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iodide and trimethylbismuthine at 200°, and forms lustrous, brick-red crystals, rather readily soluble in alcohol. It becomes black when exposed to light, and melts at 225° with decomposition.

Diethylbismuthine bromide, BiEt, Br, is a powder; it inflames in air. The chloride, BiEtCl, (Dünhaupt, Annalen, 92, 371), and the bromide, BiEt Br2, were prepared in like manner to the methyl-compounds. The iodide, BiEtI, forms lustrous, bright-red crystals.

Methylbismuthine oxide, BiMeO, is obtained by treating with ammonia the zinco-bromide of bismuth methyl bromide dissolved in alcohol. It inflames when warmed, dissolves readily in aqueous soda, and is insoluble in water.

Dimethylbismuthine hydroxide, BiMe, OH, is formed when bismuth methyl bromide is treated with water. It is inflammable. Water decomposes it slowly. When heated with methyl iodide at 100°, bismuth monomethyl iodide is formed.

N. H. M.

Furfuran-derivatives. By G. NUTH (Ber., 20, 1332-1338).Hantzsch described (Abstr., 1886, 707) the formation of complex furfuran-derivatives by the action of sodium phenoxides on ethyl chloracetoacetate, and of sulphuric acid on the resulting compound. The author has employed substituted phenols in analogous reactions.

Ethyl paranitromethylcumarilate,

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formed from paranitrophenol and ethyl chloracetoacetate, crystallises in white needles, is soluble in ether and the usual solvents, and melts at 74°. The free acid forms yellow needles, moderately soluble in boiling water, ether, and alcohol; it melts at 178°. Its salts are sparingly soluble; the lead, mercury, cobalt, copper, and silver salts were prepared. The above reaction only took place when the constituents were heated together in an anhydrous condition. Metanitrophenol appears to act in a similar way, but the yield was very small. The ortho-compound gave very unsatisfactory results. Methyl salicylate yielded no furfuran-derivative.

Quinol yielded ethyl parabenzodimethyldifurfurandicarboxylate, C.HCMCCOOEt). This substance crystallises in greenish, glistening scales, very sparingly soluble in the usual solvents, insoluble in cold alkalis; it melts at 150°. The free acid forms a yellowish-green, amorphous mass containing 1 mol. H2O, which it loses at 110°. The alkaline salts are soluble, the remainder insoluble. When distilled with lime, the potash salt yields parabenzodimethyldifurfuran, C.HCM⇒CH). This crystallises in large, glistening tables, having a bluish fluorescence. It is soluble in alcohol, ether, &c., and melts at 108°.

Quinol yields only the above difurfuran-derivative. When the monosodium-compound of quinol is used instead of the di-compound the result is a diminished yield, but no monofurfuran-derivative is formed.

Catechol likewise yields only ethyl orthobenzodimethyldifurfurandicarboxylate. This crystallises in short, white prisms and melts at

155°. The free acid resembles that of the para-compound, but contains no combined water.

The para-compounds when warmed with strong sulphuric acid give the intense blue coloration characteristic of most furfuranderivatives, but the ortho-compounds give a green coloration which, on stronger heating, changes to steel-blue.

The difurfuran obtained by Hantzsch from resorcinol (this vol., p. 262) melts at 27° and not at 17° as originally given. L. T. T.

Normal Propylthiophen-derivatives: Glyoxylic Acids of the Thiophen Series. By H. RUFFI (Ber., 20, 1740-1750).-It was thought that it might be possible to oxidise propylthiophen into an acid of the formula C,SH, CO-CO-COOH, but notwithstanding many variations in the method of working, a-thiophenic acid was always obtained.

Bromopropylthiophen, C.SH,BrPra, prepared by shaking propylthiophen with bromine-water (equimolecular proportions), is a colourless oil of aromatic odour and boils at 189°. The dibromo-compound, CASH Br2Pra, is prepared in a similar manner; it is a clear yellow oil of agreeable odour and boils at 248°. A tribromo-derivative seemed also to be formed in small quantity at the same time, but attempts to prepare it by treating dibromopropylthiophen with pure bromine led to the formation of tetrabromothiophen. Iodopropylthiophen, C.SHIPra, was also prepared; it is a yellow oil of agreeable odour which volatilises with steam, but cannot be distilled alone. Dinitropropylthiophen, C1SH(NO2)2Pr2, is prepared by drawing the vapours of propylthiophen through fuming nitric acid; it is a yellow oil and can be distilled with steam.

Propylthiophenic acid, C,SH,Pra-COOH, is obtained as its ethyl salt by heating a mixture of iodopropylthiophen (20 grams), ethyl chlorocarbonate (10 grams), and 1 per cent. sodium amalgam (500 grams), and distilling the product with steam, when the ethyl salt passes over as an oil. The free acid crystallises in slender needles or lamellæ and melts at 57° (uncorr.).

