Synthesis and thermal stability of S‐trimethylsilyl esters of tetracoordinated phosphorus amidothioacids

Abstract

S-(Diethylamino)dimethylsilyl bis-(diethylamido)dithiophosphate

α‐d‐Glucofuranose and α‐d‐allofuranose diacetonides and silyl ether of α‐d‐glucofuranose diacetonide in dithiophosphorylation reactions

“…We have found that 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide 1d reacts with trimethylsilyl ether of α‐ d ‐glucofuranose diacetonide 9 in benzene at 20°C for 2 hours to give S ‐trimethylsilyl ester of O ‐[1,2:5,6‐di‐ O ‐ iso ‐propylidene‐α‐ d ‐glucofuranose‐1‐yl] 4′‐butoxyphenyldithiophosphonic acid 10 as an oily liquid (Scheme ). In the 31 P‐{ 1 H} NMR spectrum, 10 resonates with a singlet peak at δ = 72.1, essentially identical to those obtained for other S ‐trimethylsilyl ester of dithiophosphonic acids (as a rule in the range of δ = 73–75) . The IR spectrum of 10 exhibits the strong characteristic band at 1256 cm −1 due to the symmetrical deformation vibrations of the CH 3 group, CH 3 (Si).…”

“…It should be noted that we have previously developed convenient methods of synthesizing S ‐trimethylsilyl esters of phosphorus dithioacids on the basis of the reactions of S ‐trimethylsilyl derivatives of alcohols, amines, and thiols with tetraphosphorus decasulfide and 1,3,2,4‐dithiadiphosphetane‐2,4‐disulfides . We have now extended this approach to silyl ether of 1‐ d ‐glucofuranose diacetonide.…”

A Berzelius Reagent, Phosphorus Decasulfide (P4S10), in Organic Syntheses

“…433 Treatment of alkoxy-586 and alkylthiotrimethylsilanes 587 with P 4 S 10 yielded s-trimethylsilyl esters of dithio-and tetrathiophosphoric acids 588 and 589, respectively, along with bis(trimethylsilyl)sulfide 590 (Scheme 148). [437][438][439][440] A similar reaction of organogermanium 591, 441,442 organothiarsenic 592, 442,443 and organoborates 593 444,445 with P 4 S 10 produced the esters 594, 595, and 596, respectively (Scheme 149). Reaction of benzyl chloride with P 4 S 10 in the presence of K 2 CO 3 in acetonitrile (dry) at 60-70 °C for 2 h gave tribenzyltetrathiophosphate (PhCH 2 S) 3 PdS.…”

“…Treatment of alkoxy - 586 and alkylthiotrimethylsilanes 587 with P 4 S 10 yielded s -trimethylsilyl esters of dithio- and tetrathiophosphoric acids 588 and 589 , respectively, along with bis(trimethylsilyl)sulfide 590 (Scheme ). − …”