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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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<<< < Предыдущая 1 2 3 4 56 / 146 7 8 9 10 11 12 13 14 > Следующая >>>

1 1 1

- [112]. + -

1 1 . + 1 (130) 71-83%. 4 (MeOH, EtOH, CH2Cl2, MeCN) (50-65%)

40 1% .

			20 1% KHSO4
R1CHO + R2	NH + (EtO)	P(O)H		R1	CH		P(O)(OEt)2
R1CHO + R2	NH + (EtO)	P(O)H		R1	CH		P(O)(OEt)2
2	2		1.1-			NHR2
			1.1-

			130
R1 = Ar, N	; R2 = Ar, PhCH		, t-Bu
N		2
N

* Fe3*4 1

. )-Fe3O4 1 , 2 1 1 3 -

( 1) 1

1 : , 1 -50 ,,

20-55 1. 4 -

. ! 94 86% [113].

Fe3O4 (DHHA-

Fe3O4) : 1-

, 40 ,

2 , 93% [114]. 4

(EtOH, C)2Cl2, H2O, MeCN) -

(40-60%).

* 1 1 1 :

DHHA, 1 1 ,

1 1 1 ; 1

1 , 1

DHHA 1 1 , 1

1 1 .

' 2 1

: MeCN, (0, EtOH, MePh – 1 3

. + 1 20 1% TiO2

1 50 ,

98% [115]. + 15

, 22 1 2. $

(CuO, MgO, ZnO) 1-

( 60 %).

" 1- 1 (PcAlCl)

2 1

[116-117]. + 1 1

2 α-1 [116].

0.1 1% -

R1R2C=O + R3CH(NH2)COOR4 + (EtO)2P(O)H

1. , -

(EtO)2P(O)C(R1R2)NHCHR3

COOR4

+ 1, 1-

. 1 1 1-

24-72 1

. 1, 11 ,

1 [117] 1 1

/ 1 –

( ) Cp2Zr(OSO2C4F9)2·2H2O, -

, , , 1

r [118]. + 1 81-98%.

5 1% -

R1R2C=O + R3NH2 + (EtO)2P(O)H (EtO)2P(O)C(R1R2)NHR3

1.1- ,

- , 2.5 .

4 ( , , CH2Cl2, 2 2, , , 1, (0)

(48-84%). + 1-

-1, 1 1-2

1 1 1 α- -

. 4 1 ,

1 1 . " 1

1 1 1 N(III) 1, P(III) 1 α-1- α- -

. 4 1 -

(131) 3 1.

PhCHO + RNH2 + (EtO)2P(O)H

O... Zr

+ H2N.. R

Ph H

+ (EtO)2PHO

O	H	Zr
O		Zr		NHR
..		...		NHR
..		...
(EtO)2P	CH	N
- H2O	Ph	R	Ph	P(O)(OEt)2

O...	Zr			OH		NHR
						NHR
	+	(EtO)	POH
	+		2..
Ph	H		Ph	P(O)(OEt)2	Ph	P(O)(OEt)2
			Ph	P(O)(OEt)2	Ph	P(O)(OEt)2
	+ RNH2			131
				+ RNH2

" – «1 »

/ – « »

* 2 1

1 1 (II) [,u(3,4-tmtpa)](MeSO4)4

1 , 1

[119]. $ 0.16 1% 2 -

. 80 ,. + 1 90-98%. 4

1 1 , 3

, 2 1 1 1-

, 1 1 2-

. + 1 , 1, 75-94%

MeCN 80 , [120].

4 )-beta

1 76-93 %. / ,

1 1

[121].

, 1 1

1 1 1 -

1 1 1

Montmorillonite- [122]. + 1

1 - 3-8 1, 1 – 5÷10

– 75-92% 65-8%, .

1 4"+ «TWEEN-20». + 80%

1 60 , 30 1 [123].

R1R2C=O + R3NH2 + (EtO)2P(O)H	20 1%	(EtO)2P(O)C(R1R2)NHR3
	Tween-20

R1 = H, R2 = 4-AcC6H4, 3,4-CH2O2C6H3, PhCH=CH, R1+R2 = (CH2)5, R3 = Ph, n-Pr

4, 1

1 1 1 2 (132),

1 1 (133). ' 1 (134)

1 [124].

R	P(O)(OEt)2		H-P(O)(OEt)2
		TsCl	H-P(O)(OEt)2
	N	TsCl
	N
H	R				OEt
				..	OEt
				..
			TsO	P
					OEt
	-		132
	-
	Cl	OTs	R
		OTs			H
					H
	R	+	OEt		+
	R	P		N	+
			OEt	N
			OEt		R
		N	H		R
		N
	H	R		133
	H	R
		134

$ – 1-

-3-1 1 – 2 1 1

1 1 , 1-

1 2 1.

1 1 4,5-12 2 1

1 71-91%. $ -

1 [125].

/ 1 (135), -

1 [126-127]. +

1 (TMG).

1% ( /

NHR2

R1CHO + R2NH2 + (R3O)2PHO

R1CH

, 50-60 ,, 5-6 .

P(O)(OR3)2

135

R1 = 2-HOC6H4, 4-HOC6H4,

N ,

R2 = Ph-CHCOOEt,

S ,

; R3 = Me, Et, Ph

* (137) 1-

(136), 1, 1 1 -

1 1 α-1 -

[128].

