Page images

C&CI,O,Ca + 2H2O is obtained as a crystalline precipitate insoluble in water, by adding copper sulphate to a solution of the ammonium salt. The zinc salt is more soluble in cold than in hot water. It crystallises in needles. The ethylic salt, ¤¿C1,(COOEt),, melts at 60.5°, and the methyl salt, C.Cl,(COOMe)2, crystallises in prisms which melt at 92°. The acid ethyl salt, COOH-C,CI, COOEt, melts at 94-95°.


Tetrachlorophthalio chloride, C.CL<C>O, crystallises in large prisms. It melts at 118°, and boils at 336°. The tetrachloride, .CCI,. C.CLCCO, prepared by the action of phosphoric chloride on tetrachlorophthalic anhydride in sealed tubes at 200°, crystallises in rhombohedra. It melts at 140°, and is soluble in ether. Tetrachlorophthalide melts at 208.5°. It is soluble in acetic acid and in hot toluene. Tetrachloroxylylene oxide melts at 218°. It is deposited from solution in hot benzene or toluene in long needles. When ammonia is passed into the molten anhydride, tetrachlorophthalimide, C.CO.NH is formed. It melts at about 360°. Tetrachlorofluorescein dissolves in a solution of sodium hydroxide. On the addition of an acid, a compound is precipitated which contains one molecule of water more than tetrachlorofluorescein. It is tetrachlororthofluorescein. If ammonia is substituted for sodium hydroxide this compound is not formed.

Tetrachlororthofluoresceïn, C20CLH10O8, is insoluble in water, but soluble in ether. The dilute alkaline solution is distinguished from that of fluorescein by its red tint. Tetrachlorofluorescein is insoluble in ether. The diacetate dissolves freely in chloroform. Tetrachlorogallein, C20HCL,O, + 2H2O, is formed by the action of pyrogallol on tetrachlorophthalic anhydride at 190°. It is a violet-coloured crystalline powder, and yields a colourless acetic derivative, C20HCl,O,Ac..

W. C. W.

Action of Cyanamide on Benzenesulphonic Acids. By J. VILLE (Compt. rend., 104, 1281-1284).-Amidobenzenesulphonic acid (sulphanilic acid) (10 parts) is heated at 100° in closed tubes for two or three days with water (200 parts), cyanamide (about 3 parts), and 20 to 25 drops of ammonia. The hot, filtered liquid deposits prismatic lamella which, when reorystallised, form brilliant needles of the composition C,H,N,SO3. This compound is attacked by sodium hypobromite with evolution of nitrogen, and is decomposed by boiling aqueous solutions of alkalis, with liberation of amidobenzenesulphonic acid, ammonia, and carbonic anhydride. It is therefore a creatine, a-amidophenylsulphocyamine, SO,H.C2H, NH·C(NH) NH2. It is neutral, has no odour and no taste, is much less soluble in cold water than sulphanilic acid, is only very slightly soluble in boiling water, and is insoluble in ether. It dissolves to a considerable extent, however, in boiling water. a-Amidophenylsulphocyamine is decomposed by heat with formation of a yellowish-white sublimate. It dissolves in sulphuric and hydrochloric acids without change, and yields no dehydration-product corresponding with creatinine. this respect it resembles taurocyamine.


3 k


With sodium hypobromite it yields a purple-red liquid, and nitrogen is evolved. With nitric acid it forms a colourless solution; with excess of sodium hypochlorite containing a drop of phenol, it gives a fugitive carmine-red coloration. All these reactions serve to disC. H. B.

tinguish it from sulphanilic acid.

Chlornitro-derivatives of the Aromatic Series. By R. HIRSCH (Ber., 20, 1569—1571).-When amidophenolsulphonic acid suspended in water is treated with bleaching-powder solution a portion goes into solution and the liquid becomes coloured a dull violet, but as soon as sufficient bleaching powder has been added to bring about the solution of the whole of the acid, a sudden change to a very faint yellow colour occurs. The substance so produced could not, however, be isolated, and treatment of the solution with hydrogen sulphide or zinc-dust failed to effect its reduction to amidophenolsulphonic acid.

Different results are obtained when hydrochloric acid is present, and instead of a violet-coloured intermediate compound being formed quinonechlorimidesulphonic acid is obtained as the chief product of the reaction. This acid also could not be isolated from its golden-yellow solution, but was recognised by various qualitative tests, such as the production of amidophenolsulphonic acid and sulphur by the action of hydrogen sulphide, and of a deep indigo-blue solution on the addition of phenol, a- and B-naphthol, resorcinol, and other phenols, also of dimethylaniline, &c. The blue colour with phenol is ascribed to the formation of a sulphonic acid of indophenol.

