Реакции N-алкил(арил)альд- и кетиминов с эфирами кислот фосфора. Монография

1 N-(2-1-2-3) - - 1 (2a) 1 4 4 (1 )

. + 1 1 12.98 (0.118 1)

(1 ) 19.07 (0.118 1) 1 (2 ). )

1. ,1

1 1 24 . 4

1 2 1,

1. *

(8a), 3 1 1

1 (1. .). 4 2 1 26.51 (83%) *,*-1(1- -

1-2-1-2- ) (3a), . . 76°,. , ; 1) (CDCl3) δ, 1. .: 1.29 (9), ,3); 1.83 1.90 (6), ,2);

1.82-1.87 . (1), NH); 3.37 (1), ,), 2J) 20 0); 3.93 3.94 (6), (*)2, 3J) 11 0). , ; 31 (,,l4) δ: 29.3 1. .

. + 1 1 4.40 (0.040 1)

(1a) 6.53 (0.040 1) 1 (2a). )

1. ,1

30-35 1 1. 1

2 1,

1. 4 4.30 (45%) *-1(2- -

1-2-1-1- ) (8a), . . 150-151°C.

, ; 1) (CDCl3) δ, 1. .: 1.63 (9), ,3); 1.71 1.80 (6),

,2, 4J) 0 2.3 0); 4.61 (1), ,), 2J) 9 0); 3.93 (3H, *, 3J) 10 0); 9.6 . 10.9 . (2), +NH2). , ; 31 (C)Cl3)

δ, 1. .: 11.3.

* 2 1 5.4 , 1

; 31 ; 1), 1 *,*-1(1- -

1-2-1-2- ) (3a) [ ; 31 (CCl4) δ: 28.8 1. .] *,*-1(1- - -3,3-1-

-2- ) (7a) [ ; 31 (CCl4) δ: 26.5 1. .].

101

1 N-(2-1-2-3) - - 1 (2a) 6 4 4 (1 ). 4 1 5.52

(0.040 1) (1 ) 6.80 (0.040 1) 1 (2 )

19.70 (81%) *,*-2(1- -1-2-1-2-

) (3 ), - 3 1 - 1 . , ; 1)

(CDCl3) δ, 1. .: 1.08 (9), ,3); 1.28 (6), *,)2 , 3J)) 7 0); 1.28-1.44 . (1), NH); 1.60 1.64 (6), ,2); 3.03 (1), ,),

2J ) 19 0); 4.05 (4), *,)2, 3J))= 3J ) 7 0). , ; 31

(CDCl3) δ: 26. 4 1. .

-6[3-(11)-1-3-2-1]4 4-

(8 ). 4 1 5 (0.03 1) (2 ) 4.14 (0.03 1) (1 ) 9.7 (10 %) *-2[3-( - 11)-1- -2-1] (8 ), . . 145-146°C.

, ; 1) (CDCl3, δ, 1. .): 1.43 (3H, POCH2Me, J 7 0), 1.58 1.63 (6H, CHMe2, J 6.5 0), 1.67 (6H, CMe2), 3.36-3.64 1 (1H, CHMe2), 4.30 (2H, OCH2Me, 3 J H H = 3 J H H 7 0), 4.56 (1H, PCH, J 9 0), 9.67 . 10.43 . (2H, N+H2, J 10.5 0).

1 N-(2-1-2-3) - - 1 (2 ) (2-3 6)4 4 (1 ). 4 1

13.05 (0.081 1) (1 ) 16.73 (0.081 1) 1 (2 ) 25.01 (84 %) 3 O,O- (2- 2)[1-

-1-2-1-2- ] - (3 ). , ; 1) (CDCl3) δ, 1. .: 1.03 (9H, CMe3); 1.54 1.64 (6H, CMe2); 1.58-1.62 . 1 CMe2 (1H, NH); 3.1 (1),

,), 2J H 18.5 0); 3.6 1 (4), CH2Cl); 4.19 1 (4), CH2OP). , ; 31 (,),l3) δ: 27.1 1. .

