1426 PYMAN AND RAVALD: CLVI.-o- and p - Tol?~eneaxoglyoxalines. By FRANK LEE PYYAN and LEONARD ALLAN RAVALD. IN continuation of previous work on arylazoglyoxalines (Fargher and Pyman T. 1919 115 217) the interaction of 0- and p-toluenediazonium chlorides and glyoxaline has been studied. The methods employed and the products obtained are generally similar to those described in the previous communication. o-Toluenediazonium chloride combines with glyoxaline in aqueous sodium carbonate giving 2-0-toZueneuzogZyoxali~ne (I) in poor yield a considerable amount of bis-o-tolueneazo-o-cresol being produced as a by-product. On replacing the sodium carbonate by sodium hydroxide the yield was very little better but the by-products were of different character whilst when sodium hydrogen carbonate was used in the place of sodium carbonate bis-o-toluens azo-o-cresol was again produced but no tolueneazoglyoxaline.2 - o - Tolueneazoglyoxaline resembles 2 - benzeneazoglyoxaline closely in physical and chemical properties. On reduction with stannous chlo’ride it gives 2 @-diamir~o-4-m- tolylylyoxuline (11). The combination of p-toluenediazonium chloride with glyoxaline in aqueous sodium carbonate leads to the formation of 2-p-toluene-azoglyoxaline (111) in good yield together with a small amoun 0- AND P-TOLUENEAZOGLYOXANES. 1427 of an ~somericie doubtless 4-p-tolueneazoglyoxaline (IV) and a quantity of p-tulueneazo-p-cresol. We had expected that (111.) w. 1 2-p-tolueneazoglyoxaIine would resemble 2-y-bromobenzeneazo-glyoxaline in giving a good yield of 2-aminoglyoxaline when reduced.with stannous chloride under the condit>ions employed by Fargher and Pyman (loc. cit. p. 244) but this was not the case, 2-aminoglyoxaline being produced in a yield of less than 15 per cent. of the theoretical together with p-toluidine guanidine, ammonia and unidentified products. When 2-p-tolueneazo-glyoxaline is reduced with zinc dust and acetic acid under tho conditions previously employed for the reduction of 2-benzeneazo-glyoxaline (ibid. p. 241) p-toluidine and glycocyamidine were obtained in yields amounting to 97 and 42 per cent. of the theoretical respectively. EXP EB I M E N TAL. 2-0- Tolueneazoglyoxa.line. o-Toluidine (10.7 grams) was diazotised and the product added to a solution of 6.8 grams of glyoxaline and 20 grams of anhydrous sodium carbonate in 500 C.C.of water at 5O. After keeping over-night the brown deposit was collected and extracted with 5 per cent. hydrochloric acid. On the addition of sodium carbonate, the extract deposited 4.8 grams of crude 2-o-tolueneazoglyoxaline melting at 165q the yield amounting to 26 per cent. of the theoretical. The material insoluble in dilute hydrochloric acid amounted' to 7 grams and melted a t 120'; after recrystallisation from alcohol it gave 3.3 grams of pure bis-o-tulueneazo-o-cresol, which melted a t 147O (corr.) and was! identified by analysis [Found (mean) C = 72-4; H = 6.0 ; N = 16.6. Calc. C = 72.2 ; H=6.1; N=16*9 per cent.] and by comparison with a specimen preparedl by the action of o-toluenediazonium chloride on 0-crwl (Noelting and Werner Ber.1890 23 3260). 2-o-27olueneazoglyoxaline crystallises from alcohol in brownish-yellow crystals of indeterminate shape which melt a t 185-186O (mrr.). It is very readily soluble in alcohol or chloroform less readily so in ether or benzene (Found C=64.6 64.4; H=5.4, 5-7; N=30.1. Cl,Hl,N4 requires C=64.5; H=5*4; N=30-1 per cent.) 1428 0- AND P-TOLUENEAZOQLYOXALINES. Reduction of 2-o-Tolueneazoglyoxaline with Stafinous Chloride. Zsolation of 2 4/-Uiamino-4-m-tolylglyoxaline. TWO grams of 2-o-tolueneazoglyoxaline were dissolved in 20 C.C. of hot 2.5 per cent. hydrochloric acid and mixed with 12 C.C. of stannous chloride (40 per cent. w/v) in hydrochloric acid. On cooling the solution and adding 20 C.C.of concentrated hydrochloric acid 4 grams of a crystalline stannichloride were deposited which, after the removal of the tin gave 2 grams of 2 4l-diamino-4-m-tolylglyoxaline dihydrochloride that is 67 per cent. of the theoretical yield. 