摘要:

PHYSIOLOGICAL CHEMISTRY. P h y s i o l o g i c a l C h e m i s t r y . 57 Respiratory Exchange in Shivering. By C. RICHET (Con7pf. rend. SOC. Biol., 1893, :33--35).--Shivering is regarded as an act to produce more heat when the blood has beeii cooled. The experiments were tried on chloralised dogs, in which there is great lowering of the amount of carbonic nnhvdride produced. On shivering, this rises, especially if the shivering is’ violeni, and the respiratory qiyotient rises also. W. D. H. Prote’id-poor Nutrition. By T. ROSENHETM (Pjliiger’s Archiw, 54, 62-71).-A number of experiments on dogs are recorded in which a diet poor in nitrogen was given. The analyses of the food and excreta, and the daily weight of the animal, are given in tables. These experiments confirm the previous observations of the author, that such diets are very harmful ; the animal becomes ill and apathetic, si rriilar t,o the condition observed in starvation.Post-mol-tern ex- amination showed extensive fatty degeneration, especially of the liver and alimentary tract. Influence of Muscular Work on the Excretion of Sulphur. By C. BECK and H. BENEDICT (Piliiger’s Archiv, 54,27--61).-During muscular work the excretion of sulphur is increased. This is followed (when the work has ceased) by a corresponding diminution. The incxlase falls especially on the oxidised sulphur ; the non-oxidised sulphur due to prote’id metabolism may be lessened. The relationship of these two forms of sulphur is recommended as an indication of the disintegration of proteid in t,he body. Circulating Proteid.By E. PFL~~GER (PfEuger’s Archiw, 54, 333-4191 .-This is a long, critical, and polemical article directed against Voit’s theory of the distinction between organ proDeicl and circulating prote’id. The tendency of the article is to show that W. D. H. W. D. H.58 ABSTRACTS OF CJEEMIOAL PAPERS. metabolic processes in protejid matter occur in tlhe cells, that is, in organised proteid; but it is ndmitt’ed that iu the organised cell sub- stance there are different kiuds of organised proteid molecules, different degrees of organisation. How does Protei’d Nutrition influence Protei‘d Metabolism in Animal Cells ? By B. SCH~~NDORPF (P’iiger’s Archiv, 54, 420- 483).-The increase of urea in the blood after protejid food is not due to a diffusion of urea from the tissues into the blood, but to a real new formation of urea in the liver from the nitrogenous decom- position products of cellular activity.By leading the blood of a staming animal through the organs and liver of a well-nourished one, the amount of urea in the blood is in- creased. By leading the blood of a starving animal through the organs and liver of a starving animal, there is no change in the amount of urea. By leading the blood of a well-nourished animal through the: organs and liver of a starving animal, the amount of urea in the blood is diminished. Therefore, the amount of proteid decomposition depends on the nutritive condition of the cells, and not on the proteid contents of the “intermediate lymph stream.” The amount of urea in the blood depends on the condition of the animal, falling during hunger (minimum 0.0348 per cent.), and rining to a maximum during the time of greatest urea formation (0.153 per cent.).The decomposition products from which the liver forms urea are probably ammonium salts. W. D. H. W. D. H. Sulphur in Human and Animal Tissues. By H. SCHULZ (E’fiiige8s Archi*, 54, 555-573).-1n the dried organs of a man, aged 39, the percentage of sulphur was fomd to vary from 0.57 in the brain to 1.03 in t h e jejunum. I n the muscles of various animals, the percentage varied from 0.86 to 1.33 ; in the human aorta, from 0.45 to 0.67 ; and in the human vend cam, from 0.28 to 0.73. vTT. D. H. Non-coagulable Blood. By C. J. MARTIN (J. P h y d . , 15, 375- 379).-When nucleo albumins (Wooldridge’s tissue fibrinogens) are introduced into the circulation, a state of non-coagulability is some- times prodnced.This is considered by Wright and Pekelharing to be due to the cleavage of the nucleo-albumin into nuclein and a peptone-like substance, to the latter of which the non-coagulability of the blood is due. This view has been already questioned by Halliburton aud Brodie (Brit. Ned. J.? ii, 1893, SSl), and the present paper shows conclusively that no peptone or proteose is present in the blood in the condition in question. The method adopted is to mix the blood with an equal volume OF 10 per ceiit. trichloracetic acid. This is raised to the boiling point, and filtered hot. The filtrate gave no indications of the presence of either proteose or peptone.This method, a modification of Starling’s,, is well calculated to detect these substances, as control specimens of blood to which peptone or proteuse was added showed. TbePHYSIOLOQICAL CHEXISTRY. 59 object of boiling and keeping the mixtiire hot during filtration is that the proteoses are partly precipitable by the acid in tbe cold, but this precipitate dissolves on heating. Results of feeding Cows at Grass on Meal. By J. P. HOBERTS and H. H. WING (Bied. Uentr., 22, 728--732).-Eight cows were pastured only, whilst another eight received mixed meals in addition to the pasturstge. It was found that whilst the eight cows receiving meals gave a larger daily yield of milk, yet the percentage of fat in the milk was lower than that, found in the milk from cows fed on grass only ; at the same time, the excess of milk thus obtained paid for the extra food given.W, D. H. E. W. P. Mule’s Milk. By A. B. AUBERT and D. W. COLBY (Chem. News, 68, 168--169).--Two samples of a mule’ti milk were examined, one collected about six weeks, the other about nine weeks, after the flow of milk had commenced; the mule was 11 years old, in work, fed on oats and hay. and yielded about 2 quarts of milk daily, being milked at frequent intervals. The milk was pure white, alkaline ; turning sour, after long standing, with the separation of a fine, floating, floc- culent coagulum instead of a curd ; the fat globules were verg small ; the casein is not readily precipitated by dilute acetic acid or by carb- onic anhydride; this was especially the case with the first sample.The analytical numbera given are Sp. gr. at 15”. ....... 1.032 1.033 Total solids.. ........ 10.65 10.86 ProteYds ............. 2.94 2.31 Fat ................. 1-86 1-98 Sugar. .............. - 6-03 Ash ................ 0-53 D. A. L. Secretion of Urine. By I;. LIEBERMANN (Pfliiger’s Archiv, 54, 583-60G).-In a previous paper (Abstr., 1893, ii, 27), an acid con- stituent of the kidney substance, named lecithalbumin, is described. The proDerties of lecithnlbumin generally are discussed i n PJtiger’s Archiv, 54, 573-585. This material is obtained from the tissue av a residue after artificial gitstric digestion. It is like uucle’in ; it is believed tlo come from the nucleus, aud it possesses the power of in- teracting with a basic phosphate, N%HP04, yielding an acid filtrate.Similar substances are obtained from blood serum or from defibrinated blood. The reaction of the fresh kidney is not constant ; it is usually neutral ; it may be alkaline or slightly acid ; post mortem, it invariably soon becomes acid. T’his inconstancy indicates that the reaction of the kidney is a variable factor during life, and is prob- ably related to the stages of its secretion. The acidity of the kidney is believed to be due to the lecithalbumin, which is stated to be the most abundant constituent of the cell substance. This is confirmecl by microchemical staining; the nucleus, and to a less extent the cell protoplasm, taking up basic dyes. It is further advanced that the acidity of the urirre is due to the60 ABSTRAOTS OF OHEMIGAL PAPERS.interaction of sodium urnta and disodium hydrogen phosphate ; these are contained in the blood plasma, and their iiiteraction is brought about by the acid constituent of the cells (lecithalbumin) which the secretion on its way from blood to urinary tubules must necessnrily come in contact with. W. D. H. Fermentation and Carbohydrates in Urine, By E. SALKOWSKI (@?uger's Archiv, 54, 607-614) .-Polemical. An answer to E . Baumann. Variations of Glycogenia in Anthrax. By H. ROGER (Corn@. r e d . , 117, 488--490).-When the anthrax bacillus is cultivated in milky decoctions of liver, all the glycogen is somewhat rapidly de- stroyed, and the liquid likewise contains no sugar. Now, glycogen is never found in the liver of animals that die of anthrax, but sugar can easily be detected in the liver arid the blood.In the early stages of anthrax, before the bacilli have appeared in the blood, the liver contains large quantities of glycogen, but in later stages, when the blood has become charged with bacilli, all the glycogen has disappeared from the liver. It would seem that a s soon as the temperature reaches 39.5" the glycogen disappears, but if the temperature falls to 38", glycogen appears again i n the liver. I n most cases, however, the disappearance of the glycogen coincides with the reduction of the central temperature and the appearance of numerous bacilli in the blood. The disappearance of the glycogen is always accompanied by marked hyperglycemia. It follows that in anthrax the glycogen is rapidly converted into glucose, and the tissues then become iucapable of consuming the sugar furnished by the liver.The bacilli destroy sugar in liquid cultivations, but seem to be without the power of attacking it in the animal organism. Toxicity and Therapeutic Use of Sodium Fluoride. By BLAIZOT (Compt. rend. SOC. BioZ.. 1893, 316--31Y).-Sodium fluoride has antiseptic properties, a statement of Arthus and Huber which is confirmed in the present paper by further experiments. I t is recom- mended as a lotion in various affections of the skin and mucous membranes ; its toxicity is small, 8 centigrams per kilo. of body weight having in rabbits t o be injected intravenously to produce poisonous symptoms ; the symptoms are slight fever, salivation, aod dyspnma. l'he animal recovers in a few hours.After a dose of 1 decigram, how- ever. the symptoms are more intense, and the animal dies in a comatose condition. W. D. H. C. H. B. Physiological Action of Apocode'ine. By L. GUINARD (Compt. rend. SOC. blot., 18!43, 586--590).--The experiments were carried out on dogs, and apocode'ine hydrochloride was injected hypodermically. The heart is atfirst accelerated for a short period; the animal then becomes somnolent or sleeps, and the rate of the heart falls. This is enti~ely of central origin, and the courhe of the nervous impulses to the heart is by the pneumogastric nerves; the phenomena can beVEGETABLE PHYSTOLOGY AND AQRICULTURE. Gl prevented by section of these nerves. The blood pressure rise4 in the first and sinks in the second phase; the lowering of pressure is not, however, very great (not nearly as great as that produced by morphine), and is a result of the heart’s slower action rather than of vaso-dilat at ion.Tha body temperature is lowered during. the somnolent stage. The quantity of oxygen consumed and carbonic anhydride expired is also considerably lessened. The repose of the skeletal muscles and the slowing of the heart and respiration will partly explain these results ; but another factor is believed to be a, lessening of inter-organic combustions. W. D. H. The rate of respiration runs parallel to that of the heart. Effects of Snake Venom. By C. J. MARTIN (J. Phpiol., 15, :380-4OU).-The venom investigated was that of the Australian black snake (Pseudechis porphyrincus). The poisonous constituents are primary proteoses. The effect on the blood is principally dealt with i n the present communication. The effect resembles that pro- duced by injection of nucleo-albumin. sometimes producing intravas- cular coagulation, and sometimes, with larger doses, a ccjnclition of non-coagulability. On shed blood, a solution of the venoni retards coagulation. The venom itself contains no nucleo-albumin. Jt probably acts by liberating nacleo a1 burnin from the blood corpuscles. This view is supported by observations that show that the venom dissolves both kinds OE blood corpuscles to some extent. The very minute doses necessary bear in the same direction. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8946605057

