&

. , . & .

2013


1.
1.1.
1.1.1.
1.1.2.
1.2.
1.3.
1.4.
2.
2.1.
2.2.
2.3.
2.4.
3.
3.1.
3.2.
3.2.1.
3.3.
4.
4.1.
4.2.
4.3.
4.4.
4.4.1.
4.4.2.
5.
5.1.
5.1.1.
5.1.2.
5.1.3.
5.1.4.
5.1.5.
6.
6.1.
6.2.
6.3.
6.4.
7.
7.1.

........................................................................ 15
................................... 16
.................... 17
..................................................... 19
..................................................... 19
(pH)................................... 20
........................................................ 20
....................................................................... 23
........................................................ 24
(
) .............................................................. 26
Soxhlet ............................... 28
(rotary evaporator) 28
- ............................... 31
(Infrared, IR) .................... 31
(melting Point).............................................. 35
................................................. 36
(Refractive Index) ..................................... 38
............................................................ 41
......................................................... 41
........................................................... 43
.................................................... 43
......................................... 44
.............................................................. 44
............................................. 46
.............................................................. 49
.................................................. 50
(Thin Layer Chroma-tographyTLC).......................................................................... 50
(Column Chromatography) ................. 53
(Dry Column Chromatography) .... 58
(Partition Chromatography) 58
........................................ 59
..................................................................... 65
................................................................ 65
........................................................ 66
............................................................... 70
..................................................... 72
.................................. 75
...................................................... 75
1

7.2.
7.3.
7.4.
8.
9.

................................................... 76
....... 77
........ 78
.................. 79
.......................................................... 81

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

.................................................... 87
........................................................................... 89
.............................. 93
SOXHLET ......................... 95
............................................................ 97


......................................................................... 99
...........................103
.................................107
.......................................109
()- (BOC) ......................................................................111
.................................................................113

, .

.
:

, .

, .

.
,

, :

.
3

. Poire.

.
.
,
.
.

.
, , ,
.

.
.

.

.
4

,
,
,

.

,
.

.

.
.


.

. .

.

Claisen

10

Buchner

Paster

Hirsch

11

1.
,
,
.
,

.
,
.

.

.
:
.
,
.
.

(

, .. , ,
).

15

 () 10-7 105

cm. , ,

.

.
,
.


.


.
.

.

.
: ) , ) , ) )
) ( ).

1.1.

.
,
16

 C.G.S., ,
, .

1. , % w/w: g 100g

2. , % v/v: ml 100ml

3. , % w/v: g
100ml
4.
5.
6. , ppm:
1.000.000 ( d=1) .

1.1.1.

1.

,
(Molarity):

, mol/L.
2.

(Normality):

,
eq/L. (eq)

.

17

()

()
.

N = nM
3.

1000g , m (molality):
1000g .

4.

:
, xA,
nA

xA =

nA
n A + nB + ... + n X

1:

g
ml
g

100g
100ml
100ml

L
ml
Ll
ml

g/100g
ml/100ml
g/100ml

g
mg
mg
g

g/L
mg/ml
mg/L
g/ml

18

(% , w/w)
(% , v/v)
(%
, w/v)

mol
mmol
eq
meq
mol

(, )
(, )
(, )
(, )
( 1000g
, m)

L
ml
L
ml
1000g

1.1.2.
,
.
,
.
:

n = n
:

C V = VV
,
,
,

1.2.
Arrhenius:
/
19

 (

,
, ).
Brnsted & Lowry:
/ .
Lewis:
/

.

1.3. (pH)

Srensen
pH,

[ ]

pH = log H+ = log

1
[H+ ]

1.4.

,
pH ,

( CH3COOHCH3COONa).
, , ,
. pH
20

 , ,


.

, CHA
CA, .

MA M + + A
H + A
+ A , K a =
HA
+

HA
H + = log H + = log log K a
A
HA
pH = pK a + log
A
HendersonHasselbach

Henderson

pH .
,
+ ,
- pH .
,
- , +
, +

.

21

 ,
:

A
pOH = pK + log
MOH

22

2.


, .
,
,

, ,
.
(1) (2).
,
,
,
.

.

KA =

C2
Nerst
C1

C1 = 1(mol . L-1)
C2 = 2(mol . L-1)
KA =
1 ,
2
1, . (
> 100). < 100
1 ,
2 .
23

( )
.

