11

547

:

. .

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

119899 , , . . . , . (095)939-30-65, E-mail butin@org.chem.msu.su

, - - - , , - . - . - [1]. . , - ?. - - , , , . . , , , , , . - . -, . , . - -. . - , , . 1990 . - , JACS. 17 , . -

, -, , - ? - , , , - . , . - . -, - - . - . 1961 , , - : -. - , . - , , , . , - . . - - ? - . - - , , .

. . . (. . . - . .. ), 2001, . XLV, 2

12

-. , - ( ) , , - . . -, - , . - , , , . - . - , , , , - . , - , , , , - - . . , , - - . - . - - - , , , , - . , - - . -, ( -), . - XX , , . - , , . - . , , -, , -, ( XIX ), (1950- ). , -

- .

XX .

-

. [2], , - . - ( ) - . , 1870- , - , . - - , - (-). - - , - - . - , . , (1892 .) [3], X -, HX HOX; - -. . , , - , , , , - [4]. -, , (XIX ), , (1950- ), (1965 .) , 18- - .. , , - , () -. . - :

13

-, - :

+

+

, - :

+ +

, ; AB, A B. , 1950 , , - - ( 3) - 1 (E+ , B ):

HB

E1

, . - 1950 . [5] , - , , - (kH/kT) 1020, 1, 1,3, .. CH . - , - E+ - 2 :

E+E+H

E

H++

2

1970- , (., , [6] ).

SN2-

SN2-, - 1935 . [79]. , 1890- ,

, - - [10]. , -. , - - . - - 40 - . . [7] - 2- - , - . ( , , , . -, - 100% , 50% .) , , , . SN2-, . - , - - - 3 ( 1). sp3- , . - , - - . , (, RNH3+, R3S+) - (Cl, OH) , -. , - . - 3, [11], sp2- - p- - .

14

, () 4, - [12] , , .. SN2- , - - . ( - IVA -.)

S SCO O

Me

4

F3CSO3F3CSO3

Me MeMe

SN2- , -.

SE- - -

195070- . ( ) .. (- . . . ) - - [1316]. , -

(, , .). , - - , - [13, 17, 18], [1719], - , [13, 17,

18, 20], [21], [22] .. - , , - - - . SE- - - - -, , - . . -, , , - R2Zn , R2Cd , R2Hg -, - HCl. - - - , . - - - - ( in situ, - -). , , - . - - . RLi RMgX, , , - SE- - - , - , - . -

C6H13

H3I H

C6H13I

CH3

I +

CH3

HC6H13II

CH3

HC6H13 I

I C6H13

H3I + I

+ I

3

* *

* *

*

1. SN2-

15

S2 , SN2-, - - , S2 - , . - , () Z, :

0

E+

Z

CE+ Z

- (5), a (6) ; - , -:

+C ZE

()5

++E C Z

6()

- . , - -. SE2- - (CH3)3CCH2Z, - - . -, -. , - - [16]: -C4H9Sn(-C5H11)3 + Br2

-C4H9Br + (-C5H11)SnBr

, o-, . - 5 Z , - 6, Z , 6 - 5. - -, - . SE- - [15]. , - S- - - . Nu, -Nu (, l HgCl2 ( = HgCl+), r Br2 (E = Br+), I I3 ( = I+) .), - (, , , ..) , . - , , , - . . - , - , S l -. , S2- . , -, , S l -, S2-. S1(N), - SEi. SEi - 7, MNu ENu - . S1(N) SEi 2. - SE2, , , :

16

R M R M Nu+ Nu

R M Nu R M Nu

EE

+

SE2(C), .. SE2 , , SE l . SEi , - SE2- . , , - , - - 7, - . -- , - . , . , ,

, , ( ), - d- . - - , - e

RM + Hal2 RHal + MHal

- RM - - RM+ -- Hal. - [16, 22]. 1. SE2- SEi - :

SE2 ( )Br

R MBr

RM + Br2 RBr + M + Br

SE 2 ( )

RM + Br2 [Br...Br...R...M]

Br + BrR + M

SE i ( )

RM + Br2 RBr + MBrBBr

R M

2. -. , :

R = - -PhCHDCHD-Cp = C5H5 ()

()

Cl FeII(CO)2CpR Cl +

R FeII(CO)2Cp + Cl2

Cl

R FeIV(CO)2CpCl

3. (SET-), [22]:

SE1

RE

RM + Nu RMNu

RMNu

R + MNu

R + E

( )

RM + ENu

R + E Nu M RE + MNu

ENuRM

ENuRM

ENuR M

( )

SEi

+ENu

RM R

E

M

Nu+

E Nu

R M

7 (Nu , - Nu )

2. SE1(N) SEi

17

CH3

NO

C

N

CH3OH

DMG ()

PhCH2Co(DMG)2 + IC1

[PhCH2Co(DMG)2 IC1 ]

PhCH2Cl + ICo(DMG)2

- . 4. SN2 ( ) , :

h 2BrBr2

Me4Sn + Br Me3SnBr + CH3

BrBrCHBrCH 323 ++ ..

