.

-
, , -
.
,

. -
,
. -

,
.

-
.
(IR)
. -
-
(UV-Vis), ,
.


(NMR) (ESR)
.

.

.

6 , :

,

. ,
,
. -

.
,
, , -
,
-
.

, 2006


1.1 .......................................17
1.1.1 ............................................................................17
1.1.2 s ...........21
1.1.3 p ............22
1.2 ..............................................................................24
1.3
............................................................................................................26

2
( IR & Raman)

2.1 ...........................................................................31
2.2 .........................................................................................36
2.3
IR Raman ............................................................................................37
2.4 IR .................................................43
2.4.1 ..................................................................................43
2.4.2 , 2, 3 ...............................................................44
2.4.3 3, 2 .................................................................44
2.4.4 4.................................................................................46
2.5 IR .............................................................47
2.5.1 IR..........................................47
2.6 Raman.........................................................................................59
2.7 ................................................61
8 , :

2.1: (R) 4000-650 cm1

Infrared correlation chart........................................................................69
2.2: (R) 1500-650 cm1
Infrared correlation chart........................................................................72
2.3: (R) 800-33.3 cm1
Far infrared vibrational frequency correlation chart ..........................74

3
- (UV-Vis)

3.1 ........................................................................................................77
3.2 .....................................................................79
3.3 .....................................................................81
3.4 ................................................................................................................82
3.5 ........................................86
3.5.1 ...............................................................86
3.5.2 - .............................90
3.5.3 Jahn - Teller........................................................................91
3.5.4 ..........................................................................92
3.5.5 .........................................94
3.5.6 ....................98
3.5.7 ...................................100

4.1 ..............................................................................................107
4.2 -
..........109
4.2.1 ........................................................................110
4.2.2 .....................................................................112
4.3 ........................................................................................114
4.4 ...............................................................................................116
 9

4.5 ....................................................................118
4.1: R
Characteristic NMR spectral positions for hydrogen
in organic structures..............................................................................120

5.1 EPR..........................................................121
5.2 EPR ................................................................123
5.2.1 EPR .................................126
5.2.2 ........................................................127
5.2.3 .............................................128
5.2.4 .
...................................................................131
5.2.5 .....................................................................................132
5.3 EPR ..................................................133
5.3.1 I = 1/2 ..................................133
5.3.2 = 1 .......................137
5.3.3
....................................................................................140
5.3.4
=1/2 .......................................................................................................141
5.3.5
I = 1/2 ..........................................................................................................143
5.3.6 n
I = 1/2....................................................................................146
5.3.7 -
I = 1/2 ..........................................................................................................147
5.3.8 = 1.....149
5.3.9 EPR ..................................................150
10 , :

6.1 .....................................................................158
6.1.1 .........................................................................................158
-
........................................................................................................158
6.1.2 , S = 1/2 ...........................160
6.1.3 Van Vleck....................................................................................163
6.2 ....................................................166
6.2.1 -.................................................................166
6.3 .....................................................................................169
6.4 - ...................................................................172
6.5 ....................................................173

7.1 ......................................................................................................................175
7.2 .........................................180
7.2.1 .........................................................180
7.2.2 ...................................................................................183
7.3 ...................................................................................188

8.1 .................................................................................................................197
8.2 ................................................................................................198
8.2.1 ................................................................................198
8.2.2 () ...............................................................198
8.2.3 .............................................................................199
8.2.4 .......................................................................................199
 11

8.2.5 .........................................................................................199
8.2.6 Silica Gel......................................................................................................199
8.2.7 () ......................................................................199
8.2.8 ......................................................................................200
8.2.9 .........................................................................................................200
8.2.10 .......................................................................................200
8.2.11 () ...........................................................................200
8.2.12 ....................................................................201
8.3 ...............................................201
8.3.1 ................................................................201
8.3.2 ..........................202
8.3.3 .....................................................................................203
n-, C3CH2CH2CH2C3..........................................................203
n-, C3CH2CH2CH2CH2C3 .......................................................204
(40/60) -
................................................................................................204
, C6H12 ...................................................................................204
, C6H6 ...........................................................................................204
, C7H8 ........................................................................................205
8.3.4 .............................................................206
, CH2Cl2 ..........................................................................206
, ClCH=CCl2 ............................................................206
, CHCl3................................................................................206
, CCl4 ......................................................................207
8.3.5 ........................................................................................................207
CH3CH2OCH2CH3 ....................................................208
, THF, C4H8O .........................................................209
1,4, C4H8O2................................................................................209
8.3.6 .....................................................................................................210
, CH3OH ...................................................................................210
, CH3CH2OH .............................................................................211
n-, CH3CH2CH2OH..............................................................211
I, CH3CH2CH2OH.............................................................211
n- C3C2C2C2 ........................................................212
tert- , (2--), C4H10O ...............................212
12 , :

8.3.7 ........................................................................................................212
, CH3C(O)OCH3...................................................212
, CH3C(O)OCH2CH3............................................213
8.3.8 .....................................................................213
, C3C()CH3 ............................................................................213
, CH3CN .............................................................................214
,, DMF, (C3)2C.................................214
, DMSO, (CH3)2SO ..............................................214
, CH3NO2 ............................................................................215
, C3COOH ..............................................................................215
, C55........................................................................................215
, C3C(O)C(O)C3 ...........................................216

9.1 .....................................................................................................217
9.2 ......................................................................219
9.3 ..........................................................................224
9.4
(Chemicals Compatibility Chart) .......................................................................226

10

10.1 Schiff....................227
10.1.1
Mn(salen)(SCN), Mn(Hsaladhp)2 Ni(salen) ...............................227
10.1.2 Ligand
(HOC6H4C=NCH2CH2N=CC6H4OH) = 2salen .......................228
10.1.3 Mn(salen)(SCN) [N,Nethy-
lenebis(salicylideneiminato)](isothiocyanato)manganese...............229
 13

10.1.4 Ligand (HOCH2)2(CH3)CN=CHC6H4OH =

1,3dihydroxy2methyl(salicylideneamino)propane =
H3saladhp.................................................................................................232
10.1.5 Mn(saladhp)2 .....................................233
10.1.6 N,Nethylenebis(salicylideneimi-
nato)nickel(II) = [Ni(salen)].................................................................235
10.1.7 (template)
[Ni(salen)] ...............................................................................................238
10.1.8 .......................................238
10.1.9
Mn(salen)(SCN), Mn(saladhp)2 Ni(salen) ...............................242
10.1.10 UV-Vis..............................................244
10.1.11 ....................247
10.1.12 ...................................................250
10.2 Co(III). -
Ligands, Cl, en, NH3, acac, ox=...........................253
10.2.1 tris(ethylenediamine)cobalt()
Chloride, [Co(en)3]Cl3 ...........................................................................253
10.2.2 tris(2,4pentanedionato)cobalt(),
Co(acac)3 ..................................................................................................256
10.2.3 pentaamminechlorocobalt(III)
chloride, [Co(NH3)5Cl]Cl2 ....................................................................257
10.2.4 hexaamminecobalt(III) chloride,
[Co(NH3)6]Cl3 .........................................................................................259
10.2.5 potassium tris(oxalato)cobalta-
te(III), K3[Co(C2O4)3] = K3[Co(ox)3]...................................................260
10.2.6 ....................262
10.2.7 UV-Vis..............................................264
10.2.8 Ligands, Cl,
en, NH3, acac, ox= ..................................................................................268
10.3 Cr(III)
Tanabe-Sugano
Ligands, H2O, Cl, en, NH3, acac, urea,
SCN, ox= ................................................................................................................271
14 , :

10.3.1 tris(2,4pentanedionato)chro-
mium(), Cr(acac)3 ..............................................................................272
10.3.2 tris(ethylenediamine)chromium(III)
sulphate, [Cr(en)3]2(SO4)3 .....................................................................273
10.3.3 tris(ethylenediamine)chro-
mium(III) Chloride, [Cr(en)3]Cl32 ...............................................275
10.3.4 cisdichlorobis(ethylenediamine)
chromium(III) Chloride, cis[Cr(en)2Cl2]Cl .....................................277
10.3.5 hexakis(urea)chromium() chlo-
ride, [Cr(urea)6]Cl3 .................................................................................279
10.3.6 Potassium hexakis(isothiocyanato)
chromate(III), K3[Cr(NCS)6]................................................................280
10.3.7 Potassium cisdiaquabis(oxalato)
chromate dehydrate, cisK[Cr(ox)2(H2O)2]2H2O ............................281
10.3.8 tris(3bromo2,4pentanedionato)
chromium(III), Cr(3Bracac)3 .............................................................282
10.3.9 pentaammineaquachromium(III)
Nitrate, [Cr(NH3)5(H2O)](3)3 .........................................................285
10.3.10 pentaamminenitratochromium(III)
Nitrate, [Cr(NH3)5(3)](3)2 .........................................................287
10.3.11 UV-Vis ..............................................288
10.3.12
Cr(acac)3, [Cr(en)3]2(SO4)3, [Cr(en)3]Cl3, cis[Cr(en)2Cl2]Cl,
[Cr(urea)6]Cl3, K3[Cr(NCS)6], K[Cr(ox)2(H2O)2], Cr(3Bracac)3,
[Cr(NH3)5(H2O)](3)3 [Cr(NH3)5(3)](3)2 .....................294
10.4 4 ................................296
10.4.1 dichlorobis(triphenylphosphine)
nickel(II), Ni(PPh3)2Cl2 ........................................................................296
10.4.2 dibromobis(triphenylphosphine)
nickel(), [Ni(PPh3)2Br2] ......................................................................298
10.4.3 bis(dithiocarbamato)nickel(),
Ni(S2CNC4H9)2 ........................................................................................300
10.4.4 dichlorobis(pyridine)cobalt(),
Co(py)2Cl2 ................................................................................................302
 15

10.4.5 bis(2,4pentadionato)copper(II) ,
Cu(acac)2..................................................................................................303
10.4.6 tetraamminecopper() sulphate
hydrate, [Cu(NH3)4]SO42 ...............................................................305
10.4.7 .......................................306
10.4.8 ....................309
10.4.9 UV-Vis..............................................314
10.4.10
1) dichlorobis(triphenylphosphine)nickel(II), Ni(PPh3)2Cl2
2) dibromobis(triphenylphosphine)nickel(), [Ni(PPh3)2Br2]
3) bis(dithiocarbamato)nickel(), Ni(S2CNC4H9)2
4) dichlorobis(pyridine)cobalt(), Co(py)2Cl2
5) bis(2,4pentadionato)copper(II), Cu(acac)2
6) tetraamminecopper() sulphate hydrate
[Cu(NH3)4]SO42 .......................................................................318
10.5 5 ................................320
10.5.1 cisaquabis(glycinato)copper(II),
cisCu(H2NCH2COO)2(H2O) transaquabis(glicynato)
copper(II), transCu(H2NCH2COO)2(H2O).....................................320
10.5.2 bis(dithiocarbamato)iron(I)
chloride, Fe(S2CNC4H9)2Cl ...................................................................322
10.5.3 bis(2,4pentanedionato)
oxovanadium(IV), VO(acac)2 .............................................................325
10.5.4 .......................................326
10.5.5 ....................329
10.5.6 UV-Vis..............................................336
10.5.7
cisaquabis(glycinato)copper(II), cisCu(H2NCH2COO)2(H2O),
transaquabis(glicynato)copper(II),
transCu(H2NCH2COO)2(H2O), bis(dithiocarbamato)iron(I)
chloride, Fe(S2CNC4H9)2Cl, bis(2,4pentanedionato)oxova-
nadium(IV), VO(acac)2 ........................................................................339
...................................................................................................................341
..............................................................................................................345
 1

1.1

. -
d -

.
.

1.1.1

-
, s -
p. d -
, -
, , d .
d 5 , -
10 .

,
VIII , , , -
18 1

.
, ,
.
,
d ,
, :
-
,
. ,
,
d .
,
s p . -
, -
,
, -
,
, -
.
. -

, . -

, -
-
, -
f .
-
, -
( )
.
,
ns (n1)d,
-
, -
 19

1.1.1.
. -
( )
.

Sc Ti V Cr Mn Fe Co Ni Cu Zn
31 42 52 60 70 60 30 40 21
3 4 4 3 2 2, 3 2, 3 2 2 2
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
31 42 52 60 70 80 40 40 21
3 4 5 2, 6 4, 7 3 3 2 1 2
La Hf Ta W Re Os Ir Pt Au Hg
42 52 60 70 80 40 40 31 21
3 4 5 6 3, 4, 7 4 3, 4 2, 4 1, 3 2

1 18
, .
( 7, d5),
, -

. -
-
,
.
, -
, ,

Mo W.
d
. ,
, ( )
.
, ( -
), . ..
20 1

ClO2- > ClO3- > ClO4- .

-
.
, Fe2+, Co2+
Ni2+ .
Fe(ClO4)2 , Co(ClO4)2 , Co(ClO3)2
,
.
+2
Fe2+ < Co2+ < Ni2+.
d ,
Sc Zn .
Sc 3d14s2 , -
+3,
s d .
,
.
La 14 ,
, -
4f .
Ca, Sc,
, Al.
+3 , -
, Ce4+ ,
, Eu2+ , Yb2+,
4f14, -
, .
14 ,
-
. 5f 6d -
, -
. ,
.
, ,
.
 21

+3,
+4. -
(+7) Pu
,
d .

, -
.
Zn d p
, +2,
d10.
, -
, Hg, -
p . Hg1+
, -
HgHg.
Mg2+, -
. -
.
CdBr2
CdBr+ [CdBr3] , [CdBr4]2.

1.1.2 s

,
1 2 . Fr Ra
. -


+1 +2 .
, -
. , Li
Be,
-
.
22 1

Li Mg Be Al -
.

, -
. -
,
2 , , ,
, (, , -
, , ) .

Be Mg.
Be Mg ,
Mg(OH)2 , Be(OH)2
.

ligands
.
, -
, -
, EDTA, -, , -
ligands. ,
4, -
, ..

4 Be(MeCOO)2 + H2O 2 MeCOOH + Be4O(MeCOO)6

,

- , 4.
- .

1.1.3 p

, -
, -
 23

. 13
Ga, In Tl Al, 14 Sn Pb,
15 Bi.

.
. -
,

(2220 C).

1.1.2
p .

I Al Ga In Tl Sn Pb Bi
13 31 49 81 50 82 83
26,982 69,72 114,82 204,37 118,69 207,2 208,98
1,25 1,30 1,55 1,90 1,45 1,80 1,60
* 708 715 701
1,5 1,6 1,7 1,8 1,8 1,8 1,8
660 30 157 304 232 328 271
2467 2250 2070 1457 2620 1750 1560
2,70 5,90 7,30 11,85 7,28 11,34 9,80

* kJmol1

13 ,
, , -
,
, , ,
.
, ,
.
,
, .
24 1

(GaP, GaAs, InP,

InAs )
, .
, -
, , -

. -
,
,
.

MCl3 + 4LiH LiMH4 + 3LiCl

14
, SnF4 PbF4 -
. ,
. -

,
. -
-
. -
, , -
.
BiO+
BiO3- , , -
. ,
-
.

1.2

, , ,
, , . , -
 25

,
, -
. -
( 1.2.1).
(IR) (UV-Vis)
, -
, ,
. EPR NMR -
.

10-6 nm

10-3 nm

X
1 nm 400 nm



1000 nm = 1m

10 m
100 m 750 nm
1000 m = 1mm

1000 mm = 1m

1000 m = 1km

100 km

1.2.1.

26 1

,

, .
-
,

hc hc
= = (1.1.1)

h Plank = 6,6231027 erg s mole1 c

cms1. ergmole1. -
hc
, , , -

. -
, , .
:

c (cm s -1 ) 1
(s -1 ) = (cm -1 ) =
(cm) (cm)

To ,
IUPAC Kayser. -
1.2.1.

1.3

(..
, 3
4+ 3 + +  4+ ),
, , -
,
. -
:
 27

1
t (1.2.1)
2

:

, ,
-
.
. t -
,

1
s1 (1.2.2)
2 t

,
, t
. -
:
IR. (IR)
, -
, 0,1 cm1. -
1.2.2 :

1
0,1 3 1010 3 109 s1
2 t
1 1
t 5 10 -11 s
2 2 3 109

1011 s .
,
1011 s1,
. -
, -
.
28 1

, ,
IR .. 51013 s1 -
, , 300 cm1

1 1
t 2 10 -14 s
2 2 9 1012

NMR. NMR
0,1 Hz(cs1) -
2 s ( ) 0,5 s1 (
) (peaks).
.

, ,
NMR, .. 100 Hz

1 1
t 2 10 -3 s
2 2 100

,
5102 s1 , -
.
5102 s1 (.. )
.
, -
.
, -
.
. -
1018 s1.
,

(disorder).
Mssbauer. Mssbauer
 29

, -
. Mssbauer
. ,

( Fe 107 s),
.
, -
107 s
1
, Mssbauer .
1.2.1 -

.

1.2.1 -

(t)
Stop flow 103 s
NMR 101 105 s
ESR 104 108 s
Mssbauer (Fe) 107 s
104 108 s
IR Raman 1011 s
1018 s
 .

. ,

(A. VALAVANIDIS: FUNDAMENTAL PRINCIPLES OF MOLECULAR

SPECTROSCOPY AND APPLICATIONS IN ORGANIC CHEMISTRY)

Copyright 2008, .

(E-mail: valavanidis@chem.uoa.gr, . 210-7274479)

- :

,
: 32, , 17561
: 12, 10671
. 210-3628501
E-mail: synchronathemata@yahoo.gr
... 090013089 ( )
:

ISBN: 978-960-88130-7-6

, . 2121/1993,
.

1
1
1.1. . 3
1.2. 4
1.3. 5
1.4. 6
1.5. 7
1.6. 11
1.7. 12
1.8. .
Schrdinger 12
1.9. : 16

19
,

19
2.1. 19
2.2.
22
2.3. 25
2.4. (broadening) 27
2.5. 28
2.6. 30

33
33
3.1. 34
3.2. 35
3.3. 37
3.4. 39
3.5. 41
3.6. 44
3.7.
46
3.8. 47
3.9. spin
49
3.10. 49

52

52
4.1. 52
4.2. 54
4.3. IR 56
4.3.1. IR 57
4.4. 58
4.5. Fourier 60
4.6. 63
4.7.
64
4.7.1. 64
4.7.2. 65
4.7.3. 66
4.7.4. 67
4.7.5. 70
4.7.6. 72
4.7.7. (ROH) (C6H5OH) 73
4.7.8. , ,
(RNH2, CNH2, CN, NH2) 74
4.7.9. . 76
4.8. (R) 77

79
79
5.1.
79
5.2. 95

99
99
6.1. 99
6.1.1. () spin. 102
6.1.2. (). 104
6.1.3. . Spin- spin-spin
. 105
6.2. . 107
6.3. . 109
6.4.
. 111
6.4.1. . 112
6.4.2. NMR. 113
6.4.3. NMR. 113
6.5. . 114
6.5.1. . 115
6.5.2. . 116
6.5.3. . 117
6.5.4. (1H). 118
6.6. Spin - Spin . 123
6.6.1. spinspin spinspin . 126
6.6.2. 127
6.6.3. - -. 128
6.7. . 130
 133

133
7.1. 133
7.2. 134
7.3. 134
7.4. 135
7.5.
NMR 136
7.5.1. . 136
7.6. . 137
7.7. NMR 139
7.8. 31P 13C NMR
139
7.9. NMR 140
7.9.1. (NMR)
143
7.10. NMR. 144
7.10.1. NMR 147
7.12. NMR (DNMR) 149

151

FOURIER 151
8.1. Fourier NMR 152
8.1.1. 152
8.1.2. 154
8.2. ( )
155
8.3. H FT-NMR 157
8.3.1. FT-NMR 158
8.4. Fourier (Fourier Transform) 159
8.4.1. 160
8.4.2. (/) 161
8.5. FT-NMR 162
8.5.1. 164
8.6.
. Overhauser 165
8.7. A 13C M M X
A. 165
8.7.1. 1 166
8.7.2. 2 168
8.8. : -FT 171

173
1 13C NMR 173
9.1. Spin 173
9.2. 1 NMR 174
9.2.1. 1 NMR 174
9.2.2. 1 NMR 176
9.3. , 179
9.4. 1 NMR
181
9.5. 13C NMR 185
9.6. 13C NMR 186

191

191
10.1.
(2D NMR) 191
10.2. 203
10.2.1. DEPT (Distortionless Enhancement by Polarization Transfer) 205
10.3. /
. 206
10.4. NMR 215

217
217
11.1. 217
11.2. 218
11.3. 223
11.4.
223
11.5. 226
11.6. 227
11.7. UV-VIS 228
11.8. 228
11.9. 230
11.9.1. 230
11.9.2. (polyenes) 232
11.9.3. 233
11.9.4. , , 234
11.9.5. 235
11.9.6. 241
11.10. UV M K X M 242
11.11. 244
11.11.1. -,
. 244
11.11.2. -. 244
11.11.3. , , . 245
 247
247
12.1. 247
12.2. 254
12.3. . 255
12.4.
. 256
12.5. 257
12.6. -
259
12.7.
261
12.7.1. () 261
12.7.2. 263
12.7.3. . 264
12.7.4. . 267
12.7.5. , . 270
12.7.6. , (). 270
12.7.7. . 273
12.7.8. (, RX). 274
12.7.9. . 275
12.8. . . 275
12.9.
. 279
12.10. . 281
12.11.
283
12.12. : 286

289
RAMAN 289
13.1. Raman 289
13.2. Raman . 292
13.3. Raman 294
13.4. : Raman 302

303
303
303
14.1. 304
14.2. (Spin)
14.3. 306
14.4.
(EPR). 311
13.5. 312
13.6. 313
14.7. : (EPR) 316


,
16 ,

,
.
, o
17 .
,
.

, ,
. J.C. Maxwell
19
4 Maxwell,

.
19

Maxwell.
,

().

, ,
.


.

.
(
Maxwell)
.
,
( )
,
(hv) . Einstein

1
 ,
. Einstein

.
:
, ,

.
.


.



.


.



20
.


Albert Einstein (1879 1955)


.
( Dalton)
,
, ..
20

.
(quantum mechanics)
(wave mechanics)

.

(complementarity).


.

2

.

1.1.

,
, , , , .,
.


.

. 1900 Max
Planck


,
,

. -

,
,

. ,
,
(

).
Max Planck (1858 1947)

.

, , Stefan
Boltzmann:
= 4 (1.1)

.
,
,


.

,

3
 Planck
,
,
( ) (quanta).
:

= h (1.2)

,
h Planck ( ), 6.6256 10 27 erg s.
()
, , ,
, .

.
Planck Einstein (1905)
:

()
, Planck = h ,
, = n h , n 1, 2, 3, 4,
Einstein ,
,
.
= h ,
(momentum)
,
.

1.2.

,
,
.
,
,
,
..


.

, 1 2, 1 2
(quantum numbers) ,

4
, = 2 - 1, .
,

:
= /h (1.3)

1 (
),
2.

.
.
,

= /h
,
. .
()

.

1.3.

.

.
Lenard (1902)
()

, , (
).
1905
Einstein, Planck,
. ,
h.
,


.

h Planck.

5
 hv

1.1. (:
: ).

1.4.

(
)
(1663).
. ,

, 1800 (
)

.
1814
J. Fraunhofer
(
).

. ,

. ,
35

. Foucault
(Cl)
D
. Kirchhoff
(1859)

6

.

,


. 20


. 1907 A. Convay
()
. ,

. ,
Rutherford
,
.

1912 N. Bjerrum,
( )

.

1.5.

(Thomson Rutherford) Niels Bohr.


.
,
.


.
.
,

,
(1.2) PlanckEinstein.

. ,
.

7
 Werner Heisenberg (1901-1976)
Niels Bohr (1885 1962)

Louis de Broglie (1892-1987)

, (discrete)
(angular momentum) .
Ehrenfest, L = nh/2, n
.
, Bohr
. m,
r :

L = mr ( ), L = mr = nh/2 (1.4)

8
 n , ,
Bohr
(principal quantum number)
.



. ,

. ,
n = 1, (ro)
Bohr.

() ()

()
1.2. () spin Bohr
, () spin
, () .

9
 Bohr
.
(
)
.
Bohr ( 19131926)
,

. Bohr


(1 2 = h).

.
, Bohr
(ionization potential),

. , Li, N,
, ., ,
(
),
.

1.6.

Bohr
,
. 1920 Luis de Broglie,
Werner Heisenberg Erwin Schrdinger

.

.

.
de Broglie (1923) .
de Broglie,
, .


.

( ) : = h = mc2, c
. : h = mc2
= c/,

10
, : = h/mc = h/p, p = mc
. de Broglie
:

= h/m = h/p (1.5)

c ,
.

re,

, : 2re = n ( n
). = h/m
mre = nh/2 = n. Bohr,
. de Broglie

.

C. Davisson L.H. Germer G.P. Thomson
A. Reid .

, -
.
, ,
.

1.7.

,
.
,
.

,

.

.

1926 W.Heisenberg
(Uncertainty Principle or Principle of
Indeterminacy). Heisenberg,

. ,

11
 .
.

(broadening)
( 2,
).

1.8.
. Schrdinger.

E. Schrdinger W. Heisenberg,
, (1926)
( )

.

(wave
mechanics) Matrix
Mechanics. ,
(
)

.

