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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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PH3I

+ NH3

RNH2

+ (EtO)

2PHO

CH2Cl2

112

NHX

(EtO) P(O)

PH3I

- 3. -

NaBr

113 a

(EtO)2P(O)

NHX

PH3Br

113

X = H, i-Pr

( 1 1 1 1, 2 1

1 1 2-1 1 (114)

1 (116). , in situ -

3 1, 2, 1 -

1 (115) [89]. ( 1 1

3 .

C(O)R 1

+ R NH2

+ (R O)2PHO

- H2O

114

R NHR1

+ (R2O)

PHO

P(O)(OR2)2

- ROH

NHR1

115

R = H, Me, Et, n-Pr, n-Bu; R = H, Me;

R2 = Me, Et, i-Pr, n-Bu, i-Bu, Ph, PhCH2

OR2

R3 = Me, MeO

116

/ - 3 1 (118) , 1

1 1 3 (117) [90].

			4-R3C6H4		CHO
(R1O)2PHO + R2C6H4NH2 +



			N
				N	Ph
		117
3			NHC6H4R2
	4-R C6H4		HC
			P(O)(OR1)2

N Ph

118

R1 = Me, Et; R2 = H, 2-Me, 4-Me, 4-OMe; R3 = H, OMe

* 3 1 -2-

(120) 1 1 1 1 [91].


	COOH + PhCHO + (EtO)2PHO
	COOH + PhCHO + (EtO)2PHO			1
NH				1			2
		O	Pd(OH)2/H2, AcOH			O
		P(OEt)2				O
	N					P(OEt)2


		Ph
		Ph			NH
					NH

119	(S)- (R)-120

/ 3 (119) 1

-1 1 . ,1 2 1 (S)- (R)-(120) 3 1

1 1, 1 1 1

1. 4 1

3 2 1 (121).

		O			O
		P(OH)2			P(OH)2
	NH			NH
(R) - 121			(S) - 121
42

1.1.3.2 % /.

1 1 /, %

. + 1 1 1,

1 1 -

- -

«IRMOF-3» [Zn4O(H2N-TA)3], 2- 1 (H2ATA) 1 ' "

25°, 3 1 1 100°, 17

[92]. / 1 1-

1 1 (90-94%).

				R2	CH	1
R1NH2		4 1 %					NHR
		4 1 %					NHR
	+ ArCHO + (MeO)2PHO				P(O)(OMe)2
	+ ArCHO + (MeO)2PHO	0			P(O)(OMe)2
	2 , 60		, -
	2 , 60		, -

R1 = Ph, 4-MeC6H4; R2 = Ph, 4-NO2C6H4, 4-ClC6H4,

2-ClC6H4, 2-MeOC6H4, 3-NO2C6H4

+ 1

1 [93]. .1 1 1 [93].

R1					1		3
	3			5% 1	R	NHAr(R )
2		O + H2NAr(R ) + (RO)2PHO		5% 1		C
2		O + H2NAr(R ) + (RO)2PHO		Mg(ClO4)2 2		C	3
R				Mg(ClO4)2 2			3
					R	P(O)(OR )2
						122
	R1=H, R2=Ph, 4-MeOC6H4,		4-ClC6H4, 4-NO2C6H4,			4-HOC6H4,
4-Me2NC6H4, 2,4-(MeO)2C6H3, 2,4,6-(MeO)3C6H2, 3,4,5-(MeO)3C6H2, 2-
, 2- , 2- , 2- , 2, 2, i-Pr;
R3=Bn, c-Hex, , 1, 2-1 2, 2,2-1-
2, 1

+ 1, 1, 90-98%,

1 -

. , 2-

1 (

) – (20-30), (5), 1 (10), (10),

(50), (85). *,

2 1 1. ,

( , %) –

(40), 11 (25), (60), (40), (40), 1 (60),

(50), 1 (70), (60), (30), 1 (85).

4 1,

1. , , Mg2+1 1 1

1 1 1 1

R1	O	Mg2+ NH2Ar(R3)
R2	(RO)2 P	O H

*, 2 1 , -

1 1 3 1 1,

1 .

1 [94].

NH2

2 + (R1O)2PHO

5 mol% Cd(ClO4)2x H2O

C, -

P(OR )2

R = H, 4-iPr Cl, Br, 4-OH, 4-OMe, 4-OEt, 4-NO 2

123

R = Me, Et

R = H, F, Br, NO 2

+ 1 87-98%. +

, -

, -2 . + 2 1-

52-79%. 4 1 -

, 1 (1, 1) -

1 1 1 3 1 -

1 1 1 [95],

' in situ 1 1 Cd2+

1 1 1 -

1 .

PhCHO + Ph'NH2	PhCH	N Ph'
-H2O
R	O ..	Cd2+		NHPh'
R	O ..	O
(RO)2P(O)H	P	O
R	O	H	Ph	P(O)(OR)2
		H	Ph	P(O)(OR)2

,, 1 2, 1

1 [95] -

ceric ammonium nitrate 1-

3 1 [96].

OEt

BiNO3

. 5H2O (10 mol%)

OEt

NH2

H R1

OEt

EtO H

OEt

EtO

H2O

1 2	3		CAN	1 2	3
R R C=O + R NH2		+ (EtO)2PHO	MeCN	[ R R C=NR + (EtO)2PHO ]

R1R2C(NHR3)P(O)(OEt)2

R1 = aryl, R2 = H; R3 = aryl, Bn, alkyl

+ 1 1 -

1 [97-104]. 5 1 1 -

-1 3 -

1 1. 1 -1, 1-

10 1% FeCl3 . 4 -

- (124) [97]. "

1 (125),

3 1 (126). 4

1 (127), -

, 3 (124).