	RCHO + (EtO)2PHO +			COOH	30 1% CuI		P(O)(OEt)2
					30 1% CuI		P(O)(OEt)2
			N		30 1% DIPEA		N
							N

			H			R	136
						R

R = Ph, 4-ClC6H4, 4-BrC6H4, 2-MeC6H4, 3-MeC6H4, 4-MeC6H4, 2-NO2C6H4,
		O
		, O	, 130 oC, 20 , , DIPEA - 2 1

4-NC-C6H4CHO + R12PHO + R3NHCH(R2)COOH

30 1% CuI

DIPEA

R3 R2

4-CNC6H4

P(O)R12

137

R1 = OMe, OEt, OPh, Et, Allyl, Ph

4 1 1 1 1 -

1 (138) 1 -

1 .

	COOH RCHO		R2PHO	R2POH	P(O)R2
N		+			N
N	- H2O, - CO2	N	CuI,
H	- H2O, - CO2	N	CuI,
H		-			R
		R
		138

1.1.3.3 1 1 4 4 1 0 4 4 5 3 .

+ 5 ,

α-1

- 1

1 . 4 1,

3 : in situ 1, 3

1 -

3 . - 1 1

2- 1 1

( 2 1, 1 -

1 1 1

, 1 1 1 [129]. '

		3	4
		R	R
		2	N
		R	N
	TFE	R	O
R1R2C=O + R3R4NH + (MeO)3P	TFE		O
			P
	. ., 5 .,	1
		1
		R	OMe
			OMe
82-97%		MeO

R1=H, R2=Ph, 4-ClC6H4, 4-CNC6H4, n-Pr, 2- ; R1=R2=(CH2), (CH2)5; R3=H, 4-ClC6H4, 4-MeOC6H4; R3+R4=Ph; R3+R4=O(CH2CH2)2

+ 1 1

1 1 1 80-85 0, 1 1 1 (83-90%) [130].

Ar1CHO + Ar2NH2 + (RO)3P (RO)2P(O)CH-NHAr2

Ar1

Ar1 = Ph, 4-FC6H4, 4-ClC6H4, 3-NO2C6H4, 4-NO2C6H4;

Ar2 = Ph, 3-NO2C6H4, 4-NO2C6H4; R=Me, Et

) 1 1

1 1 .

	H			..		H
				..
		O	+	H2N		N
						N
				- H2O
				- H2O
							..	OR
							..
							P OR
								OR
	O			-		RO
				-	O
RO	P	OR		OH	O	+	OR
	P	OR			R	P+	OR
				-ROH	R
		NH		-ROH			NH
		NH					NH

* 1 / – 3 [131], -

[132], 1 (H3PW12O4) [133]

				+
	N	N		CF SO-
	R	SO	H	CF SO-
(		3		3	3	) [134]	-

. + 1

1- 1 10-60 1 1

. + 1

– 92-98%. $ 1

1 6 1 . 4 1 1 - 1 /.

	H				H	H+
	H				H
		O +	H2N		N
					N
			- H2O
		H+	- H2O
		H+					OR
						..	OR
						..
						P OR
							OR
	O					H2O
MeO	P	OMe	-		MeO
MeO		OMe	-	O
			OH		+
			OH		+	OMe
		NH	-MeOH	Me	P+	OMe
			-MeOH

						NH
			58

"1 (140), , - 3 - 1 2 (141),

MeCN 1 1 N-

-1 (142) [132].

					OEt
	H			O	P	OEt
							Ar
MeO	O		CF3COOH	MeO			NH
				MeO			NH
		+ ArNH2	+ (EtO)3P MeCN, . ., 1. .
MeO		+ ArNH2	+ (EtO)3P MeCN, . ., 1. .
MeO	CH2COOEt			MeO	CH		COOEt
						2
	141
		OEt		140
		OEt
		O P	OEt
CH3COOH/MeCN MeO			Ar
CH3COOH/MeCN MeO			N
			N
. . .
	MeO		O
			O
		142

+ 1-

1: 1 [135],

[136], , 1 [104].

1 1 [135-136]

1 1 80 0,, 1,

1 1 3 30 5 1 [104]. +

[104] 1 1 2-, -

-, - - . / -

1 1 [104, 135].

-1 1

[137-139] [140]. $1, in situ

1 1 1 2

LiClO4, 1 1 α- 1 1 85-98% [137].

			R1	NHR2
RR1C=O + R2NH2 + P(OR3)3	LiClO4/2			C
	Me	SiCl, . .	R	P(O)(R3 )2

3

4 2 (R)-1-2 1

1 1 (143).

ArC(O)H + Ph Me						Me	NH	P(O)(OMe)	2
ArC(O)H + Ph Me			+ P(OMe)	3	LiClO4/2	Me	NH
				3		C
						C			+
							Ar	H	+
								H
		NH2			Me3SiCl, . .	Ph
		NH2			Me3SiCl, . .	Ph
							(R,S)-143
	Me	NH	P(O)(OMe)2
+		NH
+		C
		C

Ar H

(R,R)-143

+ 1 1

11 (144) 1 1 ; [138].

				LiClO4/2			1						3	NR	2
1	2			LiClO4/2			R			+	2	P(OR )3		NR	2
1	2									+	2
R C(O)H +	R	2NH		. .			H	C		NR2					3	)2
												LiClO , . . .

															P(O)(OR
								144					4	R1 H
														R1 H

R1 = Ph, 2,4-Cl C H , 2-MeOC H , 3-NO C H , 4-ClC H , i-Pr; 2R2													= (CH )	, (CH )
	2	6	3	6	4	2	6	4	6	4			2 4	2 5

4 (145)

1 (146) 3 2 [140].

						Py+HClO -
(EtO)3P + R1R2C=X			(EtO)3P+CR1R2X-			4



				145
				-
	(EtO)	P+CR1R2XH	ClO				(EtO)	P(O)CR1R2XH

				4
	3			4	- CH2=CH2	2
		146			- CH2=CH2
		146
					-HClO4
X = BnN, PhN, i-PrNH

1 (III) 1 1 -

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