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Action of Hydroxylamine on Diketones. By F. MÜNCHMEYER (Ber., 20, 228).-The compound OH-N: C(CH, NMe), melts at 233°, and not at 98-99° as previously stated (Abstr., 1886, 877).

W. P. W.

Naphthoic Acids. By Å. G. EKSTRAND (Ber., 20, 219–226).The compound obtained by the reduction of dinitro-a-naphthoic acid (m. p. 265°) with hydrogen sulphide in ammoniacal solution, to which the provisional formula COOH-CH, N2: O2 was ascribed (Abstr., 1886, 948), contains sulphur either as an impurity or in combination. The purest specimen gave figures corresponding with the formula C33H18N&SO6; owing to its sparingly soluble and uncrystallisable nature it is impossible to decide whether the substance analysed was free from admixed sulphur, although none could be extracted by carbon bisulphide. If stannous chloride dissolved in aqueous potash is employed as the reducing agent, a compound is obtained resembling the preceding in its appearance, infusibility, and insolubility in alcohol.

Dinitro-a-naphthoic acid, probably [NO2: NO2: COOH = 1': 4: 1], melting point 218°. When nitro-a-naphthoic acid (m. p. 239°) is nitrated with red fuming nitric acid, three dinitro-acids are obtained, of which two, melting at 205° and 265°, have been previously described, whilst the third melts at 218° and is formed in very small quantity. It is very soluble in alcohol, from which it is obtained in hard, deep yellow, rhombic crystals, a b c = 0·9731 : 1 : 1·4424, whilst from water it crystallises in slender needles. The ethyl salt crystallises in long, hard, yellow needles melting at 129°; the calcium salt, with 7 mols. H2O, crystallises in thin, lustrous, broad, yellow needles, and is readily soluble in water. When reduced with tin and hydrochloric acid, the dinitro-acid is converted into the hydrochloride NH of an amidonaphthostyril, NH2 C10H5<CO>,HCl, which melts at a high temperature, and crystallises in long, bright yellow needles, sparingly soluble in cold water.

a-Naphthamidoxime, obtained together with a-naphthamide by heating an alcoholic solution of a-naphthonitrile and hydroxylamine in molecular proportions, crystallises in large lamina, melts at 148149°, and is readily soluble in alcohol, acetic acid, and benzene, soluble in water and insoluble in light petroleum. The hydrochloride crystallises after a long time in stellate aggregates of needles, and melts at 160°; the platinochloride forms long, prismatic, yellow needles. When heated at 100° with acetic anhydride, and the product treated with water, a-naphthamidoxime is converted into a-naphthazozimethenyl, CH,CNO >CMe; this crystallises from alcohol in long, colourless needles and melts at 36°. a-Naphthoyl-a-naphthamidoxime, C1H,C(NH·CO·C10H2): N-OH, obtained by heating 2-naphthamidoxime and a-naphthoic chloride in molecular proportions at 100°, crystallises in small, slender needles, and melts at 228; it is insoluble in alcohol and hydrochloric acid.

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B-Naphthumidoxime, prepared in manner similar to the a-compound, forms lustrous scales, melts at 150°, is soluble in alcohol, and is

gradually decomposed by boiling water. The hydrochloride forms long needles, melts at 178°, and is very soluble in water. B-Naphthazoximethenyl crystallises in large scales, melts at 87°, and is soluble in alcohol. B-Naphthazoximnaphthenyl,

NO.
C10H-CC-C10H7,

obtained by heating ß-naphthoic chloride and B-naphthamidoxime in approximately molecular proportions, crystallises in broad needles or scales, melts at 175°, and is almost insoluble in alcohol.

W. P. W.

a- and B-Naphthenylamidoxime. By E. RICHTER (Ber., 20, 227). The author has independently arrived at results which confirm those of Ekstrand (preceding Abstract); acetyl-a-naphthenylamidoxime melts at 129°. Acetyl-B-naphthenylamidoxime melts at 154°; the benzoyl-derivative melts at 179°; the ethyl salt melts at 74-75°. Ethylidenenaphthenylamidoxime melts at 121-122°.