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

61 Organic Chemistry. Metallic Derivatives of Acetylene. By E. H. KEISER (Amer: Chem. J., 15, 535-539 ; compare Abstr., 1892, 1416).-When acetylene is passed into a solution of mercuric iodide in potassium ohloride to which caustic potash has been added, a compound C2Hg is precipitated in white flakes. This substance explodes violently when heated, dissolves in hydrochloric acid with evolution of acetylene, and, when treated with an alcoholic solution of iodine, yields di-iodo- acet lene, which polymerises, after a time, to crystals that melt a t 187'; probably of hexiodobenzene. When acetylene is passed into a saturated aqueous solution of mer; curie chloride, a compound C2(HgGl)2 + 3H20, is obtained as R granular, white precipitate. It explodes but feebly when heated, and does not dissolve in dilute hydrochloric acid.Decomposition of Chloroform. By C. SCHACHT and E. BILTZ (Phawn. J. Trans., 5 2, 1005-1006) .-Chloroform is not decompose4 by the action of sunlight unless oxygen is present, when, in the firsij stages of the decomposition, chlorine is liberated, and this, acting o q the alcohol contained in the chloroform, pi*oduces hydrogen chloride, which is then found instead of free chlorine. Hence the liberation of chlorine has been disputed by some who have over- looked the presence of alcohol in the chloroform operated on. Pure chloroform begins to decompose immediately in strong daylight,' but the addition of alcohol prevents or arrests the decomposition, and will, moreover, on agitation of the liquid, remove any free chlorine and also any carbon oxychloride already liberated.The authors have found that the addition of 0.25 per cent. of dcohot suffices to preserve chloroform for a t least a month in average day. light ; 0.5 per cent. will preserve it for a year ; and 1 per cent. for many years. The amount of alcohol in a sample may be inferred from the specific gravity, which at 15" is for pure chloroform, 1.5020; with 0.25 per cent. alcohol, 1.4977 ; with 0 5 per cent., 1.4939 ; with 1 pel! cent., 1.4854 ; with 2 per cent., 1.4705. Isocyanogen Tetrabromide (Tetrabromoformalazine). Byl J. THIELE (Ber., 26, 2645-2647 ; compare Pulvermacher, this vol., i, 12) .-Amidotetrazotic acid (Abstr., 1892, 1299) yields, on oxidation in alkaline Bolution, salts of azotetrazole, ~-N>C*N:N*C<~&~. The hydrazotetrazole obtained by reducing the latter, when treated with bromine, furnishes isocganogen tetrabromid e (tc trabromoformal- azine), CBr2:N*N:CBr2 ; this crystallises from glacial acetic acid in lairge, lustrous prisms, is insoluble in water, melts at 42", and is readily volatile with steam, the warm vapour attacking the C.F. B, R. R. N-NZI VOL. LXVL i. f62 ABSTRACTS OF CHEMICAL PAPERS. mucous membrane. When warmed with concentrated sulphuric acid, carbonic anhydride and hydrogen bromide are evolved, and water precipitates hydrazine sulphate from the solution. The tetra- bromide dissolves when gently warmed with alkalis, and hydrazine is only recognised in the solution after acidification; if the alkaline solution is distilled, the last fraction contains a compound which is, perhaps, isocyanogen oxide, CO:N*N:CO, or a polymeride. When an oxidisable substance is preaent, a strong odour recalling that of an isonitrile is recognised, which may be due to isocyanogen, C:N*N:C.A. R. L. Action of Chlorine on Ethylic Alcohol. By M. ALTSCHUL and V. MEYER (Ber., 26,2756-2759).-Tbe authors have examined an oily liquid which is obtained as a bye-product in the manufacture of chloral by the action of chlorine on ethylic alcohol. The oil was separated from admixed chalk and calcium chloride by distillation with steam, and, on rectification, three fractions were obtained : the first portion (69-90") consists largely of chloroform, which appears to be formed by the action of the steam on trichloracetic acid.The second frac- tion (90-140") has not yet been investigated ; the third (140-168") ooaeists of ethylic dichloracetate, trichlorethylic alcohol, and prob- ably dichlorethylic alcohol. E thylic dichloracetate was identified by the production of ethylic iodide and dichloracetamide ; the trichlor- et hylic alcohol yields a metanitrobenzoate, NO2-C6H4*CO 0. C2H& crystallising in transparent plates ; it melts at 75", and is identical with the compound prepared from pure trichlorethylic alcohol. J. B. T, New Method of preparing Ethylic Ether and its Homo- logues. By F. KRAFFT (Ber., 26,2829-2833).-1n the preparation of ether by means of sulphuric acid, the latter compound undergoes a cer- tain amount of reduction to sulphurous acid ; this being due to the alco- hol.In point of stability towards alcohol, the aromatic snlphonic acids are superior to sulphuric acid. The author shows (see also this vol., i, 91) that the aromatic sulphonic acids can be employed for the con- tinuous etherscation of alcohols in the same manner as sulphuric acid. Thus in the case of ethylic alcohol and benzenesulphonic acid :-PhSO,*OH + EtOH = PhS02*OEt + HzO; PhS02*OEt + EtOH = PhS02*OH + Et20; the alcohol is dropped on to the benzenesulphonic acid heated to about 140O. Methylic propylic ether was prepared by this method from a mixture of methylic and propylic alcohols ; it was found to boil at 36.6-37.4" (752 mm.), and its sp. gr. at 0" was 0.7460 (compare Henry, Abstr., 1892, 27). A. R. L. Synthesis of Erythritol and of an Isomeride. By G.GRINER (Compt. rend., 117, 553-556).-The unstable liquid obtained by the action of bromine on erythrene at st low temperature (Abstr., 1893, i, 453) is the dibromide, CH2:CH*CHBr*CH2Br, which, when treated with bromine, yields the tetrabromide described by Ciamician and Magnaghi, CH,Br*CH:CHGH,Br, It is isomeric with the solid dibromide,ORGANIO CHEMISTRY. 63 which served for the synthesis of erythritol (loc. cit.), When ihese clibromides are treated with a 1 per cent. aqueous solution of potassium permanganate in presence of alcohol at about 0", the 11 quid dibromide yields a dibromhydrin melting at 135", identical with that obtained by Champion by the action of hydrobromic acid on ery- thritol, and yielding a diacetin, C4H6Br202Ac2, melting at 133-134", whilst the solid dibromide yields a dibromhydrin melting a t 83", and a, diacetin melting at 96".The dibromhydrins may be converted into tetracetins, but the process has the disadvantage of requiring somewhat high tempera- fures. It is more couvellient to convert them into dioxides by the action of dry, solid potassium hydroxide at the ordinary temperature, the dioxides being afterwards converted into the corresponding tetra- hydric alcohol by heating with water below 100". The liquid dibromide yields a dioxide which melts at 4", and boils at 39-60", under a pressure of 30 mm. ; it is soluble in alcohol and water; sp. gr. at 16" = 1,113. When its aqueous solution is heated on a water-baih, it yields a compound CaHlo04, crystallising from alcohol in small, silky tufts melting at 72", very soluble in water, and even deliquescent ; more soluble in alcohol than ordinary erythritol.This compound yields a tetracetin, C4H6OCAc1, melting at 53", and ig an isomeride of ordinary erythritol. The solid dibromide in like manner yields ordinary erythritol by conversion into a dioxide, and subsequent hydration of the latter (compare Zoc. cit.). C. H. B. Iodide of Starch. By G . ROUV~ER (Compt. reizd., 117, 461).- Measured volumes of starch and iodine solutions of known strength were mixed together, and concentrated sodium chloride solution was added. After some time, the iodine in the precipitate and that remaining in solution was determined by means of thiosulphate solu- tion. The quantity of iodine taken up by a given quantity of starch increases with the quantity of iodine solution added, until it reaches a maximum corresponding with the formula ( C6HIoO5) 1615, beyond which no further combination takes place, even with a large excess of iodine. With a given weight of iodine and starch, the quantity of iodine remaining uncombined increases with the volume of the liquid, pro- vided that the proportion of iodine is not greatly in excess of that required to give a compound containing 19.6 per cent., or the maxi.mum quantity, of iodine. If this proportion is exceeded, an increase in the total volume of the liquid does not prevent the formation of tho compound (CsH1&5)1615 (compare Abstr., 1892, 578,801, and 1171, and 1893, i, 683). Chemistry of Plant Fibres : Celluloses, Oxycelluloses, and Lignocelluloses.By C. F. CROSS, E. J. BEVAF, and C. BEADLE ((%em. News, 68, 225-227 ; also Ber., 26, 2520--2533).-Collating work done by them on jute fibre-the simplest type of lignification-the authors note that by chlorination this fibre yields 72 t o 75 per cent, of a-cellulose, but, by treatment with dilute nitric acid, or by repeated C. H. B. f 264 ABSTRAUTS OF UHEMIOAL PAPERS. bromination, or by regulated oxidation with chromic acid, the yield of a-cellulose is 60-63 per cent. Moreover, the cellulose of jute fibre under hydrolysis with hydrochloric acid yields but traces of furfuraldehyde, whereas 6 per cent. of this aldehyde is obtained from it by means of a mixture of concentrated sulphuric acid and aqueous hydrochloric acid ; under similar treatment, more resistant celluloses, such as cotton cellulose, yield only a few tenths per cent., unless they have been previously subjected to oxidation, then the yield of furfur- aldehyde may attain 8 per cent.; it seems, therefore, that jute fibre cellulose is an oxycellulose ; and, in addition, about one-sixth of the cellulose obtained by chlorination consists of P-cellulose containing two methoxyl-groups in the formula weight, C19H,,0,,. The non-celluloses, either in the raw fibre o r in the chlorinated fibre, give over 9 per cent. of furfuraldehyde when boiled with hydrochloric acid ; they also contain over 14 per cent. of methoxyl, and when ren- dered soluble by chlorination, yield quinone chlorides corresponding to 7-9 per cent. (on the fibre substance) of keto-R-hexene deriva- tives ; these derivatives are assumed to contain groups of the general - - u - form CH>CH2, condensed by union of OH groups.C(OH),*C(OH)z .~ The remaining portion of the non-celluloses consists of the complex C,sH,,O,. Jute fibre is therefore regarded as consisting of 60-65 per cent. of a-cellulose, 15-20 per cent. of P-cellulose, 7-9 per cent. of keto-R-hexene derivatives, and 18-22 per cent. of the above complex, and these substances appear to be so related chemically as to suggest a series of transitions from one extreme member to the other. Incidentally it is noted that, according to the authors’ views, the production of furfuraldehyde does not depend on the presence of 8 pentaglucose. D. A. L, Preparation of Methylmine : Constitution of Hexarneayl- enetetramine.By A. TRILLAT and FAYOLLAT (Compt. rend., 117, 628--630).-100 grams of a 33 per cent. solution of formaldehyde is mixed with a cold aqueous solution of ammonia until there is no further development of heat, 200 grams of zinc powder is added to the mixture all a t once, and then 750 grams of ordinary hydrochloric acid very gradually, the operation occupying from eight to ten hours. The product is now mixed with a large excess of sodium hydroxide, and distilled in a current of steam, the distillate k i n g received in dilute hydrochloric acid ; ammonia passes over first, and methy Iamine afterwards, the two hydrochlorides being separated by means of alcohol, after evaporating to dryness. The methylamine thus obtained is free from secondary and tertiary amines.It would seem that the action of ammonia on formaldehyde yields the compound CH,(N:CH,)*, and the latter is then reduced, yielding CH,(NHMe),, which, by the action of water, is converted i n b formaldehyde and methylamine. The authors consider that the constitution of the product of the action of ammonia on formaldehyde is more probably CH,(N:CH,), than N4(CHJ8. The first product of the reaction may be methylene-ORGANXO CHEMISTRY. 65 amine, CH,:NH, which reacts with a further quantity of aldehyde, 2CH2:NH + CH20 = CH,(N:CH,), + H20. It is known that, with formaldehyde, aniline yields the compound CH2:NPh, whilst mono- methylaniline gives the compound CH,(NPhMe),. Nitrites of Amines. By W. A. NOYES (Anzer. Chem. J., 15, 539--546).-The nitrites of some amines of the type CHR2*NH2 have been prepared, and found to be stable at the ordinary tempera- ture ; they are, however, decomposed, with evolution of nitrogen, when their solutions are boiled or evaporated to dryness.The amines were in general prepared by reducing the corresponding ketoximes. DiethyZcmbinamine, CHEtz*NH2, is a colourless liquid boiling at 89-91", of sp. gr. 0.7487 a t 20"/4" ; the hydrochloride crystallises in needles melting at 216-217" ; the platinochloride in needles ; and the nitrite in deliquescent, white needles, Di~l.o~ylcarbinai,a&ne, GHPr2a*NH2, is a colourless liquid, boils at l.39-140", and has a sp. gr. 0.7667 at 20"/4". The hydrochloride crystallises in needles melting at 241-262"; the platinochloride in pale yellow scales ; the nitrite is decomposed by boiling, much more rapidly in concentrated than in dilute solution. Di-isobuty Zcarbinawiine is a colourless liquid, boils at 166-167", and has the sp.gr. 0.772 at 20"/4". The hydrochbride crystallises in needles melting at 247-2248' ; the platinochloride in pale yellow needles ; the carbonate and the nitrite in white needles. Hexamethylenediamine nitrite is only partially decomposed when its aqueous solution is boiled. Dihydromesoanthramine nitrite yields anthracene. Dip7ienglcarbinarnine nitrite, which crystallises in white needles, yields diphenylcarbinol. Action of Sodium on Acetone. By P. C. FREEX (Amer. Chem. J., 15, 582-605).-1t is proved that when metallic sodium acts on a dilute xylene solution of acetone (1 : loo), hydrogen is evolved to the extent of about 63 per cent.of the amount corresponding with the displacement of 1 atom of hydrogen by sodium. When sodium acts on pure acetone, none of this hydrogen is evolved; it is used up in reducing the acetone to isopropylic alcohol, &c. Acetone in ethereal solution was then exposed to the action of sodium, this and other operations being carried out in an atmosphere of hydrogen. The product consisted of two parts, nearly equal in amount, and respectively insoluble and soluble in ether. The formela was found to consist chiefly of acetone sodium, together with sodium isopropoxid e and disodium pinaconate in about equal proportions, and a trace of sodium ethoxide. The part soluble in ether consists almost entirely of sodium acetone.Sodium acetone oxidises very readily, and is decomposed by cooled dilute acetic acid, yielding acetone, together with small quantities of mesitylic oxide and phorone. It appears to have the formula CH2:CMe*QNa (and not C&Na*COMe), because, when it is treated with beczoic chloride, P-allylic benzoate, CH,:CMe*OBz, is among the products. The product of the action is extracted successively with sodium hydrogen carbonate, carbon- ate, and hydroxide. The residual oil contains mesitylic oxide and ethylic, isopropylic, and P-allylic benzoates ; when hydrolysed with C. H. B. C. P. B.66 ABSTRACTS OF OHEMIOAL PAPERS. dilute hydrochloric acid, it yields benxoic acid, together with ethylic and isopropylic alcohols and acetone ; with caustic potash, no acetone is obtained, but phorone and mesitylic oxide instead.The portion s o h ble in sodium hydrogen carbonate contains benzoic acid. That soluble in sodium carbonate contains mono- and di-benzoylacetone, and yields acetophenone, ace€ic acid, and benzoic acid when dis- tilled. The higher-boiling part of the insoluble oil contains some substances which have been isolated, but not yet identified. Electrical Conductivity of Formic acid, By V. SAPOJNIKOFF (J, Buss. Chem. Xoc., 25, 109--110).-As a rule, pure substances are bad conductors of electricity, but Hartwig found that formic acid conducted comparatively well. The author has repeated the experi- ments with as pure acid as he could obtain (m. p. 8-39"), and finds for it a conductivity only one-sixteenth of that observed by Hartwig.As this acid still contailled about 0.2 per cent. of water, he is of opinion that the pure acid is practically a non-conductor. Oxymethylene Derivatives of Ethylic Acetoacetate, Acetyl- acetone, and Ethylic Malonate. By L. CLAISEN (Ber., 26,2729- 2735) .-When ethylic acetoacetate, or acetylacetone is heated in a reff ux apparatus with ethylic orthoformate and acetic anhydride, alcohol is eliminated and ethoxymethylene derivatives are obtained. A similar condensation occurs with ethylic mnlonate, but the action is much slower and requires the addition of zinc chloride. EthyZic ethox?lmethyZeneacetoacetate, OEt*CH:CAc.COOEt, is a colourless oil, boils at 265-266" under ordinary pressure, and a t 149-150" under 15 mm., and bas a sp. gr.of ,1.0736 a t 15". It combines with phenylhydrazine to form ethylic phenylmethylpyr- azolecarboxylate, which melts at 53'. When treated with water o r alcohol, it yields ethylic hydroxyinethyleneacetoacetate. This is a colourless liquid, boils a t 199-200" under the ordinary pressure, and at 95" under 21 mm. pressure, has a sp. gr. of 2.141 a t 15O, is soluble in dilute alkali' carbonates, and reddens litmus paper. With copper acetate, it yields a blue, crystalline copper salt. Ethoxymethyleneacetylacetone, CSH,02:CH*OE t, boils a t 256-258" under the ordinary pressure, and at 141" under 16 mm. pressure. Hydroxymethyleneacety~acetone melts at 47", boils at 190-200" under the ordinary pressure, and at 100" under 20 mm. pressure, and is a stronger acid than ethylic hy droxymethy leneacet oacetate.Ethylic etlzoxywzethylenemalonate, OEt*CH:C(COOEt),, is a colour- less oil, boils at 280", has a sp. gr. of 1.0855 at 15", and is not decomposed by water at the ordinary temperature. When ethylic acetoacetate and etbylic orthoformate are allowed to remain in contact with acetic chloride instead of being heated with acetic anhydride, a different reaction takes place, and ethylic acetate, ethylic formate, and ethylic et hoxycrotonate, 0 Et*CMe:CH*CO OE t, are formed. The latter melts at 31", boils a t 199-200", and, when distilled over calcium hydroxide, yields the alcohol CH2*CMe*OH, which boils at 62". Compounds containing the methenyl group CH combined with t w o C. F. B. J. W.ORGANIC CHEMISTRY. 67 residues of the group *CO*CH,*CO* are obtained by the prolonged action of.ethylic orthoformate and acetic anhydride on an excess of ethylic acetoacetate or acetylacetone. These methenyl compounds are more easily obtained by adding the alkali salts of ethylic acetoacetate or acetylacetone to an alcoholic solution of the ethoxymethylene derivatives described above. Diethylic methenyldiacetoacetate, C6H8o3:CH*C6H9O3, melts at 96". Mathenyldiacetylacetone, melts at 115", and, by the withdrawal of the elemeiits of water, yields a crystalline compound, C,H,,O,, which melts at 112'. When these methenyl compounds are treated with ammonia, they yield pyridine' derivatives. Thus, diethylic methenyldiacetoacetdte, when heated with ammonium acetate, yields ethylic dimethylpyridinedicarboxylate, and methenyldiacetylacetone, when allowed to remain in ammoniacal solution, yields aa'-diacetyllutidine (m.p. 73-74"). I n many cases it is unnecessary to prepare the methenyl compound ; thus, ethylic dimethylpyridinedicarboxylate is obtained by heating ethylic ethoxy- methyleneacetoacetate with ethylic paramidoacetoacetate. E. C. R. , CsH,O2:CHGsH,O2, Derivatives of Diethylic Succinosuccinate. By N. KIJNER (J. Rzcss. Chem. Soc., 25, 125-132).-Succinosuccinic acid (1 gram) was heated for six hours at 225" with hydriodic acid (15 c.c.) of sp. gr. 1.96. No hexamethylene was obtained, but a liquid boiling from 200" to 220O. Diketohexamethylene gave similar results. Phosphorus pentachloride with diketohexamethylene in cold chloro- form solution gives crystals which melt at 125.5" and have the com- position c6H8C14.These sublime in needles at a temperature below their melting point, and may be recrystallised from boiling alcohol. Paradichlorobenzene is formed at the same time. When the sodium compound of diethylic succinosuccinate is boiled with ethylic chloro-formate, a substance C1,Hl4OB( COOE t)z is formed, which is easily soluble in chloroform, less soluble in alcohol, and melts at 127". I t does not dissolve in alkalis, does not fluoresce, and its alcoholic solution does not colour ferric chloride. When treated with bromine, it loses 2 atoms of hydrogen, giving a compound ClzHl,Os(COOEt)~, melting a t 129" ; this may also be made from the sodium salt of diethylic quinonehydrodicarboxyIate, by treating it with ethylic chloro-formate.J. W. Action of Iodic acid on Acetonedicarboxylic acid. By A., ANGELI and E. LEVI (Gazzettn, 23, ii, 97--100).-0n treating acetone- dicerboxylic acid with aqueous iodic acid, carbonic anhydride is evolved and heat is developed. The mixture is kept cool, and, after a time, tetriodoacetone, CO(CHI&, is deposited ; it crystallises in beautiful, yellow needles, melting a t 142" with decomposition. It is very soluble in acetone, less so in benzene, alcohol, ethylic acetate, or chloroform, but its solutions soon become colonred, owing to liberation of iodine. On diatillation with hydriodic acid and a little red phos- phorus, it yields acetone, iodoform, and symmetrical diiodoacetone,68 ABSTRqOTS OF OHEMIOAL PAPERS. but it gives no appreciable quantity of iodoform when treated with alkali carbonates.W. J. P. Barium Antimony *aftrate. By E. MAUMEN~ (Compt. rend., 117,666-668).-The numbers obtained by Dumas and Piria, in their analyses of barium antimony tartrate, did not agree well with those calculated from the formula, and they attributed the divergences to the retation of water and the absorption of carbonic anhydride. The author points out thqt, according to his general laws, the formula of the salt is ~*H7.'19011.79(r37b03)1.17( B U O ) ~ . ~ , , and that the numbers calculated from this formula (0 = 8, C = 6, &c.) agree closely with tLe results of analysis, Methylic Tartrates and Ethylic Tartrates, By J. FAYOLLAT (dompt. rend., 117, 630-633) .-Lithium, sodium, potassium, and ammonium methylic tartrates, and lithium, sodium, potassium, barium, and calcium ethylic tartratss, all crystallise in anhydrous erystals. Ammonium methylic hrtrate crystallises with some difficulty, and is very hygroscopic.Polarimetric observations with (1) tartaric acid, (2) methylic hydrogen tartrate, (3) lithium methylic tartrate, (4) ammonium methylic tartrate, ( 5 ) sodium methylic tartrate, (6) potassium methylic tartrate, (7) ethylic hydrogen tartrate, (8) lithium bthylic tartrate, (9) sodium ethylic tartrate, (10) potassium ethylic tartrate, in aqueous solutions containing 1 gram molecule in 8000 C.C. of water, gave the following results. C. H. B. 1. 2. 3. 4. 5 . 6. column 20 cm. + 0*61 0.75 1-14 1.28 0.99 1-16 Observed deviation, long .......... Specific rotatory power.., . , 1 ] +16*1 18.1 26.5 28.0 21.0 22.7 7. 8. 9. 10. Observed deviation, column 20 cm. long ....................... Specific rotatory power.. ........ 21.8 28.8 27.5 21.6 o.98 1.39 1,40 It will be observed that, in each series, the deviations produced by the alkali salts are very approximately equal, which indicates a degree of dissociation practically the same for the various salts in the same series. Calcium and barium ethylic tartrates were examined in solutions containing 1 gram molecule in 16 litres, the deviations being + 1-31 and + 1.26, and the specific rotatory powers + 243 and + 20.3 respectively. The solubilities of the salts in alcohol are so small that no corn- parative observations are possible, but the results with saturated solutions show that both the methylic tartrates and the ethylic tartrates petain their dextrogyrate character., Influence of Organic Solvents on Speoific Rotatory Power. By P. FREUNDLER (Compt. rend., 117, 556-559).-The author has measured the specific rotatory power of propylic diacetyltartrate, di- propionyltartrat e, di butyryl tar trate, d i-n-valeryl t artra t e, and di-n- C. H. B.ORGANIC CBEMISTRY. 69 caproyltartrate, dissolved in ether, alcohol, acetone, butyl ketone, light petroleum, carbon bislulphide, methylic alcohol, toluene, benzene, me thylenic chloride, chloroform, carbon tetrachloride, ethylenic chlor- ide, ethylidenic chloride, chlorethylidenic chloride, methylenic bromide, bromoform, e thylenic bromide, propylic bromide, and rnethy lic iodide. The results show that the nature of the solvent exerts very considerable influence on the rotatory power of the dissolved substances.The value of [aID for propylic diacetyltartrate, for example, varies from +36.7" in carbon bisulphide to -2.6" in bromofom, the specific rotatory power of the compound itself being +13*4". Similarly, the value for the di-n-valeryltartrate varies from +8*2" in acetone to -4.7" in bromoform, the value for the salt itself being +6*7". On -the whole,. oxygen compounds have little influence, whilst haloid de- rivatives and compounds of the benzene series tend to reduce the value of [aj,, and even to change its sign. The effect of different solvents is of the same order with all five compounds. The changes in rotatory power may be due to (1) polymerisa- tion of the active molecules, or (2) combination of the active sub- stance with the solvent.Salts of the alkalo'ids, for instance, are known to combine with alcohols and with benzene, and propylic tartrate forms compounds with benzene. Cryometric measurements show that in solutions in ethylenic bromide which have normal rotatory power, the molecular weight is normal ; but in solutions in benzene which have much lower rotatory power, the molecular weight is considerably below the calculated value. It would seem khat some change o€ the nature of dissociation takes place. C. H. B. Thiocarbamides. By H. SALKOWSKI (Ber., 26, 2923) .-The -paper criticised by the author (this vol., i, 11) was by G. Mazzaron, not by G. Mazzara. J. B. T. Some Nitrogen Derivatives of the Higher Fatty Acids.By P. EITNER and H. WETZ (Ber., 26, 2840-2847).-The amides of the higher fatty acids can be distilled under diminished pressure almosb without decomposition, whilst that of the bibasic sebacic acid is almost completely decomposed. Lauramide boils at 199-200" (19.5 mm.), myristamide at 217" (12 mm.), palmitamide at 235-236", and stearamide a t 250-251" with slight decomposition, under the same pressure. The nitriles obtained from these amides have been employed for the preparation of several classes of derivatives. The imido- ethers are prepared by the action of dry hydrogen chloride on a liquid mixture of the nitrile with a molecule of isobutylic alcohol. Laurirnidoisobutyl ether hydrochloride, C16H330N,HC1, is 8 very hygroscopic, white, microcrystalline powder melting at 65-66'; i t is slightly soluble i n ether, readily in alcohol; in aqueous solution it soon undergoes decomposition.Myristimidoiso- butyZ ether hydrochloride, ClsH3,0N,HC1, has similar properties, and melts at 69-70". Palmitimidoisobutyl ether hydrochloride, C2oH,,ON,HCl, is less soluble and less hygroscopic than the above; it melts at 73". Stearimidoisohutyl ether hydrochloride, C2zH,0N,HC1,70 ABSTRAOTS OF CHEMICIAL PAPERS. is only slightly hygroscopic, and melts at 77-78'. It is also less soluble in ether than its lower 'nomologues. XebacimidoisobutyZ ether hydrochlwide, CIsH3,O2N2,2HC1, closely resembles the foregoing compound ; it melts at 135" with decomposition. From the imidoisobutyl ethers the corresponding amidine hydro- chlorides may be prepared by the action of alcoholic ammonia.These compounds form fine, white plates or thin prisms, with a spIendid silky lustre, and are not in the least degree hygroscopic. They form platinochlorides which crystallise from alcohol in slender-, yellow needles. Lazcramidine hydrochloride, C12H,,N,,HCI, melts a t 128-129"; it is readily soiuble in alcohol, slightly in water, in- soluble in ether. Myristamidine hydrochloride is only very slightly soluble in water, and melts without decomposition at 135". Palmit- amidine hydrochloride is also scarcely soluble in water ; it softens a t 1360, and melts a t 217". Stearamidine hydrochloride has been pre- viously prepared by Pinner (Die Iinidoather und ihre Derivate, S. 130). Sebacamidine hydrochloride melts at 166-167".PaZmitumidine, C,sH34N2, prepared by the action of sodium ethoxide on an alcoholic solution of the hydrochloride, crystallises from alcohol in lustrous plates melting a t 85". It distils almost without decomposition at 194" (13 mm.), The amidoximes corresponding with $he nitriles are prepared by the usual method, and resemble one another very closely. They form white, lustrous plates or broad prisms, with a faint pink or greenish surface lustre. They are insoluble in water, very slightly soluble in ether, readily in alcohol. Lauramidoxime melts at 92-92*5", myristarnid- oxime at 97", pazmitamidoxime a t 101.5-102°, and stearamidoxime a t 106-106*5". It was found impossible to prepare the amidoxime of sebncic acid. The nmidoximes unite with a, molecule of sulphurous anhydride: when this gas is passed through their solutions in benzene.The products formed cannot be distinguished from one another by ap- pearance. They are white, crystalline powders which decom- pose slowly, with loss of sulphurous anhydride; they all liquefy at about loo", and simultaneously decompose. The derivative of palmitamidoxime was converted into an ammoniwm salt by the action of dry ammonia gas; it is likewise a white, crystalline powder which decomposes in the air. These acids have the general formnla NH2*CR*N*O*S0,H, and the authors propcse to call them nmidoxime- sulphurous acids. The nitriles of the monobasic acids readily unite with hydrogen bromide. The following compounds of this class were obtained. M. p. Dilauronitrile hydrobromide, (C12H,N),,HBr. .75*5-76*0" Dimyristonitrile hydrobromide, (ClaH,N),,HBr 79*5--80*5 Dipalmitonitrile hydrobromide, (C1BH31N)2,HBr 84.0-85.0. Distearonitrile hydrobromide, (G,H,N),,HBr. . 88.5-89'5 All these substances crystallise in colourless, narrow plates, are almost insoluble in water, readily soluble in alcohol, &c., and are not hygroscopic. A. H.ORGlANIO CHEMISTRY. '71 Action of Ammonia, on Ethylic 6-Ethoxycoumalin-3 : 5-di- carboxylate in absence of Water. By M. GUTHZEIT (Ber., 26, 2795--2808).-The compound CH<,H:Co>O is named by v. Pech- mann (Abstr., 1891, 1460) coumalin instead of a-pyrone ; the author also adopts this name. It has already been shown (Abstr., 1891, 939) that when ethylic ethoxycoumalindicarboxylate is shaken with dilute aqueous ammonia, ethylic ethoxyhydroxypyridindicarboxylate is formed.If dry ammonia is passed into a solution of ethylic eth- oxg coumalindicarboxylate in benzene, a substance, CllHI3NO6, isomeric with that previously described (Zoc. cit.) is precipitated. When crys- tallised from a boiling mixture of acetone and alcohol, it forms a bright yellow powder, becomes red at MOO, melts at 199", and yields aa-dichlorodinicotinic acid (m. p. 7s-76") on treatment with phos- phorus pentachloride. When the substance melting at 199" is treated with cold dilute aqueous sodium hydroxide, or when a hot aqueous solution of it, mixed with a little alcohol, is filtered into hot aqueous sodium carbon- ate, a sparingly soluble sodium salt, CllH12N06Na + iH20, is ob- tained, together with a bitter oil.It was noticed that the longer the substance of melting point 199" is boiled with water, pre- viously to adding the solution to sodium carbonate, the more sodium salt is obtained. The compound obtained from the sodium salt by treating it with acids melts at 199", but, unlike the original substance, does not become suddenly red at 180". It therefore seemed probable that the original substance underwent isomeric change on heating. To put this to the test, the crude substance from ammonia and ethylic ethoxycoumalindicarboxylate was crystallised from a large quantity of cold acetone, when a white, flocculent compound, having the same composition as the original substance, was obtained ; on heating this in a capillary tube in the ordinary way, it becomes red at 180" and melts a t 199", but if the capillary tube is introduced into a sulphuric acid bath, heated to 178-179", the compound melts to a red liquid, almost immediately resolidifies, and melts a second time at 199".The compound melting at 178-179" gives a yellow coloration with ferric chloride, and is very sparingly soluble in solvents, so much so that its molecular weight could not be determined by the cryoscopic method, Cold dilute alkalis dissolve it, forming a yellow solution, which, on acidification, evolves carbonic anhydride and deposits an oil ; hot dilute alkalis produce the same effect, but partially convert the compound into the already mentioned sodium salt of the isomeride ; whilst boiling with concentrated alkalis causes the evolution of ammonia.When either the crude substance (m. p. 199") obtained from a boiling mixture of acetone and alcohol, o r the compound prepared from the sodium salt, is recrystallised from cold acetone, an isomeride is obtained in the form of concentrically arranged prisms ; it gradually becomes yellow when heated, melts sharply at 199", gives a deep violet coloration with ferric chloride, is more soluble in solvents than the lower-melting isomeride, yields the sodium salt when treated with hot or cold dilute alkalis, aud evolves only traces of ammonia when boiled with concentrated alkalis; il: CH'CH72 ABSTRACTS OF CBEMICAL PAPERS. molecular weight determination by the cryoscopic method established the formula C,1HI3NO6. The Silver salt is obtained as a white pre- cipitate, stable towards light, when silver nitrate is added to a soh- tion of the sodium salt; when heated with ethylic iodide, ethylic a-ethoxy-a-hydroxydinicotinate (m.p. 182") is formed, From these facts, it appears probable that the compound melting at 178-179' has the constitution CH<C(CooEt>-- CH( COOEt)*CO Co>NH ; whilst that melting at 199" has the tantomeric formula CH(CO0Et) -CO cH% (C 0 OE t)*C( OH) aN' A. R. L. Electrolytic Reduction of Aromatic Nitro-compounds. By L. GATTERMANN and K. KOPPERT (Bey., 26, 2810--2812).-A com- pound was obtained by the electrolytic reduction of paranitrotoluene (Abstr., 1893, i, 567), which was supposed to be nitramidorthobenzyl- toluene. When this compound is reduced to the diamine, the latter converted into the hydrazine, and oxidised with copper sulphate, a hydrocarbon is obtained having the same boiling point (275-280') as orthobenzyltoluene. When a mixture of paranitrobenzylic alcohol (or its acetate), para- nitrotoluene, and concentrated sulphnric acid is heated at 120-130", dinitrobenzyZf;oZuene, NO2*C6H3Me*CH2*C6H4*NO2, is formed ; it crys- tallises in yellow needles, melts at 137-138", and is converted into the diamine on reduction with stannous chloride.The dihydroxy- compound obtained from this diamine is identical with that previously described (loc. cit.). A compound identical with the nitramidobenzyl- toluene (Zoc. cit.) is obtained by heating together, at 160-170°, pas- amidobenzylic alcohol, paranitrotoluene, and concentrated snlphuric acid.These experiments, therefore, justify the assumption that, by t h e electrolytic reduction of pmanitrotoluene, paratolylhydroxylamie is first formed, and then undergoes isomeric change into par- amidobenzylic alcohol, the latter condensing with more paranitro- toluene. A. R. L. Action of Nitrous acid on Anethoi'l. By G. BOERIS (Gazgetta, 23, ii, 165-194) .-Diisonitrosoanethoi'l peroxide, OMe*C6Hrfi - EMe, is prepared by the action of sodium nitrite on anethoil in acetic acid solution; it crystallises in yellow needles melting at about 97", and was prepared by Toennies (Abstr., 1881, 167) who assigned to it a constitution differing from the above. No isbrneric modification seem8 to exist. The mononitro-derivative, CIoH9N3O6, obtained by direct nitration, forms lustrous, yellow needles melting at 88-89', The bromo-derivative, CloH,BrN20, was also prepared.a-Diisonnitrosoanethoi'E, 0Me*C6&*C (NOH)-CMe:NOH, ob tainod by reducing the peroxide with zinc-dust and acetic acid, crystallises in small, lustrous prisms melting at 125" ; potassium ferricyanide recon- verts it into the peroxide. Its diacety2 derivative, C10H10N20sA~2, N* 0 0 ONORGAhlC CHEM'ISTKY. 73 forms needles meltingat 89"; when dissolved in alcohol or potash, it slowly changes into diisonitrosoanethoil anhydride, ~-Diisonifrosoanetho~Z is obtained by heating the a-isomeride a t 125"; it melts at 206" with decomposition, and further differs from the a-compound by being very sparingly soluble in alcohol. Its djacetyl derivative forms white needles melting a t 104", and, on treatment with potash or boiling with alcohol, is reconverted into the p-dioxime ; the latter is converted into the peroxide by potassium ferricyanide.y:N>O, prepared by re- ducing the peroxide with tin and hydrochloric acid, crystallises in long, white needles melting a t 63"; it is soluble in alcohol or benz- ene, and has the normal molecular weight in freezing benzene. The mononitro-derivative is obtained by direct nitration, and forms small, lustrous crystals melting at 98-99'. The bromo-derivative is fairly soluble in alcohol, and crystallises in small needles melting at 73-74". a- Diisonitrosobromanethoi'l, OMe- C6H3Br* C (NOH) CMe:NOH, is pFepared by reducing the bromo-derivative of the anhydride with mnc-dust and acetic acid; it crystallises in very lustrous, small prisms meltling at 143-144".On heating with acetic anhydride, it yields a diacetgl derivative which forms thin needles melting a t 101-102", and soon decomposes in alcoholic solution, giving the brorno-derivative melting a t 73-74' described above. The latter is also obtained on oxidising a-diisonitrosobromanethoil with alkaline f erricyani de. p-DiisonitrosobromanethoiZ is prepared by heating the a-isomeride above its melting point ; it forms small, white scales melting at 190", and yields the peroxide on oxidation with alkaline ferricyanide. ThO diacetyl derivative is obtained in white needles melting at 130-131". On reducing the p-dioxime with tin and hydrochloric acid, the same anhydride is obtained as by direct bromination of diisonitrosoanethoil anhydride.W. J. P. Synthesis of Ethers and Ketones from Phenols. By S. I(. DZERZGOVSKY (J. Russ. Chem. SOC., 25, 154-163) .--Catecho1 and chloracetic acid in molecular proportion are melted together, and to the product phosphorus oxychloride is added in quantity equal to the weight of the chloracetic acid taken. The mixture is heated until brown and syrupy, and then treated with three times its volume of water, from which, on cooling, crystals of the chloroketone, OMe*C6H4* C:N Diisonitrosoanethoil anhydride, CsH, (OH),*CO*C HzCl, separate. The chloro- ketone crystallises in colonrless prisms with lH,O, which is given off at 110", and melts at 173". It is easily soluble in alcohol, chloro- form, ether, benzene, and carbon bisulphide.The aqueous solution is coloured green by ferric chloride, changing to purple on the addition of sodium carbonate. It reduces silver but not cupric salts, and has an acid reaction. The diacetate is insoluble in water, but crystallises The yield is 80 per cent. of the theoretical.74 ABSTRACTS OF GHEMIOAL PAPERS. from aqueous acetic acid in pearly scales melting at 95". It is solu- ble in alcohol, ether, and chloroform- On reduction with zinc and hydrochloric acid, the chloroketone gives a theoretical yield of aceto- catechone, CsH3( OH),*COMe, which crystallises in nodular aggregates of prismatic needles. These crystals contain no water of crystallisa- tion, melt at 116", and are easily soluble in most solvents. The diacetate crystallises from acetic acid in colourless plates melting at 87O.Bromacetocatechone, C6H3( OH)2*CO*CH2Br, crystallises with 1H20, and melts at 167". a- Chloropropiocntechone, C6H3( OH)2*C 0 CHCb cH3, crys tallises in prisms without water of crystallisation, and melts at 120" ; the cop responding bromo-derivative melts at 141". p-Bromobutyrocatec~Lone, c6&( OB),*CO*CH2*CHBr~CH3, is formed in an analogous manner, but the reaction in this case is hastened by the addition of zinc chloride. It crystallises in colourless prisms without water, and melts at 135". Guaiacol and quinol do not give ketones when treated with chlor- acetic acid and phosphorus oxychloride, but simply chloracetates. The chloracetate of guaiacol, OMe*C6&-O*CO*CH2C1, melts at 50", and boils at 258-259'. The dichloracetate of quinol, C6&( O0CO.CH2CI),, melts a t 123", and boils above 300'.J. W. Desmotropy in Phenols : Constitution of Tetrethylphloro- glucinol. By J. HERZLG and S. ZEISEL (Monatsh., 14, 376-3811.- When dibromotetrethylphloroglucinol (Abstr., 1890,243) is submitted to alkaline hydrolysis, it is converted into symmetrical tetrethylacetone, monobromotetrethylphloroglucinol, and oxalic acid, with elimination of bromine and carbonic acid. The constitution of the dibi-omo-corn- pound is, therefore, probably represented by the formula and that.of the phenol by the formula C O < ~ E ~ & ~ ! > C E ~ . The intermediate products may be either the unsiabli ketonic acid CHBr2*CO*CEkCO*CEt2*COOH, or tetrethylacetone and dibromo- malonic acid. In either case, dibromacetic acid is formed, and this, in the presence of alkali, is immediately hydrolysed into glyoxylic acid.The latter then reduces the dibromotetrethylphloroglucinol to .the monobromo-compound, and is itself oxidised to oxalic acid in the process. The dibromotetrethylphloroglucinol (14.58 grams) is boiled for an hour in a reflux apparatus with an aqueous solution of sodium hydr- oxide and carbonate (8.86 and 0.25 grams in 100 c.c.) in an atmo- sphere free from carbonic anhydride. The product consists of a colourless, oily layer floating on a, yellow, aqueous layer. The oily layer is separated and purified, and a further portion distilled from the aqueous layer. It consists almost entirely of symmetrical tetr- ethylacetone (Abstr., 1892, llSS), boiling at 204.9--305*9" under a, pressure of 738.5 mm.The casbonic acid was estimated in a portionORGANIC OHEMISTRT. 75 of the aqueous lager, and the monobromotetrethylphloroglucinol pre- cipitated by hydrochloric acid from the remainder, the oxalk acid being estimated in the filtrate. The monobromo-compound may be reconverted into the dibromo-compound and worked up again until the quantity is too small for treatment. JN. W. Conversion of Ally1 Compounds into Propenyl Compounds. By A. ANGELI (Gazzetta, 23, ii, 101--102).-0n heating safrole a t 200" with dry sodium ethoxide (5 per cent.), it is almost wholly con- verted into isosafrole; this process has the great advantage of dispensing with the long heating with alcoholic potash which has hitherto been necessary for the conversion of aromatic ally1 deriva- tives into the corresponding propenyl compounds.It is, in all prob ability, applicable to other similar cases. W. J. P. Action of Nitrous acid on Unsaturated Compounds. By A. ANGELI (Qazzetta, 23, ii, 124-135 ; compare Abstr., 1892, 447, 1198) .-A mononitrosite of the composition C&02'N203 is obtained on passing nitrogen trioxide through an ethereal solution of sorbic acid; it crystallises in small, white needles melting at about 110" with decomposition. Neither crotonic acid nor diallyl react with nitrous acid ; stilbene, however, yields a white, crystalline substance melting at about 132" with decomposition, but no satisfactory analyses could be made. On treating safrole with nitrous acid in ethereal or light petroleum solution, it yields the a-nitroslte having the probable constitution ; it is a yellow powder which melts a t about 130" with decomposition, and is sparingly soluble in most solvents.With piperidine, it does not give a nitrolamine, but a condensation product which forms small needles melting at 83", and has the com- position C,,H,,N204. On warming with phenylhydrazine, it yields a compound of the composition C16H17N30b, which separates from benzene in small, yellow needles melting at 87". On boiling with alcoholic potash, the a-compound is converted into the isomeric p-nitrosite; this melts at 92", and is soluble in alkalis. CH,O,:C6H3*CH,*q H 7 H2 y-0-Y 0-0 The author assigns to it the constitution C HzO~:C~H~* C H2* C H (NO2) C HXO H, When warmed with concentrated hydrochloric acid, gas is evolved, and an aZdehyde, CH202:C6H3=CH,wCH(N02) *COH, is deposited ; it orystallises in lustrous, white scales melting at 86", and dissolves in alkalis without decomposition.Its alkaline solution readily reduces ammoniacal silver nitrate ; with phenylhydrazine, it yields a hydr- uzone (?), CI6H,,N3O4, which melts at 86". W. J. P. p-Phenylpropylamine. By M. FREUND and E. K ~ N I G (Ber., 26, 2874--2873).-/%Phenylpropylamine is obtained by the reducing action76 ABSTRAClTS OF CIHEMIGAL PAPERS. of sodium on methylbenzylic cyanide dissolved in absolute alcohol. The product is distilled with steam, dissolved in hydrochloric acid, and the solution concentrated, and extracted with ether. It is a colour- less, highly refractive oil, boils at 210" (uncorr.), has a strong, basic, fishy odour, a, strongly alkaline reaction, and absorbs carbonic anhydr- ide from the air.The hydrochloride is extremely hygroscopic. The platinochloride, (C9Hl3N)2,H2PtCI6, crystallises in beautiful, lustrous, golden plates, and decomposes at about 140". The aurochloride crystal- lises from dilute alcohol, and melts a t 124'. The picrate melts a t 1 8 2 O . E. C. R. Oxidation of Aaimidotoluene. By J. A. BLADIN (Ber., 26, 2736-2738 ; see also Abstr., 1893, i, 375).-A small quantity of az- imidobenzoic acid is obtained, together with triaeoledicarboxylic acid, by the oxidation of azimidotoluene with alkaline permanganate. The two compounds are easily separated by slightly acidifying the aqueous filtrate with nitric acid and concentrating the solution on the water- bath, when the azimidobenzoic acid is precipitated. Azimidobenzoic acid, COOH.CsH3<&~>N, crystallises from acetic acid in small, colourless leaflets containing 1 mol.of acetic acid ; it does not melt at 270". The calcium salt, (C7H*N302)2Ca,4H20, and the barium salt, ( C7H4N302)2Ba,7H20, are described. Triazoledicarboxylic acid crystallises from water in large, mono- symmetric crystals with 2H20. When heated with resorcinol and zinc chloride, it yields a fluorescein which dissolves in ammonia with an intense green fluorescence. The barium salt, CaN3H( COO),Ba,H,O, is an insoluble, crystalline powder. The copper saZt is bright blue, decomposes on heating, and is soluble in ammonia, and mineral acids. TriazoZe, C2N3H3, obtained by heating the dicarboxylic acid in a current of carbonic anhydride, is a hygroscopic oil, and boils a t 308-209" under 742 mm.pressure. The benzoyl derivative, C2N3H2Bz, crystallises in long, colourless prisms, and melts at 111-115". E. C. R. Derivatives of Thiosemicarbaaide. By G. PULVERMAC~ER (Ber., 26, 2812--2813).-By the action in the cold of alkyl- thiocarbimides on hydrazine hydrate in alcoholic solution, thiosemi- carbazides, NH,*NE*CS*NHR', are formed. Yhenyzt~iosemicarbazide, NH,*NHCS*NHPh, prepared from phenylthiocarbimide, forms six- sided prisms, and melts at 140'. A. X. L. Action of Acids and Acid Anhydrides on Thiocarbimides. By P. KAY (Ber., 26, 2848--2852).-Krafft and Karstens (Abstr., 1892, 712) have shown that the di-acid anilides are not produced by the action of acids on the thiocarbimides, but that the mon-acid c&m- pounds are formed.The author has, however, succeeded in preparing the di-acid compounds by substituting the acid anhydrides for the acids. DiucetyZaZZyZumine, CH2:CH*OH2*N( COMe)z, is prepared by boiling allylic thiocarbimide with acetic anhydride, carbon oxy-ORGAN10 UHEMISTRT. 77 sulphide being evolved ; it is a colourless liquid, boiling at 88-90" under a pressure of 14 mm. Diacetanilide, NPh(COMe)2, is obtained in a similar manner from phenylthiocarbimide. It forms crystals which melt at 37-37.5", and is soluble in benzene, but only slightly so in cold water ; it boils a t 145-146" (13 mm.). Dipropionanilide, NPh(COEt),, boils at 165-166" (17 mm.), and solidifies in colourless crystals melt- ing a t &".Paratolylthiocarbimide is prepared by boiling paratolyl- thiocarbanilide with acetic anhydride for 3-4 minutes ; it melts at 25" and boils at 245-246'. Diacetoparatoluidide, C6R4Me.N( COMe),, is produced by the further action of acetic anhydride at 170-180", and boils at 160-161' (15 mm.). Dibenzanilide, NPh(COPh),, is prepared from phenylthiocarbimide and benzoic anhydride. It melts at 160-161" as stated by Steiner (AnnuZen, 178, 235). The following substances have also been prepared by this reaction, the acids and not their anhydrides being employed : -AllyZbenaamide, COPh*NH*C3H5, is a colourless oil with a faint odour and bitter taste. It boils at 173-174" (14 mm.), and decomposes when heated at the ordinary pressure.It combines with bromine to form a di- bromide, C,oH,lBrzNO, which crystallises in lustrous plates, and melts at 135". When treated with concentrated sulphuric acid, allylbenzamide undergoes intramolecular change, and is converted into the p-methyl-p-phenyloxazoline which has been previously described by Gabriel and Heymann (,4bstr., 1890, 1267) ; it can be very readily prepared by this means, and is also formed when a benzene solution of allylbenzamide is saturated with hydrogen chloride and heated in a sealed tube. A small amount of /3-chloro- propylbenzamide is also formed by this method. AZlyZcinnamide, CHPh:CH*CO*NH*CH2*CH:CH,, forms crystals which melt at 90-90*5", and boils at 223-2241" (14 mm.).; it combines with 4 atoms of bromine and also with hydrogen chloride.Allylphthal- imide, C8H402:N*C3H5, is prepared from phthalic acid and thiocarb- imide; it boils at 295" and melts at 70-71" as stated by Wallach and Kamenski (Ber., 14, 171). Ally lsuccinimide, C4H4O2*N*C3RS, boils at 130-131" (14 mm.). A. H. Preparation of Di-acid Anilides. By P. KAY (Ber., 26, 2833-2856 ; compare preceding abstract). The di-acid anilides are not formed when the mon-acid derivatives are simply boiled with an acid chloride, but they may be prepared by this reaction if the mix- ture be heated in an oil bath to a temperatnre of from 170" to 200" in a flask connected with a reversed condenser. I n this way, the acid chloride collects in the tube of the condenser and the anilide is acted on mainly by the superheated vapour.The reaction succeeds better when the acid chloride is gradually added as the conversion proceeds. All the di-acid anilides described in the foregoing abstract have been also prepared i n this way. Diacetorthotoluidide is a colourless oil which boils at 145" (11 mm.), and does not solidify at the ordinary (summer) temperature. A. H. The Solid State of some Aldoximes. By E. BOURGEOIS and J. DAMBMANN (Bey., 26, 2856-2861).-The fact that many of the VOL. Lxvt. i. 978 ABSTRAQTS OF CHEMIOAL PAPERS. ddoximes exist in n solid form has been obscrved by many chemists, a-Benzaldoxime may be obtained in a pure state by melting t h e almost pure material, a t about 30", maintaining it at a, temperature of 26-27', and introducing a crystal of the solid compound. Splendid lustrous prisms are formed, which melt sharply at 35", and may be preserved without change.It boils at 117.5" (14mm.). When the p-modification, melting at 125", is slowly heated under diminished pressure, a small amonnt of it sublimes, but the remainder is con- verted into the a-form, which suddenly boils up and distils at 117.5" (14 mm.). The solid substance melts at 48.5', and the liquid thus formed boils st 166165" (corr.), but does not solidify entirely when cooled ; the solid matter obtained liquefies in the course of two 01- three days. The melting point determination is only approximate, the temperature found vary- ing with the length of time for which the sample has been heated ; this behaviour of the substance is probably due to the presence of small amounts of impurities.Solid cenanthaldoxime can be prepared much more easily in the pure state, but behaves in a similar manner to the others. It boils at 100.5" under a pressure of 14 mm., but the distillate does not completely solidify. The solid portion melts at 55*5", and can be preserved without change. Isovaleraldoxime cannot be got to solidify completely. A. H. Galloparatoluidide. By P. CAZENEUVE (Compt. rend., 117, 633-635) .-When equal weights of crystallised paratoluidine and gallotannic acid are heated together at about 150' for an hour, and the product is treated with dilute hydrochloric acid, and crystallised from dilute alcohol, gaZlopu~atoZuidide, C6H2( OH)3*CO*NH*C6H4Me, is obtained in white, cpystalline plates melting at 211", only slightly soluble in cold water, but very soluble in hot water, and soluble in alcohol and ether; the crystals contain 2H20, which they lose a t 100".Galloparatoluidide is not affected by alkalis out of coritact with air, even in boiling solutions, but in presence of air it is slowly oxidised. When heated with hydrochloric acid in sealed tubes at 150°, it splits up into gallic acid and paratoluidine. Galloparatoluidide yields saline derivatives analogous to those of gallanilide (Abstr , 1893, i, 638). When a boiling solution is mixed with zinc acetate, it yields a very insoluble, white precipitate of the compound OH*C6H2 (0,Zn) *C O*NH*C6H4Me. Lead acetate produces a precipitate of similar constitution, and lime water and baryta water yield analogous compounds which alter when exposed to air.Mercuric and cupric acetates are reduced as with gallanilide. When boiled with nitrosodimethylaniline in presence of alcohol, gnllotoluidide yields the homologue of gallic blue (Abstr., 1893, i, 510). Orthotoluidine, methylaniline, dimethylaniline, and the so-called pupe xylidine of commerce yield no analogous compounds when heated with gsllotannic acid. C. H. B.ORGANIC OHEMISTRY. 79 Amido-arnidine Bases. By E. LELLMANN and R. HAILER (Ber., 26, 2759-2763).-The authors have endeavoured to deteymine to what extent the power of directly dyeing cotton, which is possessed by the monazo-dyes derived from dehydrothioparatoluidine, is dependent on the nature of the elements in the complex C< I , and how far it is conditioned by their arrangement, Paranitrobe.nzoparatoluidide, Noz*C6H4*Co*NH*C6H,e, prepared by heating paranitrobenzoic acid with paratoluidine for 5-6 hours a t 180-220", crystallises from glacial ace tic acid in greyish-yellow, silky, lustrous needles melting at 203'. Paranitrobenxometartitroparatoluidide, NOzoC6H~*COoNH*C6H3MeoN02, is formed from the preceding compound by the action of nitric acid (sp.gr. 1.45) a t O", and crystallises from alcohol in golden-yellow plates melting at 171-1172' ; on reducing it with stannous chloridc, paramidpbenzenyltoluyleneamidine, NHz*C6H4.C< N - >C6H3Me, is ob- tained, which crystallises from dilute ammonia in small, yellow needles, and melts at 113-114'. The sulphate, C14H13N3,H2S04 + H20, is crystalline. Metamidobenzenyltoluyleneamidine melts at 238", instead of at 227-229"as stated by Schack ; the sulphate, ( G,.,H,3N3)2,H2S04 + l$HzO, not C14H,3N3,HzS04, crystallises in plates.The tinctorial power of the diazo-derivative is less marked than that of its isomeride. Paranitro- benzometaxylidide, NOz.C6H~*CO*NH*CGH3Me2, is prepared by heating paranitrobenzoic acid and nietaxylidine at 230°, and crystsllises from alcohol in grey prisms lzzelting at 166". Paranitrobe?Lzonitrcmtefax?/E- idide, N02*C6H4*C0.NH*C6H,Mez*Noz, is obtained from the preceding compound in a similar manner to the toluidide ; it crystallises from glacial acetic acid, and melts at 139-140". Paramidobenzeng I- rnetaxylyleneamicline, NHz*C6H4*C<E!> C6HzMez, is formed by the reduction of the nitro-compound, and crystallises from dilute am- monia in slender, almost colourless needles melting at 183".The sulphate, CI5H,,N3,H,SO4 + 6H20, is deposited in slender, colourless, lusbrous needles. The tinctorial power of the diazo-derivative was not determined. J. B. T. s* c N*C NH The diazo-derivative readily dyes cotton. Protoca;P;echuic Aldehyde and Piperonal. By R. WEGSCHEIDER (Monatsh., 14, 382-389) .-In order to convert piperonal into proto- catechuic aldehyde, it is not necessary to isolate the dichloropiperonal (compare Fittig and Remsen, Annalen, 159, 148). Piperonal (28 grams) is shaken with phosphorus pentachloride (I 20 grams) in a reflux apparatus, the temperature not being allowed to rise, and the action is completed by heating the mixture at 108-109"; the product is then treated with water (1512 c.c.), and the mixture heated, and finally boiled.The lower oily layer, which contains the protocatechuic aldehyde, is extracted with ether, and the aldebyde 9 280 ABSTRAOTS OF OHEMIOAL PAPERS. thus obtained is recrystallised from toluene ; the yield is SO per cent. Opianic acid yields only 8 per cent. of protocatechuic aldehyde when boiled with hydrochloric acid, and the intermediate product, vanillin, yields 20 per cent. Protocatechuic aldehyde melts at 153-154'. The lead and mercury compounds and the oxime are described. The pheny2hydrazone exists in two, probably stereoisomeric, modifications. The first, which melts at 174-175", is formed when cold alcoholic soIutions of the aIdehyde and phenylhydrazine are mixed. The second is obtained on heating the first with an alcoholic solution of phenylhydrazine, and melts a t 127-128" ; in contact with cold water, it is slowly transformed iuto the first modification.An attempt to synthesise piperonal from protocatechuic aldehyde and trioxymethylene yielded only traces, whilst by heating the lead and mercury compounds with methylenic iodide, none was formed ; when, however, the aldehyde ( 5 grams) was heated with methylenic iodide (14.7 grams) and alcoholic potash (6.3 grams in 10 C.C. of methylic alcohol) for 94 hours at loo", and then for 22 hours at 135-140", a small amount (0.020 gram) of piperonal was obtained (m. p. 35-36') ; the piperonic acid, obtained on oxidising it with permanganate, melted at 221.5-224.5". Violet Perfme. By F. TIEMANN and P.RR~GER (Bey., 26, 2675-2708).--The characteristic fragrance of violets is also pos- sessed by dried iris root, which has been employed by the authors as the source of the fragrant oil which forms the subject of the present paper. It has been found impossible to obtain sufficient material from violet blossoms themselves to ascertain whether the odoriferous substance contained in them is or is not identical with those described. To isolate the fragrant oil, the dried iris root is repeatedly extracted with ether, and the extracted matter then distilled with steam. The non-volatile portion consists mainly of resinous matter and a little myristic acid, irigenin, iridic acid, &c., whilst the readily-volatile fraction contains the irone or fragrant oil, together with a consider- able amount of myristic acid and its methylic salt, olejic acid, an ethereal oleate, olejic aldehyde, and small amounts of other substances.The acids and ethereal salts are removed from the more volatile por- tion, obtained by the repeated fractional distillation of the oil with steam, by dissolving it in cold alcoholic potash and precipitating with water. Aldehydes are next oxidised by warming with water and silver oxide, and the irone finally purified by conversion into the phenylhydrazone, which is then decomposed by distillation with dilute sulphuric acid. Irone, C13H200, is an oil which is scarcely soluble in water, readily in alcohol, &c., boils a t 144" under a pressure of 16 mm., and has a sp. gr. of 0.939 at 20'. Its index of refraction, rtD, is 1.50113, and it is dextrorotatory.The smell of the pure substance is sharp, and, in the concentrated form, quite unlike that of violets, but when largely diluted resembles that of the natural flowers. The phenylhydruzone is a yellowish- brown oil. The oxime, C,H20:NOH, crystallises with JN. W.ORQANIC CHEMISTRY. 81 very great dificulty in lustrous, white plates melting at 121.5", but is generally obtained as an oil. Irone is a methyl ketone, yielding chloroform on treatment with sodium hypochlorite. When treated with hydriodic acid and phosphorus, irone loses a molecule of water, and forms irene, C,3H18, which is a colourless oil boiling at 113--115" (9 mm.). It has a sp. gr. of 0.9402 at 20", and a refractive index of 1.5274. It dissolves in concentrated sulph- uric acid a t the ordinary temperature, decolorises a solution of bromine in acetic acid, and is gradually converted into a resin by the action of the air.When oxidised with vigorous reagents, irene is broken up into compounds containing only a small number of carbon atoms, such as formic, acetic, and pyruvic acids ; but when the oxida- tion is more carefully conducted, a series of compounds is obtained the nature of which throws much light on the constitution of irene itself and irone. Oxydihydroxydeh y droirene, CsH3Me < CMe2*?H*oH formed by the CO--CH*OX.' action of chromic acid in acetic acid solution, crystallises in highly refractive rhombohedra melting at 154-155", and has feebly acid properties. Iregenonedicarbox y Zic acid, C 0 0 H*CO*CsH3Me* CMe2* C 0 OH, is pro- duced by the action of alkaline permanganate on the foregoing com- pound.It crystallises from hot water in short needles or oblique prisms melting at 227'. Ireg enone tricarboxy Zic acid, C 00 H- C 0 * C6H3 ( CO OH) *CMe2*C OOH , is formed by the further oxidation of the foregoing, and crystallises from water, at 5", in granular prisms containing water of crystallisa- tion. At 110", the crystals become anhydrous, and melt with decom- position at 227". The Irirnethylic salt forms compact crystals melting at 127-128". Ioniregenetricurboxylic acid, C6H3( COOH),*CXe2*COOH, is the final product of the oxidation of irene, when this is carried out a t first by gentle, and then by more powerful, oxidisers. It crystallises in white needles, and is slightly soluble in hot water, alcohol, and ether.At 150" it loses water, and is converted into an anhydride which is also formed when iregenonetricarboxylic acid is heated above it5 melting point, carbonic oxide and water being evolved. The salts of the acid, which are also formed by dissolving the anhydride in alkalis, crystallise well. The acid is very stable, and is not altered by oxidising agents or by warm concentrated sulphuric acid. The anhydride can be distilled without decomposition. The trimethylzc salt crystallises in colourless needles melting at 93". The anhydride, COOH*C9H,< >O, crystallises from benzene in plates melting at 214". When the ammonium salt of ioniregenetricarboxylic acid is heated in a current of carbonic anhydride, the corresponding imido- co co acid, COOH-C9Hg<CO>NH, co is produced.It is a white, crystalline powder which is insoluble in the usual solvents, melts above 300°, and boils a few degrees higher than this. Its s i h e r salt is a white powder, which, when heated in a current of carbonic anhydride,82 ABSTRACTS OF CHEMICAL PAPERS. CMe2*$:0 yields the imide of dimethylhomophthalic acid, C6H4<C0 --NHI previously prepared by Gabriel (Abstr., 1887, 725). The oxidation products of irene may therefore be looked on as derived from a hypothetical substance, dehydroirene, of the formula CMe2*$H CM%*CH, C6H3Me<~~Z -CH Or C 6 H 3 M e < ~ ~ - 6 ~ - ' I n order to throw further light on the constitution or" irone and irene, a series of synthetical researches was made, starting with geranaldehyde (citral), a substance which has been shown by Semmler (Abstr., 1891, 540) to have the constitution CHMe2*CHz*CH:CH*CMe:CH*COH, since, when treated with potas- sium hydrogen sulphate or hydriodic acid, it is quantitatively con- verted into cymene.Geranalde h yd e undergoes con densat ion with acetone, yielding pseudoionone, CHMe2*C H2*C H:C H*CMe:CH* CH:CH*C OMe. This substance is an oil, boiling at 143-145" (12 mm.), has a sp. gr. of 0.9044, and a, refractive index of 1.5275. Thephenylhydruzone and the oxime are thick oils. It does not combine with sodium hydrogen sulphite. When pseudoionone is heated with dilute sulphuric acid and a little glycerol, it is converted into the isomeric ionone, c&&,,o. This substance boils at 126-128" at 12 mm., has a sp.gr. of 0.9351, and a refractive index of 1.507, and is optically inactive. It has SL char- acteristic odonr resembling that of violets, and, at the same time, that of the vine blossom. When heated with hydriodic acid and phos- phorus, it loses water, and yields ionene, CI3Hl8, which boils a t 106-107" (10 mm.), has a sp. gr. of 0.9338, and a refractive index of 1.5844. It resembles irene very closely, and, like it, has the properties of a terpene. When cautiously oxidised with chromic acid, it yields a mixture of the following compounds, which can be separated by means of their calcium salts. Iongeuogonic acid, C6H3Me<Co ~>CHGOOH, forms white needles melting at 237". Ionegenedicarboxy Zic acid, C 0 OH*CsH3Me*CMe2* C 0 OH, forms vitreous prisms readily soluble in alcohol, &c., but only slightly in boiling water.When rapidly heated, it melts at 130-131", but when gradually heated a t a few degrees lower, it is converted into the uvLhydride, which crystallises from light petroleum in long, white needles melting at 105". The acid is bibasic, and its calcium CMe salt, when distilled Gith soda lime, yields cymene. Ionegeneulide, , crystallises from benzene in transparent CMe2*$!H*OH CJ33Me< co-0 plates melting at 175". This substance possesses feeble acid pro- nerties, and has the composition of tbe semi-aldehyde of ionegenedicarb- oxylic acid. It does not, however, appear to contain the aldebyde group, and is therefore probably an anhydride of the constitution shown. It is very readily converted by oxidation into ionegenedicarboxylic acid.Ionene is converted, by oxidation with alkaline permanganate, intoORGANIC CHEMISTRY rn 83 inn egenonetkarbosy tic acid, C,H,( CO OH) ,*CMe2* C 0 * CO OH, which crystallises with 2H20. When rapidly heated, it melts at 140-145", and decomposes above this temperature, the anhydride of ioniregene- tricarboxylic acid being formed. The final product of the oxidation ,.of ionene itself, and of the oxidation products just described, is ionib regenetricarboxylic acid, identical with that obtained from irene. The isomeric hydrocarbons, irene and ionene, are shown by the nature of their oxidation products to be trimethyl derivatives of a te trahydronaphthalene. They both contain three ethylene linkings (refractive index), of which two are probably in the ring which by the removal of two hydrogen atoms is converted into the benzene ring, as this is necessary to account for the terpene-like properties of the two substances.The constitution of ionene follows from that of ionone, which is shown, by its formation from pseudoionone by intra- molecular change, to be probably $lH2*CMe2.yH-C H: CH C OMe CH:CH--CHMe CH:CH-CH*CH:CMe $?H,*CMe2*QH*CH:yH I. Ionone. 11. Ionene. Ionene therefore has the formula 11, whilst the constitution of the isomeric irene is most probably represented by IV. Irone is related to irene in the same way as ionone to ionene, and therefore has the formula 111, I;;H*Cllle2*FH*CH:CH.COMe I;;H*CMe2*QH*CH:QH CH*CH2 -CHMe CH*CH2 -CH.CH:CMe 111. Irone.IV. Irene. Ionone and irone are both without injurious effect on the animal organism. The odours of ionone and irone are extraordinarily alike, arid can only be distinguished by observers of great experience, and this is looked on by the authors as an additional confirmation of the great similarity in constitution of the two componnds. It is probable that either irone, ionone, or some optically isomeric anbstance is present in the blossoms of the violet, but this question has not yet been decided experimentally. Compounds of the Geranaldehyde (Citral) Series. By F. T~EMAYK and F. W. SEMMLEB (Be~.,.26,2708--2729) .-Germaldehyde {citral), CHMe2.CH2*CH:CH*CMe:CH*COH (Abstr., 1891, 539), is converted, by careful reduction with sodium and alcohol, ir,to optically inactive geraniol, CHMe,*CH,*CH:CH*CMe:CH.CH,.OH, and can be obtained from the latter by oxidation (Abstr., 1891, 30).Several substances of the formula C,,H,,O isomeric with geraniol are known. Among these are coriandrol, which is dextrorotatory (Abstr., 1891, 540) ; rhodinol, feebly 1Evorotatory (Abstr., 1892,203) ; and linalool. The rotation of the last of these compounds varies with the origin of the substance, but it is probable that the compounds described as aurantiol, lavendol, nerolol, and linaloiil (Abstr,, 1892, 868, 1236) are in reality identical, the slight differences observed between them A. H.84 ABSTRACTS OF OHEMICAL PAPERS. being due to accidental impurities. All these cornpounds of the formula CloHl,O, as well as geraniol, are converted by cautious oxidation into geranaldehyde.In order to account for the existence of these optically active forms isomeric with geraniol, it is necessary to assume that they have a different structural formula from the latter, such as CMe2:CH*CH:CH*CHMe*CH2*CH,*OH or CH2:CMe*CH2-CH:CH*CHMe*CH2*CH2*OH, and that on oxidation a change in the position of the ethyleen linking, analogous to that observed by Fittig, takes place. Geranaldozime, CloH6:NOH, is a yellow oil, boiling at 143-145' (12 mm.), and has a sp. gr. of 0.9386 at 20" and a refractive index [%ID of 1.51433. When distilled at the ordinary pressure, the corresponding nitrile is formed. GernnaZpheny Zhydrazone, CloH6:N2HPn, is a red oil which cannot be distilled. GerunaZarziZide, CloHla:NPh, is obtained by heating the constituents together at 150'.It is a yellow oil boiling at 200" (20 mm.). GeranionitriZe, CgH16*CN, is prepared by heating geranaldoxime with acetic anhydride. It is a colourless liquid which boils at 210" (10 mm.), has a sp. gr. of 0.8709 at 20", and a refractive index of 1.4759. When digested with an alcoholic solution of hydroxylamine, an oily amidoxime is formed. Geranic acid, CgHu*COOH, can be obtained from the nitrile by the action of alcoholic potash much more readily than by the oxidation of geranaldehyde with silver oxide (Abstr., 1891, 323). It is an oil, boils a t 153" (13 mm.), has a sp. gr. of 0.964 at 20", and a refractive index of 1.4797. When geranaldehyde is carefully oxidised with chromic acid at a low temperature, an uncrystallisable acid of the formula Its odour resembles that of the higher fatty acids.CHMe2*CH2*CH:CH*CMe( OH)*CH( OH) GOOH is obtained, together with methyl hexylene ketone. The same products are obtained, under the same conditions, from geraniol. Methylhexylenecarbinol, CHMe2*CH2*CB:CH*CHMe*OH, is formed, together with geranic acid and methyl hexylene ketone, in the hydrolysis of geranionitrile. It boils at 175", has a sp. gr. of 0.8545 at 20", and an index of refraction of 1.4505. This substance is identical with the compound previoi~sly prepared by Wallach by the reduction of methyl hexylene ketone (Abstr., 1893, i, 598). Methyl hexylene ketone, CHMe2*CH2*CH:CHCOMe, has been previously described by Wallach (Abstr., 1890, 1314). The formula ascribed above to this compound differs from that proposed by Wallach, CHMe,*CH:CH*CR,*COMe.The authors point out that their formula explains the various reactions of the compound, and is, moreover, in agreement with the formuls of the other compounds derived from geranaldehyde ; they propose to examine the question further. Methyl hexylene ketone is converted by the action of bromine an& sod a into tribromomethy Zhex y Zcurbinol, C8H12Br30 OH, which separates from light petroleum in snow-white crystals meliing at 98-99',ORGANIC CHEMISTRY. 85 Geraniolene, CHMe,*CH,*CH:CH*CMe:CH,, is formed when geranic acid is distilled at the ordinary pressure, carbonic anhydride being evolved. It boils at 142-143", has a sp. gr. of 0.757 a t 20°, and a refractive index of 1.4368. It combines with 4 atoms of bromine, forming an oily additive compound, C9HI6Brd.Geranic acid, its nitrile, and geraniolene are, like pseudoinone (see preceding abstract), converted into cyclic compounds of the same molecular weight by the action of dilute acids. V I Isogeranic acid, C H < ~ $ ~ ~ ~ > C H * C O O H , is obtained by shaking the oily geranic acid with 65 per cent. sulphuric acid. It crystal- lises from water or light petroleum in white needles melting at 103*5O, and is only slightly soluble in hot water, readily in alcohol and ether. It boils at 138" (11 mm.), and can also be distilled without decom- position at the ordinary pressure. The dibromide is formed by the direct addition of bromine, using a solution in chloroform. It separates from light petroleum in white crystals melting at 121".Dihydroxydihydroisogeranic acid, is foimed by the action of potassium permanganate on a solution of the acid in sodium carbonate. It separates from absolute alcohol in well-developed crystals melting a t 195-196". Isogeranionitrile, CH<cH.CHMe>CH*CN, is formed from the nitrile of geranic acid by the action of 70 per cent. sulphuric acid. It boils a t 87-88" (11 mm.), has a sp. gr. of 0.9208 at 20°, and an index of refraction of 1.4734. When the nitrile is hydrolysed. isogernnic acid is obtained. The nmidoxirne of the nitrile is solid, and melts at 165". Isogeraniolene, CH<CH,CH-e>CHZ, CH, CMe, is produced in a similar manner from geraniolene; i t boils at 138--240", has a sp. gr. of 0.7978 at 28", and an index of refraction of 1.4434.It will be observed that all the cyclic isomerides have a lower boiling point, higher sp. gr., and somewhat lower index of refraction than the corresponding members of the geranaldehyde series. CH, CMe, A. H. Synthesis of Aromatic Hydroxyketones. By M. NENCKI (J. RUSS. Chem. Soc., 25, 110--124).-Zinc chloride (15 grams) is dissolved in glacial acetic acid (40 grams), and to the solution dry gallobenzo- phenone (10 grams) is added, the mixture being heated on the water bath in a flask connected with a reflux condenser until the ketone is completely dissolved. Phosphorus oxychloride is then added drop by drop, and after 10 minutes' heating the mixture is poured into cold water. Recrystallisation from boiling alcohol gives rhombic needles which melt a t 165".The substance is a double ketone, COPh*CeH( OH),(OAc) *COMe, whose monophenylhydrazone melts a t Hydrolysis of the componnd C,,Hla06, by means of 70 per cent. 248-249'.86 ABSTRACTS OF CHEMIOAL PAPERS. sulphuric acid, yielded the compound COPhgC6H(OH)3*COMe ; this gives a diphenylhydrazone melting at 233-234'. Chloracetic acid and phenol, with phosphorus oxychloride, or zinc chloride, give the ethereal salt CH,Cl*COOPh (m. p. 44"). Pyrogallol behaves differently from phenol, giving, with phosphorus oxychloride and chloracetic acid, the ketone C6H2(OH)2*CO*CH2C1. This gallochloracetophenone melts at 167-168", is easily soluble in alcohol, ether, a i d boiling water, but only sparingly in cold water. Phenylhydrazine gives a hydrazone-hydrazide, CZoH,O3N4, which melts at 197-198".Aniline gives the compound C,H, (0 H) 3. C 0.C H,*NHP h , which melts at 132", and may be recrystallised from alcohol or boiling benzene. Caustic alkalis or calcium carbonate give the oxide C6H2(QH)2<Co>CHz soluble in boiling water, and melting at 824". Gallobromacetophenone may be obtained by using bromacetic instead of chloracetic acid. It melts at 159'. J. W. 0- Dimethylamidobenzoic acids. Ry C. LAUTH (Compt. rend., 117, 581-583) .-001.thodinzethylainidobenzoic acid is obtained by the action of methylic iodide on a, hot alcoholic solution of sodium orthamido- benzoate. It crystallises in long needles melting at 175", dissolves in 500 parts of cold water, and is very soluble in alcohol, ether, and benzene, forming solutions which have a blue fluorescence.Itl combines with both acids and alkalis, forms no nitroso-compound, but yields vellow, orange, or brown colouring matters with diazo-derivatives. 'When treated with oxidising agents, and especially with cupric chloride or chloranil, it yields a reddish-violet colouring matter, COOH*C,H3(NH2)*C (OH) [ C6H3( NMe,)*COOH]2, which has the general properties of triphenylmethane derivatives, together with special properties resulting from the presence of the COOH group ; it is soluble in alkalis, and is precipitated from its solutions by acids, dyes metallic mordants, and also dyes wool and cotton mordanted with tannin, in the same way as basic colouring matters. Ortbodimetbylamidobenzoic acid condenses with tetrarnethyl- diamidobenzhydrol, and, after oxidation with lead peroxide, yields a blue-violet monocarboxyhexamethylrosaniline.With benzaldehyde or metanitrobenzaldehyde, i t yields a beautiful blue colouring matter, OH*CPh[ C6H3(NMe2)*COOH],, which dissolves i n alkalis, and dyeP wool and mordanted cotton. It yields no colouring matter when oxidised, and with condensing reagents, it yields hexamethylrosaniline-violet and malachite-green, which do not contain the carboxyl group. ~ e t a d i n i e t ~ y l ~ t m i d o ~ e n z o i c acid, prepared in a similar way, or by transforming Griess' beiizobetahe, yields no colouring matters, either with oxidising or with condensing reagents. It would seem that the introduction of the group COOH into YnraclimethlJlamidobenzoic acid is obtained in a similar manner.ORGANIC CHEMISTRY.87 dimethylaniline, and the orientation of this group with respect to the NH2 group, confers peculiar properties on each of the three isomer- ides, and determines whether, on oxidation or condensation, they will yield colouring matters containing the carboxy-group, colouring m;ttters not containing this group, or no colouring matters a t all. C. H. B. Ethereal Salts of Anhydrohippuric acid. By F. WEISS (Ber., 26, 26341-2645) .-The phenylic anhydrohippurate obtained by the action of phosphorus oxychloride on phenylic hippurnte is found by the cryoscopic method to have the formula assigned to it (Abstr., 1893, i, 579); the constitutional formula which best explains its behariour is NBz<l CH I It combines with 2 atoms of chlorine forming a compound which readily loses hydrogen chloride.If treated with phosphorus pentachloride, the product, on hydrolysis with water, yields pherzylic hyd!roxyhippurate, NHBz*CH(OH)*COOPh, which melts at 170", and when heated with alkalis decomposes into benzamide, phenol, and glyoxylic acid. The homologous conzpound NHBz*CMe( OH) SCOOPh (from phenylic anhydro-a-benzoylamido- propionate) melts at 134". I f the hydroxyl group in these compounds were replaced by the group SPh, deril-atives of the mercapturic acids would be obtained. A. R. L. COPh' Hexahydrosalicylic acid. By A. E~NHORN and R. WILLSTXTTER (Ber., 26, 2913-2914).-By the action of sodium on salicylic acid in amylic alcoholic solution hexahydrosalicylic acid, OHC6H:lo*C0 0 H, is formed, together with a mixture of various other acids which have not been investigated. It is readily soluble in water, and .crystallisea in prismatic needles, or tetragonal plates, melting at 105".The acid gives no coloration with ferric chloride, and, in alkaline solution, decolorises potassium permanganate slowly ; it boils without decom- position under the ordinary pressure, and the odour of the vapour resembles that of the higher fatty aqids ; the crystals are odourless. Anthranilic acid, on reduction in a similar manner, yields hexahydro- salicylic acid and ammonia. The methyZic salt is a colourless liquid, with an ethereal fruity smell ; it boils without decomposition, and gives no coloration with ferric chloride. Metahydroxybenzoic acid yields two acid reduction products ; both crystallise readily, and melt a t 112-114" and 130" respectively.Paramidobenzoic acid and dimethylparamidobenzoic acid are con- verted on reduction into it crystalline acid which melts at about 40". p-Naphtholcarboxylic acid yields an acid melting at 241". Thymotic acid has also been reduced in the same manner. By the action of sodium on tetrahydroparatoluic acid dissolved i n ethjlic alcohol, hexahydroparatoluic acid is formed ; it is liquid at oidinary temperatures, and boils at 245-298". The amide melts a t 195". a-Bromohexnhyd?-oparatoluic acid melts a t 94", and on treat- ment with quinoline, yields tetrahydropnratoluic acid (m. p. 47").88 ABSTRACTS OF OHEMIOAL PAPERS. The authors points out that v. Baeyer (1879) was the first t o em- ploy sodium as a reducing agent in ethylic, or amylic alcoholic solution, and therefore that the method should bear his name rather than Wischnegradskg's, Ladenburg's, or Bamberger's.J. B. T. Canaigre Tannin. By H. TRIMBLE and J. C. PEACOCK (Pharm, J. l'rans., 53, 42--45).-Canaigre is the tuberous root of Rzcmex hymenosepalus, growing abundantly in the sandy soil of Texas, New Mexico, and Arizona. The green roots contain 11.46 per cent- tannin (by hide) of 71 per cent. purity. The paper describes in detail the extraction of the tannin, its chemical characteristics, and behaviour with various reagents. The results indicate that this tannin belongs to the group of which those from mangrove and rhatany are typical examples. R. R. Hydroxg-P-phenylcoumarin. By S. v. KOSTANECKI and C, WEBER (Ber., 26, 2906-2908).-Metadihydroxy-/3-phenylcoumarin is not obtained when phroglucinol and ethylic benzoylacetate are treated with concentrated sulphuric acid.Ethylio benzoylacetate, however, easily condenses with pyrogallol in the presence of sulph- uric acid, and yields p-phenyldaphnetin, C15H1001 ; this crystallises with 1H,O in long, lustrous, yellowish needles, loses its water a t loo", and then melts at 100-192". It gives a red Yolution with alkalis, and with ferric chloride a green coloration which turns red on the addition of soda. Ammoniacal silver solution is easily re- duced by it with formation of a mirror. The diacetyl compound crystallises in broad, white needles, and melts a t 133-134". Metadihydroxy-/3-phenylcoumarin, C15R1L,04, is obtained by warming ethylic benzoylacetate with phloroglucinol and zinc chloride on the water bath.It crystallises in colourless needles, melts at 23&235", is indifferent to mordants, and reduces ammoniacal silver solution. It gives an intense yellow solution with alkalis, and a dirty violet coloration with ferric chloride. It is evidently not identical with chrpin. The diacetyl compound crystallises in white, prismatic needles, and melts at 180-181". E. C. R. Conversion of Diphenylsulphone into Diphenylic Sulphide and Diphenylic Selenide. By F. HRAFFT and W. VORSTER (Ber., 26, 9813-2822) .-Diphenylsulphone melts at 128", and boils at 232.5" (18 mm.). When a mixture of diphenylsulphone and sulphur is heated to its boiling point, sulphurous anhydride, diphenylic sulph- ide, and diphenylic bisulphide pass over.The bisulphide is formed by the action of sulphui* on the monosulphide, and when heated with phenylsulphone, it is converted into the monosulphide. The yield of the bisulphide may, therefore, be reduced t o a minimum by the following method :-The mixture (above mentioned) is heated in a retort until sulphurous anhydride ceases to be evolved, the cause of which is that the boiling point of the diphenylic sulphide (292"), which then forms the main portion of the product, is below the temperature at which the reaction takes place. The phenylieORGANIC CHEMISTRY. 89 sulphide is now distilled off, and the residue subsequently reheated, when the bisulphide reacts with the sulphone, producing more mono- sulphide.Diphenylic sulphide boils at 157-158" (16.5" mm.), and its sp. gr. a t 15.2" is 1.1175. pp-Dinaplithylic sulphide is obtained from P/3-dinaphthylsulphone (m. p. 177") and sulphur. Dipara- and dimeta-tolylsulphone do not react in the same manner aa the above-mentioned sulphones. Phosphorus in either of its forms appears not t o interact with diphenylsulphone even at 250". When diphenylsulphone is heated with red selenium, the latter is first converted into the grey modification, which subsequently dissolves in the fused sulphone; if the product is distilled, after the evolu- tion of sulphurous anhydride has ceased, diphertylic selenide, Ph2Se, passes over. On reheating the residue and again distilling, a further quantity of:diphenylic selenide is obtained. It is a colourless, highly refractive oil, resembling the sulphide, boils at 301-302" under ordinary pressure, and a t 167" under a pressure of 16.5" mm.Its sp. gr. a t 15.2" is 1.3561. Negative results were obtained with dlphenylsulphone and tellurium. Diphenylic sulphide forms a dibromo-substitution derivative, but when bromine is added to a cold ethereal or alcoholic solution of diphenyl selenide, a dibromo-additive compound, Ph2SeBr2, separates as an orange-red, crystalline precipitate which melts at 140" with decomposition. When the dibromide is boiled with alcohol or water, or, preferably, gently warmed with 15 per cent. sodium hydroxide, diphenylic selenoxide, Ph2Se0, is formed. It is a white substance which, when dried in a vacuum, melts at 113-114". If heated in a tube over a direct flame, slight detonation accompanied by a reddish flash occurs, and an oil is formed ; when a small quantity is distilled under diminished pressure, diphenylic selenide passes over.Diphenylic selenoxide yields a dichloride, Ph2SeC1,, when treated with hydrochloric acid ; it melts at 179-180'. Experiments made with the object of preparing a selenone by oxid- ising diphenylic selenide with potassinm dichromnte showed that diphenylic selenoxide is obtained under these circumstances. When diphenylsulphone is dissolved in hot xylene, and sodium is added, benzenesulphinic acid and diphenyl are formed. To isolate the sulphinic acid, the product is shaken with water, the aqueous solution of the sodium salt coiicentrated in an atmosphere of carbonic anhydride, and hydrochloric acid added in the cold, when the sulphinic acid separates.A. R. L. Action of Sulphuric Anhydride on Nitriles. By P. EITNER (Bcr., 26, 2833-2839 ; compare Abstr., 1892, 713).-Sulphuric anhydride combines with acetonitrile to form an additive product of the formula 3MeCN,2S03, which is a very hygroscopic, sandy, yellow mass, readily soluble in water, insoluble in all indifferent sol- vents. The hydrate, 3MeCN,2S03 + H20, is precipitated as a white, flocculent mass on adding alcohol and ether to an aqueous solution of the substance. Its, solution is strongly acid, but definite salts have not been obtained.90 ABSTRACTS OF UHEMIUAL PAPERS. When fuming sulphuric acid is substituted for the sulphuric an- hydride, an additive compound of the formula BXeCN,S03 is ob- tained as a yellow, crystalline mass, which combines with 1H,O.The substance thus formed is analogous to that obtained in a similar manner from benzonitrile, and is therefore probably acety Zsulyh- acetamidinic acid, COMe*NH.CMe:N*SO,H. This formula is con- firmed by the fact that the aqueous solution of the compound, after a t h e , contains diacetamide, NH(COMe),, and amidosul~honic acid, NH,S 03H. Paratoluonitrile is converted by the action of sulphuric anhydride into paratoluy lsulphoparatoleny lnmidinic anhydride, It is a yellow, sandy mass, which is scarcely hygroscopic, and crys- tallises from benzene in colourless, lustrous prisms, containing + mol. benzene ; it turns yellow at 145", and melts at 161.5-162". When treated with concentrated sulphuric acid, it is decomposed with formation of imidodiparatoluylamide, C,H4Me*CO*NH*C ( C6H4Me):NH, and finally of diparatoluylamide, NH( CO*CsH4Me),.When its soh- tion in benzene is digested with water and alcohol, ethylic para- to1 u at e an d szc lp 72 opar ato Zen y 1 arnidinic acid, S 0,H.N: C ( NH2) C 6H4Me, are produced. The latter is a white powder, which does not undergo alteration in the air, crystallises from water or alcohol in prisms, and melts at 250-251'. The barium salt crystallises in splendid, colour- less prisms. 1 When sulphoparatolenylamidinic acid is treated with dilute sulph- uric acid, it is decomposed into sulphuric acid and the corresponding amidine, HN:C(NH2)*C6H4Me, which is obtained in the form of the acid suZphate.This salt forms fine, white plates, melts at 240-241', and is readily soluble in water and alcohol, almost insoluble in ether. Paratoluonitrile therefore behaves towards sulphuric anhydride in a manner precisely similar to benzonitrile. A. H. 2' : 3'-Diphenylindoles. By F. R. JAPP and T. S. MURRAY (Ber., 26, 26Zb-2641) .-The authors observed that 2' : 3'-diphenylindoles are formed by heating to its boiling point a mixture of benzoi'n with an excess of a primary aromatic amine in presence of zinc chloride, and in this way they had prepared a number of these compounds, which were, however, in the meantime, described by Bischler and Firemann (Abstr., 1893, i, 519), the latter having obtained them by heating desyl anilide o r desyl bromide with an aromatic amine. The authors show that desyl anilide (Zoc.cit.) and Voigt's anilbenzo'in (J. pr. Chem., 31, 544; 34, 2) are one arid the same substance; i t melts at 98-99'. Indole derivatives are only obtained from desyl anilide and an amine in presence of a trace of desyl bromide ; they are formed, how- ever, when desyl bromide is heated with an amine, a fact which indicates that the eliminated hydrogen bromide effects the conden- sation of the initially formed desyl anilide. The authors then foundORGANIC CHEMISTRY. 91 that indole derivatives are obtained by heating desyl anilide with a mixture of an amine and its hydrochloride, which led to the discovery that by boiling benzoin with a mixture of an amine and its hydrochlorids, a much bether yield of indole derivative is obtained than by the use of zinc chloride (see above).The zinc chloride method is, however, the better one f o r the preparation of 2' : 3 ' 4 - phenyl-p-naphthindole, because of the tendency to form 13-dinaphth yl- amine (Bischler and Fireman, ZOC. cit.). 2' : 3'-Diphenylorthotolindole (Zoc. cit.) melts at 135-136" (not 128'). 2' : 3'-DiphenyZ-a-naphIhirtdole, Cl,H6< NH >CPh, forms colourless needles, and melts at 141". The compounds prepared by Lachowicx (this vol., i, 39) by t h e action of aniline hydrochloride and its analogues on benzo'in a t 160" are probably the intermediary substances in the formations of indoles. 2 : 3-Hydroxynaphthoic acid. By S. v. KOSTANEUKT (Bey., 26, 2897-2900) .-Phenylazohydroxynaphthoic arid [PhN, : OH : COOH = 1 : 2 : 31 is obtained from the hytiroxy-acid in the usual way.It crystallises in reddish-brown needles, melts at 232", and only yields pale colours with mordants after some time, probably on account of the insolubility of the dye. Nitrosohydro~yiiaphtlLoic acid crystallises in red tablets, melts at lS5" with decomposition, .gives a brownish-yellow coloration with concen- trated sulphuric acid, and a beautiful green wrth iron mordants, which is, however, unstable to boiling soap solution. Naphthalened ioximeanhydridecnrboz y lic acid, CO OH*CloH5<~> 0, is obtained by heating the above nitroso-compound with hydroxyl- amine hydrochloride and alcohol in a reflux apparatug. It crystallises in white needles, melts at 294", and sublimes without decomposition. When boiled with excess of alkali or with 50 per cent.sulphuric acid, it is converted into naphthalenedioxime anhydride, CloH6<z> 0 (Goldschmidt and Schmid, Abstr., 1884, 1327), which crystallises ill needles, and melts .at 78". The formation of this compound proves that the hydroxynaphthoic acid melting at 216' is the 2 : 3-compound. By F. KHAFFT and A. Roos (Bey., 26, 2823-2829).-1t has been already shown (Abstr., 2893, 1219) that alkyl sulphonates are produced by the action of aromatic sulphonic chlorides on alcohols in the cold. The authors now find that when the sulphochlorides are heated with the alcohols in sealed tubes, the sulphonic acids and the ethers corresponding with the alcohols are formed. Alkyl chlorides are also obtained, due apparently, not to a direct decomposition, but tq the reaction between the hydrogen chloride directly formed and the alcohol.The authors confirm Armstrong and Rossiter's observation (Proc., 1891, 184) with regard to the action of alcohol on 1 : 4-dibromonaphthalene- sulphonic chloride. When the latter is heated on the water bath CPh A. R. L. E. C. R. Ethereal Salts of Sulphonic acids.92 ABSTRACTS OF CHENICAL PAPERS. with an excess of alcohol, it is entirely converted after a short time into the free sulphonic acid. That hydrogen chloride playa no im- portant part in the change, is shown by the fact that when ethylic 1 : 4-dibromonaphthalenesulphonate is heated with absolute alcohol in a sealed tube, the products are the free sulphonic acid and ethylic ether. A. R. L. Thionaphthens.By L. GATTERMANY and A. E. LOCKHART (Ber., 26, 2808-2809) .--ThionuphShen, C6H,<gf>CH, is obtained by adding a solution of the diazo-derivative of orthamidochlorocinn- amene, NH2*C6H,*CH:CHCI, t o one of potassium xanthate in the cold, whereby the diazoxyxanthate separates ; if the product be warmed on the water bath, nitrogen is evolved aud an oil, probably OEt.CS*S*C6H~*CH:CHC1, is formed. When this oil is boiled for several hours with alcoholic potash, it yields thionaphthen, together with other compounds; a cold alcoholic solutiou of picric acid is now added to the mixture, whereby the sparingly soluble picrate of thionaphthen separates in golden-yellow needles ; it melts a t 149", and on decomposition with ammonia, yields thionaphthen. The latter is driven over with steam, and forms colourless plakes, melts at 30-31", resembles both naphthalene and naphthylamine in odour, and gives a red coloration with concentrated sulphuric acid.Orientation in the Terpene Series. By A. BAEYER (Ber., 26, 2861-2869) .--Cases of cistrans-isomerism have not hitherto been observed in the terpene series, although the study of the hexahydro- phthalic acids has rendered their existence probable. The author has found that the dihydrochloride and dihydrobromide of dipentene and terpin itself do exist in two forms, the series of lower melting point being looked upon by him provisionally as the cis-form. D@entene cis-dihydrochloride is formed when cineol or eucalyptol is treated with hydrogen chloride at the temperature of melting ice.It is a white, camphor-like mass, and melts at about 25", whilst the already known trans-form melts at 50" { Wallach). Dipentene cis-dihydrobromide is prepared by treating eucalyptol with a solution of hydrogen bromide in acetic acid at 0'. A mixture of the two isomerides is obtained from which the sepamte compounds may be isolated by dissolution in alcohol, and fractional precipitation with water. The cis-form crystallises in pointed plates melting a t about 39", whilst the already known trans-form crystallises i n rhombic tablets, and melts at 64". The relative proportion of these two dihydrobromides formed by the freatment of the various compounds of the series with hydrogen bromide or phosphorus tribromide is shown in the following table. A. R. L.Dihydrobromide. < 7 cis- trans- 1. trans-Terpin + HBr - almost exclusively 2. Terpineol cryst. + HBr - 3. cis-Terpenhgdrate + HBr - 7 9 9,ORGANIC OHENISTRY. 93 Dilly drobro m id e. 7 --L- cis - trans- 4. cis-Terpin + HBr a little much 5. Lirnonene + HBr a little much 6. cis-Terpin + PBr, about half about half 7. Cineol + HBr the greater a little portion Both forms yield the same dipentene, but different terpins. The cis-dihydrobromide, when treated successively vi-itli silver acetate and alcoholic potash, gives the well-known terpin, the hydrate of which melts at 117.5". The trans-dihydrobromide, on the other hand, when similarly treated, gives a new trans-terpin, which crystallises without water and melts a t 156-158". It is readily soluble in alcohol, but only slightly in water, ether, or ethylic acetate, from which i t separates in short prisms or six-sided tablets, with a strong, vitreous lustre. It boils at 263-265", whilst Wallach found that the old cis-terpin boils at 258.5".Since cineol yields almost exclusively the cis-dihydro- bromide, it is most probably itself a cis-derivative, and the anhydride of the previously known cis-terpin. A trans-cineol has not yet been obtained. It is to be observed that-(1) cis-terpin, when treated with hydrogen bromide, undergoes molecular change and yields the trans- dihydrobromide, whilst cineol, its anhydride, does not ; and (2) that the molecular change takes place in the conversion of terpin into the dihydrobromide, whilst no molecular change occurs in the inverse production of terpin from the dihydrobromide.This apparently anomalous behaviour is probably to be explained by the intermediate formation of an unsaturated compound in those cases in which mole- cular change occurs. A. H. Chrysin. By S. v. KOSTANECKI (Bey., 26, 2901-2305).-Chrysin, C15H,,0a, when boiled with alkali, yields phloroglucinol, benzoic and acetic acids, and also some acetophenone. It yields monalkyl ethers, which are insoluble in alkali. The monomethyl derivative is identical with tectochrysin. A diacetyl derivatiw, CI5H804Ac2, obtained by boiling it with acetic anhydride and anhydrous eodium acetate, crystallises in white needles, and melts at 185". The sodium salt of tectochrysin is obtained by adding sodium hydroxide to the alcoholic solution ; it crystdlises in intensely yellow needles, and is almost insoluble.Acetylchrysin wonomethyl ether, OMe*C,,H803Ac, crptallises in white, lustrous needles, and melts at 149". The above reactions of chrysin are most easily explained by assign- '-EPh [OH: OH = 1: 31. COGH iiig to it the formula C6H,(OH)2< Dry Distillation of Jalapin. By E. KLIMENKO and Y. BANDALIS {J. Racss. Chem. SOC., 25, 136--142).-Jalapin was distilled in portions VOL. LXVI. i. h E. C. R.94 ABSTRACTS OF OHEBllCAL PAPERS, of 20 grams from a small glass retort, at as low a heat as possible. The chief products obtained were- 1. An aqueous liquid boiling at 102-103”. This proved to be a solution of acetic acid of constant boiling point. 2. A brown liquid passing over between 170” and 220°, which, after treatment with sodium carbonate, and decomposition of the sodium salt with hydrochloric acid and extraction with ether, yielded tiglic acid.3. A liquid collected above 2.20”, which partially solidified in the receiver. The solid, after purification, was found t o be palmitic acid. J. W. Constituents of Coto Bark. By 0. HESSE (Ber., 26, 2790- 2795) .-A continuation of the discussion with Ciamician and Silber. Mixtures of “ methylprotocotoin ” (‘‘ oxyleucotin ”), and “ methyl- hydrocotoh ’’ (“ benzoylhydrocoton ”), or of “ isomethylhydrocotoh.” resemble “ leucotin,” both iii appearance and melting point (Abstr., 1893, i, 417), but the melting point of leucotin is constant, whilst that of the mixture is not. The remainder of the paper deals with “ para- coto’in,” “ bromoparacoto’in,” “ paracotoinic acid,” ‘‘ coto’in,” and “ dicotoh” A.R. L. Colouring Matter of Cochineal. By W. v. MILLER and G. ROHDE (Ber., 26, 2647-2672) .-Hlasiwetz and Grabowsky (AnnuZen, 141, 329) considered that De la Rue’s carminic acid (AnnaZen, 6 4 , l ) was a glucoside yielding on hydrolysis carmine-red and a sugar ; t h e authors show, however, that this is incorrect, and that carminic acid is not altered in composition by boiling with dilute sulphuric acid. They have obtlained 1.4 per cent. of tyrosine from cochineal exkract, whereas de la Rue found only 0.4 per cent. It has been pointed out by Will and Leymann (Absti., 1886, 252), that a- and p-bromocarmin yield methyldibromohydroxyphthalic acid [Me : Br2 : OH : (COOH), = 1 : 4 : 6 : 5 : 2 : 31 on oxidation. The authors find that the last-named acid is formed, together with bromo- form, when a-bromocarmin is warmed with an excess of soda solution ; they consider, therefore, a-bromocarmin to be an indone derivative of the constitution C6hleBr,( OH) CBr, (compare Zincke, Abstr., 1888,291,1198).Bearing in mind Zincke’s observation, that indone derivatives are formed by the molecular degradation of halogenated derivatives of hydroxy-cx-naphthaqninone, i t seemed not improbable that /3-bromocarmin, which contains in its molecule 1 atom of carbon less than a-bromoca,rmin, might belong to the latter class of com- pounds, especially as it bears a great resemblance to DiehI and Merz’s bromhydroxynaphthaq uinone (Ber., 11, 1066). This hypothesis is borne out by the fact that P-bromocarmin is convertible into a-bromo- carmin (see below).Whan p-bromocarmin (1 mol.) is dissolved in a solution of sodium carbonate (2 mols.) and treated in the cold with bromine (1 mol.), the hydroxy-acid, 1 4 , 6 5 COORGANIC CHEMISTRY. 95 is formed. It crystallises with 3H20, and melts a t 106" or 208", according as it is Leated rapidly or slowly ; if crystallised from ether; two melting points (somewhat higher) are also observed. When the hydroxy-acid is warmed with 50 per cent. acetic acid and bromine, it is converted into a-bromocarmin. These results show, therefore, that B-bromocarmin has the constitution represented by one of the ' CBrZCMe g*CO*f*OH CBrZCMe g*CO*qBr formulae I or I C(OH):CBr~C*CO*CBr C(OH):CBr.C*CO*C*OH' .I If p-bromocarmin is dissolved in aque6us alkali, and the warm solution is treated with zinc-dust, it is converted into the quinoZ, C(oH):?'oH, which crystallises in almost colourless C( 0H):CH C6MeBr2( OH) < needles, and darkens without melting when heated. The tetracetyl derivative, Cl9HI6Br2O8, me1 ts at 206". When the quinol is dissolved in alkali, and the solution is exposed to the air, a red salt separates ; this, on treatment with acid, yields a substance which crystallises in yellow needles, melts a t 263-265", and I-esembles ,&bromocarmin ; when warmed with acetic acid and bromine, it is converted into a- bromocarmin. The authors are unable to confirm Will and Leymann's observation (Zoc. cit.), that p-bromocarmin yields a colouring matter resembling carminic acid when treated with alkaline stannous chloride, and exposed to the air; the product is a yellowish-red compound, resembling the substance of melting point 263-265" mentioned above. Carminic acid is, therefore, closcly related to one of the two h ydroxy-derivatives of methyl-a-naphthaquinone having the formuh Cd%Me ( OH)202 1 4,6 5 [Me : OH : O2 : OH = 1' : 3' : 1 : 4 : 2, or 1' : 3' : 1 : 4 : 31.The authors' analytical values for carminic acid and those of De la Rue agree well, but they are about 10 per cent. lower in carbon than those required for a compound of the above formula ; compared with a dihydrate of such a compound, which might be the analogue of leuconic acid or triquinoyl (Xietzki and Benckiser), the agreement is better, but even then not satisfcctory.It is pointed out, however, that carminic acid has, up to the present, only been obtained in an amorphous state. The authors find also that ruficoccin yields a-bromocarmin when treated with bromine in acetic acid solution ; hence it must be nearly related to carminic acid, and they no longer accept Liebermann and van Dorp's statement (Zoc. cit.) that it is an anthracene derivative. A. R. L. Instability of Colouring Matters containing Carotene. By M. GERLACH (Bied. Centr., 22, '786).-The fadmg of dyes containing carotene is not due to light, but to the oxygen of the air, as the change takes place in darkness as well as in light, but the colour is permanent in light when oxygen is excluded; at the same time t h s change is assisted by light. E.W. P.'36 ABSTRAOTS OF UHEMICAL PAPERS. Conversion of Indoles into Quinolines. By A. FERRATINI (Gazzetta, 23, ii, 105--124).-This paper gives a detailed account of the work of which a short notice has already appeared (Abstr., 1893, i, 602). Action of Bhenylic Isocyanochloride on Derivatives of Phenylhydrazine. By M. BREIJND and E. K ~ N I G (Ber., 26, 2869- '2874) .-Phenylic isocyanochloride, NPh:CCl,, is obtained by treating phenylthiocarbimide dissolved in chloroform with dry chlorine. It is a colourless oil, and boils at 205". CH*? is obtained by PJLen y lphen y limido-oxy b iazoline, heating dry formylphenylhydrazine with phenylic isocyanochloride. It crystallises in concentric, white needles, melts at 99", and is not altered by boiling with water or soda solution.The hydrochloride crystallises in white needles, melts a t 185--186", and is decomposed by water. Pormylamidod+ heny Zcarbamide, NHPh* C O*NP h*NH* CH 0, is o b- tained by heating moist formylphenylhydrazine with phenylic iso- cyanochloride. It crystallises in leaflets or needles, melts at 164", is a feeble base, and is not altered by boiling with dilute alcoholic potash. It is also obtained by evaporating on the water bath, an alcoholic solution of the preceding oxybiazoline mixed with concentrated hydro- chloric acid. NeNPh*C:NPh' CMe*Q NPh.C:NPh' is obtained Phen y lmethy ~ h e n y limido-oxybiazoline, N< from acetylphenylhydrazine in a similar way to the above oxybiaz- oline. It crystallises in white needles, melts a t 75", yields an oily hydrochloride, and, when boiled with alcoholic potash, yields a red solution which contains free phenylhydrazine.The platinochloride crystallises in tufts of shining needles, and melts at 92". Acet y larnidodipheny lcarhamide, NHPhG 0 9Pr'Ph.NH.C OMe, is ob- tained in a similar way to the above formyl compound. It crystallises from absolute alcohol in needles, melts at 181", and is a weak base. CPh*? is obtained by NPh*C :NPh' Pheny limidodiphen y lox y b iazoline, N< boiling benzoylphenylhydrazine with phenylic isocyanochloride and tolnene. It crystallises in white needles, sinters at 102", melts a t 106", and is insoluble in hydrochloric acid. C (N H P h)*y NPh- C:NPh' is P gny lamidophen y linaido~heny lthiobinzoline, N< obtained by warming diphenylthiosemicarbamide (m.p. 176") with chloroform and phenylic isocyanochloride, and then decomposing with soda, the hydrochloride thus obtained. It crystallises in white needles, and melts at 154". The hydrochZo?-ide crystallises in pale yellowish- green, rhombic tablets, evolves hydrogen chloride at 140", and then melts at 215". The nitroso-cornpound is obtained in small, golden- yellow needles, melts at 110", and is so unstable that it cannot be recrystallised.ORGANIC CHEMISTRY. 97 C (N :NP h) NeNph -__ C:NPh' is Benzeneaxqheny limidopheny lthiobiazoline, obtained by warming phenylic isocyanochloride with a solution of diphenylthiocarbazone in chloroform. It c~~ystallises in cherry-red needles, and melts at 180-181". The hydrazo-compound, obtained by boiling i t with a solution of ammonium sulphide in dilute alcohol, crystallises in white needles, and melts at 150".E. C. R. Derivatives of Oxybiazolone and Thiobiazolone. By E. K~~NIG (Bey., 26, 2876 ; see also Ber., 24, 1178).-Orthotoly~henyZ- oxybiarolone, C,H,*N<z,g>CPh, crystallises from alcohol in needles, and melts at 1.20". Orthotoly lphen y 1- 9-thiobiazolone, C7H7*N <Fs:g>CPh, cry stallises O~tkotolylamido-oxybiazolone, C7H7*N<FG.E>C*NH,, crystallises from a mixture of chloroform and light petroleum in interlacing needles, and melts at 131". Ortho to1 ylamidothiobiazolone, C7H7-N < Gz>C.NH2, is ob taiiied from orthotolylthiosemicarbazide (m. p. 156") and carbonyl chloride. It crystallises in needles, and melts a t 2'78-279". from light petroleum in pale yellow prisms, and melts at 96".E. C. It. Triazole Derivatives. By M. FREUND and S. WISCIICWIASSIIY (Ber., 26, 287L-2881) .-Thiocarbamides of the type R-NH. CS-NH-NH- C S*NHR , when treated with carbonyl chloride, lose 1 mol. of hydrogen sulph- ide. and are converted into bases of the triazole series having the - N-YH NH*N NR-CS Or NR:C<NR, -8 .SH' constitution NH R* C< Hydrazodicadonthioamide, NH,*CS*NH*NH*CS-NH,, is obtained by boiling hydrazine sulphate with ammonium thiocyanate ; it melts a t 208". When dissolved in toluene and heated with carbonyl chloride at 150-160", it yields a yellow, insoluble compound which does not melt at 290", and gave on analysis C, 23.11-22.65: H, 2.47-2-68; N, 36.93 ; and S , 26.8 per cent. Hydrazodicarbon- nmide, when treated with carbonyl chloride under the same conditions, is decomposed with the formation of ammonium chloride.HydrazodicarZ,onthioaZlyZanzide, N,H,*( CS.NH*C,H,),, is obtained by heating in a reflux apparatus hydrazine sulphate mixed with the theoretical quantit'y of sodium carbonate and a slight excess of allyl- thiocarbiniide dissolved in alcohol. When heated with carbonyl chIoride and toluene, hydrogen sulphide is eliminated, and a base of the composition C8H,,N,S is formed. This base is also obtained by boiling the allylcarbamide with sodium carbonate or concentrated hydrochloric acid. It crystallises in interlacing needles, and melts a t98 ABSTRACTS OF CHEMICAL PAPERS. 147". The hyc7rocI~lo1-ide crystallises with 3H,O, ?nd melts at 49". The p7atinoclzZoride is obtained as a ~ryst~alline, sparingly soluble pre- cipitate, and does not melt a t 280".The nitroso-compoz~nd crystal- lises in yellow leaflets, and melts at 105". When the base is heated with methylic iodide and alcohol, it yields the methyl compound C8HllMeN4S,HI, which crystallises in leaflets, and melts at 167"- The h!,drochJoI-ide of this last compound crystallises in leaflets, and does not yield a nitroso-derivative. Hydrazodicarbonthiophenylamide, N2H2* (C S-NHPh),, obtained in a, similar way to the above ally1 derivative, crystallises in white scales, and melts at 187". When heated with carbonyl chloride, it yields the compound C,,H,,N,S, which melts at 239-240O. Formazyl Methyl Ketone. By E. BAMBERGER and P. DE GRUYTEE (Ber., 26, 2783-2786).--The compound of melting point 183", obtained by the action of alcoholic ammonium sulphide on formazyl methyl ketone (Abstr., 1892, i, 158), is acetylainidraaone, (compare this voI., i, 23).The ureide, N,HPh:CAc-NH-CO*NH,, prepared by treating it with potassium cyanate, melts at 183". The osaaone, N,H P h: CMe*C ( N,HPh) *NH,, obtained by treating acetyl- amidrazone or formazyl methyl ketone with phenylhydrazine, or boiling the former with dilute sulphuric acid, forms small, white needles, melts a t 224", and becomes reddish-violet on exposure to the air ; concentrated sulphuric acid dissolves it with an intense bluish- violet coloration, whilst alkalis colour its alcoholic solution red. The sulphate melts at 211"; the hydroch2oride melts at 114-1150 apparently with dissociation.When the osazone is heated with glacial N:?Me , i s acetic acid at l80", phen yZamidometh~losotriazole, NPh< N: C*NH 2 formed ; it is volatile with steam, and melts at 73". Acetylamidrazone yields an acetyl derivative, NHAc*CAc:N,RPh, which forms yellowish-white, satiny needles, is insoluble in dilute mineral acids, melts at 143", and, when heated with dilute acetic acid, is converted into phen~lacettllal.ethy ltriazole, NPh< melting at 88-89". The latter gives a crystalline compound with sodium hydrogen sulphite, an oxime melting at 211-212", and a phenyzhydrazorte which crystallises with 1 mol. of acetic acid, and melts at 128", but loses the acetic acid, and becomes oily on exposure to the air. A. R. L. E. C. R. NH~*CAC:N~HP h N = p C C" ?.Forrhazyl Phenyl Ketone. By E. B A m E R G E n and K. WITTER (Ber., 26, 2786-2790) .-Formazy1 phenyl ketone, COPh*C(N2Ph):N2HPh, is formed, together with a smaller amount cf Claisen's phenylazo- benzoylacetone (Abstr., 1888, 8%), by the action of benzoylacetone or of benzoylacetic acid on diazobenzene in presence of free alkali ; i t crystallises in red, felted needles of a metallic lustre, and meltsORGANIC CHEMISTRT. 9 9 at 141-142". derivative, C0Ph.C (NzPh):N2 AcPh, melts at 154". The silver salt explodes when heated, and the acetyl is produced, to- N:y N: C-COPh' a-Pheizyltriazyl phenyl ketone, C,H,< gether with aniline, by the action of concentrated mineral acids on formazyl phenyl ketone ; it crgstallises in golden-yellow bunches of needles, melts at, 114", and forms a hydrazone melting at 18.5".Benzoy lamidrazone, C0Ph.C ( N2HP1i) *NH2, is formed, together with aniline, when formazyl phenyl ketone is reduced with alcoholic ammonium sulphide; i t melts at 152", and gives Biilow's reaction. The acetyl derivative melts at 143-156", according to the rapidity with which it is heated, and also gives Biilow's reaction. When heated, the acetyl derivative yields meth~il2phenylbeizzoyltriazole, - NPh<N = ?'CoPh, which cry s t k s e s in colourless, silky needles, CMe:N and melts at 55.5". A. R. L. Isoquinine and Nichine. By E. LIPPMANN and F. FLErssNEri (Monalsh., 14, 553-558 ; compare Abstr., 1893, 81 aud 83). -The authors confirm their previous statement (Zoc. cit.) as to the indi- viduality of the base isoquinine, which melts at 185", and which has been stated by Skraup (Abstr., 1893, i, 56) to be a mixture of pseudo- quinine and nichine. Nichine may be obtained in largest yield by taking hydriodo- quinine, recently precipitated in a crude form by ammonia, and adding to it silver nitrate, in slight excess above that required to com- pletely precipitate the iodine ; after removing the excess of silver with hydrochloric acid, the base is precipitated with ammonia. Nichine forms a well characterised hydrate, YC19H,,N,0, + 2Hz0, which crystallises in needles, and melts a t 70". The anhydrous base melts at 130-132". Its acid solutions have a marked fluorescence, and give the characteristic quinine reaction with chlorine water and ammonia. The di h y d rochloride, C19H24N202, 2 HC 1, f orms small, granular crystals ; the acid sulphate crystallises in long needles, and, like the acid oxalate, is very sparingly soluble in water and in alcohol. G. T. M. Relation between the Optical Rotary Power of Cinchonid- ine and its Salts: Inflience of the Solvent on the Rotation. By C. A. SCHUSTER (Monatsh., 14, 573--595).-Cinchonidine and its salts, including the hitherto unknown hydrobromide and hydriodide, are lsvorotatory. In alcoholic solution, all the salts, with the exception of the sulphate, show a maximum rotation, for like concentration, in 50 per cent. alcohol, and a minimum rotation in absolute alcohol. In the case of the sulphate, the maximum rotation is also given in a solution of 50 per cent. alcohol, but the minimum rotation is given by the aqueous solu- tion. The difference in rotatory power of the various cinchonidine salts in aqueous solution is exceedingly small, and very closely resembles that calculated for the base, the maximum divergence100 ABSTRACTS OF CEEMICAL PAPERS. being obtained when the base is united with some weak acid, such as acetic acid. This behaviour is in harmony with the Arrhenius' disso. ciation theory. Comparisons of the rotatory powers of the compourtds of cinchonidine with the halogen acids show that the rotation diminishes with increase in the molecular weight, according to Gupe's rule. G. T . M. Alkaloi'da of the Root of Corydalis cava. By &I. FREUND and W. JOSEPHI (AnnuZen, 277, 1-19 ; compare Abstr., 1892, 1366).-- Corydaline, C22H2,N04 (compare ZOC. cit., also Dobbie and Lauder, Trans., 1892, 944 and 605).-The specific rotatory power of the base in chloroform solution is [a], = +300*1. The hydrochlode crystal- lises with 2H20, and melts at 206-207" ; and the Aydriodide decom- poses at 220". When the methiodide is digested on the water bath with silver chloride and aqueous alkali, methy Zcoryda line, C&E&gNOd, is obtained; i t crystallises from alcohol in colourless prisms, and melts at 112" ; the hydrochloride crystallises with 6H,O. Methyl- coyydaline methiodide, C23H2gN04MeI, melts at 195-196" ; both it and tshe methochloride are stable towards alkalis, thus recalling the similar indifference of the methohalogen compounds of hydrohydr- astinine (Abstr., 1891, 1519)' and the authors consider it probable that corydaline also contains a hydrogenised isoquinoline nucleus, havillg a methyl group united to the nitrogen atom. Rulbocapnine.-T he formula previously assigned by the authors to this base (Zoc. cit.) is incorrect ; their present analyses agree with the formula C19H19NOa. The base crystallises from alcohol in rhombic, hemi- hedral prisms, a : b : c = 0.72700 : 1 : 0.73682; its specific rotatory power in chloroform solution is [ a ] ~ = +237*1. The hydrochloride, hydrobmmide, hydriodide, and nitrate are anhydrous, and decompose above 230" ; the acid subhate has the formula ClgHf,,NOa,H,S04 + 2H,O ; and the methiodide crptallises from water in lustrous needles, and melts at 257". A determination by Zeisel's method indicated the presence of a single niethoxy-group in bulbocapnine. Bearing in mind Dobbie and Lauder's observation that corydaline contains four methoxy-groups, the relation of the two bases is, perhaps, Cl8&N ( OH)3*OMe and C d W (OM@)(. Corycavine, C2,HZ3NO, (see Zoc. cit.). CorybuZbine is the name given by the authors to a base isolated from commercial corydaline (Zoc. cit.) ; it; differs from Dobbie and Lauder's corytuberine (Trans., 1893, 485) in being insoluble in water. Lack of material precluded the determination of its formula. The autliors leave the further development of the subject to Dobbie and Lauder. A. R. L.

