

-6 :
) ( CO2
.
RMgX + CO2
] [ RCOOMgX H

2O
RCOOH
+ Mg ( OH )X
CH3CH2CH2 MgCl
CH3CH2CH2 Cl + Mg CO2
382
+
CH3CH2CH2 COOH
H
CH3CH2CH2 COOMgCl
Br MgBr
+ Mg
CO2
COOH COOMgBr
+

H

-7 :

HCl
:
CH3 COONa + CH3 CH2 OH

CH3 COOCH2 + NaOH

CH3 COONa + HCl

CH3 COOCH2 + NaCl

-8 :
383

.
O
||
CH2 O-C -R
CH2 OH
|
CH O-C R + 3NaOH
CH - OH + 3 RCOO Na
+
|| |
O CH2 OH
CH2 O C R H+
||
O 3RCOOH
:

.

:
CH3 COOH + NaOH
CH3 COONa + H2O

)
( .
:

:
PCl3 PCl5 PCl2
384

COOH COCl
+ SOCl2
+ SO2 + HCl

HCl , SO2
:

:
CH3COOH + NH3 CH3CONH2

CH3COONH4

HCl

.
:
H+
RCOOH + R'OH RCOOR' + H2O

COOH COOCH3
+ CH3 OH + H2O
385

)
( :
'RCOOH + HOOCR
RCOOCOR' + H2O
O O
|| ||
2CH3 COOH
CH3 C O C CH3 + H2O

:

) ( LiAlH4
:
4RCOOH LiAlH
(RCH2O)4 AlLi H
4
O
4RCH2OH+LiOH2
+ Al (OH)3 1

.
386
:

.
CH3 CH2 COOH + Br2 P CH3 CH COOH
|
Br
Cl2 / P
-2
CH3 CH COOH
|
Cl
-2
.

:
NH3
CH3 CH COOH
|
NH2
-2
NaOH
CH3 CH COOH CH3 CH COOH
| |
Br OH
-2
NaCN
CH3 CH COOH
|
CN
-2
387

:
CH3 COOH + Cl2 P CH2 COOH Cl
CHCl2COOH 2
|
CN
Cl2 / P
CCl3 COOH

:
RCOONa NaOH
/ CaO
RH + Na2CO3

) ( :
2RCOONa 2 R R + 2CO2 + 2KOH + H2

H O 2

388

CO2 :
O O O
|| || ||
CH3 C CH3 + CO2
CH3 C CH2 C OH
-3
O
||

CH C COOH

O
||
CH3 C CH2 CH2 COOH

.

.
389
" " " "
.
HOOC-COOH
HOOCH2 COOH
HOOC(CH2)2 COOH
HOOC(CH2)3 COOH
HOOC(CH2)4 COOH
HOOC(CH2)5 COOH
COOH
-21.

COOH
390
COOH
-31.

COOH
COOH
-41.

COOH
-1 :

) ( :
+
CH2COOH HO
ClCH2COOH NaCN CH2(COOH)2
/H 2
|
CN

CN
CH2 Br CH2 +
| 2 |
NaCN
HO HOOC (CH2)2COOH
/H 2
CH2 Br CH2
CN
-2 :
O
||
K HOOC (CH2)4 COOH
2 Cr2 O 2
+

HNO 3
H
391

-3 :

:
OH
CH2
] [O
HOOC COOH
CH
OH
-4 :

) (

.
CO2CH2CH3 COOH
CH2 CH2 +
2 CH2CO2CH2CH3 2

Ag

H

CH2 CH2
Br COOCH2 CH3 COOH

:

.
392
:
:
HOOC COOH HOOC COO + H+

K2
HOOC COO
OOC COO + H+

.
.
:

.

)
( ) (
:
COOH

HCOOH + CO2
COOH

393
COOH
CH2
CH3COOH + CO2
COOH

O
||
C
CH2 COOH CH2

O + H2 O
CH2 COOH CH2
C
||
O
O
||
C
COOH CH2

( CH2 )3
CH2 O
COOH CH2
C
||
O

CO2
:
394
O
||
HOOC ( CH2 )4 COOH + H2O + CO2

)
(
.
HOOC H COOH
C HC
|| ||
C HC
H COOH COOH

) ( Maleic
.
)
) 288 (
130 :
H COOH
CH2 COOH C

||
H O CH COOH C + H2O
H COOH

) 130 (
250
395

.
O
||
C
CH COOH CH H C COOH
|| ||

O +

H 2O
||
CH COOH CH H C COOH
C
||
O

150

O
||
C
O
C
||
O

:
396

6.4 10-5 5.9 10-2 189
2.0 10-6 1.4 10-3 136
2.5 10-6 6.9 10-5 182
3.9 10-6 4.6 10-5 98
2.4 10-6 3.7 10-5 153
3.9 10-6 1.3 10-3 231
2.5 10-5 2.9 10-4 245
1.5 10-5 3.1 10-4
3.6 10-5 9.3 10-4 307
8.6 10-7 1.4 10-2 131
397
" "
(1
3 4 5 .
(2 :
)( . )( -4 -2 .
)( -N,N . )(
)( . )(
)( . )( .
)( . )( .
)( . )( .
)( .
)( -2 - .
(3 :
- . - / .
- H+ / . - .
(4 :
- . - .
- . - .
- . - .
- .
398
(5 :
- . - . - . - .
- . - .
(6 :
- . - .
- . - .
- -2 .
- .
(7 :
1) CH3 COOCH2 CH3 + NH3

2) C6H5CONH2 + NaOH

3) C6H5OH + CH3 COCl Base

4) CH3 COOCOCH3 + CH3 CH2OH

5) C6H5COCl + C6H5NH2

+
6) C6H5MgBr + CO2
H

+
7) CH3 CH2 COOCH3 + H2O
H

8) C6 H5 COOH + NaHCO3 aq.

9) C6 H5CN + H2
Ni

10) C6H5 CH=CH2 KMnO

4
399
(8 ) ( :
- . - .
- .
- .
- .
-2 - -2 .
- .
- .
- -2 .
- ) ( .
- .
400
401
402

.

.

R2NH RNH2 : . R2N

.

) (
.
403
OH OH
| |
HO CHCH2NH2 HO CHCH2NHCH3
HO HO
) ( ) (
:

) ( .
CH3NH2 NHCH3 (CH3CH2)3N

.

