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saccharates, an anhydrous crystalline salt, and an amorphous salt containing 2 or 3 mols. H2O. At 150°, saccharic acid is decomposed by strong hydrochloric acid, yielding dihydromucic acid.

W. C. W. Metasaccharic Acid. By H. KILIANI (Ber., 21, 1422-1424).Maquenne (this vol., p. 677) has recently stated that the diphenylhydrazone of saccharic acid melts at the same temperature and has properties similar to those of the diphenylhydrazone of metasaccharic acid (ibid., p. 46), and has suggested that the two acids may be identical. The author, however, points out that the diamides of the two acids are not identical, and that potassium metasaccharate, unlike the saccharate, does not yield the potassium hydrogen salt on treatment with acetic acid. Dextrose and gluconic acid, when oxidised under the same conditions as arabinosecarboxylic acid, are not converted into the double lactone of metasaccharic acid, and it was not found possible to obtain saccharic acid by heating the double lactone with water, as the latter almost completely decomposed.

W. P. W.

Alkyl Salts of Sulphoacetic Acid and Ethylidenedisulphonic Acid. By R. MAUZELIUS (Ber., 21, 1550-1552).—Diethylsulphoacetate, SO,Ĕt·CH, COOEt, is prepared by the action of ethyl iodide on the silver sulphonate of ethyl acetate. The product is extracted with ether and dried with calcium chloride; on distilling off the ether, a yellowish liquid is obtained which can be made colourless by heating it in a beaker. It does not distil without decomposition.

Diethyl ethylidenedisulphonate, CHMe(SO,Et)2, is formed when the corresponding silver salt is gently heated with ethyl iodide. It is a slightly red oil of peculiar odour, readily soluble in alcohol and ether, insoluble in aqueous soda and in water. It decomposes readily when heated. The silver salt, CHMe (SO,Ag)2 + H2O, crystallises in slender needles. The sodium-derivative, CMeNa(SO,Et)2, prepared by the action of sodium ethoxide on the ethyl salt, forms globular groups of small needles.

Butanedisulphonic acid, CMeEt (SO,H)2, is formed when the above sodium-derivative is boiled with alcohol and ethyl iodide in a reflux apparatus. The product is dissolved in water and neutralised, when the sodium salt separates in long, flat needles, very readily soluble in water. N. H. M.

Action of Iodobenzene on Silver Nitrite. By A. GEUTHER (Annalen, 245, 99-101).—Silver nitrite does not act on iodobenzene at a temperature below 135°, but between 140° and 150° a reaction takes place resulting in the formation of trinitrophenol, silver iodide, and metallic silver. W. C. W.

Additive Product of Tribromodinitrobenzene and Tetrabromodinitrobenzene. By C. L. JACKSON and G. D. MOORE (Ber., 21, 1707–1708).—An additive product, 2C,HBг3(NO2)2,C,Br1(NO2)2, is formed when tribromodinitrobenzene (2 mols.) and tetrabromodinitrobenzene (1 mol.) are mixed together in benzene solution. It crystallises from alcohol in rhombic leaves melting at 165°, which are

tolerably stable and can be recrystallised from ordinary solvents, but are partially decomposed by methyl alcohol or by a mixture of methyl and ethyl alcohol. F. S. K.

Desmotropy in Phenols. Bisecondary Pentethylphloroglucinol. By J. HERZIG and S. ZEISEL (Monatsh., 9, 217-226).Pentethylphloroglucinol,