ISSN:0368-1769    

DOI:10.1039/CA8946600061

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

66 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry, Detection of Chlorine, Bromine, and Iodine in the same Mixture. By J. TORREY (J. Anal. and Appl. Ohern. 6, 667-669).- The author has slightly modified the process originated by Hart and communicated by Kebler. The bulb tube arrangement has been replaced hy a small tube having only one small bulb blown on it, the tube being bent slightly away from the perpendicular about half an inch above where it leaves the cork. Above the bulb tbere should be about half an inch of tube left. The flask containing the mixture is charged with ferric snlphate as usual, and the iodine evolved is rciadily detected by holding in the steam a small piece of starcb- paper. When iodine fumes can no longer be detected, a crystal of potassium permanganate is added, and, on further< heating, bromingANALYTICAL OEEMISTRY. 6 7 is given off, which is best detected by allowing the fumes to act on iodised starch paper.Tho boiling must be quite brisk, or else the bromiiie will not be completely expelled. The residue is then tested for chlorine in the usual manner. The author advises working on a very small quantity of substance. L. DE I(. Titration of Caustic Liquors containing Chlorine. By C. ULL~~ANN (Chem. Z e i f . , 17, 1208-1209) .-A measured quantity of the lye is mixed with an excess of standard solution of snccinic acid and heated until the odour of hypochlorous acid has gone off. The excess of acid is then titrated with standard Roda, using phenol- phthale’in as indicator. Succinic acid expels carbonic anhydride and hvpochlorous acid, but is without action on chlorides, and is also proof against oxidising or Estimation of Nitrogen in Manures containing Nitrates.By V. SCHENKE (Chem. Zeit., 17, 977--979).-After reviewing a large number of processes, the author finally recommends the follow- ing, which is really a combination of K-jeldahl and Ulsch’s pro- cesses. A few grams of the sample is introduced into a 300 C.C. flask, and treated with about 4 grams of reduced iron and some 10 C.C. of dilute sulphuric acid (1-2). After applying a gentle heat to complete the reduction, a sufficiency of sulphnric acid containing 80 per cent. of phosphoric anhydride is added, and also a little copper oxide. chlorinating agents. L. DE K. The mixture is now further treated as in Kjeldahl’s process.By A. ANGELI (Gazzetta, 23, ii, 102).-A new reaction for hydroxylnmine consists in adding to its neutral aqueous solution first0 sodium nitroprusside, then caustic soda; on boiling the mixture, i t becomes coloured a fine magenta red, The red colour produced by yhenylhydrazine under similar conditions disappears on heating. The test is very sensitive, but should not be applied to solutions containing a large excess of ammonium salts. L. DE K. Reaction of Hydroxylamine. W. J. P. Estimation Qf Yellow Phosphorus. By G. T ~ T R (Chem. &t., 17, 1244--124S).-The phosphorus is dissolred in carbon bisulphide, and the solution is diluted with olive oil and ayitated with solution of silj-er nitrate. The argentic phosphide thus obtained is oxidised by means of dilute nitric acid, and the aqueous layer is separated from the oil.The phosphoric acid is now estimated by the molybdate method and calculated to phosphorus. I n f o u r test experiments, 78, 93, 93 and 100 per cent. of phosphorus was respectively recovered. L. DE K. Estimation of Sulphur in Steel, Iron, &c, By H. A. HOOPER (Chem. News, 68, 191).-The steel or iron is dissolved in hydro- chloric acid, and the sulphur, evolved as hydrogen suiphide, is absorbed iu caustic soda and subseqvently titrated with 8r ahndardised solw68 ABSTRACTS OF CHEMICAL PAPERS. tion of lead nitrate. method. D. A. L. Rapidity and delicacy are claimed for the Volumetric Estimation of Lead. By A. P. LAURIE (Chem. News, 68, 211).-To estimate lead in the presence of hydrocbloric acid, it is directed to neutralise tho acid, add sodium acetate, avoiding large quantities of other salts, then to titrnte with standardised potassium dichromate, made np to precipitate 0 00.2 pram of lead per c.c., using silver nitrate as indicator, a yellow tint in the precipitate of silver chloride indicating tbe end of the reaction.The sensitiveness is influenced by the proportion of chloride present, the most satisfac- tory amount being from 0.5 to 0.2 gram of sodium chloride in 100 C.C. To obviate inconvenience, arising from the formation of basic salts and from floating particles of lead chromate, most of the required quantity of dichromate is added at once, and the liquid is gradually heated to boiling with frequent stirring. Assay of Copper Sulphate.By J. RUFFLE (Analyst, 18, 279- 281).-The author estimates the copper electrolytically, and calculates i t into the crystallised sulphate. This, on being heated at 100" to constant weight, loses 28.91 per cent. of water. If now a sample loses more water than corresponds with the copper sulphate it con- tains, the excess map be put down to adherent moisture. For the pupose of estimating any free sulphuric acid, 20-50 grams of the sample is powdered and repeatedly extracted with absolute alcohol. The alcoholic filtrate is diluted with water, mixed with a few drops of phenolphthalein, and titrated with standard soda. D. A. L. L. DE 3(. Separation of Copper from Cadmium by the Iodide Method. By P. E. BROWNING (Amer. J. Sci.. [3], 46, 280--283).-The author recommends the following modification of the iodide process.The solution containing the two metals is mixed with potassium iodide as long as a precipitate forms, and the liberated iodine is boiled off. The cuprous iodide is collected on a weighed asbestos filter, washed, dried at 120-150°, and weighed. The filtrate is heated with potas- sium nitrite and sulphuric acid to decompose the excess of iodide, and when every trace of iodine is expelled, the cadmium is precipitated by boiling with sodium carbonate. The cadmium carbonate is next eollected on an asbestos filter, and converted iuto oxide by ignition. The toest analyses are extremely satisfactory. L. DE I(. Quantitative Analysis by Electrolysis. By A. CL~SSEN (Zeit. anwg. Chem., 5, 231-236).-A rejoinder to Rudorff (Abstr., 1893, ii, 391).Effect of Platinum in Iron Solutions. By R. W. MAHOX (Amer. Chenz. J., 15, 578--582).-When the insoluble residue of all iron ore is fused with sodium curbonate in a platinum crucible, and the melt dissolved in hydrochloric acid, some platinum, usually about 1 milli- aram, goes into solution, and this atlects the estimation of the iron k t h standard dichromate, in the case when the iron is reduced to theANALYTI GAL (3HEMISTRY. 69 ferric state by means of stannous chloride, the excess of the latter being removed with mercuric chloride. The platinum chloride func- tions continuously, undergoing a cycle of changes the net result of which is to oxidise the ferrous to ferric chloride at the expense of mercuric chloride, which is reduced to mercurous chloride.The error introduced may thus be large; it is increased by protracted fusion, by the presence of much free hydrochloric acid, or by the addition of a large excess of stannous chloride. It may be made small by avoiding these conditions ; but, to ensure an accurate result, it is best to free the iron from platinum by precipitating it with ammonia, and redissolving the washed precipitate in hydrochloric acid. C. F. B. Estimation of Ferric Oxide and Alumina in Mineral Phos- phates. By G. MARIANI and E. TASSELLI (Staz. Sper. Agrar., 23, 31-37) .-The method of estimating ferric oxide and alumina by precipitating the phosphates with ammonia and acetic acid has been almosi entirely superseded by Glaser’s method (Abstr., 1890,420), on account of the partial precipitation of lime and the partial solubility of the phosphates in the acetic acid.Another cause of error which aeems to have been overlooked is the sparing solubility of ferric ortho- phosphate in hot water (Sestini, Stao. 5per. Agrar., 1875). The following modification is recommended as giving accurate and con- cordant results as shown by experiments with solutions of known strength. Glaser’s method gave somewhat lower results except with basic slag ; in this case, however, the results were higher, owing to the presence of manganese, which is liable to be precipitated with the iron and aluminium. The phosphate (1-5 grams) is boiled with hydrochloric acid (15 c.c.) for about 10 minutes, diluted with water (2 parts), and oxidised by means of crystals of potassium chlorate and a few drops of nitric acid, the whole being boiled to expel most of the chlorine.It is then filtered, washed, the filtrate made up to about 150 c.c., and a solution of ammonium phosphate (0.5 gram) added, then glacial acetic acid (2 c.c.) and, drop by drop, ammonia until a slight permanent precipitate is produced, after which slightly ammo- niacal water is gradually added until a slightly alkaline reaction is obtained ; acetic acid (2 c.c.) is now added, the whole shaken, and left for two hours. The clear liquid is decanted through a filter, the precipitate being washed with a 1 per cent. solution of ammonium phosphate ; the funnel containing the precipitate is put over the same flask, and the precipitate redissolved by pouring on, drop by drop, hydrochloric acid (sp.gr. 1.12). After washing the filter snffi- ciently, the iron and alumina are again precipitated as before, then left for an hour, decanted through a filter, mashed with ammonium phosphate solution, dried, ignited (with filter) at a dull red heat, and weighed. This modification gives as good or better results than Glaser’s, but it may be possible to improve the method still further. N. H. M. VOL. LXYI. ii. 770 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Chromium in Ferrochrome. By J. SP~~LLER and S. KALMAX (Chenz. Zed., 880, 1207--1208).-The authors mix 0.35 gram of the finely-powdered substance with 8 ?rams of sodium hydroxide and 4 grams of sodium peroxide, and ignite for about an hour in a silver dish with occasional stirring.After cooling, the mass is dissolved in water, and any sodium ferrate or manganatct decomposed by adding more sodium peroxide ; the excess of the latter being removed by passing a current of carbonic anhydride, and gently warming. The chromate is then estimated by means of a ferrous salt according to Schwarz’s method. h. DE K. Assay of Tin Ores. By H. W. RENNIE and W. E. DERRICK ( J . SOC. Chem. Ind., 11, 662-667).-The ore is pulverised until it will pass through a sieve of 60 meshes, o r for low grade ores contain- ing much iron one of 90 meshes, to the linear inch ; 250 grains of it is then boiled for half an hour with 3 02. of hydrochloric acid and + 02. of nitric acid, and the residue carefully washed by decantation ; wolfram, if present, may be dissolved out by ammonia.The residue is then washed on a vanning shovel, when, by skilful manipulation, the free silica can be washed away without the loss of a trace of tin, leaving nearly pure cassiterite. I n many cases the percentage of cleaned cassiterite furnishes sufficient information, but when it is required to know the actual percentage of tin, 50 grains of this oxide is reduced by potassium cyanide with the following precautions. The cyanide should be pure and finely powdered, and both it and all the apparatus should be thoroughly dry ; crucibles about 3 in. high, of a fine-grained clay and of a, smooth interior, should be used, otherwise numerous minute prills of tin adhere to the crucible and cannot be collected. A layer of cyanide is first rammed into the crucible, then the mixture of oxide with 300 grains of cyanide, and finally a covering of cyanide.The crucible, closely covered, is then placed in a muffle, already at a low red heat that the cyanide may fuse rapidly, but not froth. After 10 minutes, the crucible is gently shaken to wash down prills from the sides; the heat is then raised to a bright red for another five minutes. The traces of silica present form a globule of greenish slag, less fusible than the cyanide. As the temperature is raised, this detaches itself from the metal and rises to the surface. As soon as this has occurred, the crucible is allowed to cool, and its contents treated with boiling water, when the button of metal is left in a state fit for weighing. The results leave nothing t o be desired in point of accuracy.M J. S. Separation of Copper from Bismuth. By E. F. SMITH (Zeit, anorg. Chem., 5, 197-198).-A rejoinder to Classen (Abstr., 1893, i, 495). Separation of Copper from Bismuth. By A. CLASSLN (Zeit. anorg. Chem., 5, 299).-A reply to Smith, who has pointed out a& error in the author’s work on electrochemical analysis.ANALYTICAL CHEMISTRY. 71 Quantitative Separation of Metals in Alkaline Solutioa by means of Hydrogen Peroxide. By P. JAXNASCH and J. LESINSKY ( B e y . , 26, 2908-2912 ; compare this vol., ii, 32).-8eparation of Bis- muth from Copper.-Bismuth and copper (about 0.3 gram of each) are dissolved in concentrated nitric acid ( 5 c.c.), diluted with water (50 c.c.), and the bismuth precipitated by means of a mixture of 3 per cent.hydrogen peroxide (50 c.c.) and concentrated ammonia (15 c.c.), care being taken to avoid loss by frothing. The precipitate is washed first with a mixture of hydrogen peroxide (2 vols.), concentrated am- monia (1 vol.), and water (8 vols.), secondly with warm dilute am- monia (1 : €9, and finally with hot water ; the complete removal of the copper is attained with difficulty. The bismuth oxide is dried a t 90-95", ignited with the filter paper i n a platinum dish, and the residue dissolved in nitric acid, and ignited until its weight is constant. The copper, after conversion into sulphate and removal of the nitric acid, is precipitated by the prolonged action of hydrogen sulphide, and the precipitate converted into oxide by ignition in a stream of oxygen.The analytical results show that the amount of bismuth obtained is in excess of the theoretical by 0.2-0-3 per cent. Heating the liquid immediately after the precipitation OE the bismuth appears to be without marked result, except that traces of copper are retained by the bismuth oxide, and can only be removed by redissolvingit and re- precipitating. The addition of hydroxylamine (Abstr., 1893, ii, 500) is attended by a similar result, the bismuth oxide being deposited as a white, crystalline powder. Estimation of Gold and Silver in Antimony or Bismuth. By E. A. SMITH (J. SOC. Ckem. h d . , 12, 316--319).-Assay of Antimony foy Gold and Silver. 1st Method-The sample is powdered in an iron mortar, passed through a sieve of 80 holes to the linear inch, and well mixed.500 grains of the powder is then mixed with 3000 grains of litharge, put into an earthen crucible, and fused in an air furnace, the crucible being partly covered during the operation, which lasts about 15 minutes. The melt is poured into an ingot, and, after cooling, detached from the slag. The lead button, although a little hard, is malleable, and, after being scorified to a convenient size, it may be cupelled in the ordinary way. The gold is afterwards parted from the silver by means of nitric acid. When assaying samples fairly rich in gold or silvey, amall quantities of the precious metals may be retained by the slag. The latter should therefore be again fused with 500 grains of litharge and 20'grains of charcoal, and the lead button thus obtained cupelled as before.2nd Method.-500 grains of the sample of antimony is fused with 1000 grains of litharge, 200 grains of nitre, and 200 grains of sodium carbonate. The fusion is generally complete in 15 minutes, and the buttons of lead may be at once cupelled without previous scorifica- tion, thus saving considerable time. The test analyses are satisfac- tory. dssuy of Bismuth.-The metal is melted under a layer of charcoal, and, after adding a piece of resin, it is poured into moulds so as to J. B. T.72 ABSTRACTS OF CHEMICAL PAPERS. obtain buttons weighing about 500 grains. After adjusting them to exactly 500 grains, they are at once carefully cupelled in a muffle at a, slightly lower temperature than that employed for the cupellation of lead.The resulting buttons of gold and silver are then treated as before with dilute nitric acid. L. DE K. Sodium Peroxide in Water Analysis. By S. RIDEAL and H. J. BULT (Chem. News, 68, 190--191).--It is found that on treating potable water, or water contaminated with fresh sewage, with sodium peroxide (in a solution containing 2 grams per litre) instead of with alkaline yermanganate, only part of the organic matter is attacked, and, consequently, after such treatment, the waters yield a further quantity of ammonia with permanganate ; this residual organic matter is, however, much more readily oxidised than the organic matter that bas not been treated with the peroxide. Amount of Glucose in Beets and in Diffusion Juice. By H. CLAASSEN ( B i e d . Centr., 22, 769--771).-The percentage of gluc- ose present in beet-root should be estimated in the root itself and not in the expressed juice.Slices of the root are digested in water, basic lead acetate is added (not in excess), and the whole further digested ; the solution is then neutralised by calcium carbonate, in order that there may be no free alkali. After filtration, the lead is precipitated by soda, and the sugar present estimated by means of Eehling’s solution. Estimation of Glycogen. By J. WEIDENBAUM (PJliiger’s Archiv, 54, 319-332) .-The research consisted in a critical investigation of D. A. L. E. W. P. Frankel’s method of separating and estimating glycogen (Abs‘ir., 1893, i, 386). ’ Thi glycogen obtained by this method is very impure ; dissolved in dilute potash, it gives, after neutralisation with hydrochloric acid, a fairly heavy precipitate witb Briicke’s reagent.The longer the organ is treated with trichloracetic acid, the greater is the nitrogen present in the so-called glycogen extracted; in some cases, almost half the substance is proteid. The residue, also, is not freed from glycogen by the extraction, nearly a third of the total glycogen being left behind. W. D. H. Colour Reaction of Phenylhydrazine on Lignin and Alde- hydes. By E. NICKEL (Chem. Zeit., 17, 1209, 1243--1244).-Wood, immersed in a solution of phenylhydrazine hydrochloride, h r n s pale yellow, the colour deepening on the addition of dilute hydrochloric acid. After the lapse of an hour, or sometimes several hours, the colour changes t o a distinct green. Wood, and particularly bamboo, immersed in a solution of hydrazine sulphate, acquires, after a few minutes, a clear yellow colour, which turns orange on adding hydro- chloric acid.Hydrazine sulphate, added t o a solution of vanillin, produces a deep yellow coloration, but no precipitate ; the addition of hydrochloric acid gives a floocnlent, yellow precipitate, but this did not turn orange,ANALYTICAL OHEMISTRY. 73 Piperonal, parahydroxybenzylaldehyde, and salicylaldehyde give similar colorations. L. DE K. Estimation of Oxalic acid. By A. GUNN (Pkarm. J. Trans., 53, 408-410).-The author proposes to use the yellow colour of ferrous oxalate as a means of determining oxalic acid in certain cases where the ordinary methods are not readily applicable. Absolute accuracy is not claimed for the process, but it appears t o be specially useful for estimating oxalic acid when mixed with tartaric acid.The solution of ferrous salt preferred is that of the phosphate, which is nearly colourless, and the determination is made colorimetrically by com- parison in Nessler glasses with a standard solution. The colour is destroyed by the strong mineral acids, and the reaction is also inter- fered with by the presence of much alum. The results are improved by a preliminary neutralisation of the acids by ammonia. Coloured solutions may be first treated with animal charcoal, and any residual tint allowed for i n the coniparison. R. R. Estimation of Tannin and Gallic acid. By W. P. DREAPER (J. Soc. Chenz. lid, 12, 412--415).-The author recommends the following process.The solution containing the tannin and gallic acid is heated to 80°, and, after adding some pure barium carbonate, a standard solution of copper sulphate is added until a drop of the supernatant liquid gives a faint brown coloration when mixed with potassium ferrocyanide. Another portion of the solution is preci- pitated by means of gelatin, and, after filtering, the titration is repeated. The difference in C.C. of copper solution between the two estimations is the measure for the amount of tannin. The copper solution should, of coume, be checked with pure tannin and also with gallic acid, as the latter requires a much larger amount of copper Analysis of Tanning Materials. By A. GAWALOWSKY (Zeit. anal. Chern., 32. 618--619 ; from Brestewski’s Handworterbuch fur Pharmacie) .-An extract of the material is precipitated with the smallest possible excess of copper acetate, and after a time is filtered by suction through a dried and weighed filter; the precipitate is washed with cold water, dried until the weight is constant, and in- cinerated.The ash is dissolved in nitric acid and again ignited to determine the copper as oxide. The difference gives the total tannin, gallic acid, pectin, &c. Another part of the extract is evaporated to a syrup, treated with alcohol-ether (2 : l), and the pectin with traces of albumin and casejin filtered off; the alcohol-ether is evaporated from the filtrate, and the residue dissolved in hot water and filtered from fat and resin. The cold filtrate is now mixed with copper acetate and ammonium hydrogen carbonate ; this precipitates the tannin, leaving copper gallate in solution.The pectin precipitate is dissolved from the filter with hot water, and the cooled solution precipitated with coppcr acetate. Both these precipitates are treated like the former one ; the ga!Iic acid is then known from the difference. for precipitation than tannin does. L. DE K. M. J. S.74 ABSTRACTS OF OHEMIOAL PAPERS. Separation of Uric acid from Xanthine. By J. HoRRAczEwsKr (Zeit. physioZ. Chem., 18, 341-350) .-In view of a certain amount of hostile criticism which has followed the publication of the author’s views on the origin of uric acid in the organism from nuclejin, he admits that the separation of uric acid from xanthine bases is difficult.Artificial mixtures of uric acid and xnnthine showed a loss of uric acid when that substance was estimated by Fokker’s method. The separation of the two substances by means of hydrochloric acid led to better results ; but there is still a noteworthy loss. By meails of concentrated sulphuric acid, the mixture being allowed to stand five hours, the loss is inconsiderable, the greatest difference being 0.005 gram. If longer than five hours is allowed to elapse, some xanthine is precipitated also. The same method was successfully wrried out in the separation of uric acid from guanine. Precipitability of Uric acid and Bases of the Uric acid Group as Cuprous Oxide Compounds. By M. KRUGER (Zeit. physiol. Chem., 18, 351--357>.-By the use of copper sulphate and sodium hydrogen sulphite, all xanthine-like substances which contain a sub- stituted EH-group are precipitated from hot solutions as compounds with cuprous oxide.Theobrornine is a noteworthy exception. As a quantitative method, it is as good as ammoniacal silver solution. The use of sodium thiosulphate as a reducing agent gives a means of separating adenine and hypoxan thine, and probably also of guanine and xanthine. W. D. H. W. D. H. Assay of Naphtholsulphonic and Naphthylaminesulphonic acids. By W. VAUBEL (Chem. Zeit., 17,1265-1266).-The sulph- onic acids may be divided into three classes :-1. Those which gener- ally absorb only 1 atom of bromine ; 2. Those which slowly absorb several atoms of bromine; 3. Those which do not combine with bromine a t all.Only those of the first class can be readily assayed by tbe author’s process. They comprise : a, naphthionic acid; b, Dahl’s disulphonic acid I1 ; c, Dahl’s disulphonic acid I11 ; d, para- monosulphonic acid (2Br) ; e, naphthylenediaminemonosulphonic acid. The analysis is carried out by dissolving a known weight of the compound in water, and adding excess of potassium bromide and dilute eulphuric acid. Standard solution of potassium bromate is then added from the burette until the liquid contains free bromine. L. DE K. Hubl’s Iodine Absorption Process. By W. FAHRION (Clzem. Zeit., 17, 1100).-The author (Abstr., 1893, ii, 103) has demonstrated that the action of Hubl’s reagent on oils is not quite so simple as has been supposed, and that iodine is also absorbed by other fatty con- stituents.In this view, the author is supported by Gantter, who has found that even saturated fatty acids combine with iodine. The author has tried to improve the process by substituting methylic alcohol for ethylic alcohol in preparing the reagent, but,ANALYTICAL CHEMISTRY. 75 excepting the fact that the solution keeps better, no special advantage accrues therefrom. L. DE K. Reducing Action of Rancid Fat and Lard on Silver Nitrate. By G. MARIANI (Xtuz. Xper. Agrur., 23, 355-359).-Experiments were made with BrullB’s nitrate of silver test for margarine (Abstr., 1891, 506). Pure butter gave no coloiir, and pure margarine did not give the red colour mentioned by BrullB. But in presence either of rancid butter or rancid margarine there was either a blackish deposit or a mirror, according to the degree of rancidity.Fresh hog’s fat, on the other hand, reduced the silver salt, acquired a more or less intense red colour, and formed a. brownish deposit. An examination of the deposits obtained on the one hand from rancid butter and margarine, and from fresh lard on the other, showed that, whilst the former consisted of silver oxide and silver, the latter contained sulphide as well as oxide of silver. It is thus seen that lard, like the oils of some Crucifer=, contains mlphur. In con- firmation of this it was found that Benedikt’s reaction f o r colza (Anal. d. Fette, 227) is also shown by lard. The reaction is thus useless for the detection of margarine in butter. Pennetier’s Method for detecting Margarine in Butter.By A. PIZZI (Xtax. Sper. Agrar., 22, 131-137, and 23, 35-43).-- Several examinations, by Pennetier’s microscope-polarisco pe method, of pure butter and butter mixed with Farious amounts of marprine were made, the results of which are shown in a coloured plate. An examination was also made of the fat of natural butter, which was obtained by melting the butter, allowing it to partially solidify, and separating the solid portion ; this, when examined with the polari- scope, showed a red ground with detached yellowish and greenish particles, whilst ordinary butter shows a red ground mostly covered with a confused mam of various colouts. Some of the objections to Pennetier’s method are the difficulties introduced by conditions of temperature, the effect of added crystal- line and amorphous substances, and the manner in which the mar- garine may have been mixed with the butter.As regards the first, the author observed no difference between butter which had been melted and cooled quickly and butter which had been slowly cooled. With butter containing margarine which had been kneaded in, the method, gives good results, but when churned with the butter the mixture behaved like pure butter. The inner portions of rancid butter, which had no mould on the surface, gave a negative optical reaction, whilst the outer portions gave a The method will show the presence of margarine, but is limited i n its application. N. H. M. Estimation of Nicotine in Tobacco. By R. KISSLING (Zeit. anaZ. Chem., 32, 567--571).-The author vindicates his method against the strictures of Vedrodi (Abstr., 1893, ii, 504), aud asserts N.H. M. Very rancid and mouldy butter gave the margarine reaction. positive reaction. kWC.hk76 ABSTRACTS OF CIHEMICAL PAPERS. that if his instructions are accurately followed, the ethereal extract will contain no ammonia, that no nicotine will be lost during the distillation of the ether, and that the results of his method agree closely with those of Popovici (Abstr., 1889, 802). The extraction with ether should, however, follow as quickly as possible the addition of the soda to the tobacco, as otherwise a loss of nicotine may take place. M. J. S. Furfuraldehyde Reactions of Alkaloids. By N. WENDER (Chem. Zeit., 17, 950-951).-When two or three drops of a mixture of sulphnric acid and furfuraldehyde (5 drops to 10 C.C.acid) is added to a minute particle of an alkaloid, a characteristic colour makes its appearance, and the author has tabulated the results. The method is, however, only of distinct value in the case of reratrine. This, when rubbed with a glass rod moistened with the reagent, gives first a, yellowish-green, and then an olive-green mixture ; the edges, and the whole of the mixture afterwards, turn a beautiful blue. On warming, the mixture gradually acquires a purple-violet colonr. The blue sub- stance obtained in the cold is insoluble in alcohol, ether, or chlorofbrm. The least amount of water, or alkali, decolorises the solution, and on adding much water a fairly permanent yellow solution is obtained, Excepting sabadilline, no other alkaloid gives the reaction, al- though the test with that alkaloid is not quite so satisfactory. If instead of sulphuric acid other acids are used, the reaction does not manifest itself. h. DE K. Estimation of Nitrogen and Protei‘ds in Milk and its Pro- ducts. By L. CARCARO (Staz. sper. Agrar., 22,261-263).-Accord- ing to L’H6te (Abstr., 1889, 438 and 746), and Oddy and Cohen (Abstr., 1890, 1466), Kjeldahl’s, method is not suitable for certain substances ; with some, it gives coloured solutions after prolonged heating, and low results are obtained owing to incomplete oxidation, and to loss of ammonium sulphate during the heating. Menozzi, and also Musso (Gnzzetta, 61, estimated nitrogen in milk and its products by Dumas’, and by Will and Varrentrapp’s methods; they both found that the Will and Varrentrapp method gave low results (com- pare also Violette, Abstr., 1889, 546, and Aubin and Alla, ibid., 648 and 925). The author estimated the nitrogen in milk, Emmenthaler cheese, and cheeses prepared from mare’s milk and from sheep’s milk, &c., employing both Dumas’ and Kjeldahl’s methods. Proteids were also dgtermined in milk by Ritthausen’s method. The modification of the Kjeldahl process was that recommended by the Directors of the Italian Agricultural Stations, with due regard to precautions men- tioned by Zecchini and Vigna (Abstr., 1889, 649), and by Proskauer and Ziilzer (Chem. Centr., 1885, 17). In every case except one, the Kjeldahl results were somewhat lower than those obtained by Dumas’ method, but the difference was generally very slight. For milk analysis, the K jeldahl process is much less troublesome than Dumas’ method, and, although somewhat slow, several deter- minations can be carried on at once. N. H. 31.

