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diphenylene ketone oxides from salicylic acid (Perkin, Trans., 1883, 35) and the intermolecular change of sodium phenyl carbonate to sodium salicylate, suggest that the naphthyl ethyl carbonate may have become changed to the ethyl salt, OH C10H COOEt, and that 2 mols. of the latter have condensed with formation of the compound C2H2O2; this would then be dinaphthylene ketone oxide,

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The isomeride obtained by boiling ß-dinaphthyl diethyl orthocarbonate (loc. cit.) crystallises from benzene in thin prisms melting at 194°. When phenyl ethyl carbonate is heated at 300° for 3-4 hours diphenylcarbonate is formed.

Paraditolyl carbonate is obtained by heating paratolyl ethyl carbonate at 300°; it is insoluble in water, moderately soluble in hot alcohol, and melts at 115°.

Thymyl ethyl carbonate is a thick liquid boiling at 260°; at 300° it decomposes into dithymyl carbonate, melting at 60°.

Orthonitrophenyl ethyl carbonate is prepared by the action of ethyl chlorocarbonate on potassium orthonitrophenoxide. It is a heavy yellow oil which boils with decomposition at 275-285°. The amidosalt, NH, CH,O.CO.OEt, melts at 95°; it is soluble in alcoho!, moderately soluble in boiling water. When distilled, it gives off alcohol with formation of anhydro-orthamidophenyl carbonate, C,H,NO2; the latter dissolves in alkalis. The silver salt, C,H,AgNO2, forms an amorphous, colourless precipitate. The ethyl salt is obtained. by boiling the compound with alcoholic potash and ethyl iodide. When heated with fuming hydrochloric acid, it yields ethyl orthamidophenol and carbonic anhydride; the constitution of the substance is NEt. therefore CH-0NE CO. The phenylhydrazine compound of anhydro-orthamidophenyl carbonate, C.H.<_>C: N·NHPh, crystallises in yellow needles, which melt at 208°. The acetyl-derivative melts at 97-98°. A mononitro-compound was prepared; it forms long yellow needles melting at 256°. Bromine acts on the anhydro-compound with formation of a monobromo-derivative; this crystallises from water in plates melting at 196°. When treated with phosphoric chloride, the compound C,H,CINO, is formed.


N. H. M.

Parahydroxybenzyl Alcohol. By J. BIEDERMANN (Ber., 19, 2373— 2376).- Parahydroxybenzyl alcohol, OH CH, CH2OH, is prepared by dissolving parahydroxybenzaldehyde (1 part) in a mixture of water (10 parts) and alcohol (5 parts); it is then acidified with dilute sulphuric acid and gradually treated with 3 per cent. sodium amalgam (40 parts). Grey crystals of diparahydroxyhydrobenzoïn and oily drops of diparahydroxyisohydrobenzoin separate. When hydrogen is no longer evolved, the solution is made strongly acid and left for 12 hours, it is then filtered, the filtrate extracted with ether, and the ethereal extract treated with hydrogen sodium sulphite. On evaporating the ether, the alcohol separates in needles; these are purified by dissolving them in hot chloroform and precipitating with light petroleum. It forms slender

white needles, readily soluble in water, alcohol, and ether, sparingly in benzene and chloroform; sulphuric acid dissolves it, yielding a splendid red-violet solution. It melts at 110°. The alcohol is also formed when parahydroxybenzaldehyde is kept dissolved in alcoholic potash for several weeks, but the reaction is still very incomplete. The acetyl-derivative, OH·CH¿CHOAc, is prepared by heating the alcohol with a mixture of glacial acetic acid and sulphuric acid. It crystallises from water in small yellow needles, melting at 84°, and is readily soluble in alcohol and ether, sparingly in water, benzene, chloroform, &c. The diacetyl-derivative, OAc CHACH2OAc, is obtained by heating parahydroxybenzyl alcohol with an excess of acetic anhydride at 160° for 5-6 hours. It forms yellowish needles melting at 75°, readily soluble in alcohol and ether, sparingly in benzene, &c.

