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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- = 1.410 .
, [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
L
L2
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
L
L2
(3)
L = 1.42757236 .
, 1.5,
cc L = 1.42757236 .
1.5,
L = 1.42757236 :
L = 1. 42757236 = 2221 .34518418
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)
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
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
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
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
tg BAO = OC
AC
AB
OC = AC . tg BAO = 2 . tg BAO
:
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..
..N. ..O..
NO
.+
NO2
...O
.
.O....
. ._
.
N
.+._ .+
_+.
+. .
.O.. ..O.
_
NO 2
..
...
.
..O... ....O..
..
_ +_
_+ N + _
+
..O.. .O...
.
23
. .. . .. . .. .
.
.
. . .. .. . .. ..
. . . . . . .. . . . . . . . . .
. .. .. . . .. . .. . . .. .
..... . .... ... . ..
. .. .. . .
+
_
+
_
+
_
_+
+
_
_ +
+
_
+
_
+
_
,
, ,
( ) ().
,
,
. (
)
.
(2.420 ).
,
.
, 3.35
( - 1.42 ) [8].
.
2.420
( ), , .
, (
, ) ,
,
,
).
24
.
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
.
-N (L=1.33 ) = 1.686
- = 2
- (L=1.27 ) = 1.486
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