: 1
2
.

2.1.
.
1/3
(
2/3 ).
.
,
.
,
(
). ,

2-3 ,
.
.

24

 ,
.

- . ,
.

.
,
.
,

,
, . ,
(3-5)
.
i. , ,
:
ii.

25

iii. ,
.
, d
.
iv.
, .
v.
vi.
vii. ,
,
, ,
.

2.2.
( )
,
.
. ,

.

.

26


4
1

Soxhet

,
. ,

-
.
Soxhlet ,
,
. Soxhlet

.
,
,
.
, .

27

2.3. Soxhlet

:

O
H3 C

CH 3

CH3
,
cola .
.
, 1.0-3.5 %.

Soxhlet.

2.4.
(rotary evaporator)
,
.
,
Clausius Clapeyron:

28

d ln P
H
=
dT
RT 2
P =
=
=
R =
..
. ,
.
,

.

.
,

.

,


,

.
29


,
. :
i.

ii.

iii.

iv.

v.

vi.

vii.

viii.

30

3. -
3.1.
(Infrared, IR)


.
,

.


. ,
,
.

, , .
, , -
(.. NH2 CH3) ir
( )
, .

31

 +
C

CO2

O
O

2 +
C

O
O

( , )
H

H 2O

F
O

H
O

,

H

:
1. (stretching vibration):


.
2. (bending vibrations)

3. (wagging vibrations, )

4. (rocking vibrations, p)

32

5. (twisting vibrations, )


6. (scissoring or deformation
vibrations, s)

IR
:

. IR

.

.
.

1400 800 cm-1

.
,
.

33

, c m - 1
1050-1400
1150-1360

CO (, )
SO2 ( ) 2

1315-1475

CH ( )

1340, 1500

NO2 (2 )

1450-1600

C=C ( )

1620-1680

C=C ( )

1630-1690

C=O ( ) 2

1690-1750

C=O ( )

1700-1725

COOH

1770-1820

COCl ( )

2100-2200

CC ( )

2210-2260

CN

2500

SH

2700-2800

CH ( )

2500-3000

OH ( COOH)

3000-3100

CH ( C )

3300

CH (o C )

3020-3080

CH ( o C )

2800-3000

CH ( )

3300-3500

NH ( )

3200-3600

OH ( ROH ArOH )

3600-3650

OH

2100

OD

34

.
,
NaCl,
NaCl.
KBr
Nujol (

Nujol 2920, 2860, 1460, 1380 720 cm-1.

3.2. (melting Point)

,
,
. '
.

.

.

, .
,
.

, ,

35

 2C.
.

,
. ,
, .
,
& ,
.
, .
. ,
, ,
.

3.2.1.

,

,
36

rj .

.

.
.
.

.
, .
,
.

3mm .
.
37

 20C
2C .

.
,

.

(sintering)

.
,
, .
.

3.3. (Refractive Index)

.
.
38

 .

,
.

1
1
h a

n 1 / 2. :
)

(D- = 598 nm),

D (nD).
)

.
.

39

40

4.

.

.
.

:

,
.

4.1.
:"

".
.
,
.

,
2.
41

, ,

, ,

(
) 15 20C
. ,
,
.

( ).
20
42

 -700C.
.

4.2.

.
,
.

.

.

4.3.
,
.

.
.

. :

.
43

4.4.
4.4.1.
,
10 - 20mg
.
( 3).
, ,
3 ()

250C

250C

78.5

6.2

38.6

6.0

37.5

4.7

36.7

4.2

32.6

2.4

24.3

2.3

20.7

2.2

2-

18.3

2.2

12.3

2.0

1,2-

10.4

n-

1.9

,
( )
44

 . , ,
.
,
.
.

.


.
, ..

2.0

24.3

2.0

,


,

,
.

45

4.4.2.

(>5g)
- :
4

1.

2.

3.

4.

. ,
,
.
.

,
,
.
,

( 1). 0.2 0.3g
1-2 .
46

3
1
2

5
4

1.

2.

3.

4.

5.

1: . .

,
.
,
, ,
.

( / ) /
"" .
.
47



( 1).
Buchner .

.

(1-2mm <

) Buchner.

.

, ,

48

5.
,

.

.
,
, , .
,
, .


.

.
,
.



.

.

,

49

 .

.

gel

permeation

chromatography gel filtration).