Anisic alcohol, OMe C,H,CH,OH[= 1:4], is formed when parahydroxybenzyl alcohol is dissolved in methyl alcohol and digested with potash and methyl iodide for some hours at 100°. The product is treated with water, heated to expel methyl alcohol and iodide, and extracted with ether. On evaporating the ether, it is obtained as an oil which gradually solidifies when kept over sulphuric acid. It crystallises from water in needles melting at 45° (compare Abstr., 1886, 460). N. H. M.

Synthesis of Betorcinol (B-Orcinol). By S. v. KOSTANECKI (Ber., 19, 2:18-2324; comp are Abstr., 1886, 242).-Paraxylorcinol [Me2: (OH), = 1:4:3: 5] was prepared from metadinitroparaxylene by replacing the nitro-groups successively by amido- and hydroxylgroups; it is identical with Stenhouse and Groves's betorcinol (Trans., 1880, 396). The crude product obtained by nitrating paraxylene is crystallised from alcohol to remove most of the orthodinitroparaxylene, dissolved in hot alcoholic ammonia, and treated with hydrogen sulphide for about one hour; it is then evaporated to dryness. The paradinitro-compound, being more readily reduced than the metacompound, is thus converted into paranitroparaxylidine, which is extracted by means of hydrochloric acid. The residue, insoluble in acid, was extracted with boiling alcohol, and yielded crystals of pure metadinitroparaxylene. This was reduced by dissolving in alcoholic ammonia and treating for two hours with hydrogen sulphide, and the nitroxylidine [Me: NO.: NH2 = 1:4:3: 5] so obtained was converted into the corresponding nitroxylenol. The latter crystallises in yellow plates melting at 91°. It was reduced with tin and hydrochloric acid, and the amidoparaxylenol diazotised; to 1 gram of the hydrochloride 10 grams of sulphuric acid and 100 grams of water were used, and the whole kept cold by means of ice and salt.

Paraxylorcinol so prepared has all the properties ascribed to it by Stenhouse and Groves (loc. cit.), except that it yields a green fluorescent solution when treated with dilute soda and chloroform.

Metaxylorcinol (Pfaff, Abstr., 1883, 918) crystallises from chloroform in white monoclinic crystals, a:b: c = 1·7237:1:?; ß = 38° 21′. It boils at 276-279°. When heated with sodium carbonate solution at 130°, metaxylorcinolcarboxylic acid, CHMe.(OH), COOH, is formed.

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The latter crystallises from dilute alcohol in well-formed prisms which melt with decomposition at 196°, and give a deep blue coloration with ferric chloride. N. H. M. Acetalresorcinol. By CAUSSE (J. Pharm. [5], 13, 354-358). -The author has examined the action of sulphuric acid and heat on a solution containing acetaldehyde and resorcinol. The crystals obtained are insoluble in water, ether, chloroform, and benzene. They are soluble in alcohol, which yields them again partly changed. Anhydrous ether dehydrates them, converting them into a powder, which in time aggregates to yellow, translucent crystals. Thus purified, the compound decomposes on fusing with regeneration of resorcinol. Its composition is indicated by the formula C1HO C,H,O + 2CHO, H2O. The action of heat on the compound apparently removes the elements of water. Heated at 120°, a reddish powder was formed which could be obtained in large brown crystals. These had the composition C28H16O7 = 2C11H1O. — H2O.


The diacetyl compound, C6H19O12, melts at 282°. The reactions. indicate that the yellow crystals are a molecular combination of aldehyde and resorcinyl ether, C,H,O,O(C,H,OH)2.

J. T. Benzylamine. By T. CURTIUS and G. LEDERER (Ber., 19, 2462— 2463). When benzaldehyde and amidoacetic acid are heated together at 130°, carbonic anhydride is evolved and benzylamine formed. Similar reactions seem to take place when cinnamaldehyde, salicylaldehyde, or orthonitrobenzaldehyde, are substituted for the benzaldehyde, but the products are not so easily isolated.

