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

[ -C4)9]+, 152 (100) [C4)11NO3P]+, 150 (20.4) [C4)9NO3P]+, 125 (10.7) [C8)15N]+, 110 (52.5) [C7)12N]+, 88 (35.4) [ +2], 79 (36.4) [C2)7P]+, 57 (42.9) [C4)9]+.

4

*,*-1(1- - -3,3-1-2-

)- (29 ), . .126°,. ; 1H (CD3C(O)CD3) δ, 1. .: 1.821.86 (6), ,2); 3.93 3.97 (6), (*)2, 3JP) 11.3 0); 7.05. . (1), +NH); 3.78 (1), ,), 2J ) 3.1 0); 1.52 (9H, CMe3). ; 31 (CH3CN) δ: 13.6 1. . ), %: C 35.51; H 6.79; N 4.00; 9.35; Cl 11.03. ,10)23NPO7Cl. +, %: C 35.77; H 6.86; N 4.17; 9.24, Cl 10.58. MS, m/z (%): 235 (1.3) [ +1], 220 (5.3) [ - ]+, 178 (14.3) [ - C4)9]+ , 152 (100) [C4)11NO3P]+, 150 (28.3) [C4)9NO3P]+, 125 (10.8) [C8)15N]+, 110 (79.7) [C7)12N]+, 79 (15.6) [C2)7P]+, 57(43.3) [C4)9]+.

+ 1 0.50 (0.0015 1) *,*- 1(1- - -3,3-1-2- ) (29 )

1 1 1 1

1 3 1 . ,1 24 . *

1 (30 ) (86%), . . 119 °,. , ; 1) (CD3OD) δ, 1. .: 1.90 1.94 (6), ,2); 3.98 4.10 (6), (*)2, 3JP) 11.4 0);

7.15 . . (1), +NH); 3.83 (1), ,), 2J ) 2.2 0); 1.60 (9H, CMe3); 3.40 (4), ,4)8*2). ; 31 ( O)) δ: 15.6 1. .

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

-2- )4 4 (29 ). 4 1 7.20 (0.0306 1) (7 ) 35 1 6.73 (0.0306 1) 40% (28 ) 10.36 (92.2%)

1 1 (30 ), . . 115-117°,. , ; 1) (CD3OD) δ, 1. .: 1.64 (9H, CMe3); 1.97 2.01 (6), ,2); 3.59 (4), ,4)8*2); 4.01 4.05 (6), (*)2, 3J 11.4 0); 4.34 (1), ,), 2J 17.6 0); 6.65 . (1), +NH). ; 31 (CD3OD) δ: 14.4 1. . MS, m/z (%): 235 (1.4) [ +1], 220 (5.5) [ - ]+, 178(20.2) [ -C4)9]+, 152 (71.5) [C4)11NO3P]+, 150 (15.5) [C4)9NO3P]+, 125 (7.8) [C8)15N]+, 110 (100) [C7)12N]+, 88 (12.2) [ +2], 79 (29.0) [C2)7P]+, 57(45.6) [C4)9]+.

4

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

111

-2- ) (29 ), . . 117 °,. , ; 1) (CD3OD) δ,

1. .: 1.64 (9H, CMe3), 1.97 1.98 (6), ,2); 3.90 (1), ,), 2J) 16 0); 3.96 3.94 (6), (*)2 , 3J 11.4 0); 7.06 . (1), +NH).

; 31 (CD3OD) δ: 13.5 1. . MS, m/z (%): 235 (16.0) [ +1], 220 (66.1) [ - ]+, 178 (88.6) [ -C4)9]+, 152 (100) [C4)11NO3P]+, 125 (83.2) [C8)15N]+, 110 (100) [C7)12N]+, 79 (86.9) [C2)7P]+, 57 (94.8) [C4)9]+.

+ 1 0.50 (0.0015 1) *,*- 1(1- - -3,3-1-2- ) (29 )

1 1 1 1

1 3 1 . ,1 24 . *

1 (30 ) (89%), . . 115-117°,. ; 1) (CD3OD) δ, 1. .: 1.60 (9H, CMe3); 1.90 c 1.94 c (6), ,2); 3.40 (4), ,4)8*2); 3.98 4.10

(6), (*)2, 3J 11.4 0); 3.83 (1), ,), 2J) 17.6 0); 7.05 . (1), +NH). ; 31 (CD3OD) δ: 14.4 1. .

