ammonia, phenacylaminophenanthrone, CH CNH2)·CH2· CO·C2H ̧ ̧ CH CO analogous to the acetone-ammonia derivative, was obtained. The same substance is formed by the action of ammonia on phenacylhydroxyphenanthrone. The ease with which these compounds break up into their generating substances rendered a detailed study of their reactions impossible. Other ketones, such as methyl ethyl ketone and diethyl ketone, appeared to act in a similar manner with phenanthraquinone and ammonia; but it was found impossible to obtain the resulting compounds in a condition suitable for analysis. EXPERIMENTAL. Action of Alcoholic Ammonia on a Mixture of Phenanthraquinone and Acetophenone.-20 grams of phenanthraquinone, 28 grams of acetophenone, and a large excess of alcoholic ammonia were heated in an open flask on the water-bath. In proportion as the ammonia was expelled and the boiling point of the mixture rose, the greater part of the phenanthraquinone passed into solution. The filtered liquid deposited, on cooling, yellow, lustrous needles, which, by their appearance and melting point (158-159°), were recognised as phenanthraquinonimide. Later on, a colourless substance began to separate. The liquid was therefore again filtered, and, on standing overnight, deposited a large quantity of this second substance in tufts of colourless, silky needles, which, when heated in a capillary tube, decomposed about 150°, without showing a definite melting point. In some preparations of this substance, the portions first deposited showed a pinkish tinge; but, by filtering at this stage, the colourless substance was obtained from the filtrate. As we found it impossible to recrystallise this substance without decomposing it, it was merely washed with cold alcohol, and dried for analysis in a vacuum desiccator. It was perfectly homogeneous in appearance. Analysis gave figures agreeing with the formula of diphenacyldiaminodihydrophenanthrene, CH, C(NH)·CH2· CO·C2H ̧ C.H, C(NH,)•CH, CO CH 0.1570 gave 0.4657 CO, and 0.0794 H2O. 0.1454 0.4317 CO2 6 5 0.0738 H2O. C=80·90; H=5·62. 0.3049 16.2 c.c. moist nitrogen at 11° and 740 mm. N=6.17. 0.2928 15.5 13° 754 mm. N = 6.20. C30H26N2O2 requires C80.72; H=5·83; N = 6.28 per cent. Hydrolysis of Diphenacyldiaminodihydrophenanthrene.-In this experiment, the method employed by Japp and Miller (loc. cit., p. 17) in 3 z VOL. LXXV. the hydrolysis of acetonylaminophenanthrone to acetonephenanthraquinone, was followed. The diphenacyldiaminodihydrophenanthrene was first moistened with alcohol-since otherwise it is not readily wetted by water-ground with water to a thin cream, and then poured into a large excess of a cold concentrated aqueous solution of oxalic acid, stirring well. Almost everything dissolved. The solution was quickly filtered through a large folded filter-an operation which must be rapidly performed, as the separation of the new compound begins almost immediately and the filtrate, which speedily became yellow and turbid and smelt strongly of acetophenone, was allowed to stand over night. There was a large deposit of a pale yellow substance ; this was filtered off, thoroughly washed with water, dried in a vacuum desiccator, and purified by recrystallisation, first from ether, allowing the solvent to evaporate spontaneously, and afterwards from ethylic acetate, the latter giving the better result. It was thus obtained in fairly large thick prisms or six-sided plates which had a scarcely perceptible yellowish tinge, and are doubtless colourless when pure. It melted between 125° and 130°, turning dark yellow. Boiling the substance with solvents must be avoided, as this treatment decomposes it. Analysis gave figures agreeing with the formula of phenacylhydroxyphenanthrone (acetophenonephenanthraquinone), (H_*((OH)-CH, CO CH 2 0.1716 gave 0.5053 CO, and 0.0791 H2O. C-80·31; H=5·12. 0.1568 0-4622 CO2 0.0717 H2O. C-80-39; H=5.08. C2H6O3 requires C-80-49; H= 4.88 per cent. 22 16 As acetonephenanthraquinone, when boiled with fuming hydriodic acid, yields diphenylenemethylfurfuran (Trans., 1890, 57, 663), we subjected the foregoing compound to the same treatment, in the hope of obtaining a diphenylenephenylfurfuran, but found that it broke up, before reduction, into acetophenone and phenanthraquinone, the latter then yielding phenanthrone and tetraphenylenefurfuran. By passing gaseous ammonia into an ethereal solution of phenacylhydroxyphenanthrone, we obtained phenacylaminophenanthrone, CH, C(NH) CH, CO-CH. This compound is, however, more readily prepared by the method described in the next paragraph. Action of Aqueous Ammonia on a Mixture of Phenanthraquinone and Acetophenone.-20 grams of phenanthraquinone, 14 grams of acetophenone, and an excess of the strongest aqueous ammonia were introduced into a strong flask; this was tightly corked, and the mixture shaken vigorously, at intervals, during several hours. The organic substance solidified in the form of yellowish granules, whilst the aqueous portion was red. The solid substance was separated, ground with water, thoroughly washed, and dried over sulphuric acid. It was then digested with a small quantity of chloroform in the cold, to remove unaltered phenanthraquinone, after which the residue was treated with sufficient cold chloroform to dissolve nearly the whole. On adding light petroleum to the filtered chloroform solution, a bulky, white precipitate was obtained; this was filtered off and dried at the ordinary temperature. The substance, which was yellowish after drying, was dissolved in cold ether which had been previously saturated with ammonia (in order to check the tendency of the substance to decomposition), and the solution was allowed to evaporate spontaneously. In this way, the compound was obtained in small, colourless, six-sided plates, which melted with decomposition about 160°, turning green and evolving gas. The loss in purification by the above method is very great. Heating with solvents decomposes the substance completely. Analysis gave figures pointing to the formula of a phenacylaminophenanthrone, CHC(NH2)·CH, CO C2H2. The substance was diffiCH, CO 5. cult to burn, and the value for carbon was low. 0.1175 gave 0.3449 CO, and 0.0570 H2O. C=80.05; H=5·39. 