substituted ethyl-group was eliminated, the above three compounds must have yielded amides which were identical.

In preparing methyl ethylacetoacetate the author found that if ethyl alcohol was employed as the solvent, the larger quantity of the methyl salt was converted into the ethyl salt. Making further experiments, he found that isobutyl or isoamyl salts could be readily obtained by the action of the respective alcohol on the ethyl salts, the action. taking place especially easily in the presence of a small quantity of sodium. He was similarly able to convert ethyl ethylacetoacetate into the methyl salt in the presence of sodium, but the action was less complete than when replacing a lower by a higher alkyl-group.

α

L. T. T.

Isomeric Dialkylsuccinic Acids. By C. A. BISCHOFF (Ber., 20, 2988-2992). The author, in conjunction with Voit, has saponified ethyl -B-dimethylethenyltricarboxylate on the large scale, and has confirmed the results previously obtained by him in conjunction with Rach (Abstr., 1885, 885). In addition, a second acid is also formed which melts at 120°, and is identical with the readily soluble butanedicarboxylic acid (Abstr., 1887, 45), and the product of change from the sparingly soluble dimethylsuccinic acid of high melting points. Voit has also succeeded in converting the two isomeric dimethylsuccinic acids into pyrocinchonic acid.

Two symmetrical diethylsuccinic acids are obtained by saponifying either ethyl diethylacetylenetetracarboxylate or the compound CEt(COOEt), CHEt COOEt; one of the acids is sparingly soluble, melts at 189°, and can be converted into the second, which is readily soluble, and melts at 127-128°. These acids are probably identical with Hell and Mühlhäuser's isosuberic acids (Abstr., 1880, 542). Experiments are in progress with the object of splitting into two optically active compounds the optically inactive diethylsuccinic acid corresponding with racemic acid. W. P. W.

Symmetrical Diethylsuccinic Acids. By E. HJELT (Ber., 20, 3078-3080).-Symmetrical diethylsuccinic acid,

COOH CHET CHEt COOH,

is prepared by the action of ethyl a-bromobutyrate on ethyl malonate and sodium ethoxide. The ethyl ethylbutenyltricarboxylate so obtained, which boils at 280-282°, is saponified, and the acid (m. p. 147°) heated at 150°. The residue is then crystallised from hot water, when two acids of the same composition are obtained; the one melts at 189-190°, and is identical with that prepared by Otto by reducing xeronic acid (Annalen, 239, 279), and gives an ethyl salt boiling at 233°, which is identical with that obtained by Hell (Ber., 6, 30) by the action of silver on ethyl a-iodobutyrate. The second acid melts at 127°. When the acid melting at 189-190° is heated, it is converted into an anhydride which boils at about 240°; when this is boiled with water, it yields the acid melting at 127°. 100 parts of water at 23° dissolve 061 part of the acid of higher melting point, and about 24 parts of the lower melting acid. The two acids differ also in crystalline form (compare Otto and Rössing, this vol., p. 45).

N. H. M.

Action of Ammonia on Alkyl Salts of Fatty Acids. By S. RUHEMANN (Ber., 20, 3366-3371; compare Trans., 1887, 403).— Phenylhydrazine reacts with ethyl diacetyltartrate, acetylphenylhydrazine being formed. When ethyl diacetyltartaric acid is treated with ammonia, tartramide, CH,NO4, is formed. In a similar manner, mucamide is obtained from ethyl tetracetylmucate.

Ethyl aconitate boils at 174-175' under about 22 mm. pressure. When left in contact with aqueons ammonia for 2 to 3 days, it is converted into citrazinamide (loc. cit.).

When bromine is added to a solution of citrazinamide in strong hydrochloric acid, the compound C,H,Br,NO, separates as a yellow crystalline precipitate. This is stable when dry, but decomposes slowly in presence of moisture; hot water decomposes it with evolution of carbonic anhydride. It dissolves very readily in ammonia and in aqueous potash. The corresponding chloro-derivative, CH,C,N2O3, resembles the bromine compound, but is more stable; it can be crystallised from water, but the solution decomposes when boiled for some time. Both halogen-derivatives react with aniline, orthotoluidine, and piperidine.

N. H. M.

Apparatus for Distilling Zinc Methyl and Zinc Ethyl. By A. KAULFUSS (Ber., 20, 3104-3105).-The apparatus, of which a sketch is given, is so constructed that the distillation can be conducted in an atmosphere of carbonic anhydride. N. H. M.