2.3.2 1 4 4 0

4 1.

1 , -1(1- - -3,3- 1-2- )4 4 (29 ) 1 1. + 1

0.90 (0.0019 1) (29 )

1 3 1 1. ,1 3

. * 0.90 (95%) *,*-1(1- -1-2-1-2- 1) (31). * ; 1) 31

. 91.

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

-2- )4 4 (7 ) 3 (28 ). +

1 3.00 (0.0128 1) (7 ) 25 1 2 1 1 0°,

1 3.29 (0.0256 1) (28 ) 2 1 2. ) -

1. ,1 1 1- 48 . 4 2 1 1

, -

1. 4 5.66 (90%)

112

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

(33), . . 87-88°,. ; 1) (CDCl3) δ, 1. .: 1.16 c (9H, CMe3); 1.58 c 1.66 c (6), ,2); 3.85 (6), (*)2, 3J)) 11 0); 3.91 (1), ,), 2J ) 18 0); 6.41 (1), CHCl22); 6.47 (1), CHCl21); 8.60 . (2), +NH2). 31 ; (CDCl3) δ: 27.3 1. . ), %: N 2.80; 6.35; Cl 28.45. ,14)26NPO7Cl4. +, %: N 2.84; P 6.28; Cl 28.75.

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

]4 4 (35).

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

(35 ). + 1 1 10.02 (0.055 1) N-

- -2,2- 1 (34) 6.05 (0.055 1) 1- (1 ), 1

1 20°,. ,1 24

1 1. 4 1 2 1

13.6 (85%) *,*-1[1-( -1)-2,2-

]- , . . 60 °, (2). , ; 1) (,DCl3,

δ, 1. .): 1.29 (9H CMe3), 2.30 . (1H, NH), 2.38 (3H, CMe), 3.67 (1H, PCH 2JPH 20 0), 3.91 3.93 (6H, MeOP, 3JPH 11 0). , 31P (CCl4, , δ, 1. .): 26.93. ), %: , 36.89; H 7.02; N 4.67; P 10.53.

C9H20NCl2O3P. +, %: C 37.00; H 6.90; N 4.79; P 10.60

, - (2-3 6)[1-( -1)-2,2-3-

]4 4 (35 ). + 1 1 5.20 (0.025 1) (2- 2) (1 ) 5.10 (0.028 1) 1 (34 ),

1 1 20-22°,. ,1 -

1 1 48 . 1

2 1, 1 1. 4 2 1 1 1

8.7 (90%) *,*- (2- 2)[1-( -1)-2,2-

] (35 ), - 3 1 - 1 . , ; 1)

(,DCl3, δ, 1. .): 1.20 (9H CMe3), 2.1 . (1H, NH), 2.24 (3H, CMe), 3.6 (1H, PCH 2JPH 18 0), 3.371 (4H, CH2OP), 3.741 (4H, CH2Cl). , 31P (CCl4, δ, 1. .): 25.3 ), %: , 33.65; H 5.46; N 3.43; P 8.03. C11H22NCl4O3P. +, %: C 33.96; H 5.70; N 3.61; P 7.91

113

1 , -1[1-( -1)-2,2- 3]4 4 (35 ) 4 . 2.9

(0.01 1) (35 ) 20 1 2 1 1

1.14 (0.01 1) 10 1 2 2. )

1. ,1 . 4 2

1 3.71 (92%) *,*-1[1-( -

1)-2,2- ] (37) -

. , ; 1) (d- , δ, 1. .): 1.43 (9H,

CMe3), 2.47 (3H, CMe), 3.98 3.96 (6H, MeOP, 3JPH 11.30), 4.03 (1H, PCH, 2JPH 18.70), 8.09 (2H, N+H2)., 31P (CHCl3, δ, 1. .): 27.58

4 1 (37) 2

3 3 *-1- [1-( -11)-2,2- ] (38), . . 107108°,. , ; 1) (d- , δ, 1. .): 1.64 (9H, CMe3), 2.65 (3H, CMe), 3.72 (3H, POMe, 3JPH 11.20), 4.30 (1H, PCH, 2JPH 140), 8.61 (2H, N+H2). , 31P ( , δ, 1. .): 6.19. ), %: , 36.29; H 6.69; N 5.65; P 11.63. C8H18NCl2O3P. +, %: C 36.38; H 6.87; N 5.30; P 11.73.