, - (1, 2, 3) - . : , - , , . , , . -, [22], , SET-, - - , . SE- -- , , , , - , , -.

[23]

-, -, - -. , , - , ,

, . - , - . , , - , .. . , - ( ) . , , . - , CH2 , , . , - , , . -,

A2XY A2X + Y+

A2X+ Y , , , Y , , , A2X+ . , , -, -. , - , - . -, . , - , - . , _ , - . : -, , - -. [24]. , ( , ). , - . - () - . . , -

18

, - . - . , - (8) , , - , 9, - 500 C [25]:

500C8

9Fe(CO)3

- , 8 9 - , , , [23]. , , , , , -. , . -. - , - . -, CH3 (7), CH2 (6), CH3+ (6). CH3 , . - - ( OH, F - , , - CH3, - , -). - . , , - ( [26] ).

-: , , -.

- XVIII , - - . [27] 1900 . - . , - , . 70 , 10 [28] . ; - 11 [29].

10

Ph 3C

H

Ph

Ph2 Ph 3C

Cl5

C3

11

RN

R

O

12

- 12 [30] . - - 1929 . [31]. - [32] , . 50 . CCl2 . 1950 . - :

2HCCl3 + 7OH HCOO + CO + 4H2O + 6Cl

Cl

Cl

13

-, - 13 [34]. 1959 . [35] - , CH2 -

19

103 1,12 A. - [36]. - ( -) . 1922 . - [37]. , - . SN1-. 195070- . , ( ) SO2, SO2ClF, SO2F2 ., - - . 1H 13C - , - . - - -. - (), - 1s-, - [3840]. 1960- - [41]. ( - ., , [42].) 1939 ., [43] , , 14 - (15) (16), 17 [37].

Cl Cl+

15 14 16 1952 . . [44] 2-- 17:

+

17 18, 19 20.

18 19 20 , : - - , .. , ( - ) - H3+, - B2H6. . , - - , 2-- - (. [45] ). - , 100 , - ( - -), 6 C1, C2:

126 1 12

26 6

. - 17 , 2- . 2- . , , - . , : - - . - , , , - . , : , - (), , -, (-, ) .. - ,

20

, , . -, . - CH-, - ; CH- . , CH- NO2CH2SO2Ph, NO2CH2COPh 9- pKa (- - ) 7,1; 7,7 8,4, , HI pKa = 9,2, HCl 13,0, .. [46]. - CH- , - , - . , , [47]. - CH- , , - - 1930- - [48] - [49]; - . [50]. - - - - [51, 52]. 196070- - , - - -, - , .. , . , - , - , -, .. [53, 54], , - .

( - ) , , (NH3, H2O, HF .), - - (4). - -, . - , - :

H3CH + H+ (H = -525 /)+HH

H3C

, (H= 1740 /). -, ((HI) 10), -, . , : ;

, - . ( = 54 NH3 HNO3) - ( 50 HI). . 1 - [55]. , . - . , ( ) , : HI > HBr > HCl > HF. ,

, -- C=C, C=O, ,,, ,

> > >

(/)1255 1670 670 880 520 630 170 500

, - (, )

-

21

, . , -- . - dpK()/dpK(H2O) 0,8 - , . , , - -, - , - . , , - -, , , - - ( ), ( -). - . -. . - , .. :

HNO3 > CHCl2COOH > C6H5COOH > CH3COOH > > C6H5OH > CF3CH2OH > AlkOH

, - , -, .. . :

CH3OH > H2O > C2H5OH > (CH3)2CHOH > (CH3)3COH ( )

15,5 15,7 15,9 17 18

, , , (+I)-, ( ) , .. . :

(CH3)3COH > (CH3)2CHOH > C2H5OH > CH3OH > H2O ()

268 269 271 273 281

(+I)- , - 3 < 25 < -37 < -49. [56], ( ) - , . , , .. :

-lkA O

Alk O

------

+++

+

-----

++++

, : CH3NH3+ > C2H5NH3+ > > (CH3)2CHNH3+ > (CH3)3CNH3+. , , .. - :

+-++

+++

+

++++

---------

, - (.. ), .