0.3090 11.7 c.c. moist nitrogen at 18° and 754 mm. N = 4.33. C22H17NO2 requires C=80·73; H=5·20; N=4·28 per cent. CHEMICAL DEpartment, UNIVERSITY OF ABERDeen. CII.-Furfuran Derivatives from Benzoin and Phenols. By FRANCIS R. JAPP, F.R.S., and ANDREW N. MELDRUM, B.Sc. By the action of cold, concentrated sulphuric acid on a mixture of benzoin and phenol, Japp and Wadsworth (Trans, 1890, 58, 965) obtained paradesylphenolsulphonic acid, from which, by hydrolysing it with strong hydrochloric acid at 150°, paradesylphenol, was prepared. * (1:4), We now find that by heating a mixture of benzoin and phenol with sulphuric acid of 73 per cent. strength, the foregoing condensation occurs without sulphonation of the resulting compound, and an * Corresponding with the hydrate H2SO4, 2H,O. A sulphuric acid of this strength was first used for condensations by Bistrzycki aud Oehlert (Ber., 1894, 27, 2632). excellent yield of paradesylphenol is obtained. The various condensations about to be described were effected by means of sulphuric acid of this strength. If the desyl group were to take up the ortho-position towards the hydroxyl of the phenol, it is evident that, by a further elimination of water, a furfuran derivative might be formed: With phenol and benzoin, no such reaction occurs: the para-compound alone is formed. With thymol and benzoin, however, a mixture of desylthymol and cymodiphenylfurfuran is obtained. In the case of resorcinol and of quinol, either one or two diphenylfurfuran groups may be introduced. With phloroglucinol, only the compound containing three such groups was obtained. Up to a certain point these reactions resemble those studied by Hantzsch and his pupils (Ber., 1886, 19, 1290, 2927, and 2934), in which furfuran derivatives were obtained by the action of ethylic a-chloracetoacetate on the sodium compounds of phenols. Starting with phenol, a benzomonofurfuran derivative was thus prepared ; whilst from di- and tri-hydroxybenzenes, compounds containing either one, or two, or three furfuran groups were obtained, just as in the reactions described in the present paper. But there is an important distinction to be drawn between the mechanisms of the two sets of reactions. In Hantzsch's reactions, the first stage is the formation of an ether of the phenol in question-thus of ethylic a-phenoxylacetoacetate in the first of the syntheses referred to—and the linking of carbon to carbon is a subsequent process. In the reactions here described, the first stage is the linking of the desyl group to the nucleus of a phenol, whilst the closing of the furfuran ring by oxygen follows. Were this otherwise, phenol and benzoin would yield only diphenylbenzofurfuran, instead of, as actually happens, only paradesylphenol. We may mention that the present research was completed last year, before the publication of Graebe's investigation of benzoin yellow (Ber., 1898, 31, 2975), in which it is shown that, by the action of sulphuric acid on a mixture of benzoin and gallic acid, a compound containing a diphenylfurfuran group is formed. EXPERIMENTAL. 1. Benzoin and Phenol. * 20 grams of benzoin, 9 grams of phenol, and 80 grams of 73 per cent. sulphuric acid were heated by means of an oil-bath at 120—150° for 20 minutes, frequently shaking the flask. The product, which was dark-coloured, was allowed to cool, the aqueous portion was poured off, and the organic substance was boiled, first with water and then with a solution of sodium carbonate, after which it was recrystallised from a mixture of benzene and light petroleum. It melted constantly at 133° and exhibited all the other properties of paradesylphenol (Trans., 1890, 57, 966). The yield was good, and the method is a great improvement on that previously described (loc. cit.). Afterwards, when we had ascertained that various other phenols yielded furfuran derivatives, a second preparation of the foregoing compound was made in order to ascertain whether any benzodiphenylfurfuran was formed at the same time. For this purpose, the operation was conducted as just described, except that the crude product, after extraction with sodium carbonate, was dissolved in ether, and the solution shaken with dilute caustic soda as long as the latter removed anything. Any benzodiphenylfurfuran would thus remain behind in the ether; but, on evaporating the ethereal liquid, only a small quantity of an uncrystallisable resin was obtained, closely resembling the product of the action of sulphuric acid on benzoin alone. 2. Benzoin and Thymol. 20 grams of benzoin and 40 grams of thymol were melted together, 80 grams of 73 per cent. sulphuric acid were added, and the mixture was heated, with shaking, for 20 minutes at 150-170°. The viscid product was washed with water, and then steam-distilled as long as any thymol passed over. The dark-coloured solid which remained was dissolved in boiling alcohol. The filtered solution deposited, on cooling, a resinous substance; the liquid, poured off from this, gave, on standing, cauliflower-like aggregates of crystals (A). The filtrate from these contained, along with much resin, a very soluble, crystalline substance: this was obtained, by crystallisation from a mixture of alcohol and light petroleum, in colourless lamina melting at 126°. It is readily soluble in alcohol and benzene, sparingly soluble in light petroleum. Analysis gave figures agreeing with the CH, CH CH2(CH3)(C2H2)OH CH; CO formula of a desylthymol, * From our experience with other phenols, it is probable that the employment of an excess of phenol in this experiment would have given a still better result. |