W. P. W. Chloronaphthalenesulphonic Acids. By P. T. CLEVE (Ber., 20, 72-75)-1:4' Chloronaphthalenesulphonic acid, CHCI SO2H + 2H2O, obtained by diazotising the amido-acid corresponding with a-nitronaphthalenesulphonic acid, crystallises in colourless tables readily soluble in water. A chlorosulphosulphonic acid,

C10HCI SO2 C10H6 SOзH,

is also formed in this reaction, this yields an insoluble amorphous potassium salt. Potassium chloronaphthalenesulphonate crystallises in lustrous needles; the sodium salt forms thin scales; the silver salt forms thin tablets sparingly soluble in water; these salts are anhydrous. The barium salt with 2 mols. H2O is a sparingly soluble, indistinctly crystalline powder. The ethyl salt melts at 46°, and crystallises in large, monoclinic prisms, a:b: c = 1.6785: 1:?; B68° 58', which show distinct pleochroism. The chloride forms triclinic crystals resembling hexahedra, melts at 95°, and is soluble in chloroform; the amide crystallises in lustrous scales, melts at 226°, and is sparingly soluble in alcohol.

1: 4 Chloronaphthalenesulphonic acid (Abstr., 1883, 595) can be prepared by diazotising naphthionic acid. The ethyl salt melts at 104 and crystallises in large, thin, monoclinic tables, a:b:c 1.32807: 1:1·12623; ß = 80° 59′. The chloride melts at 95°, and crystallises in triclinic forms; the amide melts at 187°.

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a-Chloronaphthalene-B-sulphonic acid (probably 1': 2) is prepared by diazotising the amido-acid from the author's B-nitronaphthalenesulphonic acid (this Journal, 1877, i, 469); it crystallises in colourless rhombic tables and is readily soluble in water. The potassium salt forms very thin, glistening tables sparingly soluble in cold water; the barium salt, with 1 mol. H2O, is a sparingly soluble, crystalline powder. The ethyl salt melts at 111°, is soluble in chloroform, readily soluble in hot alcohol, and crystallises in well characterised monoclinic forms; a: b:c043067:1:?; B = 86° 45', the crystals being either long prisms almost quadratic in section, or thick tables. The chloride

ß

forms small scales, melting at 114-115°; the amide forms thin scales, melts at 216°, and is soluble in alcohol. W. P. W.

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Brönner's B-Naphthylaminesulphonic Acid. By S. FORSLING (Ber., 20, 76-81).-Brönner's B-naphthylaminesulphonic acid. NH3 C10H SO2H + H2O, obtained by the action of ammonia on ßnaphtholsulphonic acid at 180°, crystallises in colourless lamina of silky lustre, and is very sparingly soluble in water, the solution having a blue fluorescence. The potassium salt with 1 mol. H2O forms long, white needles, and is soluble in cold water to the extent of 1 in 40° to 45°; the ammonium salt with 1 mol. H2O forms broad, white needles, and when heated at 180° gives off the whole of its ammonia; the sodium salt with 2 mols. H2O forms white needles, and dissolves to the extent of 1 in 40 in cold water; the silver salt with 1 mol. H2O is an indistinctly crystalline powder. The barium salt with 6 mols. H2O crystallises in long, white needles, and requires 450 parts of cold water for its solution; the calcium salt with 6 mols. H2O crystallises in laminæ, and dissolves in 225 parts of cold water; the magnesium salt with 6 mols. H2O crystallises in lamina or broad needles. The crystals of all these salts have a silky lustre, dissolve sparingly in water, and give solutions showing blue fluorescence. The lead salt with 2 mols. H2O is very sparingly soluble in water; the zinc salt with 4 mols. H2O forms well-characterised, microscopic crystals, and is sparingly soluble in water: the copper salt with 4 mols. H2O forms microscopic needles, is very sparingly soluble in water, and has a mosaic gold colour which changes to red in the anhydrous salt. The corresponding diazonaphthalenesulphonic acid, CH,N2SO, a yellow microcrystalline powder, yields, by Sandmeyer's reaction and subsequent treatment with phosphoric chloride, the chloride of Arnell's B-chloronaphthalenesulphonic acid melting at 110° (Abstr., 1886, 555), from which e-dichloronaphthalene, melting at 136°, is obtained by distillation with phosphoric chloride. The amide, C10H CI SO2NH2, crystallises in needles and melts at 183-184°.

