Dithiophosphoric Acids and Tetraphosphorus Decasulfide in the Synthesis of Boron Dithiophosphates

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

“…A similar reaction of organogermanium 591 , , organothiarsenic 592 , , and organoborates 593 , with P 4 S 10 produced the esters 594 , 595 , and 596 , respectively (Scheme ).…”

“…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.…”

New methods of synthesis of boron, germanium, and tin derivatives of pentavalent phosphorus thioacids

“…Thus, trialkyl borates do not appear to react with dithiophosphoric acids in the absence of any additives [1]. We have recently established that tri-isobutyl borate reacts with O,Odialkyldithiophosphoric acids under the influence of low frequency ultrasonic irradiation (22 kHz, power 130 W) at • C for 0.5 h to give S-(O,O -diisobutyl)boron O,O -dialkyldithiophosphates with the elimination of isobutyl alcohol [29]. In this connection, we expected to observe the same low reactivity of trialkyl borates in the substitution reactions with S-trimethylsilyl esters of pentavalent phosphorus thioacids.…”

“…They are nonvolatile even under reduced pressure, and stable at room temperature. The thermal stabilities of boron trithiophosphonates (3a,b) are lower than those of the boron aryldithiophosphonates previously obtained by the treatment of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides with alkyl borates [44] or boron dithiophosphates [28,29]. Compound 3a was isolated by column chromatography, whereas substance 3b tended to decompose partially when falling-film distillations were used in attempted purification.…”

“…We have recently developed convenient methods for the synthesis of S-(O,O -dialkyl)boron O,O -dialkyldithiophosphates and -aryldithiophosphonates by the reactions of tetraphosphorus decasulfide and 1,3,2,4-dithiadiphosphetane-2,4-disulfides with alkyl borates, O,O -dialkyl dithiophosphoric acids with trialkyl borates promoted by ultrasonic irradiation, and ammonium O,O -dialkyldithiophosphates with fluorodialkyl borates [27][28][29][30], which were summarized in a review [31]. S-Triphenyl or trialkylgermyl esters of dialkyl dithiophosphoric and tetrathiophosphoric acids, and 4-methoxyphenyldithiophosphonic and -trithiophosphonic acids were easily obtained by the reactions of tetraphosphorus decasulfide and Lawesson's reagent with triphenyl and trialkyl (alkoxy)germanes, and with -(alkylthio)germanes [32][33][34].…”