ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
On Organophosphorus Compounds, XVIII: Bifunctional Dithiophosphinic Acids HS(S)P(R)—R′—P(R)(S)SH and Some of Their DerivativesBifunctional dithiophosphinic acids are easily obtained by nucleophilic fission of perthiophosphonic anhydrides (RPS2)2 with di-Grignard reagents XMgR′MgX. By this method numercus compounds of the type XS(S)P(R)—R′—P(R)(S)SX (X = H, Na, NH4, (CH3)3NH; R = CH3, C6H5, 4-CH3OC6H4; R′ = 1,4′C6H4, [CH2]n with n = 4-10) were prepared. These could be easily converted into the corresponding esters, amides, and -chlorides as is shown by some examples. Oxidation of H4NS(S)P(R)—R′—P(R)(S)SNH4 (R = 4-CH3OC6H4; R′ = [CH2]6) with I2, CU2+, or Tl3+ gave a mixture of oligomeric disulfanes (—(S)P(R)—R′—P(R)(S)—S—S—)n (n = approx. 2-4), hydrolysis of the methyl ester CH3S(S)P(R)—R′—P(R)(S)SCH3 (R = 4-CH3OC6H4; R′ = 1,4-C6H4) gave the bifunctional monothiophosphinic acid HO(S)P(R)—R′—P(R)(S)OH.
Notes:
Durch nucleophile Spaltung von Perthiophosphonsäureanhydriden (RPS2)2 mit Di-Grignard-reagentien XMgR′MgX können bequem bifunktionelle Dithiophosphinsäuren XS(S)P(R)—R′—P(R)(S)SX (X = H, Na, NH4, (CH3)3NH; R = CH3, C6H5, 4-CH3OC6H4; R′ = 1,4-C6H4, [CH2]n mit n = 4-10) erhalten werden. Diese können leicht in die entsprechenden Ester, Säureamide und -chloride übergeführt werden, wie an einigen Beispielen gezeigt wird. Bei der Oxidation von H4NS(S)P(R)—R′—P(R)(S)SNH4 (R = 4-CH3OC6H4; R′ = [CH2]6) mit Iod, Cu2+ oder Tl3+ entstand ein Gemisch oligometer Disulfane [—(S)P(R)—R′—P(R)(S)—S—S—]n (n = ca. 2-4), bei der Hydrolyse des Methylesters CH3S(S)P(R)—R′—P(R)(S)SCH3 (R = 4-CH3OC6H4; R = 1,4-C6H4) die bifunktionelle Monothiophosphinsäure HO(S)P(R)—R′—P(R)(S)OH.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19781110222
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