Schrdinger


.
Schrdinger
Erwin Schrdinger(1887 1961)
()

.
( de Broglie)
.
.
, (function)
(x, y, z) :

(x, y, z) (1.6)

12
 ()

()

()

()

1.2. ()
, () , ()
, ()

=0.

(
) Max Born, ||2 * ,

(x, y, z) t.
,
(x) ,

13
 .
:
d2 4 2
= (1.7)
dx 2 2
, ,
,
42/2.
(.
) ,
de Broglie (1.4) = h/m 2 = h2/(m)2 :
h2
2 = (1.8)
2 m( E U )
1
m2
2
U. ,
:
d 2 8 2 m( E U ) d 2 8 2 m( E U )
= + = 0 (1.9)
dx 2 h2 dx 2 h2

.
,
,
, U
.
, ,
. eigenvalues
eigenfunctions.
.

(eigenvalues) ,
.

, .
.
,
, :

= n (/2), n = 1, 2, 3, .

, Schrdinger
,
( ).

.

14

,
(x, y, z),
.
,
: 2/x, 2/y, 2/z .
:

2 2 2 8 2 m
+ + + ( E U ) = 0 (1.10)
x 2 y 2 z 2 h2
:
8 2 m
2 + ( E U ) = 0 (1.11)
h2
2
.

1.3. .
L () .
.

.
Schrdinger
.

.

15
1.9. : ,

1. Karagounis G. Introductory Organic Quantum Chemistry. Academic
Press, New York, 1962.
2. Sandorfy C. Electronic Spectra and Quantum Chemistry. Prentice-Hall,
New Jersey, 1964.
3. Hanna MW. Quantum Mechanics in Chemistry. WA Benjamin, New
York, 1965, 1969, 1980.
4. Pilar FL. Elementary Quantum Chemistry. McGraw-Hill, New York,
1968.
5. Anderson JM. Introduction to Quantum Chemistry. WA Benjamin, New
York, 1969.
6. Laidlaw WG. Introduction to Quantum Concepts in Spectroscopy.
McGraw-Hill, New York, 1970.
7. Levine IN. Quantum Chemistry: vol 1, Quantum Mechanics and
Molecular Electronic Structure, vol 2, Molecular Spectroscopy. Allyn and
Bacon, Boston, 1970, 1974.
8. Atkins PW. Molecular Quantum Mechanics. Clarendon Press, Oxford,
1970, 1983 (2nd ed).
9. Paglia La SR. Introductory Quantum Chemistry. Harper and Row, New
York, 1971.
10. Daudel R. QuantumTheory and Chemical Reactivity. D Redel Co,
Dordrecht-Holland, 1973.
11. Atkins PW. Quanta: A Handbook of Concepts. Clarendon Press, Oxford,
1974.
12. Zimmerman HE. Quantum Mechanics for Organic Chemists. Academic
Press, New York, 1975.
13. Chilsolm CDH. Group Theoretical Techniques in Quantum Chemistry.
Academic Press, London, 1976.
14. Goodisman J. Contemporary Quantum Chemistry. Plenum Press, New
York, 1977.
15. Lowe JP. Quantum Chemistry: students edition. Academic Press, New
York, 1978.
16. Mc Quarie DA. Quantum Chemistry. University Science Books. Sausalito,
California, 1983.
17. Schaefer HP. Quantum Chemistry. Clarendon Press, Oxford, 1984.
18. . .
, , 1984 (3 ).
19. . I:
. , , 1985.
20. Rae A. Quantum Mechanics, Hilger Bristol, 1985.
21. Pauling L, Wilson EB. Introduction to Quantum Mechanics with
Applications to Chemistry. Dover publs, New York, 1985.
22. . . ,
, , 1986.

16
23. . II:
. , ,
1986.
24. Mehra J, Rechenberg H. The Historical Development of Quantum Theory.
Vols 1 5. Springer Verlag, 1982 1987.
25. Seleri F. . Gutenberg, , 1987.
26. Glick TF, ed. The Comparative Reception of Relativity, Reidel, Boston,
1987.
27. Hawking S. A Brief History of Time. Bantam Books, Toronto, 1988.
28. Carbo R. Quantum Chemistry: Basic Aspects, Actual Trens. Elsevier
Science publs, Amsterdam, 1989.
29. Feynman R. The Character of Physical Law. Penguin Books, London,
1992.
30. Schatz GC, Patner MA. Quantum Mechanics in Chemistry. Prentic Hall,
Englewood Cliffs, NJ, 1993.
31. Stehle P. Order, Chaos, Order: The Transition from Classical to Quantum
Physics. Oxford University Press, New York, 1994.
32. Cushing JT. Quantum Mechanics. Historical Contingency and the
Copenhagen Hegemony. University of Chicago Press, Chicago, 1995.
33. Jammer M. The Conceptual Development of Quantum Mechanics.
McGraw Hill, New York, 1996.
34. Cox PA. Introduction to Quantum Theory and Atomic Structure. Oxford
Science Publications, Oxford, 1996.
35. Atkins PW. . (: ,
). , , 1996, , 2 , 1999.
36. Simons J, Nichols J. Quantum Mechanics in Chemistry. Oxford University
Press, New York, 1997.
37. Atkins PW. Friedman RS. Molecular Quantum Mechanics. Oxford
University Press, 3rd ed, 1997.
38. Atkins PW. Physical Chemistry (Quantum Theory: introduction & theory,
p. 285). 6th ed, Oxford University Press, Oxford, 1998.
39. Green NBJ. Quantum Mechanics. No 1 & 2. Oxford Science Publications,
Oxford, 1998.
40. Levine IN. Quantum Chemistry. Prentic Hall, Englewood Cliffs, NJ, 5th
ed, 1999.
41. Kragh H. . 20 .
, , 2004. (Kragh H. Quantum Generations A history in
the twentieth century. Princeton University Press, Princeton, 1999).
42. Pilar FL. Elementary Quantum Chemistry. Dover Publications, New
York, 2001.
43. Schaefer HF. Quantum Chemistry: The Development of Ab Initio
Methods in Molecular Electronics Structure Theory. Dover publs, New
York, 2004.
44. Hey T, Walters P. . 2 . . ,
, 2005.

17
18


()
( )
.



( )
.

,
.

2.1.
()
.
(3X108 m/s)
90 0 .

2.1.
, x.

19

.
2.2 ( ),

, m.

2.2. .

, y =
B, c 03600
(02 rad). ,
rad/s ( = t) ,
2/ .

2.3. .

20

() .
SI Hertz ()
s-1. :

y = B = Bt = B2t (2.1)

,
(t) (x), x = ct
(c ). 2.1 y=B2t=B2x /c .
(
) :

2.4. .

.
, , ().
() :
c
= (2.2)


( ).
m (micrometers),
1m = 10-6 m.

( ), ( =1/),
(cm).
.
, (IR)
4000 10 cm-1 ,
100 1 m (10-5 - 10-6 m).
( ) ( ) : = cv ,
c
(31010 cm s-1).

21
2.2.
.


(
) ,
.

,

() .
:
1. (Radiofrequency): 3106- 31010Hz,
10m 10cm.
spin ( ) .
: (Nuclear
Magnetic Resonance, NMR)
(Electron Paramagnetic Resonance, EPR).

(spin, ) (
). spin
,
.
2. (Microwave): 31010- 31012Hz, 1cm 100m.

. (Microwave
Spectroscopy).
( HBr,
+
H Br , 2, ),
,

.
3. (Infrared): 31012 - 31014 Hz, 100m 1m.
.
(Infrared Spectroscopy)
.
( , )


.
4. (Visible, Ultra Violet): 31014 - 31016 Hz,
1m 10nm. (

22
 )
.

.
.
5. x (xray): 31016 - 31018 Hz, 10nm 100pm.

.
.
6. (ray): 31018 - 31020 Hz, 100pm 1pm.
.
Mssbauer
(Mssbauer spectroscopy).
7. (cosmic rays): ~1022 Hz, 0.01pm.
.

, Raman,

, (Photoelectron
Spectroscopy), (Flame Spectroscopy), -
(Fluorescence) (Phosphorescence),
(Laser) , .

23
 2.1. .

:
pico Angstrom nano micro milli centi deci kilo mega giga
(p) () (n) () (m) (c) (d) (k) (M) (G)
10-12 10-10 10-9 10-6 10-3 10-2 10-1 10 3 10 6 10 9

2.3.

, .


(, , ,
) ,
() , 1 2.
= (2 - 1)/h ,
,
.
, ,
(
).
,
.
,
(, )

24
( ,

).
(
)
: () (signaltonoise ratio) ()

(resolving power), .

.
. ,

. .

.

.
,
.
, .

2.5. .
.

25
 ( 2.5)
,

(). (scanning)
, (, )
(exit split)
( 2.5).
().
,
.
,
. ,
.

( ) .

2.4 (broadening)
(broadening)
,
, .

2.4.1.


,
.

.
,

.
,
. , ,
.

2.4.2. Doppler
Doppler
( )
( ).
( )

Doppler.
,

26
, .
.
Doppler,
(natural line width).

2.4.3.
Heisenberg
Heisenberg
()
(.. ) .

. ,

.
dt ,
: dE x dt h/2 10-34 J s ( h
Planck). () ,
, , (dt=),
dE=0. , , 10-8 sec,
: dE=h/2dt=10-34 /10-8 = 10-26 J (2.4)

: d = d /h h/2hdt 2dt (2.5)
dt = 10-8 s, d = 108 Hz. ,
.
(1010) - (1020)
() . ,
108 109 Hz ( spin
) .

2.5.
.

2.5.1. (transition probability)

-

(selection rules), ,

. .

2.5.2. (population of states)

,

27
 .
Boltzmann (Boltzmann
Distribution Law). ,
,
:

= e / k (2.6)

= , 0 k
Boltzmann k = 1.38 x 10-23 JK-1.
(NMR).

2.5.3. .

,
.
(dI)
I dx C (mol/l)
dI = C I dx,
(absorption coefficient)
. dI/I = C
dx dlnI = C dx
. ,
(path length) cm, I,
:
I I
Io
d ln I = aCdx (2.7).
0

, C
x :
I = I o e aCl (2.8)
Beer-Lambert-Bouguer :
log I / I o = C l (2.9)
( = /2.303)
(extinction coefficient or molar extinction coefficient)
(, cm2/mmol). To C l
(optical density or absorbance).
, , :
log I o / I = C l (2.8)
100
log I o / I = ( Absorbance) = log( )= C l ,
%Transmission
%Transmission = I / I o 100 . (Absorbance , Transmission ).

28
 2.6. :
1. Walker S, Straw H. Spectroscopy, Vols 1 and 2. Chapman and Hall, London,
1961, 1962, Strangham BP, Walker S, 1976.
2. Silverstein RM, Bassler G, Morrill T. Spectroscopic Identification of Organic
Compounds. John Wiley and Sons, New York, 1963, 1974, 1981.
3. King GW. Spectroscopy and Molecular Structure. Holt, Rinehart and Winston,
New York, 1964.
4. Dixon RN. Spectroscopy and Structure. Methuen, London, 1965.
5. Dyer JR. Applications of Absorption Spectroscopy of Organic Compounds.
Prentice-Hall, New York, 1965.
6. Freeman SK. Interpretive Spectroscopy. Chapman and Hall, London 1965.
7. Williams DH, Fleming I. Spectroscopy Methods in Organic Chemistry.
McGraw-Hill, London, 1966, 1980 (3rd ed).
8. Banwell CN. Fundamentals of Molecular Spectroscopy. McGraw-Hill, New
York, 1966, 1972, 1983.
9. Nakamoto K, McCarthy PJ. Spectroscopy and Structure of Metal Chelate
Compounds. Wiley, New York, 1968.
10. Pasto DJ, Johnson CR. Organic Structure Determination. Prentice-Hall, New
Jersey, 1969.
11. Scheimann F. (ed). An Introduction of Spectroscopic Methods for the
Identification of Organic Compounds. Pergamon, New York, 1970.
12. Brittain EFH, et al. Introduction to Molecular Spectroscopy: Theory and
Experiment. Academic Press, London, 1970.
13. Rao CN, Ferraro JR. (eds). Spectroscopy in Inorganic Chemistry, vols 1 and 2.
Academic Press, New York, 1970, 1971.
14. May L. Spectroscopic Tricks. Adam Hilger, London, 1971.
15. Wiffen DH. Spectroscopy. Longman, London, 1971, 1972.
16. Chang R. Basic Principles of Spectroscopy. McGraw-Hill, New York, 1971.
17. Nachod FC, Zuckerman JJ. (eds). Determination of Organic Structures by
Physical Methods, vol 4, Academic Press, New York, 1971.
18. Creswell CJ, Runquist OA, Campbell MM. Spectral Analysis of Organic
Compounds. Longman, London, 1970, 1972.
19. Woodward LA. Introduction to the Theory of Molecular Vibrations and
Vibrational Spectroscopy . Clarendon Press, Oxford, 1972.
20. Howarth O. Theory of Spectroscopy. Nelson, London, 1973.
21. Parikh VM. Absorption Spectroscopy of Organic Molecules. Addison-Wesley,
Reading Mass, 1974.
22. Steinfeld JI. Molecules and Radiation. An Introduction to Modern Molecular
Spectroscopy. Harper and Row, New York, 1974.
23. Robinson JW. (ed). Handbook of Spectroscopy. CRC Press, Florida, 1974.
24. Kemp W. Organic Spectroscopy. MacMillan, London, 1975, 1987.
25. Rao KN. (ed). Molecular Spectroscopy: Modern Research. Vols 1 and 2.
Academic Press, New York, 1975, 1976.

29
26. Levine IM. Molecular Spectroscopy. Wiley Interscience, New York, 1975.
27. Kroto MW. Molecular Rotation Spectra. Wiley Interscience, New York, 1975.
28. Lambert JB, et al. Organic Structural Analysis. Macmillan, New York, 1976.
29. Strangham BP, Walker S. (eds). Spectroscopy. Vol 1: Atomic, NMR, ESR, MQR,
Mssbauer Spectroscopy, Vol 2: Molecular symmetry, Group theory,
Microwave, IR. Raman, far-IR, Vol 3: Valence, electronic spectrum, quantum
numbers, Photoelectron spectroscopy etc. Chapman and Hall, London, 1976.
30. Jones DW. Introduction to the Spectroscopy of Biological Polymers. Academic
Press, London, 1976.
31. Smith RA. (ed). Very High Resolution Spectroscopy. Academic Press, London,
1976.
32. Richards WG, Scott PR. Structure and Spectra of Atoms. Wiley, London, 1976.
33. Drago RS. Physical Methods in Chemistry. WB Sannders, Philadelphia, 1977.
34. Guillory WA. Introduction to Molecular Structure and Spectroscopy. Allyn and
Bacon, Boston, 1977.
35. Dyke SF, Floyd AJ, Sainsbury M, Theobald RS. Organic Spectroscopy: An
Introduction. Longman, London, 1978.
36. Crooks JE. The Spectrum in Chemistry. Academic Press, London, 1978.
37. Pavia DL, Lapman GM, Krits GS. Introduction to Spectroscopy: A Guide for
Students of Organic Chemistry. John Wiley and Sons, New York, 1980.
38. Vanasse GA. (ed). Spectroscopic Technique. Academic Press, New York, vol 1,
1977, vol 2, 1981, 1985.
39. Clero JT, Pretsch E, Seibl J. Structural Analysis of Organic Compounds. Elsevier,
Amsterdam, 1981.
40. Paponek D, Aliev MR. Molecular Vibrational and Rotational Spectra. Elsevier,
Amsterdam, 1982.
41. Richards WG, Scott PR. Structure and Spectra of Molecules. John Wiley and
Sons, Chichester, 1985.
42. Sternhell S, Kalman JR. Organic Structures from Spectra. John Wiley and Sons,
Chichester, 1986,
43. Hollas JM. Modern Spectroscopy. John Wiley and Sons, Chichester, 1987.
44. Gilbert A, Pethybridge AD, Stebbings EV. Primer in Spectroscopy. Univ. of
Reading, Reading, 1987.
45. Williams DH. Spectroscopic Methods in Organic Chemistry. McGraw-Hill,
New York, 1987.
46. Brown DW, Floyd AJ, Sainsbury M. Organic Spectroscopy. John Wiley and
Sons, New York, 1988.
47. Struve WS. Fundamentals of Molecular Spectroscopy. John Wiley and Sons,
New York, 1988.
48. Sorrell TN. Interpreting Spectra of Organic Molecules. Oxford University Press,
Oxford, 1989.
49. Silverstein RM, Bassler GC, Morrill TC. Spectroscopic Identification of Organic
Compounds. 5th ed, John Wiley, New York, 1991.

30
50. Banwell CN, Mc Cash E. Fundamentals of Molecular Spectroscopy. McGraw
Hill, New York, 1994.
51. Williams DH, Fleming I. Spectroscopic Methods in Organic Chemistry.
McGraw-Hill, New York, 1995.
52. Havel HA, ed. Spectroscopic Methods for Determining Protein Structure in
Solution. Wiley VCH, New York, 1996.
53. Harwood LM, Claridge TDW. Introduction to Organic Spectroscopy. Oxford
Chemistry Primers. Oxford Univ Press, Oxford, 1996.
54. Pavia DL, Lampman GM, Kritz GS. Introduction to Spectroscopy: A Guide for
Students of Organic Chemistry, 2nd ed, Saunders, Fort Worth, PA, 1996.
55. Hesse M, Meier H, Zeeh B. Spectroscopic Methods in Organic Chemistry.
George Thiem Verlag, Stuttgart New York, 1997.
56. Lambert JB, Shurvell HF, Lighter DA, Cooks RG. Organic Structural
Spectroscopy. Prentice Hall, U. Saddle River, NJ, 1998.
57. Crews P, Rodriguez J, Jaspars M. Organic Structural Analysis. Oxford
University Press, Oxford, 1998.
58. Hollas JM. High resolution Spectroscopy. 2nd ed, John Willey, Chichester, 1998.
59. Shriner RL, Hermann CKF, Morril TC, Curtin DY, Fuson RC. The Systematic
Identification of Organic Compounds. 7th ed, John Wiley, New York, 1998.
60. Silverstein RM, Webster FX. Spectroscopic Identification of Organic
Compounds, 6th ed, Wiley, New York, 1998.
61. Workman J, Springsteen A, eds. Applied Spectroscopy, Academic Press,
London, 1998.
62. Sternhell S, Kalman JR, Field LD, eds. Organic Structures from Spectra. John
Wiley, New York, 2002.

31
32


(Infrared Spectroscopy, IR)

,

.
.

(IR)
,

.
, (wagging),
(rocking), (twisting),
(scissoring), ..

H
H H H
C C C
H H

Symmetric Stretch Scissoring Wagging

(~2853 cm-1) (~1450 cm-1) (~1250 cm-1)

H
H H H
C C C
H H

Asymmetric Stretch Rocking Twisting

(~2926 cm-1) (~720 cm )-1 (~1250 cm-1)

3.1.
.

33
3.1.
(.. HCl),

.
,
,
.
.
,
3.2.

3.2.
(r).

,
, r.
(vibrate,
oscillate)
, .

Hooke:
F = f ( r r ) (3.1)
f r .
, 3.2,
3.2:
1
E = f (r r ) 2 (3.2)
2
(
), ,
(simple harmonic oscillator
model) ( )
.

34
3.2.

:
1 f
= cps, Hz (3.3)
2
f
m1 m2
( = m1
m1 + m2
m2, reduced mass).

=/c ( c ), :
1 f
= cm-1 (3.4)
2 c
IR.
3.2 ,
(), ().
1 2
, .

,
.

3.2.1.

( )
.
(kinetic)
(potential).
, r r = r
, 3.2.
, ,

Schrdinger.

:
1
E = (n + )h Joules (3.5)
2
n = 0, 1, 2, ( )
(vibrational quantum number), h Planck
cps.

35
, n=0,
- (zero-point energy).
-,
1
3.5 h ,
2
, .
.

() h, =2,
2. ,
(transitions)
() ,
= n+1 En = h. , 2 ,
h h
E o + 1 +
2 .
(selection rule).

3.3.
.

,

,
.

,
( 3.3). IR,

, ,
.

36
3.3.
,
. ,
( 10%),
.
(anharmonic oscillator)
( 3.2), 3.4,
.
:
[
E = D 1 exp ]
a ( r r ) 2
(3.6)
D
(dissociation energy),
. 3.6,
3.2 Schrdinger,
( ) :
1 1
2
1 1
2

E n = h n + X e n + E n = h c n + X e n + (3.7)
2 2 2 2
n = 0, 1, 2, , Xe
. 3.5

2
1
h cX e n + ,
2
n.

3.4. .

: n = 1, 2,
3, , n = 1 ,
n = 2, n = 3 ,
2 3
.

37
 IR,
n = 1, 2 3
.
Boltzmann n = 1
1 1%
(n = 0)
.

.
n=0 n=1
(fundamental absorption),
n=0 n=2 n=0 n=3
(first &second overtones), .
IR HCl, ,
2886 cm-1, 5668 cm-1
8347 cm-1.
(overtone frequencies)
. 1-4,
,
,
IR.

3.4.

,
.
,
,
IR.

ro = r1 + r2 m1 m 2 .
r1 r2

m1 r1 = m2 r2
m1 m2 ro = r1 + r2
Z
ro

3.5. ( ).

38
, , . ,
= 0. = .

3.6. .

:
2 2
= m1 r1 + m2 r2 (3.8)
m1 m2
: m1 r1 = m2 r2 , ro = r1 + r2 = :
m1 + m2
= r
2
(3.9)
ro .

m1 (m1 m2 ) ,
,
,
. ,
.
Schrdinger, :
h2

J = J ( J + 1) Joules (3.10)
8 2 I
J = 0, 1, 2, 3, (rotational
quantum number).
E J J = 1 ,
J = 2 :
2h 2

J J +1 = ( J + 1) (3.11)
8 2 I
, = /h (Hz)
E J
J = ,
hc
h2
J = 2 ( J + 1) cm-1 (3.12)
8 I

39
 3.12, h 8 2 I c = B
(rotational constant)
, :
J = BJ ( J + 1) (3.13)
3.13 J = 0, J = 0
. J = 1, J = B(1 + 1) = 2 B ,
.

(J = 0)

J = 1 . J = 2 B cm-1
. J = 1 J = 2 4 cm-1, .
J=1,

2, 4, 6, 8 cm-1 ., 2 cm-1,
.

.
, D, (centrifugal
distortion constant) 3.10.

3.5.

( 100 ) .
(
) ,
Born-Oppenheimer (Born-Oppenheimer
approximation),
. , :
= + Joules (3.14)
3.7 3.13,
,
DJ 2 ( J + 1) 2 , :
1
[ ]
2
1
E = hv n + X e n + + hc BJ ( J + 1) DJ 2 ( J + 1)
2

2 2
:
E 1 1
2

J = = n + X e n + + BJ ( J + 1) DJ 2 ( J + 1)
2
(3.15)
hc 2 2

40
 ,
n = 1, 2 , J=1.

n = 0 n = 1
3.7.

,
(
).
J=0 ( )
(n = 0 , n = 1),
:
J , n = J ', n =1 J '', n = 0 (. 3.7), :
1 1 1 1
J , n = BJ ' ( J '+1) + 1 2 X e BJ ' ' ( J ' '+1) + X e
2 4 2 4
= (1 2 X e ) , J , n = + B( J ' J ' ' )( J '+ J ' '+1) cm .
o o -1

3.7.
.

41
 (P R) :
() J = +1 , J ' = J ' '+1 J 'J ' ' = +1 , J , n =
o
+ 2 B ( J ' '+ 1)
cm-1, J ' ' = 0,1,2,....
() J = 1 , J ' ' = J '+1 J 'J ' ' = 1 , J ,n =
o
2 B ( J '+1) cm-1,
J '= 0,1,2,....
:
J ,n = =
o
+ 2 Bm cm-1 (3.16)
m 1, 2, 3, (m0). (m > 0),
J=+1, (m < 0) J=1. o

(band centre or band origin).

3.16
. , 3.7,
. P ( m)
R ( m).
3.16
D,
4Dm3, D 0.01% ,

.
,
, CO 2140 cm-1
3.8.

3.8. CO
.

3.9
.

42
 3.9. CO .
. 4260 cm-1
.

3.6.
IR

. ,
.
,
x, y z.
3, 3
(degrees of freedom) .

. ,
.

.
3 3 ,
33 . ,

.
,
36 .
36
, ,
, 35.

3.6.1.
(i) (=2) 325=1,

.

43
(ii) (=3), 2
336=3, (,
).
.
3.10 3.11.

O O O

H H H H H H

() () ()

3651.7 cm-1 1595.0 cm-1
1, () 2, () 3755.8 cm-1
3, ()
3.10. 2.

C2

,
.

O O O
H H H H
H H

() 1
O O O
H H
H H H H

() 2
O O O
H H H H
H H

() 3

3.11. 2 .

44
 C2, 35 = 4 (=3),
4 .
, . ,
,

. ,

(degenerate motions).
(iv)
(C). :

H C N H C N H C N H C N

3312 cm-1 2089 cm-1 712 cm-1

3.7.

, , 2, C2 .,

.

.
, : ()
()
.
, ,
,
(,
), .
,
(combination bands, difference bands).
()
.

(accidentally degenerate). ,


.
Fermi (Fermi resonance).

45
3.8.

, n = 1
J=1.
( )
.

(rotational transitions)
.