:
CH3 CH3

CH3 C OH CH3 C NH2

CH3 CH3

404

.
:
-
) ( Amine Salt :
+
N H3 Cl (CH3)2NH2+ Cl
-
)
(
) ( Quaternary Ammonlum Salt .
+
(CH3)4N+ Cl CH3CO2CH2CH2 N (CH3)3 Cl

) (

N
:
405
CH3 H CH3
| | |
CH3CCH3 CH3CH2NCH3 CH3NCHCH2 CH3
| |
NH2 CH3

CH3
CH3N CH (CH3)2NCHCH3 H2NCH2CH2OH
| CH3 |
H CH3
-2
-N,N -2- -N -2-
-

) . ( Anline
. :
NH2 NH2 CH3
| Br Br
Br NH2
-6 4 2
NHCH3 H N CH3
|
H

N
NO
-N -N-
406
CH3
| N(CH3)2
N C 2 H5 |
-N,N
-N -N
NHCH3

CH3CHCO2H
) 2- (
:
) ( Polar

) ( Intermolecular hydrogen bonda .
N.....HN
O....HO
NH .

.
407

) (

) ( .
NH

.

:
(CH3)3N (CH3)3 CH CH3CH2CH2NH2
3 10 - 48

.
.

.

.
.
408

.

.
.
Preparation of Amines
-1 :
-
:
,
NO2 Fe
HCl %30
CO
NH3+Cl- Na
2 3
NH2

409
-
:

Cl NH
, Cu O , 3 2
NH2
900 o 300

:
NH3 CH
CH3NH2 CH
OH 3
(CH3)2NH CH
OH
(CH3)3N
OH 3 3
Al 2O 3 Al 2O 3 Al 2O 3

:
RCOOH NH
,
RCONH2
3
N
RC H
RCH2NH2 2

-2 :

.
- :

-1 . - :
-3 . -2 .
-
410
)( .

.
.

.
:
CH3 CH3

H3N2 + CH2 Br : S
2 H3N+ CH2 : Br :-
N

CH3CH2NH3+Br + : O H
CH3CH2 N H2+H2 O +Br
-

) ( Amonolysis of halides
.
SN2
CH3X

411

:
CH3 CH3

CH3 C= CH2 + NH4Br
CH3 C CH3 NH 3

Br

:
RX + NH3
RNH3 X
+ -
RNH3+ + NH3 RNH2 + NH4+

RNH2 + RX
R2NH2 X
+ -
R2NH

NH3
R2NH + RX
R3NH X
+ -
R3 N

R3N + RX
R3N X
+ -

412

) (
.

RX . :

CH3CH2CH2CH2Br+NH3 OH
CH3CH2CH2CH2NH2+Br-
%45

:
(CH3CH2)2NH + CH3CH2I
(CH3CH2)4N I
+ -

:
ClCH2CH2Cl 2
CH2=CH2 Cl 2
H2NCH2CH2NH2
NH 2

CH3 Cl 2

CH2Cl NH 2
CH2NH2

413
- NO2

.
-

.
:
) (
. SN2
:
O O
|| ||

NK++CH3CH2Br
NCH2CH3 H
2O, OH

|| ||
O C
-N
CO2-
+ H2NCH2CH3
CO2-
414

:

-
)(BrCH[CO2C2H5]2
- ) ( Imide Malonate

-

:
O O
|| ||
Br
N +BrCH(CO2C2H5)2

NCH(CO2C2H5)2
|| ||
O C
O O
|| ||
OCH
NC(CO2C2H5)2

2 5
N C H(CO2C2H5)2+C2H5OH

|| ||
O O
O O R
|| || |
X
N C H(CO2C2H5)2 +RX
NC(CO2C2H5)2
SN 2
|| ||
O O
415
O R R
|| | | CO2H
H2O, H+
N-C(CO2C2H5)2
H3N CHCO2H+C2H5OH+ +
+CO2

|| CO2H
O
- : Reduction Reactions
-1 : Reduction of Nitro Compounds
ArNO2 ArNH2
H+ : H2 ,

RNO2 RNH2

.
:
: .

:
COOC2H5 COOC2H5
H
2 , Pt
NO2 NH2

416

.
: :

.

:
NO2 NH2
CH3 NO2 (
1 ) Fe , HCl

CH3 NH2
( 2 ) OH
4 2 - 4 3
NH2 NH2
(
1 ) Sn , HCl

( 2 ) OH
NO2 NH2

-2
) (
) (LiAlH4
RCH2NH2 %70 .
417

:

(CH3)2CHCH2CN (
(CH3)2CHCH2Br CN
1 ) LiAH 4
Br ( 2 ) H 2O , H +
1 2 2
(CH3)2CHCH2CH2NH3
) 2 - 1 (
)(RCONH2

. .
:
O
||
CH3(CH2)4CNH2 + 4OH- + Br2 H
O
CH3(CH2)4NH2 +
2
%85
CO32- + 2H2O + 2Br-
. CO32-

.

.
418

2 1
.

.
:
O O O
|| || ||
..
RC N && H + OH RC N H , RC N
Br && H + Br
2
)(
..
| |
H Br
O O
|| ||
..
RC N&& H + OH RC N Br + H2O )(
..
|
Br
O -
||
C
..
R N Br
R N
&& =C=O + Br - )(
..
O
||
)(

RN=C=O RNHCO OH
OH
RNH2 + CO32-
H 2O H 2O
419
:

.

:

.
:

.

:

(CH3)3N: + H O H (CH3)3N+H + : O H

. NH2
420
O O
NH3 + R C
RC
Cl NH2

) ( :
O O

NH3 + Ar S Cl
Ar S NH2

O O

.
.

)
(
:
RNH2 R

'COCl
R'CONHR

R2NH R

'COCl
R'CONR2

R3 N R

'COCl

421

.
:
H
|

1 RNH2 Cl
SO
R N SO2
C H 2 6 5
OH

OH H 2O

+
R N SO2
H
RNH SO2

2 R2NH SO
Cl 2

R2 N SO2
C6 H 5
OH

3 R3N Cl
SO [ R3N SO2
C H 2 +

6 5
R3N +
]Cl OH
OH
-
OSO2

Cl
H+
R3N+ + HOSO2

422

:
CH3 CH3
| |
CH3CNHC2H5 CH3CH2CNCH3 CN C2H5
|| || ||
O O O
-N N,N -N -N

NHCCH3 NHC
|| ||
O O

) (

.
.

:

.

.
:
423
NH2 NHCOCH3 NHCOCH3
(C C )

3 2

ClS 3

SO2Cl

NHCOCH3 NH2
NH3 2

+

H
NHCOCH3 SO2NH2 SO2NH2

SO2Cl NHCOCH3 NH2

RNH3
2
+

H
SO2NHR SO2NHR

) (

:

.
.

) (ArN2+Cl- .
424

) RN2+Cl-
:
NH2 + NaNO2 + HCl N+N Cl- + H2O

o

N2

. I -

.

. N2
:
NaNO 2 N2
Cl
(CH3)2CHNH3 (CH3)2CH N2 Cl
HCl

+
0o
) (
[(CH3)2CH+] H
O
(CH3)2CHOH + CH3CH= CH2
2

- N :
. N-N=O
:
425

NHCH3 NaNO 2
N NO + H2 O
HCl
|
N CH3
-N N

.

.

