THE SULPHONATION OF GLYOXALINES. 1429 CLVI1.-The Sulphonation qf G'lyoxalines. By FRANK LEE PYMAN and LEONARD ALLAN RAVALD. DIRECT sulphonation of glyosalinasl has not been decked previously, but in two cases derivatives of glyoxaline2-sulphonic acid ha,ve been prepaxed i n d i r d y . Thus Anschutz (,4nnalen 1895 284 18) obtained 4 5 -diphenylglyoxadine2-~ulphmia said by the oxidation of 2-thioll-4 5diphenylglyoxaline whilst mlh of c;a$~ine-8-sulphoni 1430 PYMAN AND RAVALD: acid are formed by the adim of holt aqueous sulphita on 8-chlom-d e i n e (D.R.-P. 74045). In view of the stability and pronounced aromatic a h r d e r of glyoxaline it seemed prolbable that this base like pyrazole and pyridine would be siismptible to direct sulphonation 'and this has praved to 6e the &e it glyozalinesutphimic acid being obtained in goad yield under suitable conditions.PrBsumably sulphonation takea plam in the 4-pmitim as dms nitration (Fargher and Pyman, T. 1919 115 217; Fargher this vol. p. 668) and the investigation will be continued and extended to alkylglycsxalines to elucidate this point. E x P E R I M E N TAL. Glyaxaline in the form of its sulphate was added to snlphuric a&d cw fuming sulphuric acid and the mixture heated. The diluted solution was treated with barium hydroxide and subsequently with carbon dioxide evaporated to dryneas and extracted wit.h chloro-form. This removed the unchanged glyoxaline and left crude barium glyoxalines;ulphmate. The consequences of varying the conditions appear in the follow-ing table: 8trength gly- sulphurio Propor.of tion of fuming oxdine acid in of fuming of free No. (base) to percentage experi- sulphuria sulphur Tem-ment. acid. trioxide. perature. 1 1 2 (98%R,S04) 100' 2 1 3 12 Y 3 4 A 6 7 1 ) 260 9 99 9* 160 10 11 9 9 99 12 I9 Y Y 99 13 .f $9 9 9 9 9 9 9 4; lib '1 99 9 9 9 ) 9 9 2;o 8 99 d 6 0 100 1Y4 9 ) 99 Yield of Duration nulphonate. Glv-of heating (hours). 3 9. 9 9 6 3 9 9 9 5 9 9 9. Y9 9 9 9. Percentage oxaline of theo- recovered. reticd. Per cent. Nil. 86 Nil. 74 4 98 18.5 Ti7 9 89 I1 86 2 46 20 46 52 Trace. 55 26 78 Trace. 70 9 9 8.3 9 9 The crude barium glymalineeulphcsnate qshllised almoet m-pletely 0111 treatmeBt with waster.From the pure salt the free acid and the sodium and ammonium s a l t s were prepared by treatment with the equivalent quantit.ies of sulphuric acid and its db. G!?/o.m2i;nesitlwh.on.?:c acid crystallises from watm in large mlmr-less cubes which are anhydrous. It beejns to soften at 290° and i THE SULPHONATION OF GLYOXALINES. 1431 entirely molten a t 307O (corr.). It! is soluble in about 5 parts of cold olr 2 parta oif hotl water butl is almost insoluble in aloohol. (Found C=24*2; H=2*6 ; N=18.9. C,H,O,N,S requirea C=24*3; H=2*7; N=18*9 per cent.) Glyoxalinesulphonic acid is strongly acid to litmus whilst its salts are only faintly alkaline. It does not combine with strong aqueous acids. On adding sodium diazobenzene-p-sulphonate to glyoxaline-sulphonic acid in excess of aqueous sodium carbonate no immediate coloration is produced but a deep red colour develops in the course of a few minutes.I n the presence of sodium hydroxide the solu-tion remains pale yellow even on keeping. An attempt to nitrate glyoxalinesulphonic acid by boiling 1.1 grams with a mixture of 1 C.C. of fuming nitric acid and 1 C.C. of sulphuric acid was un-successful the glyoxalinesulphonic acid being recovered unchanged. Tbe barizim salt crystallisea frolm watler in colourless octahedra, whiclh are anhydrous soluble in 3 parts of hot water and littde less soluble in cold water butl insoluble in alcohol. (Found Ba = 34.2. (C,H,O,N,S),Ba requires ]Bas = 34.1 per ceintl.) The sodkm saltl crystallises from water in large! colourless tlableta, which contain 2H,O. I t is v e r y readily soluble in water but almost insoluble in alcohol. (Found in air-dried salt Na= 11.2; H,O = 17.7. C3H,03N,SNa,2H,0 reqniree Na= 11.2 ; H,O = 17.5 per cent.) Tbe ammonium salt crystallises from watelr in large colmrless prisms. It is very reladily sollubla in water and easily so1 in hot moist alcolhol but almsst insoluble in absohtel alcohol. It 1-ammonia atl temperatures above looo letaving the frele acid. The air-dried salt lo& 1.5 pelr cent,. of water in it vaouum ovelr sulphurio acid. (Found in salt dried in a vacuum N=25*4; loss a t 120°= 10.5. C3H,03N,S*NH requires N=25'4; low of NH,=10.3 per cent.) We desire ta thank the Salters' InstlitUte of Industrial Chemistry for t$e grant of a fellowship which has eaabled one1 of us (L. A. R.) t'o take part in tlhe investigation. MUNICIPAL COLLEGE OF TECHNOLOGY, THE UNIVERSITY OF MANCHESTER. [ReCeiVd October 10& 1920.