;

3.8.1.
:
J=1, n = 1 , J=1, n = 1, 2, 3,
.

P R ,
, 3.12
C.

3.12. C.

(
)
P R .

, ,
.

46
3.8.2.
: n = 1, J=0, 1
. J=0 ( )
,
.

3.13. ,
J=0 ( 3.7).

J=0
Q
, (
o
) .
(, , ,
) ,


o
, 3.14.

47
 3.14. HCN PQR,
.

(CO2, HCN, CH4 )

. ,
,
.

3.9. spin

spin (
) ,
. (
C) spin
( ) P R,
.

3.10.
, ,
,
.
IR, .
,
(.. CH3, CC, NO2, NH2, OH, )
, .
,

48
 IR
( ):
(characteristic or functional group vibrations) (skeletal
vibrations).

3.10.1.


.
4000 cm-1 1600-1400 cm-1.
, CH3,
CH 2850-2890cm-1,
29402980 cm-1,
( )
, , 1470 cm-1.
,
,
(.. , CO, CN, CC, CS, NH2, ).
: - (CO)
1600-1750 cm-1,
, - (CS)
1100cm-1, SH
2580 cm-1.

3.10.2.
,
,
,
. , C O (..
RCOR) ( C C )
1715 1650 cm .
-1

C C C O
(.. ),
1675 1600 cm .
-1

(.. C C O ),
2100 1100 cm ,
-1

.
,

. ,
3650-3590 cm-1.

.

49

.
,
IR,

. HCl ,
100 cm-1 20 cm-1 .

. 3.3
1 f
( = Hz),
2
.

( ):
CH CF CCl CB CO CS
~2500 1050 725 650 1750 1100cm-1

3.10.3. IR
C,
H, O, S , 1400-700 cm-1
.
,

.

,
(fingerprint
absorption bands).

3.10.4. ( ) IR

.

,
.
.
C O, C N , C C
O, , C.
IR
.
OH , NH CH .

50


4.1.
IR
4.1 .

4.1. IR.

. Ni-Cr
(Nichrome). Nernst (Zr
) .

. Globar
( )
IR. ,
IR Fourier (Fourier Tranform IR).
(slits) ,

.

51
 NCl
IR,
.

. ,
.
( ), ().

,
.
(grating diffraction)
NCl .

, ,
.
,

.
() , ,
.


, (scanning) (
) IR.

4.2.
.

( 1, 2, 3, )
, (
). ,
1 1 1
1 + , 2 + , 3 + , ( )
2 2 2
.

52
 :
d ( + ) = K (4.1)
=1, 2, 3, , d ,
,


( 4.3).
(detector)

.
IR ,

Golay. ,

.

.
( ,
IR )
,
- (chopper or rotating sector mirror),
,
.
- .

NCl.

4.2.
2, 2, CO2, .
.
,
.

,
.
,

.

IR. ,

.

53

.
(servo-
motor) ,

().
(wedge or calibrated attenuator
or variable optical attenuator),
, (
).
.
- ,
, .

()
IR (ruled chart paper)
,
.
, IR :
,
( KBr, , Nujol)
.
( ) (reference beam
attenuator)
. (
10 )
.
- ( ),
,
.
,
( )
() ().
.
.

,

. ,
,
IR.

54
4.3. IR

( )
(calibration). (
).
IR
. 1603 cm-1
( )
.

() FT-IR

() IR

4.3. , 0.05 mm, () FT-IR ()

.

55
4.3.1. IR

( , )
.
(cells)
NCl.
.
1-2 ( )
NCl
.
Nujol (
). NCl
Silica
gel.
CF2.
:
() KBr KBr.
10-20 mg 200 mg KBr
.
10-14 tonnes
. ~13 mm ~0.3 mm.
() () Nujol ( )
.
NCl . Nujol
.
CH (
~3000 cm-1) CH ( ~1400 cm-1).

.
Nujol ,
() ..
NCl.

() ()

56
 ()
NCl
( )

()
KBr
( 1:100 KBr
)

4.4. IR () , ()
, () , () KBr
.

4.4.
IR
,
,
, .
IR
, , ,
(base line) ,
.

Beer-
Lambert-Bouguer:

57
 I = I o exp( c l ) (4.2)
() ,
c , l
.
4.2 :
log I o / I = c l (4.3)
.
.
,
, % (%
Transmittance) .
4.3
:
I 100
log o = A = log = c l (4.4)
I % T
100% 0%, ()
0 ().

4.5. IR.

,
4.5, : T1 = AX T2 = BX
.
: = . .
:
100 % T1
= log = log 100 = log = log
AX
% T2 % T1 % T2 BX

58

. ,
4.4, .

4.5. Fourier
IR 4000-650 cm-1,

400-10 cm-1,
(far infra-red).
, ,
,
, ,
(200-50 cm-1) ..
IR
,
.
IR ( ,
13C) IR
Fourier (Fourier Transform IR Spectroscopy, F.T.-IR).
Fourier Fourier

.

. Fourier 13C-R.

(interferometric measurements)
.
Fourier :

59
 4.6. FT-IR
, .

(interferometer) ()
, KBr IR,
50%
.
1 2.
- (plate-beam
splitter) ,
.


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

60
2, .)
.
Fourier IR.
0,001 sec
1000
. (
), Fourier
sec , 1000
, .
1-2 , 20-100

.
F.T.-IR 4000-400 cm-1
4 cm-1.
2.
F.T.-IR .
,

.
F.T.-IR
, eue;i (,
),
.. F.T.-IR
IR.

() ()

61
 ()

4.7. FT-IR : () , ()
32 (FT-IR) , ()
FT-IR ( 1--1,2-
-2-), ()
.

4.6.
IR
.
,
. ,
.
IR
:

62
()
4000-1500 cm-1.
() 1500 cm-1
( ),
.
() ,
.
()
.
() (
) ,
. ,
.
() IR (
)
.
() (bands, lines, peaks)
(strong, s),
(medium, m), (weak, w) (broad, br).
,
..

4.7.

4.7.1. C C C C

IR
CH CC,
.
2900 cm-1 (s)
1400 cm-1. ,
1150 1350 cm-1.

H3C
. , H C C 3
1370 1385 cm-1.
CH

,
() .

63
 4.8. 2,2-.
(http://www.aist.go.jp/RIODB/SDBS/)

4.7
2900, 1375 742 cm-1.
CH.
13701380 cm-1 . ~700 cm-1
.
:
CH3

CH3 CH2 CH CH3

CH3

4.7.2. C C

( s- )
.
: , CH2 3080 cm-1 (), 2975 cm-1
() CHR 3020 cm-1 ().
3000 cm-1 .
C C
1600 cm-1. , H2C
C(CH2)5 C3 (1-) 1645 cm-1.

64
 4.9. 1-.
(http://www.aist.go.jp/RIODB/SDBS).

cis-4-,
.
3050-2900, 1400-1650 900-750 cm-1.

4.10. cis-4-.

4.7.3. (C C)

CC

3270-3315 cm-1.
2210-260 cm-1 2100-2140 cm-1 (

65
 ).
C, 2260-2210 cm-1.
IR 4.11.
1-, CH
3305 cm CC
-1

2110 cm-1.

4.11. 1-.

4.7.4.

C C C.
900 675 cm-1,
. , C C
1575-1600 cm-1.
C 3000-3100 cm-1.

4.11.
:
()
1650-2000 cm-1.
-
. -
(triplet), -

- ,

66
 ( 4.12).

.

4.12. IR (C65C3), - m- .

67
 4.13.
-, m-, p- 1650-2000 cm-1.

() ,
C
(out-of-plane). -
770-730 cm-1 710-690 cm-1, -
770-735 cm-1, - 810-750 cm-1 710-690 cm-1
- 860-800 cm-1.

4.14. IR p-, C77Cl.

68
 C77Cl 800 cm-1,
3100 cm-1
. 2870 cm-1
2940 cm-1 C
(C3).
1650-2000 cm-1 820 cm-1
-.

4.7.5. C O

1580-1900 cm-1. ,
1700 cm-1.

C O . ,

( ):

CH3 C CH3 CF3 C CH3 CF3 C CF3 F C F

O O O O
1724 cm -1 1769 cm -1 1801 cm -1 1928 cm-1
, -
. R
,
.

R NH2 OMe CH3 H I, Br NO2

R C CH3
O cm-1 1677 1683 1687 1691 1692 1700

C O .
H C O 10-15 cm-1

. ,
C 2700-2900 cm-1. 2720 cm-1
. Fermi doublet.
4.15 IR
2720 1730 cm-1.

69
 4.15. (C3(C2)2C) ,
3300 cm-1.

4.16. 2-,
(Fermi doublet) 2750 2870 cm-1.
O
C OH ,
, 1700-1730 cm-1.
:
O H O
C C
O H O

1700 cm-1. (10% )

70
 1750 cm-1.
2500-2700 cm-1,
3500 cm-1.
(coupling) C 1420
1300 cm-1 935 cm-1.

4.17. ( CCl4).

O
C OR
R
. ,
1720 cm-1, (C3C C3)
1750-1740 cm-1. ,
1100-1280 cm-1
1000-3000 cm-1, C CC .
1200 cm-1.

4.7.6. (CC)

,
CC.

CH3OCH3 (CH3CH2)2O CH3 CH O CH CH3

CH3 CH3
1190 1160 1100 1175, 1135 1100
cm-1

71
 4.18. ().

3000-3100 cm-1 .
, 1600-2000 cm-1
- 2830 cm-1
1190 cm-1 - (C3).
:

CH3O

4.7.7. (ROH) (C6H5OH)

3650-3500 cm-1. ,
R O H O R
H ,
3500-3450 cm-1 3400-3200 cm-1.

C, :
() : 1060-1025 cm-1.
() : 1140-1090 cm-1.
() : 106501015 cm-1.

72
 4.19. - p-.

-
3500-3200 cm-1 1600-1200 cm-1.
1400 cm-1 1000 cm-1
C .

4.7.8. , ,
(RNH2, CNH2, CN, NH2).

NH, : ()
: 3300-3500 cm-1(doublet), () : 3300-
3500 cm-1 (singlet).
NH 1590-1650 cm-1
1650-1510 cm-1 .
(.. )
1250-1360 cm-1 1180-
1280 cm-1.
(R3N)
NH .
, ,
.
2200-3000 cm-1.

73
 4.20. (C6H5NH2).

3300-3500 cm-1
.
4.19.

4.21. .

IR
,
1650-1715cm-1.

2200-2300 cm-1
CN.

74
 4.22. (NCO),
.

4.7.9. .
:
C COO C CHOOH C COO Na
NH3 NH3Cl NH2
:
() 3+ 3100-2600 cm-1, ()
3+ 1660-1610 cm-1, ()
3+ 1550-1485 cm-1.
O
C
O
1600-1590 cm-1( )
1400 cm-1( ).
3333-2380
cm-1 ( NH3+ OH).
O
, 1220-1190 cm-1(,
C C C )
1755 - 1730 cm-1 ( ) -
.

75
 4.23. L-,
2 3500-3100 cm-1 1600-
1590 cm-1.

76




5.1

-
cm-1 (wave number)

A.
- (CH3)

CH
CH3 2975 -2950 (s)

CH2 2940 -2915

CH3 2885 -2860 (s)

CH2 2870 -2845

CH 2900 2880 (s)

CH2 3080 -3040 (m)

CH3CO ~ 3000 -2900 (w)

CH2CO ~ 2925 -2850

CH3O 2850 -2815 (m)
( )
CH3N
2820 -2710 (m)
()
(, ) CH
CH3 1470 -1435 (m)

77

CH2 () 1480 -1440

CH3 () 1385 -1370 (m)

CH ~ 1340 (w)
CH3CO 1360 -1355 (s)
CH2CO 1435 -1405
CH3CO 1375 -1340 (m)
CH2 1445 -1430 (s)
CH3O 1455 -1430
CH3N 1460 -1430 (s)
()

~ 1170
C(CH3)2 ~ 1145
( )
C(CH3)3 ~ 1215
( ~ 1195
)

1020 -1000
C (CH2)n C
n=2 () 745

B.

1.

C C

CH
RCH CH2 ~ 3080 (m)
~ 3020
R1R2 C CH2 ~ 3080
R1CH CHR2 cis ~ 3020 (m)
R1CH CHR2 trans ~ 3020 (m)

R1R2C CHR3 ~ 3020

C H
RCH CHR ~ 1640 (m)
1
RRC 2 CH2 ~ 1650

78
R1CH CHR2 cis ~ 1660
R1CH CHR2 trans ~ 1675

R1R2C CHR3 ~ 1670

C C C C
() ~ 1640 -1600 (m)
C Cn
1650 -1580 (m)
()
C C ~ 1630 (m)
C C C O 1660 -1580 (m)
C C X 1650(F)1593(I)
(: )
F F
C C ~ 1798
F3C F
CH
( , in plane) 1450 - 1200
CH
( , out of plane)

RCH CH2 ~ 990 910

( H , CH3)

H H H H In-plane
C C ~3080 (
C .)
~3020cm-1 R
H
~2975 C
~1600cm -1
R H out-of-plane
(

.)

2.
C C
CH ~ 3300 (s)
CC
( ) 2140 - 2100

79
CC
( ) 2260 - 2190
CH () 680 610 (s)

C6H5 , ,

CH 2-3 3100 3000 (m)

C H : ~ 1600 (m s)

C C
:
C 6H 5Cl 1596
C6H 5NO2 1604
C C C ~ 1580

C C ~ 1500

C C ~ 1450 (m)
CH2 CH3

CH ( ) 1250 -950 (w)
CH
( ) 900 960 (s)
750 20 (v.s)
, C6H5X 700 20 (s)
1,2


X 755 20 (v.s)
X

1,3

780 20 (m)
X 700 20
880 20

X
1,4 1,2,3,4 810 20 (s)

80
 1,2,3 - 780 20 (s)
1 700 20 (s)
6 2
1,2,4 810 20
5 3 880 20
4
1,3,5 880 20

1,2,3,5 1,2,4,5 880 20

H
H
H H

. ( )

1.

( , )

(ROH) ~ 3460

~ 3630
(R2CHOH)
0,005
(R3COH) CCl4 ~ 3620
(C6H5) ~ 3610
( , 3550 3450 (s)
( ) 3400 3200 (s)

H H 3760 (s)
O

1410 - 1250
( )
C
~ 1050 (m s)

, ~ 1100
.

81
 ~ 1150


~ 1200
750 -650
( )
2.
C O H ~ 950 (b.m)
O
3. ( - - - )

C N OH 3650 3500 (m s)

4.
( - -)
O 2700 2560 (m)
P
OH

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

R O H O R
R O H O R
H H
H
O H O R
H

C O

1. (R CO R)
C O
R
C O
1725 1705 (v.s)
R
()

82
 C C C R
1685 -1665 (v.s)
O
(
)
C6H5 CO R 1700 1680 (v.s)
( )
C6H5 CO C6H5 1670 -1635 (v.s)
( )
C C
1730 1710 (v.s)
O O
(-)
C CH2 C
O 1640 1535 (v.s)
O
( -)
O O 1690 1655 (v.s)
(1,4 )
X CH2 C
O 1745 1725 (v.s)
(-
)
C CO C
- 1325 -1215 (s)

- , 1225 - 1075

2. (R CO )

C 2900 2700 (w)
~2820, ~2720

C O
( CO) 1740 1720 (v.s)
- (C65CO)
1705 1695 (v.s)
C C CHO
1705 - 1680
( )

83
C CO 1400 -1000 (s)
( )
C CO 975 - 780
( )

3. (RCOOH)

,
RCOOH 3560 - 3500


, 3300 -2500 (v.b)
~ 3000 2650

C O
- (RCOOH) 1725 1700 (v.s)
- (COOH) 1700 1680 (v.s)

1715 1690 (v.s)
( C C CO)

C O 1440 1395 (w)

C O 1320 1210 (s)
950 900 (m)
O
( )
1610 1550
(COO )
1430 - 1300
4.

R C OR , CH2 n C O
O O

C O
(R COR) 1750 -1735 (v.s)


1730 -1715 (v.s)
C C COOR

- 1720 1725 (v.s)

(C65 COR)

84
 -
1800 1770 (v.s)
R COO C C

-
C C OR 1755 1740 (v.s)
O O
- 1770 1745 (v.s)
(XCH2COOR)
-
COOR
1690 -1670 (v.s)
OH

C O

1200 -1180 (v.s)
(COR)

1250 1230 (v.s)
(C3COR)

1200 1150 (v.s)

1300 1200 (v.s)

(C C COR) 1180 1130 (v.s)
5.
R C O C R
O O
C O
1840 -1800 (v.s)
(RCC CR) 1780 1740 (s)
1790 1780 (s)
(CO C)
1850 1840 (s)

(
) 1870 1830 (s)
1800 -1760
O O
O

85
C OC
1175 1045 (s)
1300 1200 (s)

6. (RCO X)
C O 1815 1785 (v.s)
(X: )

.
R NH2 , NH2 , R NH3

. ( )

(R NH2, NH2) 3500 -3300 (wm)


R NH R 3500 3300 (w)
NH R ~ 3450 (m)

3400 3300 (m)
C N H

. 3400 3100

1650 1580 (m)
~ 1500 (w)
C N
(R NH2) 1220 1020 (m)
- ,
1340 1250 (s)
( NH2)
,
( NH ) 1350 -1280 (s)
,
(R3N) 1360 1310 (s)
.
NH3
3350 -3150 (s)

R NH3

NH3
1600 -1575 (s)

86
 ~ 2700 (s)
R2 NH2
1620 -1560 (m)

2200 1800 (m)
R3NH

Schiffs 2500 - 2325
C NH

. (RCONH2)

C N
~ 3500
~ 3400 (m)
( /)

(RCONHR) ~ 3450

~ 3350 -3100
( )

H H H

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

H H H

(
()
)
C

~ 1690 (s)
( /) (s)
~ 1680 (s)
(RCONHR)
(RCONR2) 1670 1630
~
1650
1680 -1630 (s)
1670 1630 (s)

87

H
O N O
C C 1790 1720 (s)
(CH2)n 1710 - 1670

RHN C NHR
~ 1660 (s)
O

( )

1620 1590 (m)
1550 1510

1650 1620
1570 - 1515
C N
~ 1400
~ 1290
( ) ~ 700
C

N OH N O ~ 1660 (v.s)
H

. (RCH(NH2) COOH)

+
3 3130 3030 (s.b)
2800 2000


3030 - 2500

+
3
1660 1600 (w)
1550 1585 (m)
COO 1600 1560
~ 1470

88
C ( )
- 1755 - 1730
1730 - 1700
+
3 1295 -1090

I. AI (R OR)

C (CH3 O -) 2850 - 2815

C (CH3 O -) 1455 - 1430

C C
- 1150 - 1060 (v.s)
( CH2O
CH2)
1270 - 1230 (v.s)
(C6H5O R)

C C O R 1075 - 1020 (s)

1250 - 1150
(C6H5O C6H5)
~ 1250

C C ~ 890
~ 830
O

. ,

. (R C N)

C N
- (R C N) 2260 -2240 (v)
C C

2235 - 2215
C CHC N

2240 -2220
( C C N)

. R N C R N C

89
N C
-(R NC) 1690 -1640 (v)

2125 -2115
( C2NC)

. (R N C )
N C 2275 -2240 (v.s)

. R C N OH
N C 1690 -1640 (v)


1660 - 1630
C C C N OH

. R C N
N C 1690 - 1650 (m)
. ( N N ) 1575 - 1650
. (R N C N R)
- 2140 - 2130 (v.s)
(R N C N R)
2140 - 2150 (v.s)
( N C N )

R NO2 , R C NO
NO2
(R NO2) 1565 - 1545 (s)
1385 - 1360
( NO2) 1550 - 1510
1365 - 1335 (s)
CN
920 - 830
860 - 840 (m)

R C NO
1600 - 1500 (s)

~ 1100 (s)
CN

R N NO

90
 1500 - 1430 (s)

SH
2590 - 2550 (w)
(RSH)
2600 - 2500 (w)
(C65SH)
C S

1200 - 1050 (s)
C S
S
1070 - 1030 (v.s)
(R2S )

O
R S O H ~ 1090 (v.s)

~ 1130 (v.s)
O
R S O R

S2
(R2S2) 1350 -13 0 (v.s)
1160 - 1140 (v.s)
1210 - 1150 (v.s)
1060 - 1030 (v.s)
1420 - 1330 (v.s)
1200 - 1195 (v.s)
1370 - 1330 (v.s)
(S2) 1180 - 1160 (v.s)
1375 1340 (v.s)
(S2) 1190 - 1160 (v.s)
N. (RX),

CF
1100 -1000 (m)
(R F)
1400 - 1000 (s)
CCl
750 - 700 (m)
(, )

91
 800 - 700 (s)
Cr
600 - 500 (s)

C 620 - 490 (s)

.

: (symmetric, sy) (asymmetric,
as):
() (stretching vibration). : st v(C O) 1600cm-1
() (bending vibration). :
.
() (wagging vibration). :
() (rocking vibration). :
() (twisting vibration). :
() (scissoring vibration). : s
.
,
:
() (strong) : (s) (very strong) : (v.s).
() (medium) : (m).
() (weak) : (w).
() , , (broad) : (b).
() : (m s).
, ,
, variable
(v).


.

92
5.2.

5.1. .

5.2. L-,
2 3500-3100 cm-1 1600-
1590 cm-1.

93
 5.3. - , .

5.4. D-.

5.5. 4--4--2-.

94
 5.6. t- -,
.

()

() ()
5.7. FT-IR FT-IR
( .()Real-time FT-
IR ,() Synchronous 2D-IR , ()
Asynchoronous 2D-IR .

95
5.3. :
1. Makanishi K. Infrared Absorption Spectroscopy Practical. Holden Day,
San Franscisco, 1962.
2. Szymanski HA. Infrared Theory and Practice of IR Spectroscopy. Plenum
Press, New York, 1964.
3. Colthup NC, Daly LH, Wiberley SE. Introduction to IR and Raman
Spectroscopies. Academic Press, New York, 1964, 1975 (2nd ed).
4. Conley RT. Infrared Spectroscopy. Allyn and Bacon, Boston, 1966, 1972.
5. Van der Maas JC. Basic Infrared Spectroscopy. Heyden, London, 1966,
1972.
6. Cross AD. An Introduction to Practical IR Spectroscopy. Butterworths,
London, 1969.
7. Makamoto K. IR Spectra of Inorganic Coordination Compounds. John
Wiley and Sons, New York, 1970, 1986 (4th ed).
8. Finch A, et al. Chemical Applications of FAR IR Spectroscopy. Academic
Press, London 1970.
9. Cook BW, Jones K. A Programmed Introduction to IR Spectroscopy.
Heyden and Son, London 1972.
10. Miller KGJ, Stace BC (eds). Laboratory Methods in IR Spectroscopy.
Heyden and Son, New York, 1972.
11. Wright HC. Infrared Techniques. Clarendon Press, Oxford, 1973.
12. Bellamy LJ. The Infrared Spectra of Complex Molecules.; Methuen,
London, 1975, 1981 (4th ed).
13. Bellamy LJ. Advances in Infrared Group Frequencies. Methuen, London,
1975.
14. Maslovaki E. Vibrational Spectra of Organometallic Compounds. Wiley
Interscience, New York, 1977.
15. Makanishi K, Solomon P. Infrared Absorption Spectroscopy. Holden Day,
San Francisco, 1977 (2nd ed).
16. Griffiths PR. Chemical IR Fourier Transform Spectroscopy. John Wiley and
Sons, New York, 1975.
17. Hill HC, London AG. Interpretation of IR Spectra A Programme and
Introduction. John Wiley and Sons, New York, 1975.
18. Mattson JS, et al. Infrared Correlation and Fourier Transform Spectroscopy.
Marcel Dekker, New York, 1977.
19. Smith AL. Applied Infrared Spectroscopy. Wiley Interscience, New York,
1976.
20. Ferraro R, et al. Fourier Transform IR Spectroscopy: Application to
Chemical Systems. Academic Press, New York, 1978, 1985.
21. Durig JR (ed). Analytical Application of FT IR TO Molecular and
Biological Systems. Reidel D Co, Dordrecht, Holland, 1980.
22. Ferraro JR, Basile LB (eds). Fourier Transform IR Spectroscopy: Techniques
Using Fourier Transform Interferometry. Academic Press, London, 1984.

96
23. Theophanides T (ed). Fourier Transform Infrared Spectroscopy. Reidel D
Co, Dordrecht and Boston, 1984.
24. Durig JR (ed). Chemical, Biological and Industrial Applications of Infrared
Spectroscopy. Wiley Interscience, New York, 1985.
25. Philips Analytica. Principles and Practices of Infrared Spectroscopy. Pye
Unicam Ltd, Cambridge, 1986.
26. George B, McIntyre P. Infrared Spectroscopy. Analytical Chemistry by
Open Learning Series. John Wiley and Sons, Chichester, 1987.
27. Griffiths PR, De Haseth JA. Fourier Transform Infrared Spectroscopy. John
Wiley and Sons, Chichester, 1986.
28. Clark RJH, Hester RE (eds). Advances in Infrared and Raman
Spectroscopy. Vols 1 12, John Wiley and Sons, London, 1975 1985.
29. Ishida H (ed). Fourier Transform Infrared Characterisation of Polymers.
Plenum, New York, 1987.
30. Siewsler HW, Ozaki Y, Kawata S, Heise HM. Near-Infrared Spectroscopy.
Principles, Instruments, Applications. Wiley-VCH, Weinheim, 2002.
31. Stuart B. Infrared Spectroscopy: Fundamentals and Applications. John
Wiley & Sons, Chichester, 2004.

