THE UNUSUAL OXIDATION OF A 1,5,2,4-DIAZADIPHOSPHORINAN-6-ONE WITH TETRACHLORO-ORTHO-BENZOQUINONE

被引:40
作者
SHEVCHENKO, IV [1 ]
FISCHER, A [1 ]
JONES, PG [1 ]
SCHMUTZLER, R [1 ]
机构
[1] TECH UNIV CAROLO WILHELMINA BRAUNSCHWEIG,INST ANORGAN & ANALYT CHEM,HAGENRING 30,W-3300 BRAUNSCHWEIG,GERMANY
来源
CHEMISCHE BERICHTE-RECUEIL | 1992年 / 125卷 / 06期
关键词
1,5,2,4-DIAZADIPHOSPHORINAN-6-ONE; TETRACHLORO-ORTHO-BENZOQUINONE; OXIDATION; SPIROPHOSPHORANE; SPIROPHOSPHORATE;
D O I
10.1002/cber.19921250605
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The oxidation of 2,4-bis(diethylamino)-1,5-dimethyl-1,5,2,4-diazadiphosphorinan-6-one (1b) with two equivalents of tetrachloro-ortho-benzoquinone (TOB) (2) leads to the cleavage of the original heterocycle and to the formation of a mixture of compounds, including the 1,3,2-diazaphosphetidine 6 (''lambda-6P-'') and the spirophosphorane 7. Compound 7 exists as two isomers that undergo slow spontaneous transformation in solution to compound 9, containing a six-coordinate phosphorus atom. When the oxidation of 1 b is carried out in two stages, with the second equivalent of TOB being added after an interval of four days, the cleavage of the original molecule does not occur, and compound 17, containing a seven-membered ring with two phosphorus atoms of opposite formal charge and different coordination number (''lambda-4P+, lambda-6P-'') is formed. The structures of 6, 7, 9, and 17 were established by low-temperature X-ray analysis. Compound 6 displays crystallographic twofold symmetry; the coordination at phosphorus is octahedral, but distorted by the phosphetidine ring. The phosphorus atom in 7 possesses square pyramidal coordination geometry, the pyramid base being defined by the four oxygen atoms. Compound 9 (''lambda-6P-'') crystallized with two molecules of CDCl3. Compound 17 crystallized as a dichloromethane solvate. Distorted octahedral and tetrahedral geometries were observed for P1 and P2, respectively. The four-membered ring is planar. The bridging hydroquinone ligand displays much wider O-C-C(-O) and C-O-P angles than the chelating hydroquinone.
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页码:1325 / 1332
页数:8
相关论文
共 22 条
[1]   TRIETHYLAMMONIUM "TRIS(ORTHO-PHENYLENEDIOXY)PHOSPHATE - CRYSTAL AND MOLECULAR-STRUCTURE [J].
ALLCOCK, HR ;
BISSELL, EC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (10) :3154-3157
[2]   CRYSTAL AND MOLECULAR-STRUCTURE OF SPIROPHOSPHORANE (C6H4O2)2PC6H51 [J].
BROWN, RK ;
HOLMES, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (10) :3326-3331
[3]   HEXACOORDINATE PHOSPHORUS .1. PREPARATION AND PROPERTIES OF NEUTRAL CARBAMATES AND THIOCARBAMATES OF PENTAVALENT PHOSPHORUS AND THE CRYSTAL AND MOLECULAR-STRUCTURE OF (N,N-DIMETHYLCARBAMATO)METHYLTRIS(TRIFLUOROMETHYL)PHOSPHORANE [J].
CAVELL, RG ;
THE, KI ;
GRIEND, LV .
INORGANIC CHEMISTRY, 1981, 20 (11) :3813-3818
[4]   NEUTRAL 6-COORDINATE FLUORO-PHOSPHORUS COMPOUNDS [J].
CAVELL, RG ;
VANDEGRIEND, L .
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 1983, 18 (1-3) :89-92
[5]   DERIVATIVES OF O-PHENYLENEPHOSPHATE .15. SYNTHESIS OF TRIS-(O-PHENYLENEDIOXY)-PHOSPHORATE(V) [J].
GLOEDE, J ;
GROSS, H ;
ENGELHARDT, G .
JOURNAL FUR PRAKTISCHE CHEMIE, 1977, 319 (02) :188-194
[6]   CRYSTAL-STRUCTURES OF 2 FLUORODIAZADIPHOSPHETIDINES [J].
JONES, PG ;
SCHMUTZLER, R .
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 1991, 56 (1-4) :173-177
[7]  
KALCHENKO VI, 1984, ZH OBSHCH KHIM+, V54, P2207
[8]  
KALCHENKO VI, 1983, ZH OBSHCH KHIM+, V53, P932
[9]   ADDITION OF SILYLAMINES + SILAZANES TO ISOCYANATES [J].
KLEBE, JF ;
BUSH, JB ;
LYONS, JE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (20) :4400-&
[10]  
KONIG M, 1976, J CHEM SOC P2, P955