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Башкирский Государственный Аграрный Университет

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[НЕСОРТИРОВАННОЕ]

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

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1.2.1 1 -,% N- -2-3 5 1 1

1.2.1.1 3 !

5 3 0.

$ '" N- -2-1 1

2008 1 0(. [169]. / ,

. + , 1 -

1 1 1 P(IV):

MeO(O-)P(O)CH(Cl)CMe2CH2N+H2Bu-t. *, -

1 . 1 , 1

. 4 2 1

1 P(IV) N(III) 1

,1 P(IV) N(III) , 3

*,,

2 1 1

, 1 1

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

( ) .

+ 1 1 (2) 1

1 '" (1). ,1 1 1

24 . + 1 (1) c 1 (2) -

1 1 (3),

26 - 29 1. . (

R2=t-Bu R1=Me (3 ) -

1 1 1

4 1 15-20

1 3 1

. % 3

1 P(IV)

. 4 R2 = i-Pr Bn N(III), 3

(3) , 1

R2 = t-Bu. +, R2 = t-Bu - 1 (4) , 1 R2 = i-Pr Bn -

	Cl			Cl
(R1O)2PHO +		2	1
	Me2CCH=NR		(RO)2P(O)CHCMe2

1	2		NHR 2
			3

(R1O)2P(O)CH CMe2 (R1O)2 P(O)CH CMe2

	+		NHR2
-	NHR2	Cl	NHR2
Cl
	4	5

1, R1 = Me (a), Et ( ), i-Pr ( ), Bu( ), ClCH2CH2( ). 2, R2 = t-Bu( ), Bn ( ), i-Pr ( ). 3, R1 = Me, R2 = t-Bu ( ); R1 = Et, R2 = t-Bu ( ); R1 = ClCH2CH2, R2 = t-Bu ( ); R1 = Me, R2 = Bn ( ); R1 = i-Pr, R2 = Bn ( ); R1 = Bu, R2 = Bn

( ); R1 = ClCH2CH2, R2 = Bn ( ); R1 = ClCH2CH2, R2 = i-Pr ( )

(, 1 (2- 2)

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

(2 ), 2-1-

(6 - ) -2 (7 - ). 4

1 2 1 , -

3 (6). $ 2 1

(7) 1

(3).

(7 ) -

1 (3) 1

1 [169]. 4, -

(4).

1, (7)

1 1 - 1 (4). + 3 -

(3) , 1 , 1

1 1 1 (8),

1 1 (4).

				Cl
1		CMe2 + (R1O)2 P(O)CH
(R O)2P(O)CH		CMe2 + (R1O)2 P(O)CH			CMe2
-	+				NHR2
4 ClR2 N		H		5	NHR2
(R1O)2 P(O)CH			CMe2	+ (R1O)2P(O)CH CMe2
	6	Cl	+NH2R2	Cl-	NR2
	6				7

6, R1 = i-Pr, R2 = Bn ( ); R1 = Bu, R2 = Bn ( ); R1 = ClCH2CH2, R2 = Bn ( ); R1 = ClCH2CH2, R2 = i-Pr ( ). 7, R1 = Me, R2 = t-Bu ( ); R1 = Me, R2 = Bn ( ); R1 = i-Pr, R2 = Bn ( ); R1 = Bu, R2 = Bn ( ); R1 =

ClCH2CH2, R2 = Bn ( ); R1 = ClCH2CH2, R2 = i-Pr ( ).

, (4) -1 1 -2

3 1 (5) 1 1 1

P(IV). "1 (5) 1 (4), 3

(7). * 11 (6),

1 2 . ,

(6) 1 P(IV).

R1 = ClCH2CH2 , R2 = i-Pr t-Bu – , R1 =

1 (8).

(R1O)2 P

C(CH )

3 2

C(CH3)2

- R Cl

+ 2

NHR

NHR Cl -

R1OP

C(CH3)2

R1OP

C(CH3)2

R1Cl

NHR

NH2R2

8, R1=Me, R2 = t-Bu ( ); R1=Me, R2 = Bn ( ); R1=Et, R2=Pr-i ( )

+ (6)

11 1, 2 1 ,

1 ". +

1 1 (9) 1 -

1 1 2 ,

(8).