ISSN:0368-1769    

DOI:10.1039/CA8946605066

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

General and Physical Chemistry. Observations on Optical Rotation. By J. A. LE BEL (BUZZ. SOC. Chirn., [3], 9, 674--680).--The experiments recorded in this paper were mnde to throw light on the law of the change of sign when the radicles of optically active compounds are replaced by others, notably by acidyl groups and halogen atoms. The author euters at length into his own theoretical views and those of Guye. His conclusions are not definite, but he states that the optical action appears to increaae with the mass (Guye’s bypothesis). Methylpropylcarbinol is prepared by the hydrogenation of the mixed ketone obtained by distilling calcium acetopropionate. After growing Penicillium glaucum in its solution, it becomes laevorotatory ; the chloride is slightly dextrorotatory, and the iodide more so.The tartaric chlorhydrins, methylpropylcarbinol and its derivatives, as well as ethylpropylcnrbinol, were examiiied. The iodide from the laczt compound is laevorotatory, not dextrorotatory, as stated (Abstr., 1895, i, 246). Derivativw of methylamylcarbinol, propylglycol, the etherea t lactates, and isobutylamyl etlher were also examined. A. ki. L. Electromagnetic Rotation of the Plane of Polarisation of some Acids and Salts in different Solvents. By 0. HUMBURG ( Z e i t . phykkat. Chem., 12, 401-415). -In order t o ascertain whether a connection exists between the magnetic rotation of an electrolyte and its electro!ytc dissociation, a number of fatty acids and of in- nrpanic salts were examined in solution in m ater and in other solvents.Benzene and toluene were uxed as solvents for the fatty acids, and mcthylic alcohol for the salts examined. The rotation of the fatty acids is independent of the solvent, and is the same in ayueoiis solu- tion, in benzene, and i n toluene ; this holds even in the case of the chloracetic acids, w tiich must be regarded a s strongly dicsociated in aqueous solution. The inorganic salts taken mere potassium iodide, sodium and baiium bromides, and ammonium nitrate. The molecular conductivities of these salts is much smaller when measured in the methylic alcohol solntions than in water, and, therefore, as was to be supposed, the dissociation is relatively much smaller in the first case. The rotation, however, remains practically unchanged with change of solvent, showing that it is independent of the dissociation.From the results of these experiments, therefore, it appears that electrolytic dissociation has no appreciable inff uence on the magnet c rotation. The rotations of chlorine and bromine derivatives of some of the fatty acids and of some hjdrocarbons were measured, and from thePe the atomic rotations of chlorine and bromine were calculated. The numbers obtained weye, for chlorine 1-606 in the case of the fatty acid derivatives, and 1.675 from hydrocarbon dei iratives ; for bromine, 3.525 and 3-563 in corresponding cases. The numbers are practically identical in the t w o series. H. C. YOL. LXVI. ii. 8'7 8 ABSTRACTS OF OHEMIOAL PAPERS. Optical Rotation and Electrolytic Dissociation. By H. HADEICH (Zed. physikul.Chem., 12, 476--497).-Accordinp to Oude- mans, the molecular rotation of salts in dilute solution is independent of the character of the inactive ion of the salt, a result which is in full accordance with the electrolytic dissociation theory. This view .-has bee11 called in question, notably by Frankland (Trans., 1893, 312), and in this paper the author submits i t to further experimental in- vestigwtion. The salts examined were, in the fimt instance, those of the alkaloi'ds morphine, quinine, conquinine, cinchonidine, brucine, and strychnine. In each case in sufficiently dilute solution, the rota- tion is found to be independent of the inactive acid, and, therefore, the same for the different salts of any one alkaloid. This is also true of the methylammonium salts of the alkaloids.Jn these cases, thepefore, the law of Oudemxns is fully confirmed. Roryl, arseny', and antimony1 tartrates were also examined, and these in dilute solu- tion are found to obey Oudernans' law. The rotation of these salts differs from t,hat of the other tartrates, and therefore the active ion is not that present in tartaric acid imelf. H. C. Reverberatory Electrical Furnace with Movable Electrodes. By H. MOBSAN (Compt. rend., 117,6'79--682).-Tlie furnace consists of a parallelopiped of Courson limestone, in which is cut a somewhat large cavity, also a, parallelopiped in shape, which is lined with alternate plates of magnesia and carbon, about 10 mm. thick, so arranged that magnesia is in codtact with the limestone, whilst carbon forms the internal liuing of the cavity.A lid, of alternate plates of magnesia and carbon, covers the cavity, arid a block of Conrson limestone is placed above this lid. The electrodes are movable, and pass through slots cut in opposite sides o f the furnace. At right angles to the electrodes a carbon tube, 10 to 20 mm. in diameter, passes through the furnace, and is so arranged as t o be 10 mm. below the arc, and 10 mm. above the bottom OF the cavity. If necessary, the tube can be lined with magnesia. By inclining the tube a t an angle of about 30°, the furnace can be made to work continuously, the reducible material being introduced a t the higher end, whilst the product of reduction is drawn off a t the lower end. With a current of 600 amperes and 60 volts, 2 kilos. of fused metallic chromium can be obtained in about an hour, the metal being received in a crucible made of chromic oxide.The metal is white, finely granular, and ver-y hard, and takes a high polish. The magnesia is prepared by heating strongly the basiccarbonate, digesting the product with ammonium carbonate solution, and again strongly heating. With this furnace, silicou carbide and vanadium carbide can be readily obtained by the direct combination OP carbon vapour with the vapours of silicon and vanadium. It is then moistened with water and compressed. C. H. B. Electrolytic Thermoelectric Cells. By A. GOCKEL (Ann. P ~ Y S . Chem., [2], 50, 696--704).-'l'he author has investigated the electro- motive force of thermo-elements constructed on the following plan :GENERAL AND PHYSICAL CHEMTSTRY.H,rr I solid Hg salt' : s2lt solution : solid Hg salt I Hg cold I hot H e finds that in genera1 the thermoelectric force for 1" difference of temperature increases with dilution of the solution, and that ill equivalent dilute soliitions of similar salts of an acid it is practically the same. He confirms in general Ebeling's observation, that the worst conductors are thermoelectrically the most, activs,. and that Sortie show a maximum therrnoe!ectric force at the concentration of maximum conductivity. J. W. Velocity of Ions. By P. KOHLHAUSCH (Ann. Phys. Clzenz., ['t], 50, 385--408).-1n the present paper the author has collected and discussed all the available data bearing on the speed of electrolytic ions, tire uumerical values being made as far as possible comparable.First, he gives a table of t h e Hittorf numbers for the anion of 23 electrolytes at different dilutions. He then shows that the speed of the chlorine ion is the same in solutions of the alkali chlorides st equivalent concentrations from semi-normal downwards, and that the fipeeds of the two ions of these and ~imilar salts are additive in dilute solutions. As a first approximation, he considers that the increase of the molecular conductivity for the same amount of dilu- tion of different salts is the same. The following table of the molecular conductivity a t infinite dilu- tion and 1bo, and the corresponding speeds of the ions is given. U and V denote the velocities of the kation and anion respectively in centimetres per second ; u and v the velocities referred to mercury units ; X the conductivity at infinite dilation.KCl ................ NaCl ............... LiC1. ............... N H, C1. ............. HC1.. .............. KI ................. KNO, .............. NaNO, ............. AgNO, ............. HNO, .............. KC10,. ............. NaC2H302. ......... KOH. .............. NaOK ............. AgClO, . . . . . . . . . . . -4gC10, ............. AgC,H,,SO, ......... KC3H302 ........... AgC2H3O;. .......... ~ ~- A, * 10-7. -- 123 103 95 122 353 123 118 98 109 3 50 115 94 73 2-2 801 103 1 U6 83 73 u. 10--7. -- 60 41 33 60 290 60 60 40 52 (290) 41 58 36 51 52 53 52 2). 10-7. 6 3 62 62 62 63 63 58 58 57 (60) @;) 32 165 165 53 54 30 21 U. 10-5. 66 45 36 66 320 66 66 44 57 (320) (gl 45 64 40 57 57 58 57 v.1c-5. -- 69 69 69 68 70 69 64 64 63 (65) (;:) 35 18 1 181 57 60 34 23 J. W. 8-280 ABSTRACTS OF CHEMICAL PAPERS. Electrical Conductivity of Cupric Chloride Solutions. r Irc. J. HOLLAND (Ann. Phys. Chem., [ Z ] , 50, 349--360).-Solutions cupric chloride show a regularly diminishing rate of increase of tlie cond nctivity as the temperature rises, and then varies with the con- centration, the maximum Conductivity being obtained wihh a solution containing about 18 per cent. of anhydrous Halt. The temperature coefficient varies with the concentration, and reaches a maximum at about 40”. J. W. Change of Conductivity of a Solution by the Addition of a Non-electrolyte. By R. J. HOLLAFD (Ann. Phys. Ch.em,., [ Z ] , 50, 261-292 ; compare Abstr., 1892, 1382).-The author gives the following account of his general results. The electrical conductivity of a solution of an electrolyte in methylic alcohol diminishes on the addition of a non-conductor, the diminution varying with the nature of the non-electrolyte and with the degree of dilution.The fonr Don-electrolytes benzene, toluene, xyl’ene, and oil of turpentine diminish the conductivity in the ordcr given. The diminution varies for each volume per cent. of non- electxoljte added from 1.7 to 2 per cent. of the conductivity of the correspoiiding normal solution for 0-01-normal solutions ; 1*G-l.i5 per cent. for 0.001-norma1, and 1-4-1.6 per cent. for O-0005-norrnal. The temperature coefficients of alcoholic solutions increase wit h increasing dilution ; are only half as great as in the case of aqueous solutions ; and are very little affected by the addition of a non-con- ductor.The conductivity of‘ methylic alcohol solutions up to a concentra- tion of 20 per cent. of non-electrolyte is very exactly represented by Arrhenius’ formula (Abstr., 1892, l0:38). No connection between elactrical conductivity and fluid friction was evident. ‘Heat of Dissociation in Electrochemical Theory. By H. EBERT (Ann.. Phys. Chem., [‘L], 50, 255--860).-The molecular heat of dissociation of the hydrogen molecule into atoms, as calculated by E. Wiedemann, is about 1.1 x 1013 ergs; the same magnitude for iodine, calcula,ted by Boltzmann from Meier and Crafft’s data, is 1.2 x 1OI2 ergs. A calculation on the assumption that the valenciev holding two atoms together are electrical leads to a value for the heat of dissociation equal to 4.3 x 10l2 ergs.The author, therefore, con- cludes that chemical affinity is essentially of an electrical nature. The Hydrogenaton of Closed Chains. BY F. STOHMANN and H. LANGBEIN (J. pr. Chem., [a], 48, 447-453 ; compare Abstr., 1891, 3‘76, 1146).-The following values are gken (table, p. 81). Inasmuch as these values are known for benzene and hexane, there is now a complete series of values for the hydrogenation of benzene. A comparison of them shows that the attachment of each pair of hydrogen atoms to the benzene molecule is not accompanied. by the same thermal change. It must, therefore, be concluded that there are not three double bonds of equal value in the benzene ring.The bonds in benzene itself require a greater energy for their opening J. W. J. W.GENERAL AND PHYSICAL CHEMISTRY. Constant pressure. 81 Constant volume. Heat of combustion of 1 gram molecule. Dihydrobenzene . . . . . . Hexahydrobenzene . . . . Tetrahydrobenzene . . , . I 848 -0 Cal. 933 -2 ,, 931 -5 ,, 846 -8 Cal. &92 -0 ,, 890 -5 ,, Heat of formation from elements. ~ - 8 '0 Cal. + 17 -0 ,, +44*8 ,, up than those in any of the hydrogenated benzenes. The bonds in di- and tetra-hydrobrnzene require less energy than those of either benzene or hexah) drobeiizene, whilst those of the last-named com- pound require less than those of benzene. A. G. B. State of Matter near the Critical Point. BY B. GALITZINE (dnu. Yhys. Chem., [23, 50, 521-544).-The author arrives at the following conclusions from his observations :- The temperature of the actual appearance of the meniscus on cooling must lie considerably lower than the critical temperature, so that the opt>ical method as usually carried out by observations of clouding in the tube must lead to erroneous values for the critical point.If the cooling is conducted very slowly and regularly, there is no clouding. The temperature at which the meniscus really appears, and the temperature at which the last traces of inhomogeneity vanish, must be regarded as independent of the quantity of substance in the tube. The density p of a liquid in contact with its saturated vapour, and the density 6 of this vapour, vary with the time at the same constant temperature, and also if they are heated fieveral times beyond the critical point, p decreasing, and 6 increasing.These two magnitudes, therefore, are not functions of the temperature alone. At temperatures considerably higher than the critical poiut, a substance can have two different densities at almost the same pressure, the difference amounting to as much as 25 per cent. J. W. Weight of a Litre of Normal Air: Densities of Gases. By A. LEDUC (COWL@. rend., 117, 1072-1074) .-The proportion by weight of oxygen in the air at Sorbonne was found to vary from 23-14 to 23.20 per cent., and since this variation would make a differ- ence of 0.1 milligram in the weight of a litre of air, it is useless to attempt to reach a higher degree of accuracy in such determinations unless the composition of the air is determined at the same time.The weight of a litre of average air a t Paris at 0" and 760 mm. was found to be 1.29315 gram. The author defines as normal air air collected on a plain in calm weather at some distance from a town, and containing a little more than 23.2 per cent. of oxygen by weight, or almost exactly 21.0 per crnt. by volume. A litre of such air weighs 1.2932 grams at 0" and 760, and its mass is 1.2758 grams under 1 atmosphere c.g.8.82 ABSTRACTS OF CHEMICAL PAPERS. In accurate estimations of densities of gases i t seems preferable to take nitrogen as the standard, since this gas is easily obtained in a state of purity, and its density is so near that of air that the presence of a small qcantity of the latter in the apparatus introduces 110 ap- piy!ciable error.The weight of a litre of nitrogen a t Paris under normal conditions is 1.2570 grams, and its mass under a pressure of 1 atmosphere c.g.s. is 1,24006 grams, or better, 1-24. grams. Critical Pressures in Homologous Series of Carbon Corn- pounds. By E. MATHIAS (Compt. wnd., 117, 1082--1085).-1n the homologous series of the primary alcohols, the dkyi chlorides, the dkyl salts of formic, acetic, and propionic acids, the simple and mixed ethers, and the alkyl derivatives of ammonia, the critical pressnres 7, like the critical densities, are a continuous function of the total weight of the molecule, and, except in the case of the ammonia deri- ratives, it is possible to pass from one curve to the other by a simple linear substitution of the form T‘ = an- + /3 ; cc and P being numerical constants which separately may be nil.Within the limits of the experimental errors, the curves of the critical pressnres can be assimi- lated to arcs of eqnilateral hyperbolas, with asymptotes parallel with the axes of the coordinates, and can, therefore, be represented by the equation (T + a)(% + b) = c. I n the case of the alcohols, and, therefore, in all the monosubstitution derivatives, b = 3. By the method of substitution it is found that the critical pressure of hydrogen is 72.613 atmos., a valne wliich is much higher than t h a t obtained directly by Wroblen-ski, and which explains the diEculty of obtaining liquid hjdrogen in a static condition. The critical pressures of the nlkyi salts derived from the primary alcohols are represented by the formula C. H.B. where n’ is the number of carbon atoms in the acid. The critical densities A and the critical pressures 7r in a given homologous series being continuous functions of the molecular weights, it, follows that in each series there is a relation between A and T which is independent of the pa~4kxlar compound considered. C. H. B. Dissociation of Water. By J. J . A. WIJS (Zeit. phydkal. Chem., 12, 51&523).-1n a former paper (Abstr., 1893, ii, 364), the extent t o which pure water may be regarded as dissociated electrolytically was calculated from the rate of hydrolysis of methylic acetate by water. The number then obtained was considered as being too low, owing to the fact that the acetic acid liberated i n the reaction retards the hydrolj~is during the first period, by the influence of its dissociated hydrogen ions on the hydroxyl ions of the water.In order to calculate and allow for this influence, fresh determinations of the rate of hydro- lysis of methylic acetate by water have been niads, the acetic acid liberatcd being determined by measuring the conductivity of the solution. From these results the concentration of the hydroxyl ions in water i s calculated as 0.14 x b u t the author is somewhatGENERAL AND PHYSICAL CBEMISTRY. 83 doubtful of the piirily of the water used, and proposns to repeat the experiment under circumstances that will ensure greater accuracy. H. C. Action of Salts on Acids. By R. W. WOOD (Amer. Chern. J., 15, 663-670).-Duggan’s work on “ absolute neutrality ” (Abstr., 1886, 765) cannot be considered conclusive, as the diastase used as an indicztor was not sensitive enough.His view that, the amylolytio function of that ferment is due to the presence of small traces of acid or alkali is not in accordance with his experimental results. It is more probable that the inhibition is due to free ions, of hydrogen i n the case of acids, and of hydroxyl i n the case of alkalis, ‘. absolute neutraiity” occurring only when these ions are formed a t equal rates. The salts of ‘‘ weak” acids in solution may be regarded as partly hydrolysed into the acids and bases ; a n d as the latter split up more readily than the former, there is a tendency for normal salts to appear alkaline towards diastase. The author prepares diastase directly from pale barley-malt by precipitating the cold aqueous extract with alcohol, and drying the washed precipitate in a vacuium over sulphuric acid.The ferment thus obtained is both powerful and sensitive ; it is capable of hydro- lysing 70 times it& weight of starch, and the rate s f hydrolysis is distinctly lowered by the additisn of 1 part per million of sodium hydroxide (phenolphthalein is sensitive only to 8 parts per million). The emulsion of starch (2 grams in 80 C.C. of water) was heated to 5.5” in a chamber surrounded by acetone vapour, the diastase (0-01 gram) added, and the mixture heated for 30 minutes. Aqueous soda (2 C.C. of 10 per cent.) was then added to inhibit the action of the diastase, and the reducing sugar formed estimated with alkaline copper tartrate.The inhibitory effect of acids is less powerful than that of alkalis. I n every case the initial action is to increase the activity; this is probably due to the presence of a, trace of impurity in the starch. ?’he action of the first five normal acids of the fatty series is much affected by tempera,ture, the inhibitory power of the acids increasing faster than the hydrolytic power of fhe diastase. Nelitral salts of “ weak ” acids have a slight inhibitory action, as stated above, but tnose of “strong” acids are without action; in general, the “weaker ” the acid the less the effect. The addition of free acid to normal saltr first increases the inhibitory effect and then decreases i t ; but the variation is less marked than in tho absence of the salt.At the maximum, the amount of acid may be varied between considerable limits without affecting the rate of hydrolysis. This is probably due to a want of sensitiveiiess even of the purer diastase ; Duggan’s results, therefore (Zoc. cit.), may readily be accounted for. JN. W. By H. C. JONES (Zeit. physikuZ. Chern., 12, 62;?-656).-The author has determined the freezing points of the solutions of the following electrolytes between the limits of about 1/10 normal and 1/1000 normal:- Hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, potassium hydroxide, sodium hydroxide, ammonia, potdssium carb- The experiments were made on a uniform plan. Freezing Point of Dilute Solutions.84 ABSTRACTS OF CHEMICAL PAPERS. onate, and sodium carbonate.In general the degree of dissocia- tion calculated from the depression of the freezing point agrees fairly well w i t h that calculated from the electric conductivity, being some- what less in the case of the acids and bases, and affected by hydrolysis in the case of the carbonates. The following organic compounds (practically non-electrolytes) were also investigated :-Cane sugar, glucose: carbamide, phenol, ethylic alcohol, propylic alcohol. The depression constant obtained for the most dilute solutions of these substances is much greater than the calculated constant for water. With increasing concentration, the molecular depression sinks to a minimum, and then either remains constant, or again increases, as in the case of the two carbohydrates.With phenol, the minimum was apparently not reached. For the feeble conductors acetic acid and succinic acid, there is an approximate agreement between the values of the dissociation ratio calculated from the freezing point depression and from the electrical conductivity . The depression constants obtained for water from solutions of carbamide, ethylic alcohol, and propylic alcohol were 1&38,1-876, and 1.878 respectively, the value calculated from the latent heat of fusion (/9.7), by means of Vsn't HOB'S formula, being 1-87. Rate of Crystallisation of Supercooled Liquids. By €3. MOORE (Zeit. physikal. Chem., 12, 545-554).-A U-tube, open a t both ends, was filled with a liquid (for example, acetic acid), and kept at a constant temperature below the freezing point of the latter.Crystallisation of the overcooled liquid was then induced in one limb, and the time taken for the boundary between the solid and liquid to pass downwards from one mark to another on that limb was noted. This time was found to be independent of the width of the tube, and approximately inversely proportional to the degree of overcooling. Experiments were made with phenol containing various proportions of water, in order to ascertain if the rate of crystalli~atiun remained the same for the same degree of overcooling of the different mixtures. This was found not to be the case, the velocity in the mixture in- creasing at a much smaller rate with the degree of overcooling than when phenol alone was used. C'resol mixed with phenol greatly diminished the rate of crystallisation.Solubility of Mixed Crystals. By A. POCK (Zeit. ph ysikal. Chem., 12, 65 7-662) .-The isomorphous double salts 2KC1,CuC1,,2H20 and 'LNH4Cl,CuC'l2,2H2O were mixed in various proportions, dissolved in water, and the solutions allowed to crystallise by spontaneous evapora- tion at 17". As soon as a quantity of mixed crystals sufficient for analysis had separated, they were removed and analgsed along with a sampleof the solution taker1 a t the same time. The solutions always con- tained a larger proportion of the salt 2KC1,CuC1,,2H20 than the mixed crjstah, and as evaporation proceeded, proportionately more and more ammoiiiiim salt was removed from the solution. The series of mix- tures, howerer, is not continuous, c r j s t d s containing 27.77 and 54.87 molecules of 2KC1,CuCl2,2H2O per cent.respectively forming the J. W. J. W.GENERAL AND PHYSICAL CHEMISTRY. 85 limits at the temperature observed. The replacement of ammonium by potassium in the solution appears to cease when these limiting crystals exist together in contact with the solution, the composition of the solution remaining constant until all the crjstals of 27.77 per cent. have been removed, or transformed into those of 5487 per cent. When solutions of ammonium sulphate and potassium sulphate were allowed to crystallise together, i t was found that the molecular percentage of ammoninm sulphate in the mixed crjstals was very nearly proportional to the concentration of the solution with respect to ammonium sulphate. J. W. Isomorphism.Part VIII. By J, W. RETGERS (Zeit. physikal. Chem., 12, 583-622 ; compare Abstr., 1891, 146, and 1131 ; Abstr., 1892, 10.18 ; Abstr., 1893, ii, 161).-Scbroder van der Kolk (Abstr., 1893, ii, 280) suggested that the ferric chloride contained in Scheele’s ruby-coloured ammonium chloride crystals might be in the form of an isomorphous admixture of the regular hydrate of ferric: chloride described by him. The author rejects this suggestion on the ground that the regular hydrate of ferric chloride is colourless, and could not pi.odnce the intense colour of the mixed crystals. He is of opinion that isomorphism in this case is altogether excluded, and that the most satisfactory explanation is that the ferric chloride is merely an encloged hydrate, probably Fe2C16,7H20.The regular crystals he considers to be most probably an unstable form of a hydrate with much more water than the yellow hydrate, Fe2CI6,12H20. When sulphur and selenium crystallise together from their solu- tion in methjlenic iodide, the sulphur crystals are coloured yellow- ish-brown by admixture of selenium. No such mixed crystals are formed when sulphur and tellurium are crptal!ised simultaneously from warm met hylenic iodide. The sulphur crystals i n this case are pale yellow, and crystallise out qnite independently of the opaque, metallic tellurium which separates beside them. The author con- s deis that tbis shows that whilst sulphur and selenium are isodi- rnorphous, sulphur and tellurium are not. From an extensive series of experiments on the crystallisation of snlts from aqueous solutions strongly coloured by organic dyes, the author finds that in almost all cases colourless crjstals separate. The exceptions are strontium nitrate, which is coloured by vegetable dyes, as observed by Sknarmont ; potassium sulpbate, which is coloured by Bismarck-brown ; potassium nitrate, which is coloured by nigrosin ; ammonium nitrate, which is coloured by indnlin ; and barium chloride, which is coloured by “ Wasserblau.” Sknarmont’s speculation that salts with much water of crystallisation would show the property of absorbing colourinp matters was not con- firmed, most of the above-mentioned salts being anhydrous, and no coloration taking place with such strongly hydrated salts as Glauber’s salt, alum, sodium thiosulphate, and sodiiim phosphate.Endothermic Reactions effected by Mechanical Force. By M. C. LEA (Amer. J. Xci., [3], 46, 241--244).-In A former paper J. W.85 ABSTRACTS OF CHERlICAL PAPERS. (Abstr., 18'33, ii, 69), the author showed that silver IiaIo'ids may be decomposed by the application of a high pressnre, and he has been thus led t o examine whether tbe same agent, mechanical force, would not be capable of bringing about analogous chemical changes in other compounds. Pressure was applied as before by means of a combina- tion of screw and lever, the calculated maximum pressure obtainable without allowing for loss by friction being over a million pounds per square inch. The material was wrapped in either platinum or silver, usually platinurn, foil. There was no action in any case on the metal, which preserved its full brightness in the parts in contact with the material, so that the effects observed were due to pressure only.Silver sulphite in platinum foil was moderately darkened by two days pressure. Silver salicylate was rendered very dark by two days pressure. Silver carbonate was moderately darkened by a somewhat longer pressure. Silver tartrate and silver oxide were not affected. b'erric oxide, recently precipitated and dried, was unaffected by pressure, no ferrous oxide being formed. Potassium P1atinobromide.-W bere the pressure was greatest the brilliant red colour. of this substance was blackened, not superficially only, but all through. Ammonium platinobromide showed moderate but well markpd darkening. Potassi urn Ch1orate.-When this substance was subjected to pres- sure by itself, no effect whatever was produced, and not a trace of chloride was formed.But when it was mixed with silver nitrate, both in fine powder, and subjected to pressure, there was an evident formation of silver chloride. The material was no longer completely soluble in Rater, but left an abundance of white flakes which darkened when exposed to light. Mercuric oxide darkens slightly but very distinctly, and this change seems to be accompanied by a slight loss of weight, requiring, however, very careful weighing to detect it. The darkened part, as well as the rest, dissolves without difficulty in acetic acid, and con- sisted, therefore, probably of traces of mercurous oxide and not of metallic mercury.Mercurous chloride and mercuric chloride re- inained unchanged. Mercuric iodide darkened considerably. arid a t points where the pressure was greatest, it became absolutely black, It did not appear, however, that any iodine was set free ; none could be extracted with alcohol. With mercuric oxfctiloride, 2HgO,HgCI,, heav-j pressure caused much darkening. Sodium thiosulphate compresses to a hard, translucent cake, but does not decompose. Although in a11 these instances the darkening is well marked, the actual proportion of material affected is small, so that in many cases i t is difficult to apply tests to decide as to the precise nature of the substances formed. I n some cases, however, t h i s can be done, and the author concludes that many of the salts of easily reducible metals, especially of silver, mercury, and platinum, undergo reduc- tion by pressure. Such reactions are endothermic, and it therefore follows that mechanical force can bring about reactions which require expenditure of energr, which energy is supplied by mechanical forceGENERAL AND PHYSICAL CHEMISTRY.87 in the same WRY that light, heat, and electricity supply energy in the endothermic ehanges which they bring about. H. C. Note by Abstractor.-Formation of allotropic modifications, a t any rate in the case of the mercuric compounds, appears possible. H. C. The Diamond as the Standard for the Determination of Atomic Weights. By G. HINRICHS (Corn@. rend., 117, 1075-1078). -The author proposes that the diamond should be adopted a s the standard matter for the determination of atomic weights.It is solid, compact, non-absorptive, and sufficiently hard to resist the mechani- cal effects of the necessary manipulations, and its resistance to the action of energetic chemical reagents makes the removal of impuri- ties comparatively easy. Moreover, its purity is unquestionable, and it is not liable to contain mechanical inclasions. Oxygen has almostl invariably to be determined by difference, whilst hydrogen is prob- ably the worst standard that could be selected, owing to its low atomic weight, the difficulties of manipulation, and the difficulty of obtaining it pure. If C = 12, it follows from the determinations of Dumas,Erdmann, Marchand, and Roscoe that 0 = 16, and from the determination of Er.dmann and Marchand, that Ca = 40.The mutual dependence of all the atomic weights can be repre- sented by means of a parabola, with diamond at the vertex and calcium at the focus, the primary elements being placed on the curve at the proper distance from the vertical passing through the zero of the atomic weights. The secondary axis passing through this point will be the locus of the atomic weights determined indirectly. Adopting recognised experimental results, it appears that, with very small errors, P = 31, Fe = 56, Zn = 65.5, Cd = 112, Hg = 200, P b = 207, and H = 1.0, Mg = 24, S = 32, Be = 9, Cu = 63.5, and F = 19. For the proper determination of the atomic weights of the halogens, a revision of the atomic weight of silver is necessary, and this element mightl then serve as a secondary standard.Beckmann’s Method for determining Molecular Weights. By G. BARONI (Gazzetta, 23, ii, 249-291 ; compare Abstr., 1893, ii, 511).-The small variations in the barometric height which ofteii occur during the determination of molecular weights by Beckmann’s method have a considerable influence on the accuracy of the result ; they are, therefore, not negligible, as is usually supposed. The error introduced by variations in the atmospheric pressure during tlie determination may amount to one-half the molecular weight of the substance. The author has determined the molecular weight of sodium bromide, strontiiim and mercuric chlorides, potassium and silver nitrates, potassium sulpliate, chromate, and dichroniate, iodic, succinic, oxalic, tartaric, and citric acids, mannitol, and cane sugar in aqueous solution, and of phenol and resorciP-01, using benzene a s the solvent. The curves plotted with the concentrations a s abscissae and the molecular weights as ordinates rise, in the majority of rases, in accordance with the requirements of the dissociation hypothesis. C. H. B.88 ABSTRACTS OF OEEMIOAL PAPERS. The curves obtained for potassium chromate, bromide, and chloride, and for citric acid, first rise and then fall; in the cases of barium, sodium, and strontium chiorides, sodium bromide, and tartaric acid, the curves fall throughout the whole length examined. The cause of this behaviour is unknown. W. J. P. Graphochemistry of Oxides and their Combinations, By E. NICKEL (Zeit. physikal. Chem., 12, 663-669) .-The author has applied his graphochernical method (compare Abstr., 1892, 1158) to the tabulation of the oxides with respect to their composition, proper- ties, and combinations with each other. To obtain a, table for their composition, he makes use of the following considerations. If E is the symbol of an element, each oxide may be expressed as and if p be the atomic weight of the element and z the percentage of oxygen in the oxide, then p/16n = (100 - x)/x. The table is constructed by taking the values of p and n (or ltjn) as ordinates and abscissae re- spectively, x then appearing as a bundle of rays diverging from the origin. All the oxides of each element are found in rt horizontiil line, and all the oxides with the same atomic oxygen ratio in the same vertical line. If the elements are gone through in the order of their atomic weights, a curve like Lothar Meyer's spiral is obtained when the typical oxides are considered. J. W.

ISSN:0368-1769    

DOI:10.1039/CA8946605077

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

88 ABSTRACTS OF OEEMIOAL PAPERS. In organ ic C h e m i s t r y, Molecular Weight of Hydrogen Peroxide. By G. TAMMANN (Zeu. physikal. Chew., 12, 431--436).-A redetermination of the molecular weight cf hydrogen peroxide by the cryoscopic method gives the molecular formula H202, in place of H,04 as formerly given by the author (Abstr., 1890, 106), and accords, therefore, with the ,results of Carrara's determination (Abstr., 1893, ii, 163). H. C. Occurrence of Hydrogen Peroxide in the Atmosphere and in Atmospheric Discharges. By E SCH~KE (Ber., 26, 3011- 3027) .--During 1874-75 the author carried oat systematic observa- ions of the atmosphere in the neighbonrhood of Moscow, and was led !o affirm the presence in it of hydrogen peroxide. This conclusion vns questioned by L. Ilosvay in 1889, whose arguments may be thus ' ummarised.1. The reactions with potassium iodide, starch, ferrous ulphate, guaiacum tincture, and malt extract are not characteristic of hydrogen Peroxide, and may also be produced by nitrous acid. 2. Cha- racteristic reagents fail to show the presence of hydrogen peroxide in the atmosphere. 3. No chemical process is known by which hydrogen ueroxide and ozone are produced in cature. 4. Ozone is not formed Iuring rapid combustion, and hjdrogen peroxide only in circum- stances which prevent its passing into the atmosphere. 5 . TheINCRQANlC C HEMISTKT. S9 negative results obtained from certain special experiments designed to show the presence of hydrogen peroxide. The author criticises and refutes these conclusions in detail. 1.Ilosvay's statements about the reagents are partly due to errors of manipulation and partly to lack of precautions in the preparation of the various solutions. 2. Titanic acid, which is stated to be the only characteristic reagent for hydrogen peroxide, is capable of detecting not less than 1 : 90,000, but in only two cases out of 500 has the author found more than 1 : 1,000,000. 3. Apart from electrical dischar-ges, the author s a g - gests that the action of sunlight, air, and moisture on ethereal oils and similar substances would result in the production of ozone and of hydrogen peroxide. 4. The formation of hydrogen peroxide during combuhon has been proved bj- the independent observations of several chemists by more exact methods than Ilosvay's.5. The results of Ilosvay'~ crucial experiments are invalid for the following reasons. (u) The air was taken from the streets of Budapest; ( b ) the volume (171-500 lit.) was far too small; (c) as hydrogen peroxide is unstable in presence of alkalis, the soda employed to absorb i t would cause its decomposition during the long coutinuance (6-5 weeks) of the experiments; ( d ) the passage of the air through the various purifying solutions (soda and dilute sulphuric acid) would cause the complete absorption of hydrogen peroxide, and consequently account for the various reaqents such as thallium paper and tizo- benzenenaphthylamine being unaffected. Samples of rain water, tested during the past two years, show that there is no connection between the quantities of hydrogen peroxide and nitrites which they contain.J. B. T. Manufacture of Oxygen from Calcium Plumbate. By G. RASSNER (Chem. Zeit., 17, 1242).-In investigating the dissociation of calcium plumbate, H. Le Chatelier (Abstr., 1893, ii, 524) found that for the evolution of oxygen by heat alone it is necessary to raise temperature about 200" higher than in the case of barium peroxide ; on the other hand, at lower temperatures the oxygen is more quickly and completely reabsorbed from air by the plumbate than by the barium oxide. The author now calls attention to the fact that whilst in his earlier communications he mentioned the evolution of oxygen from calcium plumbate by heat alone, be recommended, as more generally useful, several other methods ; the following is especially advantBgeous.Porous calcium plumhate is moistened with steam and subjected to the action of washed furnace gases. preferably, at a temperature below 100". The carbonic anhydride of the furnace gases is rapidly absorbed, and the material, which retains its poroiis condition, then consists of a mixture of calcium carbonate and lead peroxide. This is transferred to a retort kept constantly at a red heat, and in this the oxygen is evolved, the evolution being much helped by the introduction of a current of steam. After the evolution of the oxygen, the current of steam is continued, and the temperature raised, when carbonic anhydride is liberated, arid may bo collected for use. The calcium plumbate is then regenerated by means of a, current of air. The author also refers to Peitds patented90 ABSTRACTS OF CHEMICAL PAPERS.modification, in which it is proposed tc decompose the plumbate by means of a current of pure carbonic anhydride a t a red heat. The author claims for his plumbste process. as advantages over the Brin barium oxide process, ( a ) obtaining pure carbonic anhydride R S a bye-product.; (6) the use of low temperatures, and consequent saving in fuel and in wear and tear of retorts. (See also Abstr., 1891, 392.) L. T, T. Molecular Weight of Persulphates and Permolybdates. By G . MOELCEK ( Z e i t . physikal. Chem., 12, 555-563) .-The molecular weights of potascium persulphata and of ammonium persulphate were found by the author, from a consideration of the electrical conduct- ivity and the cryoscopic bebavioar of t'heir solutions, to be i n corre- spondence with the €ormul= K2S208 arid (NH4),S,08 (compare Bredig, Abstr., 1893, ii, 572).The conductivity and freezing point depressions o€ PBchard's pot,assium perinoly bdate and ammoniiirn permolybdate p i n t to these substances having the formula KzPvloz08 and (NH4),Mo208 respec- Action of Nitric Peroxide on Metals and Metallic Oxides. By P. SABATIER and J. €3. SENDERENS (Bull. Xoc. Chim., p j , 9, 668- 669 ; compare Abstr., 1892, 1390) .-Brown tungstic dioxide becomes incandescent in nitric peroxide a t 300", and yields yellow tungstic anhydride mixed with a little blue oxide, W,Os. Sodium is not oxidised by nitric peroxide in the cold, and is but dowly attacked on heating. Reduced nickel ignites a t the ordinary temperature, and forms nickelous oxide. A New Sulphide of Carbon.By B. v. LENGYEL (Rer., 26, 2960--2968).--When pure, dry carbon bisulphide is boiled in a reflux apparatus, the vapour being exposed to an electric arc main- tained between two carbon poles for two or tthree hours, the interioi. of the apparatus becomes blackened, and a black substance is found suspended in the liquid. If this is filtered off, a cherry-red liquid is obtained, which has a remarkably strorig odour, and produces great irritation of the eyes. This liquid is allowed to stand for 6-6 days over metallic copper to remove free sulphur, and is then evaporated by means of a current of dry air. A deep red liquid IS thus left which has the composition of a tricarbon bisulphide, C,S,. It evaporates in the air very slowly, and its vapour has a most vigorous action on the mucous membrane, a very small trace causing violent catarrh.The sp. gr. of the liquid is 1.27389. When heated, it is converted into a hard, black mass of almost the same percentage composition, which is probably tt polymeride. When the liquid is rapidly heated to 100-120", this change takes place with explosire violence, but occurs gradually when it is gently warmed. The same substance is formed when the liquid is prcserved for a few weeks, and its formation is in all cases accompanied by the production of a little carbon bisulphide. The liquid can be distilled under diminished .pressure a t 60--70", but tivel y. J. w. W. T. Placed on the skin, it merely prodnccs a black spot.IKORGANIC CHEMISTRY.91 a portion of it is always converted iuto tlie solid modification. The liquid substance is insoluble in water, in which it sinks, but is readily soluble in alcohol, ether, chloroform, benzene, and carbon bisulphide. From a concentrated solution in the solvent last mentioned, tbe solid modification is deposited, but a dilute solution is more stable. I t burris with a luminous, smoky flame, carbonic and sulphurous anhj drides being formed. Aqueous potash and soda give almost black solutions, in which acids produce black precipitates, whilst alcoholic potash acts vigorously and yields a deep brown solution. A drop of con- centrated sulphuric acid causes violent hissing, and the whole mass is converted into the solid modification. Concentrated nitric acid causes ignition, whilst a more dilute acid dissolves the liquid, neither carbonic anhydride nor sulphuric acid being formed.The analyses of the liquid show rather less carbon, those of the solid rather more, than that required by the formula C,S,. A deter- mination of the molecular weight from the freezing point of the solution in benzene gave numbers which agree well with the formula. The solid modification is hard, has a fine, granular fracture, and is insoluble in water and all ordinary solvents. Aqueous potash dis- solves i t completely, and i t appears to be precipitated unaltered on the addition of an acid. When heated, it decomposes, with for- mation of sulphur, which sublimes, and a gas which contains sulphur, b u t is not carbon bisulphide, and is being further ipvestigated.When bromine is added to a solution of the liquid tricaybon disulphide in chloroform, heat is evolved, and a yellow precipitate produced ; this has the composition C3S2Br6, has an aromatic odour, and is insoluble, or oiily rerg slightly soluble, in all solvents. Under similar conditions, a yellow precipitate is produced with chlorine, but not with iodine. The author is investigating the structure of this bromide. A. H. Preparation of Metallic Lithium. By GUNTZ (Compt. rend., 117, 732-735) .-In the preparation of lithium, the yield is higher the lower the temperature a t which electrolysis takes place. Lithium chloride melts at 600°, a mixture of equal weights of lithium and potassium chlorides melts at about 450°, and a mixture of the two chlorides in molecular proportion at about 380" ; a mixture of 2 mols. of potassium chloride with 1 mol.of lithium chloride melts a t about 550°, and potassium chloride alone at 740". The best mixture for electrolysis contains equal weights of the two ohloridea, for then the melting point of the saline mixture falls as de- composition proceeds. The negative eIectrode should be a rod of carbon about 8 rnm. in diameter, and the positive electrode a rod of iron 3 to 4 mm. in diameter, surrounded by a glass tube about 20 mm. in diameter. A current of 20 volts and 90 amperes is nccessary, and the metal obtained contains from 1 to 2 per cent. of potassium. It would seem that when electrolysis takes place at a red heat, the lithium at the negative electrode combines with the lithium chloride to form a subchloride, Li2Cl, which has B higher resistance than the original chloride, and tbus reduces the intensity of the current. The92 ABSTRACTS OF CHEMICAL PAPERS.subchloi*ide diffuses through the liquid and combines with chlorine at the positive electrode. At 500", or below, it would seem that tbls formation of subcbloride does not take place. By TASSILLY (Bull. SOC. Chim., [3], 9, 629--630).-Cnlcium oxyiodide, Ca12,3Ca0 + 16 H20, has been ob- tained in needles, sometimes 2 cm. long, by heating quicklime with n concentrated solution of calcium iodide in a sealed tube at 150' for six hours. I t is also formed by the addition of quicklime in small por- tions to a boiling concentrated solution of calcium iodide, Long needles are obtained on cooling this solution, which cannot be freed from adhering lime.W. T. C. El. B. Calcium Oxyiodide. Double Salts of Potassium and Magnesium Sulphate : Schonite and Potassium Astrachanite. By J. K. VAN 1)ER HEIDE (Zeit. physikal. Chem., 12,416-430).--The author has already recorded the formatioil of potamium nstmchanite, MgSO4,K,SO4,4H,O, from a polution of schotiite, MgS04,K2SOd,6HZ0 (Abstr., 1893, ii, 276), and in order to obtain further data respecting the conditions under which it is produced, has now examined the behaviour of the sulphates of potassium and magnesium towards one anofher in solution at all possible terrrperatures. The following are the principal facts result- ing from this investigation. 1. Temperature, -4.5". Formation from ice and the two sulphates of the saturated solntion of the latter.2. Temperature, -3". Formation of schiinite from the two sulphntes 3. Temperature, 47.2". MgSOa,7H20, cbanges in the presence of schonite into MgS04,GH20. 4. Temperature, 72". Potassium astrachanite is formed from schonite in the presence of MgSOd,6HZ0. 5. Temperature, 92". Potassium astrachanite is formed from schonite i n the presence of K,S04. 6a. Temperature, 102". Boiliug point of tbe saturated solution of potassium astrachauite and snlphate. 66. Temperature, 103". Boiling point of the saturated solution of potawium astrac hani te and MgS04,6H20. 7. Temperature, 106". Formation of kieserite in the presence of potassium astrachanite. H. C. Modifications of Silver. By H. L~~DTKE (Ann. Phys.Chem., [2], 50, 678-695) .-The silver of deposited silver mirrors has properties different from those of ordinary silver, and the author has investi- gated these electrically with the following results. Lehmann's assumption that a thin layer of sodium silicate on all glass surfaces has something to do electrolytically with the deposition of silver, must be incorrect, for silver mirrors may be deposited on mica, porcelain, quartz, Iceland spar, platinum, &c. The electrical resistance of several sorts of silver mirrors decreases considerably as time elapses. There is no such decrease in the cabe of mirrors reduced by milk sugar or by Martin's method.Ih'OROANIO CHEMISTRY. 93 The allotropic mirror silver may easily be converted into ordinary silver by heat, light, chemical reagents, &c. The mirror silver and other allotropic preparations show an initial difference of potential of about 0.1 volt against ordinary silver in dilute acids, the allotropic modification being the positive pole.The difference is smaller in silver nitrate solution, and the ordinary silver is then the positive pole. All the properties of mirror silver indicate that in its original modification it is identical with solid colloidal silver. The black silver sponge obtained by reducing silver nitrate solution with zinc passes into a grey modification on contact with acids. This transformation is accompanied by an increase in the electric con- ductivity. J. W. Method of Formation of Silver Nitride. By A. AEGRLI (Gazzetfn, 23, ii, 292--294).-On adding a saturated hydrazine sulph- ate solution to a cold saturated solution of silver nitrite, the liquid immediately becomes turbid, and silver nitride separates in white needles.The reaction probably proceeds in accordance with the ful- lowing equatioiis. NH2.NH, + HRO, = NH2*N:N*OH + HzO. NH2*N:N*OH = NsH + H20. This simple method of preparing the salt forms a very striking Preparation of Cuprous Oxide. By E. J. RUSSELL (Chem. News, 68, 308).--P, fairly concentrated solution of copper snlphate along with excem of sodium chloride is thoroughly reduced by treatment with gaseous sulphurous anhydride, the excess of the latter is then expelled by heating, and solid sodium carbonate is added to the hot solution ; bright red cuprous oxide is precipitated and is readily washed by decantation.Stability of Dilute Solutions of Mercuric Chloride. By 1,. VIGNON (Compt. rend., 117, 793-795) .-Aqueous solutions containing 0.1 per cent. of mercuric chloride gradually deposit a white precipi- tate if exposed to the air, but remain practically unchanged for many days in well closed Tessels. In presence of magenta or indigo- carmine the quantity of precipitate formed in a given time is reduced, and in this respect indigo-carmine is a better preservative than magenta. In presence of 0.1 per cent. of hydrochloric acid of 22", or of 1 per cent. of sodium, ammonium, or potassium chloride, the solu- tion remains practically unchanged for a much longer time. Stability of Mercuric Chloride Solutions. By TANRET (Comyt. rend., 117, 1081--1082).-The formation of a white precipi- tate in dilute solutions of mercuric chloride (preceding abstractj is due to the presence of ammonia in the atmosphere, and does not take place with pure air even when large quantities of the latter are passed through the liquid, lecture experiment, and may be very rapidly performed.W. J. P. D. A. L. C . H. B. C. H. B. TOL. LXVI. ii. 994 ABSTRACTS OF OHEMICAL PAPERS. Action of Mercurous Chloride on Silver Chloride in presence of Ammonia. By U. ANTONY and G. TURI (Gazzetta, 23, ii, 231- 237) .-Pesci (Abstr., 1892, 685) has shown that the black precipitate obtained by treating mercurous chloride with ammonia contains metallic mercury ; this observation explains the well-known fact that, on adding ammonia to the white precipitate obtained with hydro- chloric acid in a mixed Rolution of silver and mercurous salts, silver is retained in the black precipitate. If the precipitate remains long in contact with ammonia, the reaction represented by the following equation may occur :- 4HgCl + 4AgCl + 8NH3 = 2(NHg2Cl,NH,Cl) + 4Ag + 4NH4C1.On repeatedly washing the mixture of silver chloride and mercurous chloride with ammonia solution on a filter, a residue was ultimately obtained which contained 1.16 per cent. of silver, instead of 30 per cent. as indicated by the above equation. When, however, the mixed chlorides precipitated from a solution containing excess of silver salt were digested with ammonia for some time, the resulting precipitate was found to contain the quantity of silver indicated by the equation.During a qualitative analysis, therefore, if silver is not found in the filtrate from this black Itrecipitate, the latter should be examined for the metal. W. J. P. Sublimation of Red and Yellow Mercuric Iodides. By BERTHELOT (Cornpt. r e d , 117, 827--828).-The author confirms Frankenheim’s statement that when s mixture of red and yellow mercuric iodides is carefully heated on a glass plate and allowed to condense on another plate held at a short distance above it, the sub- limate is a mixture of the red and yellow iodides. The result, how- ever, cannot be regarded as proof of the existence of the red iodide in the state of vapour. There is little doubt that solid particles of the red iodide are mechanically projected from the lower plate to the upper, and bring about the immediate conversion of the yellow iodide that condenses in contact with them.C. H. B. Action of Water on Glass. By F. KOHLRAUSCH (Ber., 26, 2998-3003) .-Analyses have been made of the substances extracted by water at ordinary temperatures from finely powdered glass of vnrious kinds. A comparison of the soluble portion with the original glass shows that, in the former, the relative quantity of alkali increases and that of the silica diminishes ; in one case, the solution contained three times 8,s much alkali and half as much silica as the original glass, which was rich in alkali. With Bohemian potash glass (rich in silica), the discrepancy was less. Both of these glasses are largely employed in the manufacture of chemical apparatus. At present, it is impossible to decide whether the solution of the alkali precedes and causes that of the silica, but the author’s experiments show that practically they dissolve simultaneously.A sample of Jens “ apparatus ” glass and two of a glass free from alkali were examined in a similar manner, and, aEter two months’ treatment with water, the solutions contained 72,.85, and 57 milli-INORGANIC CHEMISTRY. 95 prams per litre respectively. A flask of the Jena glass, after two days at ordinary temporatures, lost 0.005 milligram, after 200 days 0.066 milligram, after 24 hours at 94', 0.8 milligram per sy. dm. Experiments were also conducted to show the relative insulating power of different sorts of glass under varying conditions of atmo- spheric moisture ; glass of poor quality conducts after exposure for a few seconds in presence of 40-50 per cent.of moisture, whilst the glass free from alkali insulates well in presence of 80 per cent. The composition of the alkali-free glass, in equivalents per cent., is as follows:-BaO = 12, Zn0 = 3 - 7 4 . 6 , A1203 = 3-3-3.7, B,O, = 13-15, Si02 = 65-68. J. B. T. Nitro-metals. By P. SABATIER and J. B. SENDERENS (BUZZ. SOC. Chim., [3], 9, 669-674 ; compare Abstr., 1892, 1390 ; 1893, ii, 374). --Nitro-cobalt.-This substance ia best prepared from cobalt reduced at a low temperature. Nitrogen peroxide, suitably diluted with nitrogen, is passed over the reduced metal in the reduction tube, when black nitro-cobalt, Co2N02, is formed. Water acts on nitro- cobalt very vigorously, but gives less nitric oxide than with nitro- copper.A solution of cobalt nitrate containing very little nitrite is produced, with, sometimes, a precipitate of bluish-green, insoluble basic nitrite mixed with cobalt. Heatad in a current of nitrogen, nitrous fumes are first evolved, and then decomposition takes place with almost explosive violence, a residue of metallic cobalt and oxide being formed. Nitro-cobalt explodes when mixed with combustible matter. Nitro-)zickeZ.-This compound resembles the cobalt compound in method of formation and properties; it has always been obtained mixed with oxide. It appears to give no special reaction with carb- onic oxide. Nitro iron.-This substance is much more difficult to prepare. Some nitric peroxide is first absorbed, and then deflagration takes place, even in a much diluted atmosphere of nitric peroxide.Chromium Sulphates and Double Sulphates. By T. KLOBB (BdZ. SOC. Chim., [3J, 9, 663-668).-The double sulphate, CrZ( S04)3,3(NH4)2S04, has been prepared by adding chromic oxide to a large excess of ammonium sulphate kept in it state of quiet fusion. I n this case, a clear, green, crystalline powder is obtained, whilst if violet ammonium chromium alum is substituted for the oxide, a pul- ~erulent powder is obtained not so readily washed. It forms needles, 0.05 mm. long, and short, spindles. The crystals are but slightly attacked by boiling water, not acted on by a concentrated solution of ammonium sulphate, and completely decomposed by boiling potash. Boiling concentrated wlphuric acid gives Traube's red sulphate. The salt is not decomposed by heating at 350" on a lead bath, but takes a transient violet colour.By calcination, it yields a very adherent, light oxide. The double sulphate, Cr2(S04)3,(NH4)2S04, is formed if the preced- ing preparation be heated so far as to volatilise most of the ammonium snlphate. I t forms tabular, hexagonal crystals, which are more stable W. T. 9-296 ABSTRACTS OF CHEMJCAL PAPERS. than the needles described above, as they are not attacked by boiling water or concentrated hydrochloric acid ; boiling pot,ash (sp. gr. 1.8) acts on them but very slowly. Heat and concentrated sulphuric acid have the same action as on the needles. These double sulphates correspond with the ferric ammonium sulphates obtained by Lachand and Lepierre.They may be viewed as derivatives of Recoura's chromosulphuric acid, HZCr,(SO4),, and chromotrisulphuric acid, H2Cr2(S01)6 (Abstr., 1893, ii, 470). Attempts to prepare the corresponding potassium and sodium tialts failed, as the chroinosulphates could not be obtained free from am- monia ; potassium chi-omotrisulphate is obtained by fusing potassium chromium alum with excess of ammonium sulphate and potassium Saul p h ate . The red sulphate of chromium, referred to above, prepared in three different wajs, has the forniula Cr,(SO,),, and is, therefore, a normal salt. It is a powder, rose-coloured in daylight,, but appears green by gas-light. W. T. Complex Acids derived from Molybdic acid and Titanic and Zirconic acids. By E. P~CHARD (Compt.r e d , 117, i88-790).- When hydrofluosilicic wid is added to a warm solution of ordinary animonium molybdate, the latter becomes yellow, and, on cooling, deposits a crystalline precipitate, if the solution is not too dilute. If hydrochloric acid is added to a dilute solution even, there is an immediate precipitation of the silicomolybdate, 2 (NX,)20,Si02,1~~~o0,, described by Parmentier. Part of the molybdate is converted, at, the same time, into oxyfluormolpbdate. Ammonium silicofluoride can be substituted for hydrofluosilicic acid, and a precisely similar method yields titanomolybdates and zircono- moly b d n t es. Ammonium titunonzolybdate, 2 ( ~ ~ ~ ) , 0 , T i O Z , l 2 n i ~ c , 0 , + 10HzO, is obtained by adding ammonium titanofluoride solution to ammonium molybdate solution until the intensity of the yellow colour no longer increases, and then adding hydrochloric acid.It is completely insoluble in solutions of ammonium salts, but dissolves in water and in acids, and crystallises in small, yellow octahedra, which act strongly on polarised light. Potassium titunomolybdate, 2Kz0,Ti0z,12M003 + 16Hz0, is an efflorescent salt, obtained in yellow priams by adding potassium chloride to a hot concentrated solution of the preceding compound and allowing the liquid to cool. TitanomoZylbdic acid, Ti0,,12M00,,22Hz0, crystallises in golden- yellow octahedra, melting a t about GO", and very soluble in water. It is obtained by adding hydrochloric acid to mercurous titanomolyb- date, which is prepared from one of the p.receding salts by double decomposition.A more rapid method is to agitate with ether an aqueous solution of the ammonium salt acidified with hydrochloric acid and allow the heavy ethereal solution to evaporate spontaneously. Zirconomolybdates are obtained in a similar way and are strictlyINORGANIC CHEMISTRY. 97 analogous in composition. The ammonium salt crystdlises with 1OH,O in yellow octahedra, and the potassium salt with 18H,O in efflorescent, yellow prisms. C. H. B. Action of some Metals on Acid Solutions of their Chlorides. Ry A. DITTE and R. METZNER (Conzpt. Tend., 117, 691--694).-When a b a r of tin is placed in a vessel containing a concentrated solution of stannous chloride in hydrochloric acid, on the top of which i s a layer of water, crystals of tin rapidly form on the bar in the neighbourhood of the surface of separation of the two liquids.The system, as thus arranged, clearly consists of two identical electrodes immersed in two different liquids, and the two sources of electromotive force are the action of the acid on the tin and the diffusion of the acid into the supernatant water. If a bar of tin is placed simply in a hydrochloric acid solution of stannous chloride, no crystals are formed ; i f a thin layer of water is poured on the solution, it mixes with the subjrtcefit liquid and becomes a conductor; if the layer of water is deep, it has its highest conductivity at the surface of separation, and the conduc- tivity decreases gradually in a vertical direction as the upper surface of the water is approached.and, since the current traversing succes- sive layers of the liquid diminishes in a similar manner, the size of the tin crystals shows corresponding variations, the deposit changing from well-defined crystals to a spongy, grey mass, and, finally, in the highest layers, to a very finely divided black powder. Above the surface of separation, the bar of tin merely plays the part of the negative electrode, and can be replaced by any other con- ductor without any alteration in the phenomena. I f , on the other hand, the metal rod or bar consists of two parts separated by some insulating material, and the latter lies on the surface of separation, no formation of crystals takes place until, by the progress of diffusion, the upper and lower parts of the rod are put into conlmunication by two conducting liquids of different composition.The formation of the crystals is dependent on the action of the hydrochloric acid on the t i n ; no similar effect is produced by a solution of stannous chloride containing no free acid. It is also dependent on the energy developed by the diffusion of the acid into tlhe supernatant water, neither cause alone being sufficient to electrolyse the stannous chloride. Similar phenomena are observed with cadmium chloride and cad- mium, the metal beisg attmked with difficulty by very dilute hydro- chloric acid, but zinc, which is easily attacked by the dilute acid, does not give similar results. Nickel gives negative results, probably because the snrface of the metal becomes polarised, and antimony and bismuth give negative results because they are not attacked by hydrochloric acid. C. H. B. Solidification of Dilute Solutions of Antimony in Tin. By F. W, RUSTER (Zeit. physikaZ. Chem., 12, 508--5i3).-Hegcock and Neville (Trans.,. 1890, 376) were the first to point out that the solidi- fying points of dilute solutions of antimony in tin are hither than that of piire tin, a result which they explain by assuming the forma., ban of solid solutions in these cases. The author shows that this is98 ABSTRACITS OF OHEMlOAL PAPERS. most probably an instance of isdmorphous mixture similar to those' which he has himself investigated (Abstr., 1890, 1209). Action of Water on Disodium Platinum Thioplatinate. New, Thioplatinum Salts. By R. SCHNEIDER (J.pr. Chew., [Z], 48, 411-1 424 ; compare Abstr., 1892, 944).-When disodium platinum thio- platinate, 2Na2S,2PtS,PtS2 (Artnalen, 138, 618) i8 heated with water, with exclusion of air, a deep-red solution and an insoluble residue are obtained. The solution contains sodium thiop latinosate, NhPtS,, which, however, is speedily decomposed in accordance with the equation 3Na2PtS2 + 4H20 = 2H,PtS2,Na2PtS2 + 4NaHO. The insoluble residue consists of the salt sodium platinum thioplatinate, NhS, PtS,2PtS2, a, micracrys tal line, kennes- brown powder, which is decomposed by air with the formation of sodium carbonate and plati- num bisulphide, and by hydrochloric acid with liberation of t.he corre- sponding acid, H2S,PtS,2PtS2. H. C. A. G. B.