Disulphones, R"R', (SO2), and R2(SO2)2. By R. Orro and R. C. CASANOVA (J. pr. Chem. [2]. 36, 433-451; compare Abstr., 1885, 261 and 537).—Ethylenediethyldisulphone, C2H(SOEt), is prepared by heating an alcoholic solution of sodium ethylsulphinate (2 mols.) with ethylene dibromide (1 mol.); or by heating an alcoholic solution of sodium ethylenedisulphinate (1 mol.) with ethyl bromide (2 mols.). The identity of the products of these two reactions tends to show that the sulphur in these sulphinic acids is hexavalent. The sulphone crystallises in colourless needles, and melts at 136-137°. Nascent hydrogen in alkaline solution converts it into sodium ethylsulphinate and alcohol. When heated with aqueous potassium hydroxide, it yields a thick oil, which, with benzoic chloride, gives ethylsulphoneethyl benzoate, SO2Et CH2 CH2OBz, melting at 118°; the corresponding alcohol could not be isolated.

Ethylenedimethyldisulphone, C2H(SO2Me), is formed when methyl bromide is substituted for ethyl bromide in the above reaction; it crystallises in pearly scales, melts at 190°, and is soluble in hot

water.

Ethylenedipropyldisulphone, CH(SO2Pr)2, forms crystals with a pearly lustre, melting at 155°.

SO2

Diethylenedisulphone, C.H.<>CH, prepared by the action of sodium ethylenedisulphinate on ethylene dibromide, is identical with the oxidation product of diethylene disulphide.

Metaphenylenediethyldisulphone, C.H.(SOEt)2, prepared by the

action of potassium benzenedisulphinate on ethyl bromide, forms. colourless tables melting at 142°.

SOCH,, obtained by heat

Phenylene-ethylenedisulphone, CH<SO

ing ethylene dibromide with potassium metabenzenedisulphinate, forms very small crystals, insoluble in most solvents. A. G. B.

Synthetical Researches on and Constitution of Uric Acid. By J. HORBACZEWSKI (Monatsh., 8, 584-593).—The author has shown that uric acid may be synthetically produced from trichlorolactamide and carbamide; it is also formed, although in smaller quantity, from trichlorolactic acid, as also from amidoacetic acid and carbamide. This last change doubtless depends on the intermediate formation of a glycocine-carbamide which reacts with the carbamide to form uric acid, water, and ammonia, thus: COOH-CH2 NH2,NH, CONH2+ NH CCO NH

NH2

200<NH,

= CO

||| + 2H2O + 3NH3. Similarly, methylNH.C.NH.CO

uric acid may be obtained from sarcosine and carbamide, as also from methylhydantoin and biuret or amyl allophanate. The formation of uric acid from trichlorolactic acid shows that uric acid is an ureide of acrylic acid, whilst the formation of methyluric acid from methylhydantoin shows that it is a hydantoin cyanate. The relation of uric acid to lactic acid is of especial physiological importance, as Minkowski has shown that on removal of the liver from geese, considerable quantities of ammonia and lactic acid occur in the urine, whilst the proportion of uric acid is diminished. It has further been shown by Kaněra and the author that in the human organism the proportion of uric acid is increased by doses of glycerol. On the other hand the synthesis of uric acid from amidoacetic acid is of interest, as v. Knierem has proved that in the organism of birds amidoacetic acid (glycocine) is converted into uric acid and expelled as such in the urine; the same phenomenon has also been observed, to a less degree, in the human organism, since the glycocine is for the most part converted into carbamidę. V. H. V.

Furfuracrylic Acid. By H. B. HILL (Ber., 20, 3359).-Bromine acts on furfuracrylic acid with formation of a crystalline compound, C,H,Br,O,, which is decomposed by water into dibromofurfurethylene and carbonic anhydride. From the dibromo-compound, monobromofurfuracrylic acid crystallising in long needles, and dibromofurfuracrylic acid can be readily prepared. (Compare Markwald, this vol., p. 135.) N. H. M.

Thiazole Compounds. By A. HANTZSCH and J. H. WEBER (Ber., 20, 3118-3132, and 3336-3337).-Thiazole is the name N CH. given to the isomeric compounds, <CH: CH>S and <CH: CH>S; CH N. no simple thiazole-derivative is known, but by the condensation of

certain ortho-benzene-derivatives benzene-thiazoles are formed; for instance, hydroxyphenylthiocyanate gives the compound

and all thiocyanic compounds of ketonic or aldehydic nature in which the carbonyl radicle is in the ortho-position to the thiocyanic group are, in their stable form, thiazole-derivatives, the atomic complex, CN

CO:CH S CN, changing into CSC.OH. The term meso-derivative is suggested for all compounds in which the hydroxyl-group is displaced. From thiocyanacetone, Tscherniac and Norton (Abstr., 1883, 568) obtained a peculiar base, thiocyanopropimine, to which they gave the formula NH: CMe CH2 SCN; this substance is, howN: C(NH)S; by neither of ever, meso-amidomethylthiazole, Hofmann's reactions can it be proved that this compound is a primary amine, and with nitrous acid it yields only resinous products, but from its behaviour towards methyl iodide only two hydrogen-atoms can be in combination with nitrogen; the study of its acetyl-derivatives and of thiocyanacetone prove the above formula to be correct.