L. T. T.


Citric Acid Derivatives of Paratoluidine. (Ber., 19, 2352-2354).-Citroparatoluidide, CH ̧O1(ÑH•C‚H;) ̧, is obtained by heating citric acid (1 mol.) and paratoluidine (3 mols.) at 140-145° for 10 hours. It crystallises from alcohol, in which it is sparingly soluble, in lustrous, microscopic needles, melting at 189°.

Citrodiparatoluide, C,H,O,(NH-C,H,): N.C,H,, is formed when citric acid (1 mol.) and paratoluidine (2 mols.) are heated at 160-170° for three hours. It melts at 205°, is insoluble in water, rather readily soluble in ether and alcohol, and separates from the latter solvent in small, yellow, well-formed crystals. When heated with citric acid at 140-145°, it is converted into citroparatoluidide. Ammonia acts on it, yielding a salt of citroparaditoluidic acid, C,H,O,(NHC,H1)2OH. The latter crystallises from alcohol in groups of needles, melting at 161°. It is soluble in water, insoluble in alcohol and ether.

Citroparatoluidic acid, CHO.(OH): NC,H,, is prepared by adding paratoluidine (1 mol.) to a hot concentrated alcoholic solution of citric acid (1 mol.). On cooling, the solution yields clear prismatic crystals; these are heated for two hours at 160-170°, and crystallised from water. It melts at 172.5°, and dissolves readily in alcohol, ether, and hot water. N. H. M.

Azc. and Diazo-compounds. By O. WALLACH (Annalen, 234, 350—364).— Paracetometatoluylenediamine, obtained by the action

of acetic anhydride on metatoluylenediamine (Abstr., 1883, 329) can also be prepared by converting nitrotoluidine (m. p. 77.5°) into the aceto-compound (m. p. 144-5°), and reducing this substance with iron filings and acetic acid. By means of the diazo-reaction, the acetometatoluylenediamine is converted into acetamidocresol (m. p. 225°), proving that the acetyl-group occupies the para-position. Paracetamidotolueneorthazodimethylaniline,

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is formed when a solution of the diazo-compound is poured into an ice-cold alcoholic solution of dimethylaniline. The substance crystallises in golden plates and melts at 200°. It unites with acids to form salts, which dissolve in water, yielding deep-red solutions. The acetyl-group can be eliminated by boiling with dilute sulphuric acid. Paramidotolueneorthazodimethylaniline crystallises in golden scales. It melts at 145°, and dissolves in hot alcohol, chloroform, and benThe diazo-compound unites with phenol, forming tolueneacodimethylanilineparuzophenol, NMe2 C2H, N, CH2Me•N2 C2H ̧·OH.

This substance dissolves in dilute solutions of the alkalis, and is reprecipitated by carbonic acid. It also dissolves in strong acids, and is reprecipitated by the addition of water. It dissolves freely in alcohol, ether, chloroform, and benzene.

The corresponding B-naphthol-compound melts about 244°. It is insoluble in water, sparingly soluble in alcohol, but dissolves in strong sulphuric acid, with a red coloration.

Paracetamidotolueneorthazodiethylaniline crystallises in needles of a reddish-brown colour. It melts at 159°, and dissolves freely in alcohol, ether, chloroform, and in acids. The salts are decomposed by large quantities of water. Orthacetometatoluylenediamine, NHACCH M.NH, [Me:NHAC :NH, = 1:2:4], prepared from orthoamidoparanitrotoluene (m. p. 107°), crystallises in white needles, and melts at 140°. It is soluble in alcohol, in ether, and in hot water. Orthacetamidotolueneparazodimethylaniline melts at 192°, and dissolves freely in alcohol, chloroform, benzene, and ether. Orthamidotolueneparazodimethylaniline melts at 215°, and is freely soluble in



Acetamidobenzenemetazodimethylaniline, NHAc·C2H ̧•N2°C ̧H ̧•NMe2, crystallises in plates, and melts at 184°. Amidobenzeneuzodimethylaniline forms golden scales, soluble in alcohol, which melt at 165166°. W. C. W.