W. P. W.

Some Essential Oils. By P. SOLTSIEN (Chem. Centr., 1886, 936— 937). An examination of Oleum citri, Oleum bergamotte, and Oleum cort. aurantiorum dulcium. These oils were prepared specially and were therefore pure. The author has examined them with Heppe's copper butyrate reaction and also various turpentines (Abstr., 1885, 1163); he finds that it is of little value, as the action depends on the age of the oil. He also re-examined the bromination of the oils, and confirms Wallach's statements in the main. G. H. M.

Isomeric Camphols and Camphors. By A. HALLER (Compt. rend., 104, 66—68).-Camphol from madder, discovered by Jeanjean, crystallises from light petroleum in hexagonal plates similar to the crystals of the other camphols. Borneo camphol is similar to the others, but its rotatory power, though equal in amount, is opposite in direction. Its derivatives, however, correspond in rotatory power and other properties with the derivatives of other camphols. Cam

phol from amber crystallises from light petroleum in the ordinary form, but differs from the other camphols in its rotatory power and its behaviour with bromine. When treated with bromine, it yields a buttery product, which contains a small quantity of a dextrogyrate monobromocamphor melting at 75°, but the greater part of the product melts below 50°. The corresponding camphoric acid also differs from that derived from other camphols, since it melts at 202° and is less soluble in water.

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The author's investigations show that all camphols are chemically identical, and differ only in their action on polarised light. The camphols from madder, valerian, N'gai, and Bang-Phien have the same molecular lævorotatory power, [a]p -37°, and the corresponding camphors are identical with that from fever-few (matricaire). The camphor from Dryabalanops camphora has a rotatory power equal in amount but opposite in direction. Its derivatives are, however, identical with those from the other camphols. Camphol from amber is mainly a racemic camphol mixed with a dextrogyrate borneol.

C. H. B.

Carveol, Borneol, and Menthol. By R. LEUCKART (Ber., 20, 114-116). The author gives the name carveol to an alcohol, C10H15 OH, which he has obtained by reducing carvole with sodium and alcohol. It is a thick liquid, has a characteristic odour quite different from that of carvole, and boils at 218-220°. The acetate and benzoate are liquid. With phenyl cyanate, even in the cold, it yields carvyl phenylamidoformate, NHPh COO-C10H15. This compound forms small needles, easily soluble in alcohol, sparingly so in ether, and melts at 84°. Borneol similarly forms bornyl phenylamidoformate, NHPh COO C10H17, crystallising in needles soluble in boiling alcohol and melting at 133°. Menthol, under similar circumstances, yields menthyl phenylamidoformate, NHPh COO CH19, which crystallises in silky needles soluble in boiling alcohol and melting at 111°. No corresponding compounds are obtainable from carvole, camphor, or bromo-camphor, which seems to point to the absence of a hydroxylgroup in the latter substances. At higher temperatures, reaction takes place between carvole and phenyl isocyanate; carbonic anhydride is evolved, and diphenylcarbamide is among the products of the reaction.

