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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >SYNTHESIS OF TRICYCLIC (LAMBDA(5))-PHOSPHORANES - UNUSUAL N-DEMETHYLATION/N-ALKYLATION REACTIONS DURING THE OXIDATIVE ADDITION OF HEXAFLUOROACETONE AND TETRACHLORO-ORTHO-BENZOQUINONE TO BENZODIAZA-LAMBDA(3)-PHOSPHORINONES - SINGLE CRYSTAL X-RAY DIFFR
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SYNTHESIS OF TRICYCLIC (LAMBDA(5))-PHOSPHORANES - UNUSUAL N-DEMETHYLATION/N-ALKYLATION REACTIONS DURING THE OXIDATIVE ADDITION OF HEXAFLUOROACETONE AND TETRACHLORO-ORTHO-BENZOQUINONE TO BENZODIAZA-LAMBDA(3)-PHOSPHORINONES - SINGLE CRYSTAL X-RAY DIFFR

机译：三环（LAMBDA（5））-磷烷的合成 - 六氟丙酮和四氯邻苯醌氧化加成苯并二氮杂-Λ（3）-磷酸醌过程中不寻常的N-去甲基化/N-烷基化反应 - 单晶X射线衍射

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The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N'-methylanthranilamide derivatives 2-4. Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1H)-1,3,2-benzodiazaphosphorin-4-o nes 5-7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1H)-1,3,2-benzod iazaphosphorin-4-ones 8-10 and 12. With 2-chloroethylammonium chloride/triethylamine the P-NHCH2CH2Cl-substituted compound 11 was obtained from the (PCl)-Cl-III-species 6. The reaction of 8-10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH2CH2Cl groups was found to alkylate the CH3N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13-16. The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a lambda 5-ox-azaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18-20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16, and for the precursor compound 9. The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14: the (lambda(5))-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the lambda(3)P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms. References: 25
机译：甲基靛红酸酐1与苄胺反应生成N-苄基-N'-甲基邻氨基酰胺衍生物2-4。它们与三氯化磷反应生成了2-氯-1-卤苄基/苄基-3-甲基-4（1H）-1,3,2-苯并二氮杂磷杂-4-酮5-7，在与双（2-氯乙基）氯化铵/三乙胺反应后，转化为对双-（2-氯乙基）氨基-1-卤苄基/苄基-3-甲基-4（1H）-1,3,2-苯并氮杂磷杂环己烷-4-酮8-10和12。用2-氯乙基氯化铵/三乙胺从（PCl）-Cl-III物种6中得到P-NHCH2CH2Cl取代的化合物11。8-10 和 12 与六氟丙酮 （HFA） 的反应采取了不寻常的过程：除了 HFA 的氧化加成和全氟频哪酰基环系统的形成外，发现两个 CH2CH2Cl 基团中的一个烷基化 CH3N 原子，并在三环磷烷 13-16 中形成五元（二氮杂磷烷）环。11与HFA的反应也产生了螺磷烷17，其涉及λ 5-氧杂磷杂磷皮苷环体系。在8、10和12与四氯邻苯醌的反应中，发现发生了伴随N-烷基化并形成三环磷烷18-20的氧化加成反应。描述了磷烷 13、14 和 16 以及前体化合物 9 的单晶 X 射线结构测定。同工结构化合物 13 和 16 以及乙醚半硅酸盐 14 具有以下共同特征：（lambda（5））-螺磷原子位于其共同的环的其他原子的平面之外，并且二氧磷环表现出扭曲构象。在 lambda（3）P-化合物 9 中，磷原子也位于其他环原子的平面之外。[参考文献： 25]

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