CO2Ets (OH) [OH: Et2 : 0 : Et2: 0: Et = 1:2:3:4:5:6],

is prepared as follows: phloroglucinol (1 mol.) is mixed with potash (3 mols.), dissolved in lukewarm 25 per cent. alcohol, and ethyl iodide (3 mols.) added. After the first somewhat energetic reaction ceases, the mixture is warmed for two hours, the alcohol distilled off, and the residue dissolved in water and extracted with ether. The ethereal solution is then shaken with potash until the latter is no longer coloured yellow, and on evaporating the ether a yellow, indifferent oil (Benedikt, this Journal, 1876, i, 250; Will and Albrecht, Abstr., 1884, 1335) remains. The potash is neutralised with hydrochloric acid with addition of a little sodium sulphite, and extracted with ether; when the ether is distilled, a brown product remains which is again treated with potash and ethyl iodide as described above, and the products separated as before. A yellow, indifferent oil and a compound which is soluble in potash are again obtained. The potash solution is acidified, extracted with ether, and the ether distilled, when the greater part of the residual pentethylphloroglucinol quickly solidifies. It crystallises from alcohol in white plates melting at 91-94°, but when the alcohol is too dilute, it separates in an oily condition and then solidifies to leafy crystals. It is not acted on when boiled with hydrogen iodide for two hours, and neither this compound nor the indifferent oil shows the pinewood reaction of phloroglucinol.

Hexethylphloroglucinol, CO,Et, is obtained by treating the pentaderivative with potash and ethyl iodide, but even with a large excess of the reagents a considerable quantity of pentethylphloroglucinol remains unchanged. It is an oily compound and completely insoluble in potash. One ethyl-group is readily and quantitatively eliminated as ethyl iodide, when it is treated with hydrogen iodide according to Zeisel's method.

The indifferent oil alluded to above is probably a mixture of the ethyl-derivatives of various pseudo-forms of phloroglucinol.

F. S. K. Preparation of Nitramines from Nitrophenols. By A. BARR (Ber., 21, 1541-1549).-Merz and Ris (Abstr., 1886, 872) obtained ortho- and para-nitraniline by heating the corresponding nitrophenols with aqueous ammonia. In a similar manner Witt (Abstr., 1886, 947) prepared dinitronaphthylamine from a-dinitronaphthol.

Dinitraniline, [NH2: (NO2), = 1:2: 4], is obtained by heating 3 grams of dinitrophenol (m. p. 112°) with 10 c.c. of 27 per cent. ammonia for 16 hours at 175°; the product is filtered and the red needles shaken with water containing ammonia and ether. The ethereal solution is separated, dried, and the ether distilled off. It

crystallises in light-yellow crystals melting at 176° (not 182°). The yield is 60 per cent. of the weight of dinitrophenol.

Metanitroparatoluidine is prepared by heating 3 grams of pure nitrocresol with 8 c.c. of 35 per cent. ammonia for 16 hours at 170— 180°. The yield is 63 per cent. of the weight of the nitrocresol.

Dinitrotoluidine, [Me: NH2: (NO2), = 1: 2: 3: 5], is formed when 3 grams of dinitrocresol is heated with 10 c.c. of 27 per cent. ammonia for 20 hours at 175-185°. It crystallises from xylene in yellow prisms melting at 208°.

Dinitroisobutylaniline, NH2 CH2(C,H,) (NO2)2, prepared by heating 3 grams of the dinitrophenol with 10 c.c. of 27 per cent. ammonia for 15 hours at 175°, crystallises from warm alcohol in slightly yellowishbrown, feathery crystals melting at 127°. It sublimes in yellow needles, is readily soluble in ether and warm alcohol, insoluble in boiling water.

Dinitrophenylenediamine, [NH2: NO2: NH2: NO2 = 1:2:34], is obtained when 4 grams of dinitroresorcinol is heated with 15 c.c. of 27 per cent. ammonia for 20 hours at 115°. It crystallises from glacial acetic acid in groups of light yellowish-brown needles which melt with decomposition at about 250°. It is very sparingly soluble in alcohol, ether, and benzene. The isomeric dinitro-amido-compound described by Nietzki and Hagenbach melts at about 300° (Abstr., 1887, 477).

