Über Reaktionen des P₄S₁₀ mit siliciumorganischen Verbindungen

Abstract

P4S10 (1) kann mit Silicium–Stickstoffverbindungen abgebaut werden. 1 reagiert mit (CH3)3Si–N(CH3)2 (2a) bzw. (CH3)3Si–N(C2H5)2 (2 b) zu S = P[N(CH3)2]2SSi(CH3)3 (3a) bzw. 3b. Die Umsetzung von 1 mit [(CH3)3Si]2S (4) ergibt in hoher Ausbeute SP[SSi(CH3)3]3 (6). Um den Reaktionsverlauf aufklären zu können, wurde (C6H5PS2)2 (7) als Modellsubstanz mit 2a bzw. 4 umgesetzt, wobei C6H5P(S)[N(CH3)2]SSi(CH3)3 (9) bzw. C6H5P(S)[SSi(CH3)3]2 (10) entstehen, Der Reaktionsmechanismus wird diskutiert. Die Kernresonanzdaten und Massenspektren werden mitgeteilt.

Reactions of dithioxo‐1,3,2λ 5 ,4λ 5 ‐dithiadiphosphetanes with arsenic derivatives containing the As‐O, As‐S, and As‐N bonds

“…The 31 P NMR spectrum of 7 in benzene solution shows a singlet at d ‫ס‬ 69.0 (Table 2). The 31 P NMR spectrum of the corresponding PhP(S)(SSiMe 3 ) 2 is reported to resonate in practically the same region (d ‫ס‬ 62.0-63.1) [11,12]. In the 1 H NMR spectrum of 7 in a C 6 D 6 solution, the CH 3 O protons appear as a singlet at d ‫ס‬ 3.31.…”

“…It is noteworthy that the reactivity of thiobisarsines like 6 is higher than that of the corresponding silicon derivatives, such as bis(trimethylsilyl)sulfide, toward 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides [11]. The 31 P NMR spectrum of 7 in benzene solution shows a singlet at d ‫ס‬ 69.0 (Table 2).…”

“…In a continuation of the comparison of the chemical behavior of silicon and arsenic derivatives containing reactive E-X bonds (E ‫ס‬ Si, As; X ‫ס‬ O, S, N) toward 1,3,2,4-dithiadiphosphetane-2,4-disulfides, we have tried to extend these reactions to compounds that have an As-N bond. S-Trimethylsilyl phenyl-N,N-dimethylamidodithiophosphonate was previously obtained by the reaction of 2,4-diphenyl-1,3,2,4-dithiadiphosphetane-2,4-disulfide with trimethyl(dimethylamino)silane in refluxing methylene chloride [11]. The formation of products of similar structure could be expected by use of aminoarsines.…”

Disilyl dithiophosphonates in the synthesis of open chain and cyclic organothiophosphorus compounds

“…Common methods of synthesizing tris(trimethylsilyl) tetrathiophosphate and bis(trimethylsilyl) phenyltrithiophosphonate containing three or two S SiMe 3 fragments were usually based on the reactions of bis (trimethylsilyl)sulfide with tetraphosphorus decasulfide and 2,4-diphenyl-1,3,2,4-dithiadiphosphetane-2,4-disulfide or addition of sulfur to disilyl or trisilyl phosphines [1,2]. In this article, a method is presented for synthesizing new O-trimethylsiloxyorganyl S-trimethylsilyl aryldithiophosphonates on the basis of the reactions of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides with disilyl derivatives of diols.…”

“…The chemistry of derivatives of tetracoordinated phosphorus thioacids containing a few trimethylsilyl groups have recently been developed [1][2][3][4][5][6][7]. Common methods of synthesizing tris(trimethylsilyl) tetrathiophosphate and bis(trimethylsilyl) phenyltrithiophosphonate containing three or two S SiMe 3 fragments were usually based on the reactions of bis (trimethylsilyl)sulfide with tetraphosphorus decasulfide and 2,4-diphenyl-1,3,2,4-dithiadiphosphetane-2,4-disulfide or addition of sulfur to disilyl or trisilyl phosphines [1,2].…”