Acetopropylthienone, C,H,SPra COMe, is prepared by heating propylthiophen dissolved in light petroleum with acetic chloride and aluminium chloride. It is a yellow oil of fruity odour and boils at 255° (uncorr.). The phenylhydrazide is crystalline and melts at 60°. The oxime, CASH,Pra CMe: NOH, crystallises in slender needles and melts at 55°.

Propylthienylglyoxylic acid, C.SH,Pra-CO-COOH, is obtained by oxidising acetopropylthienone with an alkaline solution of potassium permanganate at the ordinary temperature, as an oil which gradually crystallises.

a-a-Methylthienylglyoxylic acid, CSH2Me CO COOH [= 2 : 5], is prepared by acetylising a-thiotolen (obtained from levulinic acid) and oxidising the ketone so obtained. It melts at 80°. The calcium and barium salts were prepared. a-B-Methylthienylglyoxylic acid, [= 3:5 ?], is

prepared in like

manner from B-thiotolen (from pyrotartaric acid). It crystallises in long needles, melts at 142° and sublimes, even at the

ordinary tempera

ture. When heated with hydroxylamine and aqueous potash it yields a nitroso-acid, C ̧SH2Me·C(ÑOH)·COOH, which crystallises in colourless needles and melts at 104°. The phenylhydrazide melts at 141°. The acid does not react with bromine.

a-a-Dimethylthienylglyoxylic acid, C,SHMe2 CO-COOH [= 2 : 5 : 3], is formed, together with an acid melting at 106°, by oxidising acetothioxylen (Messenger, Abstr., 1885, 1205). It is obtained as an oil which gradually solidifies.

From these results it follows that the acetylised thiophens when oxidised first yield glyoxylic acid, and this, whether or no the carbonatom to which the acetyl-group is attached is in direct union with the sulphur-atom. A. J. G.

Bye-products of the Manufacture of Thiophen. By V. MEYER and K. NEURE (Ber., 20, 1756).-The material worked on was an oil boiling above 220° obtained in the manufacture of thiophen by distilling succinic acid with phosphorous sulphide. When exposed to cold, the greater part crystallised; the crystals proved to be thiosuccinic anhydride. Small quantities of succinic anhydride were also obtained. The liquid portion when distilled with steam, gave a distillate heavier than water, most of which was soluble in alkalis. The insoluble portion was too small for proper investigation; it probably contained the still unknown thiënyl sulphide. The substance soluble in alkali proved to be thienyl mercaptan, and as a considerable amount was obtained further investigation of its derivatives was made.

The acetate, CASH, SAc, is a colourless oil boiling at 230-232°. Thienyl disulphide, S(C,SH3)2, obtained by the spontaneous evaporation in contact with air of a solution of the mercaptan in concentrated alcoholic ammonia, crystallises in yellow, lustrous needles and melts at 55-56°. The silver salt, C.SH, SAg, is obtained as a yellow precipitate on adding silver nitrate to a neutralised solution of the mercaptan. Methyl thienyl thioether, C,SH, SMe, is obtained by the action of sodium hydroxide and methyl iodide on the mercaptan; it is a colourless oil and boils at 186°.

If thienyl mercaptan is mixed with powdered diazobenzenesulphonic acid and a little water added, the liquid boils with vigorous evolution of gas, and an oil soluble in ether is formed. This reaction, which differs very essentially from that of phenyl mercaptan, could not be further studied from want of material.

A. J. G.

Formation of Croconic Acid from Benzene-derivatives. By R. NIETZKI (Ber., 20, 1617-1620).-When aqueous potash or soda is added to a solution of an alkaline salt of rhodizonic acid, the intense reddish-yellow colour changes to a pale-yellow and is not restored on neutralisation with an acid, whilst the resulting solution on acidification with acetic acid and treatment with barium chloride remains clear, and only begins to deposit the yellow barium croconate after remaining for one day. The intermediate compound thus evidently formed during the conversion of rhodizonic into croconic acid is obtained as a flocculent, orange-yellow barium salt on addition of ammonia to the acetic acid solution after treatment with barium

chloride, and the yield is equally good whether the operation is conducted in air or hydrogen. The new barium salt is identical with the barium salt of croconic acid hydride (Abstr., 1886, 449), but on analysis gives figures which agree better with the formula C,H2O,Ba + 2H2O than that previously assigned to the compound. Croconic acid hydride, CHO, most probably has the formula


and adopting the suggestion thrown out by Zincke (Ber., 20, 1267, footnote), the author considers that rhodizonic acid first yields a CO·C(OH).

labile hydroxy-acid, <CO.C(OH)>C(OH)-COOH, which at once breaks up into carbonic anhydride and croconic acid hydride.