8

23

Hi

HBr

12

3 456 7 9

280

1918 17

16 1514 1312

11 10

24

2221

20

270

260

250

240

230

a

25

10 0 10 20 30 40pKa H2O

pKa

. 1. a [55]:

HHal; -; -. () . [55]

22

1

, ,

, , - H

Y+HY

S

S

- HH

H H

I

I -

H

H

H

H

I

I

- ( ) XH Me Me

Me

Me

Me

Me

MeHH

NH2

NH2NH2+ + +

( )

NO2

NO2NO2MeO OMe

- -

NO2

NO2NO2OO

-

NH2

NH2

O

O

CNCl

Cl CN

NH2

NH2

O

O

CNCl

Cl CN+

23

CH2(COOH)2 CO C C C O C C O- CO

P2O5 h

- CO

C

N NTs

C

+ C

Na

Me Me

O OC

MeMe

MeC

Me

C O

Me

HCH2+ C

N2O N2 + Oh

R C C H RC C OH RC C

H

O+ O

Ar H + O ArOH

COS CO + S

CH3

CH3HCH3

CH3CH

CH3CH2SH

CH3

CH3CH3

SHS + +

9:1

N2 N

Cl

Ph N

Cl

Ph ClCH2Ph

NPhC N+ N

CC +

--

R R

R

R R

-

1,2-

IIO

O

24

1,2-

I

I

1,5-[3.2.0] 1,4-[2.2.0]

NNTs

Na

( )

O

Cl

O

Cl

OCOOH COO

OH- OH-

-Cl-

- Ph

PhC O

O

O

Ph

PhPh

Ph OCH3

O

OO CF3

CF3Ph

Ph

O3 MeOH

(CF3)2CO

, ,

BrCF2O

ClCF2 C O CF2 CF2

F2C

(CH3)2C

C

O

O

Zn+ CO

RC S

O

OR

R

RH

S Cl

O

O

SO2R

R

R'2N

SO2O2S

RR

R R

R'2NCH=CH2B

Ph NHSOCl PhN S

O N S

O

OPh

Ph

Ph

PhPh

C O

25

-- , ( ) - , - - . , , -. -, -: HNO3, , , 2,2,2-. , , , .. . , (I)- CF3 , , , - - , . - , - , . , (652) - , - (652). (652Na+) - - . . 1 [23]. - - . , - , -, , , - . .

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

, , .

.

1965 . . . - - [5759] , - , , , 1,3- -, , , - : - , - . -

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

+

+

N

NCH2

NN

N

N

1,3-

1'2'

3'

32

1

[3,3]-

1'2'

3'

32

1

1'2'

3'

32

1

26

100%). -, - -, .. , . - - , , , . -, - , - (-). , -, . , , - : , - , :

Ph Ph

[3,3]-

Ph

h

Ph:

h

, -, XIX , 1965 . - , ( , ), . , -, . (- , - -) - - -, - . - , - ( -

, - ), - . ( - .) , - - (, -, -), . - - - . - . , , . - . - . .-. [60] , : -- ( ) - , . - (DFT). 193050- -, - - , - - . , : , . , . . , - [61]. , - [60]. . , - , . - , - : 1) [62, 63], 2) - [57, 58, 6466] 3) - [67, 68]. -

27

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

, - . - ( ) , - , 4n+2, - 4n. - , - 4n - 4n+2. , - -, - . - , , - - .

XX : ?

-. : , - , . , - , - - . , - - , - . - - , 1990- .

[69]

- - ( 3). 21, 1937 . [70] -. . [71] SO2/SbF5 , 22 [72]. -, , -, Br2 - 23, - ( 4) [69].

- -

(4s + 2s)--

. 2. - . - - (. [74])

28

- Br+ - [73] , - -/ , , (D2d), :

Br+ BrBr+

++

BrBr

+

+ +

, - -, - , -

(. 3). - - -, ..; 5. Br+ , , - .

O

Br

Br

Br

Br+

Br+

+ Br2Br2

Br2

Br -

Br3-

HOSolv

+ Br2

21

21

Solv

3.