( )
.

5.1.
5.1.1.

(Thin

Layer Chroma-tography- TLC)

,
.
(silica
gel), (alumina) (cellulose),
,

.

(.. Sephadex, Biogel P).
,
.
50

 , ,
,

,

. 2,
3
.

1-2cm.

.
,
.

()

()

3: () ()
51

 Rf ,
:

Rf =

2,
:

Rf ( 1) =

Rf ( 2) =

Rf

.
,
,
,
,

.
,
,
.
Rf ,
,
:
52

, :
1.

2.

3.

.
5

4.

5.

( g 1mg)

6.

,
,

7.

5.1.2.
(Column Chromatography)
, ,
,
53

 ,

(Flash chromatography) ,
4.

, ..

.
,
.


(.. , ...)

.
54


(
.. , , , ...)
( Al2O3,
) (pH =
10), (pH = 7) (pH = 4).
,
.
.. ,

( )
. .

(silica gel)
,

, MgO, MgCO3, BaCO3, Ca(OH)2, CaSO4,
, .
,
.

, :

55

Cl , Br , I

OCH3

C C

CHO

C O

CO2R

NH2

SH
CO2H

OH

>

> , , > , ,
> ,
()
.
,


.

, ,
, .
,
.

,
.

.
56

 ,
.

,

.

:

- 80:20
- 80:20
- 60:40
- 20:80

- 99:1

1-

57

5.1.3. (Dry Column

Chromatography)

, ,
.

.
.

5.1.4.

(Partition Chromatography)

, ,


.
(Reversed phase
partition chromatography)
.

58

,
,
.
silica gel,
.
, .
,

2,2,4-.

( ) 60% ( )
.

,
.

, ,

.

5.1.5.

Gas

Chromatography

(High

GC)

Performance

Liquid

Chromatography HPLC). ,
,

59

.


.
.

( ), , ,
(- , Gas
Solid

Chromatography,

GSC),

(-

, Gas Liquid Chromatography, GLC).

, - .
-

( ),

( ).

.

:

, .

.
60

,
,
.

,
,
.

.
.

.



GLC ,
,
,
.
GLC ,
, , ,
61

.
,
GLC,

, ..
,

.
.
-

(GC-MS)

Fourier (GC-FTIR).
(High Performance Liquid
Chromatography HPLC)
,
,

,
.

HPLC

.
,

.

62

 , .
,
, ,

.

( )
,
. ,

(High

Pressure

Liquid

Chromatography, HPLC)
,
(High Speed Liquid Chromatography, HSLC)

5 HPLC
63

 HPLC : 1)
2)
3) 4) 5) .
.

HPLC,
.
,

, .

,

.
HPLC

,
,
, .

.

64

6.


.
.

,
. :
, ,
.

6.1.


. :

Raoult,

.
P. = P1 + P2
P1, P2, 1, 2.

2 1,
(P2 0).

65

 1 , 2

1 2 ,
(P1 > 50 P2),
.
1 ,
,
2.
500C ,
.

6.2.

,
.
.( 6)
100

100

90

90

80

80

70

70

60

6
66

60

, ().
,
.
b,
b.

.
.

.

.
Raoult.

Po
Y1
P o X1
= 1o
(6.1) 1o =
P2
1 Y1 P2 1 X 1

X1
Y1
=
(6.2),
1 Y1
1 X1
1 & 1 1

1
2 = 1, :

Y1
1 Y1

X2
X1
=
1 X2
1 X2

,
2, :
67

X2
X1
X1
Y2
=
=
= 2
(6.3)
1 Y2
1 X2
1 X1
1 X1
:

X1
Yv
= v
(6.4)
1 Yv
1 X1

, 6.4
( )
1 2.
= 1,
(6.2)

4
3

7)

. >

4 5

, .

45
.

1.
1 1,
1,
2 = 1. 2
68

2,

3 .

45
7
1.

.

8.

.

( ' ) .
(.. ).
, (
).

69

 .
5-10oC
.

6.3.
(760 Torr)
35-1500C.
, .
1500C .

.
CLAUSIUS CLAPEYRON ( 6.5).

d ln P H
=
(6.5)
dt
RT 2
, P =
=
= (0)
R = (1.986 cal mol-1 0K-1
(6) :

ln P =

H
+C
RT

log P =

H
+ C (6.6)
2.303 RT

logP 1/ (6.6)
. ,
(
9).
70


..
P mm

..
760mm
Pmm

, :

150C
.
10 15 Torr,
10-3 Torr. 10
.