The production of chlornitro-derivatives by the action of bleachingpowder on the aromatic amines appears to be a general one, inasmuch as acetanilide chloride (this vol., p. 44), paramidodimethylaniline chloride, and also the chlorides of sulphanilic acid, naphthionic acid, and metamidobenzoic acid have been obtained and recognised by colour reactions. W. P. W.

Sulphimido-compounds. By P. T. CLEVE (Ber., 20, 1534— 1538).— Orthosulphimidobenzene, C.H.<S>, is obtained when a solution of orthonitrobenzenesulphonic chloride in benzene is mixed with hydriodic acid diluted with glacial acetic acid. The crystalline product is washed with alcohol and crystallised from boiling glacial acetic acid from which it separates in slender, yellow needles melting at 193°; it is sparingly soluble. Metasulphimidobenzene, C,H,NSO, prepared in a manner similar to the ortho-compound, crystallises in yellow needles very readily soluble in boiling alcohol. It melts at 83°. The para-compound is an oily substance very readily soluble in glacial acetic acid.


Sulphimidonaphthalene, CH<i> [? SO2 : NH = 1 : 4′], is prepared from a-nitronaphthalenesulphonic chloride, and forms a very sparingly soluble, crystalline powder melting at 167°.

B-Sulphimidonaphthalene, [NH: SO2 = 1' : 2], crystallises in slender,

yellow needles, very sparingly soluble in glacial acetic acid and alcohol. It melts at 180°.

-Sulphimidonaphthalene forms lustrous, slender, lemon-coloured needles melting at 124°. It is very sparingly soluble.

-Sulphimidonaphthalene resembles its isomerides, and melts at N. H. M.


Ethyl Benzoic Sulphinide and Ethyl Orthosulphaminebenzoate. By C. FAHLBERG and R. LIST (Ber., 20, 1596-1604).— .CO Sodium benzoic sulphinide, C.H.<C>NNa + 2H2O, is formed when pure benzoic sulphinide is exactly neutralised with aqueous soda or sodium carbonate. It crystallises in large, rhombic tables, is extremely soluble in water, sparingly soluble in hot alcohol, and has an intensely sweet taste. If the anhydrous salt is heated with ethyl iodide for some hours at 230°, an almost quantitative yield of ethyl benzoic sulphinide, C,H,SO,N, is obtained; this crystallises in long, white needles, begins to fuse below its melting point, and melts at 93-94°. It is very readily soluble in alcohol and ether, and, unlike benzoic sulphinide and its salts, is without taste. When heated with hydrochloric acid, the ethyl salt undergoes hydrolysis and yields ethylamine and orthosulphobenzoic acid: a reaction which affords confirmatory evidence in favour of the above formula for the sulphinides.

Potassium orthosulphethamidobenzoate, COOK CH, SO2NEtK.— Ethyl benzoic sulphinide is not attacked by boiling with concentrated aqueous potash, but when heated in alcoholic solution with alcoholic potash at 100°, is converted into the potassium salt of orthosulphamidobenzoic acid, which crystallises in nacreous scales, is strongly alkaline, and extremely soluble in water. The sodium salt crystallises in tufts of slender needles; the silver salt forms aggregates of needles and is soluble in water; the copper salt crystallises with 2 mols. of H2O in dark-green prisms, sparingly soluble in water. The acid is obtained as an oil on the addition of an acid to the aqueous solution of the potassium or sodium salts; it crystallises in needles, is soluble in water, readily soluble in alcohol and ether, and has no definite melting point, inasmuch as it begins to fuse at 102°, and is not completely fluid below 116°.

Ethyl orthosulphaminebenzoate, COOEt C,H,SO,NH2, is obtained when a solution of benzoic sulphinide in absolute alcohol is saturated with hydrogen chloride. It crystallises in long, white needles, melts at 83°, and is readily soluble in boiling water, alcohol, and ether. On saponification with potash, it yields potassium benzoic sulphinide and alcohol, and similar products are obtained by the action of ammonia, lime, barium hydroxide, and even sodium carbonate in the cold. The ethyl salt is formed if a mixture of ethyl iodide, sodium ethoxide, and orthosulphamine benzoic acid in molecular proportions is heated for some hours, but cannot be obtained by saturating an alcoholic solution of the acid with hydrogen chloride, inasmuch as in this case benzoic sulphinide is the sole product.

An alcoholic solution of sulphamine benzoic sulphinide (Abstr.,

1881,816), when saturated with hydrogen chloride, yields ethyl disulphaminebenzoate, COOEt C&H (SO,NH2)2, which is converted into the .CO potassium salt NHK SO2 C2H2SO, >NK, when treated with alcoholic potash, and into sulphaminebenzoic sulphinide with aqueous potash. W. P. W.