Trinitrophenylenediamine, CH,NO, obtained by boiling diethyltrinitroresorcinol with alcoholic ammonia for a short time, separates from its solution in glacial acetic acid in crystalline grains which do not melt at 250°, and detonate slightly when heated in a flame. It is almost insoluble in the usual solvents except glacial acetic acid. Boiling aqueous sodium carbonate decomposes it with liberation of ammonia. When reduced with tin and strong hydrochloric acid, pentamidobenzene hydrochloride, CH(NH2)5,3HCl, is formed. This crystallises in hair-like needles, very readily soluble in cold water, almost insoluble in alcohol and ether. When the aqueous

solution is exposed to air, it becomes violet and a dark substance separates. The free base was not isolated. The pentacetyl-derivative, CH(NHAC), forms an almost insoluble, amorphous powder. Pentamidobenzene reacts without difficulty with benzaldehyde, phenanthraquinone, and benzil, &c., with formation of crystalline compounds.

Trinitrophenylenediamine could not be prepared from trinitroresorcinol and ammonia. N. H. M.

Cyanacetates of the Benzene Series. By A. HALLER (Compt. rend., 106, 1171–1174).—An aqueous solution of sodium nitrite containing 1 gram-molecule per litre, and a solution containing 1 grammolecule of aniline and 3 gram-molecules of hydrochloric acid per litre are prepared, and likewise hydrochloric acid solutions of orthotoluidine and paratoluidine half the strength of the aniline solution.

100 c.c. of the aniline solution or 200 c.c. of toluidine solution is cooled at 0° and mixed with 100 c.c. of the nitrite solution and a solution of ethyl sodiocyanacetate obtained by treating 113 grams of

ethyl cyanacetate in 50 grams of ethyl alcohol with 2.3 grams of sodium dissolved in 50 grams of alcohol. If methyl-derivatives are required, 9.9 grams of methyl cyanacetate in 30 grams of methyl alcohol is substituted for the ethyl cyanacetate and sodium methoxide for the ethoxide. The product separates as a yellow precipitate which is dissolved in potash, precipitated with sulphuric acid, washed with water, dried, and recrystallised from alcohol.

The derivatives thus obtained are yellow crystalline compounds insoluble in water, slightly soluble in cold alcohol, soluble in hot alcohol and in benzene, chloroform, ether, and alkalis. They also dissolve in hot solutions of alkaline carbonates.

Methyl azobenzenecyanacetate forms slender needles which melt at 86-5°. The corresponding ethyl salt melts at 124.9°. Methyl azotoluenecyanacetate [1:2] forms silky needles which melt at 167.2°. The ethyl salt melts at 125 8°. Methyl azotoluenecyanacetate [1: 4] melts at 133 5o, and the ethyl salt at 74-4°.

The solubility in alkalis indicates that these compounds have the constitution R·N2·CH(CN)·COOR, and not R⚫NH•N•C(CN).COOR, and the solubility in alkaline carbonates shows that the introduction of N, into the CH-group of the cyanacetates has greatly increased the activity of the acid function.

C. H. B. Bromacetorthotoluide and some of its Derivatives. By P. W. ABENIUS and O. WIDMAN (Ber., 21, 1662—1664).—Bromacetorthotoluide, prepared by the action of bromacetic bromide on orthotoluidine dissolved in benzene, crystallises in white needles melting at 113°. When this compound or the chlorinated derivative (m. p. 111-112°) is boiled with aqueous potash, diorthotolyldiketopiperazine, This crystallises in

C,H,Me.NCH, CONC.H.Me, is obtained.
COCH,

well-formed plates which melt at 159-169°, is insoluble in bases and in dilute acids. The platinochloride (with 4 mols. H2O) melts at 176°. When boiled with an excess of alcoholic potash for half an hour, orthotolylglycinylorthotolylglycine (orthotolylglycinorthotolylamidoacetic acid), CH, NH·CH2 CO·N (C2H1)·CH2·COOH, is formed; this melts at 129°. Phosphorus pentachloride reacts with ditolyldiketopiperazine at 140° with formation of the compound

C,H,N-CCI.CO

CO.CCI N.C,H,

which crystallises in slender needles melting at 200-201°.

