Phenarsazine chloride

DM Adamsite, Phenarsazine chloride, Diphenylaminechloroarsine,10-chloro-5,10- dihydrophenarsazine... 

Diphenylamine chlorarsine (arsenical gas, also known as Adamsite (phenarsazine chloride))... 

DIPHENYLAMINECHLORARSINE (ADAMSITE) (DIPHEN-YLAMINEARSINE CHLORIDE) (PHENARSAZINE CHLORIDE)... 

S-Aza-10-arsenaa nthracene chloride 10-Ch loro-5,10-dihydroarsacridine 10-Chloro-5,10-dihydrophenarsazine Dibenzo-1 -ch loro-1,4-arsen Ine Dl phenylaminochloroarsine Phenarsazine chloride... 

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. 

In order to attain the degree of subdivision of diphenyl chloroarsine, diphenyl cyanoarsine or phenarsazine chloride which has been mentioned above, it is first necessary to volatilise the substance by some method and then to allow the vapour to condense in the air. This is carried out by means of the so-called irritant candles. ... 

Various analogous and homologous compounds of phenarsazine chloride have been studied. Among the more important may be mentioned phenarsazine bromide, obtained by the action of arsenic bromide on diphenylamine, phenarsazine iodide and phenarsazine fluoride, as well as phenarsazine cyanide A All these compounds have toxic properties similar to those of phenarsazine chloride. ... 

These substances, which are very similar in properties to phenarsazine chloride, have the drawback that their preparation is iti each case very laborious. 

Wieland obtained phenarsazine chloride by treating diphenyl-amine with arsenic chloride ... 

American Method. The process used by the Americans at Edgewood Arsenal for the manufacture of phenarsazine chloride is based on the reaction of diphenylamine with arsenic chloride ... 

In order to prepare phenarsazine chloride by this method it is sufficient to mix diphenylamine hydrochloride with arsenious oxide and heat to 130° C. After the mixture is melted, the temperature is gradually raised to 200° C. When the evolution of water ceases, the reaction is complete. Yield 95% of the theoretical.. 

Fig. 18 shows a diagram of the plant proposed by Professor Contardi for the industrial preparation of phenarsazine chloride. 

With a battery of four kettles of this description, it is possible to make 6 tons of phenarsazine chloride by this method in 24 hours. 

Phenarsazine chloride in the crude state is a crystalline solid, dark green or sometimes brown in colour. It may be obtained in the pure condition by crystallisation, or, better, by vacuum sublimation. It is then of a canary-yellow colour with a melting... 

Water. Phenarsazine chloride, unlike the arsenic compounds previously described, is slowly hydrolysed by water. On adding a little water to the alcoholic solution, a turbidity appears which consists of phenarsazine oxide. ... 

Bromine. By the action of bromine on phenarsazine chloride in acetic acid solution, a brominated derivative is not obtained. 

Hydrochloric Acid. When phenarsazine chloride is treated with gaseous hydrochloric acid at 160° C. it decomposes, forming arsenic trichloride and diphenylamine as follows ... 

Hydriodic Acid. On treatment with aqueous hydriodic acid on the water-bath, phenarsazine chloride forms diphenylamine as in the previous reaction ... 

Alkalies. Phenarsazine chloride reacts with the alkalies to form phenarsazine oxide, according to the following equation ... 

Ammonia. When a current of dry ammonia is passed through a solution of phenarsazine chloride in xylene, a compound of the following composition is obtained ... 

Oxidising Agents. Oxidising agents react with phenarsazine chloride, converting the arsenic atom from the trivalent to the pentavalent condition. Hydrogen pearoxide in acetic acid... 

Sodium Cyanide. Phenarsazine chloride, when treated with sodium cyanide in methyl alcohol solution, does not form phenarsazine cyanide, but the corresponding methoxy- compound,... 

Potassium Thiocyanate. When phenarsazine chloride is treated in acetone solution with an aqueous solution of potassium thiocyanate, phenarsazine thiocyanate is formed ... 

Chloramine-T. On treatment of phenarsazine chloride in cold aqueous alcoholic solution with chloramine-T, phenarsazinic acid is formed (see above). 

Grignard Reagent. By the action of the Grignard reagent on phenarsazine chloride, the corresponding alkyl or aryl derivative is formed, i.e., ... 

When phenarsazine chloride is heated it begins to melt at about 193° to 195° C. and remains unaltered until the temperature reaches 320° C. when it becomes dark brown. On further heating to 370° C., no more decomposition takes place. On cooling rapidly it solidifies to a crystalhne mass of much darker colour than the original substance. 

Unlike diphenyl chloroarsine, phenarsazine chloride attacks iron, steel, bronze and copper. 

Detection of Phenarsazine Chloride On heating a solution containing phenarsazine chloride with an aqueous solution of hydriodic acid on the water-bath, diphenylamine is formed (see p. 324), which can be distilled off in a current of steam and detected by means of the well-known reaction with nitric acid in sulphuric acid solution. 

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