Вы находитесь на странице: 1из 27

.

.
E-mail:bezvold@ukr.net .
.
,
. , y = a + b/x + c/x
.
- .
,
.
: , , ,
, .
.
.
.
.
.
6, 10 .. ( 4n + 2)
, 4, 8 ..
.
,
, .
, -
.

,
( , , ).
,
,

(A A, A B). , ,

, .

, -
1.5 ,
. ,
.
.
.
,
(),
( 1 2):

.... .....
.......
H

_+ C _ +
_
H
+
C
_C
_+
+
_
+
C
C
_
_
H
H + +C _+

.. ..
..

6_
5+

+1

+ -

_2

4_

+3

_ -

H
1

,
( 2).
. 2.
1 2 6 ( 2)
(1 (+), 2 (-), 6 (-)), 1 ()
2 6. , 1 6, 1 2 1.210 ,
, 1.397 ,

120. 1 6, 1 2
, [1]:

.. . .
..

6_
H3C

CH3

Lc _ c = 1.543

H2C

CH2

HC

Lc = c = 1.338

LC

CH
C

5+

= 1.205

+1

1.210

4_

_2

+3

L 1 _ 2 = 1.210

, 1 2, 1 6
,
1 (+) 2 (-), 1 (+) 6 (-) .
.
, 1 2 6
( 3):

.. .. .. ..
.. ..

6
a

a+b
b

5+

+1

_2

5+

+3

.. ..
..

6_

+1

_2

+3

+1

2.420

5+

+3

L1 _ 2 = L 1_ 6 = 1.210
L1 _ 4 = 2.420

4, ( 4)
, , , 1
, 1 (+) 4 (-)
. 6 (-) 3 (+),
2 (-) 5 (+). 1 4 2.420 .
3

,
1 2, 1 6 (1.210 2 = 2.420 ).
, ,
. ,
, , ,
1.5.
, - ,
.
- 1 (+) 4 (-), 2 (-) 5 (+), 3 (+)
6 (-) 5:

.
.
.. ..

6
5+

.
.
.. ..
_

+1

+3

5
sp .
:

= 3/2 = 1.5

8 (3 + 3 + 2 = 8). ,


.
,

. .. .
.. . ..
...

.
...
_

,
, ,
, .
,
,
,
,
.
,
, [2],
[3].

2_


1,3,5,7- [4], [5].
- 1.41 .
CH3
CH3

2_

L c-c ~
~ 1.41

H3C
CH3

,
(15) ,

. ,
,
.
[2, .79].
(- [10]-).
+
. ._
.
+.
_.
.+
.
+ . . ._

+
.
.
._
+.
_.
.+
.
+ . . ._

n = 10

B
. . .C

4.309

ABC = 144 oC
Lc-c = AB = BC = 1.400

n = 10


, .
,
(4.309 L- = 1.400 ),
(24)

.
80. -
- , ,
[2, .84], [6].

,

( ),
. .
Lc-c = 1.397

Lc-c = 1.410

6_

8_

5+

.. ..
..

+1

+3

L1 _ 2 = L 6 _ 1 = 1.210
L 1_ 4 = 2.420

.. . ..
...
+1

7+

+5

_2
+3

_4

L1 _ 2 = L 8 _ 1 = 1.303
L 1_ 5 = 3.404

.. . . ..
.. . .

Lc-c = 1.400
+1 _ 2
10 _
+3
_

9+
_
8

7+

+5

L 1_ 2 = L10 _ 1 = 1.331
L1 _ 6 = 4.309

, 1 2
1.210 , 1.303 , 1.331 (
). ,

(0, 15, 24) ,
(2.420 ; 3.404 ; 4.309 ),
1 2 (1.210 ; 1.303 ; 1.331 ),
. ,
() .
,
( 1.210 2.420 ). ,
.
. .
, Lc-c = 1.400
L(1-5) = 3.380 ,

L(1-2) = L(8-1) = 1.293 ,

L- = 1.410 .

