2404

CROSS, BEVAN, AND BACON : CHLOROAMINE

CCXLIV.-Chloiaoa~~i.ILeBeccctioias. Mcthyleaechloroami.iLe."
By CHARLES FREDERICK CROSS,EDWARD JOHN BEVAN, and WILLIAM BACON. CRLOROAMINE, NH,CI, although not yet isolated, has been closely characterised by its reactions in solution. Raschig (Bey., 1907, 40, 4586) has verified the above formula by the synthesis of hydrazine
according to the equation : NH,Cl+ NH, = H,N*NH,,HCl. I n oxidising actions, the chloroamine chlorine reacts as the chlorine of hypochlorites, thus : NH,C1 -I2HI = NH,Cl+ I, , from which, and in view of its formation by interaction of hypochlorites and ammonium salts, it might be formulated as NH,OCl. From a general view of its oxidising reactions, however, these are found in many and typical cases to be sharply differentiated from those of the hypochlorites, and hence its formation from hypochlorites is rather represented by the equation : NH, + M*OCl= NH,Cl+ M*OH. It may be inferred from Rnschig's investigations that such reactions would be a general characteristic of amino-compounds, and me have studied certain of these in relation t o their conversion into chloroamines. As a result, we have been able to characterise the compounds obtained from proteins by the action of chlorine as chloroamines (Cross, Bevan, and Briggs, J. Xoc. Chem. Ind., 1908, 27, 260). Such compounds have been known since 1840 (Mulder, Beraelius' Jahyesber, I , 734), and their formation has been made the bmis of S quantitative analytical methods (Ridenl and Stewart, Analyst, 1897, 22, 228), depending on the separation of these derivatives, which are insoluble in water, followed by nitrogen estimations in the precipitated compounds. These methods we find are much simplified by estimations of chloroamine chlorine according to the well-known chlorimetric met hods. We have described such methods in detail as applicable to the estimation of gelatin, and we have also applied similar reactions to the elucidation of ind'ustrial processes which are attended by the formation of chloroamines, notably the bleachiug of flax textiles (ZOC. cit.). I n the case of gelatin it is noteworthy that the chloroamine
a This name is retained pending the final settlement of the constitution of the compound, in order to indicate its relation to chloroamine,

REACTIONS.

METHYLENECHLOROAMIKE.

2405

derivative is of constant composition, the chloroamine chlorine ( = ( 1) 2, representing 18 3 per cent. of origiual gelatin, and after dehydration is stable in the air. JIethyknechloroccmine. The typical reactions of chloroamine, especially with aromatic amines and phenols, have further been elucidated by Raschig (Chem. Zeit., 1907, 31,1 2 6 ; Zeihch. angew. Chem., 1907, 20, 2065). I n extending these investigations, we have observed a reaction OF special interest which we will briefly describe, as it involves a new chloroamine, readily obtainable in crystalline form. Formaldehyde and chloroamine in aqueous solution react according to the equation : CH,O + H,NCl = UH,:NCl+ H,O, t-he resulting methylenechloroamine separates in well-formed crystnls, and on recrystallisation from chloroform, in which it is easily soluble, it is obtained in needles of 10 to 15 mm. in length. To prepare this corn, pound, approximately semi-normal solutions of hgpochlorites (C1= 1.8 grams per 100 c.c.) are treated with ammonium chloride, and formaldehyde solution added in the cold, The proportions are taken somewhat in excess of the calculated. On keeping at, or under, 1 5 O , the solution becomes milky, and the compound then crystallises. It is obtained as a mass of brilliant, felted needles. The yields under these conditions are 30 to 40 per cent, of the calculated, For analysis, the substance is dissolved in chloroform, the solution being left for some hours in contact with calcium chloride, and poured off through a dry filter, when, after some time, the substance crystallises out. Many preparations have been analysed, and the numbers are i n close accordance wlth the formula CH,NCl. The following results are typical : Total c h l o k e , by digestion with sodium sulphite and precipitation as silver chloride : 0.1255 gave 0*2815 AgC1. Aciive c h 2 0 i i q by digestion with potassium iodide solution and titration of the liberated iodine : 013124 liberated 1 = 99.8 C.C. N/lO-thiosulphate. ,?Titi-ogen, by digestion with ferrous sulphate, in presence of sulphurous acid, and distillation from alkalis ; the nitrogen being obtained as ammonia : 0.1135 gave NH,= 18-2 C.C. N/lO-HCl. Found, Total C1= 55.4 ; Active C1= 56.7 x 2 ; N = 22.4. CH,NC1 requires Total C1= 55.9 ; Active C1= 55.9 x 2 ; N=22*05 per cent.
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VOL, XCVll.

SQ

2406 CHLOROAMINE REACTIONS. METHYLENECELOROAMIKE.

Molecular - weight determinations even by uryoscopic methods present difficulties, due to the instability and reactivity of the compound, but the following numbers calculated from the depression of the freezing point of benzene were obtained : Found, M.W.= 133.0, 132.7, 131.7. SCH,NCl requires B1.W. = 127. Our incidental obeervations indicate a change of solubility in benzene from 2 7 t o 1-5 per 100 C.C. at 5 O , and poiyinerisation probably has to be taken into account. This point mill be resolved by further investigatioii. ~ e t h ~ Z e . n e c h E o r o ~is asoluble in 20 to 30 parts of ether at the n ~~~ ordinary temperature, and similarly in benzene, as indicated above ; it is only sparingly soluble i n paraffinoid hydrocarbons. It decomposes spontaneously in ordinary air, and when heated at 60-60" it decomposes explosively, leaving n residue of ammonium chloride. A s shown by the analytical results, it may be quantitatively bydrolysed and reduced, ammonia and formaldehyde being regenerated, and by certain decompositions it yields hydrocyanic acid as a main product The investigation is being continued.
4, NEW COURT: LONDON. W.C.