linked by three bonds, but indirectly by the intervention of other carbon atoms, thus (Fig. I): a formula made up of three hexamethylene rings. The formula we propose for camphene is derived from this triple hexamethylene spheric formula, thus (Fig. II). By breaking the link marked a, we derive the formula of camphor; whereas by breaking the two links marked ß, and leaving the link a, we derive camphoic acid. In the first case, a pentamethylene and a hexamethylene ring are left, while when the links ßß are broken, a hexamethylene ring only is left, which is, moreover, different from the hexamethylene ring of camphor. Further, we represent turpentine or pinene by the same structure as camphene, omitting the link y, and introducing one double linking. The production of camphene from turpentine hydrochloride is readily explained by this hypothesis, which, we believe to be borne out by other reactions of turpentine and its oxidation products. The universally-accepted structure for citrene and cymene is also readily derived from that of turpentine by eliminating the linking 8, and from camphene by elimination of both and links. The camphor and camphoric acid formule, derived from the above camphene formula, differ from those proposed by Marsh in 1889 only in the position of the methyl group in the ring. Against those formulæ, no serious objection has been brought forward except that they do not account for the production from camphoric acid of trimethylsuccinic acid. But the formation of trimethylsuccinic acid appears to us to indicate such a complete breaking down of the camphoric acid molecule, that it would not seem likely to have any more value for the determination of the formula of that compound than, for example, VOL. LXIX. H the formation of methylsuccinic acid from tartaric acid or of alcohol from sugar has for determining the constitution of tartaric acid or of sugar respectively. The formula now proposed for camphor and camphoric acid, differing, as we have said, from the earlier ones only in the position of the methyl group, are represented below as derived from camphene. In conclusion, we believe that the formulæ suggested in this paper account in a simple manner for the principal facts relating to the terpene and camphor groups. They account 1. For the conversion of turpentine, citrene, and camphor into cymene. 2. For the conversion of camphor into carvacrol. 3. For the conversion of turpentine into camphene and into citrene. 4. For the oxidation of camphene to camphor and to camphoic acid. 5. For the absence of double linkings in camphene, and for the presence of one double linking in turpentine and two in citrene. 6. For the production from camphoric acid of camphanic acid, and campholactone. 7. For the relationship of camphoric acid and camphoic acid to hexahydroisoxylene. 8. For the general analogy of camphoric acid and camphopyric acid, and for the stereoisomerism manifested by them. University Laboratory, Oxford. 91 IX.-The Action of Sodium Alcoholate on Amides. By JULIUS B. COHEN, Ph.D., and WILLIAM H. ARCHDEACON, B.Sc., The Yorkshire College. Ar the meeting of the British Association in 1894 (Brit. Assoc. Reports, p. 625) a communication was read by one of us on the constitution of the amides, containing a brief reference to the action of sodium methoxide on acetanilide. As this action appeared to us to have an important bearing on the constitution of the amides, we have studied it more fully, and now bring before the Society the results which we have obtained. If, to a solution of acetanilide in dry ether, powdered sodium methoxide is added in molecular proportion, it dissolves; but after the lapse of a few minutes, a voluminous crystalline compound is deposited, filling the liquid. This substance has the formula CH•NH COCH,CH, ONa. Similar compounds have been prepared with ortho- and para-acetotoluidide and a- and B-acetonaphthalide on the one hand and with sodium methoxide and ethoxide on the other. Benzanilide and formanilide form similar compounds. With formylphenylhydrazide, however, no additive compounds are formed; but the sodium appears to displace the hydrogen in the amido-groups. In the case of benzamide, a fine granular compound is obtained, which appears to be a mixture of the alcoholate additive compound with sodium benzamide. With propionanilide, butyranilide, diphenylacetamide, and ethylacetanilide no definite compounds have so far been obtained by this method. In the case of propionanilide and butyranilide such compounds appear to exist in solution; for if a little ether be added to either of these substances, sufficient to dissolve a fraction of the whole, the addition of the sodium alcoholate will at once produce a clear solution; on evaporating the ether under diminished pressure, nothing separates out until the greater portion of the ether has gone, when crystals of the unchanged anilide are deposited. Acetanilide Sodium Methyloxide, CH, NH.CO.CH,,CH,'ONa.