Oxygen Chemistry of the (CF3)2P Group: the Diphosphoxane; the Phosphinous Acid, Esters and Related Phosphine Oxides; Phosphinyl Halides and Infrared Spectra
Oxygen Chemistry of the (CF3)2P Group: the Diphosphoxane; the Phosphinous Acid, Esters and Related Phosphine Oxides; Phosphinyl Halides and Infrared Spectra
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(CF3)2P 基团的氧化学：二磷氧烷；
DOI：
10.1021/ja00877a005
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发表时间：
1962
影响因子：
15
通讯作者：
A. Burg
中科院分区：
文献类型：
--
作者：
J. E. Griffiths;A. Burg
二磷氧烷（CF 3）2 POP（CF 3）2（mp-53; bp est. 78），由（CF 3）2 PI和Ag 2CO 3制成，在250 ℃下稳定，表现为弱刘易斯酸而不是碱;但HC 1很容易将其转化为（CF 3）2 PC 1和H键相关的质子酸（CF 3）2 POH（mp-21; bp est. 61）。它不会重排成（CF 3）2 HPO;事实上，这种由（CF 3）2 PH和HgO制成的氧化膦会变成（CF 3）2 POH、（CF 3）2 PH和（CF 3）2 POOH。然而，由P2（CF 3）4的ROH裂解制得的亚膦酸酯（CF 3）2-POR可通过CH 3 I催化重排为R（CF 3）2 PO-当R为叔丁基时非常容易，但当R为甲基时困难。类似的Arbuzov型重排反应可以解释为什么（CH 3）2 POP（CF 3）2不能由（CH 3）ZPH和（CF 3）2 POP（CF 3）2合成，而是得到（CF 3）2 PH、P2（CF 3）4、（CH 3）2 PP（CF 3）2和似乎是（CH 3）4P 2 O2（mp 132;真空升华）;该反应的某些阶段被证明。所有这些（CF 3）2 PO化合物的红外光谱进行了比较，确认归属。在此关系中，（CF，）2 POCl（bp est. 52)和（CF 3）2POBr（mp-35; bp est. 78)烃-磷-氧类型的化合物R2 POH和R2 POPR 2一直缺乏，显然是因为它们会以Arbuzov方式重排成R2 Ph和R2 PPr n，其中任何一个都会很快不成比例。但当R是碳氟化合物基团时，R2 POH和R2-POPR 2是永久稳定的2;事实上，（CF 3）2-HPO实际上转化为（CF 3）2 POH。3在这里，
The diphosphoxane (CF3) 2POP (CF3) 2 (mp—53; bp est. 78), made from (CF3) 2PI with Ag2C03 and stable up to 250, behaves as a weak Lewis acid rather than a base; yet HC1 easily converts it to (CF3) 2PC1 and the H-bond associated protic acid (CF3) 2POH (mp—21; bp est. 61). This doesnot rearrange to (CF3) 2HPO; indeed this phosphine oxide, made from (CF3) 2PH and HgO, changes to (CF3) 2POH,(CF3) 2PH and (CF3) 2POOH. However, the phosphinousesters (CF3) 2-POR, made by ROH-cleavage of P2 (CF3) 4, can be rearranged to R (CF3) 2PO by CH3I catalysis—very easily when R is/-butyl but with difficulty when R is methyl. A similar Arbuzov-type rearrangement would explainwhy (CH3) 2POP (CF3) 2 could notbe made from (CH3) ZPH and (CF3) 2POP (CF3) 2, which gave instead (CF3) 2PH, P2 (CF3) 4,(CH3) 2PP (CF,) 2 and what seemed to be (CH3) 4P202 (mp 132; vacuum-sublimable); some stages of this reaction were demonstrated. The infrared spectra of all of these (CF3) 2PO compounds were compared for confirmation of assignments. In this relation (CF,) 2POCl (bp est. 52) and (CF3) 2POBr (mp—35; bp est. 78) were made by different methods and used for a spectroscopic recheck of the electronegativity of the CF3 group.Compounds of the hydrocarbon-phosphorus-oxygen types R2POH and R2POPR2 have been lacking, evidently because they would rearrange in the Arbuzov manner to R2Ph and R2PPr „either of which would disproportionate very soon. But when R is a fluorocarbon group, R2POH and R2-POPR2 are permanently stable2; indeed,(CF3) 2-HPO actually converts to (CF3) 2POH. 3 Here it