DERIVATIVES OF %NITROTOLY I,-4-HYDRAZINE. 1 14 1 CXXII.-Deiivatives of 3-NitrotolyE-4-hydraxine. By FRANK GEO. POPE and JAS. MORTON HIRD. SOME years ago, one of the authors, in conjunction with J. T. Hewitt, described m-bromo-p-tolylhydrazine and its derivatives (Trans., 1898, 73, 174), from which it was thought that closed ring compounds might be produced by elimination of halogen from the nucleus and hydrogen from the side chain. A t the time, however, no satisfactory results were obtained, although by the action of heat on the anhydrous potassium salt of the pyruvic acid hydrazone, two substances, one being acidic in character and the other phenolic, were formed. Their nature mas not further determined at the time, and experiments are still being carried on in the hope of eliminating hydrogen bromide from the compounds.It has occurred to us that the corresponding nitrohydrazine might be more suitable for the formation of such closed rings, and experi-1142 POPE AND HIRD: DERIVATIVES OF ments are now being carried out in this direction, but as none has yet been brought to a perfectly definite conclusion, we think it advis- able to give a short account of the preparation and properties of the hydrazine and some of its chief derivatives. For the purpose of obtaining the hydrochloride of this hydrazine from m-nitro-p-toluidine, V. Neyer and Lecco's method (Ber., 1883, 16, 2976) was employed. The double tin salt of the hydrazine was freed from tin by hydrogen sulphide; on filtering off the precipitated tin sulphide and carefully evaporating the solution, the hydrazine hydro- chloride was obtained in orange-red plates or needles.The recrystal- lised salt melts and decomposes a t 190-191', and is soluble in water with slight decomposition. In aqueous solution, the salt shows the characteristic reduction of Fehling's solution, On analysis : 0.0872 gave 15.8 C.C. nitrogen a t 1 8 O and 744.5 mm. N = 20.36. C7H2,0,N,Cl requires N = 20.68 per cent. The hydrazine is obtained from a solution of the hydrochloride in water, by the addition of sodium acetate, as a dark red precipitate. This, after being dried over sulphuric acid and recrystallised from ether, separates in dark red tufts of needles melting a t l l O o . On analysis : 0.0949 gave 20.5 C.C. nitrogen at 1 9 O and 757 mm. N = 24.80.CtH90,N, requires N = 25.15 per cent. The base is very soluble in acetone, and moderately so in ether, ethyl acetate, chloroform, or benzene, but only slightly so in light petroleum. Pyruuic acid ntit.rotoZyZhydrazoe, N0,*C7H,*NH*N :C(CH,)*CO,H, is precipitated immediately on mixing aqueous solutions of the hydr azine hydrochloride and pyruvic acid as a chrome yellow, amorphous substance. This, when recrystallised from alcohol, melts a t 203' with decomposition. It is soluble in acetone, ether, ethyl acetate, benzene, or chloroform, but only slightly so in light petroleum. 0-1024 gave 16.1 C.C. nitrogen at 2 5 O and 747 mm. On analysis : N = 17.50. C,,H,,O,N, requires N = 17.72 per cent. The ethyl egter, NO,*C:H,*NH*N:C(CH,)*CO,C,H,, was prepared by boiling the hydrazone with its own weight of sulphuric acid and ten times its weight of absolute alcohol for 10 hours in a reflux apparatus.The mixture was then poured into dilute sodium carbonate solution, when the ester separated in yellow flocks, which, on crystallisation from alcohol, formed small, orange needles melting at 140'. On analysis :3-NITROTOLYL-4-HY DRAZINE. 