1 N-(2-1-2-3)1

(2 ) 1 4 4 (1 )

. + 1 8.47 (0.077 1) (1 ) 15.10 (0.077 1) 1 (2 ). ( 1 1 30º,. 4

1 24 1 1,

1 1 22.20(94%) 3 *,*-1(1-1-2-1-2- -

) (3 ). , ; 1) (,DCl3) δ, 1. .: 1.69 1.70

102

(6H, CMe2); 1.85 . (1), NH); 2.29 3.74 (1), ,), 2J H 16.2 0); 3.73 3.78 (6), 2 O, 3J H 10.6 0); 4.00 3.85 (2), ,)2Ph, 2JHH

12.60); 7.17-7.29 1 (5), Ph). , ; 31 (,)Cl3) δ: 25.5 1. .

. + 1 1 8.47 (0.077 1)

(1 ) 15.10 (0.077 1) 1 (2 ). )

1. ,1 -

30-35 1 1. 7 2 1 5

1 2 1.

1. $ 1 2 1 1 3 2 1. 4 11.20

(63%) *-1(2-1-2-1-1- ) (8 ).

. . 161-163°,. , ; 1) (,D3OD) δ, 1. .: 1.65 1.67 (6H, CMe2); 3.74 (3), OP, 3J H 10.3 0); 4.22 (1), ,), 2J H 10.6 0);

4.23 4.29 (2), ,)2Ph, 2JHH 12.6 0); 7.44-7.56 1 (5), Ph); 9.50 .(2), +NH2). , ; 31 (Me*)) δ: 13.6 1. . ), %: N 5.0; Cl

11.85; 10.45. ,12)19NClPO3. +, %: N 4.60; Cl 12.00; 10.10.

4 2 1 7.44 (90%

) *,*-1(1- -3,3- 1-2- ) (7 ). , ; 1) (CDCl3) δ, 1. .: 1.45 (1), ,), 3J H 18 0); 1.33 1.42 (6H, CMe2, 4J H 2.5 0 0);

3.70 (2H, CH2Ph, 4J H 3.2 0); 3.64 3.51 (6), 2 *, 3J H 10.7 0); 7.20-7.40 1 (5 ), Ph). ; 31 (Me*)) δ, 1. .: 24.9 (90 %); 18.3 (3 %);

10.5 (7 %).

1 N-(2-1-2-3)1

(2 ) 4 4 (1 ). + 1

1 3.82 (0.023 1) (1 ) 4.50 (0.023 1) 1 (2 ). ,1 1 1 60 . 7 2 1 1 4 2 1

. 4 1.90 (21%) *,*-

Me3Me4CH6OP, 3JH3H6 = 3JH4H6 6.1 0); 1.6 c 1.82 (6), C 2); 4.01 4.29 (2), CH2, 2J)H 12.7 0); 4.83 (1), *,)5Me1Me2, 3JPH5 =

3JH1H5 = 3JH2H5 = 6.0 0); 4.98 (1), *,)6Me3Me4, 3JPH6 = 3JH3H6 =

3JH4H6 = 6.0 0); 5.18 (1), ,), 2J H 9.5 0); 8.84 . 12.04 . (2), +NH2). , ; 31 (,),l3) δ: 16.3 1. . ), %: N 3.65; Cl

103

17.50; 7.45. ,17)30NCl2PO3. +, %: N 3.50; Cl 17.80; 7.80.

