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Analysis of Mineral Waters from Servia. By S. M. LOSANITSCH (Ber., 20, 1114-1115).-The table gives the analyses expressed in parts per 1000 of the springs of (I) Wrnjačka banja, (II) Bukowik, (III) Palanka, (IV) Alexinačka banja, (V)Ribarska banja, (VI) Wranjska banja, and (VII) Brestowačka banja :

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Analysis of the Water of a Saline Lake near the Stolüpin Mineral Springs. By P. BULITSCH (J. pr. Chem. [2], 35, 360-363). -The author has analysed the water from a triple lake about 40 miles from Balakowo, Samara. 1000 parts contained in grams 25-855 Cl, 0.009 SiO2, 0·002 Fe2O3, 2:343 SO3, 1·755 CaO, 2.099 Mg, 4·722 KCI, 28.497 NaCl, 0.019 Br, and total solid residue 45.483. The water was colourless, had an odour of hydrogen sulphide, a bitter saline taste, and a sp. gr. 1.0348 at 18°.

1.21 at 18°, The mother1000 parts

The water was concentrated till it attained a sp. gr. of during which process calcium sulphate crystallised out. liquor had a yellowish colour, and slightly acid reaction. contained in grams 160-575 C1, 0·025 SiO2, 1·399 SO3, 11.908 CaO, 11.200 Mg, 17·617 KCl, 174-244 NaCl, 0.793 Br, and a total residue of 262 606 grams. L. T. T.

Organic Chemistry.

The Relation between Petroleum and the Hydrocarbons of Coal-tar and Shale-tar. By G. KRAEMER and W. BÖTTCHER (Ber., 20, 595-609).-The results arrived at by the authors in an examina

tion of German petroleum combined with those obtained by Markownikoff in the case of Baku oil (Abstr., 1884, 1276) are held to prove that the hydrocarbons of petroleum and those present in coal- and shale-tar differ, not in character, but in the relative proportions of the two classes of hydrocarbons: those unattacked and those attacked by concentrated sulphuric or nitric acids. To the first group belong the paraffins and naphthenes, and to the second benzene- and, according to the authors' views, naphthene-derivatives. W. P. W.

New Class of Ferrocyanides and Ferricyanides. By J. A. MULLER (Compt. rend., 104, 994-996).-The formation of a violet precipitate on adding ferric chloride to certain solutions of ferri- or ferro-cyanides has been observed by Ortlieb and by Schützenberger, but the substance was not examined.

The author has obtained a considerable quantity of this violet substance, and has submitted it to investigation. The substance was treated with a warm solution of potassium carbonate insufficient for complete decomposition, filtered, the filtrate made alkaline with potash, boiled, again filtered, concentrated to saturation, and mixed with alcohol to precipitate potassium ferrocyanide. The last filtrate when carefully concentrated yields thin scales and rectangular tablets of the composition (K,FeC ̧Ñ¿O)2 + 7H2O, which become anhydrous at 110°. 100 parts of water at 18° dissolve 148 parts of the salt. The solution is neutral to litmus and phenolphthaleïn, and gives the following reactions with solutions of metallic salts: cadmium chloride, a white precipitate soluble in hydrochloric acid; cobalt nitrate, a pale-pink precipitate, becoming blue when heated, but regaining its original colour on cooling, insoluble in hydrochloric acid; copper sulphate, an apple-green precipitate, insoluble in hydrochloric acid; ferrous ammonium sulphate, a white precipitate which immediately becomes blue on addition of nitric acid; manganese chloride, a bulky white precipitate, soluble in hydrochloric acid; ferric chloride, a violet coloration, and after one or two days a precipitate of the same colour, partially soluble in cold dilute hydrochloric acid; ammonium molybdate in nitric acid, a canary-yellow precipitate; auric chloride, a red-brown coloration; uranium nitrate, an orange-yellow precipitate, insoluble in acetic acid, but soluble in ammonium acetate solution.

When heated at 300-400°, out of contact with air, until evolution of gas ceases, the anhydrous salt loses 9.05 per cent., and yields 8:33 per cent. of carbonic oxide (calc. 8·47 per cent.), together with potassium cyanide and iron cyanides. The composition and properties of this compound involve the assumption of the existence of a trivalent .CO. radicle, carbonyl-ferrocyanogen,<>Cy.

