Haloarsines

Secondary aisines, which can be synthesized by methods analogous to those used for piimaiy arsines, are obtained in good yields by the reduction of arsinic acids (44) or haloarsines (45) with amalgamated zinc and hydrochloric acid. They can also be prepared by the alkylation of primary arsenides (46) ... 

Other methods for preparing tertiary arsiaes have been employed, but they have limited usefiilness. These methods include the cleavage of quaternary arsonium compounds (68), the cyclodehydrohalogenation of haloarsines (69), the reaction of dia2onium salts with arsenic trichloride in the presence of a metal such as 2inc or iron (70), and the disproportionation of halo- or dihaloarsines (71). 

Haber process, 116 Hafnium complexes alkyl alkoxy reactions, 358 phthalocyanines, 865 porphyrins, 823 pseudohalides, 228 Hafnium(IV) complexes cupferron, 512 Haloarsine compounds, 1004 Halogen complexes, 675-687 bridge systems, 677-684 asymmetry, 678 theoretical studies, 682 double bridged, 681... 

Caution. This preparation should be performed in a good hood. Contact of all solutions with the skin should be avoided not only because haloarsines have a vesicant action but also because many organoarsenicals can produce allergic contact eczema if contact is frequent. 

Dinnclear arsines containing a bridging methylene nnit, R2 AsCH2 AsR2, have been prepared from the parent haloarsine nsing RLi. With PhC CLi, cleavage of the ASCH2AS backbone occnrs and As(C=CPh)3 is isolated. 

The haloarsines are most commonly prepared from the reduction of the arsonic or arsinic acids by sulfur dioxide... 

R As(NR2)3- , are routinely synthesized by the aminoly-sis of a haloarsine or transamination of another aminoarsine (eqnations 64-68). 

The direct reaction between a tertiary phosphine and a haloarsine yields an arsinophosphonium salt (equation 105). 

Optically active alkylphenylarsinous acid esters can be prepared by treating chloro-alkylphenylarsines with alcohols in the presence of ( —)-brucine or (— )-iV,iV-diethyl-a-methylbenzylamine. Secondary haloarsines react with the lithium derivative of (— )-cinchonidine to give the crystalline cinchonidine esters of arsinous acids 131 and 132 Another route to optically active arsinous acid esters is given in Scheme 14 ... 

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