) ; 1)

(8 ) (CDCl3, δ, 1. .): 1.68 c (9H, CMe3); 1.76 1.83 (6H, CMe2); 3.92 (3 ), POMe, 3JPH 11 0); 4.60 (1), PCH, 2JPH 8.5 0); 9.62 10.91

. . (2), N+H2, J 11 0). , (8 )

2 1 1 1, 1 ; 1 1 ," ( . 3).

. 3. * 3 ( ) ( ) 1

(8 )

, 1 ," 3 (8 ) 3 -

1 1 1 1-

-*… HN+ ( . 3 ).

1.2.1.2 !

1 5 3 0

, 1 1-

1 (4)

(3) 1 1. *,

–

. $ 1

(3) 1 1 -

1. $ 20-25% (3) 1.

2 1,

1 1 .

+ 1 1 1 1

(3 ) 0°, 2- 1. 8 24 1, ; 31 ,

– (7 , δ 28 1. .), 1

1. 4 R=CH2CH2Cl 96 (7 )

; 31 90% (δ 26.9 1. .). 4 (7 )

3 1 1 ; 1) 31

, . . 1 1

MeOH

+ Et N, 24

(RO)2PCH

CMe

(RO)2PCH

CMe2

(RO) P(O)CH

CMe

0°,

- Et3N.HCl

NHBu - t

t -Bu-NH

NBu-t

7,R= Me (a); R= CH2CH2Cl ( )

+ 1 1 (3 )

1 1 48 . +

; 31 1

δ 21 1. ., 3 1 -(12). 4, ,

1 (4 ) 1

1 1 (10). + 1

1 1 1 96 . *

1 1

1 1 (14, δ 11 1. .). 4 10- 1 1 1

, 1 ; 31 , 1

(12) (13) 1:1. 4

1 1 1

1 (13).

MeOH

(MeO)2

PCH

CMe2 MeOH

(MeO)2P

CMe2

. .,48

NHBu - t

t- Bu - NH

4 a

OMe

(MeO)2P(O)CH

CMe2

(MeO) P

CMe

t -BuHN

N+H Bu-t

HOMe

MeCl

OMe

(MeO)2P

CMe2

MeOP

CH-

CMe2

MeOP

CH-

CMe2

1.1.

Cl -

N+H Bu-t

-O

NH Bu- t

NH Bu

12 , = 21 1. .

13 , = 11 1. .

+ 1 1 (3 ) -

1 1 48 , . .

1 ; 1) 31

(12). + 1 2 1. + 2- 1 1 3 1 (14, δ 31 1. .).

Et N

( O)2P

C 2

. ., 48

( O)2P

C 2 - Et N3 .HCl

( O)2P

C 2

N+H Bu-t

NHBu - t

( 1 1, 1 -

(3 ) 1 -

1 (14), (12), (7)

(13).

, (3)

1 1 1 -2-

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

(3) 2 1 1 1 .

MeONa + MeOH

- NaCl

MeOH

Me2C

CHP(O)(OR1)2

Et NH

Me2C

CHP(O)(OR )2

NH Bu-t

N Bu-t

-Et2NH2Cl

NaBH4 + MeOH

- (NaCl + BH3)

+ 1, 1

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

2 1 3 -

1 [170].

, (7) 2 1 1 1

1 ; 1), 31 13,,

(CDCl3, δ, 1. .): 0.97 (9H, CMe3), 1.15 (3H, MeCMe) 1.22

(3H, MeCMe, J 2.3 0), 1.52 (1H, CH, 2JPH 22 0), 3.5 (POMe, 3J) 11 0). ; 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). ; 31P (CDCl3, δ, 1. .): 26.40.

, 1, -

. (,

(15) 1 1 -

2 1 [171].

		Ph		Ph
X				Ph
	DMSO				+ *,
Ph2C=CNO2 + (EtO)2PHO	DMSO
		HN

					P(O)(OEt) 2
					P(O)(OEt) 2
X=Ph, Me
			X
			15

4 1,3-1 1 -

*,*- -(2-2) -

1 (16 ) (16 ), 1-

1 1 1 [172]. 4 1

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

-3) (17).