* 2 4.05 ,

1 ; 31 ; 1), 1 *,*-

(1-1-2- ) (3 ) [, ; 1) (,DCl3) δ, 1. .: 1.29 1.32 (6), Me1Me2,)5*, 3JH1H5 = 3JH2H5 6.3 0), 1.32 1.34 (6), Me3Me4CH6OP, 3JH3H6 = 3JH4H6 6.3 0 ); 1.75 1.71 (6), ,2); 2.1 . (1), NH); 2.93 (1), ,), 2J H

17.34 0); 4.10 4.89 (2), CH2Ph, 2J)H 12.3 0); 4.75 (1),

, ; 31 (EtOEt) δ: 21.9 1. .] *,*- (1- -3,3-

1-2- ) (7 ) [ , ; 1) (,DCl3) δ,

1. .: 1.25 1.24 (6), ,2, 4J H 3 0 0); 1.44 (1), ,), 2J H 17.3

3 4CH6OP, 3JH3H6 = 3JH4H6 6 0); 7.20-7.26 1 (5), Ph). , ; 31 (EtOEt) δ: 22.3 1. .] 3 : 1.

1 N-(2-1-2-3)1

(2 ) 4 4 (10). 4 15.95 (0.031 1) (1 ) 6.01 (0.031 1) 1 (2 )

3.27 (27%) *,*- (2-1-2- 1-1- ) (6 ), . . 122°C. , ; 1)

(,D,l3) δ, 1. .: 0.94 0.95 (6), 2 CH2 , 3J)H 7.0 0); 1.69

(4), 2 CH2CH2, 3J)H 7.0 0); 1.43 1 (4), 2 *CH2CH2); 1.63 1.82 (6), C 2); 4.03 1 *,)2 (2), CH2 h, 2J)H 12.7 0); 4.19-4.35 1 (4), 2 ,)2*); 5.25 (1 ), ,), 2J H 10 0); 7.42-7.58 1 (5), h); 11.90 . 8.90 . (2), +NH2). , ; 31 (,),l3) δ: 17.91 1. . ), %: N 3.65; Cl 16.90; 7.40. ,17)34NCl2PO3. +, %: N 3.30; Cl 16.70; 7.30.

* 2 5.55 , 1 ; 31; 1), 1 *,*- (1-1-2-

) (3 ) (δ 23.3 1. .) *,*- (1- -3,3- 1-2- ) (7 ) (δ 22.5 1. .)

3:1.

104

1 N-(2-1-2-3)1

(2 ) (2-3 6)4 4 (1 ). 4

1 13.35 (0.063 1) (1 ) 14.14 (0.063 1) 1 (2 ) 13.34 (45 %) *,*- (2- - 2)[2-1-2-1-1- ] (6 ), . . 152153°C. , ; 1) (CDCl3) δ: 1.67 1.81 (6H, CMe2); 3.76 1 (4), CH2OP); 4.50 1 4.59 1 (4), CH2Cl); 4.02 4.29 (2), ,)2Ph,

2JHH 12.3 0); 5.50 (1), ,), 2J H 9 0); 7.28 - 7.57 1 (5), Ph); 8.50. 12.10 . (2), +NH2). , ; 31 (CDCl3) δ: 18.7 1. .

), %: N 3.25; Cl 32.00; 7.05. ,15)24NCl4PO3. +, %: N 3.00; Cl 32.25; 6.70. * 2 11.95

1 ; 31 ; 1) 1 *,*- (2-

2)[1-1-2- ] (3 ) [, ;

31 (CDCl3) δ: 24.5 1. . , ; 1) (CDCl3) δ, 1. .: 1.75 1.76 (6), CMe2); 3.08 (1), ,), 2J H 16.3 0); 7.10-7.26 1 (5), Ph)] *,*-

( 2)[1- -3,3-1-2- ] (7 ) [, ; 31 (CDCl3) δ: 25.6 1. . , ; 1) (CDCl3) δ, 1. .:

1.21 1.32 (6H, CMe2), 1.47 1 (1), ,), 2J H 18.9 0), 3.44 3.67 (2), ,)2Ph, 2JHH 13.5 0), 7.16-7.24 1 (5), Ph)] 1:4.

1 N-(2-1-2-3) - 1 (2 ) (2-3 6)4 4 (1 ). + 1

1 20.14 (0.097 1) (1 ) 14.35 (0.097 1) 1 (2 ). )

1. ,1 1 1 3

. + 2 1 1 5

2 1.