NR2 :
HCl , 0 10
NANO
2 , (CH3)2N
o
(CH3)2N N=O
N,N N,N

N .
: HO-
426
NO2 NO2
+
N2+ Cl HO
,H 2
o
OH
100

H3PO2
NH2 .

H3PO2 :
N2+ Cl- H
3 PO 2
H
0 25
o
427
" "
-1 :
( (
( (
( (
-2 :
( .
( .
( .
-3
:
(
(
( ) ( HOCH2CH2NH2
-3 -1
-4
:
( -N N
(
(
( -1 -1
( -2 -4
428
( 6 2
( -N N -
-5 (CH3)3+NCH2CH2OH
.
.
-6
:
( -N N ( -N
( -2 -3 (
( ( ) -4 4 (
-7 1
:
( 1 .
( .
( NaOH .
-8
:
( -N + .
( + .
( ) Br2 + ( .
( . HCl + NaNO2 +
( NaCN + .
429
-9 P-CH3.C6H5.N2+HSO4
:
( . ( .
( . ( .
( ). (OH-
( -N N .
-10

.
( 4 3 .
( -5 3 .
( -3 4 .
( 4 2 .
( .
-11

:
- 1 - 2 - 1 - 3
- 1 - 2 .

.
430
-12
:
)(C6H5CH2CH CO2H (
|
NH2
)(CH3)2 CH CH2 CH CO2 H (

|
NH2
.
-13

NH O NH
431
433
434

:

.
) ( R C = O
.
.
O O
|| ||
R C OR R C Cl

O
||
R C OH

O O O
|| || ||
R C NH2 R C O C R

.

.
435
: :

.
:

PCl3 : PCl5-
SOCl2 :
O
||
R COOH + PCl5
R C Cl + POCl3 + HCl
O
||
R COOH + SOCl2
R C Cl + HCl + SO2

.
) ( HCl,SO2
.

.
436
:

. :
O O O O O
|| || || || ||
R C Cl > RCOCR > R COR > R C NH2
:

.

:
437
O O O
|| || O ||
CH3 C Cl + NaOOCCH3
CH3 C C CH3

O
O ||
|| C CH3

+ CH C Cl AlCl 3
+ HCl
,
.
:
438
:

.
:

) ( :
RCOCl + CH2 N2 H

2O
RCH2 COOH
: :

.
:
:
-1 :

:
O O O O
|| || || O ||
R C OH+H O C R
R C C R + H2 O
439

. CO
-2 :
)
( ) (
.
O O O O
|| || || O ||
CH3CCl + NaOCCH3
CH3C CCH3 + NaCl

-3 :

) ( :
440
:
O
||
CH3 COOH CH2 = C = O
CH3 C CH3
o
AlPO 750
4
o
500
O O
|| O ||
CH2 = C = O + CH3 COOH
CH3 C C CH3
-2
:
O O
|| O ||
CH+CH3COOH
HC CH3C CCH3+CH3CHO

139
%12 .
441

.
.
:

:
442
: :

O
||
'R C O R

.
.

.
:
:
-1 :

. :
H+
RCOOH + R'OH RCOOR' + H2O
CH3 COOH + CH3 CH2 OH CH3 COOCH2 CH3 + H2O

443
COOH COO CH3
H+
+ CH3 OH + H2O

.
) ( O18
HCl

. :
COOH COO18CH3 + H2O

H+
+ H O18 CH3
-2 :
RCOOAg + R' Br
R COOR' + AgBr
-3 :
RCOOH RCOOCH3 + N2

+ CH2 N2

444
-4 :

:
CH3COCl + CH3CH2OH
CH3COOCH2 CH3 + HCl

CH3COCl + OH
CH3 COO + HCl

O O
|| ||
CH3OH + CH3 C O C CH3
CH3 COOCH3 + CH3COOH

-1 :

) ( :

RCOOH + ( CH3 )2 SO4 NaOH RCOOCH3
RCOOCH2 CH3
RCOOH + ( CH3 CH2 )2 SO4 NaOH
:
-1 :
- :
. :
H+
CH3 COOCH2 CH3 + H2O CH3 COOH + CH3 CH2OH
445
- :
RCOOR' + NaOH
RCOO N a+ + R'OH
H+
RCOOH
-2 :
:
CH3 COO CH2 CH3 + NH3
CH3 CONH2 + CH3 CH2 OH

:
RCOOR' + NH2CH3
RCONH CH3 + R'OH
RCOOR' + NH (CH3)2
RCON(CH3)2 + R'OH
CH3 COO CH2 CH3 + NH2 NH2

CH3 CONHNH2

446
-3 :

:
) RCOOR + 4( H
RCH2OH + R OH
COOH3 CH2OH
) + 4( H
+ CH3OH
-4 :

:
O O
|| ||
CH3COCH2CH3 + H CH2COOCH3 NaOET
CH3CCH2COOCH2CH3

: :

.
O
|| H
RCN
H

447

.
O O
|| H || R
RCN RCN
'R 'R
.
:
HC ONH2
CH3 CONH2
CH3 CH2 CONH2
C6 H5 CONH2
CH3
N,N HCON
)(DMF CH3
-N NO2 CONHCH3
CH3 CH2 CH CONH2

-2
CH3
CH3
-N N CH3 CON
H
:

448

.
:

:
(1

CH3 COONH4 CH CH3 CONH2 + H2O
COOH 3

(2
:
CH COCl + 2NH3
CH3 CONH2 + NH4Cl
O O
|| ||
CH3 C O C CH3 + 2NH3
CH3 CONH2 + CH3COONH4
CH3 COOCH3 + NH3

CH3 CONH2 + CH3 OH
449
:
-1 :
H+ RCOOH + NH4+
RCONH2 + H2O
H
RCOONa + NH3
-2 :

.
RCONH2 4
LiAlH RCH2 NH2 + H2O
-3 :

:
CH3 CONH2 P

2O 5
CH3 C N + H2O

-4 :

:
RCONH2 + O = N OH
RCOOH + N2 + H2O
450
-5 :

.
CONH2 NH2
Br
2 /
NaOH
+ Na2 CO3 + 2NaBr + H2O
) ( NaOBr
: :

) ( :
Cl

CH2 COOH CH COOH CH2 CH2 COOH

Cl Cl Br
2,2 3

:

.

:
FCH2 COOH > Cl CH2 COOH > Br CH2 COOH > I CH2 COOH
451
:
X3C COOH > X2 CH COOH > X CH2 COOH > CH3 COOH

.