, [18]-, ( ).
. ,
= f(L) = f(L), , L ,
7

/ y = a + b/x + c/x
(C-C, C-N, C-O, C-S, N-N, N-O, O-O, C-P).
, , .
[1]:
H3C CH3

H2C

CH2

Lc_ c = 1.543

Lc = c = 1.338

HC
LC

CH
C

= 1.205

- , 1, 2, 3.
[1, c.116]:
H3C

CH3

- =347.9397 /

H2 C

CH2

HC

CH

= 615.489 / = 812.278 /

( . ) ,
,
. ,
.
:
cc = 0. 06040343

= 2221 .34518418

5.67787529 11. 28562201

L
L2

5065 .62912191 1699 . 18638789

L
L2

(1)

(2)

:
cc (L = 1.397 ) = 1.658
cc (L = 1.42 ) = 1.538 1.54
Ecc (L = 1.397 ) = 534.0723 /
Ecc (L = 1.42 ) = 503.3161 /
, , ,
.

.... .....
.......
_

HC
+
HC

H
C

CH
_

.. ..
..
_

CH

+ -
_ -

C +
H

,
1.5, :
1 . 5 = 0. 06040343

5. 67787529 11. 28562201

L
L2

(3)

L = 1.42757236 .
, 1.5,
cc L = 1.42757236 .
1.5,
L = 1.42757236 :
L = 1. 42757236 = 2221 .34518418

5065 .62912191 1699 . 18638789

1.42757236
1.42757236 2

Ec c (L = 1.42757236 ) = 493.3097 /
, - 1.658
Ecc = 534.0723 /, :
E = 534.0723 / 493.3097 / = 40.7626 /.
40.7626 / , -
. , :
E1 = 40.7626 / 2 = 81.5252 / (19.472 /).
,
, :
E = 3E1 = 3 81.5252 / = 244.5756 / (58.416 /).

.. . .
..
_

.. ..
..
_

..
.. . .
_

3 E = 244.5756 /


(, - ).
- :
E2 = 3Ecc + 3Ecc = 2890.286 /
cc 1.658 :
E3 = 6 534.0723 / = 3204.434 /
,
:
E = E3 E2 = 3204.434 / 2890.286 / = 314.148 / (75.033 /).

.

. = f(L) E = f(L) - ,
, L , /.

3_
_
2
_
1

, /

..
.

..
.

L,

L,

, .
[1]:
H3C CH3

H2C

CH2

Lc_ c = 1.543

Lc = c = 1.338

HC
LC

CH
C

= 1.205

- , 1, 2, 3.
[1, c.116]:
H 3C

CH3

- =347.9397 /

H2 C

CH 2

HC

CH

= 615.489 / = 812.278 /

10

,
(), y = ax + b ,
b :

xy x y /n

a=

b=

(4)

x x / n
2

y / na x / n

(5)

n .
,
,
2

[ xy x y / n ]

r =

x 2 x /n

][

y 2 y / n

(6)

r2 ,
.
, = f(L) = f(L)
y = a + b/x + c/x2 ,
.
y = a + b/x + c/x2 , X = 1/x,
Y=

y y 1
1 / x1 / x 1

, b 1 = b + c/ x 1 , : Y = b1 + X, ,

c=

1 / xY 1/ x Y /n

b1 =

(7)

1/ x 1 / x /n
2

Y / nc 1/ x / n

(8)

n Y.
a : y = na + b(1/x) + c(1/x2),
n = 3.

11

(9)

= f(L) CC, C=C, CC.


1. = f(L).
1/x

y y 1

1/ x y y 1

1/ x1/ x 1

1/ x1/ x 1

1/x

x (L, )

y ()

0.74738416
0.82987552

0.55858308
0.68869338

10.07089756
11.00186391

7.52682927
9.13017751

1.543
1.338
1.205

1
2
3

1.57725967

1.24727645

21.07276147

16.65700678

4.086

1/x1 = 0.64808814

x1 = 1.543

y1 = 1

(1/x2) = 1.66729469

(1/x) = 2.22534781

c = 11.28562201

b = - 5.67787529

, = 0. 06040343

n = 3
a = - 0.06040343

5.67787529 11.28562201

L
L2

(1)

:
CC () = 1. = () = 2. () = 3.
CC () (L = 1.42 ) = 1.538 1.54.
CC () (L = 1.397 ) = 1.658
, - 1.658, 1.667
[2, .48].
, y = a + b/x + c/x
(1, 1), (2, 2) (3, 3 ) , b, ,
() . ,
. ,
y = a + b/x + c/x = f(L) E = f(L)
. , = f(L)
(Lcc = 1.397 ,

= 1.667) r = 0.9923

= -0.55031721, b = -4.31859233, = 10.35465915. ,


= f(L) E = f(L)
, , b, (
, ).
.

