Реакции N-алкил(арил)альд- и кетиминов с эфирами кислот фосфора. Монография
.pdf. ! (Hal=Cl, Br, I)
1 2-5 – 6785%, – 3 1 98% [105]. ' 1
: Bi(III) , 1 (III)
, in situ 1. ( 1 1 (III) 1 . 4 1
1 . " 1
1 (III) [141].
+ α-1
. 4 1
96.2 80%, 1 – 57 95%
2 2,
[106]. 20 0,. 0-1 2 1 1
1-
1 (15 1, 94%). 4
( , 1, 2, 1,
, ) 1 (20-68%) [142]. / 1 1
. +
– 82-96%. 4, /
1 1, 3 in situ. [143]
0 1 2
1 1 (1 – 5-9 1, 85-95%),
61-77%
60 1 [144].
" 1 1, 2 1,
1 1 1
, 1 2.
1 1, ,
96% [145]
61
20 1% .
R1R2C=O + R3NH2 + (EtO)3P 
R1R2C(NHR3)P(O)(OEt)2
1.1.
R1=H, R2=Ph, 4-MeC6H4, 4-MeOC6H4, Furyl, PhCH=CH, Het, i-Pr, PhCO; R1+R2 = (CH2)5; R3=Ph, 4-NO2C6H4, 4-NH2C6H4, 3-FC6H4, 4-MeOC6H4
4 1 , 1 -
, 2 .
+ 3
- 1 1
[146-148]. ' N,N,N´,N´-1-
HO3S |
+ |
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NMe2 |
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N,N´-(3- )2 11-1,2 ( |
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SO3H |
2HSO4 |
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NMe |
2 |
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2 1 1 1
1 1 1 -
. + 83-96%. 4 1, -
1 1 1
[146-148].
+ -
– -n- -
11 (R3N+(CH2)mSO3H HSO4-, R=Me, Et, n-Bu; m=3, 4).
3 1 1 10-60 1 1 1 [147]. 1 1 -
.
( 1
– 1 1,3- –
, 1
1 1 [148] , 1, ,
3 α-1 1 1 -
1 1, 3 1 in situ [149-151].
62
ArCH=NMe + R1COCl 
ArCH=N+(Me)COR1 Cl- 
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H |
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) |
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O |
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( |
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P |
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)2 |
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O |
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t |
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E |
P(O |
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( |
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Si |
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M |
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e |
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3 ) |
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3 |
ArCHP(O)(OEt)2
N(Me)COR1
ArCHP(O)(OSiMe3)2
N(Me)COR1
PhCH=NPh + MeCOCl 
PhCH=N+(Ph)COMe Cl-
(EtO)
2
P(O)H
PhCHP(O)(OEt)2
N(Ph)COMe
R1 |
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1 |
H |
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R |
+ |
- (RO)3P |
N + |
HCl |
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N |
Cl |
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R2 |
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2 |
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R |
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147 |
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Cl- |
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(RO)2P(O)CHR1NHR2 |
R O |
P(OR)2 |
-RCl |
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CHR1-NHR2 |
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/ , -10°,
1 (147), 1
[151].
+ [152] ,
1 1 1
(148), 1. $ 1 1 1 (149) 1
1.
63
N
+ |
RN=C=X + |
(PhO)
2
P(O)H
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(PhO)2P(O)H |
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N+ |
X |
N+ |
X (PhO)2PO- |
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-NR |
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NHR |
148 |
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149 |
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X
N
NHR
P(O)(OPh)2
+ 1 1 1
α-1 1
1 3
Schwartz (Cp2ZrHCl). " -1
1 [153].
1.2-2.0 2. .
R1CONR2R3 + R2PHO (0, 600,, 12 . R2P(O)CHR1NR2R3
R1, R2, R3 = Ar, alkyl, H; R=Ar, RO; 65-98%
" 1 1
(150).
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Cl- |
2 |
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Cp2ZrHCl |
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H |
R |
R2PHO |
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R1CONR2R3 |
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1 2 3 |
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1 |
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N |
3 |
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R2P(O)CHR NR R |
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-HCl |
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R |
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R |
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150 |
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4 O,N- (151) SOCl2 -
1 (152), 0 , [154].
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SOCl |
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R1(R2O)P(O)H |
(EtO) |
P(O)CH(OMe)NMe |
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2 |
(EtO) |
P(O)CH=N+Me |
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Cl- |
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2 |
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151 |
152 |
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(EtO)2P(O)CH(NMe2)P(O)(OR2)R1 |
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-HCl |
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R1 = Me, R2 = Bu; R1 = Ph; R2 =Et, Bu |
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1.1.4 1 1 0- 1 4 4-
5 1 1.
$ (153-155)
1
[155-156].
(RO)2P(S)SH |
(RO)2P(S)OH |
(RO)2P(O)OH |
153 |
154 |
155 |
, (154) (155) -
1 1 1 1. * 1 1
, 3 2
N- - 1 1 [157]. * 1 1
1 1
1 (156).