.
:

. :
) (1 :
Cl
|
CH2COOH CH2COOH CHCOOH
Cl 2 Cl 2
CCl3COOH
hv
| |
Cl Cl
) (2 :
452

) ( HBR )
( :
CH2 = CH COOH
CH2 CH2 COOH
HBr

Br

) (3 :
CH3CHCOCl H
CH3CHCOOH+2PCl5
2O
CH3CH COOH

OH Cl Cl
-2
:

) ( -COOH

.
453

. -OH, -NH2, -CN :
:
) (1 :
CH2COOH+ NaOH
CH2 COOH
CH2COONa HCl

Cl OH OH

CH2CH2COOH+KOH

CH2CH2COOH CH2=CH COOH
OH2

Cl OH
: :

:
CH2 CH2 COOH CH3 CH COOH CH3 COOH

OH OH OH

454

:

.
) (1
:
CH2 COOH H
O
2
CH2 COOH

OH OH
) (2 ) ( NaNO2 / HCl
CH2 COOH
CH2COOH + HNO2

N
CH2 COOH + N2
2
N = N OH
NH2 OH

.
) (3 :
O
||
H C COOH + 2 H
CH2 COOH
|
OH
O
||
CH3 C COOH + 2 H CH3 CH COOH
455
|
OH
:
:
CH2 CH2 COOH
CH2 = CH COOH
H 2O

OH ) (
) (1 :
R CH COOH + NaOH
R CH COONa + H2O

OH OH
) (2 :
H+
R CH COOH + R'OH R CH COOR' + H2O

OH OH
) (3 :
R CH COOH + NH3
R CH COONH4

H O 2
456
OH OH RCHCONH2

OH
) (4 :
R CH COOH + CH3 COOH

OH
R CH COOH

O C CH3
||
O
) (5 :
R CH COOH + HCl
R CH COOH

OH Cl
) (6 :
R CH COOH + 2Na
R CH COONa

OH ONa
) (7 :
O O
|| ||
] [O ] [O
CH2 COOH H C COOH COH

OH COH
||
457
O

O
||
] [O
CH3 CH COOH CH3 C COOH

OH
: :

.
.
:
-1 :
.
-2 :
:
CH2 (CH2)2 CH COOH

NH2 NH2 Lysine
-3 :
:
HOOC CH2 CH COOH

NH2
) (
458
:

) ( )(

.
:
:
NH2CH2 COOH + CH3COCl
NH CH2 COOH

COCH3
459
:
NH2CH2 COOH + Ph COCl
NH CH2 COOH

COPh
) (2
:
NH2CHRCOOR NH2CHR COOH NH2CHR COONa

R OH NaOH
HCl 2
PCl5 ) (

) (
HCl . NH2 CHR COCl

) (4 :
:
CH2 CH COOH
CH2 = CH COOH
NH 3

NH2 H
460
" "
-1 .
-2 :
-
-
-3 .
-4 .
-5 .
-6 .
-7 .
-8 :
- .
- .
- .
-9 .
-10 .
-11 :
- .
- .
- .
461
-12
.
-13 .
-14 .
-15 :
- .
- .
-16 .
-17 .
462
463
464

.
) (
.
) (

.
CO2
.

Cx(H2O)y
. Cx(H2O)y
465

.
Simple Sugars -
- Poly Saccharides

. .

.
.
:
:
- - -

) ( D

.
466

:
) (1 Trisaccharides :
3 ) (
Raffinose
.
Poly Saccharides

.
) (2 : Disaccharides :

Lactose Glucose
. Galactose ) ( Maltose
) . ( Glucose
) (3 Monosaccharides :

) ( OH
.
467

) ( .
Aldose
Ketose
. Ose

) . ( Ose
3 .
3 Trtroses
) 4 ( 5 ) Pentoses ( Hexoses
) 6 ( 7 ) Heptoses ( .

Ketotetrose Aldotetrose
. Ketohexose Aldohexose Ketopentoses Aldopentose
:

. Geometrical and optical isomerism
468

Assymmetric
.

Hexoses Pentoses Tetroses Trioses

) 6 ( ) 5 ( ) 4 ( ) 3 (

CHO CHO CHO CHO

CHOH CHOH CHOH CHOH
CH2OH
Aldoses
CHOH CHOH CHOH
)

CHOH CHOH CH2OH (

CHOH CH2OH

CH2OH
CH2OH CH2OH CH2OH CH2OH

C = O C = O C = O C = O

Ketoes
CHOH CHOH CHOH CH2OH
)

CHOH CHOH CH2OH (

CHOH CH2OH

CH2OH
:

:
469
(1 .
(2 .
(3 .
Open chain -
Ring chain -
Branched Chain -
Unbranched Chain -
-
-
: Glucose
Dexreose

) ( .
:
-

. C6H12O6
- ) (

) (
.
470

.
-
Acetic Anhydride Acetic Chloride
Acetate
Franchimont

OH

.CH(OH)2

.

. Gluaric
-

Hydroiodic
2-Iodohexane .
471
Aldose Aldhexose

. Polyhydroxy aldyhde
:

) ( Enantiomorphs
:
)(1 )(2 )(3
CHO CN COOH
| | |
CHOH CHOH CHOH
| | |
CHOH CHOH CHOH
| | |

CHOH HCH
CHOH

CHOH
| | |
CHOH CHOH CHOH
| | |
| CHOH CHOH
| | |
CH2OH CH2OH CH2OH
Glucose P/H I
COOH
|
CH2
|
CH2
|
CH2
|
CH2
|
CH2
|
)CH3 (4
Heptanoic
472
CH2OH CH2OH CH2OH
| | |
CO C (OH) CN C (OH)CO2H
| | |
CHOH CHOH CHOH
| | |
CHOH HCH
CHOH

CHOH
| | |
CHOH CHOH CHOH
| | |
CH2OH CH2OH CH2OH (3)
(1) (2)
P/HI
CH3
|
CH.CO2H
|
CH2
|
CH2
|
CH2
|
CH3 (4)
2- methythexanoic
* "!#

+, . $0 $%

1 2 1 Aldotriose
Aldotetrose
2 4 2 Keto pentose
Aldo pentose
4 8 3 Ketohexosls
8 16 4 Aldohexoses
473
) ( Arabinose
3 4, 3, 2 8
8 = 22 D . L
L D .
3
8 ) ( 8 = 22
.
D . L
CH2OH CH2OH CH2OH

| | |
C=O C=O C=O
| | |
H C OH HO C H H C OH
| | |
HO C H H C OH H C OH
| | |
H C OH H C OH H C OH
| | |
CH2OH CH2OH CH2OH
D- Sorbose D- Fructose D- Psicose
CH2OH CH2OH CH2OH

| | |
C=O C=O C=O
| | |
HO C H H C OH HO C H
| | |
H C OH H C OH HO C H
| | |
HO C H HO C H H C OH
| | |
CH2OH CH2OH CH2OH
L- Sorbose L- Tagatose D- Tagatose
474
CH2OH CH2OH
| |
C=O C=O
| |
HO C H H C OH
| |
HO C H HO C H
| |
HO C H HO C H
| |
CH2OH CH2OH
L- Psicose L- Fructose
H C=O H C=O H C=O

| | |
HO C H H C OH O CH
| | |
| | |
| | |
CH2OH CH2OH CH2OH
D- arabinose D- ribose L- ribose
H C=O H C=O
| |
HO C H H C OH
| |
H C OH H C OH
| |
HO C H HO C H
| |
CH2OH CH2OH
D- Lyxose D- xylose
C OH H C=O
| |
H C OH HO C H
| |
H C OH H C OH
| |
HO C H HO C H
| |
CH2OH CH2OH
L- lyxose L- xylose
475
:
Dectro Levo
Levo Dectro
.
H C=O H C=O
| |
H C OH HO C H
| |
HO C H H C OH
| |
H C OH HO C H
| |
H C OH HO C H
| |
CH2OH CH2OH
Dectro Levo
D L .
H C=O H C=O
| |
HO C H HO C H
| |
CH2OH CH2OH

