Paradiazobenzoic acid with methyl alcohol yields benzoic and ethylparahydroxybenzoic acids, which can be separated as in the preceding case; the latter acid melts at 107°. Orthodiazobenzoic acid is completely converted into benzoic acid. With phenol, metadiazobenzoic acid yields metaphenoxybenzoic acid; this crystallises from dilute alcohol in long, white needles, melting at 145°. It is almost insoluble in boiling water, but dissolves readily in alcohol and other; it can be distilled in small quantities without decomposition. The barium salt, (OPh.C,H;COO),Ba + 3H2O, crystallises in small, white, ill-defined leaves. Paradiazobenzoic acid and phenol give paraphenoxybenzoic acid, which has already been described by Klepl (Abstr., 1884, 446). Orthodiazobenzoic acid yields hydroxydiphenylene ketone, orthophenoxybenzoic acid, and a new compound, which crystallises in white, shining needles, melting at 205, and is tolerably readily soluble in hot water. This product seems to be isomeric with orthophenoxybenzoic acid. Hydroxydiphenylene ketone melts at 96°, not 91° as stated by Richter (Abstr., 1884, 325). Orthophenoxybenzoic acid is identical with the phenylsalicylic acid obtained by Graebe (this vol., p. 477). The sulphate of orthotetrazodiphenic acid, C12H.(N2SO,H),(COOH)2, a compound which is obtained from the sulphate of orthodiamidodiphenic acid by treating it with nitrous acid, when warmed with ethyl alcohol, yields aldehyde, sulphuric acid, nitrogen, and a new diphenic acid, CH(COOH)2 [(COÓH), = 3 : 3′]. The latter is precipitated from its dilute ammoniacal solution in white, microscopic needles, and crystallises from boiling alcohol in small leaves. It is almost totally insoluble in cold water, and dissolves only sparingly in hot water, but more readily in hot alcohol, ether, and chloroform. The barium salt is tolerably readily soluble in water, from which it crystallises only slowly in nodular masses, having the formula. CHO,Bа + 34H2O. If the aqueous solution is evaporated down by boiling, the salt separates in needles which only contain 1 mol. H2O. When the salt is subjected to dry distillation, it yields diphenyl (m. p. 70°) and barium carbonate. F. S. K. Action of Potassium Ferrocyanide on Diazobenzene Nitrate. By M. LOCHER (Ber., 21, 911-913).-The yellow, crystalline compound (m. p. = 150°) obtained, together with azobenzene and an oil, by Griess by the action of a cold saturated solution of potassium ferrocyanide on diazobenzene nitrate (this Journal, 1876, i, 932), when heated with aniline hydrochloride and aniline at 160°, yields an induline which is insoluble in alcohol. When reduced by the action of hot hydrochloric acid and tin, or by heating with concentrated hydriodic acid and amorphous phosphorus at 120-130°, Griess' compound is converted into aniline and paramidodiphenyl, and must therefore be regarded as benzeneazodiphenyl, Ph N, CH,Ph. The hydrazo-derivative, CiH16N2, obtained by treating its solution in absolute alcohol first with ammonia and then with hydrogen sulphide, crystallises in needles or thin scales, melts at 127°, and is readily converted into benzeneazodiphenyl VOL. LIV. 2 2 r by exposure to the air and by distillation. Concentrated sulphuric acid dissolves it with a dark-red colour, which afterwards changes to green. When the hydrazo-derivative is boiled with acetic anhydride, the acetyl-derivative, C1sHN2Ac2, is formed; this crystallises in small, white needles, decomposes partially at 190° with the production of a yellow colour, and melts at 202-203°. Under like conditions, potassium ferrocyanide reacts with diazo-anaphthylamine (? naphthalene), and two compounds are obtained; one of these crystallises in dark-red, spherical aggregates, melts at about 200°, and seems to be azonaphthalene. W. P. W. Hydrazones. By E. FISCHER (Ber., 21, 984-988).-The name hydrazone is proposed for the compounds of hydrazine with aldehydes and ketones, and the term osazone for those compounds containing two neighbouring hydrazone-groups. Other compounds containing two hydrazone-groups may be named dihydrazones. Since phenylhydrazine is almost the only reagent employed, the word phenyl" may usually be dispensed with. 66 The author gives the following reasons why the hydrazones must be considered as isomeric and not identical with the azo-compounds :(1) Hydrazone-formation takes place equally well with a primary or with a secondary hydrazine, but in the latter case the formation of an azo-compound is excluded. (2) Most hydrazones regenerate the hydrazine bases when boiled with acids; only in isolated cases are indoles formed instead. (3) The hydrazone of acetaldehyde is isomeric with benzeneazoethane. Of the two formulæ for hydrazones, R⚫NH⚫N:C and NR >C, the author considers the former as the most probable, and that the osazones are similarly constituted. In taking the melting point of a hydrazone, it should be borne in mind that many of them melt with decomposition, and constant melting points can only be obtained by raising the temperature as quickly as possible. F. S. K. NH. Compounds of Phenylhydrazine with Sugars. By E. FISCHER (Ber., 21, 988-991).