Ar1N=CHAr2 + (R3O)2P(O)OH |
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Ar1N+H=CHAr2 (R3O)2P(O)O- |
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156 |
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' 2 1 ,
α-1 (157).
Ar1N=CHAr2 + (EtO)2P(O)OH
(EtO)2P(O)OCH(NHAr1)Ar2
157
65
(154) 1 1 1 1
1 2 (158). * 1 1 (159) 1 1 $, ; [155].
R1C=NH + (R3O)2P(S)OH |
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R1C=N+H3(R3O)2P(S)O- |
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OR2 |
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OR2 |
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154 |
159 |
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' R1R2P(S)SH
– 2 ,
P(S)S [156]. 4 2 1
1
1 1, ,
1 1 [1-2, 155-156, 158].
4 1
1-1 , 1
- , *,*- (153),
- (161) 1 – N-1 (160) [159].
(R1O)2P(S)SH + R2C6H4CH=NC6H4R3 
R2C6H4CH-SP(S)(OR1)2
153 |
160 |
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NHC6H4R3 |
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161 |
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*, 2 1 - 1 1 ,
- 1
1 1 (162) [160]. 4
1 1 1 3
(163). 4 (163)
1 1 [160].
66
(R1O)2P(S)SH + PhCH=NR2 
PhCH=N+HR2 -S(S)P(OR1)2 
PhCH-SP(S)(OR1)2
162 |
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NHR2 |
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163
/ , , 1 1 1 1 2 1 ,
2 1 1 1 (164),
1 3
C=N [3].
(RO)2P(S)SH + CCl3CH=NX |
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CCl3 |
CH-SP(S)(OR)2 |
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164 |
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NHX |
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165 |
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165, X=Ac, Ar; R=Et, i-Pr |
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( 1 1, 1 0 , 1-
1 1 -
:
, –
2 1 - 1 1: 1
N (III) 1 ,
1 – C=N. $ 1 -
(153) 1 ,
1 1 1,
1 1 – 1,
1, 1 , 1 1 [158].
(RO)2P(S)SH + HCHO + XYNH 
(RO)2P(S)SCH2NXY
X=H, Y=Ph, MeCO, HCO, H2NCO, H2NCS; X=Y=Et; X=Me, Y=MeNHCH2CH2
67
1.2 / 4 4 0 0 1 ! 1 N-5 1 1
2-0 1 1
1 1. $ 1-
3 1970 . $1
, 1 [161]
, [162]. + 1 2-1
1 , 1 -
1 1
. $
1 , 1
3 2-1.
4 , 2 1 3 1
, 1, , , -
, -, - . $ 1 3
1 . * 1 1,
2 1 1 3 -
3 1,
1 1 3.
1 3 ,
,-, . - , ,
1 1 2,
1, -
-2 1, 1 1 (1 3 Mg- ) ,
1 1 1 -
.
2-0 1 2 1 1 1 (COOR, COR, SO2NMe2, SO2F, COCCl3) 1
, 1, 1, 1 . 4
2-1 1 ( 1 3 LiAlH4 NaBH4) 1 -
1 3 1 1 , ,
, 1
. -3 2- -
1 1 ,
2 1, 2,3- 1. ),
68
1 3 1 2-1
, 1 1 3:
, -
1, 3- -
[3,3]-1 .
8 , -
1 2-1 1. $
. !3 1966 -
, 2 1, N-
1 3 1 1 1 1 -
1 [163].
CCl3 |
NH |
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NP(O)(OEt)2 |
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NR2 + (EtO)3P |
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Cl CH |
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NR |
+ EtCl |
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2 |
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+ 1 ( 1)1 - 1 1 3 1 1 1,
[164].
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OH.. |
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O |
N |
OH |
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N |
N |
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+ Ph3P |
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PPh3 |
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P+Ph Cl- - HCl |
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Ar |
Cl |
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Ar |
3 |
Ar |
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N- 1 1- 1 1 1 [165-166].
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NCOPh |
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(MeO)3P |
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P(O)(OMe)2 |
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CCl3 H |
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- MeCl Cl2C NHCOPh |
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+ 3-
1 2 1
69
. * 1
1 3 1 1 [167].
Cl |
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R |
.. |
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R |
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+ PPh3 |
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+ Ph P+Cl |
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Ph |
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N- |
Ph |
3 |
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N |
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- HCl |
R
Ph + Ph3P=O
NH
2-"-1,3 1,3-
1 (III). + 1 [168] 1
1 1 1 1 1 , 1
1 ,
3 1.
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N |
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C(CF3)2 |
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R |
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N(R1)CH(CF ) |
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3 2 |
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R |
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+ (R1O) P |
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(R1O) P(O) |
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R=Ph |
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PPh3 |
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R=Et, Ph |
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Ph3P |
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Ph |
N CH(CF3)2 |
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N |
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Ar |
P(OR)3 |
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Ph |
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N |
Ph |
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CF3 |
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Ar |
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R= Me, Et |
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CF3 |
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OR |
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C |
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CF3 |
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CF |
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RO |
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OR |
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3 |
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( 1 1, 1 1 2-
1 1, 1 1 -
1 , 1
.
70