L- Glyceric Aldehyde, D 5
D L- Glucose
Aldo . L- Glyceric Aldehyde
476
L
L- Glyceric Aldehyde
Hexoses , Pentoses , Tetroses
Cyanhydrin Glycerde Aldehyde . L,D
CN CN
| |
H C = O + HCN
H C OH + HO C H
| | |
R R R
HCN D- Glyceric Aldehyde

Cyanhydrins
HC=O CN CN
| | |
H C OH + HCN
H C OH + HO C H
| | |
CH2OH H C OH H C OH
| |
CH2OH CH2OH
Cyanhydrins
COOH COOH
| |
H C OH HO C H
| |
H C OH H C OH
| |
CH2OH CH2OH

) Aldotetroses (
H C=O H C=O
| |
H C OH HO C H
| |
H C OH H C OH
| |
CH2OH CH2OH
477
) ( D- Erythrose HCN
) Pentoses ( .
H C=O H C=O
| |
HO C H H C OH
| |
H C OH H C OH
| |
H C OH H C OH
| |
CH2OH CH2OH
D- AEABINOSE D- RIBOSE
D-Threose

H C=O H C=O
| |
HO C H H C OH
| |
HO C H HO C H
| |
H C OH H C OH
| |
CH2OH CH2OH
D- LYXOSE D- XYLOSE

8
) D- Hexoses ( .
L- Glyceric
Cyanohydrin
) . ( D- Glyceric Aldehyde
OH
. D- Sugar
478
D OH
L- Glyceric Aldehyde
) L- Sugar . ( L
:

C6H12O6 16 .
CHO CHO CHO

| | |
H C OH HO CH H C OH
| | |
HO CH HO CH HO CH
| | |
H C OH H C OH HO CH
| | |
| | |
CH2OH CH2OH CH2OH

479
:

.

.

) (

) -
( .
480

.
$%
9
" 2 $%
56
" 2
@A
$ ;#
$ < ;#
$%
G;" 56DE $%
BC 56
" " Levo
$%
" 56 DE
Dextro
481

:
Monochromatic
) ( Nicol

.
:
.
:

.
482

:
- .
- ) (
.

:
100O N
= [ ] T
$K $B ) C x (
D
] = [ ) ( T T
D :
) ( D 546
[a ] T546 20
.
.
O100 N
=C
[ ] TD
D
Levo L
Dextro
.
483
D Dextro
) (d ) (+
) (l ) .. (- )L (-) D (-) D (+
. L (+) .
CHO COOH COOH
| | |
| | |
CH2OH CH2OH CH2OH
:

:
-

.
- .
- CHO CH2OH
.
CHO CHO CHO CHO

Idose Galactose Talose
484
COOH COOH COOH
COOH COOH COOH

Levo tartaric Dextro tartaric Meso tartaric
l tartaric d tartaric m tartaric
D tartaric L tartaric

CHO
CH2OH
CHO CHO CHO CHO

D- Ribose D- Arabinose D- Xylose D- Lyxose
485
CHO CHO CHO CHO

Allose Altrose Glucose Mannose
:

HCL
+159 -34
. Glucoside , Methyl D-glucoside Methyl B-D-

.

.
486

Ketoses
D- Glucose
) ( +112

. +52.5

98c +19 +52.5
-D-glucose, -D-glucose
" " .
D glucose +52.5 -D-glucose
-D-glucose D-glucose -D-glucose

+19 +112

.
487
-D-Fructose D-Fructose -D-Fructo-furanose
-D-Fructopyranose
Anomers
" " .
Osazones
.
:
Methylation :

) ( HCl
Methyl -D-Glucoside . Methyl -D-Glucoside
488
) (1
Hemiacetal
.
) (1 Schiff
.
) (2 Mutarotation
+112 +52
.
:

.
- :
) (1

Hydrazones . Osazones
489
. H2N NH C6 H 5
H2O .
H C=O H C = N - NHC6H5
| |
H C OH H C OH
| |
HO C H HO C H
| |
H C OH H C OH
| |
H C OH H C OH
| |
CH2OH CH2OH
D- Glucose D- Glocose Phenythydrazone
2 H2N NHC6H5

H C = N NHC6H5
|
C = N NHC6H5
|
HO C H
|
H C OH
|
C6H5NH2 . NH3 . CH2OH
Osazones Hydrazones
.
H C = N NHC6H5
|
C = N NHC6H5
|
HO C H
|
H C OH
|
H C OH
|
CH2OH
D- Fructose Phenylosazones
490
Osazones Osones
.
H C = N NHC6H5 - HC=O
| . 2H2O

HCL
|
C = N NHC6H5 C=O
| |
R R
.
2C6H5NH NH2
Osazone Osone

Osazone Phenyl Hydraine
1 2 :
491
) (2 :
Aldose Ketoses

.
Aldose

D- Glucose ) . ( D- Sorbitol
Galactose Dulcitol
Mannose D- Mannitol D-
Fructose D- Sorbitol . D- Mannitol

) ( -Ose ) ( itol
) . ( Hexitol
. Pentitol
Sodium
Amalgam .
) (3 :

Lime Water

.
492

) ( Lobry Debruyn Alberda Van Ekenstein

D- Fructose D- Mannose D- Glucose
.
D- Mannose D- Fructose

) ( 1 2 Enediol
Mannose
. Fructose
NaOH% 0.04 D-
) Fructose ( 30% ) ( 1%
D- Allulose . 2,3 Enediol
493
) (4 :
HCN
) ( Asymmetric
Cyanohydrin
CH
|
H C = O . HCN
H C OH
| |
R R

CN
|

HO C H
|
R
COOH COOH
| |
H C OH HO C H
| |
R R

HC = O HC = O
| |
HO C H + H C OH
| |
R R
) (5 :

) ( Oximes
494
H C=O
|
H C OH
|
HO C H
|
H C OH + H2N OH
|
H C OH
|
CH2OH
D- glucose
H C = N OH
|
H C OH
|
HO C H + H 2O
|
H C OH
|
H C OH
|
CH2OH
D- glucose oxime
) (6 :
- :

Aldonic

.
Aldose
Aldonic :
495
Br2 + HOH
HOBr + HBr
Gluconic
Galactonic Mannoic
Mannose Galactose Arabinose
Arabonic .
H CO COOH
| |
H C OH H C OH
| |
HO C H + HOBr
HO CH
| | + HBr
H C OH H C OH
| |
H C OH H C OH
| |
CH2OH CH2OH
D- glucose D- gluconic
- :
Aldoses Aldonic
:
I2 + 2NaOH NaOI + NaI + H2O

R HO + NaOI + NaOH
R COONa + NaI + H2O
( Gluconic ) Aldonic
Lactone
496
.
.