-1.35 grams of acetanilide is dissolved in dry ether (complete solution is not necessary) and 0.54 gram of finely powdered sodium methoxide is added; on shaking, a clear solution is obtained, but very soon a pasty magma of needle-shaped crystals forms. The crystals are collected, washed with ether, and dried over sulphuric acid in a vacuum. The substance forms a white, apparently amorphous mass. It gave the following results on analysis. I. 0·2455 gave 0·0942 Na2SO. Na = 12·47. II. 0.4359 0.1695 Na = 12·59. III. 0.2620 16.1 c.c. dry nitrogen at 13° and 770 mm. N=7·45. IV. 0.1890 0.372 CO, and 0-1115 H2O. C = 56·98; H = 6·55. C,H12NaNO2 requires Na 12-17; N = 740; C = 57·14; H = 6·35. In some of the subsequent determinations, the sodium has been estimated by decomposing the compound with water and titrating with decinormal oxalic acid, using phenolphthaleïn as indicator. The above compound is quickly decomposed by water and alcohol and also by boiling ether and acetone, which dissolve out the acetanilide. It is also decomposed by acid chlorides, forming the methylic salt of the acid, sodium chloride, and acetanilide according to the equation CH•NH COCH,CHONa + •R’COC1= CH, NH.CO.CH, + NaCl + CH,COOR'. If acetyl chloride is added to the calculated quantity of the substance suspended in ether, methylic acetate, sodium chloride, and acetanilide are formed; the latter was identified by decomposing it, with potash, into acetic acid and aniline, and by a nitrogen estimation. 0.1905 gave 17.5 c.c. moist nitrogen at 752 mm. and 16°. N≈ 10:48. CH,NO requires N = 10:37 per cent. Benzoyl chloride acts similarly. From 2 grams of the sodium methoxide compound and 1.79 gram of benzoyl chloride, 1 gram of methylic benzoate, and 1·29 gram of acetanilide were obtained. On heating the compound in a stream of dry hydrogen for four hours to 100°, methylic alcohol distils together with a little aniline; the aniline was identified by converting it into the platinochloride and analysing it. 0.294 gave 0.0955 Pt. Pt = 32.48. (C&H, NH2)2, H2PiCl, requires Pt 32 66 per cent. The residue consisted for the most part of sodium acetanilide. 0.231 gave 15 C.C. moist nitrogen at 759 mm. and 13°. N = 7·65. C,H,NNAO requires N 7:40 per cent. Further, the sodium acetanilide obtained in this way was treated with benzoyl chloride, when benzanilide, melting at 160°, is formed. The substance was analysed with the following result. 0.1745 gave 11.3 c.c. moist nitrogen at 21° and 760 mm. N = 7:38. C1HNO requires N 7·11 per cent. = The action of iodine on the sodium methoxide compound suspended in ether gives rise to a number of products, among which phenylcarbamine, acetanilide, and iodoform were identified. Ethylic iodide yields ethyl methyl ether and acetanilide. The following compounds have been prepared in a manner similar to acetanilide sodium methoxide. Where the amide is but slightly soluble in ether, the sodium alcoholate has been added to the substance suspended in the ether, well shaken, and then filtered or decanted. The clear filtrate, on standing, deposits crystals of the new compound. Acetanilide sodium ethoxide, CH, NH.CO.CH3.C2H, ONa.-The preparation of this compound is identical with that of the sodium methoxide compound, and the substance is not distinguishable from the latter. The following results were obtained on analysis. 0-283 required 13.9 c.c. decinormal oxalic acid. Na = 11·3 per cent. 0-2345 11.7 Na = 11·4 Paracetotoluidide sodium methoxide, CH,C,H,NH.CO.CH,, CH, ONa. Orthoacetotoluidide sodium methoxide, CH3-CH, NH·CO·CH2,CH,'ONa. = 0-1705 required 7-8 c.c. oxalic acid. Na 10.52 per cent. CHUNO,Na requires Na = 11:33 per cent. 3 a-Acetonaphthalide sodium methoxide, CH, NH.CO·CH3,CH3·ONa. This substance crystallises in brilliant, needle-shaped crystals. 0-2875 required 11.6 c.c. oxalic acid. Na 9.3 per cent. CH,NO,Na requires Na= 9.6 per cent. Paracetotoluidide sodium ethoxide, CH, CH, NH.CO.CH,,C2H;'ONa 0.176 gave 0.0566 Na2SO. Na = 10.4 per cent. 0-1413 required 6.5 c.c. oxalic acid. Na = 10.6 per CHNO,Na requires Na= 10.6 per cent. cent. Orthoacetotoluidide sodium ethoxide, CH, CH, NH.CO.CH,,C2H, ONa. 0.1335 gave 0.0440 Na2SO1. Na 10-6 per cent. CHINO,Na requires Na 10.6 per cent. a-Acetonaphthalide sodium ethoxide, CH, NH •CO-CH3, C2H, ONa. 0-4035 required 15.8 c.c. of oxalic acid. Na = 90 per cent. CHINO2Na requires Na = 9.1 per cent. B-Acetonaphtalide sodium ethoxide, C10H, NH.CO⚫CH, C2H2ONa. 0-346 gave 0.1 Na2SO4. Na = 9.3 per cent. CHINO,Na requires Na = 9.1 per cent. |