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

“…Over the past few years, we have been involved in the development of alternate methods of synthesizing boron, germanium, and tin derivatives 27 of pentavalent phosphorus thioacids. 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].…”

“…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].…”

Borylation of calix[4]resorcinols under ultrasonic irradiation

“…In order to increase the reactivity of borates in these reactions we exerted ourselves to search for initiators of these transformations. We have previously shown that the reaction of thiophosphorylation of trialkyl borates under ultrasonic irradiation occurs considerably faster, at lower temperatures and with higher yield [29,30]. Now we prepared tetraalkoxyborato-cavitands IIIa and IIIb by irradiation with ultrasound (22 kHz, power 400 W) a mixture of octahydroxytetraoctyl[l 4 ]metacyclophane I with trialkylborates IIa or IIb, respectively, in toluene (100°C, 45 min).…”

“…Compound IIIa is characterized by the presence in the IR spectrum of two absorption bands of moderate intensity in the region of ν 1350 and 1381 cm -1 of symmetric bending δ-vibration of the geminal methyl groups (CH 3 ) 2 C in the isobutoxy substituents, as in [31]. Boron atoms of the cavitands III appear as a narrow singlet signal in the 11 B NMR spectrum at δ B 18 ppm, which corresponds to compounds with tricoordinated boron atoms [32][33][34]. In the 1 H NMR spectrum of the borate IIIa the methine proton of the CH 2 CHAr fragment gives two triplets with chemical shift δ 4.13 ppm ( 3 J HH 6.7 Hz).…”

“…Previously, we used cyclic hydroxylboranes as borylating agents at the S-H group of phosphorus thioacids [34]. Now we explored the phosphorylating ability of hydroxyborinanes in the reactions with calixarenes.…”