Triphenyl silver cyanate

TViphenyl Telluronium Cyanate1 0.15 g (1 mmol) of silver cyanate are dissolved in 850 ml of boiling water, 0.394 g (1 mmol) of triphenyl telluronium chloride dissolved in 50 ml of hot water are added, the mixture is stirred for several minutes, then cooled, and filtered. The filtrate is concentrated to a volume of 5 ml under vacuum, and the concentrate is cooled to 5° and filtered, The filtrate is allowed to stand for 48 h open to the atmosphere, the crystals are collected, crushed, and dried at 24 over phosphorus pentoxide yield 0.34 g (90%) m.p. 152°. Recrystallization from chloroform yields crystals containing 0.5 molecule of solvent. Similarly prepared was diphenyl methyl telluronium thiocyanate (m.p. 1250)2. 

Silver cyanate (0.3 g, 2 mmol) was added to an acetone (50 ml) solution of oxybis(triphenyl-bismuth) dichloride (970 mg, 1 mmol) and the mixture was stirred for 5 h at around 5°C. It was then filtered and the filtrate was concentrated under vacuum. By adding water to the solution, oxybis(triphenylbismuth) dicyanate was obtained as a fine white powder. The compound was filtered and crystallized twice from dry acetone and diethyl ether Yield 40%, m.p. 139°C (decomp.) [72JOM(36)323]. 

Triphenylbismuthine dichloride, ( 6115)361012/ occurs when chlorine is passed into a solution of triphenylbismuthine m ether, petroleum ether, chloroform or carbon tetrachloride. It crystallises in stout needles, M.pt. 126° C., soluble in alcohol, chloroform or benzene, practically insoluble in ether or petroleum ether. Moist silver oxide, alcoholic potassium hydroxide, potassium cyanate and other inorganic salts react with the dichloride giving varying yields of triphenyl-bismuthme. When a chloroform solution of the dichloride is treated with moist ammonia, one chlorine atom is removed and triphenylbismuthine hydroxychloride results. When the dichloride is added to concentrated sulphuric acid it yields triphenylbismuthine sulphate and hydrogen chloride is evolved. A dry benzene solution of the dichloride when boiled undergoes partial decomposition with formation of diphenyl-chlorobismuthinc. 

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