2404 CROSS, BEVAN, AND BACON : CHLOROAMINECCXLIV.-Chloiaoa~~i.ILe Beccctioias. Mcthyleae-chloroami.iLe."By CHARLES FREDERICK CROSS, EDWARD JOHN BEVAN, andWILLIAM BACON.CRLOROAMINE, NH,CI, although not yet isolated, has been closelycharacterised by its reactions in solution. Raschig (Bey., 1907, 40,4586) has verified the above formula by the synthesis of hydrazineaccording to the equation :NH,Cl+ NH, = H,N*NH,,HCl.I n oxidising actions, the chloroamine chlorine reacts as the chlorineof hypochlorites, thus :from which, and in view of its formation by interaction of hypo-chlorites and ammonium salts, it might be formulated as NH,OCl.From a general view of its oxidising reactions, however, these arefound in many and typical cases to be sharply differentiated from thoseof the hypochlorites, and hence its formation from hypochlorites israther represented by the equation :NH,C1 -I- 2HI = NH,Cl+ I,,NH, + M*OCl= NH,Cl+ M*OH.It may be inferred from Rnschig's investigations that such reactionswould be a general characteristic of amino-compounds, and me havestudied certain of these in relation t o their conversion intochloroamines.As a result, we have been able to characterise the compoundsobtained 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, IS, 734), and their formation has been made the bmis ofquantitative analytical methods (Ridenl and Stewart, Analyst, 1897,22, 228), depending on the separation of these derivatives, which areinsoluble in water, followed by nitrogen estimations in the precipitatedcompounds. These methods we find are much simplified by estimationsof chloroamine chlorine according to the well-known chlorimetricmet hods.We have described such methods in detail as applicable to theestimation of gelatin, and we have also applied similar reactions tothe elucidation of ind'ustrial processes which are attended by theformation of chloroamines, notably the bleachiug of flax textilesI n the case of gelatin it is noteworthy that the chloroaminea This name is retained pending the final settlement of the constitution of the(ZOC.cit.).compound, in order to indicate its relation to chloroamineREACTIONS. METHYLENECHLOROAMIKE.2405derivative is of constant composition, the chloroamine chlorine ( = (21,)representing 18 3 per cent. of origiual gelatin, and after dehydrationis stable in the air.JIeth yknechloroccmine.The typical reactions of chloroamine, especially with aromatic aminesand phenols, have further been elucidated by Raschig (Chem. Zeit.,1907, 31, 126; Zeihch. angew. Chem., 1907, 20, 2065).I n extending these investigations, we have observed a reaction OFspecial interest which we will briefly describe, as it involves a newchloroamine, readily obtainable in crystalline form.Formaldehyde and chloroamine in aqueous solution react according tothe 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, itis 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, andformaldehyde solution added in the cold, The proportions are takensomewhat in excess of the calculated. On keeping at, or under, 1 5 O ,the solution becomes milky, and the compound then crystallises. Itis obtained as a mass of brilliant, felted needles. The yields underthese conditions are 30 to 40 per cent, of the calculated,For analysis, the substance is dissolved in chloroform, the solutionbeing left for some hours in contact with calcium chloride, andpoured off through a dry filter, when, after some time, the substancecrystallises out.Many preparations have been analysed, and the numbers are i n closeaccordance wlth the formula CH,NCl.The following results are typical :Total c h l o k e , by digestion with sodium sulphite and precipitation0.1255 gave 0*2815 AgC1.6 ‘ Aciive ch20iiq’’ by digestion with potassium iodide solution and013124 liberated 1 = 99.8 C.C.N/lO-thiosulphate.,?Titi-ogen, by digestion with ferrous sulphate, in presence ofsulphurous acid, and distillation from alkalis ; the nitrogen beingobtained as ammonia :as silver chloride :titration of the liberated iodine :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.VOL, XCVll.7 S2406 CHLOROAMINE REACTIONS. METHYLENECELOROAMIKE.Molecular - weight determinations even by uryoscopic methodspresent difficulties, due to the instability and reactivity of thecompound, but the following numbers calculated from the depressionof 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 inbenzene from 2 7 t o 1-5 per 100 C.C. at 5 O , and poiyinerisation probablyhas to be taken into account. This point mill be resolved by furtherinvestigatioii.~eth~Ze.nechEoro~na~~~ is soluble in 20 to 30 parts of ether at theordinary temperature, and similarly in benzene, as indicated above ; itis only sparingly soluble i n paraffinoid hydrocarbons.It decomposes spontaneously in ordinary air, and when heated at60-60" it decomposes explosively, leaving n residue of ammoniumchloride.As shown by the analytical results, it may be quantitatively bydro-lysed and reduced, ammonia and formaldehyde being regenerated, andby certain decompositions it yields hydrocyanic acid as a main productThe investigation is being continued.4, NEW COURT:LONDON. W.C