97
98


(Nuclear Magnetic Resonance, NMR) 1945 Bloch
(Hansen, Packard) Stanford
Purcell . NMR

(
1952). , ,
1H, 13C, 14N, 19F .,

. NMR
Fourier (Pulse Fourier Transform NMR,
FT-NMR) NMR
,
NMR .

6.1.

: spin
(nuclear spin) (angular momentum)
. spin
spin .
spin () ,

,

spin.
, spin ,
, ,

, ,
, .
spin
.

99
 6.1.() ,
() , (), () ()
spin.

,

Planck (h/2). ,
spin 0, , 1, 1+ , 2, ., =
h/2. spin
. (1, 3, 5, )
spin () 1/2, 3/2, 5/2, .
spin .
spin 1, 2, 3, . ,
1H, 19F, 13C, 15N, . =1/2, 1H, 12C, 16, 32S

spin () .
, (+)

. () (nuclear magnetic
moment) :
I h
= (6.1)
2

100

(magnetogyric ratio) .
6.1 :
= p (6.2)
Ih
, p = . spin
2
,
= h/2 spin .

6.2. spin I
(0).
spin = 1 (-1, 0, +1).

.

.
()
.
spin , 2+1
.
spin (mI) (magnetic quantum number of spin).
mI , -+1, , -2, -1, . , spin
=3/2 (2 x 3/2 + 1 = 4): mI = - 3/2, - 1/2, +1/2 + 3/2, ,
, spin =1/2 mI= - 1/2, +1/2.

101
6.1.1. () spin.

,
,
. mI

( ), mI

.

6.3. spin
.

()
I h
(), E . = mI
2
:
h
E = H o E = m H o (6.3)
2
( EH o =0 EH o )
spin
I=1/2, I=1 I=3/2 .

102
 m m m m m
Ho Ho
mH mH mH mH

mI = +1/2 mI = -1/2 mI = +1 mI = 0 mI = -1
I = 1/2 I=1
mI= -3/2
E mI= -1/2 E mI= -1 E
DE mHo mI= -1/2
Ho Ho Ho
mI= 0
mHo mI=+1/2
mI=+1/2 mI= +1
DE=hv mI=+3/2

I = 1/2 I=1 I = 3/2

mI = 1/2 mI = -1, 0, +1 mI = -3/2, -1/2, +1/2, +3/2

6.4. I=1/2, 1 3/2.

( , ).

,
mI ,
mI = 1. :
h
= Ho (6.4)
2
mI =1, ( CGS Gauss
SI Tesla 1Tesla=104G), (
CGS erg/Gauss SI Ampere/m2 ) o (
CGS Gauss/s SI radian/Tesla x s).

( )
(
)
. 6.5 :
h
= h = = (6.5)
2 2

( )
. NMR.

(), ()
() .
NMR 10

103
100 KGauss ,
, 5 400 Hz.

6.1.2. ().

6.5 spin =1/2.
,
mI=1/2 mI= -1/2,
6.4.
.
:
(i) (ii)
( ).

E mI= -1/2

=hv
Ho

mI= -1/2

6.4. . (: ).

NMR .

(= ).

Boltzmann, 2.
.
,
Boltzmann:

hv
Na Na
= e k = e k (6.6)

k Boltzmann, =hv
. e X =1X, <<1,
/= 1 hv/kT (hv<<kT).

104

, > .
,
, 1, = 2.35 Tesla
v = 100 MHz ,
: =hv=(6.63 x 1034 J s) (100 x 106 Hz s1) = 6.63 x
1026 Joules. Boltzmann k=1.38 x 1023 J K1
=27 + 273 = 300 , :

6.6310 26
Na 5
= e 1.3810 300 = e 1.610
23

Na
: 1 1.6 10 5 .


. 105

( ). ,
NMR
,
.
NMR IR UV. ,
,
, NMR
.

6.1.3. . Spin-
spin-spin .

,
,

. NMR
( )
Boltzmann,
,
.

( , relaxation process). ,
1 = 1/k ,
spin ( ,

105
spinlattice relaxation time).
1 0.1100 s,
, .
spin
NMR
, t =h.
1 ,
h/1,
1/1 (

NMR). spin
( )
NMR (line width broadening). 10-2 Hz
102 Hz 1 . H spin

(longitutinal relaxation time) FT-NMR.
1
.
.
spinspin
(spinspin relaxation time, transverse relaxation time:
). 2
1 ,
(natural line width).
,
2 :
1 1
T2 = W1 / 2 = (6.7)
W1 / 2 T2
W1/2 1/2 .
2 ( 104 s), 2 1
(104 10 s). ,
NMR
NMR (
).

(saturation).
( ) ,
(
NMR)
(
) .

106
 NMR ( )
spin .

6.2. .

,
,

.
(chemical shift) spin (spin couplings),
.
( 10000 25000
Gauss) , spin
, 1,
.

o
6.5. 1
=1/2.

H ,
. ,

.
,
(precess) ,
6.6.
, , L,
:

107
 L = Ho (6.8)
dp I h
= p L = , p =
dt 2
:
d
= Ho (6.9)
dt
(
).
:
d
= o (6.10)
dt
radianss1 (
).
6.9 6.10 = .

:
Ho
o = o = (6.11)
2 2
6.11 Larmor.
Larmor,

.
, 1,
( 6.6) ,

.
1 spin.
spin .
1
,
Larmor, .
,
. ,
NMR ,
spin ,
(
). 1
Larmor ,

NMR.
1025 KGauss.
Larmor , ,

108
 , Megahertz (1 MHz = 106 Hz, 1 Hz = cps :
).
=14100G
:

14 2 13 31 19 1
N H C P F H

0 10 20 30 40 50 60 v (MHz)
6.6. Larmor 14100 G

NMR,
,
. , ,

.

6.3. .

NMR
spin .
,
() ()
= H :
H = (6.12)

= h/2 :
H = h H o I (6.13)
2

.
[ :
.
,
, , .,

.

, :

109
 = = ( xHx + yHy + zHz)

x, y z ].

, :

h
E mI = H o mI (6.14)
2

mI , +1, , 1, .
2+1 ,
.
,
.

.
NMR
.

6.7. 2+1 : ()
=3/2 () =2.
,
.

110
6.4.
.

NMR :
(CW, continuous wave)
Fourier (FT-NMR, Pulse Fourier Transform
Spectrometer).
(Highresolution NMR) NMR
(RF)

(
).

6.8. (NMR).

NMR ( 5
mm)
.
(RF)
(single-coil
spectrometer) (cross-coil spectrometer).
, -
. RF ,
. NMR
(precalibrated recorded charts)
,
(tetramethylsilane, TMS).

111


. 0,5 Hz 60 Hz,
1/108, NMR.

.
25 Gauss,
( )
. 1H NMR
60, 80, 90, 100 Hz,
200, 300, 360 500 800 Hz.

20cm .
,

.
, .

( NMR, multinuclear NMR)
( ,
).

6.4.1. .

NMR ( 15 cm 0,5 cm) 2-3
(TMS DSS, . 6.5.3.)
( 2-3 cm)
~30 /s ( 100-
200c/s).
( TMS
=0) (internal locking signal).
NMR /
.
,
RF (.. 60 Hz),
1,4 Tesla - ()
(field-
sweep generator)
. -
(field-sweep spectrum),
- (frequency-sweep

112
spectrum). ,
. , (..
) ,
RF
,
( )
.
10-20 mg 1, 19F 31P
0,5ml 5min.
, 13C (.. 1.108%)
100 mg. ,
. FT-NMR
( ) 1-10 mg
1 .

6.4.2. NMR.

1 NMR (98-99%)
.
: CDCl3, CD2Cl2, CDCl2CDCl2,
CD3COCD3 -d6, C6D6,
(CD3)2SO, CD3OD, D2O ..
, , :
CCl4, CS2, CFCl3, CF2BrCl, C6H12, C4H8O2,
CH2CHCl, C6H5NO2 .., .
(>140 C)
1,1,2,2-, DMSO,
1,2,4. :
, , ,
(THF) ( < 150C).

.

6.4.3. NMR.

( spin I 0)

.
NMR :

113
 6.1. .

Spin I NMR (MHz)
(h/2) 23.5G NMR

1 99.98 1/2 100.0 1.00
13C 1.108 1/2 25.19 0.016
14 99.63 1 7.22 0.001
15 0.37 1/2 10.13 0.001
19F 100.0 1/2 94.08 0.83
31P 100.0 1/2 40.48 0.07
17 0.0037 5/2 13.56 0.03
33S 0.74 3/2 7.76 0.0023
35Cl 75.5 3/2 9.8 0.0047
195Pt 33.7 1/2 21.5 0.01
27Al 100.0 5/2 26.06 0.21
29Si 4.67 1/2 19.86 0.08

6.5. .

NMR

(chemical shift).
,
.
, ,
6.5,
, (nuclear shielding).
.

:

= 10 6 ppm (6.15)

(reference)

(sample or induced field).

114
 6.9.

.

,
:

= (6.16)

(shielding or screening factor).

, (effective)
. 6.14
:
= = (1) (6.17)

6.5.1. .

s
.
,
.

( 6.17). s
,
(diamagnetic shift)
(diamagnetism).
, p p
.
,

.
(paramagnetic shift).

115
6.5.2. .

,
, (Hz=cps)
.
,
, (ppm),
.
Larmor,
,
, :

o = H o (1 ) (6.18)
2

( RF) :
() RF
, =/2 (1) =/2 (1),
.
:

6
= 10 ppm (6.19)

()
, : =(/2)(1)
=(/2)(1) :

H H 6
= 10 ppm (6.20)
H

: ()
( ),

, ,
()

.
,
.
1H NMR (
), TMS,

116
 (=0).
TMS 1-12
.

,
, NMR.
6.11,
:

=10 (6.21)

6.10. 1H NMR
O
CH3CH2OCCHCl2 60 Hz (1ppm=60 Hz).

6.5.3. .

1H 13C NMR,
, Si(CH3)4 (TMS).
,

. TMS
.
TMS 5% 2-3 .

117
 2,2--2-
-5- (DSS, (CH3)3SiCH2CH2CH2SO3Na).
DSS ( CH3) =0.
DSS .

6.2. NMR
NMR.

TMS (0.0)
(1.63)
1H (6.95)
(2.216)
(2.059)

TMS
13CS
2
13C CH313COOH
K213CO3
CCl3F
CF3COOH
19F CF4
C6F6

6.5.4. (1H).

, p
.
1H
10 ppm, 200
ppm. ,
C3, ,

( ).

6.3. 1H C3.

(C3) () (C3) ()
Si(CH3)3 0.0 1.90 I 2.16 2.65
H 0.13 2.20 Br 2.68 2.95
CH3 0.88 2.60 Cl 3.05 3.15
CN 1.97 OH 3.38 3.50
NH2 2.36 3.05 F 4.26 3.90

118
 , 1H

.

6.4. 1H .

(0.5) (0.5) (0.5) (0.5)

RCOOH 11.53.0 1.5 CH3OR 3.3 6.7
RCHO 10.03.0 CH2COR 2.4 7.6
H
C 5.3 4.7 CH 2.2 7.8
R
H
C 5.0 5.0 CH3COOR 2.1 7.9
H
CH2OCOR 4.2 5.8 CH3COR 2.1 7.9
CH3
CH3OCO 4.0 6.0 C 1.8 8.2
R
CH3OCOR 3.7 6.3 C CH2 C 1.5 8.5
CH2OR 3.5 6.5 C CH3 0.9 9.1
* (.) (,)
() .

,
1H 6.5.

119
 6.5. 1H .

120

Shoolery , ,
: CH2XY CHXYZ, X, Y, Z
.
H
C C

. ,
(C6H5)
.


.
.

6.6. ( ) gia
(-), (m-) (p-)
.

NO2 0.95 0.26 0.38
COOCH3 0.71 0.11 0.21
COCH3 0.62 0.14 0.21
CHO 0.56 0.22 0.29
CN 0.36 0.18 0.28
F 0.29 0.02 0.23
Cl 0.03 0.02 0.09
Br 0.18 0.08 0.04
J 0.39 0.21 0.00
OH 0.56 0.12 0.45
OCH3 0.48 0.09 0.13
OCOCH3 0.25 0.03 0.13
CH3 0.20 0.12 0.22
NH2 0.75 0.25 0.65
( = 7.262
)

,

.


,
,

121
 . , s


, .
,
NMR
().

6.11.
, -,
z.

6.12.
( ).
(diamagnetic anisotropy).

122
6.6. Spin - Spin .

NMR spinspin (spinspin coupling).
(, )
.. ,
,
( NMR,
0.01 ).
,
( )
. ,
=
. , ,
CHCl2CHO, ()
(CHCl2CHO),
.

6.14. 1 NMR CHCl2CHO 60 z.

. H
H.
mI =+1/2,
[+ () ] H mI=1/2,
[ () ]
H. H
H
.
H H.
,
H.
spinspin (spinspin coupling constant)

123
 J. J H H,
z.

,
spin ,
,
.
, 1,1,2- (CHCl2CH2Cl)
. CH2
(,
)
( CH),
CH
spin CH2.
( H ): , , ,
, mI =+1, mI =0 mI = 1 ( 6.4.).

(triplet) (J)
1:2:1, mI =0 spin.

6.14. 1 NMR CHCl2CH2Cl 60 z.

, CH3CHO,
spin
(CH3), :

124
 1.aaa, +++ mI = +3/2

2.aab, _
++

3.aba, + _+ mI = +1/2

4.baa, _
++

5.bba, _ _+

6.bab, _+_ mI = -1/2

7.abb, __
+

8.bbb, ___ mI = -3/2

spin
CH3
spin CHO,
J
(quartet).

6.15. 1 NMR , CH3CHO 60 z.

.
spin mI=1/2 (
) ,
1:3:3:1. CH3 CHO,
,
(doublet).

NMR, spinspin , :

125
 n (n=1, 2, 3,) ,
, n+1
( )
(1+)n, n=3
1:3:3:1, n=4, 1:4:6:4:1, ..

Pascal. (1+)n :

n=0 1
n=1 1 1
n=2 1 2 1
n=3 1 3 3 1
n=4 1 4 6 4 1

spinspin
,

.
NMR

.

6.6.1. spinspin spinspin .

spin .
(
NMR) ,
.
: ()

, ()
()
spin s-,

, (contact term).
,
, . ,

. . ( ).
, - - (C.C, F.F)

126
 - - (C.,
. F).

6.6.2.

- , 3JHH (vicinal proton-proton coupling).
3
. NMR

Karplus:

s
.
C C , Jtrans
Jcis.
,
, CH.
2

spin-spin
:

(Hz)
Jcis = 11.7
H 2C CH2
Jtrans = 19.0
HC CH J = 9.5
CH
J = 7.6
CH

4
3 J23 = 5.5
J34 = 7.5
2
N

, spin-spin 2JHH (geminal spin-
spin coupling).
-20 +40 Hz.

127
 (Hz)
CH4 J = -12.4
CH3CCl3 J = -13.0
CH3COCH3 J = -14.4
CH3F J = -9.6
H2C O J = +41
H2C CH2 J = +2.5
H2C CHF J = -3.2
H2 C CHLi J = +7.1
BrCH2CH2OH J = -10.4

-, nJHH, (long-range HH coupling)

.
.
- :

(Hz)
4J
cis = -1.7
H2 C CHCH3 4J
trans = -1.3
* *
5J = 1.2
cis
CH3CH C(CH3)COOH 5J
* * trans = 1.5

CH3C C C C CH3 7J = 1.3

* *
CH3

1 Br 4J = -0.63
2 (Me H6)
6
5J
(Me H3) = +0.40
5
6J
(Me H4) = -0.58
3
Cl
4

6.6.3. - -.

spin-spin
-.
1JC (-)
s-
CH.

128
 -, 1JCC 13CNMR
CH,
, 13C.
,
, -
.

( 13CNMR)
.

129
 6.7. .
1. Pople JA, Schneider WG, Bernstein HJ. High Resolution Nuclear Magnetic
Resonance. McGraw-Hill, New York, 1959.
2. Roberts JD. Nuclear Magnetic Resonance. McGraw-Hill, New York, 1959.
3. Emsley JW, Feeney J, Sutcliffe LH. High Resolution NMR Spectroscopy.
Pergamon Press, Oxford, 1965.
4. Hecht HG. Magnetic Resonance Spectroscopy. John Wiley and Sons, New
York, 1967.
5. Carrington A, Mclachlan AD. Introduction to Magnetic Resonance. Harper
and Row, New York, 1967, 1969.
6. Carrington A, Hudson A, Mclachlan AD. Introduction to Magnetic Resonance.
Chapman and Hall, London, 1984.
7. Mathieson DW. NMR for Organic Chemists. Academic Press, New York, 1967.
8. Bovey FA. NMR Spectroscopy. Academic Press, New York, 1969.
9. Becker ED. High Resolution NMR. Academic Press, New York, 1969, 1980.
10. Andrew EP. Nuclear Magnetic Resonance. Cambridge University Press,
Cambridge, 1969.
11. Diehl P, Fluck E, Kosfeld R (eds). Basic NMR: Principles and Progress.
Springer-Verlag, Berlin, 1970.
12. Farrar TC, Becker ED. Pulse and Fourier Transform NMR: Introduction to
Theory and Methods. Academic Press, New York, 1971.
13. Maclachlan KA. Magnetic Resonance. Clarendon Press, Oxford, 1972.
14. Dwek RA. NMR in Biochemistry. Oxford University Press, New York, 1974.
15. Myers RJ. Molecular Magnetism and NMR Spectroscopy. Prentice-Hall, New
Jersey, 1973.
16. Dwek RA, et al. NMR in Biochemistry. Academic Press, London, 1977.
17. Harris RK, Mann BE. NMR and the Periodic Table. Academic Press, London,
1978.
18. Abraham RJ, Loftus P. Proton and Carbon-13 NMR Spectroscopy: An
Intergrated Approach. Heyden, London, 1978.
19. Harris RK. Nuclear Magnetic Resonance Spectroscopy. Pitman, London, 1983,
1986 (revised edition, Longman, London).
20. Jardetsky O, Roberts GC. NMR in Molecular Biology. Academic Press, New
York, 1981.
21. Shaw D. Fourier Transform NMR Spectroscopy. Elsevier, Amsterdam, 1984,
1987.
22. Williams D. Nuclear Magnetic Resonance Spectroscopy (Analytical Chemistry
by Open Learning Series). John Wiley and Sons, Chichester, 1986.
23. Yoder CH, Schaffer CD, Introduction to Multinuclear NMR. Benjamin-
Cummings, California, 1986.
24. Paudler WW. Nuclear Magnetic Resonance: General Concepts and
Applications. Wiley-Interscience, New York, 1987.

130
25. Kemp W. NMR in Chemistry: A Multinuclear Introduction. Macmillan,
London, 1987.
26. Sanders JKM, Hunter BK. Modern NMR Spectroscopy: A Guide for Chemists.
Oxford University Press, Oxford, 1987.
27. Sanders JKM, Constable EC, Hunter BK. Modern NMR Spectroscopy: A
Workbook of Chemical Problems. Oxford University Press, Oxford, 1989.
28. Abraham RJ, Fischer J. NMR Spectroscopy. John Wiley and Sons, New York,
1988.
29. Atta-Ur-Rahman HE. Nuclear Magnetic Resonance. Elsevier, Amsterdam,
1986.
30. Freeman RA. Handbook of NMR. Longman, London, 1987, 1988.
31. Ernst RR, Bodenhansen G, Wokann A. Priciples of Nuclear Magnetic
Resonance in One and Two Dimensions. International Series Monographs on
Chemistry. Oxford Science Publications, Oxford, 1990.
32. Breitmaier E. Structure Elucidation by NMR in Organic Chemistry. John
Wiley & Sons Ltd, Chichester, UK, 1993.
33. Sanders JKM, Hunter BK. Modern NMR Spectroscopy, 2nd ed., Oxford
University Press, Oxford, 1993.
34. Quin LD, Verkade JG, eds. Phosphorus-31 NMR Spectral Propertiew in
Compound Characterization and Structural Analysis. Wiley-VCH, New York,
1994.
35. Maciel GE. Nuclera Magnetic Resonance in Modern Technology. Klumer
Academic, Dordrecht, 1994.
36. Hore PJ. Nucleal Magnetic Resonance. Oxford Chemistry Primers, No 32,
Oxford University Press, Oxford, 1995.
37. Cavanagh J. Protein NMR Spectroscopy: Principles & Practice. Academic
Press, San Diego,KA, 1996.
38. Grant DM, Harris RK, eds. Encyclopedia of NMR, Vol. 1, John Wiley & Sons,
New York, 1996.
39. Macomber RS. A Complete Introduction to Modern NMR spectroscopy.
Wiley-Interscience, New York, 1998.
40. , . NMR.
.
, , 1998.
41. Claridge TDW. High Resolution NMR Techniques in Organic Chemistry.
Tetrahedron Organic Chemistry Series, Vol.19, Pergammon Press, Oxford,
1999.
42. Hore PJ, Jones JA, Wimperis A, Wimperis S. NMR: The Toolkit. Oxford
University Press, Oxford, 2000.
43. Levitt MH. Spin Dynamics-Basics of Nuclear Magnetic Resonance. John Wiley
& Sons, New York, 2001.
44. Berger S, Braun S. 200 and More NMR Experiments: A Practical Course.
Wiley-VCH, New York, 2004.

131
45. Duer M. Introduction to Solid-state NMR Spectroscopy. Blackwell Publishing
Ltd, London, 2004.
46. Frebolin H. Basic One- and Two-Dimensional NMR Spectroscopy. John Wiley
& Sons, New York, 2005.
47. Balci M. Basic 1H-13C-NMR Spectroscopy. Elsevier, Amsterdam, 2005.
48. Pochapsky T, Pochapsky S. NMR for Physical and Biological Scientists. Taylor
& Francis, New York, 2005.
49. ., . NMR.
,
, , . . ..
, , 2006.

132


7.1.

(1) -13 (13C),

NMR -19,
-14, -31 -17.
-19 (19F): 19F
.

.
100% 19FNMR. ,
spin- (1)
. ,
.
NMR 19F spin 1/2.

NMR .
-31 (31P): , spin 1/2
100%. ,
NMR 7% 1.
, 31P


.
. 31PNMR
,
(, , , .).
-14 (14): 14 99,63% spin 1.
(quadruple moment)
,
.
-15 (15) spin 1/2,
(0,37%)

133
 . 15NMR
( ).
-17 (17): 17
(0,037%)
. , 17NMR
, Fourier,
.

7.2.

, ,
1NMR
.

200 ppm.
.

spin
.

, .
,

.
, (contact interaction),
(pseudocontact interaction).
, ,
.
,
spin.
, ,
,
.
,
.

7.3.

NMR

(isotope substitution).

134
 ,
. , () 13C
0,3 ppm 13CDCl3 13CCl3,
. ,
19F 0,47 ppm CF2 CD2 .

.
, ,
,
.

7.4.

(shift reagents),

.
( ).

.

,
.
-
(Eu), (Pr), (Yb)
:
R t
Bu

O CH O C
3+ CH2
M M CH
O C O C

C(CH3)3 CF2CF2CF3
3 3

,
CCl4 CDCl3
NMR.
Eu
, Pr .

135
7.5.
NMR

NMR

.

.

.
: ()
, ()
() Van der Waals

(
0,1-0,2 ppm ), ()
, ,
, 0,5 ppm. ,
,
0,2-0,4 ppm, ()
,
()
- ,
.

7.5.1. .

. ,
, .
( )
10 ppm.
,
( ) 5,3 ppm, ( )(
) = 4,6 ppm. ( )
8,7 ppm ( )( ) = 4,3 ppm.

O H O
C2 H5 O H O C2H5 C6H5 C C C6H5
H
O H O

136
 To NMR 1
. ,
(
),
.

,
,
,
X H Z X H . ,
X H
,
.

, (
).
H
H3C C CH3
H
: 7.45 4.37 ()
C C
: 12.0 (-) : 12.1
O O O
H
CH3

7.6. .

NMR

. NMR
, ,
,
IR UV-VIS. NMR
.
,
, .
, NMR
.
,
(,
IR UV-VIS
). ,

, 13C-NMR

137

.
NMR .
NMR (
)
,
.
,
.
(intergrator) NMR
1-2% (
).
: () /
, ()
,
. ,
.

.
, 14C 13C (1,1%).
13C
.

. ,
13C,
.
(spinning sideband)

. ,


.
,

( 30 ).
13C FT-NMR
. ,
Overhauser ,
. NMR
(..
-d5 -d6),
, ,
.

138
7.7. NMR

NMR ,
,
, .
.

.

FT-NMR
. ,
,
54,7, "
" (magic angle).
.

FID ( FT-NMR).
NMR
,
NMR
.
- - ,
.

7.8. 31P 13C NMR

R
.
31P
( 1),

.
13C
, 13C.
- (precursors) 13C.
*
, ( CH3COOH [2-13C] )
13C 1 2, .

* *
(.. CH3COOH , [1,2-13C] ) 13C13C

139
 . -
(1-2%
).
-
. , 13C
.
NMR
.

7.9. NMR

NMR .
, 31P-
NMR,
. (
1) ,

NMR. NMR
, .

.