1 , -1[1-( -1)-2,2- 3]4 4 (35 ) .

1.46 (511) (3 ) 15 1 2 1

1 1.14 (511) 10 1 2. ) -

1. ,1 1 1 72

. + , -

1. 4 21 (81%)

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

(36 ), . . 102-103°,. , ; 1) (d- , δ, 1. .): 1.40 (9H,

CMe3), 2.43c (3H, CMe), 3.92 3.94 (6H, MeOP, 3JPH 100), 4.12 (1H, PCH, 2JPH 190), 6.04 . (2H, N+H2), 9.06c (2H, C6H2). , ; 31P (CHCl3, δ, 1. .): 23.50. ), %: , 34.42; H 4.57; N 10.61; P 6.01.

C15H23N4Cl2O10P. +, %: C 34.56; H 4.45; N 10.75; P 5.94

114

1 , - (2-3 6)[1- -1-2,2- 3]4 4 (35 ) . "-

3 1, 0,78 (211) (35 ) 0.46

1.03 (83%) *,*- (2-

2)[1-( -1)-2,2- ] (36 ),. . 140-141°, (2). , ; 1) (d- , δ, 1. .): 1.45 (9H, CMe3), 2.41c (3H, CMe), 3.90 (1H, PCH 2JPH 190), 3.801 (4H, CH2Cl), 4.241 (4H, CH2OP), 7.2 . (2H, N+H2), 9.02c (2H, C6H2). , ; 31P ( , δ, 1. .): 21.9. ), %: , 33.17; H 4.16; N 8.91; P 4.92. C17H25N4Cl4O10P. +, %: C 33.03; H 4.08; N 9.06; P 5.01

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

]4 4 (39). + 17.5 1 1.2

1 1 1 , 1

1 +50, 6.2 (0.021 1)

(35 ). ,1 6 1 1 1,

NaCl,1

1. 4 3.5 (65%) *,*-1[1-( -

1)-2- -1- ] (39), . . 67-68°, (0.08 11 . .) 1 1 1. , ;

1) (,DCl3, δ, 1. .): 1.10 1.17 (9H, CMe3), 2.29 2.40 (3H, CMe,

4JPH 2.90), 2.61 (1H, NH), 3.71 3.68 (6H, POMe, 3JPH 110). , ; 31P (CHCl3, δ, 1. .): 18.74 19.55. ), %: C 42.48; H 7.39; N 5.60; P 12.16 C9H19NClO3P. +, %: C 42.28; H 7.49; N 5.48; P 12.11.

2.2 / , -4 4 3 (40) N-

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

$ 3 N- - -2-(6 4 4)- 2-1 1 (41 ). 8.9 (0.55 1) N- -

-2-1-2- 1 (2 ) 50 1 ,,l4 1-

1 10.2 (0.55 1) *,*-2-

(40 ), 1 0 5°,.

1 - . ( 1

1 20°, 1

5-6 . ,1 1 1 1 .

. , 2

115

. + . 4 14.5 (76%) (41 ), . 112°,. , ; 1) (,DCl3, δ, 1. .): 1.18 (6), ,)2,)3, 3JHH 7.0 0), 1.45 (9), ,Me3), 1.80 (6),,Me2), 4.0

(4H, ,)2*, 3JHH 7.0 0, 3J H 10.3 0), 8.7 (1), ,)=N+), 14.3 . (1), N+H). ; 31 (,,l4, δ, 1. ): 87.3. ),%: , 41.57; ) 7.97;

8.81; S 18.28. ,12)27ClNO2PS2. +,%: , 41.43; ) 7.82; 8.90; S 18.42.

N- - -2-(4 4)-2- 1 1 (41 ). $ 14.1 (0.087 1) N- - -2-

1-2- 1 (2 ) 18.7 (0.087 1) *,*-

(40 ) 70 1 ,Cl4

20.5 (81%) (41 ), . 147°,. , ; 1) (,DCl3, δ,

1. .): 1.18 (12), Me2CH, 3JHH 6.1 0.), 1.52 (9), ,3), 1.85 (6),

,2), 4.62 (2), ,)*, 3JHH 6.1 0.), 8.76 (,H=N+), 14.25 . (1), N+)). ; 31 (,,l4, δ, 1. .): 85.2. ),%: C 44.89; ) 8.50;

8.18; S 16.88. ,14)31,lNO2PS2. +,%: , 44.73; ) 8.31; 8.24.; S 17.05.