12

= f(L) CC
Y=
y = a + b/x + c/x2

X = 1/x

b1 = b + c/x1

Y = b1 + cX

y y 1
1 / x1 / x 1

:
c=

1 / xY 1 / x Y /n

b1 =

1/ x 2 1 / x /n

(7)

Y / nc 1/ x / n

(8)

n Y.
: y = na + b(1/x) + c(1/x2),

(9)

n = 3
2. E = f(L).
1/x

y y 1

1 / x y y 1

1 / x1/ x 1

1 / x1 / x 1

1/x

x (L, )

y (E, /)

0.74738416
0.82987552

0.55858308
0.68869338

2694.46159281
2554.29339132

2013.79790195
2119.74555296

1.543
1.338
1.205

347.9397
615.4890
812.2780

1.57725967

1.24727645

5248.75498413

4133.54345491

4.086

1775.7067

1/x1 = 0.64808814
(1/x2) = 1.66729469
c = - 1699.18638789

x1 = 1.543

y1 = 347.9397

(1/x) = 2.22534781
b = 5065.62912191

= 2221 .34518418

n = 3
a = - 2221.34518418

5065 .62912191 1699 . 18638789

L
L2

(2)

:
Ecc () = 347.9397 / = () = 615.4890 /
() = 812.2780 /
,
, .

13

()
,
PAO = 60

AF = 1.397

AFE = 120

PQO = 60

QPO =

O
A

OA = AF

PQ = OP = AF

PQ = OP = AF

. sin 60

3
3
= 1.397 .
= 1.210
2
2

PQ = 1.210
PR = 2PO = 2 . 1.210 = 2.420

D
135o

..
K

.O

. . .B

BAO = 67.5o
tg BAO =

OC
AC

OC = AC . tg BAO =

AB . tg BAO
2

o
CD = 2 . OC = tg BAO . Lc-c = tg 67.5 . 1.410 = 3.404

AC = CB, Lc-c = AB = 1.410

OK = OC,

CD
= KO = OC = 1.702
2

:
KC 2 = KO 2 + OC 2 - 2 . KO . OC . cos COK

COK = 45 o

KC = 1.303

Lc-c = AB = 1.400 :
Lc-c = AB = 1.400
CD = tg 67.5o . 1.400 = 3.380
CD = KO = OC = 1.690
2
KC 2 = KO 2 + OC 2 - 2 . KO . OC . cos COK

COK = 45 o

KC = 1.293

14

BAO = 72 o

.O

144o

. . . . .B
K
A C

AC = CB, Lc-c = AB = 1.400

tg BAO = OC
AC

AB
OC = AC . tg BAO = 2 . tg BAO

CD = 2 . OC = tg BAO . Lc-c = tg 72o . 1.400 = 4.309


OK = OC, CD = OC = KO = 2.154
2

:
KC 2 = KO 2 + OC 2 - 2 . KO . OC . cos COK

COK = 36 o

KC = 1.331

.
, ,
, .

. ,
,
,
.
, . ,
, .
, , ( ):
1)
().

AA

AB

2) (, , )
, .
.
3) .
4) ,
. 5 2.
15

5) ( ) ,
() .
6)
.
,
, -, ,
.
.

. .+ _. .+ _
.
+.
._ .+ _. .+
_

. .+ _. .+ _
.
+.
._ .+ _. .+
_

. .+ _. .+ _. .+ _
.
+.
.
_. . _ .+ .
_ .
+
+
_

. .+ _. .+ _. .+
._
+.
_. . _. .+ .
_ .
+
+
_

. .+
. ._
_
. .+ _.+ ._+
.
+.
.
_. . _ .+
+
_

. .+ _
. .
_
_+
+
. . . ._+
.
+.
._ .+ _. .+
_

_ + _
. ..
.
_.
_
+.
. .+ _ .+._
_.
. .
.+_ + _. .+ ._. +
..
.+
._ .+ ._
+
+

16

._ +. ._
.
_.
.+._
_
+.
+.
.
+.
_.
._ . +
. _. .+ ._
+_
..
.+
._ .+ ._
+
+

H
H
H
H
H

H
H

H
H
H
H

H
H

. .+ _. .+ _
.
. .+
_ .+
H
. . HH HH . . _
+
_
H
_+
.
+
._ .+ ._ .+.