ISSN:0368-1769    

DOI:10.1039/CA8946605088

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

98 ABSTRAOTS OF CHEMlOAL PAPERS. Mineralogical Chemistry. Native Copper from Yunnan (China). By W. GOWLAND (Chem. News, 68, 307).-A specimen of. remarkably tough native copper, consisting of a flat, nodular nucleu8, without ~ryst~allirie structure, and weighing 208.6 grams, but encircled by incrusting layers of cuprite and green copper carbonates weighing 89.5 grams, wa8 obtained from an outcrop in the province of Punnan, China. The metal was found to be free from gold, lead, arsenic, antimony, bismuth, nickel, and cobalt, but to contain 0.028 per cent. of iron and 0.026 per cent. of silver; it being purer than the electrolytic copper at the author's disposal, a direct determination of copper was not made, but by difference the percentage of' copper was found to be 99.946 ; it therefore surpasses in purity many specimens of native copper hitherto examined, and in fact may be classed with the Lake Superior and Chilian specimens. Nickel Arsenide.By E. WALLER and A. J,, MOSES (Juhrb. f. Min., 1894, i, Ref. 17, from School of Mines Quart., 14, 49--51).-Tlle ore from a mine 18 miles from Silver City, New Mexico, consists of dendritic native silver, enclosed in a grey, brittle arsenide, which is found in a matrix of spatbic iron ore. The hardness of the nickel compound is 5, its streak black, and its str-nctnre granular. Analysis gave results which, on the assumption that silica and silver were present as impurities, were as follows :- AS. Ni. co. Fe. 78.67 12.25 6.16 2-92 These resnlta correspond with those demanded by the formula for D. A.L.MXh’ERALOQlCAL CHEMISTRY. 99 skutterudite, in which cobalt is replaced by nickel and iron. The authors, therefore, propose the name of ntckel-skutterudite for this mineral. B. H. B. NaturaI Oxides of Manganese. By A. GORGEU (BUZZ. SOC. Chinz., [ 3 3, 9, 650-661) .--Manganites.-Four well-crystallised samples of manganite from Ilefeld (Hartz) gave analyses as follows :- SiO,. Fe,O,,AkO3. BaO. Pb0,CnO. CaO. K20,Na20. I. 0.25 0-35 0.15 0.10 0.10 030 ‘TI. 0.45 0.25 0-30 0.10 0.20 0.20 111. 0.15 0.30 - 0.10 trace 0.15 IV. 0-05 0.25 0.05 0.15 0.23 MnO. 0 in exceaa, H20. Total. I. 79.M 9.25 10.40 200.30 11. 79.35 9.40 10.10 100.35 111. 79.90 9.15 10.45 100.20 IV. 80-05 10.15 9.40 100.35 I1 has sp. gr. 4-34!, hardness 3.5; 111 has sp. gr. 4.39, hard- ness 3.5.The percentages of water, and of oxygen in excess of that required to form MnO agree with the formula, Mn02,DIn0,H,0, excepting sample IV which appears to have begun to pass into pseudomorphiu pyrolusite. The mineral is represented as manganous hydrogen manganite, because concentrated boiling nitric acid dissolves half the manganese on repeated treatment of the very finely powdered mineral. Huusmannites.-Three samples from Ilmenau were examined ; they each gave a red streak and appeared to be free from other oxides of manganese. The most noteworthy point is the presence of zinc oxide, not hitherto noticed excepting in the silicates, although the author has found 1-2 per cent. in diallogite form Dietz. The outer friable portion of sample I contained 8.30 per cent.of zinc oxide. Analyses gave :- SiOP PP05. SO,. CO,. Fe203,A1203. CaO. MgO. K,O,N%O. I. 0.30 trace trace trace 0.30 0.10 - 0.40 11. 1-45 0.05 0.10 0.15 0-70 0.55 0.45 0.20 111. 0.13 - - I 0.20 trace k y - - J ZnO. MnO. 0. H20. Total. I . 8.60 83.40 7.05 0.05 10020 11. 1.00 88.10 6.65 trace 99.40 111. 7-20 85.40 7.03 0.16 100.12 IT: has sp. gr. 4 77 ; 111 haA sp. gr. 491, hardnesR 4.5-5. Allowing for the oxide of zinc, concentrated nitric acid extracts two-thirds of the manganese; hence the formula of the mineral is Mn02,2R0, where R represents Mn partly replaced by Zn.100 ABSTRACTS OF OBEMIOAL PAPERS. l3raunites.-Two well-crystallised specimens of braunite were an&- !ysed :-I from Saint-Marcel (Piedmont), hardness 6-6.5 ; sp. gr. 4.76 ; and I1 from Schwnrzenburg, hardness 6.0 ; sp.gr. 4.83. No. I is the only oxide examined in which cobalt occurs. Gangue. SO,. MnO. 0. Fe,O,. CaO. Pb0,CuO. COO. I. 2.80 9.40 74.68 7-50 3.80 0.50 0.15 0.30 11. 0.60 8.15 80.40 8.35 0.30 1.20 0.85 - MgO. E20,Na20. BaO. P205. HnO. Total. L-----d I. 1-00 trace 0.05 0.20 100.30 IJ. trace 0.20 0.20 0.20 99-65 These analyses indicate the formula (XnSi)02R0 for braunite, where SiO, partly replaces MnO, and 11 is chiefly manganese. Boil- i n g dilute solutions of soda or potash have very little action on finely powdered braunite ; hence silica is not present in tho free state. As the mineral is completely decomposed by hydrochloric acid, rhodonite CSi02,MnO) is not present. Dilute nitric acid (1 : 9) has hardly any action on the Saint-Marcel braunites ; hence tephroite ( SiOZ,2MnO) is absent.Rammelsberg’s formula, SiOP,Mn02 + 2(Mn02,2MnO), does not correspond with the above analyses. The gangue has been deposited later than the main snbstance in each of the minerals examined, for the crystals show no evidence of penetration by the gangue, whereas the gangue surface corresponds with the projecting angles of the mineral crystals. W. T. Heintzite. By 0. I;~?DECKE (Jahrb. f. Mia., 1894, i, Ref. 19; from Zeitschr. f. Natww., 1892, 1-8).-The author admits that his hciutzite from the pinnoite of Stnssfurt (Abstr., 1891, 528), Feit’s microcrystalline kaliborite from Schmidtmannsball (Abstr., 1892, 791), and Milch’s hintze’ite (Abstr., 1891,528) do not differ from one another. The composition of the three is 2KzB,0,, + 9MgB4O7 + 39H20.Crystallographical measurements support this view. The name of heintzite has priority. By J. LEMZERG Jahrb. f. Mirn., 1894, Ref. 7 ; from Zeit. de?ctsch. geol. Ges., 1892, 224- 242) .-The author describes various microcliemical tests for dis- tinguishing scapolite, hauyn, eudialyte, chabmite, and other minerals. Cordierite in an ‘Eruptive Rock of South Africa. By G. A. F. MOLENGHAAFF (Jahrb. f. Mir., 1894, i, Mem. 79--91).-The rock described wm obtained from the Cornelis River, near Harrismith, in the Orange Free State. It resembles most closely a diabase, and apparently forms a dyke in the Stormberg beds. Under the micro- scope, it is seen to be composed of glass in which crystals of spinel, cordierite, and augite occur. Analysis of the rock gare the following results. B.H. B. Microchemical Investigation of Minerals. B. H. B.MINERALOGICAL CHEMISTRT. 101 SiO:. Ti02. Al,03. Fe,OB. MgO. CaO. N%O. KsO, 64.54 0.79 19.16 7-23 3-39 2.47 0.57 1-13 These results correspond with those given by Osann for the cordierite-bearing mica andesite of Hoyazo. The South African rock increases the far from numerous examples of the occurrence of cordierite in eruptive rocks. Melanite from Missouri. By E. HAWORTH (Zeit. Kryst. X n . , 22, 428 ; from Proc. Kansas Acad. Sci.).-Melanite occurs in brownish- black crystah in cavities produced by solfataric action on a basic vein rock on the eastern fork of the Black River, Reynolds Co. The rock consists of triclinic felspar arid green fibrous hornblende in a vitreous ground mass.SiO,. MnO. Fe203. Al2O,. CaO. MgO. Total. 35-88 0.20 29.35 5.53 30.71 0-63 100.30 B. H. B. Analysis of the melanite gave Its sp. gr. is 3.6. This is the first recorded occurrence of garnet in Missouri. B. H. B. Iron Ore Deposit in North Sweden. By W. PETERSSON and H. SJOGREN (.Jahrb. f. %in., 1894, i, Ref. 88-89; from Geol. FCren. FGrh., 15, 45-63, 140--143).-The deposit described, known as the Eoutivare Iron Uountrtin, is Rituated about 9 miles from Quickjokk, in the Swedish province of Norrbotten. The ore (Analysis Ij consists of titaniferous magnetite associated with green spinel, olivine, and talc. The rock (Analysis 11) i n which it occurs is R highly altered gabbro. SiOp TiO,. Also3. Cr203. Fe,OR. FeO. MnO. MgO. CaO. I. 4 0s 14.25 6.40 0.20 33 43 34.58 0-45 3.89 0’65 11.47.37 0.25 23-22? 0.39 - 6-42 0.28 8.67 6-86 KsO. Na20. HzO. Pz05. I. 0.15 0.29 1.32 0.016 11. 0.63 3-25 3-25 - The mineralogical constituents of the ore are as follows. (1) Titaniferous magnetite, the main component ; (2) ilmenite ; (3) spinel; (4) olivine; (5) pyroxene; (6) chlorite; and (7), as rtcces- sory constituents, magnetic pyrites and apatite. Diabase from Rio de Janeiro. By E. 0. HOTEY (Juhrb. f. Min., 1894, i, Ref. 80-81 ; from Mia. petr. Mitth., 13, 211-221).--In the vicinity of Rio de Janeiro, numerous veins of diabase occur, whose width varies from a few inches up to 20 yards. The structure and character of these veins vary according to the thickness from the gabbro structure, with holocrystalline development in the widest, through the ophitic to porphyritic texture and hypocrystalline development in the narrowest.The author gives the results of analyses of the two extreme varieties. Augite occurs in two forms, namely, ordinary diabase-augite and augite resembling salite. 4 corn- B. H. B.102 ABSTRAOTS OF CHEMICAL PAPERS. parison of true salite from Sala, in Sweden, proves, however, that the salite-like augite of the diabase of Rio de Janeiro, New Haven, New Jersey, and Cape Blomedon is not salite. B. H. B. Sulphuretted Water from Alexeiewsk. By N. SAVTZEFF (J. pr. Chem., 49, 518--521).-Alexeiewsk is about 20 versts from Samara and 5 to 6 from Schmischlaewka. The mineral water is clear and colourless, and has a strong odour of hydrogen sulphide, a faintly saline taste, and a faintly acid reaction. On exposure to air, it becomes milky, through separation of sulphur, accompanied by a flocculent, black precipitate. The temperature of the spring is 9.3". The water contains in 10,000 parts K2SO,. Na&104. Na2S203. CaSO,. CaC03. MgSO,. MgC12. 0,1536 1.13otL 0.1036 135843 2.7287 1.7'706 0.2550 0.1387 0*1083 0.1354 Water and Sea-bottom Deposits from the Eastern Mediter- ranean. By K. N a T T E m s (Monatsh., 14, 6'24-673; compare Abstr., 1893, ii, 216).-The auther gives details of analyses of water and sea-bottom deposits, examined during the voyage of the ship '' Pola " in the Eastern Mediterranean during 1893. The sp. gr. is 1.00141 at 14". Si02. Fez&. SH2. E. C. R. G. T. M.