CMe

Methylamidomethylthiazole hydriodide, CNSH, NHMe, HI, is the principal product of the action of methyl iodide on thiocyanopropimine; it crystallises with 1 mol. H2O, and when treated with potash yields methylamidomethylthiazole; this base is a white, very deliquescent, crystalline substance, not very readily soluble in ether. It has a strongly alkaline reaction, and reacts more readily with methyl iodide than the original base, an abnormal ammonium iodide, C10H1S2N3I, and dimethylamidomethylthiazole hydriodide, being formed. The latter crystallises in large, transparent plates, with 1 mol. H2O, and melts at 54°, the anhydrous substance melting at 155; with potash, it yields dimethylamidomethylthiazole, which is a crystalline compound and melts at 96°. Trimethylamidomethylthiazolium iodide, C,NSH, NMe,I, is obtained on heating the dimethyl base in sealed tubes with methyl iodide; it is a white solid which melts at 85°, and is not decomposed when boiled with potash.

Acetylmethylamidomethylthiazole, CNSH, NMeAc, is produced by acting on the monomethyl base with acetic anhydride; it crystallises in white needles with 6 mols. H2O, and melts at 50°, the anhydrous compound, however, melts at 113°. The existence of this derivative, and the fact that a diacetyl-derivative cannot be obtained from this compound is strong evidence in favour of the formula suggested, and that thiocyanopropimine is meso-amidomethylthiazole. The acetyl-derivative of amidomethylthiazole forms salts with alkaline hydroxides, the sodium salt, C ̧H,NaN2SO + 8H2O, is obtained by warming it with concentrated soda. The formation of this compound and the nonformation of a salt in the case of the monomethylacetyl-derivative, are further proofs in favour of the author's formula, as is also the behaviour of dimethylamidomethylthiazole towards bromine; when this last-named compound is treated with bromine-water, only one hydrogen-atom is displaced. The bromo-derivative, CH,BrN2S,

crystallises from alcohol and melts at 114°. Amidomethylthiazole and methylamidomethylthiazole are completely destroyed by bromine. Since thiocyanacetone yields mesoamidomethylthiazole when treated with ammonia, it must be represented by the formula N: C(OH).

CMe: CH>S, and not by COMe CH, SCN, that given to it by Tscherniac and Norton (loc. cit.). It was obtained by their method in crystalline needles melting at 98°; with phenylhydrazine acetate, hydroxylamine, and sodium hydrogen sulphite, it does not react like a ketone, but with phosphorous pentachloride it acts like a phenol. The hydroxyl-group reacts very readily, and can be displaced by amines; by the action of aniline, anilidomethylthiazole, C,NSH,NHPh, is obtained; it crystallises from alcohol and melts at 117°. Paratoluidomethylthiazole melts at 125°; with metaphylenediamine, the compound, C.H.(NHC,NSH,), melting at 152°, is obtained.

By the action of metallic thiocyanates on ethyl monochloracetoacetate, ethyl hydroxymethylthiazolecarboxylate, <CMe: C(CO-OEt)>S, -N: C(OH)— is formed, a molecular change taking place similar to that occurring in the formation of hydroxymethylthiazole; this ethereal salt melts at 128°, and, judging from its behaviour towards phenylhydrazine, does not contain a ketone-group. A compound, C1H16OÑ2S2, which melts at 142°, is also formed in this reaction.

F. S. K.

Bromobenzenes. By A. J. LEROY (Bull. Soc. Chim., 48, 210216).-Benzene, 450 grams, and aluminium chloride, 25 grams, are mixed in a large flask, and the calculated quantity of bromine is added gradually, care being taken to keep the benzene in large excess. The product is treated with dilute hydrochloric acid, separated, and dried. In this way, monobromobenzene is obtained almost free from the diderivative.

Dibromobenzene is obtained in a similar manner, using benzene, 240 grams, bromine, 960 grams, and aluminium chloride, 30 grams. When treated with water, crystals of paradibromobenzene melting at 89° are obtained, together with a small quantity of the tri-derivative, which can be separated by fractionation. The liquid product is mainly dibromobenzene, which boils at 219° and does not solidify at -20°, mixed with some of the monobromo-derivative. The mixture is cooled to remove the para-derivative, and then treated with fuming sulphuric acid and ordinary sulphuric acid, in which the liquid readily dissolves. The product is treated with water to separate the paraderivative, and the liquid is distilled in a current of steam, when metadibromobenzene boiling at 200° is obtained, the yield being equal to about 10 per cent. of the bromine taken. The action of chlorine on benzene, in presence of iodine, yields the ortho- and paraderivatives. With aluminium chloride, no other derivative is obtained. It would seem, therefore, that in the reactions in presence of aluminium chloride there is a tendency to the formation of para- and meta-derivatives.

Paradibromobenzene, when treated with methyl chloride in presence of aluminium chloride, is mainly converted into carbonaceous pro