N- - -2-(4 4)-2- 1 11 (41 ). $ 5.8 (0.024 1) N- - -2-

1-2- 1 (2 ) 5.8 (0,024 1) *,*-

(40 ) 70 1 ,Cl4 7.6 (79%) (41 ). , ; 1) (CDCl3, δ, 1. .): 0.75 (6), ,)3,)2, 3JHH 7.1 0), 1.48 (9), ,3), 1.02 – 1.61 1 (8), CH2CH2), 1.82 (6), ,2), 3.62 – 4.02 1 (4), *,)2 ), 8.76 . (1), ,H=N+), 13.46

(1), N+)). ; 31 (,,l4, δ, 1. .): 87.4. ),%: , 47.69; ) 8.84;

7.59. ,16)35,lNO2PS2. +,%: C 47.57; ) 8.73; 7.67.

N- -2-(4 4)-2-

1 1 (410). 14.7 (0.1 1) N- -2- 1-2- 1 (2 ) 75 1 ,,l4 1

1 21.4 (0.1 1) *,*- -

(40 ), 1 0-5°,. ( 1 1 20°,

24 . . ,,l4, 2 . + . 4 29.2 (81%)

(41 ), . . 64°,. ) (%): , 43.23; ) 8.14; 8.69; S

116

17.54. C13H29ClNO2PS2. + (%): , 43.15; ) 8.08; 8.56; S 17.16. , ; 1) (CDCl3, δ 1. ., J 0): 1.12, 1.0 (12 ), 2,)*, 3J)) 6.1), 1.35 (6), 2,)N, 3JHH 6.3), 1.71 c (6H, CMe2), 4.19, 4.12

(1), NCH, 3JHH 6.3) 4.59 , (2), *,) 2, 3JHH 6.1, 3JPH 12.1), 8.93 c (1H, CH=N+), 14.06 . (1), N+)). , ; 31 (,,l4, δ

1. .): 84.8. , ; 13, (CDCl3, δ 1. ., J 0): 20.92 (N+,) 2), 23.96, 23.82 (*,) 2, 3JPC 5.03); 27.89 (SCMe2, 3JPC 7.04), 51.99

(SC, 2JPC 5.08); 57.64 c (N+CH); 75.43 (CHOP, 2JPC 8.05); 178.30 c (CH=N+).

N- -2-(6 4 4-2-1-

1 (41 ). " 3 1, 5.9 (30 11) N-

-2-1-2- 1 (2 ) 25 1 ,,l4 5.6 (30 11) *,*-2 (40 ) 6.8 (59%) (41 ), . . 118-119°,. ) (%): , 47.28; ) 6.47; N 3.50; 7.91. C15H25ClNO2PS2. + (%): , 47.19; ) 6.60; N 3.67;8.11. , ; 1) (CDCl3, δ 1. ., J 0): 1.40 (6), ,)2, 3J)) 7.0), 2.01 (6), ,2, 4J H 1.2), 4.01-4.22 1 (4H, *C)2), 5.11 (2),

PhCH2), 7.36-7.80 1(5), Ph), 8.61 c (1H, CH=N+), 15.28 . (1), N+)).

, ; 31 (,,l4, δ 1. .): 87.6.

$ 1 7 (42 ) – , - -

4 4 N- - -2-1-2-3 1 .

1 -10°, 2.14 (0.01 1) *,*-

(40 ) 5 1

5 1 1 1.62 (0.01 1) 1 (2 )5 1 . 8 5 1 1

, ,

1 1 1

1. 4 3.57 (95%) (42 )

. +, %: , 44.73; H 8.31; 8.24.; S 17.05. C14H31CINO2PS2. ), %: , 44.49; H 8.46; 8.07.; S 16.81.

1 (42 ) 6 1 1. 1

-10°, 2.0 (5.3 11) (42 ) 10 1 2

1 0.54 ( 5.3 11) 2 1, 1 1. * (1.5 ), 2

.