"Saccharin." By E. MAUMENÉ (Bull. Soc. Chim., 47, 92—94).— Fahlberg's "saccharin," as prepared by his patent, is not a definite compound, but is composed of at least two components, which appear to be mixed in equal proportions; neither the mixture nor either of its components agree in composition with the formula given by Fahlberg. A. P.

Indole from Dichlorether and Aniline. By J. BERLINERBLAU (Monatsh. Chem., 8, 180-186).-Indole is prepared by heating 50 grams of aniline with an equal volume of water in a reflux apparatus, and gradually adding 25 grams of dichlorether. After being boiled for one hour, the excess of aniline is boiled off, and the residue heated for four to six hours at 210-230°. The indole is obtained by steam distilling,

The formation of indoles from dichlorether and aromatic amines is a general reaction. N. H. M.

Synthesis of Indonaphthene-derivatives.


(Ber., 20, 1574–1576).—Methylindonaphthenecarboxylic acid,


is obtained when ethyl benzylacetoacetate is gently heated with about six times its weight of concentrated sulphuric acid for a short time. It crystallises from alcohol in needles, melts at 200°, and when reduced with sodium amalgam is converted into methylhydrindonaphtheneCHMe. carboxylic acid, CH-CH-CH-COOH, which melts at 76°. Methylindonaphthenecarboxylic acid, when suspended in chloroform and treated with bromine (1 mol.), is converted into a bromine. derivative, CH, Br-COOH. This acid crystallises in needles, melts at 245°, and is sparingly soluble in alcohol.

The dihydronaphthoic acid obtained by v. Pechmann (Abstr., 1883, 808) by the action of sulphuric acid on ethyl benzylacetoacetate is most probably identical with methylindonaphthenecarboxylic acid. W. P. W.

Preparation of Paradinitrodibenzyl. By W. ROSER (Annalen, 238, 363-366).-Paradinitrodibenzyl is formed when paranitrobenzyl chloride is treated with a strongly alkaline solution of stannous chloride. W. C. W.

Triphenylmethane-derivatives. By E. Kock (Ber., 20, 1562— 1566). Attempts to form derivatives of triphenylmethane by the condensation of primary amines of the meta-series and aromatic

aldehydes with or without the addition of zinc chloride, led either to no result or to the formation of resinous products from which crystalline compounds could not be isolated; the substitution of the corresponding hydrochlorides for the bases, or of meta- or para-nitrobenzaldehyde for benzaldehyde produced no difference. When, however, tertiary amines of the meta-series are employed, condensation compounds are readily obtained.


NO2 CHCH(C,H,Me NMе2) 2,

is formed when dimethylmetatoluidine (8 parts) and paranitrobenzaldehyde (5 parts) is heated with zinc chloride and hydrochloric acid at 110° for four hours. It crystallises from a mixture of alcohol and benzene in glistening, golden-yellow scales, and melts at 224°. The picrate, СHN,O16, forms small, bright-yellow crystals, melts at 199°, and is sparingly soluble in alcohol, ether, benzene, and light petroleum. On reduction, preferably with stannous chloride, the leuco-base, C2H3N3, is obtained, and crystallises from alcohol in greyish aggregates melting at 139°. The colour remains unaltered after lengthened exposure to the air, but the alcoholic solution of the base after addition of acetic acid gives with chloranil a wine-red colour quickly changing to a dull-brown. A platinochloride of constant composition could not be obtained.


NO, CH,CH(C&H,CI-NMe2)2,

is formed under similar conditions from dimethylmetachloraniline and paranitrobenzaldehyde, and crystallises from benzene in citronyellow scales melting at 208°. The picrate, C35H29N9O18Cl2, melts at 189°. When reduced with zinc-dust and acetic acid the corresponding leuco-base, C23H25N3Cl2, is obtained, and crystallises from a mixture of alcohol and benzene in almost colourless aggregates melting at 181°. It is unaltered on exposure to the air, yields no coloration on oxidation with chloranil or lead dioxide, and does not form a platinum salt of constant composition.

Metanisidine and paranitrobenzaldehyde readily form a condensation compound without the addition of zinc chloride; the yield, however, is a proportionately small one. The base,

NO2 C&H CH[C6H3(OMe)NH2]2,

crystallises from benzene in yellowish-brown scales, melts at 189°, and on reduction yields a readily oxidisable leuco-base, which assumes an intense bluish-violet colour on exposure to the air. W. P. W.

-Dichloronaphthalene and Monochlorophthalic Acid. By I. GUARESCHI (Gazzetta, 17, 119-126).-The chlorine atoms in 7-dichloronaphthalene, considering the methods of its formation, must be situated in two different nuclei, both being probably in the a-position. On oxidation with chromic acid in presence of acetic acid, dichloronaphthalene yields a monochlorophthalic acid, C,H,C1(COOH)2 [Cl: (COOH),: O =

« PreviousContinue »