Aliphatic Arsines

Gold(I) complexes of the type [AuCl(PPh3)ra] (n= 1, 2) or [Au(N03)(PPh3)] show an excellent performance towards oxidative addition carbonylation or aromatic amines to form corresponding carbamates, and also towards the carbonilation of aliphatic amines to produce either alkylureas or formamides.2552,2553 Cationic gold(I) compounds of the type [AuL]+ where L = phosphine, phosphite, or arsine are excellent catalysts for the addition of alcohols to alkynes.2554... 

Chlorocarbonylbis(triphenylphosphine)rhodium and chlorocarbonylbis(triphenylarsine)rhodium form bright yellow crystalline solids which are readily soluble in chloroform and dichloromethane, moderately soluble in benzene and carbon tetrachloride, and sparingly soluble in ether and aliphatic hydrocarbons. The phosphine complex (m.p. 195 to 197°) and the arsine complex (m.p. 242 to 244°) are reported to have carbonyl stretching frequencies (using KBr disks) at 1960 and 1963 cm., respectively. ... 

It has been found that while the aliphatic arsines and phenyl carbylamine chloride produce a similar turbidity at high concentration (4%), other substances such as mono-, di- and tri-chloromethyl chloroformates, chloropicrin, benzyl bromide, acrolein, the aromatic arsines, thiodiglycol, etc., do not react. 

Most of the aliphatic and aromatic arsines employed during the war of 1914-18 were substances which had been known for some time. The only new substances are the chlorovinyl arsines and phenarsazine chloride, of whose practical efficiency somewhat conflicting opinions are still held. 

The aliphatic arsines are substances which are generally liquid and oily, have a not unpleasant odour, are somewhat miscible with water, but are all more or less rapidly hydrolysed as follows ... 

These arsines differ from those of the aliphatic series which have just been described, by their physical and chemical properties, and by their method of employment, as well as by their biological action. They are solids or liquids with high boiling points, have very low vapour tensions, are quite resistant to heating and are only oxidised by atmospheric oxygen with difficulty. 

Physiologically, these compounds have a lower toxicity than the aliphatic arsines. However, they act as energetic stemutators and irritants, even at very low concentrations. This action is produced immediately after 1-2 minutes exposure to concentrations of 0-2-0-5 mgm. substance per cu. m. of air. 

Jurecev suggested the following method for the determination of the aliphatic arsines present in vapour form in the air. 

According to Delepine, this method may also be employed for the determination of the arsenic trichloride present in the aliphatic arsines. 

There are six types of tertiary aromatic arsines known, if those containing aliphatic radicals are also included ArjAs, ArAr As, ArgAlkAs, ArAlk As, ArAr AlkAs, ArAlkAlk As. For the tyj>e ArjAs, theFittig reaction forms thebasisof a method of preparation, aryl halides and arsenic trihalides reacting in ether or benzene solution in th< ))re-senee of sodium as follows ... 

In the ease of mixed aliphatic-aromatic tertiary arsines, the following equations indicate the methods available ... 

The following methods have been used for the isolation of aliphatic-aromatic halogenated arsines —... 

Silver oxide in aqueous suspension converts aliphatic-aromatic tertiary arsine hydroxyhalides to dihydroxides, wliilst picric acid leads to the formation of hydroxypicrates ... 

Mixed Aliphatic-aromatic Ketone Arsinic Acids. —These compounds are formed by the interaction of bromine-substituted mixed aliphatic-aromatic ketones, such as 4-bromoacetophenone or. S-amino-4-bromo-acetophenone, with arsenites in hot solution. 

Arsonic and Arsinic Acids. The arsonic acids, compounds of the type RAsO(OH)2, are among the most important organic arsenicals. The aliphatic arsonic acids are generally prepared by the Meyer reaction ie, heating an alkyl halide with As406 in alkaline solution ... 

ANHYDRIDE ARSENIQUE (French) (1303-28-2) Incompatible with acids, aluminum, halogens, rubidium carbide, strong alkalis, zinc. Gradually deliquesces (absorbs moisture from atmospheric air, becoming liquid) on exposure to air, forming arsenic acid. Contact with moisture, water, steam forms arsenic acid. Incompatible with sulfuric acid, caustics, ammonia, aliphatic amines, alkanolamines, amides, organic anhydrides, isocyanates, vinyl acetate, alkylene oxides, epichlorohydrin. Contact with acids or acid mists releases deadly arsine gas. Corrosive to metals in the presence of moisture. 

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