. Fe+++ CO2
.
COOH
|
H C OH
|
HO C H CHO
| |
H C OH + H2O2 Fe+++ HO C H + CO2 + 2H2O
| |
H C OH H C OH
| |
CH2OH CH2OH
D- gluconic D- arabinose
- :

Methyl D Glucoside
497
2 3
3 4 C2
.
- :
)
Aldose
) ( 50%
Aldaric Saccharic
COOH COOH
| |
H C OH HO CH
| |
HO CH HO CH
| |
H C OH H C OH
| |
H C OH H C OH
| |
COOH COOH
D- glucaric D- mannaric
D- glucosaccharic D- mannosaccharic
COOH
|
H C OH
|
HO CH
|
HO CH
|
H C OH
|
COOH
D- galactosaccharic
) D- galactaric ( music
498
Saccharic glucosaccharic

aric Glucaric Arabaric,
Xylaric
- :

. 1.2 O Isoproy Lidene D Glucose
Isopropy lidene
D glucuronic
499
" "
-1 .
-2 .
-3 .
-4 .
-5 .
-6 .
-7 .
-8 .
.
-9 .
-10 .
-11 .
-12 .
-13 .
500
501
502

:

) . ( Carbocyclic
.

.
:

) ( Cyclo
.

.
:
503
H2 H2 H2
C C C
H2C CH2 H 2C CH2 H 2C CH2
| | | |
H2C CH2 H2C CH2 H2C CH2 H 2C CH2
C
H2

:
H2 H2
CC H2
H 2C CH H2C CH C
| || || | H 2C CH
H 2C CH H2C CH
HC = CH H2C CH
12
H2 H2
C C
CH CH HC CH
|| ||
HC CH HC CH
HC CH

CO
,HO CO2H .
H2 H2
CHOH C C
H 2C C=O H 2C CHCO2H
H2C CH2 | |
H2C CH2 H 2C CH2
C
H2

504

:
CH3
O O
H 3C
CH3
O O
CH3
13 -4 4 3 2
13
-
.
-

) ( :

505

.

.

) 4 4 ( . ) 4 4 (
.
) ( 1 2 2 ) ( 2 2 2

) ( 1 2 2 ) 3 5 (

. :
506
7 8
1 1
6 2 2
7
3
4 5
5 3 6 4
C C
|| + :C | C
C C

) ( :CH2
CH2N2 :
CH2 = N = N
hv
CH2: + N2

:
507
t-BuO- + CHCl3
BuOH + C Cl3
C Cl3
:CCl2 + Cl

n-BuLi +CH2Cl2
C4H10 +LiCHCl2
:CHCl + LiCl,
Br3C.CO2Na C Br3 + CO2 + Na+
:CBr2 + NaBr
PhHgCBr3 Ph HgBr + :CBr2
) ( :CBr2
) ( Triplet
) . ( Singlet

.

.
) ( :CBr2

:
508
) ( :CBr2

) ( Insertion C H
:
- : Wurtz Reaction

3 1

:
509
CH2 Cl CH2 ZnX CH2
CH2 H2C
Zn , NaI

| H2C
CH2 Cl CH2 X CH2
3 1

] [Spiropentane
:
Br CH2 CH2 Br =CH2
C + 2Zn
+
Br CH2 CH2 Br

: Simmons Smith reaction

. .

.
:
510
:

.

4 1
.
- : Cycloaddition of olefins

.
:
- ) ( .
-
. ) ( CH2 = C = O
511

.

) ( -1 1 2 2
. .
) (
4 1
) ( ) ( .
CF2 CF2 )(
2 CF2 = CF2
| |
CF2 CF2
CF2 CCl4 )(
2 CF2 = CCl

| |
CF2 CCl2
O
||
Me Me Me
2 C=C=O
)(
Me Me Me
||
O

)(
)(
.
512
CF2 = CF2 CF2 CF2 )(

| |
CH2 = CH2 CH2 CH2
CH2
||
C )(
||
O O

:
Br MgBr
Mg
H

2O

O
||

hv
+ CO

=O

NH2 NH2 KOH
513

.
- : Diekman Reaction
- : The Acyloin Reaction
OEt
CO2Et C
O
(H2C)n 2 2

Na
(H2C)n 2
OEt
O
CO2Et C
OEt
C=O CO C=O
514
(H2C)n2 2

Na
(H2C)n 2 HOAc
(H2C)n 2
C=O CO CHOH
:

.
Ru

:
H
2 , Ni
150 o150
CO2H CO2H

Ru

H2
OH OH

Birch reduction
4 1
. :
1
H H 6 R 2 R
5515 3
4
| | H

Na
Na
H
NH 3 NH 3
H |
H H H
. 4 1
OMe OMe

Li / NH 3

.
3 1 .

|| +

:

.
516

.

80
180 .

300

.
517

:

109.5

60
. 90

) 109.5 (
60 90
.

.
.

) 49.5 ( 19.5

.
518

.
:
-

) 100 - 80 (
. :
H2 C
| CH2 Ni
o, H
2,
CH2CH2CH2
A
H2C | |
H H
- :

3 1
.
. AlBr3
FeCl3, AlCl3
:
H2 C
| CH2 + X2 3
FeCl CH2CH2CH2
AlX 3
519
H2 C | |
X X

R

.

.
:
Me
||
+ Cl2 Al
Cl 3 CH3CH CH2CH2
| |
Cl Cl
- :
H X
:
+ HX
CH2CH2 CH2
| |
H X

.
520

HBr 2 1 1 .
Me
| + Cl
H Br Al CH3CH-CH2CH3
3
|
Br
CH3
|
Me Me + HBr
Br CCH(CH3)2
Me H |
CH3
HBr

DBr HBr

.
521
" "
-1
:
( 3 (
( 3 1
-2
.
.
-3

( 12 ( 2 1 .
.
-4
.
( 2 1 .
( - 2 1 .
( - 3 1 .
( - 3 1 .
( - 4 1 .
( - 4 1 .
-5 :
522
( . ( .
( .
( .
-6
.
( 2 .
( 2 .
( 3 .
( 3 .
-7 ( :CCl2 .