ISSN:0368-1769    

DOI:10.1039/CA8946605098

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

101 0 rg a n i c C h e m i s t r y. Dinitromethane. By P. DUDEN (Ber., 26, 3003--3011).-Di- szitromethaw, CHz(NOz)z, is obtained as potassium derivative by the action of dibromodinitromet hane on arsenious anhydride, potash, and water at low temperatures ; after remaining for some time, the reaction is completed by heating in a reflux apparatus; the product is then suspended in water and ether and decomposed by dilute sulphuric acid ; on evaporating the ethereal solution a t a low temperature, the dinitro- compound remains as a yellow oil, having a characteristic acid odour. It rapidly decomposes at ordinary temperatures, even in a, sealed tube, and does not solidify at -15" ; in ethereal or benzene solntion, it is stable, and is volatile with benzene vapour, and also with steam.By the action of bromine water on dinitromethane, the dibromo- derivative is regenerated ; with hydroxides, carbonates, sulphites, and nitrites, metallic derivatives are formed, carbonic anhydride, sulphurous anhydride, and nitrous acid being liberated. The potas- sium derivative, CH(NO&K, crystallises from water in pale yellow, monoclinic cryslals ; the aqueous solution is neutral ; by the action of concentrated or dilute acids a t ordinary temperatures, decomposi- tion takes place, with evolution of nitrous fumes ; on heating it to about 205", potassium carbonate, water, carbonic anhydride, nitric oxide, and nitrogen are formed. Villiers' statement that it is unstable is incorrect ; when pure, it undergoes no change on exposure to air ; in a closed vessel, a slight, superficial decomposition takes place.The ammonium derivative crystallises from alcohol-ether in slender, pale yellow needles, which explode at about 105". The phenylhydr- azine compound forms intensely yellow needles, and melts at 101" with decomposition. The copper derivative is pale green, and readily de- composes in aqueous solution. The barium derivative, (CHNz04),Ba + 2H,O, crystallises in pale yellow needles ; on heating, it becomes anhydrous and darkens, and finally explodes. The silver derivative, CH(NOz)&, crystallises in lustrous, yellowish-green plates, and de- composes rapidly on exposure to light, on boiling with water, or on heating to 135". Dinitroethane and dinitropropane are formed by the action of methylic iodide and ethylic iodide respectively on the silver derivative at ordinary temperatures.By the action of nitrous acid on potassium dinitromethane, isonitrosodinitromethane, NOKC (NO&. ap- pears to be formed; it is extremely unstable, dissolves in ether with a blood-red colonr, and forms a sodium and a silver derivative, neither of which could be completely freed from nitrite. Ammonia is elimin- ated by the reduction of dinitromethane in acid solution, but, on treatment with sodium amalgam at 0", methylazaurolic acid, CH2N20, is formed. Potassium dinitromethane and diazobenzene hydrochloride in glacial acetic acid solution yield a compound which has the formnb C(NOz)z(NPzh)2, and crystallises in orange-red needles, melting a t 75" with decomposition; it is readily soluble, and decomposes on boiling, or by the action of alkalis.J. B. T. VOL. LXVI. i. i102 ABSTRAOTS OF CHEMICAL PAPERS. Synthesis of Nitroparaffins. By I. BEVAD (J. pr. Chem., [2], 48, 345-383 ; compare Abstr., 1893, i, 242, 382j.-The zinc alkylides react with the halogen- nitro-derivatives of the hydrocarbons dis- placing the halogen atom (1) by an alkyl group, (2) by hydrogen, and (3) by both alkyl group and hydrogen. The first reaction produces secondary and tertiary nitro-compounds more complex than those treated (see Abstr., 1893, i, 242) ; the second results in the formation of the same primary or secondary nitro-compound, whose halogen derivative was treated; whilst the third only occurs with those compounds which contain not fewer than 2 halogen atoms, and produces primary and secondary nitro-compounds more complex than those treated.A. G. B. Action of Reducing Agents on Potassium Nickelocyanide, By T. MOORE (Chem. News, 68, 295).-The author has investigated the nature of the red coloration produced when a strip of zinc is immersed in a solution of potassium nickelocyanide containing am- monium chloride and ammonia; the colour is very fugitive, and oxygen and zinc compounds aid its destruction. By treating the nickelocy~nide with sodium a,malgau in an atmosphere of hydrogen, a deep red solution is readily obtained, which gives, amongst others, the following reactions :-With silver nitrate, a heavy, black precipi- tate of metallic silver ; with mercuric chloride, a grey precipitate ; with lead acetate, a black precipitate, insoluble in potassium hydr- oxide or acetic acid, decomposed on drying, leaving yellow lead oxide ; with bismuth nitrate, a black precipitate ; with arsenious anhydride, a deep brown precipitate; gold chloride is slowly reduced.The solution is, moreover, decolorised by permanganate, dichromate, hydrogen peroxide, &c. When acidified, it yields an orange-yellow, flocculent precipitate, which, after filtration and washing with cold water, dissolves in alkalis to a red solution ; the precipitate darkens and becomes dirty blue i n the air, and decomposes completely on drying, even in hydrogen, yielding apparently a mixture of nickel oxide and cyanide. 9’he instability of the substance has, so far, pre- vented its being submitted to analysis, but experiments indicate that the red solution absorbs 2 atoms of oxygen for every 3 atoms of nickel present.D. A. L. Oxidation of Potassium Cobaltocyanide. By T. MOORE (Chem. News, 68, 295-296).-The equation 2K4COCy, + 2H,O + 0 = K&,O,Cy, + 2KHO + H,O bas been regarded as representing t h e conversion of pot>assium cobaltocyanide into the cobalticyanide in the presence of free hydrocyanic acid and with access of air. On adding a mixture of sodium hydroxide and potassium cyanide to a solution of cobalt and agitating with air until absorption ceases, the author finds that the liquid becomes deep red-brown, and that oxygen is taken up in quantities varying between 8000 to 9600 C.C. per 59 grams of cobalt, instead of 5600 C.C. as required by theory. I n similar experi- ments, with the sodium hydroxide omitted and the liquid strongly acidi tied instead, the solution became yellow, and oxygen was absorbed t o the extent of 7450 to 7516 C.C.per 59 grams of cobalt. As no bye- prodncta were observed, and as these oxidised solutions evolve oxygenORBANIU CHEMISTRY. 103 on boiling, it is suggested that there are higher cobalticyanides than the one indicated above. D. A. L. Rate of Etherification of Hydrogen Fluoride. By M. MESLANR (Compt. rend., 117, 853--856).-The action of hydrogen fluoride on alcohol at about 200" (Abstr., 1893, i, 186) is at first rapid, but after four hours becomes slower, and attains its maximum in 10 hours. The temperature exerts great influence on the rate of change; at 170" tbe velocity of etherification is 10 times as great, and a t 190" it is 20 times as great, as at 140".When the alcohol is in excess, no methylic fluoride is formed, snd the sole product is ordinary ether. An excess of hydrogen fluoride, on the other hand, greatly accelerates the change, and the velocity of etherification is 60 times as great with a mixture of 4 mols. of the acid and 1 mol. of alcohol as it is with a mixture in equivalent pro- portions. Thermal disturbances indicate the existence of stable alcoholstes of hydrogen fluoride, and i t would seem that when the alcohol is i n excess, a part combines with the hydrogen fluoride to form stable alcoholates, whilst the remainder acts on the ethylic fluoride that is formed, and produces ordinary ether, whereas, when the hydrogen fluoride is in sufficient excess, no alcohol remains uncombined, and the secondary reaction does not take place.No ether is formed when 4 mols. of the acid are mixed with 1 mol. of alcohol, and with lower proportions of the acid the apparent velocity of etherifica- tion is the difference between the real velocity and the velocity of the secondary reaction. The' presence of water greatly reduces the rate OE etherification, but some change takes place at 220", even when 2 mols. of water are present for each mol. of hydrogen fluoride. Electrolytic Oxidation of Glycerol. By W. E. STONE and H. N. MCCOY (Anzer. CI~ern. J., 15, 656--660).-A current of less than 0.3 ampere from one or two dichromate cells was passed between platinum electrodes placed in 10 per cent. aqueous glycerol, in which various inorganic substances were dissolved to lessen the resistance.With dilute sulphuric acid o r sodium nitrate (0.1 per cent.), the temperature rose, and the liquid, which in the latter case soon became acid, acquired the power of reducing alkaline copper tartrate in the cold, and yielded the rosaniline reaction for aldehydes ; glycerose- aldehyde was, therefore, probably formed, and subsequently polymer- ised into glycerose. In the first case, an odour of acraldehyde was ultimately noticeable, With a small quantity of sodium hydroxide, a yellow or yellowish- brown colour was first produced, probably due to the presence of a hexose, and after some hours the solution became acid in reaction ; the acid in one case corresponding with as much as 80 per cent.of that theoretically producible from the glycerol. The solution reduced alkaline copper tartrate in the cold, and further, on boiling, showing the ptesence of a hexose. When, the alkalinity of the solution was maintained, and the C. €1. B. No odour of acraldehyde was perceptible. i 2104 ABSTRACTS OF CHEMICAL PAPERS. current passed €or several days, the power of reducing alkaline copper tartrate in the cold was at length lost, although, on boiling, a much more powerful reduction was obtained. The presence of a hexose was coufirmed by the preparation of its osazone, which melted at 200" (m. p. d-glucosazone, 204-205"), and by its resolution into carbonic anhydride by fermentation with yeast. An unsuccessful attempt was made t o prepare the optically active modification of glyceric acid from one and the same portion of the inactive acid.JN. W. Acetyl and Bensoyl Derivatives of Pentoses. By W. E. STONE (Amer. Chem. J., 15, 653-656) .-Tetracety Zxy lose, C5H6O6Ac4, is prepared by heating xylose with acetic anhydride and fused sodium acetate. It crystallises in fine needles, melts without de- composition at 123*5-124.5", and has a bitter taste. The specific rotatory power in anhydrous alcoholic solution is [ a ] D = --25.43", without multirotation. It is resolved by acid hydrolysis into its proximate constituents. It forms a thick syrup which solidifies when immersed in a mixture of solid carbonic anhydride and ether, and afterwards melts at -7.6". The specific rotatory power in anhydrous alcoholic solution is [a], = +26*39'.Its taste and its behaviour towards acid hydrolytic agents resemble that of its isomeride. Attempts to prepare the corresponding benzoyl derivatives yielded crystalline substances having constant melting points (1 64-165" and 68-69"), but compositions agreeing with those of no single derivative ; they are probably mixtures. Constitution of Glucose and the Glucosides. By L. MARCH- LEWSKI (Ber., 26, 2928--2930).-The author has previously shown (Trans., 1893,1137) that the constitution of the glucosides may readily be explained by the help of Tollens' or other similar formula for glucose ; no evidence was, however, adduced to show with which carbon atoms the oxygen atom present in the " ethylene oxide " form is combined. Inasmuch as the glucosides do not behave as aldehydes under any conditions, it is probable that the residue combined with the glucose is united with the carbon atom from which the aldehyde group of the original glucose is produced ; and, further, as a second phenylhydr- azine residue may be combined with the carbon atom next to the aldehyde group in glucose, but not in the glucosides, it seems prob- able that the atom complex of this carbon atom has also undergone alteration.From this. the author concludes that the constitution of the Tetrucetylarubiizose is prepared in a similar manner. JN. W. -~ ~ CH*[ CH*OHJ,*CH2*OH glucosides is represented by the formula O< I CH-OR As evidence against the supposition that the radicle displaces the hydrogen of one of the alcohol groups, the author adduces the fact that an aqueous solution of sodium glucosate is totally unaffected by phen ylhydrazine. H.G. C. The Sugar of Phlorizin. By 0. HESSE (Annulen, 277, 302- 304j.-The author defends his remarks (AnnaZen, 172, 356) that theORGANIC CHEMISTRYI 105 sugar (phlorose) from phlorizin is distinct from glucose (dextrose), despite the observations of Rennie (Trans., 1887, 6341, Fischer (Abstr., 1888, 590), and Schunk and Marchlewski (Abstr., 1893, i, 384). On extracting, with methylic alcohol, the sample of sugar which was originally faintly yellowish but which after 15 years had become brom-n, glucose was obtained from the extract. Even this €ails to convince the author that the original sugar is identical with glucose; he admits merely that phlorose is capable of being con- verted into glucose, but whether or not the change is brought about by the agency of lower organisms cannot be said.A. R. L. Chloralose. By M. HANRIOT and C. RICHET (Conapt. rend., 117, 734--737).--Chloralose (Abstr., 1893, i, 247) melts at 187", and dis- solves in alcohol, but is only slightly soluble in water or ether. Its boiling aqueous solution reduces neither ainmoniacal silver nitrate nor Fehling's solution. Acids are without effect on it, but alkalis change the colour of the hot solution to brown. Chloralose is not affected by nascent hydrogen from sodium amalgam. With acids and acid chlorides, it yields di- and tetra-substitution derivatives, tetracetyl- chloralose, melting at 145", and tetrabenxoylchloralose crystallising in prisms melting at 138".Oxidation converts chloralose, with evolutioil of carbonic anhydride, into chZoraZic acid, C7H9C1306, which crystal- lises in anhydrous needles melting at 812", soluble in alcohol or ether, but only slightly soluble in water. All these derivatives of chloralose are without physiological activity . Parachloralose (lor. cit.) is insoluble in moat reagents, melts a t 227", and sublimes if heated slowly. Like chloralose, it is not affected by hydroxylamine, phenylhydmeine, or dilute acids, but it is very slowly attacked by boiling solutions of alkalis. With acids and acid chlorides, it yields di- and tetra-derivatives ; tetracetylparachloralose crystallises in long needles melting at 106", and boiling at about 250" under a pressure of 25 mm.When oxidised, parachloralose yields carbonic anhydride and parachloralic acid, which crystallises with 2H20 in ef€lorescent tables melting at 202", and very soluble in alcohol or ether, but only slightly so in cold water. These properties indicate that neither chloralose nor parachloralose have the aldehyde functions of glucose and chloral. They cannot be regarded as ethereal salts of glucose, and it would seem that they hale the following constitution. CH*CH(OH)*O*~H*CC13 O<& -- C(OH)*CH(OH)*CH,*OH although the p s i - CH*C H (0 H) * 7 (OH) *C C1, and O<bH C(OH)*CH( OH)*CH2*OH' tion of the anhydric oxygen is somewhat uncertain. Decomposition Products of Calcium Sucrate. By E. 0. v. LIPPMANN (Ber., 26, 3057--3059).-A sample of calcium sucrate which had beec preserved for five years was found to contain no C.H. B.106 ABSTRAUTS OF CHEMICAL PAPERS. sugar; the lime was combined with carbonic, formic, acetic, and axalic acids. Another sample of calcium sucrate, which had bees preserved for two years, was treated with boric acid suspended in alcohol; the alcoholic solution yielded an acid syrup from which crystals were obtained, and identified by the author as acetonedicarb- oxylic acid (m. p. 136"). E. C. R. Decomposition Products of Cane Sugar. By E. 0. v. LIPPMANN (Bey., 26, 3059--3061).-During the preparation of sugar-candy from pure white crystallised sugar, the mass sometimes becomes faintly acid, owing to the formation of decomposition products. An examination of the product showed the presence of a small quantity of a fruity ether and a dimethylfurfuran, C6H80, which melts at 94".Trihydroxybutyric acid and a small quantity of trihydyoxyghtaric acid, CaH806, were separated. The latter melts at 125", and is dextro- rotatory, a: = 20.8O. A syrupy acid was also obtained, which is probably identical with the hexepinic acid described by Maumenh, and, finally, small quantities of catecho1 and protocatechulc acid. E. C. R. Carbohydrates Soluble in Water obtained from Malt and Barley. By G. DULL (Chem. Zeit., 17, 67-68 and 100).-Jalowete came to the conclusion that the optical and reducing properties of cold water malt extract are to be altributed to the presence of dex- trin and glucose (dextrose). The author extracts malt meal with boiling 80 per cent. alcohol for five hours, distils off the alcohol, takes up the residual syrup with water, and dialyses the solution.The grains, after being boiled with 80 per cent. alcohol, are extracted with cold water, and the solution submitted to dialysis. I n this way it is shown by the optical rotation, the copper test, and the phenyl- hydrazino reaction, that the carbohydrates saccharose and invert sugar are present along with a gum (galactoxylan, and perhaps other gums), and hesides these there are inorganic matter, protejids, fat, choline, &c. (compare also Kuhnemann, Ber., 8,202 and 307 ; Kjeldahl, Zeit. ges. Brauw., [a], 4, 447). This applies both to air-dried and kiln-dried malt. There is no doubt that kiln-dried malt contains i*eady-formed invert sugar, and the author shows that the same is true of green malt, for when the latter is extracted with 0.2 per cent.ammonia, which arrests the action of the saccharose-hydrolysing enzyme, the presence of which Kjeldahl has recognised, the solution contains invert sugar. Experiments with barley showed that it contained a non-reducing sugar yielding phenylglucosazone ; the author therefore concludes that the only soluble carbohydrate present i n barley besides the gum is sacchnrose. The aqueous extracts of barley generally gave the choline reaction. A. R. L. Note,-The author makes no reference t o the well-known experi- ments of O'Sullivan on the sugars of cereals and germinated grain. It is especially surprising that the author fails to notice the fact that O'Sullivan has conclusively proved the presence of raffinose i n barley (Trans., 1886, 70).It is quite conoeivable that the presence ofORGANIU CHEMISTRY. 107 raffinose might escape detection by the osazone test, or it may be that raffinose is not an invariable constituent of barley, A. R. L. Starch. By C. SCHEIBLER and H. MITTELME~ER (Bey., 26, 2930- 2937).-In this paper, the authors reply to the recent communication of Lintner and Dull on the same subject (this vol., i, 5 ) , pointing out that the results there detailed have, in some cases, already been de- scribed by the authors (Abstr., 1891, 33). They further do not agree with the theory proposed by Lintner and Dull, and devote the chief portion of the paper to an extension of their own theory as to the constitution of starch and the dextrins. According to this there is no difference in principle between the constitution of starch and the dextrins, and that of the bioses such as cane sugar and maltose, and of the trioses such as melitriose, the dextrius and starch simply containinq a much larger numb2r of glucose residues in the molecule.The combination between two glucose molecules to form a biose may take place in two ways, according as either one or both of the carbonyl groups take part in the combination ; in the former case, the compound formed has still the properties of an aldehyde, but not in the latter; this is ex- emplified in the casesof maltose and cane sugar. The former method of combination the authors term the monocarbonyl linking, and the latter the dicarbonyl linking. I n the case of starch, the glucose residues are all combined by dicarbonyl linkings, and do not therefore reduce Pehling’s solution or react with phenylhydrazine.Wb en treated with acids or ferments such as diastase, the first action is the hydrolysis of the starch mole- cule at one of the dicarbonyl linkings, yielding two molecules, each of which contains an aldehyde group, that particular glucose residue being connected with the remainder of the molecule by a monocarbonyl linking. These new substances form the dextrins, and as the hydrolysis of the starch molecule probably takes place simultaneously at several of the dicarbonyl linkings, a number of dextrins are simnl- taneously formed ; by the further action of the ferment on these, however, they are split up into dextrins of smaller molecular weight: and, finally, when invertase is employed, into maltose ; with acids, however, the hydrolysis goes further, and the whole is converted into glucose.The process is in fact similar t o that observed in the case of melitriose, which is resolved first into melibiose and fructose, the former being in turn resolved into glucose and galactose (hbstr., 1890, 226, 1085). Crystallisation of Cellulose. By E. GILSON (Chem. Centr., 1893, ii, 530) .-Under the term “ cellulose,” the author includes the carbo- hydrates of the membrane which are insoluble i n dilute acids or alkalis, but soluble in sulphuric acid, and which are coloured blue by iodine in presence of concentrated sulphuric or phosphoric acid. The aufhor finds t h d if sections of cellular tissue are allowed to remain for a time i n contact with Schweizer’s reagent, then washed carefully first with ammonia and then with water, so that the copper compound dissolves gradually and the cellulose is precipitated slowly, H.G. C.108 ABSTRACTS OF CHEMICAL PAPERS. $he latter is found in the interior of the cells in the form of nodular or arborescent crptals. These are insoluble in dilute acids and alkalis, b6t soluble in concentrated sulphuric acid, and show also +,he other characteristics of cellnlose. To obtain the crystals certain precautions are necessary, one of these being the complete removal of starch before treating the section with Schweizer’s reagent, The reaction has been successfully carried out with a large number of phanerogams and cryptogams.Objects such as the seed grains of Co$ea arabica, Ph ytelephas macrocarpa, and Strychlnos YLUX tiomica, which contain reserve cellulose, show plainly the presetwe of two different substances in the membrane, one of which is coloured blue by iodine and zinc chloride, and can be obtained crystalline in the above manner ; the other is amorphous and gives no coloration with iodine. Cotton-wool, wood, and tunicin may likewise be partially converted into crystals. The author concludes that all membranes which are coloured by ammonia and zinc chloride can be in part obtained crystalline by the above treatment, and that only the portion which is thus coloured can be crystallised. The crystalline product has always the same appearance and properties, and appears therefore to be a distinct compound.All membranes contain cellulose, together with a, con- siderable amount of other substances which are not, coloured by the above reagent ; whilst reserve cellulose consists of a mixture of the crystallisable cellulose with other carbohydrates. As the cellulose always crystallises on the interior of the cells, it must occupy the inner portion of the membrane, and when dissolved in Sch weizer’s reagent it diffuses very little, if a t all, through the membrane. This observation affords an explanation of the fact that cellulose cannot be completely dissolved by Schweizer’s reagent, and also of the manner in which Fremy was led to believe in the existence of a metacellulose, which is only soluble in the reagent after treatment with acids, for the acid dissolves or attacks the other constituents of the membrane, and allows the reagent free access to the cellulose hitherto held in the interior of the cells.To obtain the cellulose in larger crystals, a solution of the pure sub- stance in ammoniacal copper oxide is allowed to remain in a loosely- closed vessel ; the ammonia slowly escapes, and cellulose and copper oxide are precipitated. The latter is removed by washing with hydrochloric acid and water, when the celluose remains in nodular crystals ; on treatment with acids, it yields glucose as the sole product of hydrolysis. The mannosocellulose of Schulze is a mixtum of cellulose with another carbohydrate for which the author proposes the term paramanan; this may also be obtained in the form of nodular crystals.Tbe membrane of all vegetable cells with the exception of the fungi appears to contain cellulose, which occurs in the free state. In the case of woody membraneu, however, i t is probably in combination with another hydrocarbon or allied compound. Oxidation of Aliphatic Aldehydes and Ketones by Nitric acid. By R, BEHREND and J. SCHMITZ (Annalen, 277, 310-339).- H. G. C.ORUANIO CHEMISTRY, 109 This paper commences with a bibliographical r&sume' of the subject. A preliminary account of the experiments on the action of nitric acid on acetone has already been published (compare Abstr., 1893, i, 303). The yellow oil thus obtained is decomposed when boiled with water yielding nitrous oxide, carbonic anhydride, formic, acetic, and oxalic acids, and hydrogen cyanide.Chloromethylglyoxime, obtained by warming chlorisonitrosoacetone with hydroxylamine hydrochloride (Zoc. cit.), melts with decomposition at 182-183'. Nitrosoxylmethyl- glyoxime, NOH:CMe*C(NOH) 0-NO (Zoc. cit.), obtained by treating an aqueous solution of the yellow unstable oil with hydroxylamine hydrochloride, when oxidised with nitric acid of sp. gr. 1.37 saturated with nitrous acid, gives a compound C3H3N304, which crystallises from aqueous alcohol in colourless, brittle plates, and melts at 66-67" ; when heated with alcoholic Dotash. it dissolves. forminp a vellow solution having the odour of {eppermint. Its conLtitution 7s pgbably EM" *fl*Noz, that is, it belongs to] the class of oxime peroxides first NO-ON prepared by Koreff (Abstr., 1886, 363), and subsequently studied by Hollemann (Abstr., 1888, 275; 1889, 49) and by Angeli (Abstr., 1891, 890 ; 1892, 1198; 1893, i, 310, 355).The compound of melt- ing point 188-191", obtained by treating nitrosoxylmethylglyoxime with a solution of sodium hydrogen carbonate, is shown, by the cryoscopic method, to have a molecular weight corresponding with the formula, CsH8N404. I f this is treated with nitric acid saturated with nitrous acid, a compound CsH3N305 is obtained, which melts at When paraldehyde is oxidised with nitric acid according to De Forcrand's directions (Bull. Soc. Chim., [2], 41, 242), and the pro- duct is distilled under diminished pressure until its volume is reduced to one-fourth, formic and acetic acids, together with unaltered par- aldehyde and a small quantity of formaldehyde, pass over, whilst on distilling the residue a t the ordinary pressure glyoxal passes over. In conclusion, the authors confirm Ljubavin's observation that the production of glyoxaline from ammonia and glyoxal depends on the initial formation of formaldehyde, which condenses with the am- monia and glyoxal.In the preparation of glyoxaline from glyoxal and ammonia, it is therefore advisable to add formaldehyde. 113*5-115". A. R L. Derivatives of Acetylacetone. By C. U. ZANETTI (Gazzetta, 23, ii, 299-312).--Knorr (Abstr., 1887, 275) obtained 3 : 5 : 2 : 4- dimethyldiacetylpyrroline by reducing a mixture of ethylic nitroso- acetoacetate and ethylic acetoacetate. The author obtains the same pyrroline derivative by reducing with zinc dust the product of the action of potassium nitrite (1 mol.) on acetylacetone (2 mols.) in acetic acid solution ; its aurochloride, CloH1302N,HAuC14, crystallises in small, yellow needles, which begin to decompose a t 70" and melt a t 120-130".3 : 5 : 2 : 4-Dimethyldicinnamyl~yrroline, CMH2702N, is obtained by the action of benzaldehy de on the above diacetyl derivative in alkaline solution ; it forms small needles melting at 215-216".110 ABSTRACTS OF CHEMICAL PAPERS. Nitrosoacetylacetone, CAc2:NOH, is an intermediate product in the formation of dimethyldiacetylpyrroline, and is isolated by dissolv- ing acetylacetone in the minimum quantity of 12 per cent. potash, cooling with ice, adding the calculated quantity of potassium nitrite, and then, gradually, a slight excess of dilute sulphuric acid.Ether extracts the nitroso-derivative from the solution ; it is ulti- mately obtained in pearly, flattened needles, or scales, which melt at 75". It is very soluble in water, alcohol, or ethylic acehte, but only sparingly in benzene or light petroleum. It has a marked, although somewhat transient, antipyretic action on the animal system, and toxic symptoms are observed on administering a dose of 0.2 gram per kilo. of body weight. With hydroxylamine, it yields a prodnct which seems to be a mixture. On reducing nitrosoacetylacetone with zinc dust in acetic acid solution in the cold, dimethyldiacetaldine, (?) CloH,,N202 is obtained ; it forms yellow needles melting at 102-102", and acts as a feeble base.If the reduction proceeds a t a high tem- perature, a liquid product is obtained which gives an unstableplatino- chloride ; the author proposes to examine these reactions laier. S ymme tricnl t e t race tg 1 ethane (compare Harrow, Annale n, 2 01, 144) may be prepared by adding an ethereal solution of iodine to an ethereal solution of sodioacetylacetone, filtering, removing the sodium iodide by treatment with water, and crystallising the residue from acetic acid. On boiling tetracetylethane with concentrated hydro- v QBc:CMe>O ; this ci-ys- chloric acid, it yields dimet~yldiacely Ifirfuran, C Ac: CMe tallises in long, waxy needles melting'at 62.5". >N, is prepared by 7Ac:CMe CAc:CMe 3 : 4 : 2 : 5-Dimet~yldiacetytcpyrroline, boiling tetracetylethane with ammonium acetate and acetic acid ; it separates on the addition of alkali, and crystallises from hot water in opaque, white needles melting at 180-181".It is readily soluble in alcohol or boiling water, but only sparingly in ether or ethylic acst- ate. It behaves as a feeble base, yielding a hydrochloride which crystallises in white needles ; this is decomposed by water and gives off hydrogen chloride in a vacuum. CioH1302N,~~C11 crystallises in yellow needles, and begins to decompose at 100". A list of reactions of the base is given. A crystalline hydrobromide separates from the solution of the base in fuming hydrobromic acid ; on adding bromine to the solution, however, an unstable perhornide, CloH,30,N,HBr,Br2, separates as a reddish mass, which yields the py'rroline when treated with sodium carbonate.3 : 5 : 2-Dimethylacetylpyrroline is soluble in concentrated hydro- chloric acid, and yields a fairly stable, yellow, crystalline aurochloride, C8H,40N, HAuC14. 2-Acetylhomopyrroline is moderately soluble in hydrochloric acid ; its aurochloride forms minute needles and is less stable than the preceding one. 2 : 5-Diacetglpyrroline i s very spar- ingly soluble in hydrochloric acid, and yields an uurochloride which is decomposed by water. On treating a hot alkaline solution of acetylacetone with hydrazine The aurochloride,ORGANIC OHEMISTRY. 111 sulphate, 3 : 5-dimethylpyraeole is deposited. Acetylacetone reacts with benzaldehyde, giving a mixture of several cinnnmyl derivatives ; it is perhaps possible to separate these by taking advantage of their behaviour towards phenylhydrazine.W. J. P. Condensation of /I-Diketones with Carbamide, Guanidine, and Thiocarbamide. By P. N. EVANS (J. pr. Chem., 45,489-517). N'CMe -AcetylacetonccarbamiJe, CO<NiCRlle>CH2, is obtained, as a salt, by the condensation of acetylacetone and carbamide (equal molecules) with sulphuric or hydrochloric acid. The hydrochloride crystallises in rectangular plates, and does not yield ammonizq when boiled with concentrated sodium hydroxide. It gives no precipitate with platinic chloride. When treated with diazobenzene chloride and sodium acetate, it gives an orange, crystalline precipitate which quickly turns dark red; this compound is a powerful dye. The sulphnte, C6H,N20,H2SOa, forms thick, transparent crystals, and melts at 209".Acetylacetonecarbamide is most easily obtained by treating the sulphate with barium carbonate, evaporating the filtrate to dryness, and extracting with benzene. It crystallises from water in short, thick prisms, melts at 198", and has both basic and weak acid properties. It is not altered by treatment with nitrous oxide or acetic chloride. The silver salt, CsH,N20Ag, was obtained ; the mei-ccui*y salt, C ~ H ~ N ~ O H ~ , is a yellow precipitate. On bromination, a deGvntive, C,H,,N2O3Br2 (= co <NBr-CMe( NBr,CMe(OH)>CH2?), OH) is obtained; it crys- tstllises in white, flocculent crystals, turns grey at 90", blackens at 143-145", and dissolves in ammonia. Dhrimidiacetylacetone, CH,(CMe:N*CO*NH2)2, is obtained by the condensation of acetylacetone with 2 mols.of carbamide. The hydro- chloride, C7Hi2N402,HC1, cry stallises in slender, colourless needles, melts a t 180", does not give w precipitate with platinic chloride, and easily yields ammonia when heated with potassium hydroxide. When heated with silver oxide, i t yields carbamide and acetylacetonecarb- amide. A molecular compound of the sulphates of diurimidoacetyl- acetone and carbamide, C7H12N402,CH4H20, H,SOa, crystallises in aggregates of slender needles, and melts at 142". Diurimidoacetyl- acetone, prepared by treating this sulphate with baiium carbonate. melts at 199", and is identical with the compound obtained by A and C. Combes ( B u l l . Xoc, Chirn., [2], 7, 791) from acetglacetone and carbamide. The condensation products of acetylacetone with thiocarbamide are obtained in st similar way to those with carbamide.Acatylucetonethiocarbamide, CS <N:CD/le> CH2, crystallises in yellow needles, melts at 210", and easily yields compounds with metallic salts. The siZver salt, C6H7N2SAg,AgNo3, is obtained as a white precipitate on adding silver nitrate to the aqueous solution. The aqueous solution also gives a white precipitate with mercuric chloride, a yellow precipitate with platinic chloride, an orange colora- XCMe112 ABSTRAOTS OF OHEMICAL PAPERS. tion and then a yellowish precipitate with ferric chloride, and a dirty white precipitate with copper acetate. crystallises in slender, yellow needles, and volatilises when heated on platinum. When the aqueous solution is treated with nitric acid and silvei.nitrate, it yields a white, crystalline precipitate which is not silver chloride ; when boiled with alcoholic ammonia and mercuric oxide, the sulphur is not eliminated. The aqueous solution rapidly absorbs bromine, and the sulphur is then oxidised to sulphate. The sulphate crystallises in slender needles. DitlLioz~rimidoacety lacetone, CH2( CMe:N-CS*NH&, was not obtained in the free state. The hydrochloride crystallises in yellow scales, melts a t 219", and immediately blackens. The aqueous solution gires a white precipitate with silver nitrate, which dissolves in ammonia with n dark brown coloration. The sulphute crystallises in four-sided tablets. Urimidobenzoylacetone, COPh*CH2*CMe:N*CO*NH,, is obtained by adding concentrated hydrochloric acid to an alcoholic solution of benzoylacetone and carbamide. It forms small scales, melts at 191", and, when treated with hydrochloric acid and then with ammonia, is converted in to benzoylacetonecar bamide. The hydrochloride, C,HBN2S,HC19 N*CMe Benzoy Eacetonecarbanzide, CO <N.CPh > CH2, is obtained either by heating benzoylacetone with carbamide or by treating an alcoholic solution of benzoylacetone and carbamide with hydrochloric acid.The first method does not give good results, and benzoylacetonamine, binret, and cyanuric acid are formed. It melts at 228". The hydro- chloride sometimes separates out in yellow, rhombic plates, With platinic chloride and hydrochloric acid, it yields the salt which crystallises in yellow rosettes. When heated with concentrated hydrochloric acid in a sealed tube at 160°, it remains unaltered.Benzoy Zacetoneguanidine is obtained by heating a mixture of benzoyl- acetone and guanidine carbonate. It crystallises in small, sandy aggregates, melts at 173", and easily yields salts with acids and metallic salts. The pZatinochZoride crystallises in small, yellow needles, The solution in hydrochloric acid gives a white precipitate with mercuric chloride, and a soluble precipitate with ferric chloride. The solution in dilute nitric acid gives a crystalline precipitate with silver nitrate. It yields two sulphates, crystallising in white nodules and microscopic needles. The hydrochloride and nitrate crystallise in slender needles, the chromate in yellow needles. The acetyl com- pound crystallises in nodules, and melts at 146".When it is dis- solved in acetic acid, treated with nitrous acid, and the mixture poured into water and heated, it yields a brown, crystailine powdei- which melts at 205". The author was unable to obtain a condensation product from phenacetylacetone and carbamide or thiocmbamide. 2C,,HIO~ZO,H2PtC16, Phenacetylacetoneguanid*lne, NH* C <N*- N ' C ( C H ~ P h ) > ~ ~ 2 - CMe + 4 ~ ~ 0 , isORGANIC CHEMISTRY. 113 obtained by heating phenacetylacetone with guanidine at 115-120". It crystallises in needles, and melts at 108". With platinic chloride and hydrochloric acid, it gi-ces a yellow, crystalline precipitate. E. C. R. Cupranunonium Double Salts. By T. W. RICHARDS and H. G. SHAW (Amer. Chem. J., 15, 642-653 ; compare Abstr., 1892, 953).-Cuprammoniurn acetobromide, Cu (NH3),Br-C2H3O2, is formed by treating cupric bromide with alcoholic ammonia, and dissolviug the cuprammonium bromide thus formed in alcoholic acetic acid. It forms fairly permanent, deep blue, apparently monoclinic crystals, and has the sp. gr. 2.134. Ammoniocuprammoniuum acetochloride, C u(NHJ3C1*C2H302 4- H20, is prepared by mixing concentrated solutions of copper chloride, acetic acid, and ammonia with alcohol. It forms brilliant, blue crystals of a pearly lustre, and loses ammonia and water slowly on exposure to fhe air. Complex cuprammoniurn acetochloride, [ CU( NH3)2ClC2H302] 2,3NH,*C:H,O, + 7H20, is formed when cupric chloride is treated with a large excess of concen- trated ammonia, the excess cautiously neu trdised with glacial acetic acid, and the whole treated with alcohol and allowed to evaporate, It forms brilliant, blue crystals of a violet tinge, and although soluble in a small quantity of water, i t is decomposed by larger quantities. I t decomposes when exposed to the air, losing water and ammonium acetate. Czqwammoniurn formobrornide, Cu (NH3),Br*CH02, is prepared similarly to the acetic compound.Cupric ammonic acetochloride, CuCI2,2NH4*C2H3O2, occurs as a bye- product from some of the above preparat'ions. It forms bright green, almost cubical crystals. Tetrammoniotricuprammonium bromide, 3Cu(NH3),Br2,4NH3, is formed when strong hydrochloric acid is cautiously added to a solu- tion of cupric bromide in the minimum quantity of alcoholic ammonia.It forms deep indigo crystals, and loses ammonia when moist, but is more stable when dry. It is converted by heat (160") into an olive- green subetance, Cu(NH3),Br2 (Abstr., 1891, 399), which still retains the original crystalline form. Rammelsberg's green, crystalline sub- stance, CuBr2,5NH3, may have consisted of superficially decomposed crystals of the blue substance. Syntheses by means of Zinc Chloride. By I. RONDAKOFF (J. pr. Chem., [2], 48,467-486 ; compare Abstr., 1893, i,382).-The com- pounds of zinc chloride with olefine hydrocarbons have been dealt with (Zoc. cit.). The tertiary alkyl salts may be synthesised from olefines and organic acids in the presence of zinc chloride by keeping the three substances together at 20° ; the ethereal salt is subsequently separ- ated by decomposing the zinc chloride compound with water.In this way tertiary amylic acetate has been prepared ; also t e r t i a q amyZic formate, a colourless liquid which boils at 112-113' (759 mm.), and has a sp. gr, of 0.9086 at O", and an odour of amylic JN. W.114 ABSTHAUTS OF OHEMIUAL PAPERS. acetate ; tertiary nmylic propiomate, which boils at 142-143.5" (757.3 mm.), and has a sp. gr. of 0.8769 at 0" ; tertiary amylic butyrate, which boils at 164" (757.3 mm.), and has a sp. gr. of 0.8766 a t 0'; tertiary trmylic isobutyrate, which boils at 153-135" (762 mm.), and has a, sp. gr. of 0.8706 at 0" ; tertiary amyZic isovaberate, which boils at 173-174" (7623 mm.), and has a sp. gr. of 0.8729 a t 0"; tertiary butylic acetate (b.p. 51") ; and tertiary hexylic acetate (b. p. 143" a t 757 mm.). A. G. B. Action of Ethylic Bromopropionate on Sodium Nitrite. By G. LEPERCQ ( B u l l . SOC. Clzim., [3], 9, 630-632).-When a mix- ture of ethylic bromopropionate, absolute alcohol, and sodium nitrite is heated gently on the water bath, it disengages carbonic anhydride, nitrogen, nitric oxide, and ethylic nitrite, and from the solution, a substance, C,H,NO,, can be obtained in light, colourless needles of satiny lustre. It is identified with Meyer and Zublin's ethylic nitroso- propionate by the properties of its easily-formed silver salt; its boiling point (213"), however, differs from that (233") given for the nitrosopropionate. It yields a granular solid nitrosopropionic acid, It is readily oxidised by potassium permanganate, but without the production of ethylnitrolic acid, although a nitrolic acid is obtained with nitrous acid in the ordinary way, W.T. Transformation Products of Normal a- AmidovaIerie acid. By A. MENOZZI and A. PANTOLI (Gazzetta, 23, ii, 209--214).-The iodide of potassium a-trimethylamidovalerate, COOK*C4H8*NMe,l, is obtained by heating normal a-amidovaleric acid with methylic iodide in presence of potash. It is very hygroscopic, is sohible in water or alcohol, and crystallises in long, white needles. On adding a solution of iodine in hydriodic acid to its aqueous solution, a periodide of the base separates ; this is ultimately obtained in well-developed crystals, ' having a metallic green lustre. When the periodide is suspended in water, and treated with hydrogen sulphide, a-trimet~,yZami~ovaleric acid iodide is obttcined ; this separates from dilute hydriodic acid in monosymmetric crystals containing 2H20, a : b : c = 1.4852 : 1 : 1.2459 ; p = 80" 33'.It melts at 181-182', is stable in the air, and soluble in mvater or alcohol. On crystallising it from alcohol, an iodide of the composition (COOH*C4H8*NMe&I is obtained, crystallising in cubes. On treating the iodide melting at 181-182" with silver chloride, - -~ a-trim ethy la&dounleric acid chgride, COOH*C4H8*NMe,C1, is ob: tained ; it forms small, transparent prisms, and is soluble in water or alcohol. With platinic chloride, it yields a nzethylic platinochloride of the composition (COOH*C~H8*NMez)2,~!IezPtCl~,2H,0 ; this forms yellow prisms which lose water at 100" and melt at 219".The methylic aurochloride, CO0H*C4H8*NMez,MeAuCl4, i s obtained in an- hydrous, yellow laminse which melt at 160". On treating the iodide of the potassium salt described above with moist silver oxide in aqueous solution, silver iodide is deposited : this is filtered off, the alkaline solution concentrated, and the residueOROAKIC CHEMISTRY. 115 heated at 120". product with dilute sulphuric acid, propylidmeacetic acid, CH,Me-CH:CR.COOH, is liberated; this is a colourless oil which boils at 194-195", and remains liquid at - 16" ; it has an odour resembling that of a-crotonic acid. The propyl- ideneacetic acid prepared by Ott (Abstr., 1891, 1453) and others does not coincide in properties with the authors' product ; several of the salts of the acid are described.During the preparation of this acid, a small quantity of normal a-hydroxyraleric acid is olotained. W. J. P. Trimethglamine is evolved, and, on treating the It is heavier than water at 0". but lighter at 15". Composition of Rape Oil. By G. PONZIO (J. pr. Chern., [2], 48, 487--488).-Reimer and Will (Abstr., 1887, 1030) state that rape oil contains the glycerides of erucic and rapic acids, in about equal pro- portions, and a little behenic acid. The author shows that their behenic acid is arachidic acid, which the oil contains to the extent of about 4 per cent. Arachidamide melts at 108" (compare Schweizer, Abstr., 1885, 508). A. G. B. A Nitrogenous Acidin Beet Juice. By E. 0. v. LIPPMANK (Bw., 26, 3061-3063) .-A yellow, crystalline deposit wits obtained while working up the juice of beets which had been frozen and thawed.The author has isolated from this deposit an acid which he believes to be citrazinic acid, CsH5NOa. It is a yellow, crystalline powder, scarcely soluble in boiling water, decomposes at 300" with an odonr resembling that of' burning hair, and is soluble in alkalis and alkali carbonates. E. C. R. Oxidation of Diallgloxalie acid with Potassium Perman- ganate. By S. FOKYR- (J. p. Chem., 48, 522-533).-Bulitsch has shown that a tetrahydroxyoctolactone is obtained by oxidising di- allyloxalic acid with nitric acid. On the other hand, Schutaky could not obtain this lactone by oxidising with permanganate ; the author, however, finds that by careful oxidation with this agent, under conditions detailed in the original paper, the lactone is obtained together with a lactonic acid.The Zactonic acid, OH*CHz*CH<~~~>C(OH) *CH,*COOH, is a The calcium salt, C7RlO0,Ca, yellowish syrup, and has a sour taste. and the barium saZts, C,HIoO7Ba and (C7H90&Ba, are described. Te trahydroxyoctolactone, OH~H,*CH(OH)-CH~.C (OH) <ccoHt, >CH.CH,.OH, is a syrup and has a sweet taste. The caZciurn salt, (C8H15Q7)zC~ + 2Hz0, and barium saZt, ( CaHlb07)2Ba, a yellowish, glassy, hygroscopic mass, melting at 84", were obtained. This lactone diEers from the compound obtained by the oxidation of diallyloxalic acid with nitric acid as shown by a comparison of the salts The calcium and barium116 ABSTRACTS OF CHEMIOAL PAPERS. Salts, ( CSH1507)Me", obtained by Bulitsch are glassy, whereas the calcium salt obtained by the author is crystalline.These two Salts, moreover, cannot be converted into salts of the composition (C8H1306)2Merr ; the author's lactone does not yield basic salts C8H1206Me" and ( CsH1307)2Me"3, even when boiled with the alkaline earths. Finally, Bulitsch's lactone yields an insoluble lead salt, whereas the lead salt of the above lactone is soluble. E. C. R. Ethereal Salts of Oxalacetic acid. By W. WISLICENUS and A. GROSSMANN (Annulen, 277, 37.5-383).-MethyEic oxalacetate, COOMe*CO*CH,*COOMe, is prepared by adding methylic oxalate together' with ether to solid sodium methoxide, and subsequently heating the mixture with methylic acetate on the water bath; the sodium derivative thus obtained is decomposed by dilute sulphuric acid.The methylic salt crystallises in colourless, lustrous needles, melts at 7&76", and boils at 137" under 39 mm. pressure; the alcoholic solution gives a red colour with ferric chloride. The copper derivative, ( c6H70&cu, forms small, green needles, and melts at 214-215" with decomposition. The phenylhydrazone, already de- scribed by Buchner (Abstr., 1890, 156), yields methylic phenylpyr- azolonecarboxylate, COOMe*CGH2. co . when heated above its melt- ing point; this forms white crystals, and melts at 197". Amy lic oxalacetate, C 0 O( CJT11) C O*CH2* C 0 O*C5H1 1, is obtained by adding amylic oxalate and ether to solid sodium ethoxide, and sub- sequently amylic acetate, and decomposing the sodium compound with dilute acid. It is an oil having an unpleasant odour, boils at 167" under ft pressure of 23 mm., and the alcoholic solution gives a deep red coloration with ferric chloride; it yields an oily phenyl- hydrazone, which condenses to am y lic phen y 7p yrazolonecar box ylate when heated at 190".Methy lic ethylic oxabacetate, C00Me*CH2*CO*COOEt, prepared from ethylic oxalate and methylic acetate as in the above cases, is a, colourless oil boiling at 130" (22 mm.), and at 124" (16 mm.) ; the copper derivative melts at 134-135". When the phenylhydramne is heated, it is converted into ethylic Phenyl~yrazolonecczrboxylnte, cooEt-c<GH2.bo , melting at 180-182". - r P b The copper derivative melts at 83-85". N-NPh A. R. L. Preparation of h i d e s . By A.VERLEY (Bull. SOC. Chim., [3], 9, 690-692) .-Distillation of dry potassium or sodium salts of the organic acids with ammonium (or a replaced nmmoninm) chloride gives a better yield of the corresponding amides than distillation of the ammonium salts directly, aiid the produot is readily purified. In this way 80 per cent. of the theoretical yield of acetamide has been obtained. Methylamine hydrochloride distilled with potassium acetate and a little acetic acid gives 88 per cent. of the theoretical yield of methyl- acetamide. Similarly, a yield of 91 per cent. of dimethylacetamide is obtained. With formamide, the yield is '78 per cent. Succinimide0 R G AN IC CHEMISTR I-. 117 requires the ammonium chloride and potassiuiii succinate to be inti- mately mixed.The yield of product, purified by recrystallisation after treatment with animal black, is 87 per cent. of the theoretical. Dimethylforrnanzide.-This substance is prepared exactly like dimethy1a:etamide. I t is a liquid of a feeble hut not disagreeable odour, boiling without decomposition a t 155" ; sp. gr. 0.969 at 20". W. T. Formation of Dith'ienyl Derivatives from Thiophen. By A . TSHL and 0. EBERHARD ( B e y . , 26, 2945--2947).-When sulphuryl chloride is mixed with thiophen and a small quantity of aluminium chloride added, a violent action takes place, sulphurous anhydride and hydrogen chloride being evolved. The residue contains small quan- tities of chlorothiophen, but consists chiefly of a mixture of trichloro- dithienyl and dichlorodithiengl. Trichloyodithi'enyl, C8S2H9C13, forms short, needles, and melts at 103"; it is converted by tlie action of bromine into trichZorotribromoditGeny1, C8S2CI,Br3, which crystal Lises in long, pale yellowish needles, and melts at 214-215".Dichloro- dith$enyZ, CsS2H4C12, forms thin, yellowish plates, melts a t 109-11~", and, on treatment with bromine, yields dichlorotetrabrornodithienyl, CSS2CI,Br4, which crystallises in reddish needles, and melts at 221-222". H. G. C. Action of Sulphuric acid on Chlorothiophen. By A. T ~ ~ H L and 0. EBERHARD (Ber., 26, 2947--2949).-1'he presence of small quantities of cblorottiiophen in the product of the action of sulphuryl chloride on thiophen in presence of aluminium chloride (see preceding abstract) leads to the supposition that this is the first i)roduct of the action, and that it undergoes condensation to dithjienyl derivatives in presence of sulphuryl chloride.The authors have therefore endeavoured to bring about the same condensation by treating chlorothiophen with concentrated sulphuric acid. The a-chlorothiophen is obtained i n m nch larger qnantity from sulphuryl chloride and thiophen if the mixture is diluted with ether, and may be readily prepared in this manner. When treated with sulphuric acid, i t is converted chiefly into chlorothiophensulphonic: acid and ChZorodithienyl, CsS2K5Cl, but the latter could not be obtained quite pure ; with bromine this yields chlorope?itabromodithienyl, C8S2CIBr,, which cryskallises in long, white needles, and melts at 233-240". The barium salt of chlorotbiophensulphonic acid, ( C4SH,C1*S03),Ba -+ 2H,O, crystallises from alcohol in small druses of white needles.H. Q. C. New Method of preparing Iodochlorides. By A. TOHL (Bey., 26, 2949-2950).-A very good yield of the iodochlorides may be obtained by treating the iodo-derivative with sulphuryl chloride in ethereal solution, the presence of H little water being iieressary to start the reaction. Satisfactory resdts have beer] obtained by this method wltb iodobenzene, pariodotoluene, 1 : 3 : 4-ioclometaxylene, and iodomesity lene . H. G. C. YOL. Lxvr. i. k118 ABSTRACTS OF CHEMICAL PAPERS. Electrolytic Reduction of Nitrobenzene. By C. HAEUSSERMANN (Chem. Zeit., 17, 129 and 209).-This paper was published prior to those of Gattermann and Koppert (Abstr., 1893, i, 5 6 i ; t h i s vol., i, 72).The reduction of nitrobenzene i n alkaline solution is carried out, as follows :-Nitrobenzene (25 grams) dissolved in alcohol (350 c.c.) and mixed with a solution of sodium hydroxide (40 grams) in water (50 c.c.) is introduced into a porous cell which contains the cathode (iron or platinum, according to the nature of the solution) ; the porous cell stands in an outer vessel containing a platinum or carbon anode and filled with dilute sodium hydroxide. A current of 6-43 ampAres a t a potential of 6 volts is used. The precipitation of hydrazobenzene at the cathode soon commences, and at the end of 10 hours benzidine is obtained. Orthonitzotoluene yields the corre- sponding compounds, but in smaller quantity than nitrobenzene. If the reduction is conducted in acid solution, the porous cell is charged with nitrobenzene (25 grams), sulphuric acid (30 grams), water (100 c.c.), and alcohol (350 c.c.).The current used is 5 awp&es at a potential of 4 5 volts. Benzidine sulphate soon commences to separate at the cathode, and on adding water to the fil- trate azoxybenzene is precipitated. When the solutions are pre- t.iously heated to 60°, traces of aniline are also formed, whereas the greater portion of the nitrobenzene remains unaltered, so that the el&rolytic production of aniline seems impracticable ; the same may be said of that of ortho- and para-toluidine. When, however, a solu- tion of metanitrobenzenesulphonic acid in dilute snlphuric acid is submitted to a current of 3 amphres at a potential of 4 volts, met- anilinesulphonic acid is obtained.Action of Carbonyl Chloride on Picramic acid. l3g F. RUDOLF (J. pr. Chem., [a], 48, 4%5446).--Finely powdered picramic acid, m. p. 168-169" (uncom.), WIS heated a t 130-140" for 4-5 hours with a 15 per cent. solution of carbonyl chloride in chloroform, in a sealed tube. The solid product of the reaction was washed with chloroform and crystallised from water. A. R. L. The hydroxydinitropheny 1 isocyanate, OH*CsH2(NO,)Z*N:CO [OH : N : (NO,), = 1 : 2 : 4 : 61, thus obtained, crystallises in small, nearly white, obliquely truncated prisms, and in long needles. It melts at 222-223" (uncorr.), and dissolves very sparingly in cold water, more freely in hot water, ether, acetone, concentrated sulphuric wid, and glacial acetic acid, sparingly in benzene, and not a t all in chloroform.Its solulions are acid ; when heated with water for some hours, it is hydrolysed into picramic acid and carbonic anhydride. The sodium, potassiunz, ancl silvey derivatives, corresponding with the formula were prepased. When the isocjanate is heated with ammonia in aqueous or alcoholic solution, the arnmonilrm derivative of carbamidodinit~ophennf, NLI,-O CF.HZ(N02)2*NB*CO*NH,, is obtained in the form of small, thick, OSr*C,H2( NO,) 2*N:CO,0 RGANIC OREMtSTRY. 119 red prisms. The carbamidodinitrophenol, liberated by acidifying thc a mmoniiim salt,, is identical with Qriess' uramidodinitrophenylic acid ( J . pr. Chern., 1'21, 5,l) ; by hydrolysis, it is convepted into the original isocyanate and ammonia. With aniline, the isocyanate forms phenlllcarhamidodinitrophenot, OH*C,H,( N O,),*NH*CO*NHPh, which crystallises in microscopic, red prisms, and decomposes a t 2OG".With phenylhydrazine, phenyl- hydrazine carbamidodinitrophenol pheny lhydraxide, N,H,P h, 0 H*C6H2 (NO,) ,*NH*C O*N,H,P h, is produced ; it crystallises in orange needles, and decomposes at 130" ; when heated with solvents, it loses phenylhydrazine, becoming pheiiyl- h y~azinpcarbamidodiniti-ophenol, OH.C6H,(N0,),*NH*CO*N,H~Ph, which crystalliqes in microscopic needles, and melts with decomposi- tion a t 202-203". By heating the isocyanate with alcohol, ethgZic h~droxydinitropheny~- carbamafe is obtained ; this crystallises in yellow needlcg, melts a t 153", and dissolves in the usual orgmic solvents except light petr- oleum.When heated with hydrochloric acid, it yields ethylic chloride, carbonic anhydride, and picramic acid hydro(-hloride, The urn- monitrnt, potassium, and silzTer derivatives are described. The corre- sponding methylic salt, analogously prepared, crystallises in yellow needles, and melts at 179" (uncorr.). A. G. B. Action of Sodium on -/-Bromopropylphenyl Ether. By W. SALOXINA (Ber., 26, 2987--2988).-The author describes the pre- paration of hexamethylene dei ivatives from ~~-brotnopropylphenyl ether. The latter substance, when heated with sodium, yields, in addition to sodium phenoside, a small amount of hexamethyleue- glycoldiphenyl ether, O€'h*C€T,*[ CH 7 *CH,*OPh, which crystallisej from alcohol in long needles, melts at2$3", and is unly slightly soluble in cold alcohol.When this ether is heated wibh concentrated hydrobromic acid at 150°, i t is converted into hexamethylene di- bromide, CH2Br [CH,]&H,Br, which boils at 240--24;;" without decomposition. Hydyiodic acid a t 110" converts the diphenyl ether into the corresponding diiodide, CH,I*[C H,]4*CH,T, which is an almost colourless liquid, decomposes on distillation, and solidifies, on coolinq, to a mass which melts a t -7". The author is continuing his investigations. A. H. Compounds of Picric acid with Phenols and Ketones, By R. v. GOEDIKE (Ber., 26, 3042-:3046).-The compounds are ob- tained by adding a hot saturated solution of picric acid in 50 per cer.t. alcohol to a similar solution of the pheiiol. A small excess of phenol is used, to prevent the compound being contaminated with picric acid.The picrates are somewhat stable, but decompose when hsiated at 100" or in a desiccator over sulphuric acid. 'l'hey are also decom- posed by boiling with ammonia or soda. Phenol picrate, C6H5*OH,2Cl6H3NdO7, crptallises in bright yellow needles, and melts at 53'. Orthocresol picrate, 2 C7H,*OH,3 C6H,N,07, crjst allises in orange k 2120 ARSTRACTS OF CHEMJCAL PAPERS. needles, and melts a t 88". Neither melacresol nor paracresol cornlines with picric acid. 0 r t ho-xy lenol picraf e, 5 C,H,*O H,4CSH7N.307, for rn 8 orange cry s i als. a n d melts a t 82". Paraxylenol also yields a picrate; metaxyleiiol doe4 not. 0 F the dihydroxybenzenes, only pgrocatechol combines with picric acid.The picrate, C,H4( OH),,C,H,N,O,, crystallises in orRnge needles, and melts a t 122". Guaiacol picrate crystallises in beautiful, orange needles, and melts a t 86". Creosol picrate crystallises in yellow needles, and melts a t 96". Ethytguaiacol picrate crystallises in orange ueedles, and melts at' 90". Proyylguuiarol picrate crystallises in red needles, and melts a t 59". Pyropallol and phloroglucinol do not yield picrates. Dimethyl- pyvopllol picrate crystallises in yellow needles, and melts a t 5d". Orthochlorophenol picrate, C,H,Cl-OH, CSH3N307, crjs tallises in bright Fellow needles, and melts at 81-82'. Acetoplzenone picrate, COMePh.C,H,N,O7, forms greenish yellow, quadratic crystals, and melts at 53". Gallacetophenone picrate crystallises in orange needles, and melts a t 133".The anthor draws attention to t h e fact that, as a rule, it is only the ortho-compounds which are able to form picrates. N. C. R. Essence of Tarragon and its Conversion into Anetho'il. By E. GRTM~UX (Compt. rend., 117, 1089--1092).-When essence of tsarragon is suhjected to fractional disiillntion, about 60 per cent. boils between 210" and 215", and after four distillations t h i s product boils between 910.5" and 212" under a pressure of 747.4 mm. Neither the crxde essence nor the purified product contains any anetho'il. Estrayoil C10H1202, the chief constituent of essence of tarragon, boils a t 21.5-216" (con.) ; sp. gr. at 15" =z 0.9325 ; index of refractioii for D = 1.523. Estragoil is easily conr-erced into anethoil by heatiiig it on a water bath for about 64 hours with three or four times its weight of concentrated alcoholic potash, and the product is idenGcal with the anethoil obtained from the oil of aniseed.It would seem that estragoil and anethoil differ i n the isomerism of the group C3H5, the constitution of the former being OMe*C6H4*CH,*CH: CH2, and of the'latter OMe.C6H4*CB:CHMe, the difference being the same as that which exists between eugenol and isoeugenol, safrole and isosafrole. The difference between the boiling points of the two isomerides is practically the same in all three cases. The methyl derivative of the chsvicol obtained by Eykmann from the oil of the betel nut boils a t 226", and is probably a stereoisomeride of anetho'il, and not a propenylic dei-ivatiye like estrago'il.Condensation Products of Monobasic acids with Resorcinol. By G. COHN (J. pr. Chem., [el, 48, 384-410 ; compare dbstr., 1893, i, flS).--The following conclusions are drawn :-(1) Monobasic Its boiling point is 16-17" below that o f anethojil. C. H. B.ORQANIC CHEMISTRY. 121 acids condense with resorcinol, under certain conditions, t o form fluorewek.. (2) The character of these colouring matters is inde- pendent of the nature of the acid, for they are all similar in coloiir, fluorescence, spectrnm, solubility, and in the nature of their deriva- tives. (3) All give similar tetrabromo-substitution products, eosin9 containing the bromine in the resorcinol nucleus. (4) The influeme of the acid is exhibited in the facts that (u) aliphatic fluoresceyns show a smaller affinity €or animal fibres than do aromatic fluoresceins ; and ( b ) tbe inore complex acids yield more highly halogenised, redder.derivatives. ( 5 ) Benzoic acid and benzotrichloride, with resorcipol and nine chloride, yield the same colouring matter, whilst benz- aldebyde gives a product which difEer8 from the benzeins. A. G. B. Reaction of Sodium Alkyloxides with Tribromotrinitro- benzene. By C. L. JACKSON and W. H. WARREN (Anzer. Chem. J., 15, 607-642 ; compare Abstr., 1@91, 10241.-With sodium ethoxide, tribromo trinitrobenzene yields diethyltribromonitroresorcinol, tri- et,byltrinitrophloroglucinoJ, and the products of hydrolysis of the latter. Diethyltribromonitroresorcinol is converted by boiling alcoholic 8odi urn hydroxide, with elimination o€ bromine, into diethylbromo- ~di-oresorcinol N02.C6H,Br*( OEt),, a substance crystallising in long, silky, white needles, and melting a t 115".Tr Let h y ltrinitrop hlo roglucinol, C,( NO,) (0 E t) cry s tnllises in long, slender plates, turns brown on exposure to the air, and melts at 119-120". It is hydrolysed by alcoholic sodium hydroxide into diet h y lt& it rophlo rog Zucino l, 0 H* C,( NO,),( 0 E t)2, and trinitrop h lo rog luc- inol with 1 H,O. The former crystallises i n straw-coloured needles or prisms, and melts at 89". It deconiposes alkaline carbonates; the sodium salt crystallises in fine, orange-red needles. The latter crystallises in yellow, hexagonal prisms, and, when free from water, melts at 167". The low melting point (158") found by Benedikt (Ber., 11, 1376) was probably due to imperfect dehydration.The two substances are formed in the preparation of the triethyl compound if moisture is not excluded, the hydrolysis being effected by sodium hydroxide formed by the action of moisture on the sodium ethoxide. The influence of benzene on the relative proportion of the phloro- glucinol and resorcinol cornpounds was investigated, and it was found that lesc.1 nitrous acid (33.5 per cent. of the theoretical) was evolved, and therefore less resorcinol compound formed, when benzene was present than when alcohol alone was used (45.9 per cent.). In the presence of ethylic acetate, the principal product was dinitrobromo- pheneto'il, m. p. 147", the formation of which was probably due to t h e hydrolysis of the resorcinol compounds, since when the solvents were previously dried the yield was much less.By the action of a solution of sodium methoxide in methylic alcohol on tri bro motrinit robenzene, dime t h y1 tri bro moni troresorci no1 (Zoc. cit. ) is formed together with dimethyltrinitrophloroglucinol, crystallising in yellowish needles, and melting at 77-78". The alkali salts pre yellow. Sodium propoxide in the presence of alcohol and benzene yield.;122 ABSTHAOTS OF OHEMIOAL PAPERS. t riprop y7tr;nitrophlorog lucinol, a substRnceci ystallieingin jellow prisms, and melting at 109-1 10". The corresponding isopropyl compoui,d crystallises i n coloui less prisms, and beconies orange on exposare to the a i r ; it melts a t 130". Sodium isobutoxide and isoamyloxide also react with tr.ibromot,rinitrobenzene, but the products were not examined.Xitrite as well as bromide was formed in all the abort: cases; the rclative amount of nitrite tended to diminish as the molecular weight increased. Sodium benzyloxide in benzplic alcoliol solution (prepared by dissolving sodium in benzylic alcohol) yields, with a beczene solution of t ri b ro m o trin i t ro benzen e, t r i t eFzy 1 trinitropli l w o g lucin ol an d trin it ro- phloroglucinol. The former substance crjstallises in white needles and is discoloured by the air; it melts at 171". A small quantity of benzylic bromide is also formed. Since this substance is without action on the sodium salt of trinitrophloroglucinol, its presence may be due to the direct action of the sodium beneyloxide on the trinitro- t ribromobenzene.Triph eny 1 trini~rophlor~oglncinol, C6( NO,),( OPhb, is converted by alcoholic sodium ethoxide into the curresponding ethyl compound, with elimination of phenol. JN. w. Some Peculiar Cases of Isomerism. By R. E'ABINYI ( Z e i t . physikal. Chem., 12, 564-582).-When asarone is dissolved in abso- lute alcohol, and amylic nitrite and then alcoholic hydrogen chloride are added to the coded solution, ?reen prisms (rn. p. 159-4O) of asarylaldoxime hydrochloride are obtained. If, however, the alcoholic hydrogen chloride be added first, and then the amylic nitrite, rcd prilsms are formed which melt a t 161.6". These, on analysis, were found by the author to give numbem also corresponding with asaryl- nldoxime hydrochloride, and were thus isomeric with the green prisms.The free aldoximes from these salts are both anti-aldoximes ; they differ very slightly from each other, and give acetyl compounds which are still more similar, one and the mme aldoxime being regenerated from the two acetyl derivatives. The hydrochlorides, on repeated recrystallisation from glacial acetic acid, approximate gradually to each other in colour, melting point, and solubility, the final snbatance obtained from both being golden yello~;, and melting a t 155-5". %'he liydro~hloride of the aldoxime prepared directly from asarylaldehjde crystallises in golden yellow needles which melt at 155-4". Several other examples of similar cases of isomerism w e alluded to. 3. w. New Formation of Secondary Aromatic Amines.Ry V. MERZ and S. PASCHKOWEZKY (J. pr. Cltemt , [2], 48, 44--466).-The method consists in heating halogen benzene hydrocarbons with primary amines and a strong itiorganic base. In this way, phenyl- paratolylamine is obtained from bromo-, chloro-, and iodo- benzene respectively, and paratoluidine ; also from parabromo- and pariodo- toluene respectively, and miline. Phenylorthotolylamine is obtained from bromobenzene and orthotoluidine ; diphenylamine from broruo- benzene and excess of aniline ; diparatoly lamine from parabromo-ORGANIC CHEMISTRY. 123 toluene and paratoluidine ; and aniline Erom bromobenzene an3 am- monia. A. G. €3. Isomerism in the Azo-Series. By J. T. HEWITT (Bey., 26, 2975-2978) .- 01-thocldorobenzeneazophenol, C~H~C~*N.L*C~H~*OH, pre- p 3red by treating a mixture of orthochloraniline nitrate and phenol with potassium nitrite, is precipitated from alcoholic solution by the addition of water in fine, yellow needles melting at 85".It IS very readily soluble in the usual organic solvents, but almost insohible in water, and is precipitated from its solution in alkalis by carbonic aiihydride. When heated for an hour a t go", it is converted into a light red substance of the same composition, melting at 96". This modification behaves in the same way towards solvents as the yellow form, but the latter is precipitated by acids from its solutions in alkalis, and by water from alcoholic solution. This behaviour might be accounted for either by tautomerism as expressed the modifications when treated with acetic anhydride yield ths same acetate, which crystallises i n fine yellow needles, and melts a t 100".It is insoluble in water, readily soluble i n alcohol, &c. The benzoate crystallises from hot alcohol in yellow plates, melting at 131". Metachlorobenzevieazop7Lenol crystallises from dilute alcohol in splendid, brownish-violet needles, which, after heating a t 80", become pale yellow, and then melt a t 135". The acetate sepwates from dilute alcohol in yellowish-red plates melting at 92". The benzoate forms yellow scales, and melts at 118". Parschlorobenseneazophenol, which was previously known, does not yield an isomeric form when heated. I t s acetate crystnllises from alcohol in hair-like,. yellow needles, and melts at 160". The benzoate forms small, yellowish-red plates melting at 154".A. H. Diazosulphides. By P. JACOBSON (Annalen, 277, 209-218) .- An introductory paper (see following abstracts and p. 137). The ort hodiazosulphides, unlike the orthodiazooxides, are colourless com- pounds resembling in this respect the azimides obtained by the action of nitrous acid oil the orthodiamines. They generally crystsllise well, have a characteristic, sweetish odour, and are very feebly basic. The first representative OE the class, chlorophenylene diazosulphide, was obtained by Beilstein and Knrbatow (AnnaZea, 179, 82). Bernthsen (Abstr., 1889, 775) described another member of the group, namely, diazothiodimethylaniline, whilst the simplest members were prepared by the author (Abstr., 1889, 135 and 772). A. R. b. Phenylene Diazosulphide and its Derivatives.B v P. JACOBSON and H. JANSSES (Annulen, 177, 218-231) .-Phenylene diazosnlphide, CeH4<S>N (Abstr., 1889, 135), is prepared by the action of nitmu5 acid on amidophenyl mercaptan. The compound melts at 355-3(5, N121 ABSTRACTS OF CHEMIOAL PAPERS. when heated in a capillary tube, whilst by introducing a thermometer into a quantity of the fused substance the solidifying point (?) was found to be 34-95"; it boils a t 129" (corr.) under a pressure of 10 mm., and at 188" (corr.) under a pressure of 150 mm. It is insoluble in dilute acids, but dissolves in concentrated hydrochloric acid, being reprecipitated on dilution with water ; a molecular weight determination by the cryoscopic method established the above formula. A quantity of the compound (0.3-0-5 gram) dissolved in 51 per cent.alcohol and injected subcutaneously into a rabbit. causes death in 48 hours ; the t'oxic phenomena consist in the gmdual paralysis of the central nervous system accompanied by a continuous lowering of the temperature. Theplatinochloiide, ( C6H4N,S),,H,PtCJ6, forms small, six-sided tablets ; a crystalline additive compound, c6H4N2S,HgCl2, was also obtained. Phenylene diazosulphide remains unaltered when heated in sealed tubes with alcohol at 150-160", with 20 per cent. potash at 150", and with 27 per cent. sulphuric acid a t 200", or when boiled with alcoholic ammoniacal silver solution. When boiled with tin and hydrochloric acid, orthoamidophenyl mercaptan is formed, whilst, if treated with oxidising agents, the greater portion remain8 Lnaltered, and the remainder appears to undergo complete combustion.When he lted a t 200-250" uiitil gas ceases to be evolved, S b the residue consists of diphenylene bisulphide, C,H,< >C,H:,. 76H4.N Methylphenylenediazosulphine iodide, SMeI - w, is prepared heating phenylene diazosulphide with an excess of methylic iodide in a setled tube a t 100" ; it crystallises from water in red needles. The >N forms stout, red prisms. ?6H4* N SEtI- conzp ound Meth yllDhen~kenediazosu~hine chloride, Y6H'">N, is obtained by bMeCI digesting a solutfion of tohe iodide with silver chloride ; it crjstallises in colourless, hydrated prisms. When concentrated solutions of ammonium picrate are added to those of the iodide, double decom- position ensues, and crystalline picrates are precipitated.A. R. L. Homologues of Phenylene Diazosulphide. By P. JACOBSON and E. NEY (Amalen, 277, 232-236).-The homologues of phenylene diazosulphide are ptepared from the ethenyl compounds of tbe corre- sponding amidomercaptans (compare Abstr., 1889, 772) ; the latter being heated with alcoholic potash in sealed tubee a t 180-190", and the resulting amidomercaptans treated with nitrous acid. Toluylene diazosulphide, C,H,Me<;->N [Me : S : N = 1 : 3 : 41, crystallises in coloui*less tables, melts in a capillary tube at 42-43", iznd distils without decompcsition under diminished pressure ; the solidifying point, (?) determined with a large quantity of the fused substance is 40.9". On reduction with tin and hydrochloric acid,ORGANIC CHEMISTRY.125 it behaves in a n analogous manner to phenylenc diazosulphide, and, when heated at 200-210", ic yields ditomyleue bisulpkide, which crystallises in faintly yellowish needles, and melts at 116" ; m,ethyltoluylenesul@hine iodide forms beautiful golden-yellow prisms. Xylylene diazosulphide, C,H,Me,<:>N [Me2 : N : S = 1 : 3 : 4 : 51, crystallises in lustrous needles, and melts a t 37" ; dixylylene bisulph- ide, C6H,Me2<S>C6~,Mez, S prepared by heating it at, 250", melts at 118". Xylylene diazosulphide shows little tendency to combine with methylic iodide, and, when heated in a sealed tube at 106" with it, only a very small quantity of a compound soluble in water is obtained. Cumylene diazosulphide, C6HMed<g>N, crptallises in prisms, and melts a t 85" ; its odour is faint and not characteristic, and it loses its nitrogen at a higher temperature (270") than the lower homologues, but a homogeneous substance could not be isolated from the residue.Substitution Derivatives of Phenylene Diazosulphide. By P. JACOBSON and A. KWAYSSER (Annalen, 277, 237-256).-Nitro- N carbirnidothiophenol, N02*CeH3<S YOOH, is thus prepared. Phenyl- thiocarbimide is boiled for 18 hours with absoliate alcoliol, and the phenylthiourethane thus formed is oxidised with alkaline potassium ferricyanide (see Abstr., 1886, 8 i 6 ) . The product, ethoxyphenyl- thiocarbimide, is then hydrolysed w i t h hydrochloric acid, whereby carbimidothiophenol is obtained, which is dissolved in glacial acetic acid, and treated in the cold with nitric acid of sp.gr. 1.52. The nitro-derivative crystallises in stellate aggregates of light yellow needles, and melts at 252". When an excess of soda is added to its solution in dilute soda, the sodium salt separates as a yellow, crystal- line precipitate. The ethylic salt forms faintly yellow, silky needles, and melts a t 205". Nitramidophenyl mercaptan, N0,*C6H3(KHJ*SH [NO? : NH, : SH = 5 : 2 : 31 (Mylius, Inaug. Dips., 1883), is obtained by heating nitro- carbimidothiophenol with aqueous ammonia of sp. gr. 0.95 in a sealed tabe a t 160-170" ; it forms microscopic, pale yellow needles, melts at 83-84', and is oxidised when exposed in the moist condition tu the air, forming the bisulphide, S,[C6H,(NH,)*~o,], ; this compound is, however, best prepared by oxtdising the mercaptan with ferric chloride ; it crystallises in lemon-yellow needles, and melts a t 236-237".W hcn the mercaptan is digested with concentrated formic acid, the methenyl derivative, N0,*C6Hs< >CH (Mylius, (lor. cit.), melting a t 176-177", is produced. A. R. L. N N A-tkvphenylene diazosukhide, N0,*CsH3<S >N, is obtained by the3 26 ABSTRACTS OF CHEMICAL PAPERS. action of nascent nitrous acid on the nitramidophenyl mercaptan ; it crystallises in golden-yellow leaflets, melts a t 136-137", and, when roduced with ammonium sulphide, yields the corresponding arnido- phenylene diazosulphide, which crystallises in long, colourless needles, and melts a t 112" ; when a solution of the base in hydrochloric acid is treated with sodium nitrite, a dark violet coloration is produced on the addition of a-naphthol, and a brownish-red coloration on the addition of resorcinol.Attempts to prepare the amidophenylene diazosulphide by tbe action of nitrous acid on diamidophenyl mercaptan were unsuc- cessful. The author found i t impossible to prepare hydroxypheriglene diazosulphide from the amido-derivative by the diazo-reaction. Nitrocarbimidothiophenol (see above), when reduced with stannous chloride and hydrochloric acid, yields the corresponding arnido- compound, which crystallises in dull, colourless needles, melts a t 262-223", and forms a picrate melting a t 242". ~yanocarbimidothio~henol, CN*CsH3<S >C*OH, obtained from the amido-compound, by Sandmeyer's method, forms pale yellow, micro- scopic needles, melts (not sharply) above 250", and when fused with potash yields carboxyanzidoshiophelzol, which was not isolated, but con- verted by treatment with nascent nitrous acid into carboxyphenylene diazosulphide, COOH*CeH3<S >N ; this was purified by means of the inetFylic salt (m.p. 150-151"). The free acid, obtained by the hydrolysis of the methylic salt with 10 per cent. potash, forms nodular, radiating aggregates of minute needles, melts at 138-139", and decomposes a little above this temperature with evolution of gas. By R. NIETZKI and N. PRINZ (Ber., 26, 2936-2960). -When nitrazimidobenzene is reduced with stannous chloride and hydrochloric acid, it yields the corresponding ani idoazimidobenzene, N N A. R. L.Azirnides. _- NH,*CeH3<~~>N, which crystallises from hot water in colourless plates melting a t 162". It forms two ssries of salts, one with acids as an amido-compound, and one with basea as an azimido-compound. The dihydrochloride, the monhydrochloride, and the platinochloride, C6H6N4,H,PtC16 + HzO, have been prepared, and also the szlver salt, C6H5N4Ag, which is a voluminous, somewhat gelatinous, precipitate. With acetic anhydride, only a nioizacetyZ derivative melting at 248" could be obtained. Amidoazirnido benzene can only be diazotized in strongly acid s o h - tion, and is converted by sodium nitrite, under ordinary conditions, into the azo-derivative, N3*C6H4*N,*C6H3( NH2)*N3, which forms yel- lowish-brown plates, and melts above 300". Amidoazimidohenzene also very readily combines with other diazo-derivatives, yielding azo- colours which closely resemble those obtained in a similar manner from diazobenzene.Thus diazosulphanilic acid yields with amido- azimidobenzene the azo-derivative, Hso3*C,~,*N,*C6H3N3*NH,, which separates in orange-yellow crystals on the addition of sodium acetate. This azo-derivative when subjected to reduction with stannous chloride and hydrochloric acid, yields a new substance which, fromORGANIC CHEMISTRY. 127 its composition and mode of formation, must be diamido~zimidobenrene. It has only been obtained in the form of the dihydrochlode, as the free base rapidly oxidises i n the air ; the solution of the salt, when treated with an orthodiketone such as croconic acid or glyoxal, yields azines, proving that the two amido-groups are combined with adjacent carbon atoms, the diamidoazimidobenzene having therefore the constitution BzN> C6Hz<kH>N.Whether the amido-groups occupy the 1 : 2- or 2 : 3-position is uncertain, but the authors regard the latter as the more prohable By the action of nitrous acid on Dhe diamido-compound, the two nmido-groups are converted in the usual manner into an azimido- group, diazimidobenzene, K<&>C6Hz<GZ>N, being formed. After purification, this forms colourleas needles melting above 300" ; it is an extremely stable substance, and may be dissolved in concentrated GHA(HC1)2, N H2N nitric acid, aid reprecipitated unaltered by the addition of water. H. G. C. Constitution of the Amido-derivatives of Hydroxylamine.By G. MINUNNI and G. ORTOLEVA (Gazzetta, 23, ii, 257-244; com- pare Minutini, Abstr., 1891, 697) .-On heating dibenzhydroxamic acid with phenylhydrazine on tbe water bath, benzoylphenylhydr- nzine and a little benzoic acid are obtained. The reaction probably proceeds in two stages, in the first of which benzoplphenylhydr- azine and benzhydroxamic acid are formed, whilst in the second stage the latter reacts with more phenylhgdrazine, giving the benzoSl derivative and hydroxylamine. On gently heating dibenzhydroxamic wid with aniline, benzanilide is obtained, whilst with paratoluidine the oxamic acid yields benzoylparatolnidide ; i n these cases also, the action would seein to proceed in two stages. These results can only he explained by assigning the constitution NHBz*OBz to dibenzhydr- oxaniic acid ; the formula proposed by Lossen would indicate a very different behaviour under such treatment.W. J. P. Diformazyl and its Relations to Diamidrazone. Ry l4. BAM- BERGER and F. KUHLEMANN (Bey., 26, 2978--29b2 ; compare Abstr., 1893, i, 84).-When acids containing the group -CO*CH2*CH2*CO- are treated with an excess of alkaline diaxobenzene, they are decom- posed, with formation of diformazyl, NzHPh:C(N2Pb)*C(N,Ph):N,HPh, along with other products. Thus levulinic acid, COMe*CH,*CHz*COOH, yields acetic acid, carbonic anhydride, and diformazyl ; acetonedi- acetic acid (hydrochelidonic acid), CO(CH2*CH2*COOH),, yields the same substance along with carbonic anhydride and sucomic acid, whilst the osazone of dihydroxytartaric acid (tartrazin), N,HPh:C(COOH)*C (COOH):N2HPh,128 ABSTRAOTS OF CHEMIOAL PAPERS.gives this same compound and carbonic anhydride, together with a small amount of other products. Succinic acid itself is not attacked by alkaline diazobenzene. Diforrnazyl crystallises in greenisb-brown plates, with a surface lustre which varies from yellow to dark green according to the con- ditions of crystallisatioi~. It melts at 226", gives a red powder, and forms deep red solutions in organic solvents. I t is very readily soluble in benzene, readily in hot alcohol, almost insoluble in light petroleum. With sulphuric acid, it yields a deep, indigo-blue solution. It is a strong base, forming salts which are readily soluble in water, but almost insoluble in dilute acids, so that they are precipi- tated from aqueous solution by the addition of a few drops of acid.The sulphate, C26H22NB,H2SOd, foi-ms dark, orange-red needles with a splendid golden-green reflection, and deconiposes at 232" ; it cr-ysiallises well from alcohol and chloroform, in which it is readily soluble. The hydrochloride, C26H22Ng HCI, is very similar to the sulphste; it decomposes a t 248". When treated with alcoholic ammonium snlphide, diformazyl is converted into diamidrazone, N2HP h:C (NH2).C(NH2) :N,HPh, identical with that obtained by Senf from phenylhydrazine and cyanogen. This mode of formation is a further proof of the formula proposed for diainidrazone by Bamberger and de Gruyter (this vol., i, 23). A. H. Aromatic Oxychlorophosphines. By A.MICHAELIS and G. SCHULZE (Rer., 26, 2937-2940) .- When phosphorus oxychloride and dry aniline hydrochloride are heated together in molecular pro- portions, together with a little benzene, hydrogen chloride is evolved, and anilineuxychlorophosphine, NHPh-POCl,, is formed. The lat8ter is separated from t h e oily residue by treatment with light petroleum, and it can be purified by recrystallisation from benzene and light petroleum. It forms thick, almost cubic, crystals or needles, melts st 84', and does not fume in the a i r ; it cannot be distilled without decomposition, and is slowly attacked by cold water, readily by the hot liquid. With alcohols, i t forms ethereal salts which are being investigated . Pam toluidinemyc h lorop hosphin e, C6H4Me.N H*PO C1,, is obtained in a similar manner from paratoluidine, and forms thick, white crystals melting at 104".Thioaldshydes and their Conversion into Derivatives of Stilbene. By K. KOPP (Annalen, 277, 359-361 ; compare Abstr., 18Ll2, 718 j .-p- Trithiosalicylalcleh~de, C21H,,S,03, is prepared by dis- solving salicylaldehyde in a, well cooled alcoholic solution OE hydrogen chloride, treating with hydrogen suphide for 2-2+ hours a t -lo", and allowing the product to remain f o r two days ; too large a quantity of hydrogen chloride is to be avoided. The compound separates from alcohol in six-sided plates containing 3 mols. C2H60, and, when pure, is colourless and tasteless ; it melts at 210". When iodine is added to its alcoholic solution, the compound remains unaltered ; inasmuch, there- fore, as all the known a-trithioaldehydes are by this treatment con- verted into the /?