—The conversion of any known sugar into the crystalline and sparingly soluble osazone is the best method for recognising the former, or for isolating new compounds belonging to this class of substances. By this method it was found that phlorose, the sugar obtained from phloridzin by Hesse (Abstr., 1878, 851), is identical with dextrose. Crocose, a sugar prepared from saffron, also consists of dextrose, but it was not proved whether any other sugar is present or not. Formose, the product obtained from formaldehyde and calcium hydrate (Butlerow, Compt. rend., 53, 145; Loew, Abstr., 1886, 609), is, according to the latter authority, a distinct compound, having the formula C&H12O6. The only crystalline derivative of formose is the osazone, which, according to Loew, has the formula CH2N4O3. The author finds that this osazone is a mixture of at least two, perhaps three or four osazones. One of these, CH2NO, is the normal osazone of a sugar, C.H2O; it was obtained in very slender, yellow needles, which began to soften at 130°, and melted completely at 144°. It is therefore impure, but the other compounds present are perhaps simply isomerides. It is comparatively readily soluble in hot water, and dissolves very readily in alcohol and ethyl acetate, far less readily in benzene. A second osazone, which is sparingly soluble in ether and ethyl acetate, and can therefore be separated from the preceding compound by this means, gave results on analysis which agreed for the mean of the two formulæ C12H20N ̧O3 and C18H22N ̧0. A third osazone, which is only present in small quantities, was isolated. In melting point, which is above 204°, and its very sparing solubility in hot alcohol, it resembles phenylglucosazone and a-phenyl acrosazone. Methylenitan yields an osazone which has in general the same properties as the compound obtained from formose. Loew's statement (this vol., p. 572) that methylenitan does not yield an osazone, and is on that account quite different from formose, is therefore incorrect. F. S. K. Franceïns. By C. ISTRATI (Compt. rend., 106, 277-280).— Benzene and its chloro-, nitro-, and other derivatives yield a franceïn when heated with strong sulphuric acid (compare this vol, p. 259), the proportion of franceïn obtained increasing with the proportion of chlorine in the benzene-derivative. All the franceïns are soluble in strong sulphuric acid, and some are soluble in water. With two exceptions, they dissolve in alkalis and form neutral salts very soluble in water. They are all more or less soluble in alcohol, forming highly coloured and strongly dichroic solutions. They dye cotton, linen, and especially silk, with shades varying from rose colour to maroon. The depth of colour and the tinctorial power of the franceïns increase with the proportion of chlorine. The franceïns from benzene, methylbenzene, and mono- and di-chlorobenzene are black, but they become redder and acquire a conchoidal fracture and a dark-green metallic lustre, as the proportion of chlorine increases. The action of sulphuric acid on pentachlorobenzene yields two franceïns (loc. cit.). The first has a deep green metallic lustre, and dissolves in potash, methyl, ethyl, and amyl alcohols and glycerol, but is insoluble in water. Its solution shows intense red-green dichroism, and dyes silk a rose colour. The second is formed in much smaller quantity, and is soluble in warm water, but is almost insoluble in potash, and is much less soluble in alcohol than the first franceïn. It dyes silk a peach colour. The first franceïn forms salts which differ in their solubility in water and alcohol, and also in their dichroism. Both franceïns have the composition C1HCl,О, and seem to have the functions of a phenol and a diquinone. C. H. B. Phenylisocyanuric Acid: a Fourth Triphenylmelamine. By B. RATHKE (Ber., 21, 867-873).-When the triphenylamine previously described by the author (Abstr., 1887, 662) is heated with concentrated hydrochloric acid at 160-170°, it is converted, with elimination of aniline, into phenylisocyanuric acid, this crystallises in flat needles, melts at 285-289° (uncorr.), and is readily soluble in hot water. The silver salt crystallises in lustrous, quadratic plates. To the description previously given of the triphenylmelamine, C(NPH) It melts at 221°, and crystallises in small prisms. The hydrochloride and sulphate are very readily soluble in water, the nitrate less so; a definite platinochloride was not obtained. When heated with hydrochloric acid at 100-150°, or when heated with alcohol and a little ammonia at 150°, it is converted into normal triphenylmelamine, aniline, and diphenylmelamine, melting at 202–204°. Fresh proof of the correctness of the formula usually