71

6
6

2
6

10 1. , 2. (
) 3. , 4.
, 5. , ,
& 6.

6.4.

.
,
1000C
.

RAOULT. (
)

.

72

 .
:

P1 = P1o

P2 = P2o

&

P = P1 + P2

P
,
,

.
.
.

mol 1 P1
=
mol 2 P2

73

7.
7.1.

. A -
(Nonsteroidal Anti-inflammatory Drugs, NSAIDs),

, ,
(,
, ).

,
, (),
.
.

. ,
, (excipients),

.

.


.

.
75

 (, )
(, )
() ,
,
( ).
(lubricants)
.
,
.

7.2.
-
" ".
(cyclooxugenase, COX),
,
,
, ,
,
.
.

( ).

( Ser530

COX-1, Ser516 COX-2) ,

(docking)

.
76



, ,
,
.

- ,
, COX,
.

( )

7.3.

: ' .
: C9H8O4
: 180,16
:
: 135 C ( ,
118 C)
: 1,40 g/cm3
77

 : 1 g 300 mL 25 C 100 mL
37 C
: 1 g 5 mL , 17 mL CHCl3
10-15 mL .
.
,
( ).
(pKa) = 3,49 (25 C)
LD50 ( ): 1,1 - 1,5 g/kg.

7.4.

H

H3C

HOOC

O H+

O
+

H3C
O

HOOC

CH3

H3C

-H
O
O
HOOC

CH3
+

78

O
H3C

OH

8.

.

(,
..).

, DNA,
.

, , C6H12O6,

C6(H2O)6.

,
.

. (

,

, , (
). ,
.
.
- ,

-,

,
79

 -, -, - .
(
) (
).
H

CH2OH
C O

H C OH

HO C H

HO C H
H C OH

H C OH

H C OH

H C OH

CH2OH

CH2OH

()

()

,

. :

Tollens (Ag+ 3)

Fehling (Cu2+
)

Benedict (Cu2+
)

(
Cu2O ).

.

80

9.

. , (Pro),


.
, (Pro),

(R)

O
H2N CH C OH
R

O
H3N CH C O
R
()
(). ,
...

H2N CH C NH CH C NH CH COOH
R1

R2

81

R3


- -
, .

R1

OH H
N CH

N CH C
H

OH

R2
H2O

R1

N CH C N CH
H

OH

R2

. Pauling Corey


.

C-N,
,
:

O
C

O
N

,
82

 . ,

, (coupling).
, ,
,
.

, - ,
,

.
-
.
-
.
tert- (Boc).

CH3
H 3C C O C
CH3

Boc-

-2-

(BocON).

tert

-
.

83

CF3COO
CH3

R O

H3C C O C N C C X
CH3

CH3

H (TFA)

CH3

H H

R O

H3C

CH

O H R O

H3C C O C N C C X

CH3

H H

DIEA

OOCCF3
H2N C C X + CO2 + H3C CH2 NH
CH
H
H3C
CH3

.


NaOH.
(COOH, -NH2, -OH ).

84

1.


.
.
50ml
1,5 HCl 37%w/v HCl
pH .
50ml
1%w/v pH
.
50ml
2 NaOH NaOH pH
.
50ml
12%w/v CH3COOH CH3COOH
d=1,049g/ml pH .

50ml 1M CH3COONa.

100ml 50ml 25ml
100ml . pH
. .

, pH.
87

2.
-
2.1.
,
.
, .
.
,
, .
Nernst


.
/ / ,
,
. 2 HCl /
CH2Cl2 H2O / CH2Cl2,
.
CH2Cl2 ,
,
.
,
2N NaOH / CH2Cl2.

89

2.2.

90

 3g (1g ),
,
1:1:1,
,
. ,
,
.

91

3.
(
& )
-
.

.

.

(C)

111 113

122 123

1,4-

52 53

80 82

4-

51 52

4-

132 133

157 159

111 - 114

,


.

93

4. SOXHLET
Soxhlet 10g -

170mL

2 4g MgO
.
.
(4 x 50mL).
. 7mL 10%
H2SO4

1 / 3 . CHCl3 (4 x
15mL). Na2SO4.