Br+

Br+

Br+

+

2 Br2 2 Br2

Br3

Br3

22

23

22

4. Br+

H H H H

H H H H

H H H

H H H

Br2

HBr

H H H

H H H H

H

H H H H

H H H

Br

Br

Br

+

HBr

5.

29

1990- (coarctate) (. [74] ). , . - -. , . 2. 1930- - , - , .. - . - : , - (). - , - A + . - - () - , , . , , , . , 4, - , -

- . - - :

- [74]. - , n , - (T T). - -, (.. - ) , , .. , :

T'n T, T' =

,

( )

..n 1

T

- . 3. , -, - , , - , , - (. 3).

-

1 1 12

2 2

3 3 3

44

455

5

. 3. , ,

- (. [74])

30

2

-

B O B O

O O

NN

O O

NN

OC

O

3

n = 1

n = 1

RR R R

R R

n = 1

OH

O

H

OH

n = 3

OC N N

R

Ph

R

O N NPh

NN

Ph

O

R

31

. 3 , - - - -. , , - , - : -. - , (. 4), ( 6) [75]. , , , - , .

- , - . , - SN2- - - - s- CZ . , - . , , , - [76]. , SN2- :

Nu + RZ [Nu (RZ) ]

, , - -. - , . - (RZ) Z R. - R Nu RNu. SN2- - SET- (single electron transfer). - , , , -

, (. ) . SET- , - ( ) (-, - -, ). , -, , - . - : , SET-, , - - ? . c 1985 . -

. 4. () - () (. [75])

OOO O C O

O

O

t-Bu

OO O90 C

[CH2O2] CH2O CO2

t-Bu t-But-Bu

t-Bu

t-Bu

OO O

R R

O

R R

R R90 C[CH2O2] CH2O

CO2

6. -

32

[77]. - -, - , - , . , - - . SN2- :

Nu + R Z Nu R + Z NuR , SN2. - R RZ. Nu R, - RZ, - . - - , - SN2, ( ) - - -, . , -, (, , .) [78]. , - , . , - 24, :

Ph CH NCH3

CH3

CH3

3

CH3Ph CH N

CHCH33

CH3Ph CH N

CH3

CH

H3Ph CH NCH3

CH3

C

24

: - - N

O, ? - , , 60 . , - , , , .

ArCH=OR:

ArCH OR

ArCH OR

- . - , - , - 25, 24:

ArCH O R ArCH O: R

25

Z , , , Z SN2, - . , R - , . -, , SN2 . - , R - - , - .

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

33

, , (), . , - . - -vs- ( ), , - ( ) - . - . XX - , - - ! 1999 . . - [79]. - - , , , [80]. - , -- , CF2ICF2I, , , , [79]. - 1980- , - [79]. .

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13. K.K. . .: , 1973.

14. .. . .: - , 1964.

15. .., .., .. - , .: , 1972.

16. .., .., .. . . 4, . 23. .: - , 19992001, ( -).

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18. Jones R.A.Y. Physical and Mechanistic Organic Chemis-try. Cambridge: CUP, 1979.

19. . [16], . 2, . 15. 20. .

. .: , 1964.

21. ., . . .: , 1971.

22. Kochi J.K. Organometallic Mechanisms and Catalysis. New York: Acad. Press, 1978.

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p. 123. 41. Bartlett P.D. Nonclassical Ions. New York: Benjamin,

1965. 42. .. , -

: , 1984.

34

43. Nevell T.P., Salas E., Wilson C.L. J. Chem. Soc., 1939, p. 1188.

44. Winstein S., Trifan D. J. Am. Chem. Soc., 1952, v. 74, p. 1147; p. 1154.

45. Brown H.C. The Nonclassical Ion Problem. New York: Plenum 1977.

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47. .. . .: . , 1960.

48. Conant J.B., Wheland G.W. J. Am. Chem. Soc., 1932, v. 54, p. 1212.

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p. 761. 68. Zimmerman H.E. Acc. Chem. Res., 1971, v. 4, p. 272. 69. Brown R.S. Ibid., 1997, v. 30, p. 131. 70. Roberts I., Kimball G.E. J. Am. Chem. Soc., 1937, v. 59,

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76. .. . --: . . -, 1974.

77. Pross A. Acc. Chem. Res., 1985, v. 18, p. 212. 78. . [16], . 4, . 24 ( ). 79. .. , 2000, 1, . 78. 80. Femtochemistry and Femtobiology. Ed. V. Sundstrom,

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