*,*- (2- 2)[2-1-2-1-1- -

] (6 ). 4 18.20 (53%) (6 ), . . 101°,. , 1) ; (CDCl3) δ, 1. .: 1.88 (6H, CMe2); 1.58 1.82

(6H, C)Me2, 3JHH 7.0 0); 2.30 1 (1H, C)Me2); 3.90 1 (4), CH2OP); 4.70 1 (4), CH2Cl); 5.85 (1), ,), 2J H 13 0); 8.30 . 11.20 .

(2), +NH2). , ; 31 (,),l3) δ: 18.9 1. . ), %: N 3.62;

Cl 38.25; 8.58. ,11)24NCl4PO3. +, %: N 3.82; Cl 38.65; 8.44.

* 2 11.93 1 ; 31 ; 1), 1 *,*- (2- 2)[1- - 1-2- ] (3 ) [, ; 31 (CDCl3) δ: 25.9

1. . , ; 1) (CDCl3) δ, 1. .: 1.75 1.76 (6), ,2); 3.08 (1

), ,), 2J H 16.3 0)] *,*- (2- 2)[1- -3,3-

105

1-2- ] (7 ) 1 : 4. ,1

3 1 1

. , ; 31 (CDCl3) δ: 25.6 1. . , ; 1)

(CDCl3) δ, 1. .: 1.08 1.14 (6H, C)Me2, 3JHH 7.0 0); 1.38 (6), C 2); 1.43 (1), ,), 2J H 18 0); 2.30 1 (1H, C)Me2); 3.68 1 (4), ,)2*); 4.35 1 (4), ,)2,l).

2.1.2 3 !

1 5 3 0

. + 4.19 (0.0154 1) *,*-1(1- -1-2-1-2- )

(3 ) 20 1 1 1 0°, 1

1 2.26 (0.3087 1) 2 1. ,1

1 1 24 . 4

1, 2 1,

2 1. 4 1

1 1 2.22 *,*-1(1- - -3,3-

1- -2- ) (7 ) (65%), . . 63 °, / 0.011

11. . ., nD20 = 1.4511. [, ; 1) (CCl4 + CDCl3) δ, 1. .: 1.11

(9), ,3); 1.33 1.38 (6), ,2, 4J) 0 3 0); 1.69 (1), ,), 2J) 22 0); 3.71 (6H, (*)2, 3J) 11 0); ; 31 (,)Cl3) δ: 28.1

1. .]

. 2.09 (0.0077 1) *,*-1(1- -

1-2-1-2- ) (3 ) 11 1 1

1 1 48 . 1

1 ; 1) 31 *,*- 1(1- -1-2-1-2-1)

(12) [, ; 1) (CD3*D) δ, 1. .: 1.39 (9), ,3); 1.45 1.28

(6), ,2); 3.13 (1), ,), 2JPH 13.6 0); 3.49 c (3H, *); 3.90 3.92 (6H, (*)2, 3JPH 11.5 0); 6.90 . (2), +NH2); ; 31

(*)) δ: 21.1 1. .]. 4 96

, 3-4

*-1[1-( -11)-2-1-2-1] -

(14). [, ; 1) (CD3*D) δ, 1. .: 1.61 (9), ,3); 1.63

1.72 (6), ,2, 4JPH 3.5 0 ); 3.22 (1), ,), 2JPH 12.9 0); 3.40 c (3H, *); 3.78 (3H, *, JPH 10.2 0); 8.62 . (2), +NH2); ; 31

(*)) δ: 11.5 1. .].