.

95

5.
5.1.
1g ,
.

,
. 2-3
.
.
.
,

5.2.
1g .
(20mg)
.
,
.

,
, 50mL
. 10 ,
5mL
.
.

97

 ,
.

98

6.






TLC.

.
11.

11

.
,
.
, ,
() .
, ,
. , (xanthrophylls)
.
99

OH

HO

- ()

- ()

N
N

Mg

O
H3COOC
O

- ( )

N
N

O
H3COOC
O

- ()

100

Mg

C
N

 4 Rf
(Pigment)

(Color)

Rf

(carotene)

0.93

a (pheophytin a)

0.55

b (pheophytin b)

( )

0.47-0.54

a (chlorophyll a)

0.46

b (chlorophyll b)

0.42

(xanthophylls)

0.41

(xanthophylls)

0.31

(xanthophylls)

0.17

6.1.

. TLC

. ,
UV,
Rf.


.
- (70:30).
~50g SiO2 .
101

. - SiO2,
o SiO2 (
). 2-3
,
SiO2
. 3 cm
SiO2 .

~100mg .
1ml .

-

(70:30).

~15mL

.
TLC
.
.

.
.

102

7.
50mL .
.

6
8
9

3
2
4
1

7
5

1. 1
2/3 .
, ,
. ,

, .
.
,
,

.

.
2. Claisen
103

3. .
4.

5. . ,
.
6. . .
7. .

.
8.

, 30 C
.
9.
:
i. 1
7, .
, .
, .
ii. 2 3
5.
iii.

.
, .

104

iv. ,
.
.

.

105

8.
1. 1.0g
100mL
2. , 2.0 mL

3. , 5-6
85%,
4. , 15
70-80 oC
5. , 20

6.

10mL

.
7. 5ml
. 15
.
8.
. 50ml
10ml
95%.
107

 .
.

.
9. ,
.
10.
.

108

9.

Tollens.
Tollens AgNO3

g+ g,
(=)
+1

R C

+3

2OH-

+
H

[Ag(NH3)2]+

+1

H2O

+ 2e-

x2

e-

Ag + 2NH3

+1

+
OH

+1

R C

2[Ag(NH3)2]+

+3

2OH-

+ 2Ag + 4NH 3 + H2O

R C
OH

, .

9.1.

1.

Cl 1

2.

Tollens
150ml 0,1 AgNO3

5ml

25%w/v

.
109

5ml

25%w/v 3.
!!! Tollens
,

.
3.

40% w/v

4.

40% w/v

5.

100ml 20ml
, 20ml

6.

~70C
10ml Tollens
4min

7.

110

10.
() (BOC-)
O
+

C CN

H2N CH C O

NOCOOC(CH3)3

O
C CN + (H3C)3COCOHN CH C O
H
NOH
NaHSO4
O
(H3C)3COCOHN CH C OH
H
1.5 g (20 mmol) 4.2 mL
(30mmol) (12.5 mL)
(12.5 mL). 5.4 g
(22mmol) Boc-ON, .

.
()
(2x25 mL).
30 mL H2O.
(pH ~ 2-3) 1N NaHSO4.,
111

 .
. ,
.
(86.5 87.5C).

,
:
,
, Na2SO4
.
,
Boc-.
. .

112

11.
1.

L. M. Harwood and C. J. Moody, "Experimental Organic

Chemistry", Blakwell Scientific Publications, London, 1990

2.

J. W. Zubrick, "The Organic Chem. Lab. Survival Manual", John

Wiley & Sons, Inc., New York, 1997

3.

R. T. Morrison & R. N. Boyd, "Organic Chemistry", Allyn and

Bacon, Inc., New York, 1983

4.

B. S. Furniss, A. J. Hannaford, P. W. G. Smith & A. R. Tatchell,

"Vogels textbook of Practical Organic Chemistry", Longman
Group U.K. Limited, London, 1995

5.

. . & . . , " ",

, 2000

6.

&

" ", ,
1977

7.

. , "
", , 1990

8.

. . , " ", , 1981

9.

. . , "
", , 1992

10. J. A. Fowlis, "Gas Chromatography", John Wiley & Sons Ltd.,

London, 1997

11. J. McMurry, ,
, , 2004

12. .

, , 1999
113

T T
I.

Copyright: I
A ,

T
I .
.