NO2

P(O)(OR)2

O2N-CH=CH-P(O)(OR2) +

PhN3

16a

H3C

P(O)(OR) 2

-N2

O2N

17	1 1

/ 1 1

(18) 1,2-1 2

2- 1 (1,3- 2 1 HCl) [173].

Cl	NHCOPh	NCOPh
Cl		NCOPh
	P(O)(OEt)2	NaH
		O
	O	P(O)(OH)2
O	O	O
		O

) 1 , 1 (

1,2-1 2) 1 2 2 1

1 1 – 3 1,2-2 1-

HCl 1 3 1 (19 - ).

	MeONa, 2	Me	C=C-NHBu-t
	- NaCl	2

			1	)2
			P(O)(OR	)2
Me2C(Cl)CH-NHBu-t			19a
Me2C(Cl)CH-NHBu-t

P(O)(OR1)
2
3a-	NaH, 2	19a- + H2
	-NaCl	19a- + H2
	-NaCl
	19, R1=Me (a), Et ( )

, (19) 2 1 1

1 1 1), 31 13,. ' (19 )

; 1) (CDCl3, δ, 1. .): 0.96

(9H, CMe3), 1.78 1.81 (6H, CMe2, J 1.2 0), 2.39 . (1H, NH), 3.52(6H, POMe, 2J) 11 0). ; 13C (CDCl3 δ, 1. .): 22.49 24.63

(CMe2), 31.78 (CMe3), 53.30 (POMe, 3J, 4.5 0), 56.96 (CMe3), 128(PC=, 1J, 183.53 0), 149.28 (HNC=, 2J, 30.35 0). ; 31P

(CHCl3 δ, 1. .): 22.5.

, (20), 1 1 (19), - 3 1 1 ,

1- 1 2- 2-

1 [174-176].

130 0C

Me2C=C-NR2 + P(OEt)3 Me2C=CH-NR2 + EtCl

Cl			P(O)(OEt)2
R=Me, Et			20
			20
Me C=C-NEt		+ (EtO) PHO	PdCl2 (Ph3P)2 Me C=CH-NEt
2	2	2	2		2
			20 0C
Cl				P(O)(OEt)2
				P(O)(OEt)2

, ; 1 (19) (20)

( 1 1, 1

N- -2- 1 1 -

1 1 1

1 1 . 4

-2- 1- -

1.2.21 4 4 3

N- -2-1 5 1 1

$ 2-1 1 (21) 1

, 1 1 (21 )

1, 1 (21 ). + ; 31 1, 10

1 (21 ) (1),

δ 26.14 1.17 1. ., 3

1 1 (22 ) 1 . 8 30 δ 26.14 1. . ,

δ 1.17 1. . + 1-

(21 ) (1) δ 0.8 26.50 1. .

25 1,

. ( 1 1,

1 1 (21 - ) -

(22 - ), 1 -

. + (17 - )

1. / 1 1

1 1, 1

δ 2.6 1. . ; 1)

(MeO)2PHO + (Me)2C-CH=NR (MeO)2P(O)CH-CMe2

1	Br	21		NHR
			22

R	N	H


Me2C CH .		O
.
.
MeOP
		O
23

Br NHR

RN H

		.
		.
Me2C CH		.
Me2C CH		.O
.	.	- MeBr
.		- MeBr
Me O P
24		OMe
24

R	N			H
R	N

Me2C		CH
			.
			.	O
.			.	O
.
MeOP
MeOP
.
.				O
23 .				O
23 .

Me2C CH					. NHR
					. NHR
					.
O = P(OMe)2		Me2C CHNHR		Me	C CH
		Me2C CHNHR		Me	C CH
22		+	-	2
22		+	-	- MeBr
		O P O Me	Br		O P = O
					O P = O
22, R = i-Pr (a),	R = t-Bu ( )	OMe
		OMe			OMe
					OMe
		26			25

+ 1 ; 1), 31 13, , 3

1. , 1 ; 1) 2 ,

(22 - ),

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