W. P. W.

The Halogen Carriers in the Natural Groups of the Elements. By C. WILLGERODT (J. pr. Chem. [2], 35, 391-400).-— Benzene was treated with chlorine in the dark and in presence of the various substances examined, the alteration in weight noticed, and the product then subjected to fractional distillation. Yttrium and yttrium chloride are without action, lanthanam has a slight action; titanium none, germanium and germanium chloride none; zirconium is very active, and is thus the first active element in the carbon-group; cerium and cerium chloride are inactive, thorium and thorium chloride are almost inactive. Vanadium oxychloride, VOCl2, acts slightly; niobium and niobium chloride are active, didymium chloride is inactive, but tantalum and tantalum chloride are active. Of the elements of the oxygen-group, molybdenum and tellurium have already been shown to be very active; chromic chloride is inactive, and it therefore appears unlikely that sulphur is a chlorine carrier as has been stated previously by the author, and he now shows that the monochloride is quite inactive; uranium and uranium tetrachloride are active, the latter especially so. In the fluorine-group the only known chlorine carrier is iodine.

H. B.

The Halogen-benzene Haloïds: a-Trichlorobenzenehexachloride. By C. WILLGERODT (J. pr. Chem. [2], 35, 415-416). -Reference is made to previous work and to further experiments on paradichlorobenzenehexachloride. a-Trichlorobenzenehexachloride, CHCl3, Cls [Cl, 1:2:4], is crystalline, melts at 95-96°, and when heated with alcoholic potash yields pure hexachlorobenzene. H. B.

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Action of Acetylene on Benzene in presence of Aluminium Chloride. By R. VARET and G. VIENNE (Compt. rend., 104, 13751377). A mixture of benzene (200 grams) and aluminium chloride (50 grams) was treated with a current of acetylene for five hours per day during six days. At the beginning of each treatment, the liquid was gently heated, but afterwards the heat developed by the reaction itself was sufficient. The product was washed with water and alkalis, and then fractionated. It consisted of 80 parts of cinnamene, boiling at 143-145°, 15 parts of diphenylethane boiling at 265-270°, and 5 parts of dibenzyl boiling at 280-286°.

No naphthalene hydride, C10H10, nor hydrocarbon, C12H12, was formed. C. H. B.

Influence of Light on the Action of Halogens on Aromatic Compounds. By J. SCHRAMM (Monatsh. Chem., 8, 101-106).— Chlorine acts quickly on ethylbenzene in sunlight, with rise of temperature and formation of chlorethylbenzene; if sunlight is cut off by clouds or if the chlorine is passed in too quickly, substitution takes place in the benzene nucleus. The constitution of the product was determined by the method employed by Radziszewski for determining the constitution of a-bromethylbenzene. No other product is formed.

The action of chlorine on boiling ethylbenzene is much slower than in sunlight. The product contains the same chlorethylbenzene as that formed when the reaction takes place in sunlight (compare Abstr., 1886, 451). N. H. M.

Phenol. By E. MYLIUS (Arch. Pharm. [3], 25, 308).-Various reasons have been assigned for the red colour of phenol; the author attributes it to the action of the alkali obtained from the glass containing vessel. He has previously pointed out the great difference in the solubility of various glasses, and the resulting precipitates induced in morphine and antimony solutions, &c. This is quite sufficient to account for the coloration (that is, the oxidation of phenol). Of course this is not sufficient to account for the colour where the phenol is red under all circumstances, but only when one and the same sample becomes red in one flask and not in another.

J. T.

Action of Sulphur Dichloride on Phenol. By G. TASSINAKI (Gazzetta, 17, 83-87 and 90-94).-A violent reaction takes place on mixing sulphur dichloride and phenol; if this be moderated by lowering the temperature, a yellow solid gradually separates, which can be purified by solution in alkali and reprecipitation by carbonic anhydride. The compound, hydroxyphenyl sulphide, S(CH, OH)2, crystallises in leaflets, melting at 150°, sparingly soluble in cold, more readily in hot water. The reaction leading to its formation is as follows:-2C,H,OH + SCI, S(C,H,OH)2 + 2HC1; it is, however, probable that the phenolic hydrogen is at first displaced by the sulphur, and subsequently by an intramolecular change; the sulphur-atom displaces hydrogen in the phenyl-group. The metallic derivatives are unstable, but the acetyl-derivative, (CHOAc),S, is a sparingly soluble, crystalline substance, melting at 92-94°, partially decomposed on boiling with water, readily by alkalis.


In like manner parabromophenol yields a corresponding bromoderivative, S(C,H,Br.OH)2, melting at 175-176°, converted by hydrogenation with zinc-dust into a hydroxyphenyl sulphide, crystallising in micaceous scales, isomeric with the compound above described. It melts at 128-129°, is very soluble in caustic potash, and gives a blue coloration with ferric chloride.

The homologues of phenol yield similar derivatives; in the paper are described paramethylhydroxyphenyl sulphide, melting at 117

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