Quinone-oximes. By J. SUTKOWSKI (Ber., 19, 2314—2317).— When thymoquinone-oxime is dissolved in cold, fuming hydrochloric acid, a yellow precipitate is formed, consisting of dichlorothy moquinone and monochloramidothymol (Andresen, Abstr., 1881, 590). When the precipitate is boiled with glacial acetic acid, a splendid red dye is formed. The reaction is of interest, as it shows the analogy between the reactions of thymoquinone and of thy moquinone-oxime with fuming hydrochloric acid. Andresen also obtained the same products from thy moquinonechlorimide. The oxime is therefore the hydroxyl-derivative corresponding with the quinonechlorimide.

When chloramidothymol hydrochloride and chloranil are heated in glacial acetic acid solution, the red dye above mentioned is formed. Tetrachloroquinol is formed in the reaction; it crystallises in long colourless needles melting at 232°. Analyses of the dye point to the formula C30 H35C13N2O3.


In a similar manner, a dye was obtained by the action of paramidothymol on chloranil in glacial acetic acid solution. It has the com. position expressed by the formula CH3N2O3. It dissolves in acetic acid, alcohol, ether, and benzene, but not in water. Ammonia dissolves it with formation of a blue solution. Lead acetate gives a blue precipitate. N. H. M.

Amidine-derivatives. By M. LOEB (Ber., 19, 2340—2344).— When the compound C16H12N2Cl2O2, prepared by the action of carbonyl chloride on ethenyldiphenyldiamine (Abstr., 1885, 1213), is treated with alkalis or acids, it is reconverted into the amidine. Boiling water has no action on it; boiling alcohol converts it into carbanilide, ethyl acetate, and ethyl chloride. The ethyl salt, OEt CO NPh.CMe: N⚫C,H,COOEt, separates from its ethereal solution in hard, lustrous, rhombic crystals which melt at 90.5°. When the chloride is dissolved in benzene and treated with dry ammonia, it is converted into ethenyldiphenyldiamine and ammonium chloride; aniline acts like ammonia.



Ethenylimidobenzanilide, CMeph>CO, is prepared by the action of carbonyl chloride dissolved in benzene on an excess of ethenyldiphenyldiamine; it crystallises from benzene in large, lustrous plates melting at 118°. It is identical with the compound to which the formula CO(CH3N2)2 was previously ascribed (loc. cit.). Dilute hydrochloric acid decomposes it with formation of aniline and phenyl cyanate.

When a saturated ethereal solution of ethenyldiphenyldiamine is treated with two or three drops of water and then with cyanogen until it has a wine-red colour, and allowed to remain for 16 hours, a black crust is formed which yields a compound, CHINO; the latter forms a white, crystalline powder very sparingly soluble in ether and benzene, and cannot be recrystallised, as it at once resinifies when heated with solvents. It becomes violet at 120°, and melts with decomposition at 165°. Its constitution is probably analogous to that of Griess' cyanocarbimidoamidobenzoic acid, as shown in the formula NPh CMe NPh C(NH)CN + H2O. Ethyl allophanate is formed when urethane (7 parts) and carbonyl chloride (1 part) are dissolved in benzene and heated at 75°. N. H. M.

Preparation of Aromatic Amides. By M. FILETI (Gazzetta, 16, 281-284). The method, proposed by Letts, for the preparation of the nitriles by heating the carboxylic acids with potassium thiocyanate, has been shown to yield the amides, if ammonium thiocyanate be substituted for the potassium salt. The former change is attributed by Kekulé to the greater dehydrating action of the po.assium salt, an interpretation confirmed by the observation of

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