, Larmor, =,
,
.
( )
.
,

.
FT-NMR,
-
.
NMR
.

140
 MRI
MRI

RI .
MRI

7.1. NMR . MRI (Magnetic Resonance Imaging)

,
.

141
 1 MRI 2 MRI
,

MRI MRI
(

)

7.2. MRI .
(http//:www.parksidemri.com/physician/casestudy/).

142
7.9.1.
(NMR)

1. Edelman R.
: , ,
1988.
2. Westbrook C, Westbrook C. Magnetic Resonance (MRI)) in Practice. Blackwell
Science, London, 1998.1
3. Freeman R. Magnetic Resonance in Chemistry and Medicine. Oxford
University Press, Oxford, 2003.
4. Donald W. Magnetic Resonance Imaging (MRI) from Picture to Proton.
Cambridge University Press, Cambridge, 2002.
5. Haschemi RH, Bradley WG. Magnetic Resonance Imaging (MRI) the Basics.
Lippincott Williams & Wilking, New York, 2003.
6. Jezzard P (ed). Functional Magnetic Resonance Imaging: An Introduction to
Methods. Oxford University Press, Oxford, 2003.
7. Kuzniecky R, Jackson G. Magnetic Resonance in Epilepsy: Neuroimaging
Techniques. Academic Press, London, 2004.
8. Scott SN, Song AW, McCarthy G. Functional Magnetic Resonance Imaging.
Sinaner Associates Ince, New York, 2004.
9. , . NMR.
,
, , . . ..
, , 2006.

143
7.10. NMR.

IR UV-VIS,
,
. , NMR
Larmor
,

.
,
,
.

Heisenberg (t ) (mean lifetime)

(.. 50 Hz ~310-3 s,
NMR).
, cis- trans- ,
, - ,
(proton
exchange) .,
. NMR NMR (Dynamic NMR
DNMR).
,
, :
A B (7.1.)

(nA) (nB)
nA nB .
:
() G,
n B / n A = e G / RT nA + nB = 1
()
(rate of intercorversion)
G (free energy of activation).
:
RT ( G m / RT )
k= e (7.2)
Nh
Larmor
( > )
,
, :

144
 = = 2 (7.3)
( 2 ).


, =1/2( + ) ,
,
( - ), ( - ).
,
,
.

NMR:
1. :
,
,
( - )
.
,
.
. ,
,
.
2. .
, 2, .
, t=h/2,
t.
t ,
.
W1/2:
h 1
W1 / 2 E / h 1/ (7.4)
2t h 2t

.
3. .

,
. .
, (rotating frame of reference)
, (laboratory frame)
,
, 1/2 ( - ).
,
, .

145
 NMR

.

()
1-NMR -
d11
(Bovey FA, et al. J Chem Phys
41: 2042, 1964)
()
NMR

7.3. NMR.() 1-NMR -d11

(60MHz).() NMR
(, ) ( ).

NMR
, - .

146
 CH3 CH3
H3C C N H3C C N
CH3 CH3
O O
(A) (B)

1-NMR [80MHz, (CD3)2SO, 75% v/v]

7.4. 1-NMR. ,-
.

,-
DNMR. 400
. ,
CH3
.
CH3 ,
. ,
, (coalescence point)
.

7.10.1. NMR

NMR
.
Bloch ( , Becker).

.

147
 ,
1 1
. : 0
T2( A) T2( B )

:
( ) 2
g (v ) = K (7.5)
[1 / 2( ) ]2 + 4 2 2 ( ) 2 ( ) 2
.
( 7.3. 7.4.),

:
R/ ( - ). R=1/2 (7.6)
, NMR
,
(-) Hz.
,
, (-).
7.5 :
1/ 2
1
= 1 (7.7)
( ) 2 ( )
2 2 2

.

7.7 ( = 0) :
1
= (7.8)
2 ( )

.

, pH , ..


. ,
(total line shape programs,
TLS programs), .



.
.

148
7.12. NMR (DNMR)

1. McFarlane W, White RFM. Techniques of High Resolution NMR

Spectroscopy. Butterworths, London, 1972.
2. Chan SO, Reeves LW. Mechanistic studies of chemical exchange reaction by
complete NMR line-shape. J Am Chem Soc, 95: 670, 1973.
3. Jackmann LM, Cotton FA (eds). Dynamic Nuclear Magnetic Resonance
Spectroscopy. Academic Press, New York, 1975.
4. Jackman LM, Cotton FA, Adams RD. Dynamic Nuclear Magnetic Resonance
Spectroscopy. Academic Press, New York, 1975.
5. Leyden DE, Cox RH. Analytical Applications of NMR. John Wiley and Sons,
New York, 1977.
6. Roberts JD. Aspects of the determination of equilibration rates by NMR
spectroscopy. Pure and Appl Chem, 51: 1037, 1979.
7. Laszlo P. Fast kinetics studied by NMR. Progr in NMR spectr, 13: 257, 1980.
8. Kaplan JI, Fraenkel G. NMR of Chemically Exchanging Systems. Academic
Press, New York, 1980.
9. Kanfmann EN, Shenoy GK. Nuclear and Electron Resonance Spectroscopy
Applied to Material Science. North-Holland, New York, 1981.
10. Fukushima E, Roeder SBN. Experimental Pulse NMR: A Nuts and Bolts
Approach. Addison-Wesley, Reading, Mass, 1981.
11. Sandstrm J. Dynamic NMR Spectroscopy. Academic Press, London, 1982.
12. Lindman B. Dynamic NMR Spectroscopy. Academic Press, London, 1982.
13. Levy GC (ed). NMR Spectroscopy: New Methods and Applications. Am
Chem Society publications, Washington DC, 1982.
14. Gadian DG. Nuclear Magnetic Resonance and its Applications to Living
Systems. Clarendon Press, Oxford, 1982.
15. Mehring M. High Resolution NMR in solids. Springer-Verlag, Berlin, 1983.
16. Fyfe CA. Solid State NMR for Chemists. CFC Press, Guelph, Ontario, 1983.
17. Smith JAS (ed). Advances in Nuclear Quadrupole Resonance. Heyden,
London, vols1-5, 1974-1983.
18. Michinori O. Applications of Dynamic NMR Spectroscopy to Organic
Chemistry. VCH Publishers, Berlin 1985.
19. Oki M. Applications of Dynamic NMR Spectroscopy to Organic Chemistry.
VCH Verlag, Weinheim, 1985.
20. Takenchi Y, Marchand AP (eds). Applications of NMR Spectroscopy to
Problems of Stereochemistry and Conformational Analysis. VCH Verlag,
Weinheim, 1986.
21. Derome AE. Modern NMR Techniques for Chemistry Research. Pergamon
Press, Oxford, 1987.
22. Jackson A, Buckley D, Parker GJM (eds). Dynamic Contrast-Enhanced
Magnetic Resonance Imaging in Oncology (Medical Radiology S). Springer-
Verlag, Berlin, 2003.

149
150


FOURIER

NMR
IR UV-VIS. ,
,

.

,
.

NMR,
200, 360 500 MHz (800-1.000 MHz ),
. ,
,
.
,

. ,
NMR ,
.
/ (
, .. 1000
/ 1000 = 10 ).

, Fourier 8.000
.
, 5-10 min.

, ,
,
(RF pulse).
NMR.

151
 CH2CH3

8.1. 1-NMR
(1, 10 100).
.

8.1. Fourier NMR

NMR Fourier
(Pulse-Fourier Transform NMR Spectrometer, FT-NMR)
.
( ),
,
,
Fourier.
, ,
( )
,

. FT-NMR
spin .

8.1.1.

NMR Larmor
, .
spin I=1/2 :
,
Boltzmann
,

152
 , (resultant magnetization vector)
, 8.2.

spin
Larmor

8.2. spin .

(stationary or laboratory frame of
reference).
Larmor ,

z H, 8.3.

, .

Ho
z

Mo


y'

x, y
x'

8.3. (=1/2) .

(rotating frame
reference system).

153
8.1.2.

, x
(
NMR), ,
(1) x
.
,
() x .
:
= 1 rad s-1 (8.1)
rad .
t ,
, (
8.4.):
= 1 t rad (8.2)

Mo
x'

y'
Mo

H1

RF

8.4.
t ( = y). 1 RF
.

FT-NMR
y.
.
.
360
= 1 t (8.3)
2

154
8.2. ( )

(RF)
x
.
: x = 0 , y = z = .
RF , spin
, (
-z) .
, -z

spin- 1.
spin
. z
, -y
z = , y = 0 ( y z ).
:

(M o M z ) = M o (1 ) e t / T1 (8.4)

-y( spin-spin 2)
:

M y (t ) = M y (o ) e t / T1 (8.5)

M y (o ) ,
.
, spin

o , . spin
xy(
) ,
- y
- y,
- y(
x). ,
spin, spin-spin ( 2
).
, spin-
spin , :

M y (t ) = M y (o ) e t / T21 (8.6)

155
 -z
x y, 1 2 (1 2).

,
.
spin-
.
:

1DD - (dipole-dipole relaxation)

T1SR spin- (spin-rotation relaxation)
T1Q (quadrupolar relaxation)
T1Q (scalar relaxation)
T1CSA (chemical
shift anisotropy relaxation)

spin. spin
, 13C
1.
spin-
,
.
( ) spin
spin>1/2 ( 14, 2, Cl).
.
,
13C.
,

NMR.
(scalar)
,
,
( RCN R2C=O)
13C.

.
(paramagnetic relaxation).

156
8.3. H FT-NMR

F
t ,

F 1/t. t
F1/t.
,
.
, 2,43 Tesla 1000 Hz 1, 5000
Hz 13C 10000 Hz 15. (t) 1-
100 s (10-6 s).
(
) FT-NMR.
-y,
( ) 90.
90 t
, 90 (90 pulse time).

z z z
Mo Mo Mo

y' y' y'

=90o =45o =20o

x' x' x'

8.5. :90, 45 20.

FT-NMR ,
/ 90.
, ()
51,
51
spin
. 13C 15 1
100 . ,
( ) 1.
FT-NMR, RF ,
,
( )
spin,
, . FT-NMR
NMR (CW).

157
8.3.1. FT-NMR

NMR
, FT-NMR
. ,
F, (carrier frequency)
Larmor (FL),
,

( spin ).
(free induction decay, FID)
8.6 CW.

8.6. 13C-NMR : () FID,

F F1, () (CW), () 13C-NMR
FID F FL.

o F FL,
(sine wave) F - FL.

158

. ,
. ,
, FT-NMR
( )
( 8.7).
FID (interferogram).

8.7. 13C-NMR: () FID

, () (CW).

.
FT-NMR
( )
.


( )
.

Fourier (Fourier transform programme).

8.4. Fourier (Fourier Transform)

Fourier (FT).
:

159
 +
F(v ) = f (t )

e ivt dt (8.7)

F(v) f(t)
( FID).
FT-NMR, Fourier

. 8.7
.

8.4.1.
FT-NMR :

(FID) 8.000
(), FID.
FID
, ..

8.8. (1, 2, ) FID

.
spin ( , acquisition time)
(, delay). + +
(pulse interval).

8000 FID
.

Fourier .

, (max) (min),
2.
max FT-NMR

, = .

min
Hz,
2 sec.

160
 .
/2
,
. , 13C 3000 Hz
() = 8.000 , (
spin ) ta=8.000/2X3.000 =1,38s.
.
,
( spin- ),

. ,
(spin saturation).

8.4.2. (/)

/ NFID
,
Fourier
.
( , phase correction),

a .

FID
(Fourier
transformation)

Fourier

CH2CH3

8.9. 13 C-NMR FT
.

161
 /
:
( ). 13C FT-NMR
5.000 Hz ,
24,5gauss 198,5 ppm,
(proton noise decoupling).

8.5. FT-NMR

(double resonance technique)

spin (spin decoupling)
FT-NMR .
, spin
( )
,
(RF) , ,
.

,
.
, spin ,
(C H Cl 2 C H O) :

8.10. 1H-NMR(60 MHz) 1,1-.

(,) .
( )
RF,
( ).
spin
( )
,
,
, .
JAB

.

162


NMR .

.
,
CH3 CH CHCHO :

8.11. 1-R CH3 CH CHCHO

. (1) spin, (2)
CH3, (3)
CHO .

().
(homonuclear decoupling).

13C FT-NMR.
13C .

(heteronuclear decoupling)
13C .

163
8.5.1.

13C (0,01%)
FT-NMR,
13C . 13C 13C
, 13C 1
,
13C-NMR.
13C1
,

(proton noise decoupling),
{
13C 1H { .
.

13C-FT-
NMR

CH3CH2CH2CH2 O-CH=CH2
4 3 2 1 5 6

13C-FT-NMR

8.12. 13C-NMR n-.

,

.
(off-resonance decoupling),

.

13C-
NMR (internuclear
double resonance, INDOR).

164
 (
) ,
NMR,
,
( INDOR),
( INDOR).

, .

8.6.
. Overhauser

13C,
,
.

( spin- ,
T1). spin 13C
13C,
.
Overhauser (Nuclear
Overhauser Effect, NOE).
13C1,

.
spin
( spin)
( ) ,
. Overhauser
van der Waals
,
. ,
,
.

8.7. A 13C M M
X A.

( )
13C spin- spin-
spin 1 2. spin-

spin 8.2, spin-
spin

165
 (natural width)
. , (1/2)
spin-spin
. 1 2 13C
, FT-
NMR .

8.7.1. 1

1.
(inversion recovery
method) 180
-z.
z z

Mz0 x' x'

y' y'

-Mz0

8.13. z 180

M z0 - M z0 .
-z
M z0 , spin-
.
z z z z
0
Mz
0 Mz
x' x' x' x'
0 y' 0 y' 0 y' 0 y'

-Mz

(s)

8.14.

:
M z = M z0 (1 2 t / T1 ) (8.8)

166
 z
, M z0 (1 2 t / T1 ) = 0
1, ( 1 = to/2.303log2 = to/0.693, to z =0).
FT-NMR
-z, , 180
(, s)
90
-y( ) .
z z z z

x' x' x' x'

y' y' y' y'

180 s 90
8.15. -y .

, 1
ln( M z - M z0 ) ,
(
(slope, gradient)) 1/1.
(
)
/.

(5 1)
(progressive saturation).
90
.
, 4/5
, .
(90 )n
.
ln( M z - M z0 ) ()
1/1. 1 13C
8.16.

167
 8.16. 1 13C .

8.7.2. 2

2
.
1
W1 / 2 = (8.9)
T2
8.9 ,

.
E t h/2 = h, t
spin, 1/2 t. 2
spin NMR, : 1/2t
1/2 2. W1/2 =2 W1/2 = 2/2 t = 1/ 2.
2 spin
(spin echo technique), Carr-Purcell
Meibon-Gill.

168
 spin
90. spin xy
,
spin-spin
. ,
spin 180.

8.17. spin

180
.
, 180 (
2 90),
, ,
spin spin.
180 ( 8.18).

169
 8.18. spin- (spin echo technique). (a) y
spin 2 s, () spin-
Fourier.

spin
ln( M y ' - M y0' ) s ,
1/2 ( M y0' , 90). ()
ln(Io I/Io) =K t , 1/ = 2.
( ) 1 2
.
1 13C
, 1
.
1 10-3 1 s,
<1000 1 0.1 300 s,
0.1-10
10-300 s.

170
8.8. : -FT
1. Farrar TC, Becker ED. Pulse and Fourier Transform NMR: Introduction to
Theory and Methods. Academic Press, New York, 1971.
2. Stothers JB. Carbon-13 NMR Spectroscopy. Academic Press, New York,
1972.
3. Levy GC, Nelson GL. Carbon-13 NMR for Organic Chemists. John Wiley
and Sons, New York, 1972, 1980.
4. Levy GC (ed). Topics in Carbon-13 NMR for Organic Chemists. John
Wiley and Sons, New York,, 1974, 1984 (vol 4).
5. Wehrli FW, Wirthlin T. Interpretation of Carbon-13 NMR Spectra.
Heyden, London, 1976, 1988 (2nd ed)/
6. Mullen K, Pregosin PS. FT-NMR Techniques: A Practical Approach.
Academic Press, London, 1976.
7. Shaw D. Fourier Transform NMR Spectroscopy. North Holland, New
York, 1976, 1984.
8. Brithmaier E, Voelter W. Carbon-13 NMR Spectroscopy. Verlag Chemie,
Berlin, 1978.
9. Abraham RJ, Loftus P. Proton and Carbon-13 NMR Spectroscopy.
Heyden, London, 1978.
10. Fuckes PL, Bunnell CA. Carbon-13 Based Organic Spectral Problems. John
Wiley and Sons, New York, 1979.
11. Bates RB, Beavers WA. Carbons-13 Spectral Problems. Humana Press,
Clifton, New Jersey, 1981,
12. Akitt JW. NMR and Chemistry: An Introduction to the Fourier Transform-
Multi Nuclear Era. Chapman and Hall, London, 1983.
13. Kalinowaki HO, Berger S, Braun S. 13C-NMR Spectroskopie. Georg
Thieme Verlag, Stuttgart, 1984, 1988 (Wiley NY).
14. Breitmaier E, Bauer G. 13C-NMR Spectroscopy: A Working Manual with
Exercises. Harwood, New York, 1984.
15. Breimaier E, Haas G, Voelter W (eds). Atlas of Carbon-13 NMR Data.
Heyden, London, 1986.
16. Whitesell JK, Minton MA. Stereochemical Analysis of Alicyclic
Compounds by C-13 NMR Spectroscopy. Chapman and Hall, London,
1987.
17. Agrawal PK (ed). Carbon-13 NMR of Flavonoids. Elsevier, Amsterdam,
1989.
18. Claridge TDW. High Resolution NMR Techniques in Organic Chemistry.
Pergammon Press, Oxford, 1999.
19. Levitt MH. Spin Dynamics-Basics of Nuclear Magnetic Resonance. John
Wiley & Sons, New York, 2001.
20. Balci M. Basic 1H and 13C-NMR Spectroscopy. Elsevier, Amsterdam,
2005.

171
172


1 13C NMR

( 6)
-,

. ,
spin. ,

1 13C.

9.1. Spin

spin
NMR
.

: . , C ..
( )
: 2, 3 ..
,
, Y. CHCl CHBr spin AB,
CHCl CFBr spin AX.
spin : CH2Cl CH3
23, CH2Cl CF3 23 .. spin
13 13
13C, : CH3J 3, CH3CH2Cl 32.

NMR ,

. CH2F2 1 19F
.
.
1 2
. J13 = J23 J14 = J24.
H1 F3
.
, JHF , C
1 2 . H2 F4
F3 F4
. spin
22. , CH2=CF2 1 19F

173
 . spin
.

9.2. 1 NMR

9.2.1. 1 NMR

1: 1-

9.1. 1 NMR CH3CH2CH2Br.

1 NMR CH3CH2CH2Br
3.4, 2.1 1.3 (ppm).
(spectral lines, bands)
(peaks), (triplets)
(sextet). (CH3)
CH2 , spin-spin ,
(2+1=3).
CH2r, CH2, .
1.3 ( , upfield) CH3,
3.4 ( , downfield),
, CH2r.
2.1
.
6-7 Hz.
6 Hz,
6 Hz.
CH2
CH3 CH2r.

, -

174
. , CH2
CH2r.

1 3 3 1
2 (1 3 3 1)
() 1 3 3 1

1 5 10 10 5 1

()

()

9.2. .

,
(3+1=4) CH3.
(~ 6 Hz).

( 1:5:10:10:5:1).

, () , ()
.
(intergration)

(
).


. ,
,

.

175
9.2.2. 1 NMR

1: C3H6BrCl CDCl3.

9.3. 1 NMR C3H6BrCl.

1 NMR C3H6BrCl CDCl3,

TMS, :
(, quintet) 2.5-2.0 ( 8-7. 5 )
(, sextet) 3.45-3.85 (6.15-6.5 ).
2 4
() . 1
1 (4+1 =5), 1
1,
(23=6). : CH2CH2CH2.
C3H6BrCl : X- CH2 - CH2 - CH2 -Y
( 1: , 2: , 3: ). 1 2 3
,
6.5 Hz.
1, 2 3 : (1) ,
3.7 , (2) , 2.28 (3)
, 3.55 .
1 =Cl Y=Br (

(1),
(3). 7.7 CHCl3
(CDCl3).

176
 2: C9H6SO CDCl3.

9.4. 1 NMR C9H6SO.

C9H6SO (
) CDCl3, 60 MHz .
,
:
(1) 1- ( ) 8.53 1.47
(2) 1- () 7.80 2.20
(3) 3- ( ) 7.60 2.40
(4) 1- () 6.95 3.05
7.80 6.95
(quartet) 6.7 Hz.
:
R

R R1 HB
C C
HB HA HA

() ()
R (
).
7.60
,
8.53 ( o-, m-
p- ). ().
(8.53 )
, -
, .. (), (1 8.53 ).

177
 H H1
H R H C

O
H R1 H
H H

() ()

.
( )
. :
H1 O O

C H HB
H
S

H HB H HA
S

HA
() ()

NMR
() 6.95
, ().
, ()
.

UV IR, C O.

3: C4H8O CDCl3.

9.5. 1 NMR

178
 :
(1) 3- () 1.12 CH3
(2) 1- ( ) 2.45 OH
(3) 1- () 4.15 -CH- OH
CH3

, 12 ( )
. spin
CH2 CH 8 spin 3 .
15
8 spin (
).
spin CH2 CH
, CH2
CH
.
,
,
( 15)
-CH- OH .
4
. ,

.

9.3. ,

(
).
,
, .
(
) JAB 80 Hz.
( ) (
)
.
,

.

179
 9.6.
.

,
( Hz ),

. ,
80 Hz , 4
Hz: (1):7.42, (2): 12.42, (3): 87.58 (4): 92.58.
5.0 Hz ( 12.427.42 92.5887.58).
:

92.58 + 87.58 12.42 + 7.42

= 80.16 Hz
2 2

80.00 Hz.
,
5 Hz , 4
(1): 6.46 Hz, (2): 11.46 Hz, (3): 13.45 Hz (4) 18.54 Hz.
:

18.54 + 13.54 11.46 + 6.46

= 7.08 Hz
2 2

29% 5.0 Hz.

,
:

180
 ( 1 2 ) = [(F1 F4 )(F2 F3 )]1 / 2
5.001 Hz.
F1,2,3,4 4 .

:

I 2 I 3 (F1 F4 )
= = (9.1)
I 1 I 4 (F2 F3 )

.
, ABC 3
, 2 , ,
.
NMR.
/

( ).

9.4. 1 NMR

(CH2CH2): (
) 0.9 1.5 .
( ).
C6H5 - CH2 - (CH2)8 - CH3

- CH2 - - (CH2)8 -
0.88 (CH3), 2.56 , 1.28
7.1 (C6H5).
NMR 270 360 MHz .
,
.
H2
C
H2C CH2
H2C CH2
C
H 2:
.
CH2
1.2 1.4 . 0.1-0.5
(
CC, ).
C CH2
:
4.5-6.0 ,
- . , JHH 10-17 Hz

181
 H C C H
JHH 2 Hz
H C C C H
H .
(CC):
,
.
, HCCCH2Cl
( ): 4.13 (CH2)
, 2.53 (HC) . CH2
HC (JHH 3 Hz)
HC CH2.
1 NMR HCCCH2Cl
9.7.

9.7. 1 NMR HCCCH2Cl.

(ROH): OH
,
.
, OH ,

.
(.. DMSO)
. CHn (CH2OH)
- OH,

3.4-4.0 .
(COC):
3.3-4.0 .

182
 9.8. NMR CH3CH2-O-CH2CH3.

(RX):
,
2.0-4.0 .
. , CH2Cl2
5.32 , H3C O CHCl2 ,
, 7.33
.
C O
, :
,
2.0-2.7 .

9-10 .
(CH3CHO)
: 2.21 (CH3) 9.83 (CHO)
.
(COH):
- CH COOH
,

2.0-2.7 . COOH

, 10-12 .
(2): -
R2 ,
2.0-2.8 . 2

183
 ,
.
1.0-5.0,
.

:
6.0-8.5 .

,
.
, -, m- p-,
, p-
,
( ) ,
.

.
,
(singlet).
1 NMR 1--4-
9.8.

9.9. 1 NMR 3-.

:
Grignard, CH2MX,
0.5 .
(Li) 1.3 .
, ,
1.0 .

184
9.5. 13C NMR

O 13C NMR
1 MR,
, ,
( , lock signal),
( (proton noise
decoumpling) (off-resonance
decoumpling).
, ,
, , ,
.
,
(ppm)
,
.
CDCl3, 13C NMR

9.10. 13C-[1H]-NMR --3,6- (

CDCl3).
o.

13C FT-NMR

.

( ppm TMS)
-d6 206.0
(CD3COCD3) 29.8 7
- d6 128.0 3
(C6D6)
-d1 76.9 3
(CDCl3) 79, 76 74
-d4 49.0 7
(CD3OD)

185
9.6. 13C NMR

13C NMR
.
, 200 ppm,
TMS. O -13
(1),

.

9.1. 13C (ppm TMS).