. 5.00 (0.0184 1) *,*-1(1- -

1-2-1-2- ) (3 ) 25 1 1

106

1 1 24 . 7 1

1 0°, 1 1.82 (0.0184 1)

2 1. ,1 1 1 24 . 4 1, 2 1,

2 1. $ 1

. . 73-75 °, / 0.09 11. . ., 3 2.25 1 *,*-1(1- -1-3,3-1-2- ) -

(7 ) [, ; 1) (CCl4+CDCl3) δ, 1. .: 0.66 (9), ,3); 0.84

0.91 (6), ,2, J 2.8 0); 1.21 (1), ,), J 20.8 0); 3.23 3.24

(6H, (*)2, J 11 0); ; 31 (*)) δ: 26.3 1. .] *,*-

1(1- -1-2-1-2-1)

(14) [, ; 1) (CCl4+CDCl3) δ, 1. .: 0.60 (9), ,3); 0.73

0.77 (6), ,2); 0.95 . (1), NH); 2.24 (1), ,), 2JPH 18.6 0); 2.72 c (3H, *); 3.18 3.19 (6H, (*)2, 3JPH 11 0); ; 31

(*)) δ: 31.3 1. .] 1 : 1.5.

$ , -1(1- . -3,3-1-2-)4 4 (7 ).

. + 6.08 (0.022 1)

(3 ) 35 1 1 1 2.55 1.2

1 1 1 ,

1 1 +3°,. ,1 1

1 1 24 . * NaCl, 1 - . 4 3.88 (75%) *,*-1(1- . -3,3-1-2- ) -

(7 ): . . 74°C (0.1 11 . .), nD20 1.4532. , ; 1H

.89. , ; 13C (CDCl3, δ, 1. .): 22.32 26.56 (CMe2), 30.17 (CMe3), 37.91 (PCH, J 214.5 0), 44.14 (CMe2), 53.17

(OMe, J 17 0), 55.75 (CMe3).

. + 4.19 (0.015 1)

(3 ) 20 1 1 1 2.19 (0.03 1) 2 1, 1 1 +3°,. ,1 1 1 1 24 . ,

, 1 .

4 1.84 (52 %) *,*-1(1- . -3,3- 1-2- ) (7 ): . . 73°C (0.1 11 . .), nD20

1.4522.

107

. + 0.79 (0.021 1)

57 1 1 1 5.17 (0.019 1) (3 ) 25 1 1, 1

1 +3°,. ,1 1 1 1 24 . , , 1

, 30 1 2 2 1 (3x20 1). - 1 1, 2

1 1. 4 2.68 (60 %) *,*- 1(1- . -3,3-1-2- ) (7 ):

. . 74°C (0.1 11 . .), nD20 1.4532.

$ , -1[1-( -1)-2-1-1-]4 4 (19 ).

. + 4.32 (0.18 1) NaH 50 1

2 1 1 1

15.89 (0.06 1) (3 ) 200 1 2. 1

1 1 1 1 , 1 24 . * 1 1 50 1 , 2 2 1 (2×50 1). * 6 2

1 1,

1 1. 4 9 (81 %) *,*-1[1-( .-

1)-2-1-1- ] (19 ), . . 66°, (0.09 11 . .), nD20 1.4655. , ; 1H . 80. , ; 31P

(CDCl3, δ, 1. .): 22.5.

. + 10.2 1.2 1

1, 0°,, 6 (0.022 1)

(3 ) 35 1 2. 4 1 24 ,

, ,

1 1. 4 2.12 (41 %)

(19 ), nD20 1.4660.

, -6[1-( .1)-2-1-1- ]4-

4 (19 ). 4 1 11.19 (0.037 1) (3 ) 2.66 (0.111

1) NaH 100 1 2 9.73 (70 %) (19 ), . . 76°,

(0.09 11 . ), nD20 1.4568. , ; 1H (CDCl3, δ, 1. .): 1.07 (9H, CMe3), 1.28 (6H, POCH2Me, J 7 0), 1.89 1.92 (6 H, CMe2, J 1.2 0), 2.56 . (1H, NH), 4.05 (4H, POCH2, 3 J H H = 3 J H H 7 0). , ; 31P (CDCl3, δ, 1. .): 26.4.