. .+ _. .+ _
.
. .+
_ .+
H
. . HH HH . . _
+
_
H
_+
.
+.
. .+
_. . _
+

[18]-
, ,
[18]-, .
[18]-
. , ,
,
. (12 )
( ), (6 )
( ).
[7]. ,
,
. -
.
,
( ).
, , ()
, ,

.
.

. ._
_.
.+ N ._. +
+

17

. ._
_ .
.+ N ._. +
+

_
.
.
_.
.+
N . ._ N
+
+

. ._
_.
.+
N . ._N
+
+

_
.
.
_.
.+
. .N
+ N_
+

_
.
.
_.
.
.+ N._N +
+

. .
_.
.+ N ._. +
_
+ N

N
N

.
.
_ .
.
.+ N ._ +
_
+ N

. .
_.
.+
N . ._ N
+
_
+ N

N
N

. .
. .+
N . ._N
+
_
+ N

1,3,5-

. .+ _. .+ _
.
+.
.
_
_. . .
+ N +
_

. .+ _. .+ _
.
+.
.
.
_. . _ N +
+
_

. .+ _. .+ _
.
+.
N
_. . _. .
+
+
_

18

. .+ _. .+ _
.
+.
N
_. . _. . +
+
_

. .+ _. .+
+.
.+ ._
.
_. . _ N
+
_

..N

. .+ _. .+
+.
. ._
_. . ._ N
+
_

+ _
.
.
. N .+
N
+.
._ N .+ ._ .+N ._
_

N
N

.N.

+ _. N
.
.
+
.
N
._
+.
.
_. . ._ N
N +
_

. .
.
+
+
+
_. . ._
X
_

..X

_
.
.+
+.
_. +. .
_
X

X = O, S, NH

, ,

. N.
.
+
+
._ X+. ._
_

..X

_
.
N
.+
+.
.
_. +. _
X

X = O, S, NH

, ,

. .
.
+
+
N
.
_
_. +
.
N
_

..N
H

19

_
.
.+
+.
N
_. +. ._
N

_
.
.+
+.
_. +. ._N
N

. .+
+.
+ ._N
_. .
N
_

..N

1,2,4-
_
.
N
.+
+.
N
_. +. ._
N

. N.
.
+
+
N
_. +
. ._
N
_

..N

1,2,3-

_
.
.+
+.
_. +. ._
CH

CH

O
R

.O..._
.
+..
C_.
.
+ _. .+
..O.
_+

R
O
-

O
R

N
+

O
_

20

....
.
.
.
N _.
.
+ _. .+
.O..
_ + O_
+

O
C 6H 5

..O...
.S... ..O..
... . .
.O..
_

_+

O
O

C 6 H5

+_ +

+_

.X..
R

..NH

R
2

.....
.
.... .

_
_+ X
+
C
_
+
+_ NH

X = O, S

..X ..

..

. ... ..
.. .
.
H N... C . ..

..

H 2N C NH 2

_ X
+
_
+ _ _+ _ _ +
+ NH
+

X = O, S

.NH
. _
+
_.
+
. _ _ +. + _ + .
H N . .+ . C . . . NH
_

..

H 2N

NH2

..

C NH2

21

..O...
CHO
.
.
.
..
.
C
C .. CH
.
.
.
OC H
...O.

C 2H5 O

CH

OC 2H5

O
Na

_+

+ +

_+

Na

O
CH3 C

.....
.. .
...

CH

+_O
+
_ _ _
CH3 C + + CH

COOC 2H5

Na

COOC 2H5
Na

H2C

CH

H2 C

CH2

.. . . . .

+ _ + CH _ + _ CH
2

...O..._ _+...O..
+
.+._N+.. _
.. _+
.O..._. +
-

...O..._ _+...O..
+
.+._C+.. _
.._
.O..._+.+
-

22

2 _

.....
..
...O.....S........O...
..O.
+ _O
+
_

_+

+
_
+

+_

+ _

.O. + _
.
....O... . ._..+O....
+

_+

.. O+. _.. .+._ ._. O+. ..


+ +

...O ..O..

..N. ..O..

NO

..N.+ ._..+.._ O+...

.+

NO2

...O
.

.O....

. ._
.
N
.+._ .+
_+.
+. .
.O.. ..O.
_

NO 2

..