-modifications (Baumann and Fromm, Abstr., 1892, l050), the author's conclusion that his substance is the P-compound H.G. C.ORGANIC CHEMISTRY. 129 appears justified. The sodium derivative, C,,H,,S30,,Na,, crystallises in fnintly yellowish leaflets ; the benzoyl derivative, C42H30S30,, melt< at 218". Polyrnerised benzoylthiosa7icyIaldehy~~e is obtained by the action of hydrogen sulphide on a 20 per cent. solution of benzoyl- thiosalicylaldehyde in alcohol ; the compound melts a t 95-98", and is converted into benzoyl-$t,rithiosalicylaldehyde when dissolved in ethylic iodide and heated with iodine. p-Tmthio,netahydroxyben~a~deh yde, C2,Hl,S,0,, prepared from meta- hydroxybenzaldehyde in the same manner as the isomeride, forms colourless needles containing 3 mols.C2H60, and melts a t 212" ; the bertzoyl derivative melts a t 146". Polymerised thiomethylmetichydroxy- beizzaldehyde is obtained when an alcoholic solution of methylmeta- hydroxybenzaldehyde is saturated with hjdrogen sulphide. and allowed to remain for 1-2 days; it sinters a t go", and melts a t 95-97'. I f heated a t 160", or treated with iodine in ethylic iodide solution, p-trithiomethylmetahy~rox~benzaldehyde, C24&S303, is pro- duced ; it melts at 147", and becomes brown a t 180". 13-Trithioparahydrox?/bensaldehyde, C2,Hl,S30,, commences to darken at 165", and melts at 215"; the tribeizzoyl derivative melts at 225". BenxoyZparah ydroxybenzaldeh yde, OBz*C6H4*CH0, me1 t s at 72", and is converted by hydrogen sulphide into a polymeric benzoyl thiopara- hydroxybenzaldehyde melting a t 98", which yields the p-trithio-modi- fication when treated with iodine. P-Dihydroxystilbene, O~*C6H1.CH:CH*C6H,oOH [OH:OH = 2 : 2'1, is obtained in small amount on heating p-trithiosalicylaldehyde or the polymeric compound, but more conveniently by warming dibenzoyl- oxystilbene (see below) with alcoholic potash ; it crystallises from slco- hol in transparent, flat needles hal-ing a bluish fluorescence, and melts a t 197".I f distilled, it undergoes partial decomposition ; the main por- tion, however, passes over unaltered, whilst a small quantity is con- \-erted into a-dihydrox-ystilbene, m. p. 95" (Harries, Abstr., 1892, 168) ; the two compounds are separated by taking advantage of the fact that the lower melting isomeride is more volatile with.steam than the higher. The conversion of the latter into the former was not accomplished. Attempts to convert stilbene into an isomeride by heating i t were unsuccessful. Elbs (Abstr., 1893, i, 272) bas observed the existence of two diethoxydinaphthostilbenes, which appear, bow- ever, to have different relations to each other from what the dihydroxy- stil benes have. p- Dibenzoyloxystilbene, C2,&!&4, already mentioned, is obtained when a small portion of /3-trithiobenzoylsalicylaldehyde is rapidly raised to a, temperature of 295-305"; it forms colourless needles, melts at 2 7 4 , and the dibromide melts at 176" with decom- position.Harries describes an isomeric compound (Zoc. cit.). Diorthomethoxystilbene (see Abstr., 1892, 719). DiiizethoxystiZbene, OMe.C,&.C H:CH*C6H4*OMe [OMe : OMe = 3 : 3'3, is obtained by distilling polymerised methylthiometahydroxybenz- aldehyde with a large excess of iron powder; it crptallises in rhombic tables, and melts a t 99-100". Dibenzoyloxystilbene is formed when p-trithiobenzoylmetahydroxybenzaldehyde is heated at 300" ; it melts at 160". Paradihydroxystilbene (Elbs and Hoermann, Abstr., 1889, 097) is130 ABSTRACTS OF CHEMICIAL PAPERP. obtained in small quantity by heating trithiohydroxybenzaldehyde, or in better yield by hydrolpsing its dil enzoyl derivative with alco- holic potash. The last mentinned dibenrrtyl derivative is formed when p l y merised benzojl thiopara hrdroxybe uzaldehyde is heated a t 210-220" ; it melts at 2%".A stilbene derivative is not obtained when polpmerised benzoylthioparahydroxybenzaldeh~de is rapidly heated to 250". Diparamethoxystilbene (see Abstr., 1892, 719 ; 1893, i, 272). New Synthesis of Cournarone. Ry G. KOMPPA (Ber., 26, A. R. L. 2968--2972).-Coumarone was first obtained by Pittig and Ebert (Annulen, 226, 3,541, who assigned to it the formula but did not strictly prove its constitution. The accuracy of this formula is proved by the author, who has prepared coumarone synthe- tically from orthamido- w-chlorocinnamene, NH,*C,H,*CH:CHCI. This substance has heen previously obtained by Lipp (Uer., 17, 1070), b u t was not further investigatpd by him. It crystallises from light petr- oleum in long prisms melting at 55*5-56*5", and separates from alco hol in well-form ed, monosymmetric crystals.The platinoch Zoi-ide forms long, brownish-jellow needles. Bcetyloi-thamido-w-chlol-ocin- namene, NBAc*C,H,-C HICHCl, ci~ystallises in dazzling white, matted needles, melting a t 158--159", and is readily soluble in alcohol. Orthohy~roxy-w-chZoi.ocinnanrene, OH.C6H4*CH :CH CI, is obtained by the action of nitrous acid on the amido-compound. It ci-ystallises in long, thick needles melting at 54*5-55.5", and is readily soluble in alcohol, &c., sparingly in water. It may be preserved for a considerable time in the air without change. When this hydroxy- compound is dissolved in concentrated aqueous pqtash, and the solution heated by steam, it is converted, w i t h elimi- i~ation of hydrogen chloride, into coumarone, which sepal ates a s an oil.The author is endeavouring to prepare the hitherto unknown benzothiophen in a similar manner. A. H. Some Derivatives of Methylic G allate and Dibromogallate. By A. B~STRIX (Bull. SOC. Chim., [3], 9, 692-696).-The bismuth derivative of methylic gallate, COOMe*C6H,(OH)z.o.Bi(OH)z, is a clear yellow powder, insoluble in water, alcohol, and ether. It is decomposed on melting. The lead derivative, whatever the proportion of lead acetate used to precipitate it, has a nearly convtant composition, its formula being co OMe°C6H-( OH) [ OPhO*C6H,( OH),*COOMe] ,. It is a white precipitate, insoluble in water, alcohol, and ether, and blackens on heating. Methylic lead dihromogallate, OH*C6Br2(0,Pb)*C001e, is prec i- pitated of a greenish-blue colour, rapidly becoming green.If is insoluble in all neutral solvents, and melts with decompdion.ORGANIC CHEMISTRY. 131 Methylic triacetyldibromogallate, C,Br,(OA c),*COOMe, is formed by heating together acetic chloride and methylic dibromogallate. It is a white compound melting at 150", insoluble in water, and can be crystalliseci from boiling alcohol. W. T. Iodoterephthalic acid and Iodosoterephthalic acid. Ry €3. ABBES (Bey., 26, 2951-2956).--lodoterepl~thalic acid, C6H,I(COOH),, is readily prepared by the action of alkaline permanganate on met- iodoparatolnic acid ( Abstr., 1893, i, SSl), and crystallises from hot water in slender, yellow needles, which in the crude state melt a t 274-276", but sublime when pure.The neutral sodium, barium, and calcium salts are crystalline and soluble in water, whilst the silver salt forms an amorphous, white, insoluble powder. The dirrrethqlic salt crystallises from hot water in long. yellowish needles, melts a t 77-78', has a n aromatic odour and sharp taste ; the inonomethylic salt melts at 186". lodotcreplithalic mid is converted by the action of fuming nitric acid or of an excess of potassium permanganate into the correspond- ing iodosotereplrthalic acid, 10*C6H30(COOH)z, which forms a yellowish precipitate, melts a t 260" w i t h evolution of gas, and liberates iodine from potassium iodide solution. It may also be obtained by convert- ing iodoterephthalic acid into the iodochloride, which is a yellow, wax-like mass, and acting on i t with a little soda solution.The iodoso-acid only yields salts in which one atom of hjdrogen is dis- placed by metals, the acid sodium, amnioniuin, baiium, and caZci.rrm salts being crystalline, and the silcer salt a yellow, amorphous mass. The nzononzeth!/Zic salt crystallkes in white, lustrous plates, and decom- poses potassium iodide in the cold. The fact that the iodoso-acid only acts as a monobasic acid, whilst the iodo-acid is bibasic, points to the conclusion that an intramolecular salt formation bas taken lace in the iodosoterephthalic acid, which may, like iodosobenzoic 'acid, be represented by the tautomeric formulae 9-70 HO* I--C,H,*COOH ~. IO.C,H,( COOH),. All attempts to replace the amido-group in amidometatoluic acid by iodine were unsuccessful, the corresponding hydroxy-acid being alm ays obtained, whatever metLod was employed. H.G. C. Dinitroterephthalic acids. By C. HAEUSSERMANN and E. MARTZ (Ber , 26, 2982-2985) .- Ort~~o~initrotereyhthalic acid is prepared by heating dinitroparaxylene m. p. 93", or dinitropnra- tolujlic acid m. p. 248", with nitric acid of sp. gr. 1.5 at 170". It is only sl ,ghtly soluble in pitric acid, and separates from hot water in well-formed crystals with a vityeous lustre. It melts with decom- position at above 290", and deflagrates when iapidly heated on platinom foil. Metadinitroterephthalic acid [(NOz)z = 3 : 5 j may be obtained from the dinitropara xy1ei.e m. p. 124", or fi om the dinitroparatoluylic132 ABSTRACTS OF CEIEMICAL PAPER% acid m.p. 158", by oxidation with nitric acid and by the nitration of rnonorlitroterephthalic acid. It dissolves readily in hot water, forming a yellow solution, and separates on cooling in yellowish, distorted crystals, with a vitreous lustre, which melt a t 255" with decomposition. The barium salt is a pale yellow, flocculent mass, and is readily soluble in water. Separation of barium carbonate takeq place when the solution is boiled ; and the salt completely decomposes into barium carbonate and 1 : 3 : 5-dinitrobenzoic acid, when the solu- tion is heated for some time at 200-250". The diefhyZic salt forms white, matted needles, which melt a t 197" and volatilise with decomposition at a higher temperature. It is readily soluble in alcohol, sparingly in water.Paradinitroterephthalic acid [(NO,), = 2 : 51 is formed by the oxid- ation of the dinitroparaxylene m. p. 147-148", but is best prepared from the paradinitroparatoluic acid m. p. 194". It, separates from water in small, prismatic crystals with a vitreous lustre, and dissolves readily in hot water, forming an almost coloui~less solution. It melts above 880" with vigorous evolution of gas, and deflagrates when heated on platinum foil. The barium salt is a flesh-coloured powder which is readily soluble in water. The diethylic saZt, which is rathe). less soluble in alcohol. ether. and benzene than the correspondiug ineta-compound, crystallises in lustrous needles, and melts a t 144" ; when treated in alcoholic solution with tin and hydrochloric acid, it i s converted into diethylic diamidoterephthalate, which was obtained by Baeyer (Ber., 19, 430) by the oxidation of the diimide of ethylic s uccinosuccinate. A.H. Sulphones from Benzylic Alcohol and Benzoic acid. By P. GENVRESSE (Bull. Soc. Chim., [ 3 3, 9, 707-710).-Dibromditolyl- sulphone, SO,(C,H,*CH,Br),, is obtained by brominating ditolyl- sulphone. It forms small, white crystals, melts at 108", and is soluble in hot alcohol and in chloroform. Dih~zldroxyditolyZsuZpl~one, SO,( C6H4-CH,*OH),, is obtained by treating the preceding compound with aqueous potassium carbonate. It forms a mass of fine needles. It is soluble in alcohoI and in boiling water, much less soluble in cold water. It melts at 156", and decomposes on further heating. Dicarboxydipheny ZszcZ~hhone, SO,(C,H,*COOH)z, is obtained by treating the preceding bromo-compound with potassium perman- ganate in alkaline solution.It is a white, crystalline substance, and, though insoluble in water and almost insoluble in alcohol, is very soluble in dilute alkaline solutions. I t s silver salt is obtained a s a white precipitate, not blackening in the light. A pale green copper salt has also been obtained, b u t has not yet been analyeed. Action of Sulphuryl Chloride on Aromatic Hydrocarbons. By A. T ~ H L and 0. EBERHARD (Ber., 26, 2940-2945).-Sulphuryl chloride acts on benzene with formation simply of monoohlorobenz- ene, but if aluminium chloride is added to the mixture, a consider- able quantity of benzenesulpbonic chloride and a small amount of diphenylsulphone are also obtained.Toluene is chlorinated by W. T.ORQANIC CHEXISTRY. 133 sulphuryl chloride both in the benzene nucleus and the side chain, bnt i n presence of aluminium chloride the chief product is paratoluene- sulphonic chloride, small quantities of parnchlorotoluene and parsdi- tolylsulphoue being also obtained. Metaxylene and pnraxylene behave in a similar manner to toluene, the latter yielding diparaxyZyZszdphone, which crystallises i n needles. Mesitylene is attacked by sulphuryl chloride at the ordinary temperature ; if, however, the mixture be kept cool, and aluminium chloride then added, chloromesitylene and mesitylenesulphouic chloride are formed. Pseudocumene hehaveq in R Rimilar mannei', but durene, prehnitine, and pentamethylbenzene yield only chlorinated products.Ethylbenzene is converted into para- c hlore thy1 be nzene, paret hy 1 beu zenesulphonic chloride, and et h y 2 benz- enesulphone ; the latter crystallises in transparent plates, and melts II t 102". Isopropylbenzene yields the corresponding products, the is~ropyZbenze?iesulphone melting at 109-110'. Cymene yields oiily resinous products, whilst naphthalene is converted chiefly into a-chloronaphthalene and a small quantity of a-naphthalenesulphonic chloride. H. G. C. The Strength of Orthosulphobenzoic acid. By J. SHIELDS (Bey., 26,3027--3028).-The author points out that the formation of a, mmon i urn orthosulp hobenzoat e by heating or t hosulp h obenzoic acid with ammonium chloride in concentrated solution simply proves that this acid is less volatile than hydrochloric acid, but not that it is a stronger acid, as stated by Jesurun (Abstr., 1893, i, 713).A deter- mination of the relative strength of the acids must necessarily take into account the law of mass action. J. B. T. Diketohydrindene. By w. WISLICENUS and F. REITZENSTE IN (Annalen, 277, 362-3741 .-Triketohydrindene-@-hydrazone, co C,H,<C-,>C:N*NHPh, i9 precipitated when diketohydrindene is dissolved in the smallest possible quantity of dilute soda and a solution of dinzobenzene chloride together with sodium acetate added ; it crystallises from aqueous :tlcohol in orange-yellow, prismatic needles, melts at 190", and dis- solves in concentrated sulphnric acid with a red colour, which remains unchanged on adding a drop of ferric chloride solutien, but changes first to blue and subsequently to reddish-violet on the addition of potas- cJium dichromate.When ether is added to its solution in alcoholic soda, the sodium salt separates as a reddish-yellow precipitate. When an alcoholic solution of benzylidenediketohydrindene (Annulen, 252, 75) IS treated with phenylhydraxine, benzaldephenyl- hvdrazone is obtained, together with the mono- and di-hydrazone of di ketohydrindene. It has been shown (Annulen, 252,72) that when diketoliydrindene is heated by itself o r boiled with water, R condensation prodnct, an- hydrobidiketohydrindene, CIAHl0O3, is formed ; the anthors have con- firmed this formula by the cr-yoscopic method. and the following experiments render it probable that the compound h a s the cowtitutiou VOL.1,xvI. i. tI 3 4 ABSTRACTS OF CHEMICAL PAPERS. C6H4<CO>C:C<$gt>C0. CO It dissolves in sodium hjdroxide solu- tion with ail intense red colour, which differs from that exhibited by pheno1pht;haleYn in that the colour is not destroyed by excess of alkali. When the alltalitie solution is evaporated, the residue taken up with alcohol, the alcoholic solution evaporated, and the residue triturated with alcohol, the sodium salt, CIeHgO3Na, is obtained as a dark, brownish-red powder ; the calcium salt, (C18H903)2Ca, is a bluish-black precipitate ; and the copper salt an almost black precipi- tate, The oxime, C18HloO-I:NOH, crystallises in small, yellow needlt s, commences to darken at 2 LO", and decomposes above this temperature without previously melting ; whilst its acety Z derivative forms yellow leaflets, and decomDoses above 180".When anhvdrobidiketohrdr- inderic is sufipendedlin absolute alcohol, and phenylh>dmzine (4 mbls.) added, diketohydrindenediphenylhydrazone, C6H'<C(N2H C (N2HPh) p h j>CH2 (m. p. 171-172") is obtained ; biit if less pheny1hydraZii:e (1 mol.) is used, diketohydri~denemonophenylhydrazone is formed. When an- hgdrobidiketohydrindene is treated with concentrated sulphuric acid at the ordinary temperature, or with acetic anhydride a t 150-160", further condensation takas place, and a red compound, ( C18H802)l&, which does not melt a t 310", is produced. A. R. L. Symmetrical p-Diketones of the Aromatic Series. By A. B~HAL and V. AUGER ( E d . Xoc. China., [3], 9, 696-i04).-Malonic chloride reacts with aromatic hydrocarbons in presence of aluminium chloride to give a diketone of the type R*CO*CH,CO.R, a ketone of the type R*COMe, and a hjdrocarbon.The diketones act as acidi:, forming metallic derivatives. They are crystalline substances, in- soluble in water, but soluble in aqueous soluticlns of alkalis and i n organic solvents. Their stability appears to inci ease with the num- ber of carbon atoms in the molecule ; the lower members of tlie series, such as dibenzoylmethane, are readily decomposed by alkalis into ketones and acids. Ditoluylmethane, CH,(CO.C,H,Me), [Me : CO = 1 : 41, is prepared by the actionof malonic chloride on toluene. It is very soluble in benzerie but only sparingly so in absolute alcohol, from which it is deposited in long needles; its alcoholic solution becomes violet on adding ferric chloride, and on diluting with watei; a red, c~ystalline powder of the ferric salt is deposited.I t is deconi- posed by concentrated soda into paramethylbenzoic acid and methyl- phenyl methyl ketone. DiethyEb~.ntoyZmethane, CH2(C0 C6H4Et8), [Et : CO = 1 : 41, resem- bles the above in mode of preparation and in properties. It melts at 42". When decomposed by soda, it yields parethylbenzoic acid and ethylphenyl methyl ketone; the latter has a sp. gr. 0.9719 and an odcur of aniseed. The hydrocarbon produced along with this diketone is metadiethylbenzerie (compare Abstr., 1890, 493). Diortho xuloylmethane, CH2(CO*C6H3Me2)2 [Me2 : CO = 1 : 2 : 41, 'melts a t 138'. It is attacked hy mda with difficulty, and resembles It melts a t 126".ORGANIC CHEMISTRY.13.5 the preceding compounds in its product9 of decomposition and p ~ o - perties. DimetaxyZoyZmethane [Me2 : CO = 1 : 3 : 41 is very soluble in acetic acid or alcohol. It forms prisms melting a t 82". With ferric cbloride, it gives a red coloration, becoming more violet on the addition of water. In its properties and mode of deconiposition by soda, it re- sembles the foregoing compounds. Dipa7-axyEoyZrnethane [Me2 : CO = 1 : 4 : 31, bods in a vacuum at about 250". It is yery soluble i n benzene and light petroleum, but only sparingly in 95 per cent. alcohol. It forms small crjstals rnelt- ing at 101-102". With very concentrated soda, it produces the corresponding dirnethylbenzoic acid and dimethylphenjl methyl ketone [Me, : CO = 1 : 4 : 51, boiling at 265" under i64 mm.pressare, and having a sp. gr. = 1.0154 a t 0". [Me, : CO = 1 : 3 : 5 : 21, melts at 96-97'. It requires to be heated a t 300" in a sealed tube with soda, and then yields a trimethylphenyl methyl ketone and iso- durylic acid. It gives a red coloration with ferric chloride in alcoholic s o h tion. A diketone from cymene has been obtained as an impure liquid. With soda, in a sealed tube a t 30U", it gave, in addition to an acid which was not examined further, a ketone of agreeable odour, boiling a t 240°, and yielding an oxime boiling at 176" (21 mm.) arid melting at 84". No diketone has been obtained in a pure state from naph- thalene by means of this reaction. Physical Modification of p-Carbodiphenylimide and p-C arbo- diparatolylimide.By C. SCHALL (Bey., 26, 306$-3065).-Wben 8-carbodiphenylimide is carefully heated t o its melting point and then suddeuly and strongly cooled, i t solidifies to a yellowish, arnorph- ous mass, which melts at a lower temperature and is more soluble than the /%modification. When slowly heated, i t melts a t 96-49", and at 108-130" is reconverted into the /%modification melting a t P-~nrbodiparatolylimide, when heated and cooled in the same way, is at first semi-fluid, but after a time solidifies. It now melts at 60-70", and cannot be reconverted into the P-modificdtion by further heating. Triparatolylguanidiue, when heated and quickly cooled, mells at 46- 50", and at 70-80" is reconverted into the ordinary modification, melting at 123-12P".A similar behaviour is shown by the compound obtained from 6-carbodiphenylimide and phenylhydrazine. The new modification is always amorphous, even if the primary compound is crystalline and pure. E. C. R. It gives a brown coloration with ferric chloride. Dimesitoylmethscne, CH2(C0.C6H2Me,), W. T. 158-160". Two Recent Publications on the Benzileoximes. By G. MI NUNNJ aud G. ORTOLEVA (Gazzettn, 23, ii, 244--248).-This paper deals with t b e criticisms of Auwers and Siegfeld (Abstr., 1893, i, 354) and of Claus (Abstr., 1893, i, 355) on the authors' work (Abstr., 1893, i, 97). w. 3 . P. 1 2136 ARSTRAOTS OF UHEtfICAL PAPERS. Reduction Products of BenzilehydrazoDe. By A. PuEGOT r t (Gazzetta, 23, ii, 225--331).-In a pr2vious preliminary note (Abstr., 3893, i, 354), the author described a new base, obtained by reducing benzilehydrazone ; the supposition tliat the base is arnidodibenzile is now confirmed.Small quantities of aniline and dibenzile are also produced. AmidodibenziZe, C RzPh*CHPh*NH2, is an oil having an aromatic odour, and boiling without appreciable decomposition at 3LO-31l0 under 730 mm. pressure. J t is very soluble in alcohol, ether, chloro- form, or carbon bisulphide, but only aparingly in water. l t s hydyo- chloride crysta.llises in small, white needles melting at 242--243", and the platinochloride in golden scales which meit at about 188". The oxalate is obtained as a white, crystalline precipitate melting at 158" ; the picrate melts at 190". The constitution of the base is established by the fact that on treating the hydrochloride with silver nitrite, p he n yl benzylcarbinol is: obtained.Diphenylethyloxamide, ( CH,Ph-CHPh*NH),C202, is prepared by heating the base on the water batlh with an ethereal solution of etliylic oxalate. It forms white needles melting at 212", and is soluble in chloroform or boiling benzene, but sparingly so in ether, alcohol, or water. Acetamidodibenzile, CH%Ph*CRPh*XHAc, obtained by heating amidodibenzile hydrochloride with acetic anhydride and fused sodium acetate, crystdliseg in white needles melting at 147-148". Di bewilecar barnide, C H2P h* C HP h NH* C 0 N H,, is prepared by the action of potassium cyanate on the hydrochloride described above ; it forms small, white crystals which melt at 98", and is soluble in alcohol, ether, benzene, or chloroform.W. J. P. Action of @Naphthol and a- and p-Naphthylarnines on the Nitrobenzaldehydes. By M. ZENONI (Gazzefta, 23, ii, 215-224). -The behaviour of /3-napht hol towards aliphatic aldehydes has been studied by Hosaeus and by Abel (Abstr., 1893, i, 100, 172) : the present paper gives the results obtained with the nitrobenzalde- hydes. On adding a little sulphuric acid to an acetic acid solution of orthonitrobenzaldehyde and @-naphthol, orthonitrobe.rizal-p-dinaphtho1- methane, No,*C,H,*C13[(C,,H,.oH)z, is slowly deposited ; it forms a crystalline mass melting at 207", is soluble in et,her, chloroform, or acetone, but insoluble in benzene an? in light petroleum. The corre- sponding oxide, N02*C,H~oCH<,'oH~>0, C H is obtained by boiling the acid solution during the preparation of the previous substance. It forms beautiful, pale green, acicular crystals which turn brown above 250" ; it is sparingly soluble in the ordinary solvents.Metanitrobenzal-t3- dinapht holmethane is prepared in a similar manner to its ortho-isomeride ; it melts at 184", and, on boiling with potash, yields an unstable substa,nce which crystallises in beautiful golden kales. The dinaphthol derivative yields a crystalline diacetyt derim- tive which melts at 242", and is very sparingly soluble in the ordin- 10ORGANIC CHF MISTRY. 137 ary solvents. 220". oxide being obtained instead ; needles which turn brown when heated above 260". nitrobenzaldehyde, metanitrobenzal-a-d~~a~hthylamine, The oxide is obtained in silvery white scales melting a t Orthonitrobenzal-/3-di~aphtholmethane could not be prepared, the this substance forms small, yellow On mixing acetic acid solutions of u-naphthylamine and meta- NO,*C6H,'CH ( CJ&*NH~)Q, separates.It is very soluble in ether or chloroform, and forma yellow laminae melting at 102-105". The isomeric para-derivative is oh- tained in yellow needles melting a t 161-162", and the ortho-isomerida melts a t 119-120". The metn-derivative, obtained from /3-naphthyl- aruine, forms yellow crystals melting at 90-91" ; the para-isomeride is obtained in yellow needles melting at 120-121", whilst the ortho- derivative forms yellow crystals melting a t 92-93', and is very sensitive to light. These derivatives of the naphthylamines may also be prepared by boiling the alcoholic solutions of the two constituents.If, however, fuming hydrochloric acid is added to the alcoholic solu- tions before boiling, nitrophenylhydronaphthacridines are obtained ; these will be subsequentlly studied. A Naphthylene Diaxosulphide. By P. JACOBSON and C. SCETWARL (Annalen, 277, 257-261; compare this vol., i, 123).-1t has been stated (Abs tr., 1858,1307) thatl 2 : 2- ethenylamidonaphthyl mercaptan melts at 81'. The authors find that the melting point of the compound is not sharp, and, even after repented recrystallisation from aqueous alcohol, it softens a t 68--7O', and melts a t about 80"; if, however, the crystals are kept over concentrated sulphnric acid in a partial vacuum, they effloresce and then melt sharply at 48".When the compound is heated with phthalic anhydride and zinc chloride, a phthaEone melting above 300" is formed. When the ethenyl base is heated at 220-230" with aqueous potash, the product dissolved in water, sodium nitrite added, and the solution treated i n the cold W. J. P. tvit,h dilute sulphuric acid, naplithylene diazosuzphide, CloH,<Z>N [N : S = 1: 21, is obtained; it crystallises in small needles, having a bronzy Iustre, melts at 8Yo, appears to decompose on exposure to light, and resembles phenylene diazosulphide in its hehaviour. p-Naphtholcarboxylic acid (m. p. 216") and its Derivatives. By S. ROBERTSON ( J . p r . Chtm., [2], 48,53&536).-@Naphtholcarb- oxylic acid (m. p. 216") was prepaied by heating sodium P-naphth- oxide with liquid carbonic anhjdride a t 270-280" in an autoclave.The product is converted into the ammonium salt, and then, by the action of phosphorus pentachloride, into the chloride, which, by treatment with boiling water, is converted into the pure acid. When treated with nitric acid, it yields, according to the conditions of working, either a mononitro or dinitro acid. The moizonitro-acid, NO,*C,,H,( OH)*COOH, cryqtallises in lustrous, golden-yellow prisms, melts at 233-258" with decomposition, and, A. R. L.138 ABSTRACTS OF OHEMlCAL PAPERS. when boiled with water, decomposes with evolution of carbonic anhydride. The sodium, ammonium, and potassium salts are described ; they are anhydrous, and give insoluble microcrystalline precipitates mith salts of the heavy metals.The ethylic salt crystallises i n lustr- ous, greenish needles, melts at 160°, and is easily hjdrolysed by cold a1 kalis. Amido-p-na~hthobarboxylic acid cryst allises in colourless, lustrous needles, decomposes before melting with the formation of a red dye, and yields dihydroxynaphthalenecarboxylic acid when boiled with acids. The hydrochloride crystallises in white, lustrous needles, and is hy drolysed by water or alcohol. Diaxonaphthobarboxylic acid, OH~C,,,H,<COO>N, crystallises i n long, brownish-yellow needles. Ch~orona~htholcarhosylic acid melts at 230". Dihydroxynaphthalene- cnrboxylic acid, obtained by decomposing the diazo-compound with s ulphuric acid, crystallises in long, greenish needles. Dinitronaphtholcarboxylic acid crystallises in bright yellow, lustr- ous needles, melts at 252" with decomposition, but begins t o decom- pose at 242".The ethylic salt crystallises in white, prismatic needles, and melts at 198". E. C. R. - N p-Naphtholcarboxylic acid (m. p. 216"). By R. MOHLAU (Ber., 26, 3065-3067; compare also S. v. Kostanecki, this vol., i, 91).- Naph thalen eazo-p- h yd roxynap h thoic acid, obtai I I ed by the action of diazonaphthalene chloride on p-naphtholcarboxylic acid (m. p. 216"), yields, on reduction, amido-/I-hydroxynaphthoic acid. The latter is converted by boiling with dilute sulphuric acid into the same p-naph thoquinolcarboxylic acid AS that which is obtained by t h e action of carbonic anbydride on sodium /3-naphthoquinol; it crystal- lisets in yellow leaflets, melt8 at 207" with decomposition, and gives a green coloration with ferric chloride.p-Arnidouaphthoic acid is obtained by heating the P-naphtholcarb- oxylic acid with aqueous ammonia at 260-280". It crystallises in lastrous, Tellow leaflets, mclts at 211-212", and jields phthalic acid when ox idised with potassium permanganate. The diazos ul p h ate, C0OH*C,,H,-N2*HSO4, when treated with copper powder in alcoholic solution, yields /3-naphthoic acid, which melts at 181-182". These reactions prove that the P-naphtholcarboxylic acid melting at 216" is the 2 : 3-compound. Relative Stability of certain Sulphonie Derivatives of Naphthalene. By P, FRIEDLAENDER and P. LUCH~ (Ber., 26,3028- 3034) .--The authors have investigated the relative ease with which the sulphonic group of a number of naphthalene derivatives is re- placed by hydrogen ; the naphthol derivatives were treated in dilute mid, the naphthylaminc derivatires in dilute alkaline, solution at ordinary temperatures with sodium amalgam. The following corn- pounds are practically nnaltered :-/I-Naphthalenesnlphonic acid, a-naphtholsulphonic acid 1 : 2, /3-naphtholsulphonic acids 2 : 3' and 2 : 2'.The following are slowly changed :--a-Napli tholsul phonic acids 1 : 3 and 1 : 2'. a-Naphthalenesulphonic acid, a-naphtholsulph- E. C. R.ORGANIC CHEMISTRY. 139 onic acids 1 : 4, I : 4’, 1 : I’, and /3-naphtholsulphonic acid 2 : l’, are all readily at tacked by sodi um amalgam. a-Naphtholdisulphonic acids 1 : 2 : 4 and 1 : 4 : 3‘ are converted into sulphonic acids. sc-Naphtholtrisnlphonic acid 1 : 2 : 4 : 2’ yields the disulphonic acid 1 : 2 : 2’.p-Naphtholdisulphouic acids 2 : 3’ : 1’ and 2 : 3 : 1‘ are con- verted into the sulphonic acid 2 : 3‘. The following naphthylamine- sulphonic acids are readily reduced :-a-Naphthylaminesulphonic acid3 1 : 4, 1 : 4’, 1 : l’, /3-naphthylaminesulplionic acids 2 : 4’ and 2 : 1‘. a-Naphthylamine-s-disulphonic acid I : 3 : 1’ is rapidly converted into the 1 : %acid. p-Naphthylaminedisulphonic acid 2 : 4 : 1’ yields /3-naphthylamine. The a-sulphonic acids 1 : 2, 1 : 3, 1 : 2‘, and the @acids 2 : 3’ and 2 : 2’ are much more stable. 2 : 3’-Naphthylenediamine is prepared by the reduction of the nitro- sulphonic acid from 2 : 1’-P-naphthylaminesulphonic acid, and subse- quent elimination of the sulphonic group ; it crystallises from water i n colourless plates, darkens in air, and melts at 216”.With ferric chloride, a green coloration is obtained, which becomes blue on warm- ing. Chromic anhydride, bromine water, and calcium hypochlorite all produce a dark green coloration which changes t o brown. The diacety I derivative is crystalline. The original acid, therefore, has the cmstitution “€3, : SO,H : NO, = 2 : 1’ : 3’1. I n a similar manner it is shown that the naphthylenediaminesulphonic acid from a-naphthylaminedisulphonic acid 1 : 4 : 3’ yields 1 : 3’-naphthylene- diamine, and that its constitution is [NH, : SOjH : NK, = 1 : 4 : 3’1. 1 : 3’-Dihydroxynaphthalene-P-sulphouic acid and 3‘ : l-amido- naphthol-4-sulphonic acid yield respectively 1 : 3’-dihydroxy- naphthalene and an amidonnphtbol, which has not yet been described.The following 3-sulphonic acids are not decomposed by Podium amalgam :-1 : 1‘-Dihydroxynaphthalene-3 : 3’-disulphonic acid, 2 : 3-dihydroxynaphthdene-3’-sulphonic acid, 1 : 1’-diamido- naphthalene4 : 3’-disnlphonic acid, and 2 : l’-amidonapbtho1-.3‘-sulph- onic acid. a-Sulphonic acids are, therefore, much more easilv and completely reducid at ordinary temperatures ‘than /%sulphonic &ids. J. B. T. Dihydroanthrol and Dihydroanthramine. By E. BAMBE KGER and F. HOFFMANN (Rer., 26, 3068--3072).-1n accordance with Barn- berger’s centric hypothesis, anthrol and anthramine are capable of taking up only two hydrogen atoms, and these combine with the central carbon atoms and the six-carbon atom rings become benzene rings. The properties of dihydroanthrol and di hydroanthramine are in accordance with this hypothesis ; they show the typical properties of phenol and aniline respectively. Dihydroanthrol, C6H4<~~~>C6H3*OH, is obtained by reducing anthrol with sodium and absolute alcohol.A small quantity of anthrscene dihydride which is formed is separated by ateam distilla- tion, and the filtered solution is then precipitated with acid. It crystallises in white, lustrous plates, melts at 129.5”, and dissolves in Rodium hydroxide with a yellow coloration and green fluorescence. It gives a yellow solution with concentrated sulphuric acid, which, on heating, turns greenish-yellow and then violet, It yields a raspberry-140 ARSTRACTS OF CHEMICAL PAPERS.red dye with diazosulphanilic acid. It sublimes, when heated at 200", in a current of carbonic anhydride. and i n slowly volatile with steam. Unlike anthroi, it is not altered by boiling with alcohol and hydro- chloric acid, or by heating with ammonia or with acetamidc. The acetyl compoufid is a yellow, crystalline powder, melts at 148", and dissolves in alcohol with a blue fluorescence. It gives a golden-yellow solution with concentrated sulphuric acid, which, on heating, turns green and then dark violet. The bsnmyl compound crystallises in bright yellow nodules, and melts at 164". The ethoxy-compound, C6H,:CzH4:C6H3*OEt, obtained by warming dihydroanthrol with ethylic iodide, potassium hydroxide, and absolute alcohol, crystallises in white aggregates, and melts at 107".Dihydroanthrol is not altered by boiling with amyl alcohol aud sodium. Dihy droanthramine, C6H4<CH:> CBH3*NHz, has ahead y been de- scribed by Lieberrnanii and Bollert (Ber., 15, 853). Unlike anthramine, which is intensely yellow and is a feeble base, it is colourless, and readily dissolves in very dilute acids. When treatel 1 with nitrous acid, it yields a, diazo-compound, which gives intensely coloured dyes with aromatic bases and phenols, and when distilled with steam, is converted into dihydroanthrol. CH N. C. R. Isomerism in the Terpene Series. By 0. WALLACE (Ber., 26, 3072--3077).-The author giveb: an explanation of the relations be- tween limoneue (or dipentene) derivatives and terpinol which accounts €or the dihydrohalogen additive products of limonene being inactive, whilst some limonene hydrochlor-nitrolamines are active.An asymmetric carbon atom always occurs in the latter, and not in the former, on this interpretation. Volatile Hydrocarbons in Essence of Valerian. By OLIVIERO (Compt. rend., ll7,1056--1097).-That fraction of the volatile hydro- carbons from essence of valerian which boils at about 157" consists partly of a terebentherie and partly of a camphene, which can be sepaisted by the action of alcoholic potaesium acetate on the mon- hydrochlorides. This camphene is laevogyrate ( [aID = -21"), and yields a, monhydrochloride which is doxtrogyrate. The monhydrochloiide of the terebenthene has a specific rotatory p w e r [a]= = -225". Tbe campliene and terebenthene are accom- panied by a small quantity of a, feebly laevogyrate citrene.Presence of Camphene in Oil of Spike. By G. ROUCHARDAT (Compt. rend., l17,1094-~096).-0il of spike consists almost entirely of camphor, linalol, and a small quantity of horneol and its isomerides. but also containR a small quantity of a hjdrocarbon, C1,,HI6, which boils at 158-16U0, and has all the properties of the camphenes. Its rotatory power is +89" lo', and it yields a nionhydrochioride with a rotatory powel. of -20" 15'. This hydrochloride is decomposed when heated with an alcoliolic solution of potassium acetate, and the hydro- carbon itself, when heated a t 100" with glacial formic acid, yields boineol formate, together with borne diterpilene, which is pioLably J. W. C. H. B.ORGANIC CHEMISTRY. 141 derived from a small quantity of terebenthene associated with the camphene.It is, noteworthy that borneol and a camphene occur together, according to Oliviero, in essence of valerian, and are both hvogyrate, whilst in oil of spike they are both dextrogyrate. I n both cases the camphene doubtless results from the decomposition of ethereal deri- vatives of borneol, either daring the life of the plant or by simple distillation with water. C. H. B. New Source of Rhodinol. By P. MONNET and P. BARBIER (Compt. rend., 117, 1092--1094).-When oil of pelargonium is sub- jected to careful fractional distillation under reduced pressure, it yields rhodinol, CloH17*OH, identical i n all its physical and chemical properties with the rhodinol obtained from oil of roses; it boils a t 124" under a pressure of 14 mm.; sp. gr. at 0" = 0.8886 ; refractive index nr = 1.4652 and nb = 1.4789 a t 16.7"; specific rotatory power [aln = -2" 34'. C. E. B. Constitution of Camphor and its Derivatives. By J. BIZEDT (Bey., 26, 3047-3057).-The products of the oxidation of camphor with nitric acid are camphoric acid, C10H&4, camphanic acid, ClUHl6O6, and camphoronic acid, C9H140s. They form a graduated series : thus camphoronic acid is obtainable by the oxidation of camphoric and camphanic acids, and carnphanic acid is formed by the oxidation of camphoric acid. Cainphoronic acid is a tribasic acid, somewhat resembling tricarballylic acid in its behaviour ; when sub- jected to prolonged distillation it yields carbonic anhydride, water, carbon, isobutyric acid, trimethylsuccinic acid, and small quantities of bye-products resembling phorone.From these results the author assigns to camphoronic acid the constitution and thence deduces the following constitutional formulce : camphoric COOH*CMe,*CMe( COOH)*CH,*COOH, - camphanic acid, CHZ-- YHZ CO OH*bMe*CMe,.CH*CO OH ' acid, /CH2*CHz\ CMe-- CMe,--C*COOH; 'co--0' ,CR,*CHZ\ camphor, CMe- CMe, --CH. This formula ccjrrectly expresses the 'CO *CH,/ reaction of camphor and its derivatives. Thus it explains the forma- tion of bromocamphoric acid, and its conversion into camphanic acid ; the production of dinitrocaproic acid by the prolonged actiou af nitric acid on camphor ; the formation of cymene from camphor, and of isopropylsuccinic acid from camphoric acid, &c. The author gives constitutional formulse explaining these reactiom.According to the author's fo~mula, only two isomeric camphenes are possible, namely, CMe-- CMe, -- CH and CMe-- CMe2 --C. , CH,* CH,, /CHz*CHz\ 'CH: CH' 'ca,. CHH142 ABSTRAUTS OF OHEMIOAL PAPERS. The second formula then expresseq the constitution of pinene, and from this the constitution of terpin is expressed by the formula C)H*CMe <crr:.cH:> C( OH).CHMe2, which is the formula aseigned to terpin by Wallach (Abstr., 1891, 1081) and v. Baeyer (Ber., 26, 2564). E. C. R. Bg G. MASSOL (Bu7Z. SOC. Chim., [S], 9, 719--72l).-€'uritied camphoric acid, m. p. M O O , has a solubility in water a t 8" of 4 2 grams per litre ; its solu- tion is accompanied by absorption of heat: 1.87 Gal. (200 grams in 24 litres). The heat of neutralisation by soda is 27.16 Cal., 13.77 and 13-39 Cal being developed for the first and second equivalents respec- tively (solid acid dissolved in soda solution).Sodium hydrogen camphorate is not obtained by the spontaneous evaporation of its solutior,, but varying mixtures of normal and acid salts. The heat of solution of anhydrous sodium hydrogen camphorate (222 grams in 10 litres) is +4.37 Cal. Norms1 sodium camphorate crystallises with 5H,O ; the anhydrous salt is very soluble in water with development of heat, +15.77 Cal. (244 grams in 8 litres). CH GE Heat of Neutralisation of Camphoric acid. Heat of formation of the salts in the solid &ate- CloH,,04 sol. + NaOH 801. = Cl,,HI,NaO4 sol. + H,O sol.. .................................+18*74 Cal. CloH,,NaO, sol. + KaOH sol. = C,oHl,Na204 sol. + H20 sol. ............................... +13*20 .. The total heat of formation of the sodium salt, +31.94 Cal., is much less than with other bibasic organic acids ; that of the acid salt is sensibly equsl t o the average heat of formation of the corresponding salts of the monobasio fatty acids. By E. SCEUNCK and L. MARCHLEWSKT (Annulen, 277, '261-276) .-Datiscin was pre- pared by extracting the bruised roots of Datisca cannabina with dilute alcohol, distilling off the alcohol, extracting the residue with water, treating the aqueous solution with a small quantity of lead acetate (basic ?), and concentrating the filtrate, from which datiscin separ- ates on cooling. It is repeatedly recrystrtllised from boiling water, when the crystals have but a faintly yellow t i n t .I n its general pro- perties, datiscin agrees with Stenhouse's description (AnnaZen, 98, 167) ; it is very sparingly soluble in ether, and melts at 190". Air- dried datiscin gave, on analysis, values agreeing with the formula C21H21011 + 2H20, and that dried at 130" gave values agreeing with the formula C21H2401, + H20. Specimens which had been dried at the latter temperature, however, were frequently found to have undergone decomposition. When datiscin is boiled with dilute snlphuric acid, datiscetin sepa- rates from the solution on cooling, and a sugar, which is not glucose, a s Stenliouse supposed, but rhnmnose, remains dissolved. The ihamnose was identified by elementary analysis and by its melting W.T. Datiscin and its Decomposition Products.ORGANIC OBEMISTRT. 143 point (Ol"), as well as by means of its osazone and sodium com- pound. Datiscet in, Cl5RI3O6, crystallises from alcohol in bright yellow needles, melts at 237" (uncorr.), and dissolves in concentrated sulphuric acid, forming a yellow solution, which subsequently exhibits a beautiful blue fluorescence. The above formula was confirmed bay determina- tions of the molecular weight by the ebnlloscopic method. The lead salt has the composition C,,H,,O,Pb. When datiscetin is fused with potash, salicylic acid is formed. The authors confirm Stenhouse's observations that datiscetin is converted into picriu acid on treatment with concentrated nitric acid, and into nitrosalicylic acid (m.p. 2%6"), on treatment with dilute nitric acid. They conclude that the nitro- salicylic acid has the constitution [COOH : OH : NO, = 1 : 2 : 51. It appears probable that when datiscetin is distilled with zinc dust methyldiphenylenic oxide is formed, whilst i f boiled with hydriodic acid (sp. gr. 1*7), methylic iodide is produced, together with a com- pound melting a t 13@, and having the composition of a tetrabydroxy- xanthone, c6"H4<cO> C6(OH),. Taking the whole of the above- described facts into account, the authors submit the formula ~ , ~ ~ < , o > C 6 ( ~ M e ) 3 ( ~ H ) z [(OMe), : (OH), = 1 : 2 : 3 : 41 as re- presenting the probable constitution of datiscetin. Santonin. By A. ANDREOCCI (Ber., 26, 2985-2986) .-The formula for sanfonin, which, according to Klein (Ber., 26, 2506), the author has quoted (Abstr., 1893, i, 526) incorrectly from the paper by Cannizznro and Gucci, on " Some derivatives of Photosantonic acid " (Beal.Accad. Lina., 1892, ii, 149), accurately exprcdaes all that has been proved concerning the constitution of santonin, and only differs from that put forward by Cannizzaro in the nature of the lactone combination, which is acknowledged by the last named chemist to be still an open question. Santonone. By G. GRASSI-CRISTAT~DI (Ber., 26, 2988-2990) .- The author points out that Klein (this vol., i, 51) is in error in em- ploying the formula ( C,5H1802)2 for santonone instead of ( C,,HI,C2),, and further maintains the accuracy of his original observation that the melting point of santonone is 2%3", and not 200-201" as stated by Klein. The resulting questions raised by Klein will be found answered in the anthor's original communication on the subject (Abstr., 1893, i, 110).Oxidation of Piperidine and of a-Pipecoline by Hydrogen Peroxide. By R. WOLFFENSTEIN (Rer., 26, 2991-2998 ; compare Abstr., 1892, 1484) .-Amidovaleraldehyde? prepared in the manner previously described, on extraction with ether from acid solntion, forms crystals which melt at 39" and boil at 110-111" under 55 nim. pressure. The phenylhydrazone acefate, C13H21N302, is crystalline and melts at 130". By the action of hydrogen peroxide in excess on piperidine, formic and butyric acids are formed in addition to glufaric acid. On reducing arnidovaleraldehrde with zinc and co co A.R. L. A. H. A. H.144 ABSTRACTS OF CEEMICAL PAPERS. hydrochloric acid, piperidine is regenerated. With nitric acid, the aldehyde forms a nztmte, but the slightest excess of acid converts the aldehyde into succinic acid. a- PiperidinesuZphonic acid, C5N€€,,.S0,3H, is formed from sodium hydrogen sulphite and amidovdera.ldehyde hydrochloride, and crystallises in prismatic needles melting at 180". The compound has no reducing properties and does not react with iodine and starch; on heating with fuming nitric acid and barium chloride, barium sulphate is precipitated. The sodium salt is readily soluble, and is formed from sodinm hydrogen sulphite and amido- vale ral de h y d e . Amidocaproaldehyde, NHz*CHMe*CH2*CHz*CHz*CH0, is prepared by tthe action of hydrogen peroxide on a-pipecoline at ordinary tem- peratures for 48 hours.It boils at 116-117" under 60 mm. pressure, a t 1 d closely resembles amidovaleraldebyde in properties and reducing powers. The hydrochloride, C6H13N0,HC1, which can he crystallised trom a mixture of acetone and alcohol, melts at 116". By the pro- 1 4 #u,aed action of hydrochloric acid on amidocaproaldehyde, it is con- verted into secondary tetrahydro-a-picoline (a-pipecoleine), which is also formed by distillation of the aldehyde with potash; it boils at 123.5-125.5' under a pressure of 750 mm. and is probably identical with the compound obtained by Ladenburg by the action of bromine on a-pipecoline. The hydrochloride crystallises in colourless needles melting at 204". The picrate is oily. I n addition to ainidocaproaldehyde, the oxidation of a-pipecoline gives rise to a ketonic or aldehyde acid i n small quantity ; it is con- tained in the residue after the steam distillation of the aldehyde.I t crystallises from a mixture of alcohol and acetone in stellate groups of colourless needles, melts at 103.5", and has one or otber of the formula3 CHO* CH( NH,)*CH2.CH2*CH2*COOH ; NH2* C H2* C H2. C H2-C Hz* C 0.C 0 0 H. With hydrogen peroxide in excess, a-pipecoline yields formic, acetic, and snccinic acids. Confine and p-pipecoline closely resemble a-pipe- coline in their behaviour towards hydrogen peroxide, a-picoline is much more stable, and even after a considerable time only yields small quantities of formic acid. These results, as well a8 the nume- rous syntheses of pyridine derivatives which are known show how close the connection is between this class of compounds and the members of the fatty series, and render it easier to understand the formation of pyridine compounds (alkaloids) by plants.Synthesis of Hydroquinoline Derivatives. By I. GUARESCHI (Chem. Centr., 1893, ii, 454 ; from Atti Accad. Sci. 'L'oiino, 1893).- Ethylic cyanaceta te readily acts on orthamidoacetophenone forming a substance which crystallises in d k y needles, melts at 350-332", and has the composition C,,H8N,0. It is ~ - c y a n o - a - m e t k y ~ ~ e u d o - carbostyril, or +yanoEPpidoire, C,H,<iF.'X:N j in its formation J. B. T.ORGlANlC CHEMISTRT. 145 the two compounds unite with elimination of alcohol, the cyan- orthamidoacetophenone thus obtained undergoing intra-molecular condensation with loss of water. P-Cyanolepidone is almost in- soluble i n water, sparingly soluble in alcohol, and with silver salts yields the siher compound c~,Nz&oAg.On distillation with zinc dust, it is converted i n t o lepidine, thus confirming the formula already given. If ortharnidobenzaldehyde is substitut2d for the acetophenono derivative, the corresponding cyano~seudocarbostyril, or P-pyano-a- , is obtained ; this crystallises in ketcldihydropuinoline, C&L< long needles or lustrous, yellowish plates, melts at 3'29-331" with decomposition, and yields a silver compound CloH,N20Ag. CH:F-CN NHCO H. G. C. Pyrazolidone. By R. v. ROTHENBURG (Ber., 26, 297242975). -Hydrazine hydrate acts on acrylic acid with formation of pyrazol- idone, CO<cHz.bH, ; this boils at 132-133", bas a sharp, pyraz- alone-like smell, and is insolub!e in alkalis, but soluble in acids. Ferric chloride converts it by oxidation into pyrazolone, and nitrous acid into isonitrosopyrazolone (Abstr., 1893, i, 611).It instantly reduces ammoniacal silver solution. Phenyihydrazine reacts i n a similar manner with acrylic acid, 1-phenylpyrazolidone, CO < C H2- C Hz' being produced. This sub- stance separates from benzene in crystals melting a t 119-121", and boils at 299-301". It has been previously prepared by the action of phenylhydrazine on the F-halogen-propionic acids (C. F. Bo hringer Sohne, German Patent, 53834). It behaves towards reagents in the same manner as pyrazolidone, being converted by oxidation into 1-pheny I - pyrazolone (Ber., 24, 433c), and by nitrous acid into isoszit~oso-1- the silver salt of which is a p hen y lp yrazo l o n e , C 0 < reddish-yellow, granular powder.A. H. Action of Halogens on 1-Phenylpgrazole. By 0. SEVEEJNJ (Real. Accad. Linc., 1892, ii, 391-394; compare Abstr., 1893, i, 671).- Chlorine acts on 1-phenylpyrazole suspended in water, either with or without the addition of potash, yielding 1-phenylchloropyrazole, melting at 74*5-75.5", which the author has previously prepared by the action of sodium hypochlorite on phenylpyrazole. The 1-phenyldibromopyrazole, melting at 84", is obtained on adding bromine to 1-phenylpyrazole suspended i n dilute potash (1 per cent.). Iodine has no action on 1-phenylpyrazole a t 100" under ordinary conditions; n solution of iodine in potassium iodide acts on the pyrazole in potash solution, with formation of 1-phenyZiodopyrazole, C,H,IN,.This substance is volatile in a current of steam, and crys- tallises in small, white needles melting at 76.5" ; i t is holuble in alco- hol and in ether. W. J. P. NH .NH NPh-TH NPh-N C (NOH)$H'146 ABSTRACTS OF CHEMICAL PAPERS. Synthesis of Compounds containing Carbon-Nitrogen Rings from Orthoamidobenzylamine and its Derivatives. By M. BUSCH (Chem. Centr., 1893, ii, 578-584; from Hub. Xchr<ft. Erlangen). -The substituted amidobenzylnmines are prepared by the reduction of the corresponding nitro-compounds with zinc dust and acetic: acid at a low temperature. The derivatives containing an aliphatic: alkyl group are liquid and strongly basic in character, whilst the derivatives,of the aromatic series are crystalline and less basic, but give stable salts with acids.OrtAamido- benzylmethylamine, NH2*C6H4.CH2*NHMe, is an almost colourless oil, which has a bitter taste and alkaline reaction, and is readily solu- ble in water. Orthamidobemyletlyltrmine is a yellowish oil. On%- awidodibenzylamine is an almost colourless oil, slightly soluble in water, readily in alcohol, &c. 0, tltamidohenzylamine, NHz*C6H~*CH2*PI'Hz, is a liquid. Orthamidobenzylparanisidine, NHz*C6H4*CHZ*NH*CsH4*OMe, cryst allises in yellowish-white, lustrous scales melting at 82". OrtTb- airiidobenz ylpnraphene f idine, NHz* C6H4*CH2*NH*C'sH4*OE t, crys tallises in white, nacreous plates melting at 78".Orthamidobe1azy7lparachloranil- ine, NH2.C6Hd.CHzoNH*C6B,C1, crystalIises in white, lustrous needles melting at 89-90". Orthamidobenzylparabromanili?ze forms white needles melting a t 104'. Orthamidobenzyl-x-naphthylamine crystal- lises in almost white, lustrous plates, with a faint tinge of red, and melts at 134"; its solutions show a bluish-red fluorescence. Orth- a)71idobenzyLP-nayhthylamine forms white, lustrous plates melting at 99"; its solutions have a bluish-violet fluorescence. Many of the salts of the above compounds are also described by the author, together with the corresponding nitro-compounds and other deriva- tives. Orthamidobenzylamine itself condenses with aldehydes to form NH*YHX the corresponding tetrahydroquinazolines, c6H4<c~2,~a - The substitution products of the base, 011 the other hand, form benaylidene cQmpounds of the type RHN*CHz*C6H4*N:CHX. The latter are decomposed by dilute mineral acids into their components. When treated with metallic sodium in alcoholic solution, the benzylidene compounds take up 2 atoms of bydrogen, and are converted into the subs titution derivatives of the corresponding base, With the exception of ortha~nidobenzylparachloraniline and the corresponding bromine derivative, these substances yield di-acid derivatires of the cai-boxylic acids.The condensation products of the bases described above with benz- aldehyde, salicylaldehyde, formaldehyde, and paranitrobenzaldehyde and their derivatives are a180 described in the paper. The nitrobenxylamines, when heated on the water bath with benzenes ulphonic chloride, are converted into nitrobenz ylamin ep hen j 1 - swlphones of the type NO,.C6H,.CH,.N(SOIPh)R, and these, on reduc-ORQANIC CHEMISTRY. 147 tion, yield the corresponding amido-bases, but are not converted into anh y d ro-com pou nds.The orthamidobenzylamines reach with carbonyl chloride and with carbon bisulphide to form keto- and thio-derivatives of tetrahydro- H* f.' The cornpounds quinazoline, C6H4<ZEi.Si and Cs X,< CH,*NR' thus obtained are not identical with those prepared by Soderbsnni and Widmann from the corresponding carbamide and thiocarbamide derivatives of orthamidobenzylic alcohol, although, from the method of formation, substances of identical constitution would be expected.The thiotetrahydroquinazolines are converted by the action of freshly precipitated mercuric oxide at 150" into the keto-derivatives. When treated with energetic reducing agents, the thio-derivatives are con - verted into tetrahvdroauinazolines. Both the keto- and thio-corn- U L pounds are oxidised by permanganate to the same diketo-derivativek, C6H,<C0 .hR. With the exception of the derivatives prepared NH*CO from orthamidobenzylamine itself, these keto- and thio- compounds are completely indifferent to acids and bases. Methylic iodide forms the hydriodide of the corresponding methyl derivative, and the com- pound t'hus produced has strongly marked basic characters. Ketotetrahydroquinazoline, C,N2H80, forms either a white, amorphous mass, or indistinct, white, microscopic needles melting at 180".It is soluble in alcohol and acetic acid, but almost insoluble in water. Plzennylketotetrahydroquinnxolins, C,N2H,Ph0, crystallises from ethylic acetate in transparent, four-sided plates with an adamantine lustre, and from alcohol, 011 dilution with water in broad, pointed needles or thick plates. Paratolyl- ketotetrall ydroquinaxoline crystallises from alcohol in lustrous needles and from ethylic acetate in tramparent prisms melting a t 218-260" ; i t is readily soluble in, boiling alcohol, but insoluble in water. Phenetylketotetralzydroqz&aaxoline forms fascicular groups of colour- less needles melting at 223". Parabromophen.yltetrahydroquinazo1ine crystallises in transparent, quadratic plates melting at 2'26". Thiotetrahydroquinazoline, CeN,H8S, is prepared by heating orth- amidobenzylamirie with an excess of carbon bisulphide and an equal volume of dilute alcoholic potash ; it forms white, lustrous plates melt- ing at 210-212".EthyllJ,iotetrah.~u'roquina,.oline cr_vstallises in white, lustrous plates, melts a t 185", aud is very soluble in benzeiie and chloroform. Phen?!Ithiotetrahydroquiwazoline forms colourless needles, or large transparent plates, slightly soluble in alcohol, more readily in boiling acetic acid. It softens and becomes yellow at 235". and melts at about 245". Paratolylthiotetrahydroquinazo!ine crystallises in white, flat needles, softens at 630°, and melts at 235". YkenetyZ- t7Liotetrahydroquinazoline separates in white, silky needles melting at 238". Pa~achlorophenylthiotetrahydropuinazoline forms liibtrous, silver- white plates, melts a t 228", and is soluble in carbon bisulphide and boiling acetic acid. Parabromothiotetrahydroquinazoline crystullises from absolute alcohol i n transparent, four-sided prisms melting at 2349 a-NapAthylthiotetrah ycloq Ate'nazoline crptsllises from amy 1 It softens at 186", and melts at 189".148 ARSTRACTS OF CHEWCAL P~PERQ.slcohol in transparent, lustrous plates melting a t 255". /3-NaphtAyE- thiofefr~hydroy?cinnzoline forms brilliant, transparent plates, melts a t 'L80", and is soiuble in acetic acid. Tetrahydroquinazoline, C6H4<cH,.NH , crystallises in white plates. which are soluble in wacer, and me1 ts a t 81". a-Nap7~,thyZtetmhildro- quinazoline forms white, lustrous plates, readily soluble in absolute alcohol, &c., and melts at 134".P-Naphtltyltetrahydroquinazoline forms yellowish plates melting at 135-139". When the substituted orthamidobenzylamines are treated with nitrous acid, the diazo-compounds which are first produced are imme- NH. YHz diately converted, with elimination of the elements of hydrpqen chloride, into phenodihydrotriazines of the type C6H4<N -.r CH,*NR- Thus p-phenophenyldihpdrotriazine may he prepared by the action of nitrous acid on orthamidobenzylaniline, and it is also obtained when orthamidobenxylphenylhpdrazine is treated with nitrous mid, the ni tram mine of orthnm i dobenzyl aniline, NH2-CsH4* C Hz*NPh*NQ, being probably formed as an intermediate product. I.3-Pheizop7tenyldihydrofriazine forms lustrous, yellowish plates, and melts at 128" with evolution of gas./3-PhenomEthljldihyc~rcfriazine separates from boiling light petroleum in yellowish plates, and from ethylic acetate in large, lustrous crystals melting rrt 72-73'. p-Phen- rthyldihydrotriazine is a yellow oil, and form.: ~ a l t s which crystallise well. p-PhenobenzyUihydrotriazine is precipitated in snow-white needles, on a,dding water to its alcohnlic solution and ciaystallises in large, six-sided tablets, melting a t 91" with evolution of gas. P-Pheno- parato1 yldih y d rotriazine cry stct 11 i ses from alcoh ol in g ell ow, lustrou s, rhomboidal plates, and from ether in thick crystds with m adamant- ine lustre, and melts atl 151". P-Phenoparanisyldihydrotriazine forms lustrous, crystalline scales, and melts with decomposition at 139".p- Pher,oparaphenetyldi hydrotriazine cry s tallises in golden- y ellow, lu s tr- OUP plates, melting at 1W with evolution of gas. p-Phenoparachloro- yhenyldih ydrotriazine separates from hot alcohol in golden plates, and from benzene in thick, transparent crystals melting at 134". P-Pheno- parabromophen!lEdihydrotriazine forms pale yellow, lustroiis plates, melting at 164". /3-Phenacetyldi?:h ydrotriazine separates from alcohol at 60" in lustrous plates, and from ether in flesh-coloured, rhombo- idal plates; it softens at 136O, and melts a t 138" with evolution of gas. p-Phenobenzoyldihydrotria~i~ forms white, lustrous needles melting a t 114-115" with evolution of nitrogen. The p-phenodihydrotriazines are basic compounds, and, with the exception of those containing acid redicles, which are only slightly basic, give stable salts.They are themselves very unstable, melt with evolution of nitrogen, and show a remarkable similarity to the diazo-compounds, I n aqueous solution, the salts decompose on heating with evolution of nitrogen and formation of the corresponding hydr- oxybenzylamine, whilst heating with a concentrated halogen acid leads to the formation of the correspondimg halogen derirative. With amines and phenols, they yield the deeply-coloured azo-compoundsORQANIO CHEMISTRY. 149 whicll are characteristic of the diazo-compounds. Thus with p-naphthol, the product, is of the type Oa.c,,H6*N2.C6HEI,.CH2.NIIR. These colouring matters are acted on by reducing agents in the usual manner.Gentle oxidising ngeiits have, as a rule, no action on the triazines, whilst stronger reagents cause a breaking up of the molecule. On reduction, the phenodihydrotriazines are converted into the corresponding amiclobenzglarnine, ammonia being eliminated. When p-phenotolyldihydrotriazirie is heated at its rnelting point, nitrogen is evolved, and benzylidsnetoluidine, CHPh:N*C,H,, is left as an oil. When the orthonitrobenzylnitrosatnines are reduced, the correspond- ing amidobenzylhydrazines are formed. Ort honitrobenz ylpheny Initrosamine, N02*C,H** C H,.NPh*NO, separ- ates from alcohol i n coarse, yellow cr.ystals, and from ether in clear, vitreous prisms melting at 84". Orthamidobenzylphenylhydrazine, NH2*C6H4.CH2*NPh*NH2, crystallises in vitreous needles melting at 102". Orthonitrobenxylparatolylnitrosamine forms lustrous, yellow needl es me1 t i ng a, t 80 " .Orth amidob enx ylpnrato2 y lli y draz ine crystal- lises in snow-white, lusti*ous needles meltin: at 66". Orthonitrobenzyl- ~aruphenetyZnitrosa/~/i?~e forms orange-coloured plates melting a t 95". Ort hamidobenz y I/ jaruphen et yl hydrazin e c rys t a1 lisea in colo u rl ess needles or rhomboidal tablets melting at 98". Orthonitrobenzylparac~Zoro~henyE- uitrosamnine crystallises in yellow, transparent prisms melting a t 100". Oyt hamidob enzqlparachlorop heny 1 h ydrazine forms trans parent prisms melting at 95'. OrthoiaitrobenzyLparabrorno~k~m~ylnitrosamine crystal- lises in microscopic plates rneltin < a t 107". Ortharnidobenzylparabronzo- phenylhydrazine forms lustrous tablets melting at 219-120".Ortho- nitrobenzyl-P-naphtLylr/iti.osamine crystallises in dark yellow plates MI el ting a t 102". 0 y t h amido b ert zy 1-+nap hthy lh ydrazine forms small needles melting at 76". The amidobenzyl hydrazines are powerful bases. Tbey reduce Fehling's solution and silver oxide at the ordinary temperature, form very hygroscopic salts with the mineral acids, and condense with aldehydes to form dibenzyl idene compounds. The amidobenzylhydraz'nes react with carbonyl chloride and carbon bisulphide i n a manner similar t o the amidobenzylamines, yielding products of the type These substances melt between 250" and 300" with evolution of gas and decomposition, and are much less stable than the corresponding quinazoline derivatives, into which they tend to pass.The thio- carbamides derived froni the amidobenzylhy drazines, for example, when treated with metallic sodium in alcoholic solution, yield the corresponding tetrahydroquinazolines, ammonia and hydrogen sulph- ide being evolved. These seven-ring compounds are indifferent towards both acids and alkalis. A. H. Action of Cyanogen on Hydrazine. By A. ANGEL^ (Guzzetta, 23, ii, 103--104).-0n passing a rapid curretit of cyanogen into an VOL. LXVI. i. m150 ABSTRACTS OF C tIEJlICAL PAPERS. aqueous solution of hydraziue, arid strongly cooling, a substuitce of the composition CZNGH-I, separates ; i t fovms large prisms which do not melt a t 2:30". It readily acts on aldehydes and ketones, and may therefore have the constitution C(N II0NH,),( NB),.When treated with nitrous acid, it gives a white, crystalline product ; this is prob- ably the d;tetrazoZe, I I N--N N-N >CWNH.+. W. J. P. N*NH Sparte'ine. By F. B. AHRENS (Ber., 26, 30954042; compare Abstr., 1893, i, 232) -The author has already described the forma- tion of trioxysparte'ine by the action of hydrogen peroxide on oxy- sparteine. If oxysparteyne hydrochloride is treated with dilute hydrogen peroxide, no trioxysparte'ine is obtained, but a quantitative yield of a new base, C15H22NLOL, which crystallises from ether in white needles. The hydrochloride, C15K2iNL02,HC1, crystallises. with 3fH,O, in white needles. The dihydrocl~loride, C,H,,N,O,,BHCL + 3+H,O, crystallises in transparent prisms. The Aydrobrornide, C15HzrN202,HBr + 4H20, forms transparent crysi5als.The platinochloride, crystallises in orange leaflets or needlns, and decomposes a t 236". The aurochlordde crystallises in lustrous leaflets, darkens a t 186", and melts at 194" with decomposition. A bdse of the composition CI5H,,N,O is obtained by boiling spart- e'ine with freshly repared silver oxide or mercuric oxide and water. iodide, CI5Hl6N20,HI, crystallises in leaflets, and melts atJ 211". The platinochloride forms small, sparingly soldble C I g%tals, and melh a t 108". The cturochloi*itZe fohns rnicroJcopic crystals, and melts a t 175" with decomposition. A bdse isomeric with the preceding is obtained by boiling sparte'ine with freshly prepared lead peroside and water. It is a hygroscopic resin, easily soluble in water.The platinochloride forms sniall crys- tals, darkens at 'L:30°, and decomposes a t 256". Tho aurochlom2e is a crystalline powder, and melts a t 178-180" with decomposition. Dehydrosparteiw, CI5H2JV2, is obtained by shaking spar te'ine with a concentrated solution of bleaching powder. I t is a liquid closely resembling sparte'ine, and boils a t 314-316" (uncorr.) without de- composition. The hydrochloride, C,,H,,N,,'LHC~ t 2$H20, forms large, colourless crysta Is resembling ammonium chloride, and carb- onises a t 270". The ?i ydr- iozide, with 1H20, melts at 2Fi8O. The phtr'nochloride, with 2H20, crystallisps in beautiful, indented plates, and melts a t 237" with decompositidh. The azwoch Idride crystal lises in sparing1 y soluble needles, gradually blackelis when heated, and froths up at 168".Sparteine sulphate, when distilled under 16-20 min. pressure with zinc-dust ahd zinc oxide, yields a mixture of bases, namely, diethylmethylamine, pyridine, a-picoline, a base which was not identified. 2: 3 : 6-trimethylpyridine, sparte'ine, and a base of the formula C,,H,N,, which melts a t 9.+--101": and yields a n awochloride me1 ting It is an oil wbic 1 quickly darkens on exposure t o air. The hy?r- The h y h b r o m d e crystallises with lH,O. at 190- wit 11 decc~mposi tion. E. c. R.ORGANIC OHEMISTRY. 151 Meconinemethyl Methyl Ketone and Di-meconinemethyl Ketone. By F. HEMUDIELNAYR (iionatsh., 14, 390--399).--Meconine- >CH.CH,.COMe (Absty., 1892, methyl methyl kctone, 179), is hydrolysed by boiling baryta water partly into the hydroxy- acid by severance of the lactone bond, and partly into opianic acid and acetone.When, however, a mixture of opianic acid and acetone ia boiled with barytn water, condensation occurs, and meconinemethyl methyl ketone is formed. The ketone is hSdroiped by alkaline per- mnngai;ate also into opianic acid and acetone, the latter substance being of course further oxidised to forniic acid. The hydrolpsis is not due to the action of the alkali. Thephenylhydrazone is described ; it melts a t 159-160". Meconinemethyl methyl ketone is converted by boiling bromine water into a monobroi~2o-dt.riuative. D i-meconinemethyl ketone, CO [ CH,-CH <C6H2(*Me)z>C0]z O--- (Zoc. cit.), is hydrolysed hy boiling baryta water in the same way as the mono-compound. The author claims priority in the preparation of a phenylhydrazine- lactone additive compoiiiid, namely, the dihydrazone of meconine- methyl phenyl ketone (Abstr., 1893, i, 181).YO- 0 C6Hz ( O&le)z JN. W. Action of Methylic Iodide on Papaverinic acid. Ry I?. SCHBANZHOFER (Mmatsh., 14, 597).-The author finds that the normal barium salt of the methylbeta'ine of papaverinic acid, C3aH2sNz0,4Ba (this vol., i, 59), crystallises with 6HzO. G. T. M. Cinchonine. By M. FREUKD and W. ROSENSTEIN (AnnuZen, 277, 277-290) .-A preliminary account of the author's experiments has already bee9 published (Abstr., 1892, 8il2). The specific rotatory power of dirnethylcinchonine dihydrochloride, tbat is, of the basic hydrochloride (Zoc. c i t ) , dissolved in dilute hydrochloric acid is [a]= = +5.37" a t 20".When to the last-men- tioned solution platinic chloride is added, a platinochloride, is precipitated. The hydrobromide, Cz,Hz,N,O,HBr, melts at 118-120" (not 111" ; loc. cit.). The picrate, C,,H,6N,0,2C,H,N,07, melts at 160" ; the rincochloride, C21H26N20,HZnC13, melts at 220' ; and the mercurochloride at 222". Dimethylcinchonine ethipdide melts a t 138" ; dimeth ylcinchonz'ne benzylic chloride was prepared. Methylcinchonine, dimethylcinchonine, methglcinchonine mgtho- sulphate, and dimetbylcinchonine methosulphate all yield cin- choninic acid when oxiclised by Skraup's method (AnnuZen, 201, 291) ; this fact shows t l a t the alkyl groups are combined with one and the same nucleus. When dimethylcinchonine methiodide is boiled with concentrated alkali, i t decomposes into trimethylamine, and a base which yields a yelio w, amorphous p ZatinochZoride, ( C,9Hl,N0)~,H2PtC16, that does not melt at 280".152 ABSTRACTS OF CHEMIOAL PAPERS.The presence of a quinoline nucleus explains how the nitrogen atom in one-half of the molecule of cinchonine is combined, whereas the function of the second nitrogen atom is still obscure. A. R. L. Pseudocinchonine. By E. LIPPMANN and F. FLEISSNER (Monatsh., 14, 371-.375).-When cinchonine trihydriodide is heated with water (h to 2 t-01.) for 5-6 hours at 15O-16O0, it gradually dissolves, and, on keeping the solution, a yellow, acicular precipitate gradually falls, consisting of the hydriodide of pseudociuchonine, a base isomeric with cinchonine.The base may be isolated by means o€ the sparingly soluble normal sulphate. The product, of the above action is precipitated with ammonia, and the mixed bases suspended in water and cautiously neu tralised with dilute snlphuric acid. Pseudocinchonine snlphate soon separates, whilst the sulphates of cinchonine and iso- cinchc,n;ne remain in solution. The free base is precipitaked by amrrionia from the hot aqueous solutioii. Pseudocinchonine, C19H 22N20, is a white, flocculent or granular sub- stance melting a t 214-216" (cinchonine melts a t 250-2,52", and iso- cinchonine a t 126-127"). It is soluble in ether, and may be fhus readily separated from cinchonine. The normaZ sulphate forms long, slender, asbestos-like needles, and, unlike the corresponding saltq of cinchorline and its other isomerides, is anhjdrous.Theplatino- chhride and dihyd~iodide are described. .JN. W. By R. v. BUCHER (Monatsh., 14, 598-611).-When chitenine, the oxidation product of quinine, is heated for two hours with 24 times its weight of benzoic chloride, the benzoyl dericatz're, C19H21NZ04B~, is obtained. It is readily soluble in alcohol, ether, and benzene, and is precipitated by light petroleum from its benzene solution in the form of a pale yellow powder, which melts a t 85". The plaiinochloyide, ClgH2,N20eBz,H2PtCI(;, is a bright yellow, crys- talline powder. The pZatr'noch7oride, CleR,,N,O~Ac,,H,PtCI, + 3H20, obtained from the ace/yZ deiii.atize of chitenine is also a microcrys- talline powder. On passing hydrogen chloride through a cooled solution of chitenine in absolute alcohol, the ethyl derirati?ie, C19H21N,04Et, IS obtained; it crystallises in needles, melts at 198", and unites with ethylic iodide to form the compound C,,H,,N2O4Et,EtI, which crys- tsllises from alcolrol in slender, white p~isms, and melts at 210".Clzitenol, Cl,H,,,N20, + H20, is obtained on heating chitenine with 19 times its weight of rolonrless hydriodic acid for three hours a t 100". It crystRllises from hot water, in which i t is only sparingly soluble, in sicnder, white needles; dissolves iendily in acids and alkalis, decomposes at 270°, without previously melting, gives the quinine reaction with chlorine water and excess of ammonia, and yields the following salts :-The subhate, C18H&N204,HzS04 + H20, is fairly soluble in water, and crystallises in slender, bright yellow scales ; the hydi.ochlo?-ide, C,,H2,N204.2HC1 + H20, crysballises in plates, and the plafiitocF,Io~ide, ( Cl,H,,N,04) ,>I HC1,HzP tC16, in yellow Chitenine.ORQANIC CHEMISTRY.153 prisms. On oxidising cbitenol with alkaline permanganate, products are formed from which two calcium salts can be obtained. Of these, one is insoluble, and contains pcr cent., C, 35.69 ; H, 2.36 ; Ca, 16-59. The other is rea,dily soluble and contains per cent., C, 40.04+-4225 ; H, 2.65-4.10 ; Ca, 12*36-13*83 ; N, 5.43. G. T. M. Alkaloids of Belladonna. By 0. HESSE (Annulen, 277, 290- 300 ; compare Abstr., 1891, 748 ; 1892, 1498).-Merck (Abstr., 1S92, 1255) stated that atropamine was identical with Pesci's apoatropine (Abstr., 1882, 740); he has since shown (Abstr., 1893, i, 491) that the latter alkalo'id, like atropamiue, may be conveited into belladonnine. Apoatropine could not be prepared by following Pesci's direc- tions, but is obtained without secondary products when a solution of atropine sulphate in nitric acid of ~ p .gr. 1.381 is kept a t the ordi- nary temperature for 24 hours ; or when atropine sulphate or hyos- cynmine sulphate is dlssolved in concentrated sulphuric acid in the cold, and the solution poured into water; or when the last-named salts are heated a t 85" with acetic, benzoic, or phosphoric anhydride ; but not when they are treated under any circumstances with hydro- chloric acid. The base is difficult to obtain i n a crjstalline condition, and the author now confirms Mwck's observations (Zoc.cit.), that it is identical with atropamine. Belladonnine is obtained when a solution of atropine or of hyos- cyamine in concentrated sulphuric acid is allowed t9 remain for a short time. The platinochloride melts a t 229", and the aurochloride at 120". If hyoscyamine is slomly raised to a temperature of 120-130", i t is first converted into atropine, thence into apoatropine, and finally into belladonnine. When apoatropine is treated with alkalis or with hydrochloric acid, it is converted either into belln- donnine or decomposition products of the latter, or undergoes more advanced decomposition ; the reason therefore that both Pesci and Merck obtained tropine from apoatropine was, that they subjected the alkaloid to too violent treatrriciit with alkalis, and thus precluded the formation of belladonnine. When apoatropine is heated in a sealed tube with fuming hydro- chloric acid (8 parts) for eight hours a t 85--200", bellfitdonnine and tropine are formed ; if, however, the solution is heated for 16 hours a t 140°, bellntropine is obtained.The platinochloride, C8HI5NO2,H2PtClG, melts a t 212", and the aurochloride at 163". The base cryst allises in colourless prisms. A. R. L. Hyoscine. By 0. HESSE (Annalerz, 277, 304-308 ; compare Abstr., 1893, i, 679).-The author brings forward fresh evidence in support of the following views. Ladenburg's liyoscine is identical with scopolamine ; it has the composition represented by the formula C,7H21NOd, and on decomposition a t 60-100" yields oscine, CBHI3NO2, which is identical with scopoline.Scopolamine (hyoscine) hydro- bromide is therefole not a new mydriatic. A. R. L.154 ABSTRACTS OF CHEMICAL PAPERS. Melting Point of Cocaine Hydrochloride. By 0. HESSE ( A n n u l e n , 277, 308-3b9 ; compare Abetr., 1893, i, 679).--FVhen cocajine hydrochloride is heated a t 160-161" in a Rot,h's apparatus, it sinters at the end of 15 minutes, swells up after 25 minutes, and is completely fused in 31 minutes; these changes take place, although more slowly, even a t as low a temperature as 152-154". Alkaloids from the Rind of Pomegranate Root. By G. CIAMICIAN and P. S~LBER (Her., 26, 2738-2753; compare Abstr., 1893, i, 287).-Pseudopelletierine appears to be a ketoamine ; it does not contain hjdroxyl or methoxyl, and is probably a higher homo- logue of tropine, which it closely resembles.Their experimental results are insufficient to enable the authors to suggest a const,it,u- tional formula for the base; they propose the term grnnafonine in place of pseudopelletierine, so as to bring the nomenclature of the derivatives into uniformity with those of tropine. The productlion of granatoline, CgH;,NO, from granatonine (pseudo- pelletierine) has been previously described (Zoc. cit.) ; the reduction is more readily accomplished by means of sodium and alcohol than by sodium amalgam and water ; i t forms feathery, colourless crystals, melts a t lOO", boils a t 251" under 761 mm. pressure, and does not combine with hydroxylamine. The yield is theoretical. The hydro- chloride is hygroscopic. The aurochloride melts a t 213" with prcvious softening, not.at 203". The methiodide, C9H15K0,Mel, crystallises in colourless cubes melting at 307"; on distilling it with potash, the base is regenerated. The benzoyl derivative was analysed in the form of its platinochloride, (CgH16NOBz),,H,PtC16, which is yellow and crystalline. Gunatenine, C9H15N, is prepared by the action of hydriodic acid and phosphorus on granatoline; it is, a viscid liquid of some- what unpleasant odour, and boils a t 186' under a pressure of 751 mm. The aurochloride, C9H,5N,BAuC14, is obtained in stellate crystals melting at 220" with decomposition. The rnethiodide, CgH,,N,MeI, crystallises in cubes which are not melted a t 315". On distillation with potash, the methiodide undergoes a similar decom- position to that of tropidine methiodide with formation of methyl- granatenine, C9HI4NNe ; this closely resembles P-methjltropidine, and boils at 210-220". The aurochloride, picrate, and nzeihiodide are crystalline and unstable.Granatuldeh?/de, CsHI20, the acalogue of tropilen, is formed, together with dimethylamine, by heating the preceding base in hydrochloric acid solution ; i t is a, mobile, readily soluble liquid, with an aromatic odour, boils a t 200-201" under '758 mm. pressure, and readily reduces amnioniacal silver solution. The phenylhydrazone is an oily, unstable 1iqu;d; an additive compound is formed with hydrogen sodium sulphite, but conld not be isolated. The dibrornide, CBH120Br2, is formed a t 0", and crystallises from light petroleum in colourless needles melting a t 100". Granatyl iodide, CgH ,,NI,HT, is occasionally obtained as a bye-pro- duct in the preparation of gramatenine (see above), but the exact conditions necessary for its formation remain undetermined. It is A. R. L.ORGANIC CIIEhIISTRY. 155 deposited from water in coiourless, feathery crystals melting at 200" with decomposition, blackens on expxure to lig i t , and is readily con- verted into gmnatenine on treatment with alkalis. By the action of hydriodic acid and phosphorus on granatenine or gratlatoline a t 2 &'do f o r 8-12 hours, two bases are formed ; the one is termed granatanine, t,he other, which corresponds to " norhydro- t ropidine," is called norgraiiatanine. Granatanine, C9HI5N, is a camphor-like substance with an odnur resemblincr that of coriiioe ; i t molts a t 49-50', boils at 192-193" under 763 mm. pressure, is readily soluble i n water, and has a strongly alkaline reaction. The uurochZoride, C9H1,N,HAuC14, crystallises in feathery, pale yellow needles melting at 229". Norgranatanine, CRHljN, was obtained in small quantity, and separated from the preceding base bg means of its crystalline curbamate. The awochdoride is deposited in yellow plates which melt at 225". J. B. T. Ipecacuanha. By €3. H. PAUL and A. J. CowNr,m (Phni-m. J. Trans., 53, 61-63).-The so-called " emetine '' is a mixture of a t least two different alkalo'ids, the greater part being an amorphous substance, of marked alkalinity, and forming definite neutral salts, which are. also amorphous, and cannot be obtained crystalline by any means yet tried. The amorptidus alkaloid is associated with others that are dist,inctly crystalline, and much less soluble in ether, chloroform, or bonzene. In the stem of Brazilian ipecacuanha, a crystalline alkalojid is present i n a larger proportion, yelatively to the amorphous alkalo'id, thah ifi the root. The authors are seek- ing nieans of separating the alkalojids with the view of determining their several amounts add their chemical and therapeutic properties. They find that the quariti€y of the mixed alkalo'ids obtainable from different samples of ipecacnanha root does not vary much from 2 per cent. R. R. Alkaloids of Pereiro Bark; By 0. HESSE (AnnaZen, 277, 300- 302).-The author fouud (Annaleu, 202: 141) that pereiro bark contained, besides geissospermine and pereirine, another alkalojid which appears to be identical with that described by Freund and Fauvet (Abstr., 1803, i, 446) under the name of geissospermine. It differs from the author's geissospermine i n having a higher meltirig point (189"). Both dissolve in nitric rlcid with a purple-red colour, but the coloration produced by Freund and Fauvet's base is more persistent. The same retnnrks apply to the behaviour of the two compounds with an acid solution of molybdic sulphate ; the colourless solution of Freund and Fauvet's base becomes intensely purple-red when heated. Geissospermine hgdrdchlaride is amorphous, but the hydrochloride of the other base is crystalline ; other differences art: I-ecorded. A. R. L. Nucleic Acid. By L. LIXBERMANN a n d B. IT. B r T T 6 (Oheni. C e v t ~ . , 139;3, ii, 649 ; from Centr. Med. Wigs., 1893, 465-%67).--The nucle'ic acid prepared froin beer yead by Altmann's method may oe shown by the test proposed by Liebermanri t o contain metaphosphoric acid.156 ABSTRACTS OF CHEMIOAL PAPERS. The analysis of the b<rrytn precipitate gave, after subtraction of the organic mat,ter, Ba 43.87, PO, 51.12 per cent. Althouqh the compo- sition calculated for Ba(P0,)3, is Ba 46.44, and PO, 53.56 per cent., the authors believe that the relation of Ba to PO, can only correspond with barium met>aphosphate. Kossel has also come to hold the view which he formerly opposed, that the phosphoric acid in nucle'ic acid is present in the form of metaphosphoric acid. It is not neces- sary to submit nucle'ic acid to a prolonged digestion, or to any severe treatment, in order to obtain xanthine substances. A. H. Thymin; a Decomposition Product of Nucle'ic acids. By A. KOSSEL and A. NEUMANN (Ber., 26, 2753--9756).-The nucle'ic acids, of which at least four appear to exist, are compounds of an acid with various bases, such as adenine, hypoxanthine, guanine, and xanthine. The nucle'ic acid prepared from the thyroid gland of calves yields adenine on boiling with water, and is therefore termed adenylic acid. I n addition to the adenine, two acids are formed : both are soluble in dilute hydrochloric acid; the one combines directly with albumin to form an insoluble compound, and is, perhaps, the nucle'ic acid corresponding to paramuclejin. The second acid is termed thymic: acid, it does not precipitate albumin, and, on heating with sulphuric acid (30 per cent.), tZiyviirb, C23H26NB067 is formed. This substance has neither basic nor acidic properties ; it decolorises bromine water, sublimes without decomposition, melts above 250", and is deposited from water in quadratic and hexagonal crystals. Thymin is also obtained in small quantity by heating adenylic acid. The authors differ from L. Liebermann, who regards the nucleins as cwmpounds of albumin with metaphosphoric acid ; they consider that this view is disproved by the production of thymin. Glucoside Constitution of Prote'id Matter. By F. W. PAVY (Yruc. 12cly. Xoc., 54, 5{-5i).--By the action of potash on protejid mat,ter (purified coagulated egg albumin), the author has obtained a product m-hich forms a hard, glassy mass when dry, gives readily a (*lear solution with water, yields no coloration with iodine, and does not reduce Fehling's solution. It is precipitated by absolut,e alcohol, a,ud closely resembles Landwehr's " auimal gum." By the action of mineral acids, it is converted into a substance which reduces Fellling's solution ; this substance presents the appearance of a sugary extractive, and has a pronounced baked sugar odour. It is very soluble in water, but only slightly so in absolute alcohol ; it is readily diffusible, and dissolves cupric hydroxide in presence of excess df potash without producing a biuret reaction. Heated on the water bath for 2 to 3 hours with phenylhydrazine and acetic acid, i t gives a, crystalline osazone, and has the cha,racteristics of a sugar. It seems to be optically inactive, or possibly very slightly laevorot'atory. J. W. J. B. T.