assigned to normal triphenylmelamine was obtained by heating it with hydrochloric acid at 180°, when it yielded cyanuric acid, showing that the phenyl-groups were not in direct union with the ring. Hofmann's statement that normal triphenylmelamine is destitute of basic properties is incorrect. The salts are insoluble in water and very unstable; the platinochloride, (C21H18N6)2, H2PtCl, crystallises in needles. When the platinochloride in alcoholic solution is treated with zinc-dust, it yields a new base crystallising in silvery, six-sided plates, and melting at 146°. A. J. G. Dimethylanilinequinonimide. By J. FOGH (Ber., 21, 887— 890). If paramidophenolsulphonic acid, made into a thin paste with water, is treated with chlorine until complete solution takes place (compare Hirsch, Abstr., 1887, 834), and the excess of chlorine is removed by the addition of small quantities of the acid until no more is dissolved, a solution of quinonechlorimidesulphonic acid is obtained, which on the addition of dimethylaniline becomes bluish-violet owing to the formation of the dimethylaniline-derivative of quinonimidesulphonic acid, O<CH(SO,H) N(CH, NMe) This separates in flocks having a bronze lustre, and consisting of microscopic needles which contain mol. H2O, are practically insoluble in cold water, ether, and benzene, and sparingly soluble in hot alcohol, but are readily soluble in aqueous alkalis, yielding intensely blue solutions from which acids precipitate the compound unchanged. The compound dissolves in concentrated sulphuric acid with a cherry-red colour, is decolorised by boiling with dilute mineral acids, and when heated at 100° or treated with reducing agents, is converted into a leuco-derivative. It is probably identical with the compound obtained by Schmitt and Andresen from trichloroquinonech lorimide and dimethylaniline (Abstr., 1882, 400). Dimethylanilinequinonimide (phenol-blue) can be prepared by adding dimethylaniline (50 grams) to a concentrated aqueous solution of oxalic acid (50 grams) containing quinonechlorimide (30 grams) in suspension, and shaking the mixture until complete solution occurs. The blue colour of the solution then changes to green, and green flocks of the oxalate separate, from which the dimethylaniliue-derivative can be obtained by treatment with cold aqueous soda. It is identical with the compound obtained by Möhlau from dimethylphenylene-green (Abstr., 1886, 146). Quinonechlorimide is best prepared by reducing 100 grams of paranitrophenol with 100 grams of tin and 500 to 600 grams of concentrated hydrochloric acid, filtering, diluting to 1 litre, and treating the solution, further diluted with four times its volume of water, and cooled to 5°, in small quantities at a time with bleaching-powder solution until both the precipitate and solution are coloured a pure yellow; the precipitate then only requires to be washed. The yield amounts to 70-80 per cent. of that theoretically possible. W. P. W. Base from Bromacetophenone and Acetamide. By M. LEWY (Ber., 21, 924-931; compare this vol., p. 55).-The base from bromacetophenone and acetamide yields benzoic acid when oxidised with a very dilute permanganate solution. Fuming nitric acid converts it into a nitro-derivative, NO2 C10H,NO, which crystallises in long, bright-yellow needles, melts at 156-157°, is readily soluble in hot alcohol and benzene, insoluble in water, and on oxidation with dilute permanganate solution yields paranitrobenzoic acid. When treated with stannous chloride and hydrochloric acid, it is reduced to the amido-derivative, NH2 C10H,NO; this crystallises in long, lustrous, colourless needles, melts at 114-115°, is readily soluble in alcohol, ether, and hot water, and readily yields a diazo compound, which forms with dimethylaniline a violet, with resorcinol a yellow, and with B-naphthol a red colouring matter. The tetrahydro-base, CH, NO, is obtained by gradually adding sodium in large excess to a boiling alcoholic solution of the aceta nide base. It is a colourless oil of repulsive odour, boils at 248251°, and is readily soluble in alcohol, ether, and concentrated acids. The benzoyl-derivative, C1H12BzNO, crystallises in small, white, concentrically grouped needles, melts at 140°, and is readily soluble in hot alcohol, ether, and benzene. The acetamide-base does not react with hydroxylamine, phenylhydrazine, or phosphorus pentachloride, and is not decomposed on distillation either with soda-lime or with zinc-dust. When heated with hydriodic acid and amorphous phosphorus for 12 hours at 210, it is converted into a hydrocarbon, CH, which boils at 270-280°, and seems to be identical with a compound obtained by Graebe from acetophenone under similar conditions (this Journal, 1875, 457). The author regards the acetamide-base as a N:CMe methylphenyloxyazole, and ascribes to it the formula <CH:CPh>0, and to its tetrahydro-derivative the formula <CH, CHPh>0. NH W. P. W. |