() ()

0-8
5-25 CH3 5-25
RCH3 5-25 RCH2X 5-38
RCH2R 22-45 R2CHX 30-62
R2CHR 30-58 R3CX 35-75
R3CR 28-50

100-143 RCOOR 160-177
RCOOH 162-183
C C

75-95 100-133
(CC)

,
CH3 45-60 RCHO 185-205
RCH2 42-70 RCR 190-220
R2CH 65-77

CH3NH2 10-45 RCH2S 22-42
RCH2 NH2 45-55 RCH2P 10-25
R2CH NH2 50-70 RCN 118-123
R3C N 60-75 ArP 120-130
ArN 130-138

:
2-50 ppm TMS (0).
, ( -

186
). , 13C
( ppm):

CH4 CH3 - CH3 CH3- CH2- CH3 CH3- CH(CH3)2 (CH3)4C

2.1 5.9 16.1 25.25 27.95

, -
(
-). :

CH3 - CH3 CH3- CH2- CH3 CH3- CH(CH3)2 CH3- C(CH3)3

~ ~ ~ ~
5.9 15.6 24.3 31.5

( -)
13C
- 13C.
:

CH3- CH2- CH3 CH3- CH2 - CH2- CH3 CH3- CH2 - CH(CH3)2 CH3- CH2 - C(CH3)3
~ ~ ~ ~
15.6 13.2 11.5 8.7

13C FT-NMR
.
13C FT-NMR - (
).

9.11. 13C FT-NMR CH3(CH2)5CH3.

- 4 .
,
, .
14.2

CH3- CH2 - CH2 -CH2 -CH2 - CH2- CH3
1 2 3 4 3 2 1 .

187
 C4.
C2
C1, 9 ppm, C3
~ 9 ppm. - C4
C3 2 ppm.
13C .
: 100-
165 ppm. 1-.

9.12. 13C FT-NMR 1-. : (1) 139.2 ,

(2) 114.2 , (3) 34.1 , (4) 32.2 , (5) 29.8 , (6) 29.6 , (7) 29.4 , (8) 29.2 , (10)
14.2 .

:
,
75-95 ppm. 1-,
:

CH3 - (CH2)3 - C CH
4 3 2 1
C2 C1 C3 C4
84.5 68.1 30.7, 21.9, 18, 1 13.5

: 13C

( )
.
13C , 110-130 ppm.
13C
() 1.
13C 128.5
.
, -
(ppm):

188
 6 7
1
5 C OCH3

4 2 Br
3
C1 C2 C3 C4 C5 C6 C7
156.0 133.2 128.5 121.8 112.2 11.7 56.0

9.2.

C-1 (ppm) - (ppm) -(ppm) -(ppm)

H 0 0 0 0
CH3 9.3 0.8 0 -2.9
CH2CH3 15.6 -0.4 0 -2.6
CH(CH3)2 20.2 -2.5 0.1 -2.4
CH2OH 12.0 -1.0 0 -1
COOH 2.1 1.5 0 5.1
COOCH3 2.1 1.1 0.1 4.5
CHO 8.6 1.3 0.6 5.5
CN -15.4 3.6 0.6 3.9
OH 26.9 -12.7 1.4 -7.3
NH2 18.0 -13.3 0.9 -9.8
NO2 20.0 -4.8 0.9 5.8
F 34.8 -12.9 1.4 -4.5
Cl 6.2 0.4 1.4 -1.9

9.13. 1H 13C-NMR 1--3-.

189
 :
. ,
200-160 ppm. :

13 C

CH3 - CO - CH3 205.08

CH3 - CO - H 199.6
CH3 - CO - OH 177.27
CH3 - CO - Cl 168.59

,

.

9.3. 13C
.

co X co
H 199.6 OCH3 170.7
H3C C X CH3 205.08 N(CH3)2 169.63
(Ar-) 196.0 Cl 168.59
O
CH=CH2 197.2 Br 165.65
OH 177.27 I 158.9

, : -,
- - OH,
O = Cl, Br, I, F .

. ,
( -) ,
.

190


NMR (NMR 2D, Two Dimensional

NMR), 1971 (Prof. Jeener)
1980

NMR.
, NMR
(1H, 13C )
spin . NMR ,


.
NMR (2D NMR)

,

Fourier .
2D NMR
.


.
2D NMR

.

10.1.
(2D NMR)

2D NMR
.
.
.

,

191
 t1.

,
t2.

2D NMR :

(i) (preparation):

.
,
( , )
.

(ii) (evolution):

t1,

. x y

(iii) (mixing):

spin ,
, spin .

(iv) (detection):

(FID, Free Induction Decay) t2.

10.1.

192
 10.1. 2D NMR
1 -1 1H-13C 2D NMR.

193
 10.2. 2D NMR f1 &2) contour plot
(topographical plot, ) stacked plot
( ).
,
( NMR ).

2D NMR
NMR. FID (free
induction decay) FT
,
(t1) FID (116).
Fourier (FT)
( t1 , t12 , t13 ... ),
( ),
. f2 FID

194
( ) f1
( 10.1). , 2D NMR
,
f1 f2. f1
(.. 1) ,
f2
f2.
2D NMR
: (autocorrelated) - (cross-
correlated). 2D NMR
COSY-NMR (COrelated SpectroscopY) 2D NMR
. ,
spin
off-diagonal ( )
[1-1 COSY].
H
-
(NOESY- NMR, Nuclear Overhanser Effect SpectroscopY).
cross-correlated ,
.
2D-JNMR (J= ). f2
2D NMR (J),
(homonuclear)
(heteronuclear),
f2.
. 1-1 COSY
,
, (HOMCOR, homonuclear
correlation). , 1-13C COSY
13C
(HETCOR, heteronuclear correlation).
2D NMR.

195
 10.3. () 2D NMR, 1-1 COSY NMR -
(CH3CH2CH2CH2-O-CH=CH2). contour-plot (
) .
.
.
. ()
1- NMR -. [(): 6.459, ():
4.169, (C): 3.964, (D): 3.67, (E): 1.61, (F): 1.39, (G): 0.94]

196
 10.4. 2D NMR CDCl3.(a) 400 MHz 1H
shift-correlated 2D-NMR, contour plot COSY-90 t tdelay = 0.4 s, () 1D
NMR 1H- NMR , () 2D
NMR , 400 MHz 1H shift-correlated 2D stacked plot (
).

197
 10.5. 2D NMR 1-1 COSY NMR.
( F1
F2 ppm). contour plot ( )
(multi-colour digital plot).
contour plot
.

198
 10.6. 2D NMR (stacked plot) 1H-13C. 2D
NMR - (carbon-proton chemical
shift correlation) Mycinamycin ().
(stacked plot).

199
 10.7. () 1H-13C NMR COSY (J=140 Hz)
(pinanediol), () 1H-1H 2D NMR COSY.

200
 10.8. 1H, 13C 1H-1H-COSY NMR (
) 4-.

201
 10.9. NMR C6H12O (5--1-).

202
10.2.

NMR


,
(1H, 13C, 19F, 31P)
NMR.

NMR :
DEPT (Distortionless Enhancement by Polarization
Transfer).
3000 MHz
500 900 MHz, .
NMR
.


NMR.
13C- NMR
C
CH3, > CH2, CH .

203
 10.6.
. , 15
. NMR
7.0-7.5 ppm 500, 750 900 MHz
.

204
10.2.1. DEPT (Distortionless Enhancement by Polarization
Transfer)
NMR
C, CH, CH2 CH3.
DEPT (Distortionless Enhancement by
Polarization Transfer)
.
C
, CH, CH2 CH3
(),
. t
(C-H)
.

10.7. 13CNMR 75.6 MHz

, CH3, CH2 CH,
13CNMR .

205
10.3. /
.
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respective product pages.

208
ACD/2D NMR Predictor is an easy and powerful data processing and prediction orogram that
allows you to calculate the 2D spectrum crresponding to a wide variety of 2D experiments of
several correlation types: H, H COSY, C, C COSY (INADEQUATE), C, H COSY, N,H COSY
and H, H and C, H, J-resolved.

http://www.vsnmr.org/index.html

Virtual NMR Spectrometer

A computer program for efficient simulation of modern NMR
experiments
Version 3.5 User's BETA-
Publications Download
(beta) Manual testing
Examples of Simulated
Spectra

A 1D NMR
experiment
COSY, phase
sensitive, using
phase cycling
COSY, using
gradient
selection
COSY, Double-
Quantum
filtered, using
gradient
selection
1H-15N HSQC

spectra, coupled
and decoupled
TROSY spectra,
selection of
Graphical User Interface various
components
A 3D NMR
experiment:
HNCO

209
 10.8. 1H-NMR :
,
.
(http://spectroscopynow.com/Spy/basehtml/SpyH)

210
 1H-NMR

13C-NMR

10.9. / NMR.

211
 ()

()

10.10. 13C-NMR ()
() () (proton noise decoupling) n-.

212
 13C-NMR
()

()
13C-NMR

10.11. 13C-NMR
.

C CH3

OH

10.12. 13C-NMR CH(OH) CH3 off-resonance

decoupled .

213
 ()

()

10.13. () 1H D-NMR (COSY correlation) bovine

basic pancreatic trypsin inhibitor pH 4.6 80C 12/22, ()
topographical contour map ( ) D-NMR COSY spectrum.

214
9.8. NMR

1. .
.
. .
. , 1983.
2. Benn R, Gunther H. Angew Chem Int, Ed Engl, 22: 350-380, 1983.
3. Ernst RR, Bodenhansen G, Wokaun A. Principles of Nuclear Magnetic
Resonance in One and Two Dimensions. Claredon Press, Oxford, 1986.
4. Schraml J, Bellama JM. Two-Dimensional NMR Spectroscopy. Wiley
Interscience, John Wiley & Sons, New York, 1988.
5. Richars SA. Laboratory Guide to Proton NMR Spectroscopy. Blackwell,
Oxford, 1988.
6. Wthrich K. The development of NMR Spectroscopy as a technique for
protein structure determination. Accounts of Chemical Research, 22:34-44,
1989.
7. Vuister GW, de Waard P, Boelens R, Vliegenthhart JFG, Kaptein R. The
use of ED NMR in structural studies of oligosaccharides. J Am Chem Soc,
III: 772-774, 1989.
8. Brey WS (ed). Two-Dimensional NMR Spectroscopy and Related
Techniques. Academic Press, New York, 1986.
9. Martin GE, Zektser AS. Two-Dimensional NMR Methods for Establi-
Molecular Connectivity. VCH Verlag, New York, 1988.
10. Atta-Ur Rahman HEJ. One and Two Dimensional NMR Spectroscopy.
Elsevier, Amsterdam, 1989.
11. Grant DM, Harris RK. Encyclopedia of Nuclear Magnetic Resonance.
Wiley & Sons, Chichester, UK, 1996.
12. Aldrich FT-NMR Library with Spectral Viewer on CD-ROM (high
resolution 300 MHz 1H 75 MHz 13C 1 FT-NMR ). 15000
. Aldrich Chem, Milwaukee, WI, 2001.
13. Becker ED (ed). High Resolution NMR, Academic Press, New York, 1999.
14. Ernst RR, Bodenhausen G, Wokann A. Principles of NMR in One- and
Two- Dimensions. Clarendon Press, Oxford, 1987.
15. Croasmun WR, Carlson RMK. Two Dimensional NMR Spectroscopy:
Applications for Chemists and Biochemists. VCH, New York, 1987.
16. Schraml J, Bellama JM. Two Dimensional NMR Spectroscopy. Wiley, New
York, 1988.
17. Nakamishi K. One- dimensional and Two-dimensional NMR spectra by
Modern Pulse Techniques. Univ Science Books, Mill Valley, Ca, 1990
18. Martin GE. Two Dimensional NMR Methods for Establishing Molecular
Connectivity. VCH, New York, 1988.
19. Pouchert CJ, Behnke J (eds). The Aldrich Library of 13C and 1H NMR
Spectra. 12000 chemicals. Aldrich Chem, Milwaukee, WI, 1992.
20. Van der Ven FJM. Multidimensional NMR in Liquids: Basic Principles and
Experimental Methods. Wiley/VCH, New York, 1995.

215
21. Aldrich FT-NMR Library with Spectral Viewer on CD-ROM (high
resolution 300 MHz 1H 75 MHz 13C 1 FT-NMR ). 15000
. Aldrich Chemicals, Milwaukee, WI, 2001.
22. Friebolin H, Becconsall JK , eds. Basic One- and Two- Dimensional NMR
Spectroscopy. 3rd edition. Wiley-VCH, New York, 1998. (Completely
revised & updated 2005).
23. Breitmaier E. Structure Elucidation by NMR in Organic Chemistry: A
practical Guide, Wiley, New York, 3rd revised ed, 2002.
24. ACD/Labs for NMR Spectroscopy. NMR Prediction Software
Aldrich/ACD (Advanced Chemistry Development) Library of FT NMR
(www.nmrsoftware.com), 2005.
25. Smith BD, Boggess B, Zajicek J. Organic Structure Elucidation Workbook:
http://www.nd.edu/~smithgrp/structure/workbook.html.
26. SpectroscopicTools:
http://www.chem.uni-potsdam.de/tools/index.html.
27. Merlic CA, Fam BC, Miller MM. WebSpectra: on line NMR and IR Spectra
for students. J Chem Education 2001, 78:118-120.
28. James TL, ed. Nuclear Magnetic Resonance of Biological Macromolecules,
Part C, vol. 394. Methods in Enzymology, Elsevier/Academic Press,
Oxford, 2005.

216


(Ultra Violet, UV) (Visible, VIS)

.
, ,
,
.
,

.
10 380 nm
380 780 nm.

11.1.

.
, ,

Schrdinger.
,
.

,
.
,
, 2.

(quantum numbers):
() n (principal quantum number) 1, 2,
3, , .
() l (orbital or azimuthal
quantum number) (n1), (n2), .,
.
() m, ms (magnetic quantum number)
1, (l 1), , 0,
.

217
() spin s (spin quantum number)
ms = 1/2, spin ,
.
4
,
95% .

(the orbital).
s, p ,
4 , 11.1.
y

z s
x

1s 2s 3s
n=1 l=0 m=0 n=2 l=0 m=0 n=3 l=0 m=0

p

2pz 2py 2px

n=2 l=1 n=2 l=1 n=2 l=1

m=+1, 0, -1
11.1.
.

11.2.

(MOT, Molecular Orbital Theory)

. MOT


UV-VIS. MOT

, .

Schrdinger,

218

(linear combination of atomic orbital,
LCAO).

:

= 1 + 2 = 1 - 2 (11.1)

1 2 .
, 1 +2 1 - 2 ,

2

.
(2),
:

H 2 = 1s + 1s (11.2)

1s ( )
.
H 2 .
11.2,
, .

.
.
(bonding orbital) 1s (
1s ).

, , :

H 2 = 1s - 1s (11.3)

, , ,
(
) (
).
.
(antibonding orbital)
1s * (
). ,

.
,
( )
, .. :

219
 + + +

( ) ,
, (node).

+ +
- -

+ + +
1s*
1s 1s 1s
E 1s 1s
_
+ _ + +
1s
1s 1s 1s*
11.2.
.

,
. , ,
,
.
(inversion)
. 2,
() . 1s *
( ) (+) g (
gerade=), 1s g. ,
, ,
u ( ungerade=).
1s u 1s *u.
.
1s g 1s *u
( 11.3).

220
 11.3. .

p
( 11.4).
= 2 pZ + 2 pZ __ ++ _
+
_
+
+
2pz 2pz 2pu*

= 2 pZ 2 pZ __ + _ _
+
_ + _

2pz 2pz 2pg

_
+
++
++

= 2 p y 2 p y +
+
_
_

_ _ _

2py 2py 2pg*

+
++
++

= 2 p y + 2 p y +
_
_
_

_ _

2py 2py 2pu

11.4. 2pz
2py . 2px ,
z.

221
 (Molecular Orbital), d, f
.

11.5.

11.5. : () ,
() .

: ,
1s 1s g ,
spin ( Pauli).
.
.
1s g2 .
,
, (
n). ,
, spin ( l
s)
. ,

.
(ground state)
.
( , excited states)

UV-VIS ,
.

222
11.3.

UV-VIS
.
, , .
,


.

(
)
.
UV-VIS
(wavelength)
, max, Angstrom (1 = 10-10m )
(1nm = 10-9m), .
3 :
() (VIS) 400-750 nm ( 4000-
7500 25000-13300 cm-1 ).
() (near UV) 200-400 nm ( 2000-
4000 50000-25000 cm-1).
() (far UV) 200 nm ( 2000
50000 cm-1).


.

Beer-Lambert-Bouguer:

Io
log = c l (11.4)
I
c , l
,
(
), (extinction coefficient)
5105 1
.

11.4.

3 : -, - n-
(non bonding)

223
 , .
- ,
,
- n- . ,
, n- - .


UV VIS. * ( -
- )
, *
n n* UV
UV n * .

11.6.

11.6. UV-VIS .

,
n *, * n *.
, * ,
UV,
, CH4 CH3CH3 122
135 nm .
,
2, n *

*. , CH32 *
170 nm n * 213 nm.
UV-VIS ,

.

,
. ,

224
 * UV
. C C , CC, C O
C N 170, 170, 166 190 nm
), n *
. C O, C N , = C S
280, 300, 350 500 nm .

n-

(, S).
(
) .
, (CH3)2CO C5H10CO
max 272 290 nm .
, , max
. UV-VIS

.
UV-VIS
.
, , ..,
C C C C
* n *

.
.

1: - *

max (nm)
C=C 170 16000
C=CC=C 220 21000
C=CC=CC=C 260 35000

2:

max * max n *
(nm) (nm)
C=O 166 280
C=CC=O 240 320

O O 245 435
(p-)

225

*,
UV .
.
p-
(435 nm)
( ) .

.

.

11.5.

,

.

.

(chromophore).

.
,

.

,
C C , CC , C, C O , = .,
*
UV . , , R (R=), 2, --SH
, . (
)
, 190 nm.
(auxochromes)

,
,

226
 11.1. .

max max
(nm) (nm)

R OH n * 180 R NO2 n * 271

ROR n * 180 R CHO * 190
R NH2 n * 190 R CHO n 290
R SH n * 210 R2C=O * 180
R2C = CR2 * 175 R2C=O n * 280
R CC R * 170 RCOOH n * 205
R CN n * 160 RCOOR n * 205
R N=N R n * 340 RCONH2 n * 210

11.6.

UV-VIS

.
.
FranckCondon,

.

, *,

. -

. max
( ).

10-20 nm ,
.
(red shift). , n * (
)
(max) .

-
. ,
max 279 nm, 264,5 nm.

(blue shift).

227
11.7. UV-VIS

UV-VIS
.
.
: , 95% (CH3CH2OH) -
(CH3(CH2)4CH3),
.
: (190 nm),
240 nm), (195 nm, ), 1,4- (215
nm), (205 nm), (195 nm) .


,
,
. (
) ( ).

11.7. UV ,
.

11.8.

UV-VIS
( UV
VIS).

228

( ). ,
, ,
(sample cell)
(1-2%)
.
.

, ,
,
.
( ,
, , )
( Silica Gel).

11.8. UV-VIS
.

229
 11.9. quartz UV.

UV-VIS 190-
750 nm. 400-750 nm (-)
190-400 nm. 190 nm (
220 nm)
,
,
.

.
UV-VIS
(
/ log
x y (
), logIo/I,
(optical density) .

11.10. UV .

230
 , 4
UV-VIS.
() (bathochromic shift, red
shift)
( ).
() (hypochromic shift, blue
shift)
( ).
() (hyperchromic effect)
.
() (hypochromic effect)
.

11.9.

UV-VIS.

11.9.1.
, (CH2=CH2),
180 nm, *, .

. 4
200 nm.

R H R H R R R R
C C C C C C C C
H H H R H H R R
trans- cis-
177 nm 180 nm 180 nm 200 nm

, ,
(max) 190 nm,
,
,
.
UV
. 1,3- ,
,
.

CH2=C CH=CH2 CH2=CCH2 CH2 CH=CH2

max =217 nm ( = 21000) max =185 nm ( = 20000)

231

,
:


.


,
.
Woodward (1941) Fieser (1959)
.
:

11.11. UV .

4 261, 271,
282 294 nm . Woodward-
Fieser, 282 nm (
) ,
.

11.9.2. (polyenes)
.

, .
, trans- CH3 (CH=CH)5CH3
298, 315, 330 340 nm. ,
,

232
 max +30 nm 6

.
- 11
. max
400 nm, 6
, max 452 nm.

11.9.3.

C O

. 190
280 nm ( ) * n *
.
270,5 nm,
,
, . -
n *
.
190 290 nm. , ,
- .
(enones),
,
.

.
220-260 nm *
.
310-330 nm n *
.
, ,
(Woodward, Fieser, Scott) :

233


(
).
4--3--2-
237 nm,
239 nm.

11.9.4. , ,

200-205 nm .
(
) ,
. (CH3CH=CHCOOH)
max 205 nm .
( )
.
:

C O
(CH2)n
O

, 200 nm,
240-250 nm ,-
( ):

C O
(CH2)n
NH

11.9.5.
184, 203 254 nm (
) .

. :

234
 max (nm)

H3C CH3 274

1, 2, 4, 5- 279

(C6H5COOH) 273

(C6H5-CH=-COOH) 273

,
.

11.12.

11.12. UV .

.
-
o-

(
).
:

235
 CH3

max 249 nm max 236.5 nm

.

UV . ,

- .

CH3

H3C CH3
max 248 nm max 245 nm

,
2, 4 6
.
cis- trans-
max ,
.

cis- trans-
max =224 nm (=24000) max =228 nm (=16400)
max =280 nm (=10500) max =295 nm (=29000)

() ,
- .
210-230 nm.
-
. 270 nm,
, 254 nm ,

236
 210 nm.
()
:

OH O O C CH3 O C CH3

O O

() () () ()
max 235 nm max 261 nm
(=9400) (=300)

,
(,) , ,

, -
, .
(R-C6H4-R)
: ()
(.. 2 2)
-.
( ).

O
H2N N O2N NO2
O

() ()
max =375 nm (=16000)

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

237
 11.2.
C6H5-R.
R max (nm) &
(:2 e
H 203.5 (7400) 254 (204)
NH3 + 203 (7500) 24 (160)
Me 206.5 (7000) 261 (225)
I 207 (7000) 257 (700)
Cl 209.5 (7400) 263.5 (190)
Br 210 (7900) 261 (192)
OH 210.5 (6200) 270 (1450)
OMe 217 (6400) 269 (1480)
SO2NH2 217.5 (9700) 264.5 (740)
CN 224 (13000) 271 (1000)
CO2- 224 (8700) 268 (560)
CO2H 230 (11600) 273 (970)
NH2 230 (8600) 280 (1430)
O- 325 (9400) 287 (2600)
NHAc 238 (10500)
COMe 245.5 (9800)
CH=CH2 248 (14000) 282 (750) 291 (500)
CHO 249.5 (11400)
Ph 251.5 (18300)
OPh 255 (11000) 272 (2000) 278 (1800)
NO2 268.5 (7800)

11.3.
R-C64-R.( )

R R max (nm) &

OH OH o- 214 (6000) 278 (2630)

OMe CHO o- 253 (11000) 319 (4000)
NH2 NO2 o- 229 (16000) 275 (5000) 405 (6000)

OH OH m- 277 (2200)
OMe CHO m- 252 (8300) 314 (28000)
NH2 NO2 m- 235 (16000) 273 (1500)
Ph Ph m- 251 (44000)

OH OH p- 225 (5100) 293 (2700)

OMe CHO p- 277 (14800)
NH2 NO2 p- 229 (5000) 375 (16000)
Ph Ph p- 280 (25000)

238


(: max 207, 230 280 nm).

(C6H5-COCH3) 4 199,
246, 279 320 nm, 320 nm n *
. Scott
(1964)
246 nm,
.
: (C6H5COOH)
max 202, 230 279 nm. 230
nm ( ) Scott

.

12.13. UV-VIS ( ) (1) , (2)

, (3) , (4) , (5) p-, (6)
, (7) p- , (8) p-, (9) p- (), (10) p-
, (11) p-, (12) p-, (13) p-
().

239
 12.14. UV-VIS , ,
.

12.15. UV-VIS 9,10- ( ),

3,4- ( 95% ) ( ).

240
11.9.6.

:
, :
.

N O S

max 210 nm max 200 nm max 231nm
max 240 nm max 205 nm
max 211 nm

: , ,
(
) .
270 nm ( ) n *
.
.
-
() ().
.

OH O

N N N
H
() () ()
max 195 nm
max 251 nm
max 270 nm

:
226, 270, 300 313 nm, 218, 266, 305 318 nm (
).
,
.

241
 N
N

max 226 nm max 218 nm
max 270 nm max 216 nm
max 300 nm max 305 nm
max 330 nm max 318 nm
: 260,
262 280-290 nm ( ). 262

.

N
H

11.10. UV M K X
M

UV

. 11.12 etai
, pH , 4,4,6,6-
-2-- -1,3,5-.

11.16. UV pH. () 1.22, ()

3.38, () 4.31, () 4.73, () 5.41, () 13.

242
 OH O O O O O O OH O O

OH O OH O O

() () () () ()
256 m (Chan & Hassall, J Chem Soc, 1956, 3497).

12.17. UV-VIS.
UV Ag 350 nm
0, 2, 4, 6, 90 min.

243
 11.11.

11.11.1. -,
.