108

$ -1(1- -3,3-1-2- )-

4 4 (23 ). + 1 1.44 (0.0075 1)

(21 ) 0.83 (0.0075 1) 1

(1 ). ,1 1 1 48 . +

, 1 2 1, 1 1,

. + *-1(1- -3,3-1-2-

) (23 ) 0.57 (37%), . . 125-126oC. , ; 1), 13,, 31P . 83.

-1(1- - -3,3-1-2- )4 4-

(23 ). $ 2.26 (0.01 1) N-(2-1-2-1) -

1 (21 ) 1.10 (0.01 1) 1

(1 ) 1.23 (56 %) (23 ), . . 132oC. , ; 1), 13,, 31P . 83. M - , m/z (%): 222 (3.6), [M++1], 221 (1.9), [M+], 206 (2.9) [M-CH3]+, 164 (11.4) [M-C4H9]+, 138 (100.0) [C4H11O3P]+, 127 (39) [C8H17N]+, 112 (66.6) [C7H14N]+, 96 (41.0) [C6H10N]+, 94 (1.5) [CH3OPO2]+, 70 (62.3) [C4H8N]+, 57 (53.5) [C3H7N]+,

41(34.3) [C2H3N]+.

2.1.3( 4 4 0 3

/ 4 1

2.1.3.1 $ , -1(1- - -3,3- 1-2- )4 4 (29)

, -1-(1- - -3,3-1-

-2- )4 4 (29 ). + 1 0.47 (0.0017 1) (7 ) 2 1 2 1

1 0.60 (0.0017 1)

(28 ) 2 1 2. ) -

1. ,1 1 1 24 . + ,

2 1. 4 0.90 *,*-

1-(1- - -3,3-1-2- )

(29 ) (97%), . . 120 °,. * ; 1) 31 . 88.

109

1 , -1(1- - -3,3-1-

-2- )4 4 (7 ) 2,4,6-4 1 (28 )

. + 1 4.10 (0.0179 1)

(28 ) 25 1 1 1

1 4.21 (0.0179 1) (21 ) 10 1 1. )

1. ,1 1 1 24 . + 1. 4 1 10.20 (60%) *,*-1(1- - -3,3- 1- -2- ) (29 ) *,*-1(1-

-1-2-1-2-1) (31)

1:1. , ; 31 (CD3OD) δ, 1. .: 16.6 20.7.

. + 1 1.95 (0.0085 1)

(28 ) 2 1 1 1

1 2.00 (0.0085 1) (21 ) 2 1 1. )

1. ,1 1 1 2-3 . + ,

2 1. 4 2.84 (67%),

*,*-1(1- -1-2-1-2- 1) (31), . . 115-117°,. ; 1) (CD3OD) δ,

1. .: 3.88 3.9 (6), (*)2, 3J) 11 0); 3.31 (1), ,), 2J) 15.5 0); 1.44 1.53 (9), ,3); 1.48 (6), ,2); 8.10 . (2), NH2); 8.84 (2), Ar); ; 31 (CD3OD) δ: 20.7 1. .

3 , -1(1- - -3,3-1-

-2- )4 4 (29 ). + 1 2.30 (0.0085 1) (7 ) 15 1 1

1 13°, 1 0.99 (0.0085 1) 67.5 %

(28 ). )

1. + 1 2 1 3.21

1 1 (30 ) (86%), . . 119°,. ; 1)

(CD3OD) δ, 1. .: 1.82 1.86 (6), ,2); 3.97 3.95 (6), (*)2

, 3JP) 11.4 0); 7.05 . . (1), +NH); 3.78 (1), ,), 2J) 2.2 0); 1.52

(9H, CMe3); 3.67 (4), ,4)8*2). ; 31 (C)3O)) δ: 15.6 1. . ), %: C 37.51; H 7.01; N 4.10; 8.25; Cl 9.03. ,12)27NPO18Cl. +, %: C 37.94; H 7.11; N 3.69; 8.17, Cl 9.35. MS, m/z (%): 235 (1.5) [ +1], 220 (5.2) [ -C)3]+, 178 (17.0)

110