2 1 (44). , ; 1) (44)

117

(CDCl3, δ, 1. .): 1.41 (12), Me2CHO, 3JHH 6.1 0), 1.53 (9), CH3CH2,

3JHH 7.1 0), 3.41 (6), CH3CH2, 3JHH 7.1 0), 4.81 (2), ,HOP, 3JHH 6.1 0), 10.08 . (1), N+H). , ; 31 (CDCl3, δ,

1. .): 108.0.

+ N- - -2- 1-2- 1 (2 ), . . 61-62 0, (40 11. .1.). nD20

1.4285. , ; 31H (CDCI3, δ, 1. .): 1.29 c (9H, CMe3), 1.77 c (6H, CMe3), 7.69 c (1H, CH=N).

, 1 ; 1H 31 1

1 – N- - -2-*,*- -

-2-1 1 (47), 1

1 . *,

(42 ) 3

11 (41 ), 1 2 1 HCl ,

3 1 (47).

1 (42 ) 1 4 4 1. -

1 -10°, 1.97 (5.3 11) (42 ) 15 1

2 1 1 0.65 (5.3 11) 1 5 1 2. ,1 24

1 1. ,

1. + . . 70-73°, (0.08 11. . .), 1 :

1) *,*- -S-1 (45). , ; 1H

(CDCl3, δ, 1. .): 1.36 (12), Me2CH, 3JHH 6.0 0), 2.32 (3), SMe, 3JHH 17.0 0), 4.82 (2), CHOP, 3JHH 6.0 0). , ; 31 (CDCI3,

δ, 1. .): 92.96.

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

(3a). , ; 1) (CDCl3, δ, 1. .): 1.14 (9), ,Me3), 1.67

c 1.73 (6),,Me2), 1.82-1.87 . (1), NH). 3.15 (1H, PCH, 3JHH 20.0 0), 3.76 (6H, POMe, 3JPH 11.0 0). , ; 31 (CCI4, δ, 1. .):

30.0.

- 0 5 (42). , (42 )

, 3 . 4

1 CCl4, ,

*,*- -11

(46). , ; 1H (CDCl3, δ, 1. .): 1.47 (12), CH2CH, 3JHH 6.1 0),

118

1.74 c (9H, CMe3), 4.80 (2), CHOP, 3JHH 6.1 0), 8.14 . (3), N+H). , 1 ; 1H 2-1-2-

. , ; 1H (CDCl3, δ, 1. .): 1.70 (3), CH3, 3JHH

7.0 0), 4.51 . (1), CHCl, 3JHH 7.0 0, 3JHH 5.0 0), 9.71 (1), ,)*, 3JHH 5.0 0).

119

$ $% $"9* : " 2# 2( )

1. , $. +. 4 / $. +. , %. ". / // , 0.. - 1991. - 146 .

2.8, . ". - . ,

1 1 1 / . ". 8, +. $. 0 //

. 1. - 1998. - (.67, @ 10. . 940-968.

3.7 1, . 0. 1,

3 1 - / . 0. 7 1, ). 0. 7,

. ". 8, ". ). 4 // B*5. - 1980. - (. 50, @ 4. ,. 1458. 4.Gazizov, M. B. New products of the reaction of aldimines with

dialkylphosphites / M. B. Gazizov, R. A. Khairullin, A. I. Alekhina, I. A. Litvinov, D. B. Latypov, A. A. Balandina, R. Z. Musin, O. G. Sinyashin // Mendeleev Communications.- 2008. - Vol. 18, @ 5. - P. 262-264.

5.Gazizov, M. B. Reaction of dialkylphosphites with N-alkyl-2- chloraldimines / M. B. Gazizov, R. A. Khairullin, A. A. Minnikhanova, A. I. Alekhina, A. A. Bashkirtsev, O. G. Sinyashin // Russian of General Chemistry. - 2010. - Vol. 80, @ 12. - . 2425-2429.

6.0, . /. + 1

N-(2-1-2- )1 1 / . /. 0, . ". 5, ". ". , ". $. " , ". ". /, *. 0. , 3 // ' " 1 . - 2010. - (. 433, @ 3. - ,. 352-356.

/ O.+. Ko , A.C. ", +./. ,, A.). 4 // $ . "). ,. 1. – 1998. – ,. 1408-1412.

11. Wieczorek, J. S. Synthesis and physiological activities of new acyclic aminophosphonates / J. S. Wieczorek, R Gancarz, K. Belecki, E.

120