:

)(DFT

:
1 2 ....................................................................................................
1 1 2 ............................................................................
12 3 ..................................................................
:1-2-1 4 ........................................................
:2-2-1 4 ........................................................
1 3 4 ................
131 5 .......................................................
132 5 ....................................................
14 6 ..........................................
1 5 7 ...........................................
16 8 ...................................
17 8 .......................................................
1-7-1 9 ..................
8-1 OH 10 .................................................
19 10 ..................................................
191 10 .............................................................
192 11 ........................................................................

193 12 ........................................................
194 13 ...................................................................... NMR
195 13 .......................................................... :
1 96 14 .....................................................................
14 ...................... :
1 10 14 ...........................................
1101 15 .......................................................
110 2 16 ......................................................
1 103 16 .......................................................... :
1 104 16 ..........................................................
111 17 ............................................... :
1 12
17 ............................................................................................ :
1121 17 ..................................................... :
11212 18 ........................................................................
112 13 19 ...................................................................
1121 4 19 ..................................................
11215 20 ................................................................... :
:13-1 1HNMR - 20 ............................................

 :
21 26 ...............................................................................................
22 26 ...............................................................:
23 26 .....................................................................
2 4 28 .................................ab initio
24 1 29 ......................................................................
25 30 ..........................................................................................
2 51 30 ............................................................................
2 5 2 31 ...........................................................................
2 5 21 32 .........................................................
2522 33 ...................................................
2 5 2 3 33 ...........................................
2524 33 ........................................................
2 52 5 34 ............................................................
26 35 ............................................................................
261 36 ........................................................
27 )37 ..................................................................... (DFT

 :
:
41 44 ...............................................................................................
4 2 44 ..............................................................
43 46 ......................................................................
44 48 ...
5-4 51 ..............
-6-4 -
55 .....................................................................................................
:7-4 - 60 ..........................
14 6
63 ..................................................................................
47
63 ...............................................................................
8 -4 64 ............................
:1-9-4 3200 cm -1 99 .........................................................
:4-9-2 99 ..................................................................C-H
:3-9-4100 ......................................................... 1800-800 cm -1
:4-10 104 ........... :

1
]7 [1

.

. DNA
.

.

.
1 1
.
1920 :
.

.
] [8 1 1939
.
2 1940
:

1- Lewis
2- Pauling

. .
.


.
1991 1
:

. .

[9] .





. .
12

][10
1

40K15

mol

cal

1- Zeegers - Huyskens

154

3 K1 - 4

mol

mol

K cal

cal

.

.
.
H+ H+
.
:1-2-1

3
.
.
:2-2-1

. C Si
1 3
-1
-2

131

XHy
x y

1-1

]13[11
132


. -2
. OO 2/61A
.

(150 ) O-HO .
.
.


.
.
:
.

OH 2700cm-1.


.
14
1 1960 ]15 [14

] .[16
.

- Sutor

2-1

1 5
.
]18 .[17

3-1 3

4 5 6
.
1/4
2/1 2/5 .

16

4-1

. O-
HF .
10KJ ][19
Ab initio -2 ][20
-2 2 6 ) ( - ][21
OF 2/77A 2/66 O-HF 140 134
.
17

.
A-HB B A
.

)(1

A H + B A H ... B A .... H B + A + H B

HA B .
]25 [23
]29 [26 .

) (1 A B A-H
H-B+ .
27] IR [25 ].[28
] [29 31] NMR [30 .
] [32 OH OH ...N O ...HN +

.
C=O 1715cm-1

) 1517cm-1 1400( .
1-7-1
.
(1 CH OH
Enol

Keto

.
(2 OH
1HNMR .
(3
.OHO
.
1HNMR .
1HNMR
1HNMR .

10

8-1 OH
.

.
.
self consistratin reaction field
]38 [36
.
1-1 OH NO2 .
1-1 OH barrier NO2

19
1920
:
191

nROH (ROH)n

11

ln k H

=
T
RT 2

].[38
E = K = HA (I ) / R

1-2

HA I R
.
.

) (
. .
192
X
.
X
.
X X
X

.
X

. X
.

12

.
X .
A-H.B .

.
.
193

HA B .


.

].[40

B....H A B H + .... A .
317/9
402/5
.


.

13

194 NMR
NMR NMR
HA A-HB
HA A-H.B
. 15 1H 3H 3C 17O 14N N

15

H-AB .

.
.
195 :


. ].[41

.
.
:
A-H . O-H N-H C-H

3.
: HB

A-HB )300cm-1 (1800 .

a .

14

1 96
IR
IR
A-H .
.

.
:
IR
IR

.
1 10
AH
.
B AH AH
.
.
3 :
: AH
: HB
: B, A

15

B AH

B
] [5-1
.

5 : 1 )( )(

AHB A B
.


1101
] [1-5

. AHB B

AH HB
. .