1143 0.1353 gave 18*9 C.C. nitrogen at 34' and 768 mm. C,,H,,O,N, requires N = 15.85 per cent. Nitrot olylsemicarbaxide, NO, * 0, H, * NH*NH CO*NH,, is immediately precipitated on mixing aqueous solutions of the hydrazine hydro- chloride (2 grams) and potassium cyanate (0.81 gram) as a light yellow, sandy powder, This, when recrystallised from much hot water, in which it is only slightly soluble, is obtained in small, yellow needles which melt at 201' with decomposition, and are only slightly soluble in the usual solvents, N = 15.79.On analysis : 0.1449 gave 33.9 C.C. nitrogen at 25' and 751 mm. C,Hl,0,N4 requires N = 26-67 per cent, An aqueous solution of this Substance, on treatment with alcoholic potash in the cold, gives a deep violet colour, and if left to stand for some days, a crystalline precipitate is obtained. Salicylccldehyde nitrotolyzhydraxone, NO,*C,H,*NH*N:CH*C,H,*OH, was obtained in the following manner : 1-25 grams of salicylaldehyde were covered with water, and 2 grams of the hydrazine hydrochloride, dissolved in water, added ; the whole was then well shaken after the addi tion of excess of sodium acetate solution. A brilliant scarlet pre- cipitate was immediately produced ; this was recrystallised from benzene, in which it is very soluble, separating in the form of needles which melt at 226O.It dissolves only sparingly in ether, ethyl acetate, chloroform, or light petroleum. N=26*44. On analysis : 0°1083 gave 15.1 C.C. nitrogen at 20° and 737 mm. C14H1303NI requires N = 15-50 per cent. Furfuraldehyde nitrotolylhydraxone, NO,* C7H,* NH*N: CH*C,OH, was obtained in an analogous manner, giving a bright scarlet precipi- tate, which was recrystallised from hot alcohol, forming red needles melting at 165-1664 It dissolves easily in the ordinary organic solvents except ether and light petroleum, N = 15.46. On analysis : 0.1285 gave 19.6 c,c. nitrogen at 15O and 755 mm. C1,H,,03N3 requires N= 17*14 per cent.Benxaldehyde nitrotolythydrccxone, NO,*C,H,*NH*~:CH'C,H,, was also obtained in the same manner, and crystallised from benzene in rod needles which melted at 166'. It is only slightly soluble in light petroleum or acetone. N = 17-75. On analysis : 0.0996 gave 15.2 C.C. nitrogen at 26' and 759 mm. C14H1302N3 requires N = 16-47 per cent. P ~ n y l n ~ ~ o t o ~ ~ ~ t h ~ o s e r n ~ c a r ~ a x ~ ~ e , NO,*C7H,*NH0NH*CS*NH*~,H~, was prepared by mixing ethereal solutions of the free hydrazine and N = 16-74,1144 HENRY : THE CONSTITUENTS OF THE SANDARAC RESINS. phenylthiocai bimide in molecular proportion, and allowing the solu- tion to stand for about half an hour. When recrystallised from ether, i t gave tufts of golden yellow needles melting and decompos- ing at 188'. On analysis : Cl4H1,O,N,S requires N = 18.54 per cent. NO, * C7H, NH*NH* CS*NH C,H,, was prepared in a similar way, and formed yellow needles melting a t 168-170" when recrystallised from dilute alcohol. 0.1120 gave 21 C.C. nitrogen at 28' and 759 mm. C,lHl,O,N,S requires N = 21 5 2 per cent. Acetylnitrotolylhydrazine, NO,*C~H,*NH*NH*CO*CH,, was prepared by boiling the hydrazine with an excess of glacial acetic acid for 4 hours in a reflux apparatus, pouring the product into water, filter- ing, washing with cold water, and recrystallising from hot water. It formed small, golden needles melting at 161O. 0*1010 gave 16.8 C.C. nitrogen at 1'7' and 750 mm. Nityot olylallylt hiosemkarbazide, N= 18.91. On analysis : N = 21.0. On analysis : 0.1012 gave 17.5 C.C. nitrogen at 19' and 768 mm. We hope t o be able to communicate further results as t o the N=20.25. CgH1,O,N, requires N = 20.10 per cent. behaviour of certain of these compounds shortly. EAST LONDON TECHNICAL COLLEGE.