...
.
..O... ....O..
..

_ +_
_+ N + _
+

..O.. .O...
.

23

. .. . .. . .. .
.
.
. . .. .. . .. ..
. . . . . . .. . . . . . . . . .
. .. .. . . .. . .. . . .. .
..... . .... ... . ..
. .. .. . .

+
_

+
_

+
_

_+

+
_

_ +

+
_

+
_

+
_

,
, ,
( ) ().
,
,
. (
)
.
(2.420 ).
,

.
, 3.35
( - 1.42 ) [8].
.
2.420
( ), , .
, (
, ) ,
,
,

).

24

E = a + b/L + c/L2 = a + b/L + c/L2


.
3 4 (a, b, c)
(C-C, C-O, C-N, C-S, N-N, N-O, O-O).
- .
( ) ,
.
.

. (

E = a + b/L + c/L2 )

. (N-H
):

.+..O..
_.
+
+
.
_ _ +. _ + _ .
+ . C . . . NH
H N. .
_

..
HN
2

O
C

.NH
.

LC-N = 1.33 , LC-O = 1.27 (8)


-N = 1

-N (L=1.33 ) = 1.686

- = 2

- (L=1.27 ) = 1.486

EC-N = 291.834 / [1, .116]

C-N (L = 1.33 ) = 523.790 /

EC-O = 728.538 / ( R2C=O) [1, .116]

EC-O (L = 1.27 ) = 496.940/

E1 = EC-O + 2EC-N = 1312.206 /

E2 = EC-O + 2C-N = 1544.520 /

E = E2 - E1 = 1544.520 / - 1312.206 / = 232.314 /


, ( )
232.314 / (55.487 /).
.

25

: ,
.
1.5,
(,
),
, ( ).
, .
,
.

8,

(3.5) (3)
(2.5)).
,
,
, ( )
.
, , a, b, c 3 4
= f(L) E = f(L).
3. = a + b/L + c/L .

C-C

-0.06040343

-5.67787529

11.28562201

C-O

26.03252883

-72.46498138

52.43899244

C-N

0.63817306

-7.56455294

11.91384503

C-S

55.33256579

-198.81807222

181.87538814

N-N

0.96407492

-6.68791795

9.79339013

N-O

46.00756377

-123.75637485

84.79763896

O-O

23.89786759

-66.85172754

48.79304255

C-P

28.76548555

-109.46128312

107.52805439

- ,
L .

26

4. E = a + b/L + c/L .

C-C

-2221.34518418

5065.62912191

-1699.18638789

C-O

11420.81052442

-31359.17576343

22207.04265404

C-N

-2332.69568587

4450.61712191

-866.48412671

C-S

-27772.64385690

90244.55278987

-71414.57485742

N-N

7067.14065437

-20274.81508318

14878.53765631

N-O

-6564.31416262

15895.54907490

-8769.11638979

O-O

10590.40848780

-29935.02909385

21430.93279023

E - /,
L .
.
1. . . , , 1973 , .143 (
Structure and mechanism in organic chemistry. Second Edition, INGOLD C. K., Cornell
University press Ithaca and London, 1969).
2. . . , . 4- . , ,
1987 , 1, .84 ( Advanced organic chemistry. Reactions, Mechanisms, and
Structure. Third edition. Jerry March, Professor of Chemistry Adelphi University. New York, 1985).
3. T.J.Kats, Journal of the American Society. 82, 3784, (1960).
4. ., . . 2- . , ,
1981 , 1, .335 ( Advanced Organic Chemistry. Francis A. Carey and
Richard J. Sundberg, University of Virginia, Charlottes, Virginia. Plenum Press, New York, 1977).
5. J.F.M.Oth, G.Anthoine, J.M.Gilles, Tetrahedron Lett. 6265, (1968).
6. S. Masamune, K. Hojo, Kiyoti Hojo, G. Bigam, D. L. Rabenstein, Journal of the American Society.
93, 4966, (1971).
7. . . . 2- . , , 1981 , 1, .583
( Contemporary organic chemistry. Second edition. Andrew L. Ternay. University of
Texas, Arlington, 1979).
8. . . , , 1988 , .3, .17-18 (
Structural inorganic chemictry, fifth Edition, Wells A. F. Clarendon Press, Oxford, 1986).

27

Вам также может понравиться