1. Gillan AE, Stern ES. Introduction to Electronic Absorption Spectroscopy in

Organic Chemistry. E Arnold, London, 1958.
2. Jaffe HH, Orchin M. Theory and Applications of UV Spectroscopy. John
Wiley and Sons, New York, 1962.
3. Scott AI. Interpretation of the Ultraviolet Spectra of Natural Products.
Pergammon Press, Oxford, 1964.
4. Rao CNR. Ultra-Violet and Visible Spectroscopy: Chemical Applications.
Butterworths, London, 1967.
5. Sutton D. Electronic Spectra of Transition Metal Complexes. McGraw-Hill,
London, 1968.
6. Stern ES, Timons CJ. Electronic Absorption Spectroscopy in Organic
Chemistry. Arnold E, London, 1970.
7. Knowles A, Burgess C. Practical Absorption Spectroscopy. Chapman and
Hall, Vols 1-3, London, 1981, 1982.
8. Burgoss C, Knowles A. Techniques in VIS and UV Spectroscopy Series.
Chapman and Hall, London, 1984.
9. Denney R, Sinclair R. Visible and Ultraviolet Spectroscopy (Analytical
Chemistry by Open Learning Series. John Wiley and Sons, Chichester, 1987.
10. Perkampus HH, Grinter HC, Thelfall (translator). UV-VIS Spectroscopy and
its Applications. Springer Verlag, New York, 1992.
11. Grog S. Ultraviolet-Visible Spectrophotometry in Pharmaceutical Analysis.
CRC Press, Boca Raton, Fl, 1995.
12. Thomas MJK. Ultraviolet and Visible Spectroscopy. Wiley, Sussex, 1996.
13. Gottwald W, Heinrich KH. UV/VIS Spectroscopie fr Anwender. Wiley-
VCH, Weinheim, 1998.
14. Misra P, Dubinski MA, Dubinski MA. Ultraviolet Spectroscopy and UV
Lasers. Marcel Dekker, New York, 2002.

11.11.2. -.

1. Lang L. Absorption Spectra in UV and VIS Regions. Academic Press, New

York, Vols 1-20, 1971-1976.
2. UV Atlas of Organic Compounds. Butterworths, London, 1966-1971.
3. Simons WW (ed). The Sadtler Handbook of Ultraviolet Spectra. Sadtler-
Heyden, Philadelphia, 1979.
4. Phillips JP, Bates D, Feuer H, Thyagarajan BS. Organic Electronic Spectral
Data. John Wiley & Sons, Vols 1-24, 1988.
5. Penkampus HH. UV-VIS Atlas of Organic Copmpounds. Wiley-VCH,
Weinheim, 1992.

244
 11.11.3. , , .

1. Pauling IL. The Nature of Chemical Bond, and the Structures of Molecules
and Crystals. Cornell Univ Press, New York, 1969 (3rd ed).
2. Streitwieser A. Molecular Orbital Theory for Organic Chemists. John Wiley
& Sons, New York, 1961.
3. Jaffe HH, Orchin M. Symmetry in Chemistry. John Wiley & Sons, New York,
1965.
4. Dewar MJS. The Molecular Orbital Theory of Organic Chemistry. McGraw-
Hill, New York, 1969.
5. Woodward RB, Hoffman R. The Conservation of Orbital Symmetry. Verlag
Chemie, Weinheim, 1970.
6. Urch DS. Orbitals and Symmetry. Penguin, London, 1970.
7. Orchin M, Jaffe HH. Symmetry, Orbitals and Spectra. Wiley-Interscience,
New York, 1971.
8. Coulson CA. The Shape and Structure of Molecules. Clarendon Press,
Oxford, 1973.
9. Harris DC, Bertolucci MD. Symmetry and Spectroscopy: An Introduction to
Vibrational and Electronic Spectroscopy. Oxford University Press, New
York, 1978.
10. Richards WG, Scott PR. Structure and Spectra of Atoms. John Wiley & Sons,
London, 1976.
11. Douglas BE, Hollingsworth CA. Symmetry in Bonding and Spectra: An
Introduction. Academic Press, New York, 1985.
12. Hehre WJ, Radom L, Schleyer PV, Pople J. AB INITIO Molecular Orbital
Theory. Wiley-Interscience, New York, 1986.
13. Christofferson RE. Basic Principles and Techniques of Molecular Quantum
Mechanics. Springer, New York, 1989.
14. Atkins PW. Molecular Quantum Mechanics. Oxford Univrsity Press,
Oxford, 1991.
15. Advances in Quantum Theory. Vol. 31. Quantum Systems in Chemistry and
Physics. Harcourt Publishers, New York, 1998.
16. hrm Y. Elements of Molecular Symmetry. John Wiley & Sons, New York,
2000.

245
246


(mass spectrometry)

.
, ,
, ,

(, -, ,
, .) .
,

.
(tandem LC-MS-MS)
(TSQ, Triple Stage Quadrupole)
.

12.1.

()

.

.
(12.1 12.2).

12.1. .
, ,
.

247

(
) .
10-510-7 mm Hg
10-100 eV (
). 10-15 eV
(ionization-potential)

,
M + e
eV
M + + e .
(molecular ions).
15 eV,
(fragment ions)
.
70 eV
,
. 70 eV
-
,
.

12.2.
().
().

248



( 12.1.).
( )
.
O

.
60 900,
.

12.3. . .
(GCMS)
.

249
 e-
V 1/2mv2 ( m v
). :

eV () = 1 / 2mv 2 () (12.1)

, ev, , mv2/r
( r 12.3)

Hev = mv 2 / r (12.2)

(12.1 12.2) 12.3:

m / e = H 2 r 2 / 2v (12.3)

12.3
/
. (m)+ (2m)2+
V.
,

1+.

,
(voltage or electric scan)
. , V ,
(magnetic scan),
,
. ,
m/z,
4000 400 Volts.

,
, 10-7 mm Hg.
y
.

10% .
: ()
, ()
()
m/e*, .
..............................................................................................................

m/e.
mass-to-charge ratio / (m/z).

250


,


. (double-
focusing instruments).

.
(time-of-flight)
(s),

(lm),
.
,
.

12.4. . MS VG 70 SE. ,
MS . ( 5000 Da).

- (ICR-MS, Ion-cyclotron
resonance Mass Spectrometry) NMR.


,
.

251
 12.5. . Duals cell Fourier Transform Ion Resonance
mass Spectrometer (FT/ICR-MS) 3 (Tesla). [Matrix assisted laser
desorption ionization (MALDI)]. FINNIGAN FT/MS 2001.

,
(QMS, Quadrupole Mass Spectrometer),

( ) .
4
,
.
QMS ,
1000 m/z. ,

(tandem MS/MS spectrometry)
(
, )

12.6. Time-of-Flight
(TOF MS). .
.
.

252
 12.7. C60 (fullerene C60)
TOF-MS).

12.8. : Bruker BIOTOF II, Reflectron ESI-TOF

instrument. [20000 resolving power. ESI & APCI capabilities].

12.9. FINNIGAN MAT 95 MS

[double-focusing, high resolution MS].

253
12.2.

.


.
: ()
( 350
300 0,5
s), ()
( 1 1000),
.

.

,
.

.
.

.
,

, ,
12.5,
(
)
/ .
bar graph ().
( ) m/z
( 12.10).

12.10. bar graph (

).

254
 ,
, 100%
.

,
.

12.3. .

mole ( 10-2 mm Hg)
3 150 C, 0,1 0,2 mg
.
150-250 C,
.
200 C, ,
.

, .
( )
,
, (injection systems).

.
,
.
, ,
(.. ) ..
(GC) (MS)
.

,
(GC-MS).

.

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

255
 ,
,
,
.

12.4.
.

mg.

.
M

M + e M + 2e .
,
. , ,
80-90%
.
M .

(% ) . -
()
.
( )
.
%
: , ,
, , , , , ,
, , , , , ,
.

.
()
.
(.. , -18).
( m/z),
,
C, H, N, P, S, O, Se
(. ).


, .
m/z +1.
,

256
. M+

. , , ,
- m/z = 15
(CH3, = 15).
(chemical ionization)
( )
( ~10-4 Torr, ~1 Torr),
. ( CH4
CH4 CH3 ).

:
CH4 + CH4 CH5 + CH3

CH3 + CH4 C2H5 + H2
.
.

(field ionization & field desorption),

.
10 KV
. ,
,
.
.
, .
(Electrospray Ionization, ESI)
LC-MS/MS.
, 3-4 kV,
.

.

. .

12.5.

.
, 10-15 eV 5070 eV,

.
, ,

257
 , .

. ,

.

:
. ,
, ,
:
m1 m2 +

R C R + C
..
m1
m2 , m2+
m1+ . m1+
, m1+,
m2+, m2+.
, m1+ m2+ ,
m2+ m1 m2, m*

. , m*, (metastable ion).
.

. M ,

, .

.
, ,
m/z,
.
:
C7H6O2 C7H5O + HO

m/z 122 m/z 105

C6H7N C6H6N + H

m/z 93 m/z 92

,
,
.

258
12.6. -

.
, ,
- ,
.. m/z 43 C3H7+ C2H3O+. ,
,
( )
.

12.11. - m-.
(138 ) .

(heterolytic cleavage) :

X Y X + Y

(hemolytic cleavage)
:

X Y X Y X + Y

(simple fission) :
()
, -
:
A B A + B

259
 ()
-
:
A B A + B

,
( ) .

,
.
, ,

.
,

( ,

) (
),
(.. ):

C N C N

- (elimination &
rearrangement)
- .

.
.
-
.
, -
,
. ,
,
-
:

A B A + B H A BH A H + B

H H

260

.

.
H2O, CH3COOH, HCN, HX
( ) H2S,
RCH=CH2, RCCH, RCH=C=O CO2.

,
.

12.7.

12.7.1. ()

. ,

:

C ( C )n C C C C C ( C )n C C C + C

C ( C )n C C C C ( C )n C + C C

m/z C n H 2 n +1 .

m/z =1, 2 3
.


.

261
 12.12. - 2,3--.

-
+
C n H 2n +1 m/z 29, 43, 57 71
+
C n H 2n 1 m/z 27 41.

2,3-- -
+
C n H 2n +1 27, 43 71,

57 . 29
-.
,
, C 4 H 9+ (m/z 57) C 2 H 5+ (m/z 29).
(, m/z 43),

262
(, m/z 43), ,
100% .

H H

C CH3 C CH3
() ()
CH3 CH3

12.7.2.

.
-,
.
+ +
C n H 2n +1 C n H 2n 1 .

cis- trans- .
- ,
m/z 41:
R CH2 CH CH2 R + CH2 CH CH2 CH2 CH CH2

m/z 41

.
,
.

Diells-Alder.

C
+
C

12.13. 1-.

263
 .

.
: .. .
H C C CH2 R R + HC C CH2 HC CH CH2

m/z 39

12.4. 1-.

12.7.3. .

()
,
, .
,

:

1 R1 + R2 C O ()
R1
C O
R2 2 R2 + R1 C O ()

.

(, )
.

264
 R
C O R C O R C O + R
R

R( R1 R2) ,
. ,
R .
, R
m/z 29, :

R
C O R + H C O (m/e 29)

-
C n H 2 n +1CO + (m/z 43, 57, 71, ),
m/z
+
C n H 2n +1 (.. CH3CO C3H7 m/z 43).
+ +

(CO).
+
C n H 2n +1 :

R C O R + CO

. , Mc Lafferty -
R1 R2 .

H H

C C C C O C C + C C O

R R
(-) (-) (-) ()

-
.
m/z 44 +nx14 (. 44, 58, 72,
86, ). (RH)
m/z 44:

265
 H
C C O H m/z 44
H
H

12.15. .

( 12.15
12.16) .

12.16. .

m/z 44 ()
Mc Lafferty.

266
 H

CH2 CH2 CH2 C O H2C CH2 + H2C C O H

(m/z 44)
H H

m/z
+ +
C n H 2n +1 C n H 2 n +1CO (m/z 29, 43, 57)
(m/z 27, 41). 29
C2H5+ HCO+.
-
.
43 CH3CO+ -
(CH3C2). ( )
CH3C2CO+ (m/z 57), .
(+)
.

12.7.4. .

, -,
.
, ,

.

12.17. .

267

,

(, 2, R, , ).

-X HC CH
+ X C4H3 (m/z 51)

-
.

-,
.
.

H2
C R
R C CH
+ R

(m/z 91) (m/z 65)

,
Mc Lafferty.
m/e 92.

H2
C CH2 CH2
CH2

H CH
H + CH
H
H CH3 CH3

(m/z 92)

268
 12.18. .

(HCHO), ,
(ROH).

O
CH2
() + CH2O
H

(m/z 78)

()
+ CO

O O
O

C C (R=H,CH3)
()
O O
R + ROH

X H X (X=O, NH, CH2)

269
12.7.5. , .

( )
,
.

1 R + X C O
R
C O (X=OH, OR, NH2, NR2)
X 2 X + R C O

1 , ,
HOCO+ (m/z 45) 2CO+ (m/z 44),
2 .

R
C O R'O + R C O
R'O

- (3 )
Mc Lafferty
m/z 60.

12.19. .

12.7.6. , ().

270
 .
, .

R'
R
R C OH R + C OH
R
R''

1- m/e
31
CH2=OH+.

12.20. 1- ( -1-).

.
. H2O 1-
m/z 56. ,
,
, ,
:

(CH2)n
(CH2)n
RHC CHR'
RHC CHR' + H 2O
H H O

1-,
28 ,
(.. 1-)

271
 .
-18.
CO (=28)
m/z , -28.
(CO) -29 .
2-
(-) .

12.21. 2-.

(RSH)
+ . 2-
:

1
CH3CH SH + C2H5
C2H5
m/z 61
CH SH

H3C +
2 C2H5 SH CH3

m/z 75

CH2 CH SH
2,
CH2 H
(CH2=CH2) m/z 47
+
CH 2 = S H .

272
12.7.7. .

.
- . ,
()
+ .
-:

H
H H H
R C N R + C N
H H H
H

, R .
, ,
m/z 30.
.

H2
R C NH2 R + H2C NH2 m/z 30

12.22. .

.
+.
:
H H H H

NH2 NH + H + HCN + H

m/z 93 m/z 92 m/z 66 m/z 65

273
12.7.8. (, RX).

+
,
. ,
- ,
+.
,
.
, , :

H2 H2
R C C X RCH CH2 + HX

( ),
RCl RBr.
(=35.37)
(=81.79).

12.23. 1-.

+
.
C6H5+ .

274
12.7.9. .

, ,
,
.

:

C O H
R CH R CH NH2 + CO2H
NH2
m/z 45 m/z 45

H3C CO2H H3C H3C

CO2H H -H
CH CH2 CH CH CH2 C CH CH2 C NH2
H
H3C NH3 H3C NH3 H3C

m/z 87 m/z 86

12.19. .

12.8. . .

()

( )

275
 + (
).
,
(IR, UV, NMR, ) .
:
() m/z +.
( .).
m/z + ,
. , +
.
()
,
+ .
() (
)
m/z.

.
() m/z +
(.. 2,
HCN, HX, CO, CO2, ).
()

.
() , ,
.

1: C5H12S (=104).

12.20. C5H12S.

+ m/z 104
105 106,
(

276
 . ).
( ) , +1, +2
106, 244, 5. M+2
( S, : 32
95.03%, 33 0.75% 34
4.22%).
.
+ 5 .
C5H12S (

).
m/e 70 (-34)
m/z 42 [-(34+28)]. 34 H2S
(RSH). (m/e 42)
C3H6+, H2S
CH2=CH2 (MB=28) .
(, ), (6
) m/e 42.

H3C H H H3C H H
CH S CH H2C S

H2C CH2 CH2 CH CH2

C H 3C C
H2 H2
() (m/z 42) ()

,
m/z 55, 41 24
+
C n H 2n 1 , .

m/z 47 , -
. m/z 61
, . C2H5S+,
:

H
R S
H
S
H2C C H2C CH2 + R
H2

, m/z 29 (C2H5+)
1- 3--1-
[CH3CH(CH3)CH2CH2SH] C2H5+
.

277
 2:
C7H6O2 122..

12.21. C7H6O2.

+
(100% ).
m/e 76, 66, 65, 39 38
. 121 ( 29,
CHO+)
. ().
C7H6O2 .

(m/e 93)
O
HO
C C O - CO
H
HO -H
HO C O
- HO

m/e 104

278
12.9.
.

,
.
(C, H, O)
.
.

12.1.

% % %
1 99.98 2 0.02
12 98.93 13 1.07
14 99.63 15 0.37
16 99.76 17 0.04 18 0.20
19 100.00
31 100.00
32 95.03 33 0.75 34 4.22
35 75.53 37 24.47

,
. ( ) (
),
. ,

.
+
(molecular-ion cluster) , +1, +2, ..
, ().
, +
, m/e 16 (12C1H4)+ m/e 17 (12C
1 2H )+. m/e 18,
2 2
(13C 132H)+, (12C 122H2)+ ,
2 (0.02%),
2 13C.
12C1H4 13C1H4 (
),
( 13C):

M +1 1.07
100 = 100 = 1.08
M 98.03

279
 ,
C30H62,
( ).
m/e 422, 423 424 (, +1 +2). +2
, 30
13C
+2. ( ) :

M +1 1.07
100 30 100 32.4
M 98.03
13C.
,
+1 2 , :

M +1 0.02
100 62 100 1.24 ( 2 )
M 98.98

() C30H62
:

M +1
100 33.64(32.4 + 1.24)
M

, (+2/)100

.

. , Beynon Williams
(+1)/ (+2)/
C, H, O 500.
, -
.

CWHXNYOZ:

M +1
100 = 1.08W + 0.02 X + 0.37Y
M

M +2
100 =
(1.08W + 0.02 X ) + 0.20Z
2

M 200

. .

280
12.10.
.

.

.

()
( ). (10-12
10-3 g)

, ( ).
(
) ,
.
,
, (jet
separator). ( ),
,
( ) ,
, .

12.22. - (GC-MS).

281
 12.23. HPLC-MS.
HPLC-ICP-MS (ion-pair reversed-phase)
.

()

()

12.24. () ESI-MS , () I-MS/MS m/z

198 ( ).(CP-MS:
inductively coupled plasma-mass spectrometry, ESI: electrospray ionization, MALDI:
matrix-induced laser desorption ionization.

. ,

282
 ,
.
,
- (GC-MS)
.
, GC-MS (
) , ,
, , , .

GC-MS ( ,

,
, ).

30000-40000

.

12.25. HPLC-MS.

12.11.

12.2.
.



12 C 12-14
13 CH+ ,
14 CH2 , N , N2 , CO
+ ++ ++
.

283
15 CH3+
-, -
- ,
16 O , NH2+, O2++ .

() (CH4)
() (): ,
17 OH+, NH3 , , -.

() (): ( ),
,
, , .
18 H2O , NH4+ ()(3): .

(2): ,
19 H3O+, F+ , , , , .

20 HF ,++, CH2CN++ (F): .

21 C2H2O++ ( F): .
22 CO2++
23 N 21-24
24 C2 (
).
25 C2H+

26 C2H2 , CN+ .

() (C2H2): .
27 C2H3+, HCN () (CN): .

() (C2H3): (
- ), -
-.
28 C2H4 ,CO ,N , () (CN): , .
HCNH+
() (C2H4):
-, , ,
-,
o
29 C2H5+, CHO+ .
() (C): , , -
.
() (2): .

284
30 C2 ,C22 ,+, () (C2H4): ,
C26 , F , 22 - .
() (C): , ,
.

31 C3+,C32 ,CF+, () (C2H6): .

23+ () (C2): , ,
- .
() ():
( ).
32 2 ,C3 ,S ,24 () (CH3): , -
, .
() (CH32): .
() (23):

33 CH3OH2+, SH+, CH2F+ () (CH3): , -

.
() (S) .
() (2): .

34 SH2 , (OH+OH) () (CH32):

( ).
() (SH): ( ).
() (CH2F): .

35 SH3+, Cl+, (OH+H2O) () (SH2):

(- ).
() (+): .

36 HCl , C3+, (H2O+H2O) () (Cl): .

() ( +2): (-
2 ).

37 C3H+ () (Cl): .
() (2 +2): ( 2
).

38 C3H2 .

39 C3H3+ .

40 C3H4 , CH2CN+, (CH2C): .

285
 12.12. :

1. Benyon JH. Mass Spectrometry and its Applications to Organic Chemistry.

Elsevier, Amsterdam, 1960.
2. Bierman K. Mass Spectrometry: Organic Chemical Applications. Mc Graw-
Hill, New York 1962.
3. Budsikiewicz H, Djerassi C, Williams DH. Interpretation of Mass Spectra of
Organic Compounds. Holden-Day, San Francisco, 1964.
4. Kiser RN. Introduction to Mass Spectrometry and its Applications. Prentice-
Hall, New Jersey, 1965.
5. Hill HC. Introduction to Mass Spectrometry. Heyden, London, 1966.
6. Benyon JH, Saunders RA, Williams A. The Mass Spectra of Organic
Molecules. Elsevier, Amsterdam, 1968.
7. White FA. Mass Spectrometry IN Science and Technology. John Wiley and
Sons, New York, 1968.
8. Shrader SR. Introductory Mass Spectrometry. Allyn and Bacon, Boston, 1971.
9. Williams DH, Howe I. Principles of Organic Mass Spectrometry. McGraw-
Hill, London, 1972.
10. Johnstone RAW. Mass Spectrometry for Organic Chemists. Cambridge
University Press, Cambridge, 1972.
11. Litsow MR, Spalding TP. Mass Spectrometry of Inorganic and
Organometallic Compounds. Elsevier, New York, 1973.
12. McLafferty FW. Interpretation of Mass Spectra. Benjamin, London, 1973,
University Books, California, 1980 (3rd ed).
13. McFadden W. Techniques of Combined Gas Chromatography/Mass
Spectrometry: Applications in Organic Analysis. Wiley-Interscience, New
York, 1973.
14. Mayer JR. The Mass Spectrometer. Wykeham publ, London, 1977.
15. Rose ME, Johnstone RAW. Mass Spectrometry for Chemists and Biochemists.
Cambridge University Press, Cambridge, 1982.
16. McLafferty FW, Venkatavaghavan. Mass Spectra Correlations. Amercan
Chemical Society, Washington DC, 1982.
17. Message GM. Practical Aspects of Gas Chromatography/ Mass
Spectrometry. John Wiley and Sons, Chichester, 1984.
18. Chapman JR. Practical Mass Spectrometry. John Wiley and Sons, New York,
1985.
19. Gaskell S.(ed). Mass Spectrometry in Biochemical Research. John Wiley and
Sons, New York, 1986.
20. White FA, Wood GM. Mass Spectrometry: Applications in Science and
Engineering. Wiley-Interscience, New York, 1986.
21. Karasek FW (ed). Mass Spectrometry in Environmental Sciences. Plenum,
New York, 1985.
22. Duckworth HE, Barber RC, Venkatasubramanian VS. Mass Spectrometry.
Cambridge University Press, Cambridge, 1986 (2nd ed).

286
23. Burlingame AL, Castagnoli N.(eds). Mass Spectrometry in the Health and
Life Sciences. Elsevier, Amsterdam, 1985.
24. Davis R, Frearson M. Mass Spectrometry (Analytical Chemistry by Open
Learning Series). John Wiley and Sons, Chisester, 1987.
25. McLafferty FW, Stanffer DB. Wiley/NBS Registry of Mass Spectral Data. John
Wiley and Sons, New York, 1988.
26. Eight Peak Index of Mass Spectra (by the Mass Spectrometry Data Centre).
Royal Society of Chemistry, London, 1988 (3rd ed).
27. Busch KL, Glish G. Mass Spectrometry/ Mass Spectrometry Techniques and
Applications of Tandem MS. VCH Verlag, New York, 1988.
28. McLaffery FW, Abrhamm S. Registry Of Spectral Data. John Wiley and Sons,
New York, 1987.
29. Constantin E, Scnell B. Mass Spectrometry: Principles and Applications. John
Wiley and Sons, New York, 1989.
30. Chapman JR. Practical Organic Mass Spectrometry. A Guide for Chemical
and Biochemical Analysis. John Wiley & Sons, Chichester, 1994.
31. Lee Ta. A Beginners Guide to Mass Spectral Interpretation. John Wiley &
Sons, Chchester, 1998.
32. Sparkman OD. Mass Spec. Desk Reference. Global View Publishers, New
York, 2000.
33. Niess W, ed. Current Practice of Gas Chromatography-Mass Spectrometry.
Marcel Dekker, Oxford, 2001.
34. Downard K. Mass Spectrometry: A Foundation Course. Royal Society of
Chemistry, Cambridge, 2004.
35. Smith RM. Understanding Mass Spectra. A Basic Approach, 2nd ed, Wiley-
Interscience, New York, 2004.
36. McMaster MC. GC/MS. A Practical Users Guide. John Wiley & Sons,
Hoboken, NJ, 2005.

287
288


RAMAN

.
,
, ,
-, Mssbaner,
..,
. ,
Raman ,
,
.

13.1. Raman

Raman (Raman Spectroscopy)

. ,
(98%)

( Rayleigh),

. Raman (
Raman 1928).
Raman
(
).
.

Stokes (Stokes lines)
,
anti
Stokes (anti-Stokes lines),
.

.
Raman
. () h (h

289
 Planck)
( ) ,
,
hv .

,
, ,,
. , ,

/ .
Raman
(polarizability) ,

.
,

,
.

(induced electric dipole moment)
. , ,

:
= E (13.1)
(polarizability)
( ).
, 2,
,

, .
H H H H

,
.

13.1. .

, (
) :

= 2t (13.2)

290
 :

= E = 2t (13.3)

,
Rayleigh. , , ,
, ,

. , Raman

. :
() ()
.