2 4~-Diamino-4-m-toZylglyoxaline dihydrochloride separates from dilute hydrochloric acid in microscopic needles which form a white spongy mass. It is readily soluble in cold very readily so in hot water [Found (in substance dried a t 50O) C=43*0; H=5-8; N=19*9 20'1; C1= 25.7 ; H20 = 6.9. C,,H,2N,,2HC1,H,0 requires C = 43.0 ; H=5*8; N=20.1; C1=25*5; H20=6-5 per cent.]. Its reactions with potassium permanganate sodium nitro-prusside sodium diazobenzen~~-sulphonate and nitrous acid are similar to those of t.he lower homologue (T.1919 115 240). The base appears to be unstable for on the addition of ammonia to an aqueous solution of the dihydrochloride a white flocculent precipitate is formed which rapidly darkens when separated from the solution. The sparingly soluble sulphate separates as a mass of woolly needles on the addition of sulphuric acid to an aqueous solution of the salt. The dipicrute separates as a crystalline powder which melts at about 210° (corr.) after sintering earlier. It is sparingly soluble in boiling water. After drying a t 50° it contains lH20. 2- and 4-p-Tolueneazoglyoxalines. p-Toluidine (10.7 grams) was diazotised and the product added to a solution of 6.8 grams of glyoxaline and 20 grams of anhydrous sodium carbonate in 500 C.C. of water a t 5O.After keeping over-night the yellowish-brown insoluble product was collected and extracted with 5 per cent. hydrochloric acid. One gram of dark red amorphous matter remained undissolved and on crystallisa-tion from alcohol yielded p-tolueneazo-p-cresol which melted a t 1 1 2 O (corr.) and was identified by analysis (Found C=73*7; H=6*8; N=12-5. Calc. C=74-3; H=6.3; N=12*4 per cent.) and by comparison with a specimen prepared by the action o THE SULPHONATION OF GLYOXALINES. 1429 p-toluenediazonium chloride on pcresol (Noelting and Kohn Ber., 1884 17 354). The hydrochloric acid extract was basified with sodium carbonate and deposited 15-2 grams of the mixed toluene-azoglyoxalines melting a t 220'. that is 86 per cent. of the theoretical yield. On recrystallisation from alcohol 11.6 grams of 2-p-tolueneazoglyoxaline were obtained in .a pure state and small crops of impure material. From the final filtrate, 4-p-tolueneazoglyoxaline was isolated in the form of its hydro-chloride. 2-p-Tolueneazogtyo:ti~~e crystallises from alcohol in yellow leaflets which melt a t 235O (corr.). It is soluble in boiling alcohol to the extent of rather less than 5 per cent. (Found C=64*1, 64.4 ; H = 5.6 5.6 ; N =3O*1. C,,,R,,N4 requires C= 64.5 ; R = 5.4 ; N=30-1 per cent.). The hydrochloride was crystalline but deliquescent. 4-p-Totueneazoglyo~alin e prepared from the pure hydrochloride. crystallised from alcohol in vellow leaflets which melted a t 152O (corr.) (Found C=63.9; R = 5 * 5 ; N=31-0. C,,HI,N requires C=64-5; H = 5 * 4 ; N=30*1 per cent.). The hylrochloride crystallises from dilute hydrochloric acid in fine yellow needles forming a felted mass. The air-dried salt melts first a t 76O (corr.) loses 2H,O at. about 117O and melts again after darkening a t 185O (corr.). It is very readily soluble in water [Found (in air-dried salt) C1 = 13.8; H,O = 13.5. C,,H,,N4,RC1,2H,O requires C1= 13.7 ; H,O = 13.9 per cent.]. We desire to thank the Salters' Institute of Industrial Chemistry for the grant of a fellowship which has enabled one of US (L.A.R.) to take part in the investigation. MUNICIPAL COLLEGE OF TECHNOLOGY, UNIVERSITY OF MANCHESTER. [Receiued October 16th 1920.