				N	Me
NH2		MS, FeCl3		N	Me
NH2		MS, FeCl3			Me
X	+ Me2C(O)		X		Me
NH2		- 2 H2O			Me
NH2				N

					Me
	(RO)2POH				Me
	(RO)2POH			125		Me
		Me				Me
(RO)2PHO	N	C			NH C
(RO)2PHO		Me		X		CH2
X	..	CH2		X	+	CH2
	..	CH2			+
	NH	C			NH	C
		Me				Me
	126				..	-
	126				(RO)2P-O
		Me			127
	NH C	Me
	NH C
X		CH2		X = Me, NO2, PhCO

NH C

Me (RO)2P=O

- 2,

1 1- 1 1 ,

, 4-1

− Y. C 1

(128) [98].

				FeCl3/(0
H2N	Y	NH2 + ArCHO + (EtO)2P(O)H
				60 oC
	(EtO)2(O)P NH	Y	NH	P(O)(OEt)2
	Ar			Ar
		128

Y = CH2, CO, SO2

% 1 1,

Al2O3, 2 1 1-

1 , 1-

1 1- 2 1 [99].

MeCN 1 1,

92%.

+ 1 1 1

1 1 1-

, 1

1 . *, 1

1 1 1 MeCN

70-92% [100].

10 1% BiCl3

R1R2C=O + R3NH2 + (R4O)2PHO

MeCN, . .

R1R2C(NHR3)P(O)(OR4)2

R1 = H, R2 = Ph, 4-MeOC6H4, 2-MeOC6H4, 4-NO2C6H4, cyclohexyl, PhCH=CH; R1=R2=Me; R1+R2=(CH2)5; R3 = Ph, PhCH2, n-Pr; R4 = Me, Et, i-Pr

" 24 1 -

1 76-95 % 3 1 1

(0 [101].

$1 -

in situ 1. ( 1

1 1, 1-

85-92% [102]. $ 1 1 2 1

. 4 , 1 1 1 ( .), (%): SnCl2, 0.5, 100; SnI2, 0.75, 100; SnCl4, 2.5, 99; SnBr2, 2.5, 94. 4 1 ,

«1» [103]. 4 ,

SnCl2 N(III), 1 , -

1 1 1 1 1

1 .

			N
O		NH2
	H	+	H
		+

			- H2O
		SnCl2
			Cl Cl
			Sn
			----
			N .
			.
P(O)(OR)2
			H
		SnCl2
		----	-

P+

RO OR

P OR

+ 1

1 1 1. ,

1 1 [104].

R1R2C=O + R3ArNH2 + (RO)2PHO (RO)2POH P(OR)3

	OH/R
	.
	.
	.
1 2		.Z
	. .
R R C	.
			.r
			.X
	.
			.n
	.
	.
(RO)	P		O ... NH2Ar(R3)

2

	O ... ZrX [NH		Ar(R3)]
1 2	.	n 2
1 2	.
R R C	.
R R C	.
	.
	.
	.

(RO)2P=O


H Ar(R3)

	N ... ZrX [HOH/R]
1 2	.	n
	.
R R C	.
	.
	.
	.
	.

(RO)2P=O

Ar(R3)

NH R1R2C

- ZrXn

(RO)2P=O

% ( 1 92-95%) -

10 1% ZrOCl2·8H2O ZrO(ClO4)2·6H2O

, 30 1 1 1 5 1 80

+1 1-

[105]. , 1 (III) 1

[105]. 4 , 1 1 1 1 (%): Bi(OTf)3, 3 1, 98; BiCl3, 2

, 85; BiI2, 5 , 75; BiBr3, 4 , 71; Bi(NO3)3·5H2O, 5 , 67.

1, -

1. + 1 1 ,

1 1, 1,

Bi3+ 1 1 .

* ,

: La, Yb, Sc, Dy, Sm [106-109]. +

1- -3-1 1 [106107]. ' 1 1

2 1 [107]. ' 3

1 1 [108]. ( 1, 1, 2-

1 1 1 1 2 1. + 1 1 1-

0.7-2.3 82-92% 1 .

4 5-

[109].

+1 1

. ) 1

Yb(PFO)3. 4 1 1, 1 1%

1 90% [110]. $ 1 1 1 1

1 [111]. + 0 ,

2 - . +

1 (129) 90-96%.

PhCHO + (Me3Si)2NH + R2P(O)H						10 1% Yb(OTf)3
PhCHO + (Me3Si)2NH + R2P(O)H					1.1- , 2.5
					1.1- , 2.5
	Ph		CH	P(O)R2		R = OEt, Ph, n-Bu
	Ph		CH	P(O)R2		R = OEt, Ph, n-Bu

			NHSiMe3
		129

+ 2 1 3

R1R2C=O + (Me Si)			NH + (EtO)		P(O)H	10 1% Yb(OTf)3
R1R2C=O + (Me Si)			NH + (EtO)		P(O)H
3		2		2		1.1-
		R2				1.1-
	R1
		C		P(O)(OEt)2
		C		P(O)(OEt)2

NHSiMe3

' 1 1 3 1-

P(O)(OEt)2

TFA

P(O)(OEt)2

CH2Cl2, 1.1-

NHSiMe3

NH2

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