( :CBrCl

.
-8
:
( 1 1
) ( . SN2
( . SN1
( 2 1
.
523
524
525
526

Epichlorohydrin.
Atropine
Dimethyl ether
Methyl ethyl ether
Ethers
Ethylamine
Ethylbenzene
Ethylene
Reduction
Dicarboxylic acids
Carboxylic acids
Chlorobenzoic acids
Nucleic acids
Congo red
Baeyer test
Tollen's test.
527
Clemmensen reduction
Adenine
Arynes
Arginine
Coupling
Diazo coupling
Aspirin
Chromate esters
Esterification
Fischer esterification
Octyl acetate
Methyl acetate
Copper acetylides
Carbon black
Ethyl acetate
Ammonium acetate
528
Vinyl acetate
Acetaldehyde
Acetamide
Acetanilide
Acetophenone
Acetone
Acetylides
Acetylene
Acylation
Radiation
Dyes,
Direct dyes
Acridine
Acrilan
Acrylonitrile
Oxidation
529
Ethylene oxide
Amino acids.
Fatty acids,
Alanyl glycine
Ammonolysis
Aromatization
Altrose
Cracking
Aldrin
Aldehydes
Aldoses
Aldol
Resonance
Bonds
Alkanes
Cycloalkanes
530
Alkynes
Electrophoresis
Electrophiles
Alkylation
Alkoxides
Alkenes,
Cyclic anhydrides
Allose
Allenes
Amides
Amylose
Amines.
Aminopeptidase,
Dehydrohalogenation
Anthracene
Indole
531
Indigo
Enzymes
Insulin
Conjugated systems
Acetic anhydride
Benzoic anhydride
Succinic anhydride
Phthalic anhydride
Maleic anhydride
Acid anhydrides
Anomers
Anethole
Anisole
Aniline
Oximes
Olefins.
532
Epoxides
Ethylene glycol
Geometric isomerism
Stereoisomerism
Constitutional isomerism
Structural isomerism
Optical isomerism
Enol
Iodoform, test .
Benzenonium ions.
Carbonium ions
Paraffins
Paraldehyde
Poptides
Propylene
Propionaldehyde
533
Proteins
Bromoethane
Bromobenzene
Butanoyl bromide
Polymerization
Pentene
Benzaldehyde
Benzamide
Benzyne
Benzophenone
Benzonitrile
Benzoin
Benzidine
Penicillin
Polyesters
Polyamides
534
Pyroxylin
Pyrrole
Pyrrolidine
Pyridine
Butane
Butyronitrile
Biuret
Tetracyclin
Ozonization
Spectroscopy
Williamson synthesis
Fermentation
Dipolar structures
Meso structures
Trioxane
Mutarotation
535
Cope rearrangement
Hofmann rearrangement
Denaturation
Diels-Alder reaction -
Sandmeycr reaction
Wurtz reaction
Haloform reaction
Displacement reactions
Substitution reactions
Addition reactions
Elimination reactions
Friedel-Crafts reaction
Nucleophilic reactions
Dissociation
Aldol condensation
Claisen condensation
536
Pollution
Symmetry
Metabolism
coordinate covalent
Tautomerism
Terramycin
Terpenes
Tiflon
Trimethlamine.
Diethyl ether
Diamines
Diphenyl amine
Dimethylamine
Thiols
Gasoline
Dissymetric molecules
537
Galactose
Glycylglycine
Glycine
Glucose
Glyoxal
Guanidine
Fused rings
n-Caproic acid -
Adipic acid
Aspartic acid
Acetoacetic acid
Acetic acid
Oxalic acid
Capric acid
Indoleacetic acid
Palmitic acid
538
Pantothenic acid
Propionic acid
Picric acid
Benzoic acid
Benzenesulfonic acid
Pyruvic acid
Butanoic acid,
Tartaric acid
leriphthalic acid
Glutaric acid
Glutamic acid
Gluconic acid
Glycolic acid
DNA
Salicylic acid
Citric acid.
Stearic acid
539
Succininc acid
Toluic acid
Valeric acid
Phthalic acid
Formic acid
Fumaric acid
Copramic acid
Crotonic acid
Chromic acid
Chloroacetic acid
Chlorobutyric acid
Lactic acid
Laurie acid
Lewis acid
Malonic acid
Malic acid
540
Hexanoic acid
Dimerization
Dienes
Dieldrin
Derlin
Diazotization
Fats
Specific rotation
Decalin.
Asymmetric carbon atoms
Carbon tetrachloride
Phenol-formaldehyde resins
Epoxy resins
Octane numbers
Iodine number
Coordinate covalent bonds
541
Resorcinol
Palm oil
Olive oil
Oils
Drying oils
Methyl salicylate
Styrene
Stearine
Cysteine
Reducing sugars
Sucrose
Monosaccharides
Oligosaccharides
Disaccharides
Polysaccharides
Homologous series
542
Sulfanilamide
Sulfonation
Sorbitol
Cyanohydrins
Cyanides
Citronellol
Cellobiose
Cellophane
Cellulose
Cinnamaldehyde
Methyl radical
Free radicals
Waxes
Soaps
Azo dyes
Structural formulas
543
resonance energy
Paints
Toluene
Natural gas
Mustard gas ( )
Valine
Vanillin
Vinylacetylene
Fructose
Freons
Fluoroalkanes
Formaldehyde
Formalin,
Formamide
Fuchsin
Vitamins
544
Sodium phenoxide
Phenols
Phenyl acetate
Markownikoffs rule
Coal tar
Alkaloids
Schiffs bases
Caprolactam
Catechol
Caryophylene
Camphor
Ethyl hydrogen sulfate
Ethyl alcohol
Wood alcohol,
Allyl alcohol
Isobutyl alcohol
545
Crotyl alcohol
Lauryl alcohol
Absolute alcohol
Carbanions
Carboxamide
Carbohydrates
Crotonaldehyde
Cresol
Chloral
Chloroethane
Chlorobenzene
Acetyl chloride
Benzal chloride
Benzoyl chloride
Vinyl chloride
Grignard reagents
546
Coenzymes
Codeine
Cocaine
Collodion
Coumarin
Ketones
Chitin
Quinolinc
Quinine
Cubane
Cumene
Lactose
Lactides
Lysine
Urea-formaldehyde plastics
Lipids
547
Lignin
Diamond
Maltose
Mannose
Methyl phenyl ketone,
Aryl groups
Alkoxy groups
Functional groups
Acetyl group
Acyl group
Benzoyl group
Carboxyl group
Carbonyl group
Methyl group
Benedict's solution
Fehlings solution
548
Azo compounds
Amphoteric compounds
Diazonium compounds
Halogen compounds
Antibiotics
Rubber
Flavors ( )
Natural products
Menthol
Detergents
Dextrorotatory substances .
Morphine
Methane
Methanol
Sodium methoxide
Nylon
549
Nitriles
Starch
Ammonia
Optical activity
Naphthalene
Nitration ( )
Nitromethane
Nicotine
Aryl halides
Acid halides
Heptane
Hydrogenation
Thyrotropin-rcleasing hormone, (TRH)
Hexane
Gels
Halogenation
Chloral hydrate
550
Hydrazones
Hydrazine
Hydration of alkenes
Cyclic hydrocarbons
Hydroxlamine
Hydroquinone
Hemiacetals
Hemiketals
Methylmagnesium iodide
Urea
Uridine
551
552
553
554