Fe

If a solution of the potassium salt is mixed with chlorine-water until it no longer gives a violet coloration with ferric chloride, a yellow solution is obtained which contains the carbonyl ferricyanide. It gives a violet-blue precipitate with ferrous sulphate, a white precipitate with mercurous nitrate, and with silver nitrate a maroon precipitate which rapidly becomes white. When this solution is

treated with sodium amalgam, it yields the ordinary ferrocyanide and the carbonyl ferrocyanide.

Friedel points out that the existence of this compound supports the formula for ferrocyanides which he proposed some years ago. According to this view, the ferrocyanides contain a ring of carbonatoms. In Muller's compound, the group NH" is replaced by the element O" without any alteration of the nucleus.

Fe

‚N:C·C(NH)·C(NH),

N: C-C(NH)-C(NH)

Ferrocyanide.

Fe

N: C·C(NH)·C(NH).
N:CCO—C(NH)
c.co
Carbonyl ferrocyanide.

C. H. B.

Constitution of the Melamines. By B. RATHKE (Ber., 20, 1056 -1059).-The author considers that Ponomareff's observation that silver cyanurate reacts with alkyl iodides with formation of normal alkyl cyanurates, besides isocyanurates, decides the question of the constitution of cyanuric acid and melamine in favour of Hofmann's view (Abstr., 1886, 931). As the normal ethers readily change into isoethers, and the reverse reaction does not take place, the normal ethers must be the primary products of the decomposition.

The formula NHC(NR) NH-
CNR) NH>C:NR is suggested for tri-
NR)

_C(NHR):N,
>C(NHR)N>

phenylmelamine as well as the nitrile formula N<

>CNHR.

NHR.

The essential difference between these formule and that of the iso

C(NH) NR

compound NRC(NH) NR>C: NH, is that whilst in the former the

alkyl is contained in the side-chain, in the latter it is attached to the ring. N. H. M.

Thiammeline. By B. RATHKE (Bər., 20, 1059–1065).—Thiammeline is readily obtained by direct combination of dicyandiamide with thiocyanic acid; the same compound has also been obtained by Klason by the action of potassium hydrosulphide on the substance (CN),(NH2)2Cl, obtained from cyanogen chloride and ammonia. Thiammeline functions both as an acid and a base; the oxalate, (C3HыN ̧S)2C2H2O1, and nitrate crystallise in needles, the sulphate in leaflets; a potassium salt crystallising in needles, and a silver salt, a white precipitate, are described. A characteristic reaction of thiammeline is the production of a yellow, flocculent precipitate when a solution of its salt is boiled with copper sulphate and ammonia; when heated with concentrated hydrochloric acid, it is decomposed into cyanuric acid, ammonia, and hydrogen sulphide. Attempts to prepare an ethyl-derivative of thiammeline were unsuccessful, but with ethylene bromide an ethylenethiammeline hydrobromide, CH,N,S,HBr, was obtained, crystallising in colourless pyramids; the free base was not isolated. V. H. V.

Cocceryl Alcohol and Coccerylic Acid. By C. LIEBERMANN and O. BERGAMI (Ber., 20, 959-966; comp. Abstr., 1885, 1045).-The

62

formula C30H2O2, previously ascribed to cocceryl alcohol, is confirmed by further investigation. The acetyl-derivative, CH(OAc)2, is obtained by heating two parts of the alcohol with one part of acetic anhydride at 170° for two hours; it forms snow-white crystalline flocks, melts at 48-50°, and is readily soluble in ether, warm alcohol, and acetic acid, very sparingly soluble in acetone. The benzoylderivative, C30H60(OBz)2, is prepared by heating one part of cocceryl alcohol with two parts of benzoic anhydride at 210-220° for three hours; it forms white flocks, melts at 60-62°, does not readily solidify when heated above its melting point, and is less soluble than the acetyl-derivative in the solvents just mentioned. When oxidised with chromic acid in acetic acid solution, cocceryl alcohol is converted into a new pentadecylic acid, the chief product, a second acid of high melting point and sparing solubility, and a neutral compound.

Pentadecylic acid, C15H30O2, is crystalline, melts at 59-60°, and is very readily soluble in alcohol, ether, benzene, and acetic acid, less soluble in light petroleum. It begins to boil at 257° under 100 mm. pressure, but the temperature rises during the distillation. The yield amounts to 40 per cent. of the cocceryl alcohol employed. Its calcium and barium salts were analysed; the methyl salt, CH29O,Me, is crystalline and melts at 66-68°.

Coccerylic acid is only partially oxidised with chromic acid in acetic acid solution, about 40 per cent. remaining unchanged. The chief oxidation product is pentadecylic acid (m. p. 62°), and the yield amounts to 40 per cent. of the coccerylic acid employed.