Chloracetylorthotolylglycine, CH,Me•N(CO·CH2CI)·CH, COOH, is prepared by mixing ethereal solutions of chloracetyl chloride and orthotolylglycine; it crystallises from benzene in well-formed plates and melts at 116-117°; when heated with 2 mols. orthotoluidine at 160°, it is converted into diorthotolyldiketopiperazine.

Tetrabromodiorthotolyldiketopiperazine, CsHBrO2, is obtained by brominating orthacetotoluide at 160° and boiling the orthobromacetodibromotoluide so formed with alcoholic potash. It crystallises in plates and melts at 277°.

N. H. M.

Lactones derived from Glycines. By P. W. ABENIUS (Ber., 21, 1668-1669).-Glycolylorthotolylglycin,

COOH CH2 N(C,H,)·CO.CH, OH,

is formed when chloracetylorthotolylglycin (preceding Abstract) is boiled with an excess of soda. It crystallises in hexagonal leaves or prisms which melt at 143-144°, are readily soluble in water, alcohol, ether, chloroform, acetone, &c., but tolerably sparingly soluble in benzene.

.CH, CO.

2

Anhydroglycolylorthotolylglycin, CH,N<CO-CH2O, is obtained by heating the preceding compound at 160°. It crystallises from alcohol, in which it is readily soluble, in long prisms melting at 108-109°. It behaves like a lactone, dissolves slowly in cold caustic alkalis and in warm alkaline carbonates with regeneration of glycolylorthotolylglycin. F. S. K.

Pentamidobenzene. By A. W. PALMER and C. L. JACKSON (Ber., 21, 1706-1707).-Triamidodinitrobenzene, prepared from tribromodinitrobenzene melting at 192°, is an amorphous, yellow compound. It yields a colourless reduction product, the hydrochloride of which, CH(NH2)2(NH ̧Cl), or CH(NH)2(NH3C1)3, is a white powder which gradually turns brown on exposure to the air. F. S. K.

Orthazotoluene. By W. POSPECHOFF (J. Russ. Chem. Soc., 1887, 402-413).—According to Werigo and Petrieff this compound melts at 137°. The "ortho-azotoluene" of Hoogewerff and van Dorp melts at 55°, and is different from Petrieff's. Kissel, on repeating Hoogewerff and van Dorp's experiment, obtained a compound melting at 137°. Schultz, without regard to any existing discrepancies, gives the melting point as 55°. In order to settle the question, the author has reinvestigated the different processes by which orthoazotoluene may be formed. By the action of sodium amalgam on nitrotoluene, the product of direct nitrification of toluene (which according to many investigators is a mixture of symmetrical [2:3] and ortho-nitrotoluene [13]), a mixture of two azotoluenes was obtained, of which one melts at 137° and the other at 55°. The latter crystallises in short, red prisms, which were scattered about amongst the long, orange needles of the former. Petrieff's and Schultz's method consists in the reduction of orthonitrotoluene with zinc-dust. Orthonitrotoluene was purified by repeated distillation, in order to get rid of the symmetrical modification, and the product boiling at 122-123°, the purity of which was confirmed by oxidation and by reduction, was dissolved in alcohol and treated with zinc-dust in the presence of aqueous soda. After adding water, an oil was obtained, which the following day became converted into thick, red needles, melting at 55°. According to Tutkoffsky, the crystals are rhombic; axial ratio a: b: c = 0·875588: 1: 1013960; observed faces coP and Poo. They are ruby-red and pleochroic. By reduction with sodium-amalgam in alcoholic solution, this yielded colourless crystals of the hydrazocompound (m. p. 161°), which on oxidation again gave the red

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