.

:

O O
H H H H O H
H

13.2. 2.

Raman
Raman Raman,
.

Raman
.
. , ,
2, 2 ., IR ,
,
Raman. Raman

.
Raman,
: ()
,
, () (rule
of mutual exclusion) ,
Raman,
R, IR
Raman. ,

291
( )
Raman IR.
IR Raman
.

IR

RAMAN

13.3. IR Raman .
Raman 4880, 200 , .

13.2. Raman
.

IR Raman
. ,
(CO2, N2O, SO2, NO2, ClO3
ClF3)
.
2.
, , , ,
. CO2 N2O
IR, .
, .. CO2

292
 (OCO), N2O (O), N2O

(IR Raman).
CO2
, ,
Raman.

13.4. CO2.

,
, ,
IR:

hv
O C O O C O + O C O

SO2, 519, 1151

1361 cm-1 .
. IR 3

. :

S
O O

, CS2,
, 35 = 4. Raman

. 13.5.,

. , Raman

. CS2
1, 2 3 (4) .

293
 13.5. CS2 .
3 , 4 .

1 () ,
IR.
,
( ), 2, 3 4,
IR.
Raman. 1

. 1 Raman.
2, 3 4
.
Raman.
,
3 3-6 = 6 ,
.

13.3. Raman

Raman

.
. Raman
13.6.

294
 13.6.
Raman. Raman (Nicolet Almega dispersive
Raman system) .
Raman 15000 .

,

Raman. ,
,
(~1 ml) ,
. 1020 ml
.
.

.
.

.
,

. Rayleigh

295
 Raman
20cm-1 ( IR).

.
,
IR. ,
,
/ ,
( )
Raman
IR
,
. Raman
(, .).

13.7. Raman. Holobrobe Research Raman Microiscope (Kaiser

Optical Systems, MI, USA).
.

13.8. Raman .
(Bruker, http:// www.brukeroptics.com/raman/images/ramanscopehead.jpg).

296
 13.9. FT-Raman(RAMII, Bruker).
(http:// www.brukeroptics.com/raman/images/RAMII_VERTEX70_head2.jpg).

13.10. Raman.
(http:// www.brukeroptics.com/raman/images/RFShead.jpg).

M Raman
.
Raman
.

297
 13.11. IR Raman F3CCCCCCF3.

IR Raman ( 13.11.),

1300 2000 cm-1, 2300 cm-1.
CH, NH, C O, C C, ..
1180 cm-1, Raman
IR.
. IR
2200 cm-1 Raman 2240 cm-1,
. ,
.
1200 cm-1 (IR) .
,
Raman 940 cm-1 (
CH) .
IR 1200 cm-1
CF2 CF3. :

F3 C C C C N F3 C C C C C CF3

298
 ,
.

13.12. FT-Raman
1064 nm . () , (b)
, (c) .

13.13. Raman , CH3CH2CH2CHO.

299
 Raman
.
.
Raman
() -
.
.

13.14. Raman.
Raman (
offset Raman ).

13.1. Raman
.

(cm-1) /
3380 3340
3335 3300 CH
3310 3290
3175 3154

3103 =CH2 ()

3100 3000 CH

2990 2980 =CH2 C=CH2

2884 2883 CH3
2251 2232 C

300
 1974 C C ()
1870 1840 C=O 5-

1740 1720 C=O
1689 1644 C= C
1665 1650 C= ()
1654 1649 C O
( )
1614 C= C
1560 1550 2

1415 1385
1385 1368 CH3

1310 - 1175 CH2

1230 - 1200 p-

1060 - 1020 -

1030 1015 CH

933
930 - 830 COC

905 - 837 CC -

877
830 - 720

760 - 730 C4O
709 CCl CH3Cl
655 640 CBr
630 - 615

525 - 510 SS
495 - 485 C
355 - 335
267 CBr4 CBr4 ( )

200 - 160

301
13.4. : Raman

1. Szymanski HA (ed). Raman Spectroscopy: Theory and Practice, Plenum

Press, New York, vol I, 1967, vol II , 1970.
2. Gilson TR, Hendra PJ. Laser Spectroscopy. Wiley-Interscience, New York,
1970.
3. Loader A. Basic Laser Spectroscopy. Heyden, London, 1970.
4. Tobin MC. Laser Raman Spectroscopy. Wiley-Interscience, New York,
1971.
5. Konigstein JA. Introduction to the theory of Raman effect. Reidel D,
Dodrecht-Holland, 1972.
6. Anderson A (ed). The Raman effect: Theory (vol I), Applications (vol 2).
Marcel Dekker, New York, 1971, 1973.
7. Demtrder W. Laser Spectroscopy. Springer-Verlag, Berlin, 1973.
8. Freeman SK. Applications of Laser Raman Spectroscopy. John Wiley and
Sons, New York, 1974.
9. Colthup NC, Daly LH, Wiberley SE. Introduction to IR and Raman
Spectroscopies. Academic Press, New York, 1975 (2nd ed).
10. Dollish FR, et al. Characteristic Raman Frequencies of Organic
Compounds. John Wiley and Sons, London, 1974.
11. Grasseli JG, et al. Chemical Applications of Raman Spectroscopy. John
Wiley and Sons, New York, 1981.
12. Strommen DP, Nakamoto K. Laboratory Raman Spectroscopy. Wiley and
Sons, Chichester, 1985.
13. Baranska H, Labudzinska A, Terpinski J. Laser Raman Spectroscopy:
Analytical Applications. John Wiley and Sons, New York, 1987.
14. Spiro TG (ed). Biological Applications of Raman Spectroscopy. John Wiley
and Sons, New York, 1987.
15. Clark RJH, Long DA (eds). International Conference on Raman
Spectroscopy. John Wiley and Sons, Chichester, 1988.
16. Pelletier MJ. Analytical Applications of Raman Spectroscopy. Blackwell,
Oxford, 1999.
17. McCreery RL. Raman] Spectroscopy for Chemical Analysis. Wiley-
Interscience, New York, 2000.
18. Gremlich HU, Yan B. Infrared and Raman Spectroscopy of Biological
Materials. Marcel Dekker, New York, 2000.
19. Lewis IR, Edwards HGM (eds). Handbook of Raman Spectroscopy, Marcel
Dekker, New York, 2001.
20. Mayo DW. Course Notes on the Interpretation of Infrared and Raman
Spectra. Wiley-Interscience, New York, 2004.
21. Smith E. Modern Raman Spectroscopy: A Practical Approach. John Wiley
and Sons, Sussex, 2005.
22. Edwards HGM, Chalmers JM (eds). Raman Spectroscopy in Archaeology
& Art History. Royal Society of Chemistry, Cambridge, 2005.

302


14.1.

H
(Electron Paramagnetic Resonance, EPR) Spin
(Electron Spin Resonance, ESR), NMR,
ESR
spin
.
()

spin () .
:


. ,
, . ,

(paired) () spin
. ,
.. 2,
spin (), .. 2,
,
.

.
, 2 2,
() , Fe3+, [Fe(CN)6]3-,
(free radicals)
() UV,
- .
, ,
NMR , 0,3
Tesla ,
spin.

303
14.2. (Spin)

,
spin (spin angular momentum)
, spin.

spin
(spin angular
(orbital angular momentum)
momentum)

spin
(orbital magnetic (spin magnetic
moment) moment)

14.1. spin.

, spin
, ,
.
ms ( = h/2), ms = 1/2.
spin ()
.
Zeeman:
,
. :

E mS = 2 B m S B
ms = 1/2 spin
(magnetic quantum number of electron spin)
(
) Bohr magneton e/2me (me
).
Zeeman .
, spin,
,
.
( -z) ml.

304
H z = e me h , e
e
e = .
2 m e

,
()
. , e/2me /2 = e/2me
, Bohr magneton.
, -z, :

z = e me h = (eh / 2me )me = B ml (14.1)

( = z) -z,
-z (
). ml
( ) :

E = z B = B ml B (14.2)

p- l=1, o ml
+1, 0, -1. ,
, ,
ml = 1
, ml = 0
ml =-1 -. Zeeman
.
Zeeman (normal)
( ~1cm-1). ,
Zeeman (anomalous)
, spin. H
e me h , 2 e me h
spin, .
2
, .
2.002319 ge (g-factor, g= spectroscopic splitting factor,
) Land
(Land splitting factor).

305
 14.2. p- =1 ml=+1, ml=0
ml=-1.

1/2 -1/2 :

E1 / 2 = 2 B 1 / 2 B E 1 / 2 = 2 B (1 / 2) B

E1 / 2 = B B E 1 / 2 = B B .
spin :

E = E1 / 2 E 1 / 2 = 2 B B (14.3)

,
spin
(
), :

E = hv = 2 B B (14.4)

,
spin
. ,
spin
() ().
spin
, .

306
14.3.

.

.
spin spin
()
( ),
(coupling) spin spin
,
(NMR).

, spin (),
spin . spin S,
: 1/2+1/2 = 1
(, spin
).
( spin),
ms = +1, 0, -1. ,
, ms=0
. +1 0
0 1 , ms =1,
, . 14.3
.

() ()

14.3. () -
, ()
() .

307
 ,
( ) ms
= 0, 14.3 (). ms = 1 ,
+1 1
, , .
-
- (zero-field crystal-field effect)
.
,

.
spin.

.
(mI = 1/2), ,

.
, spin
, .
: = B + a m ,
(hyperfine coupling constant).
spin mI = 1/2
, : = B + 1 / 2a = B 1 / 2a .
mI = +1/2 mI = -1/2.
, ,
hv = 2 B ( B + 1 / 2a ) hv = 2 B ( B 1 / 2a ) . ,
,
( Gauss)
,
spin, .

308
 14.4.
spin [A: , :
, : (hyperfine splitting constant)].

14 spin I =
1, spin +1, 0, -1.

14 spin . 14.5
,

.

14.5. 14 (=1)
.

309
 (..
), .
, 4 .
, ,
.
CH CH , (CH ) = ,
2 3 2 1 2
4 3 121.
: ,
+1 ,
Pascal:

1
0 1 1
1 1 2 1
2 1 3 3 1
3 1 4 6 4 1
4 1 5 10 10 5 1
5 1 6 15 20 15 6 1
6

( )
C6H6 7
1615201561, 6 .

14.6. EPR .

310
14.4.
(EPR).

SR
0,11 Tesla (1-10 KGauss).
0,3 Tesla 10 GHz (1010 c/s)
3 cm-1. To 0,3


(microtesla) ,
. ,
, Klystron.

(scanning).

13.14.
.
(Field set, Scan range,
Microwave frequency, Microwave power, Modulation amplitude, Scan time, Time
constant Receiver Gain) /. ,
, .

H

(dA/dB), /
,
.
-.
.

311
13.5.

NMR,
spin- ,
. spin-

.
spin-spin
.
,
. ,

.
NMR,
.
, ,

.
spin

. ,
- () [(CH3)3C]2NO
. ()() (),

, .

() 10-4

()10-2

() 10-1

[(CH3)3C]2NO 25 C

14.8. .

312
13.6.

.
.

: CH3 ( ).

14.9. ()
(CH3)
, ()
dA/dB. (CH3) :
1331.

: CH2OH.

(1 (CH2)=17.4 G, 2 ()=1.15 G).

.
.
CH2OH
() . 23=6 .

313
 14.10.
, 2 CH2OH.

EPR ,----
, DPPH ( ).

O2N

N N NO2

O2N

314

.

.
NMR
, ,
.
. .
. , ,
(. . , /
, 2005)

315
14.7. : (EPR)

1. Ingram DJ. Free Radicals as studied by ESR. Butterworths, London, 1958.

2. Assenheim HM. Introduction to Electron Spin Resonance. Hilger and Watts,
London, 1966.
3. Ayscough PB. Electron Spin Resonance in Chemistry. Methuen, London,
1967.
4. Alger RS. Electron Paramagnetic Resonance. Wiley-Interscience, New York.
5. Fu Yen T (ed). ESR of Metal Complexes. Hilger A, London, 1969.
6. Gerson F. High Resolution ESR Spectroscopy. Wiley-Verlag Chemie,
Weinheim, 1970.
7. Poole CP, Farach HA. The Theory of Magnetic Resonance. Wiley-Interscience,
New York, 1972.
8. Wertz JE, Bolton JR. Elementary Theory and Practical Applications in ESR.
McGraw-Hill, New York, 1972 and Chapman and Hall, London, 1986 (2nd ed).
9. Blumenfeld LA, Vooevodski VV, Semenov AG. ESR in Chemistry. John Wiley
and Sons, New York, 1973.
10. Atherton NM. Electron Spin Resonance. Ellis Horwood, Chichester, 1977.
11. Ranby B, Rabek JF. ESR Spectroscopy in Polymer Research. Springer-Verlag,
Berlin, 1977.
12. Harriman JE. Theoritical Foundation of ESR. Academic Press, New York,
1978.
13. Symons M. Chemical and Biochemical Aspects of ESR Spectroscopy. Van
Nostrand Reinhold, New York, 1978.
14. Pryor WA (ed). Organic Free Radicals. Am Chem Society Symposium Series,
Washington DC, 1978.
15. Forester AR, Neugebauer FA (eds). Magnetic Properties of Free Radicals.
Landolt-Bornstein. New Series Group II, vol 9. Springer-Verlag, Berlin, 1979.
16. Swarts HM, Bolton JR, Borg DC. Biological Applications of Electron Spin
Resonance. Wiley-Interscienc, New York, 1972.
17. Pryor WA (ed). Free Radicals in Biology. Academic Press, New York, vol 1-6,
1976-1984.
18. Knowles PF, Marsh D, Battle HWE. Magnetic Resonance of Biomolecules: An
Introduction to the Theory and Practice of NMR and ESR in Biological
Systems. John Wiley and Sons, London, 1976.
19. Sealy RC, Hyde JS, Antholine WE. Electron Spin Resonance: In Neuberger A,
Van Deenen LLM (eds): Modern Physical Methods in Biochemistry. Elsevier,
Amsterdam, 1985.
20. Halliwell B, Gutteridge JMC. Free Radicals in Biology and Medicine.
Clarendon Press, Oxford, 1985, 1986, 3rd ed. 2001.
21. Niquel J (ed). The Handbook of Biomedicine of Free Radicals and
Antioxidants. vols 1-3, CRC Press, Boca Raton, Florida, 1989.

316
22. Hayaishi O, Niki E, Kondo M, Yashikawa M (eds). Medical, Biochemical and
Chemical Aspects of Free Radicals. Proceedings of the 4th Biennial Meeting of
the Society for Free Radical Research, Kyoto, Japan, 9-13 April, 1988. Elsevier,
Amsterdam, 1989.
23. Jansen EG, Blackburn BJ. Detection and Identification of short-lived free
radicals by electron spin resonance trapping technique. J Am Chem Soc, 90:
5909-5910, 1968.
24. Rice-Evans CA, Diplock AT, Symons MCR. Techniques in Free Radical
Research. Elsevier, Amsterdam, 1991.
25. Motherwell WB, Crich D. Free Radical Chain Reactions in Organic Synthesis.
Academic Press, New York, 1992.
26. Weil JA, Bolton JR, Wertz JE. Electron Paramagnetic Resonance: Elementary
Theory and Practical Applications. Wiley, New, York, 1994.
27. Fossey J, Lefort D, Sorba J. Free Radicals in Organic Chemistry. Wiley & Sons,
Chichester, England, 1995.
28. Alfassi ZB. N-Centered Radicals. Wiley, Chichester, 1998.
29. Alfassi ZB. General Aspects of the Chemistry of Radicals. Viley-VCH,
Weinheim, 1999.
30. Rosen GM, Britigan BE, Halpern HJ, Pon S. Free Radicals in Biology and
Detection by Spin Trapping. Oxford University Press, New York, 1999.
31. Parsons AF. An Introduction to Free Radical Chemistry. Blackwell Science,
Oxford, 2000.
32. Perkins MJ. Radical Chemistry-The Fundamentals. Oxford University Press,
New York, 2000.
33. Sajfutdinor RG, Ivanova L. Electron Paramagnetic Resonance in Biochemistry
and Biology. Klumer Academi, Dordrecht, 2001.
34. Schweiger A, Jesch Ke. Principles of Pulse Electron Paramagnetic Resonance.
Oxford Univerity Press, Oxford, 2001.
35. Denisov ET, Denisova TG, Polidova TG. Handbook of Free Radical Initiators,
Wiley, Chichester, 2003.
36. Gerson F. Electron Spin Resonance Spectroscopy for Organic Chemists.
Wiley-VCH, Weinheim, 2003.
37. Bender C, Berliner LJ, eds. EPR: Instrumental Methods. Klumer Academic/
Plenum, Dordrecht, 2004.

317
318


319


320

(National Institute of Advanced Industrial Science and Technology,
JAPAN)

Welcome to Spectral Database for Organic Compounds,

SDBS.
This is a free site organized by National Institute of Advanced Industrial Science and Technology
(AIST), Japan.

NMR: T.Saito, K.Hayamizu, M.Yanagisawa and O.Yamamoto

MS: N.Wasada
ESR: K.Someno
IR: S.Kinugasa, K.Tanabe and T.Tamura
Raman: K.Tanabe and J.Hiraishi

321
 (National Institute of Advanced Industrial Science and Technology,
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What's New [ Last Up Date 2006/ 4/14 ]
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spreading around the research information via internet.
Following items are published as RIO-DB from TACC
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Introduction to the Spectral Data Base System (SDBS)

SDBS is an integrated spectral database system for organic compounds,

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We started the studies on the spectral database system in early 1970s.
The construction of the database in the present format was started in 1982
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Most of these spectra were measured in our institute.

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323
SDBS
Information
SDBS No.: 673

Compound Name:
benzoic acid

Molecular Formula: C7H6O2

Molecular Weight: 122.1

CAS Registry No.:

65-85-0

Spectral Code:
Mass :
13
C NMR : in CDCl3
1
H NMR : 90 MHz in CDCl3
IR : CCl4 solution
IR : KBr disc
IR : nujol mull
Raman : 4880 A,200 M,powder

Chemical Information:
http://www.aist.go.jp/RIODB/SDBS/cgi-bin/cre

324
325
326
 IR&NMR (Dpt of Chemistry, UCLA)

Problems in NMR and IR Spectroscopy

Welcome to WebSpectra - This site was established to provide chemistry students with a library
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provides 1H NMR and 13C NMR, DEPT, COSY and IR spectra of various compounds for students
to interpret. Hopefully, these problems will provide a useful resource to better understand
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This project is supported by Cambridge Isotope Laboratories and the UCLA Department
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Project Director Professor Craig A.

NMR Facility Merlic
Contributor Dr. Jane Strouse
Copyright 1997 Craig A. Merlic, Barry C.
Fam and The Regents of University of
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Instructional Documents Awards
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WebSpectra Technical Notes National Institute of Materials and
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Software
European Molecular Biology
Laboratory, Germany

http://www.chem.ucla.edu/~webspectra/

327


NH2

O
CH3 C7H9NO
-
1--2-
-anisidine
1-amino-2-methoxybenzene

328

(National Institute of Science and Technology)
Welcome to the NIST Chemistry WebBook
The NIST Chemistry WebBook provides access to data compiled and distributed by
NIST under the Standard Reference Data Program.

The NIST Chemistry WebBook contains:

Thermochemical data for over 7000 organic and small inorganic

compounds:

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You can search for data on specific compounds in the Chemistry WebBook based on
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http://webbook.nist.gov/

329
 Standard Reference Data Online Chemistry
Data Program Gateway Databases WebBook

Hydroquinone
Formula: C6H6O2
Molecular weight: 110.11
IUPAC International Chemical Identifer:
o InChI=1/C6H6O2/c7-5-1-2-6(8)4-3-5/h1-4,7-8H
o Download the identifier in a file.
CAS Registry Number: 123-31-9

Chemical structure:
This structure is also available as a 2d Mol file or as a computed 3d Mol file.
Other names: 1,4-Benzenediol; p-Benzenediol; p-Dihydroxybenzene; p-Dioxybenzene; p-
Hydroquinone; p-Hydroxyphenol; Arctuvin; Benzohydroquinone; Benzoquinol; Diak 5;
Eldopaque; Eldoquin; Hidroquinone; Hydroquinol; HE 5; Phiaquin; Quinol; Tecquinol; Tenox
HQ; 1,4-Dihydroxybenzene; 4-Hydroxyphenol; p-Dioxobenzene; Hydrochinone; -
hydroquinone; -quinol; Artra; Benzene, p-dihydroxy-; Black and White Bleaching Cream;
Derma-Blanch; Dihydroxybenzene; Hydrochinon; Hydroquinole; HQ; Idrochinone; Melanex;
NCI-C55834; Tequinol; USAF ek-356; 1,4-Dihydroxy-benzeen; 1,4-Dihydroxy-benzol; 1,4-
Dihydroxybenzen; 1,4-Diidrobenzene; UN 2662; Dihydroquinone; Aida; component of Artra;
Eldopacque; Eldopaque forte; Eldoquin forte; Hydroquinone, 1,4-benzenediol; p-
Hydroxybenzene; Solaquin forte; Tecquinol tech. grade
Information on this page:
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Other data available:
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Infrared Spectrum

Go To: Top, References, Notes / Error Report

330
Notice: Except where noted, spectra from this collection were measured on
dispersive instruments, often in carefully selected solvents, and hence may
differ in detail from measurements on FTIR instruments or in other chemical
environments. More information on the manner in which spectra in this
collection were collected

http://webbook.nist.gov/cgi/cbook.cgi?ID=C123319&SI&Type=IR-SPEC&Inde.

331
http://webbook.nist.gov/cgi/cbook.cgi?ID=C123319&Units=SI&Mask=200

332
http://webbook.nist.gov/cgi/cbook.cgi?

333
 (CHEM EXPER)

334
http://newsearchch.chemexper.com/cheminfo/servlet/org.cheminfo.applet.nemo.

335
http://newsearchch.chemexper.com/cheminfo/servlet/org.cheminfo.applet.nemo.

336


http://www.nd.edu/~smithgrp/structure/welcome.html

337
 Problem 7 - IR spectrum
C6H10 : MW = 82

Problem 7 - 1H NMR spectrum (CDCl3, 500 MHz)

http://www.nd.edu/~smithgrp/structure/p7x.html

338
 Problem 7 - 13C NMR spectrum (CDCl3, 125 MHz)

http://www.nd.edu/~smithgrp/structure/workbook.html

339



-

340

FT NIR (FOURIER TRANSFORM NEAR INFRARED
SPECTROMETER)

http://www.sys.wakayama-u.ac.jp/mc/photon/equipment/photo/FT-
IR.jpg

341

FT NIR (FOURIER TRANSFORM NEAR INFRARED
SPECTROMETER)

FT NIR (FOURIER TRANSFORM NEAR INFRARED
SPECTROMETER)
(, NICOLET)

http://www.thermo.com/com/CMA/Images/Image_26405.jpg

342

FT NIR (FOURIER TRANSFORM NEAR INFRARED
SPECTROMETER)
(BRUKER 22/N)

FT NIR (FOURIER TRANSFORM NEAR INFRARED
SPECTROMETER)
(BRUKER VECTOR 22-NIR)

343

( )

344

( )

http://www.bk.tsukuba.ac.jp/~mmml/Photos/NMR.jpg

NMR-300 MHz

345
 NMR (900 & 300 MHz)

Ultra-Wide Bore 900 MHz NMR Magnet

http://www.chem.unifr.ch/ne/pictures/img20.jpg

346

(SUPERCONDCUCTING MAGNETS)

NMR (COSY 2-D)

347


( , contour plot): F1 F2 ppm

348


FINNIGAN FT/MS 2001

MS VG 70 SE

http://chem.umn.edu/.services/massspec/images/

349


BRUKER BIOTOF II, REFLECTRON ESI TOF INSTRUMENT

[20000 resolving, ESI & APCI capabilities]

(http://www.chem.umn.edu/services/nassspec/images/BIOTOF11590.jpg)

FINNIGAN MAT 95
(double focusing, high resolution MS)

(http://www.chem.umn.edu/services/massspec/images/mat95590.jpg)

350

(LIQUID CHROMATOGRAPHY MASS SPECTROMETRY)

351
 TANDEM MS/MS ( )

Thermo
Finnigan
LCQ DECA
XP Plus
Quadrupole
Ion Trap Mass
Spectrometer
(Peptide
Sequencing
LC-MS/MS)
Harvard
http://ucb.harvard.edu/Microchem/images/largePictures/image3.jpg

Finnigan TSQ Mass Spectrometry Tandem LC-MS/MS

352


HIGH-PERFORMANCE MS (FT ICR MASS SPECTROMETER)

(ranging from 7-12 Tesla, with Electrospray Ionizatiozation Sources)

http://www.emsl.pnl.gov/images/new/7_tesla_fticr.jpg

(LIQUID CHROMATOGRAPHY MASS SPECTROMETRY)

353
 (UV-VIS)

http://chemistry.jcu.edu/images/hpuvvis.jpg

354
 (UV-VIS)

355
http://www.imp.mtu.edu.matchar/raman.jpg

RAMAN

356
 http://www.physics.emory.edu/faculty/warncke/research/kwinstruments.html

CONTINUOUS-WAVE ELECTRON PARAMAGNETIC RESONANCE

html://www.emsl.pnl gov/capabs/images/epr.jpg

357

MAGNETIC RESONANCE IMAGING (MRI)

358