W. P. W.

Oxidation of Polyatomic Alcohols. By E. FISCHER and J. TAFEL (Ber., 20, 1088-1094).-By the oxidation of polyatomic alcohols, carboxylic acids only have as yet been obtained; the aldehydes and ketones which are formed, have not been isolated as intermediate products, owing to the inefficiency of methods used.

In this paper, the phenylhydrazine test is employed to indicate the formation of those aldehydes and ketones, and a class of substance obtained which it is proposed to call the osazones.

=

Thus on warming glycerol with nitric acid (sp.gr. 1·18), for a short time a violent reaction ensues; after removal of the nitrous acid with carbamide, a liquid is obtained, which reduces Fehling's solution, and gives with phenylhydrazine hydrochloride a crystalline substance of the composition C15H16NO, a phenylglycerosazone, which melts at 131° and decomposes at 170° with evolution of gas; it is sparingly soluble in hot water, readily in alcohol and ether. To it the constitutional formula OH CH·C(N2HPh)·CH: N2HPh is provisionally assigned, as more probable than the alternative formula

N2HPh: CH-CH(OH)·CH: N2HPh.

In order to decide whether the product of oxidation is an aldehyde or ketone, the nature of the substance obtained by treatment of dibromacraldehyde with baryta is examined. After removal of the excess of baryta, the substance formed reduces Fehling's solution and gives with phenylhydrazine a crystalline precipitate of the composition C18H22NO, resembling phenylglucosazone in physical properties and

external appearance; it is probable that a glucose is formed in the reaction thus: 2C,H,Br2O+2Ba(OH)2 CH120 + 2BaBr2.

In like manner erythrol, on oxidation with dilute nitric acid, yields a substance which reduces Fehling's solution and gives with phenylhydrazine a crystalline substance, C16H1sN.O2, melting at 166-167°, sparingly soluble in hot water, more readily in ether and benzene; the reaction with dulcitol is precisely similar. On the other hand, isodulcitol, although classified with the above hexatomic alcohols, differs from them in yielding a crystalline precipitate with phenylhydrazine without previous oxidation with nitric acid. This substance, CH10O3(N,HPh),, crystallises in needles, melting at 180° with decomposition, soluble in alcohol and ether. Thus isodulcitol belongs rather to the aldehydic or ketonic alcohols, and its formula is probably C6H12O5; it combines with water in like manner to chloral and glyoxylic acid; it is possibly the methyl-derivative of arabinose. V. H. V.

A New Galactan. Properties of Galactose. By E. O. v. LIPPMANN (Ber., 20, 1001-1008).—The liquid obtained in the manufacture of sugar from the lime sludge after being freed from lime by means of carbonic anhydride and oxalic acid and evaporated down, yielded, when kept for two months, a thick, gelatinous precipitate. This was kneaded with water until the wash-water remained colourless, dissolved in boiling milk of lime, and the liquid evaporated whilst carbonic anhydride was passed in. It was then put into tall cylinders to settle, the clear liquid drawn off, evaporated, and when cold treated with excess of hydrochloric acid and precipitated with absolute alcohol. This operation was repeated and the gum purified by fractional precipitation with absolute alcohol; it was then kneaded under absolute alcohol and finally left in small pieces in alcohol. It then forms an almost white, brittle mass, very readily soluble in water (the impure substance is insoluble in cold water and alcohol). It has the formula C,H10Os; the aqueous solution is dextrorotatory: [a]D = +238° (in a 10 per cent. solution at 20°), it does not reduce Fehling's solution. When inverted with dilute sulphuric acid, it is completely converted into galactose; the name y-galactan is therefore given to the compound.

The author's previous statement that galactose ferments when treated with yeast has been confirmed by Tollens, although according to Kiliani (Ber., 13, 2305) no fermentation takes place. N. H. M.

Preparation of Normal Propylamines and Isoamylamines. By H. MALBOT (Compt. rend., 104, 998-1000).-Normal propyl alcohol and fermentation amyl alcohol were converted into the corresponding chlorides, and after purification these were heated with an equivalent quantity of ammonia in sealed tubes at 140-165° for 12 to 24 hours (see this vol., p. 356). The proportion of primary amine diminishes as the molecular weight of the radicle increases; it is onefifth for the propylamines, one-tenth for the isobutylamines, and very small indeed for the isoamylamines. The formation of tertiary amines is probably due to a reaction between the primary amines first formed and the still unaltered alkyl chloride. C. H. B.

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