) ( 1
CCl4

CHCl3
CHI3

CF3CH Cl Br
CF2Cl2.CClF3

CH3Cl

CH3Br

CH3CH2Cl
[CF2-CF2]n

555
) ( 1
[CH2-CCl2]n

ClCOCl
ClCH2CH2SC
H2CH2Cl

PHCOCH2Cl

CH2 = CHCl
PVC
Cl2C = CCl2

..
556
) ( 2

557
) ( 3
558
) ( 4

559
) ( 5
560
) ( 5
561
) ( 6
562
) ( 6
563
) ( 7
) ( 8 Ketoses , Aldose
564
) ( 9 Ketoses , Aldose
565
) ( 10

100/
4-
104.5 6.3- 92-
5.4 7.5 69-
0.6 91 3 17-
5.1 17 80-
4.1 49 83-
4.8 78 50-
3.0 68 85-
4.0 63 104-
5.0 46 67-
0.2 185 -
10-
104.2 3.7 184 6-
7.1 196 57-
0.0006 302 53-
2.6 1.7 200 28-

5.0 203 30-
12.0 0.7 200 44
566
) ( 11

- - - - - - 132 45-
- - - - - - 156 31-
- - - - - - 189 31-
116 - 115 111- 115 - - - , +
162 8 162 48- 159 34- - - +
185 28 184 40- 182 26- - - +
89 13- 83 59- 92 34- - - , ./
178 52 173 24- 180 17- - - ./
219 87 217 7- 221 6 - - ./
285 129 285 35 287 27 - - ./
) ( 12 C-C2
569
570

" -1 " . .
. .1978 -
" -2 " . .
. 1979 -
" -3 " . .
. 1980 -
" -4 " .
. . . 1980
" -5 " . .
) 1990 ( .
" -6 " . .
. 1991
" -7 " . .
. . 1992
" -8 " .
. 1993 -
571
" -9 " .
. 1995 -
" -10 " . .

. . - .1996
" -11 " . -

. 1996 -
" -12 " . .

. 1997
" -13 " . .

.
. 1997 -
" -14 " . .

. 2003
" -15 " . -

. 2005 -
" -16 " .

. 2009 -
" -17 " .

. 2009 -
572
18- " Introduction to Organic Chemistry " Streitwieser, A.Jr
and Heathcock, C. (2004) Macmillan Publishing Co.Inc,
U.S.A .
19- " Organic Chemistry" Wingrove, A.S and Caret, R.L.

(2005) Harper and Row, U.S.A .
20- " Introduction of Organic Chemistry " Brown, W.H

(2006) Willard Grant Press, U.S.A.
21- " Elements of Organic Chemistry " Zimmerman , H. and

Zimmerman , I ,(2007) Benziges Bruce and Glenco Inc.
U.S.A.
22- " Organic Chemistry " Morrison, R.T and Boyd, R.V
(2008) Allyn and Bacon Inc. U.S.A.
573

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.

) (SP ) (S) (Px

C 1S 2S 2Px 2Py 2Pz

CH3Cl + Cl2 "6

(CH3)3 C OH >" "! +9,+

NH2 CH2CH2CH2 NH2

CH2CH2Br CH2CH2 OEt

)(4 CH3CCH2X + :B CH3CCH2X+ H:B

RCH(COOC2H5)2 +Na+ -OC2H5 RC(COOC2H5)2-Na++C2H5OH

)( (CH3)3 CCOCH3 )( CH3CH2CHO

CH3 CH3 CH3 CH3

CH3 CH3 CH3 CH3

CH3 CH3 CH3 CH3

CH3 CH3 CH3 CH3

CH3 CH CH CH3 CH3 CH CH CH2 CH3

CH3 CH CH CH2 CH CH3

+$ 06 % 5 01 01 +

CH3 COOH + HI P CH3 CH3 + I2 + H2O

CH2 CH2 COO- Ca

CH2 CH2 COOH

CH2 = CH2 CH3 CH3 CH = CH2

CH3 CH2 CH - CH2 CH = CH2 CH3 CH C = CH2

CH2 COOK :05<.

CH3 CH = CH2 + HCl

CH2 = CH2 + H2SO4

CH3 CH2OH + H2 SO4

CO2 + H2O HCOOH

0.671 - 23 - 102 CH3 C CH

0.668 9 - 122 CH C - CH2 CH3 1

0.694 24 - 27 CH3 C CCH3 2

0.695 39 - 90 C CCH2 CH2 CH3 1

CH3 CH3 H CH2

CH3 CH3 = CH(CH2)2 CH = CH CH3

HCN,CuCl /NH4Cl CH2 = CHCN

CH2 Cl2/ NH4 Cl CH2 = CH- C CH

3 (CH3)2 C ClCH2 CH3

CH3CH2CH2OH2 + HCl/Zn Cl2

(CH3)3 COH + HCl (CH3)3 CCl

PX3 = PCl3 , PBr3 , PI3 PX5 = PCl5 , PBr5 , PI5

CH3 CH2 OH + PCl5

3 CH3 CH2 OH + PBr3

CH2 Cl + NaOH CH2 OH + HCl

CH3 CH Cl2 2 CH3 CH (OH)2

2CH3 CH2 OH + 2Na

O2N Cl NO2 OH NO2

Cl NO2 NH2 NO2

O2N Cl NO2 O2N OCH3 NO2

. BrCH2 CH2 CH2 CH2 Br -.(CH3)3 CH CH2 CH2 Cl -

c. CH3 CH2 Cl + CH3 C C Na

j. CH3 CH Cl CH (CH3)2 + KOH

CH3 CH2 - OH CH3 - OH

) (OH Sp3 )(S

CH3 CH2 CH = CH2 + CH3 - CH2 CH CH2 +

CH3 CH2CH CH3

NaOH CH2 - CH - CH2

CH2 - OH CH2 - ONO2

( CH3 )3 C - OH + ZnCl2 / HCl2

( CH3 )2 CH - OH + ZnCl2 / HCl2

3.6 9.3 100 /

CH3CH = CH - CH2OH CH3CH2CH2CH2OH

CH2 CH2 CH2 CH3

CH3CH2CHO+NH3 CH3CH2CNH2 CH3CH2CH=NH

2) CH3 CH2 C (Cl)2 CH3 + KOHaq

(CH3)3 C OH >" "! +9,+

+$ 06 % 5 01 01 +

CH2 COOK :05<.

CH2 = CH2 + H2SO4

NH2 + NaNO2 + HCl N+N Cl- + H2O

PCl5 ) (

150 o150