L. T. T.

Bornylamine. By R. LEUCKART and E. BACH (Ber., 20, 104114). When small quantities of camphor (not more than 4 grams should be used in each operation) are digested with two and a half times their weight of ammonium formate in sealed tubes at 220-240°, carbonic anhydride, carbonic oxide, ammonium carbonate, and a syrupy mass are produced. The latter distils at 290-300°, and yields a compound of the formula CHINO, which crystallises in glistening scales, melts at 60-61°, and is easily soluble in alcohol and ether. When digested with aqueous hydrochloric acid, it yields a crystalline base, bornylamine, C10H1N, which melts at 158-160°, boils at 199200°, and is easily volatile in steam. It resembles camphor in physical properties, smell, and volatility at ordinary temperatures, &c. It is very sparingly soluble in water, easily so in alcohol and ether, is a strong base, and forms easily soluble salts, the aqueous solutions of

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which have an acid reaction. Its vapour-density is 5.5. It is lævorotatory, a 12.5 per cent. solution showing a rotation of [a]D -18° 35′ 41′′. The hydrochloride, C10H19N,HCl, forms small, white needles melting with decomposition at 280°. An aqueous solution of the hydrochloride, on long-continued boiling, undergoes partial decomposition, depositing camphene. The platinochloride forms goldenyellow scales, the acid sulphate, CH,N,H,SO,, rhombic plates. Formobornylamine, C10H18N COH, is obtained by the action of anhydrous formic acid on the free base, or of sodium formate on the hydrochloride. It forms glistening scales melting at 61°. This substance is identical with the original substance formed by the action of ammonium formate on camphor, and described above. Acetobornylamine, CHINAc, obtained by dissolving the base in acetic chloride, crystallises in colourless scales melting at 141°. Benzobornylamine, similarly prepared, crystallises in colourless scales which melt at 131o. Bornylcarbamide, NH, CO NH C10H17, is formed by boiling potassium isocyanate with bornylamine hydrochloride. It crystallises in colourless needles, which melt at 164°, and are easily soluble in alcohol and water. When an ethereal solution of bornylamine is allowed to act on methyl isocyanate, methylbornylcarbamide, NHME.CO·NH·C10H17, is formed; it crystallises in scales melting at 200°, and is soluble in water and alcohol. Bornylphenylcarbamide, NHPh.CO⚫NH C10H17, similarly obtained, forms silvery needles, easily soluble in hot alcohol, sparingly in cold alcohol and ether, insoluble in water. It melts with decomposition at 248°. Bornylphenylthiocarbamide, NHPh CS NH C10H17, formed from phenylthiocarbamide and the free base, crystallises in colourless needles melting at 170°.

The authors believe bornylamine to be isomeric and not identical with camphylamine, described by Goldschmidt (Abstr., 1886, 249 and 557).

The authors have also succeeded in obtaining bornylamine, although in very small quantities, by the reduction of camphoroxime by sodium amalgam. From this fact, and from its method of formation from camphor, they (accepting the ketone-formula of camphor as the most

CH2

probable one) ascribe to bornylamine the formula C.H<CH(NH)> They believe camphylamine to be very closely related to and probably only a position-isomeride of bornylamine.

The authors have also obtained from carvole a corresponding carvylamine, which is now being investigated. L. T. T.

Active Principles of Asclepias Currassavica, A. Incarnata, and Vincetoxicum Officinale. By C. GRAM (Chem. Centr., 1886, 735). These three Asclepiadeæ contain a glucoside which the author calls Asclepiadin. In the aërial parts of Asclepias currassavica the easily decomposed asclepiadin of Harnack was found; this appears to be identical with the asclepin of Feneulle. The asclepiadin isolated by the author is easily soluble in water, sparingly soluble in alcohol; it is easily converted into the less active asclepin. Only asclepidin, and no asclepin, could be obtained from the root of Vincetoxicum officinale. The asclepin which is prepared from Asclepias tuberosa by Keith and 2 c

VOL. LII.

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