Arsine sulphides

Reductive alkylation of esters of thioarsinic acids and arsine sulphides... 

In the later work, (S)-(—)-allylmethylphenylarsine, (S)-(—)-122, was obtained by reduction of the corresponding arsine sulphide (R)-( + )-121 with allyllithium which, in turn, had been obtained from (R)-( —)-114 with the same reagent (equation 17) . By chemical correlation and the aid of ORD spectroscopy, the configurations at arsenic in the enantiomers of the arsine 122 and its sulphide were determined, as indicated in Scheme 11. 

The optically active arsinous acid esters 128-134 and the arsinthious acid ester 135 have been used to prepare optically active tertiary arsines (Table 7). When the arsine sulphide 136 was heated in benzene with n-butyl or -propyl bromide, ethyl bromide was eliminated and there was a reversal in the sign of the rotation, which was attributed to the formation of the inverted n-butyl and n-propyl esters of (p-carboxyphenyl)phenyl-arsinthious acid, 137a and 137b, respectively (equation 18) . 

Under anhydrous conditions, however, optically active tertiary arsine oxides can be prepared from optically active tertiary arsines and dinitrogen tetraoxide. Thus, (-f- )-(p-carboxyphenyl)ethylphenylarsine [(-l-)-36] reacts with N2O4 in nitromethane to give a solution of (-I-)-(p-carboxyphenyl)ethylphenyIarsine oxide [(-l-)-147], which lost its optical activity over 1.5 h. The optically active arsine oxides 145,146,153 were similarly generated in solution (Table 8), but only racemates or racemic hydrochlorides were isolated . The oxides can also be prepared from the corresponding arsine sulphides... 

The tetrahedral stereoehemistry of a tertiary arsine sulphide was first established in 1925, when p-earboxyphenylethylmethylarsine sulphide (7) was resolved. Unlike hygroscopic tertiary arsine oxides, arsine sulphides are air-stable non-basic eompounds with... 

The first synthesis of an optically active tertiary arsine sulphide from an optically active tertiary arsine was reported in 1962 , compounds 157 and 158 being prepared by heating the respective optically active tertiary arsines with sulphur in benzene. Along similar lines, arsine sulphides 136,159-164 were prepared and isolated (Table 8). The sulphurization of the tertiary arsines occurs with retention of configuration at arsenic. 

The optically active arsine sulphides 115, 119 and 121 (Table 8) were prepared by reactions between appropriate menthyl esters of thioarsinic acids and Grignard or alkyllithium reagents, which proceed with inversion of configuration at the arsenic(V) stereocentre. 

The pyrolysis of arsine sulphides (R3As=S) is similar to that of the oxide analogues inasmuch as only low yields of arsinous thioesters are obtained, i.e. it is not a synthetically significant reaction. 

D. Stereoselective Syntheses via Arsenic(V) Acids and Esters and Arsine Sulphides... 

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