ISSN:0368-1769    

DOI:10.1039/CA8946600101

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

102 ABSTRAOTS OF CHEMICAL PAPERS. P h y s i o l o g i c a1 Ch em i 8 try. Respiratory Exchange. By A. MAGNUS LETT (P’iiger’s Ad&, 55, l-l2ti).-This is a very complete account of experiments on animals and men, to show the effect of inanition and diets of different kinds --fats, carbohydrates, proteid, bone, meat, mixed diet-on the re- spiratory interchanges. The calorimetric value of foods is also discussed. The methods of experiment are fully described. The most important result appears to be the absolute and relative increase of gas exchange and strength, if a proteid diet is continued for some time. W. D. H. Absorption and Elimination of Hydrogen and Nitrous Oxide. By N. GREHANT (Compt. rend. SOC. biol., 1893, 616-618).- A dog was allowed to breathe a mixture of hydrogen and oxygen (4 to 1) ; five minutes after, some blood was collected, and it was found that the nitrogen normally obtainable from blood was replaced by hydrogen; in a few minutes this was replaced by nitrogen when the dog was allowed to breathe air again.Another animal was allowed to breathe a, mixture of 126 litres of nitrous oxide and 33 of oxygen. The blood gases obtained from 100 C.C. of blood amounted to 79.2 c.c., of which 42.8 was carbonic anhydride, 7.8 oxygen, 2.1 nitrogen, and 26.4 nitrous oxide, ThePHYSIOLOGICAL OHEXISTRY. 103 mixture did not produce aneesthesia, on account of the admixture with oxygen, as P. Bert showed. The animal was then allowed to breathe air, and the blood gases analysed at intervals ; the quantity of carbonic anhydride and of oxygen fell and rose respectively to the normal, while the foreign gas rapidly disappeared, so that, in half-an- hour’s time, none was left in the blood. Pancreatic Ferments.BY A. DASTRF: (Compt. rend. SOC. Biol., 1893, 648-651) .-The experiments described show the independence of the two principal ferments contained in pancreatic juice, amylop- sin, and trypsin. Three hypotheses are advanced as possible expla- nations ; these are as follow :- 1. The amylolytic ferment is more soluble and diffusible than the proteolytic ferment, and so less firmly held by the glandular cells. The first macerations of the gland substance remove it almost completely. 2. The production of ferments by the pancreatic cell is successive ; it is an operation of two acts, of which the first is the formation of amylopsio, the second of trypsin.3. The two ferments are produced at the same time, but the tryptic one is in the condition of zymogen, only acquiring its fermentative activity after more prolonged contact with the products of the cellular activity of the gland. Conversion of Maltose into Dextrose. By M. C. TEBB (J. Physiol., 15, 421-432).-Dried pancreas, mucous membrane of the small intestine, Peper’s patches, lymphatic glands, salivary glands, liver, kidney, stomach, spleen, and striated muscle possess the power of converting maltose into dextrose. The relative activities are ex- pressed in the following numbers :-The proportion of maltose to dextrose in similar specimens beingfor the intestine 1 : 3-21 ; for the spleen, 1 : 1-35 ; for lymphatic glands, 1 : 0.93 ; for the liver, 1 : 0.8 ; for Peyer’s patches, 1 : 0.64; for the kidney, 1 : 0.66 ; for the stomach, 1 : 0.45 ; for pancreas, 1 : 0.31 ; for the salivary glands, 1 : 0.21 ; for muscle, I : 0.2.The small intestine is, therefore, the most active. Serum, bile (slightly), and Benger’s pancreatic fluid (slightly) also act in the same way. Peyer’s patches, to which Brown and Heron attributed a powerful action in this direction, are seen to be very feeble. Action of Carbonic Anhydride on the Diastatic Ferments of the Animal Body. By W . EBSTEIN and C. SCHULZE ( V~TC~OW’S Archiv, 134, 475-500) .-The ferments investigated were the diastatic ferments of saliva, of the pancreas, blood-serum, muscle, kidney, and liver. In a neutral solution, carbonic anhjdride hinders their activity; it appears to act like other weak acids in a corre- sponding degree of dilution, although i n a few experiments with saliva, a slight increase in its mtivity was noted.In an alkaline solution, carbonic anhydride neutralises some of the alkali, and thus increases the activity of the ferment. In an alkaline solution of 0.021 per cent. sodium carbonate, or 0.015 per cent. disodium hydrogen phosphate, certain salts play the same r8Ee as MT. D. H. W. D. H. W. D. H.104 ABSTRACTS OF UHEMIGAL PAPERS. 1296 *3 1091 *2 1510 *1 2492 * 2 3985 -4 2249 -8 4780 08 carbonic anhydride, neutralising the hindering action of the alkaline solution. The salts found in humen blood-serum act thus, especially sodium chloride, and in a smaller degree, magnesium phosphate, MgHPOa, also.. Acidity equal to 0.01 per cent. lactic acid stops the action of the diastatic ferments of the animal body. ~ 1nfluenc.e of Chloroform on Artificial Gastric Digestion. By DUBS (Virchow's Arclriv, 134, 519--540).-Chloroform has been recommended by E. Salkowski (Deutsch. med. Woch., 1888, No. -16) as a means by which organised ferments can be killed and the unorganised ferments left still active. Bertels (Virchow's Archiu, 130j, however, found that under certain circumstances chloroform hinders the activity of pepsin in artificial digestion mixtures. This question is taken up in the present paper with %lie following results :-Chloroform increases the activtity of pepsin in acid solutions in small doses, but hinders it in large doses; thi's appears to be due to the fact that large doses of chloroform precipi- .tate pepsin.The same is true for hydrochloric acid extracts of the ,gastric mucous membrane, except that a greater concentration of chloroform (0.6 to 0.7 per cent.) is necessary to produce the harmful effect on. the fermentative action. This ctifference depends on the presence of proteid matter in the extracts of the mucoiis membrane. .The harmful influence of passing a stream of air through the mixture is quite analogous. ' Source of Animal Heat. By M. RUBNER (&it. Bid., 30, 73- Z42).-This paper contains (1) very complete dissertation on the ,various views held by physicists and physiologists as to the source of animal heat from the time of Lavoisier onwards ; (2) a description of the methods of animal calorimetry and of the special precautions taken in the present experiments; (3) a full account of experiments on animals on different diets.The following table gives a summary of 'the results obtained. W. D. H. W. D. H. 1305 '2 1056 -6 } -' '42 1495 -3 - 0 -97 24238 -0 3958:4 } -' "' 2276 -9 4769 -3 } +' '43 Condition. days. Fed on fat . . . . . . . . Fed on meat and fat. .. .. .:.. . { 6 8 12 production. In the whole 45 days, the amount found by the calorimeter was only 0'47 per cent. less than that reckoned from the heat value of the food given. The food given is ultimately the only source of animal heat.PHYSIOLOGICAL CECEMISTRY. 105 The close ngreement between the heat production within and with- out the body is seen from the following numbera.Heat value of 1 gram of dry substance Burnt in the body. I--- --- Flesh (1) ......... Fat (1) ........... .. (2) ......... .. ( 2 ) . .......... 4 -059 4 -007 9 -334 9 -353 Burnt in Thompson's calorimeter. 4 -000 4 000 9 -423 9 423 This is not surprising nor anything new in relation to fat; but with regard to meat, consisting as it does so largely of prote'id, tlie qlosc correspondence of physical and physiological heat values is very noteworthy . W. D. H. Lymph Formation during Muscular Work. By H. J. HAM- RURGER (Zeit. Biul., 30, 143--178).-The composition of the lymph which flows from a lymph fistula in the neck of the horse is not quite constant. It is the proportion of water to solid constituents which chiefly varies ; during the night, there is an increase of water due to diminished metabolism.One must, therefore, carefully distinguish between day and night lymph. After food, the lymph is increased in quantity three or four times ; it is, therefore, necessary to distinguish between the lymph of rest and during or after feeding. Those consti- tuents of the food, such as alkaline salts, which have a water-attracting power, appear to be especially potent in producing an increase in the quantity of lymph. ' Th'e increase of lymph production cannot always be explained by rise of blood-pressure in the capillaries and veins, for if a horse is made to work, producing a fall of blood-pressure in the carotid, the lymph flows i n greater quantity than when the animal is at rest, and the quantitative composition of the lymph of work is) different from that of rest, the percentage of solids falling, but the water-attracting constituents (chlorine and alkali) rising.Even where increased flow of lymph arid rise of blood-pressure go together, the first cannot be due t o the second, as the composition of the lymph, and of ihe blood-serum .show no correspondence. This is against the filtration theory of lymph-formation. Normal lymph has a much greater osmotic equivalent than the serum of the blood. In a dead animal, clear lymph continues t o flow from the 6stula for 15 minutes or more. These facts are also against the filtration tjheory. It appears probable that the formation of lymph is due to the excitation of the capillary endothelium by the metabolic products of the tissues.W. D. H, Elementary Composition of Ox Flesh. By P. ARGUT~XSKY (Pjuger's Archiv, 55, Q45-3ti5).--E1lesh was dried, the fat andI06 ABS~’HAOTS OF OEEMICAL PAPERS. glycogen being removed. The percentage composi tion of the rwidue, mean of five analyses, was RR follows :-C, 49.6 ; N, 15.3 ; H, 6.9 : 0 and S, 23.0 ; ash, 5.2 ; C : N, 3.24. W. D. H. Formation of Sugar in the Liver. By M. BIAL (I‘fECger’s Archiv, 55, 434--468).-Frorn a review of the literature of the sub- ject, and from the author’s own experiments, be draws the conclusion that the teaching o€ Claude Bernard on the post-mortem formation of sugar in the liver is amply con6rmed. It is formed at the expense of the glycogen. Seegen considers that the sugar has its source in other substances, such as peptone : but adequate reasons are given to show that this is not the case.Liver substance mixed with peptone solution never yields sugar. The change of glycogen into sugar is further produced by a, diastatic ferment, and this is believed to be the same as that found in the blood and lymph. The fact that sugar is formed from glycogen does not, of conrse, exclude its possible formation from prote’id. W. D. H. Asparagine in the Nutrition of Herbivora. By a. WEISKE (Zeit. Biol., 30, 254-278).-Considerable discussion has occurred as to the part, if any, asparagine plays in nutrition, especially as to whether or not it is to be regarded as a prote’id-sparing food. The present contribution to the subject is grounded on experiments on rabbits.These show that asparaghe exercises a good effect on the animals, that it probably does, under certain circumstances, act as a proteyd-sparing food, but that its beneficial effect may be, in part, due t o its action on the digestive apparatus ; it certainly appears to favour the digestion of starch. Substance resembling Strychnine in the Muscles of Tetanised Animals. By J. COURMONT and M. DOYON (Compt. rend. Soc. Riol., 1893, 714--715).-Muscle rendered tetanic by subcutaneous injection of the soluble products of the Nicolaier’s bacillus (after a, constant period of incubation) contains a substance which, like strychnine, produces contraction without incnba$,ion. This sub- stance can be extracted from the muscles by means of water, and the aqueous extract produces sgniptoms resembling those caused by strychnine.This substance is considered to be the cause, not the result, of the muscular contraction. W. D. H. W. D. H. Estimation of Proteids and Extractives in Cow’s and Human Milk. By I. MUNK ( Firchow’s Archiv, 134, 501-519) .-The amount of protejid in milk is most rapidly and accurntely obtained by estimat. ing, according to Kjeldahl’s method, the amount of nitrogen contained in the precipitated prote‘id. After precipitation of the proteid by alcohol, from one-fifteenth to one-thirtieth of the prote’ids of cow’s milk remain in solution. Tannin and copper hydroxide (at the boiling tern- perature) precipitate the prote’ids entirely, and of the two precipitant s the copper method is recommended as the more rapid. Fresh cow’s milk contains, in 100 parts, 0.022 to 0.034 part of extractive nitro-PHYSIOLOGICAL CHEMISTRY. 107 7 hours after meal.gen ; human milk, 0.014-0 026 part. The proportion of extractive nitragen to total nitrogen is 1 : 16 in cow’s milk; 1 : 11 in human milk. If the total nitrogen in milk is determined by Kjeldahl’s method, siifficient accuracy is usually obtained for the protejid nitrogen by multiplying the total nitrogen by 0.94 and 0.91 in cow’s and human milk respectively. The precipitated prote‘ids consist of casein, albumin, and globulin ; the ash free product contains 15.76 per cent. of nitroqen. If the fiitrogen found by Kjeldahl’s method is multiplied by 6.34, the amount of proteyd is ubtained. Sebelien gives the multiplier as 6.3’7 (Abstr., 1889,950).W. D. H. Human Bile. By 0. ’HAMMARSTEN (EN. Ges. der Wiss. UpsaZa, Separat-abzug, 1893) .-This paper contains careful analyses of human bile. The principal new point is that the mucin is true mucin, not nucleo-albumin, as in in ox-bile. By W. H. THOMPSON (J. PhpioZ., 15, 433--448).-A f u l l account of experiments of which a preliminary statement has already been made (Abstr., 1893, ii, 542). Elementary Composition of Dog’s Urine on Flesh Diet. By F. METER (qfliiger’s Archiv, 55, 212--229).-After allowance is made for the ash. the following table gives the percentage elementary com- position of the organic material in the urine at different periods. W. D. H. Work of the Kidney. W. D. H. % hours urine. c ....... H ....... N ....... 0 .:... .. C:N ..... 6) hours after meal.Fasting condition. 23 *41) 6 -91 39 *02 30 -67 0 -60 21 -60 6 -73 39 -57 32 -10 0 -55 6 -67 39 -74 31 -08 0 -57 Xean. 6 -70 39 -66 31 -59 0 -56 22 -5 6 -8 39 -4 31 -3 0 ‘57 ~~ W. D. H. The Ferrocyanide Test for Urine. By J. P. KARPLUS (Chern. Centr., 1893, ii, 496; from Centr. klin. Med., 14, 5’77).-1n testing urine for albumin by means of potassium ferrocyanide and acetic acid, a yellow coloration is frequently observed, for which no explanation has hitherto been given. As i t was not improbable that the reaction might be due to the presence of nitrites, the author has examined a, large nnmber of samples of mine from healthy and diseased persons, and finds that when quite fresh none of these contain nitrites, but that when the urine has remained for periods of upwards of 24 hours, the presence of nitrites may frequently be detected.Fresh urine from jaundice patients was found to contain no nitrites, but 6 out of 12 samples which had been kept became green on addi- tion of acetic acid, and all these, after removal of the bile pigments, gave the nitrite reaction. In testing for biliprasin in mch urine, the108 ABSTRACTS OF UHEMICAL PAPERS. absence of nitrites must, therefore, first be proved. In the urine of patients taking sodium iodide, free iodine occurred together with nitrites. The urine bacterium recently debcribed by the author has, in addi- tion to its action in forming hydrogen sulphide and probably methylic mercaptan, the property of reducing nitrates to nitrites. By R. MAY (Zeit. Bid., 30,1-72).-The development of heat is increased in the febrile condition ; this de- pends, during hunger, on an increased decomposition of protejid, but it can be lessened by the administration of carbohydrates. Glycogen disappears in fever more rapidly than at the normal body temperature. The ratio N : C is altered in the urine of fever, febrile urine being richer in carbon.The increased prote’id metabolism in fever is, in the chief place, due to the increased need of the organism for carbohydrates. The degenei-ation of the cells in causing an increased output of nitrogen is only af secondary importance. Chemical Composition of a Lipoma. By 0. SCHULZ and G . SCHWALBACH (PJEuger’s Archiw, 55, 231-!23!2) .-The fatty tumour in- vestigated contiiined 22 per cent. of water, 225 of connective tissue, 75-73 of fat. The fat contained 7.31 per cent. of free fatty acids and 92.69 of neutral fats. After saponification, 100 grams of the fat yielded 94 grams of fatty acids, and 9.9 grams of glycerol. In the fatty acid mixture the amouats per cent. present were : Olejic acid, 65-57 ; stearic acid, 29 84 ; and palmitic acid, 4.59. Cholesterol was presentl in appreciable quantity. W. D. H. H. G. C. Metabolism in Fever. W. D. H. Physiological Action of Pentoses. By W. EBS’I’EIN (V~W~OW’S Archiu, 134, 361-363; compare Abstr., 1892, 1506, and 1893, ii, 427).-A further contribution t o the polemical aspect of this subject, in answer to criticisms raised by Cremer. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8946605102

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

108 ABSTRACTS OF UHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Tuberculin. By W. KEHNE: ( Z e i t . Biol., 30: 221-253 ; compare Abstr., 1893, i, 233).-Koch’s puiified tuberculin contains about 10 per cent. of proteid matter, and it is to this and tEe changes it undergoes under variations of culture, that the present communica- tion chiefly relates. The separation of the proteids from one another by neutral salts was similar t o that usually adopted, and the proper- ties and tests for each are fully described. There were found (1) an albumiriate ; (2) special albumino&es, for which the name acro-albu- moSeS is proposed; (3) a deutero-albnmose; and (4) traces of peptone. About one-fifth of the solid matter present is mineral in nature. Koch’s tuberculocidin appears to contain small quantities ofVEGETABLE PHYSIOLOGY AND AGIRIOULTURE.109 the same substances ; but, if these are removed by alcohol, the snb- stance is not rendered wholly inactive. W. D. H. Presence of a Diastatic Ferment in Green Leaves. By S. N. VIXES (Ann. Agron., 19, 555 ; from Annals of Botany, 5,409-412).- Wortmann, not finding a diastatic ferment in green leaves, in which, nevertheless, saccharification of starch is very active, attributed sac- charifying power to the living protoplasm itself. The author cites the following experiment to prove that leaves do contain a certain quantity of diastase. 500 grams of grass were crushed in a mortar with 500 C.C. of water, and tho liquid allowed to remain for four hours, after which six niixtures were made, thus:-(1) 50 C.C.extract and 50 C.C. thin starch paste; (2) the same, but subsequently boiled ; (3) the same, but with a little thymol added ; (4) the same, but with 5 grams of boric acid added ; ( 5 ) 50 C.C. of extract and 50 C.C. of dis- tilled water ; ( 6 ) 50 c . ~ . of starch paste and 90 c . ~ . of distilled water. On the following day, the reducing sugar present in each solution was determined by Fehling's solution, when the following amounts of sugar, in grams per 100 c.c., were obtained : (1) 0.793 ; (2) 0.450 ; (3) 0.740; (4) 0.690 ; (5) 0*&4 ; ( 6 ) none. It appears, by comparing Nos. 2 and 5 with No. 1, that about 0.34 gram of sugar was formed by the action of the diastase in the green grass. J. M. H. M. Soluble Ferments secreted by Aspergillus niger and Penicillium glaucum.By E. BOURQUELOT (Compt. rend. Soc. biol., 1893, 653-654).-These moulds, grown in Raulin'a liquid, secrete a large number of soluble ferments ; thus in AspergiZEus, a diastase, an invertin, a maltase, a trehalase (found also in several other fungi), an inulase, and an emulsin (in small quantities) were found. In PeitciZZium, there were found the same, some in only small proportions; emulsin, however, is not mentioned as being present. It is added that, in certain conditions of culture, proteolytic ferments are also formed. W. D. H. Non-organised Active Prote'id Material. By T. BOKORKY (PjZiiger's Archiv, 55, 127--142).--Ina,ctive proteid is the storage prote'id used in the nutrition of growing plants. The term active proteid is applied to that in the cell protoplasm, and it is terned non-organised, as it occurs there in granules (proteosomes) .A large number of plants were investigated by microscopic and microchemical analysis. The prote'id nature of the granules is readily demonstrable by these means. Their behaviour towards ammonia and caff e'ine distinguishes them from ordinary non-living albumin, which is indifferent to these reagents ; they also Rhow the power of reducing silver salts. The substance is coneidered to play the part of reserve material for the growth of cells and organs. Evolution of Free Nitrogen during the Fermentation of Horse Excrement. Influence of Urine on the Formation and Volatilisation of Ammonia during the Fermentation of Solid VOL. LXVI. ii.10 W. D. H.110 ABSTRACTS OF CHEMIOAL PAPERS. 71 0 '790.0 179'4 583.4 Animal Excrement. By S. JENTYS (Bied. Centr., 22, 801-803 ; from Bull. Akad. Xciences de Cracovie, 1892, 303 and 310).-The results of the author's experiments indicate that a loss of nitrogen may occur during the fermentation of horse excrement. The condi- tions on which this loss depends are unknown, but there is some reason to suppose it to be due to specific organisms, especially as there are microbes which are known to liberate nitrogen from its compounds. It seems certain that the nitrogen evolution does not depend on the presence of previouslj formed nitric acid, inasmuch as in this case there would be a greater evolution in absence of oxygen. The presence of urine does not seem to be favourable to change in the nitrogen compounds of the solid excrement.The loss of ammonia in the mixed excrement is greater the larger the proportion of urine present. Decomposing solid excrement hinders, to some extent, the evolution of ammonia, which becomes fixed, partly by acids and partly by microorganisms. It is possible that the dilution of the urine has some effect on the loss of ammonia. N. H. M. 139'7'0 978.9 802.8 930.1 2836.1 852.1 3124-0 855.8 Exchange of Carbonic Anhydride and Oxygen between Plants and Air. By T. SCHLOESING, jun. (Conq't. rend., 117, 756--759 and 813-816 ; compare Abstr., 1893, ii, 180).-The method of experiment which has been already described (loc. cit. and Ann. Inst. Pasteur, January, 1893) consisted in growing the dif- ferent plants in quartz sand in enclosed vessels under conditions which enabled measured amounts of gases to be introduced and removed.Excess of oxygen was absorbed by means of heated copper. Check experiments without plants were made f o r each series of experiments. 2529-6 1'778.3 4115.0 4415'3 761*2 1. Flax ... .. .. .. .. 2. Peas. .. .. .. .. .. 3. White mustard.. 8- 9 9 9 ) t. 1550.7 0'90 848-2 0.95 3262.9 0.87 3559.5 0.88 532.4 0.77 --- 5. Algs. . . . . . . . . . . Carbonic anhydride. 0 xy gen . Initial. 1468 '0 I532 '8 3015 -5 3707 '4 477 -8 Final. 1 Loss. 1 Initial. 66'3 411 5 228'8 1 - 1 O2 Iiber- I-I-- In the first series a gain of 8 C.C. of carbonic anhydride and a loss of 12 C.C. of oxygen were observed; in the second series losses of 10.3 and 9.7 C.C.of carbonic anhydride and oxygen respectively. These errors are taken into account i n the table of results given above. The peas did not grow well for want of sufficient nitrogen, not having been microbe-seeded. * Including amounts absorbed by copper. f Sodium carbonate mixed with soil.VEGETABLE PHYSIOLOGY AND AGRIOULTURE. 111 As a check, the carbon supplied in soil, in seeds, and in the carbonic anhydride was estimated, as well as the final amounts in soil, plants, and carbonic anhydride recovered. The results were as follows :- Experiment. 1. 2. 3. 5. C at commencement.. . . 854.4 1088.8 1687.9 265.6 C a t conclusion , . . . . . . . 787.0 1090.3 1648.1 256.9 Difference . . . . . . . . . . . -47.4 3-1.5 -39.8 -8.7 The losses in Experiments 1 and 3 are probably due to absorption by the glass, which was always very alkaline.Assuming this to be the case, and applying the correction, the relations CO,: 0, would become for (1) 0.84 and for (3) 0.85. I n the case of Experiment 5 with alge (mainly Protococcus vulgaris, with Chlorococcum infusionurn, Ulothrix subtilis, and Scenedesnaus quaari- cauda) the following nitrogen results are given :-Nitrogen gas introduced 863.1 c.c., extracted 863.3 C.C. ; gain = 0.2 C.C. The indirect method, in which the initial amounts of nitrogen gas, nitrogen i n the soil and in the nutritive solution, and the final amount as gas and in soil and algm together were determined, gave identical results, namely, 1107.7 milligrams of nitrogen. Chemical Nature of Cytoplasm and Cell Nucleus. By E.ZACHARIAS (Chern. Centr., 1893, ii, 461 ; from Ber. deutsch. Bot. Zeit., 11, 293).-The author regards the following points as -proved with regard to the distribution of prote'id compounds in the cells : the cell protoplasm and cell nucleus consist to a large extent of substances which are insoluble in artificial gastric juice, the greater proportion of these being the chromatin substances of the cell-nucleus (nuclein). Tn their reactions, the latter agree with the undigested portion of the salmon spermatozoa from which Miescher prepared nucle'ic acid. The other insoluble portions show different reactions, and are classed together by the author under the name plastin. The cell protoplasm and cell nucleus contain in addition prote'ids soluble in the digestive fluid, the nucleoli being in many carefully- examined cases especially rich in these substances, whereas cell protoplasm, especially in fully-grown plant cells, frequently contains them in but small quantity.N. H. M. H. G. C. Carbohydrates of the Fruit of the Kentucky Coffee Nut Tree (Gymnocladus canadensis). By W. E. STONE and W. H. TEST (Anter. Chem. J., 15, 660--663).--The fruit consists of a leathery pod from 3 to 10 in. in length, and contains from two t o six brown, oval, and very hard seeds embedded in a greenish, waxy pulp or gum. This gum has a sweet but very disagreeable taste, and at the time of ripening is soft and easily removed, although later it becomes horny. It contains no galactose, galactan, or starch, but abundance of soluble reducing sugars and pentosans.The alcoholic extract yielded cane sugar (15 per cent.), [a],, = -65.40, alld glucose (15 per cent.). The gummy residue, on hydrolysis with dilute suiphuric acid, 10-2112 ABSTRACTS OF CHEMICIAL PAPERS, yielded an insoluble substance resembling cellulose, and a thick, reduc- ing sjrup which gave the furfuraldehyde reaction for pentoses. The osazone melted at 175-180", indicating a mixture. This was separ- ated by means of alcohol and water into two fractions : the first proved to be glucosazone (m. p. 2 0 L 2 0 5 " ) , soluble in alcohol but insoluble in boiling water: the second (m. p. 153") was probably arabinosazone (m. p. 158-160"), insoluble in alcohol but soluble in boiling water. The latter gave abundance of furfuraldehyde when boiled with strong hydrochloric acid, and its alcoholic solution was optically inactive, so that it was not xylosazone.The glucose and arabinose probably exist in the original gum in combination as gluco- araban. JN. W. Sugar from Apple Pectin. By R. W. BAUER (Laizdw. Versuchs- Stat., 43, 191).-Apple pectin, extracted with alcohol, was boiled f o r four hours with 0.5 per cent. sulphuric acid, filtered, and polarised, when a rotation of +17" was observed. The filtrate, treated with an equal volume of alcohol, became clear after being kept for a year, and had an agreeable odour of ethylic malate. After neutralising with baryta, and evaporating the filtered solution under diminished pres- sure over sulphuric acid until of constant weight, a substance (2.76:% grams) was obtained which proved by its optical properties ( [ a f D = -+ 18.77") and its osazone (microscopic, gold-coloured needles melting at 170") to be xylose, produced, by hydrolysis from xylan present in apple pectin.N. H. M. Formation of Pectin by the Action of Lime on the Sugar-Cane. By H. C. P. GEERLJGS (Chem. Ceatr., 1893, ii, 531 ; from Arch. Java Suikerindustrie, 1893).-The pectin which is always found in the juice of the sugar-cane during the manufacture of sugar is formed by the action of lime on the fragments of the cane which are present. Its formation may be prevented by carefully filtering off the latter, or it ma,y be precipitated with barium chloride in alkaline solution. The crude wax of the sugar-cane may be purified by recrystallisa- tion from alcohol, and then forms white, crystalline plates melting a t 82", and boiling at 146" [?I.Unlike other waxes, it does not consist of ethereal salts of fatty acids, but is chiefly composed of a saturated alcohol having the formula C,,H,,O [? J ; the latter, on distillation with soda lime, yields a hydrocarbon melting at 92", and boiling at 225". Dumas and Leroy have recently obtained similar results in the case of American sugar-cane wax. When the syrup from the centrifugals is heated by live steam, a thick froth is formed which may readily be removed, and which otherwise adheres to the sugar, crystallising out on direct evaporation. It has approximately the same composition as t h e syrup, but contains rather more ash and fat. The froth can only be obtained from a purified syrup to which these impurities have been added, by mixing with them a little bicarbonate, from which i t would appear that, the evolution of gas is necessary for its formation.In the crude syrup this is probably brought about by the carbonic anhydride evolved in the decomposition of the glucin present. H. G. C .VEGETABLE PHYSIOLOGY AND AGRICULTURE. 113 Occurrence and Detection of Indican in Plants. By H. MOLISCH (Chena. Centr., 1893, ii, 667-668 ; from Zeit. dstem. Apoth. Verein, 31, 524) .-Indican only occurs in about 10 phanerogamona species of the vegetable kingdom. Whether a plant contains indican can be rapidly decided by the following test:-Fragments of the plant are boiled for about half a minute in a test tube with 2 per cent. ammouitt solution, filtered over a platinum cone, and extracted with a, little chloroform.A similar experiment is carried out with B per cent. hydrochloric acid. In the presence of indican, one or bot,h of the chloroform extracts is coloured blue. Indican may occur in many of the organs and tissues of the indigo plants, but is mainly found in the foliage leaves. The statements found in the literature of the subject that indican occurs in Mercurialis peren&, Me 1 amp yrurn arvense, Pol y g onwn Fag op y rum, Ph y t ol acca decandra: Moil ot ropa Hypopi t ys, Frazinus excelsior, Coro n ill a Emerus, and Anzorpka fructiosa, are inaccurate. A chromogen does occur in the organs of the fresh toothwort, (Lathma Xquamaria), which yields a blue colouring matter with dilute hydrochloric acid ; but this is quite distinct from indigo.A. H. Amount of Maltose and the Fermentability of Wort and other Extracts. By 0. REINKE (Bied. Centr., 22, 839-840).- Malt dried at 80" contained water (5 per cent.), and extract (7315 per cent.) yielding 70 per cent. of maltose and 17 per cent. of dextrin after inversion and deduction of the maltose. When very lightly dried, the maltose was 5 per cent. higher and the dextrin 5 per cent. lower. I n highly-dried malt, the amounts of maltose and dextrin were respectively 7 per cent. lower and 7 per cent. higher. 90 per cent. of the maltose fermented at 30". As regards extracts for the manufacture of spirit, the following percentage results are given for sweet potato extracts :- 1. 2. 3. 4. Maltose in extract.. .. 64.84 67-16 60.60 68-09 Dextrin in extract.... 14.04 13.46 14.41 15.90 Fermentable maltose. . 38-36 60.44 54.54 61.28 Saccharimeter" Ball . . 25.00 20.80 25.10 17.3 Maltose. ............ 16-21 13.97 14.00 11.78 Fermentable maltose.. 14.59 12.57 12.6 10.6 Dextrin. ............ 3-51 2.80 4.02 2.75 In the filtrate : When the fermentation is complete, there is generally only 6 per cent. of dexti-in left. When the 90 per cent. of fermentable maltose is calculated as dextrose, and the amount of dextrose corresponding with half the dextrin added, and the whole multiplied by 64.64, the remlt gives the amount of alcohol to be obtained from the extract. N. H. M. Composition of Seeds and Etiolated Sprouts of Hemp (Cannabis sativa) and of Sunflower (Helianthus annuus). By S. FRANKFURT (Landw.Versuchs-Stat., 43, 143-182) .-A qualitative ex:Lmination, the details of which are given, showed the presence114 ABSTRACTS OF CHEMICAL PAPERS. of the following compounds in hemp seeds :-Protei'ds, nucle'in, and other indigestible nitrogenous compounds, organic bases, lecithin, chol- esterol, glycerides, cane sugar, non-crystalline soluble carbohydrates, hemicellulose, citric acid, cellulose, pentosan, and mineral matters. Detmer failed to find soluble carbohydrates in the seeds (Physiol. Chem. Untei-suchung uber d. Keimung olhaltigern Xamen, p. 38). The quaatitative results are next given (per cent.). Glycerides and Prote'ids. Nuclein, &c. Lecithin. Cholesterol. free fatty acids. 18.63 3.36 0.88 3-07 50.92 Cane-sugar and other Crude Soluble soluble carbohydrates.fibre. organic acids. Ash. Not determined. 2.59 26-33 0.68 5.531 11.03 As regards the changes which take place during germination, Detmer (Em. cit.) showed t h a t the fat diminishes in amount, and is replaced by starch, cellulose, &c. Owing to the difficulty of obtain- ing large enough quantities of sprouts, the author only made a quantitative examination for certain constituents. Asparagin and two compoiinds, probably glutamic and glyoxylic acid respectively, were found. Tho sunflower seeds and sprouts were more thoroughly investi- gated. The seeds were separated from the shells, and the two portions, which had the relation 53.6 : 46.4, separately examined. The percentage composition was found to be as follows :- Seeds without shell.Yrot5ds ............................. Nuclei'n, &c ........................... Lecithin ............................. Crude fat ............................ Cane sugar and other soluble carbohydrates Crude fibre.. ......................... Soluble orgauic acids .................. Ash. ................................ Not determined ....................... 24 '06 0 '96 0 '44 55 '47 3 -78 2 '24 0 '56 3 -66 8 '83 -I Shells. 1 -33 - - 1 *GO 64-54 1 '93 31 '20 - - Whole seeds. -- 13 -50 0 '51 0'23 30 -19 2 '13 31 -14 0 -30 2 -86 19 '14 The seeds freed from shells contain also pentosan (soluble, 0.87 ; insoluble, 1.87 per cent.). They contain no, or almost no, hemi- cellulose.. The shells are very poor in nitrogen. They contain hemicellulose. When the shells are kept in contact with 0.5 per cent.soda for a day, and the residue washed and boiled with 2 per cent. sulphuric acid, EL sugar was obtained which, when isolated, proved to be xylose. The quantitative examination of the etiolated sunflower sprouts showed the presence of asparagine and glutamine, malic acid, and considerable amounts of soluble carbohydrates. Nitrogenous organic bases were present only in very small amounts. Cane sugar, cellulose, hemicellulose, and pen tosans were also found. TheVEGETABLE PHYSIOLOQP AND AGRICULTURE. 115 percentage composition of the dried sprouts freed from shelIs was as follows :- Asparagine and Cane sugar, Protei'ds. Nuclei'n, &o. glutamine. Lecithin. Fat. &C. 15.00 4-56 4.05 0.85 24-59 14-75 Soluble 2-43 11.52 4-09 18.21 organic acids.Crude fibre. Ash. Not determined. I n order to compare the composition of the seeds with that of the sprouts, the quantities were calculated on the assumption that the amount of ash in both is practically the same. The results show first a great diminution in the amount of prote'ids, whilst the in- soluble nitrogen compounds (nuclein) increased considerably (0% to 4.05). Unlike the etiolated sprouts of vetches and lupins, which contain considerable quantities of nitrogenous organic bases, the sun- flower sprouts contained a very small amount. Another difference is the increase of lecithin (0.44 to 0.71 per cent.). Schulze observed a loss in lupins and vetches. The percentage of fat became much lower during germination, whilst the soluble carbohydrates increased.There was no loss of nitrogen during germination. N. H. M. Development and Maturation of Cider Apples. By L. LINDET (Compt. rend., 117, 696-698) .-Apples were taken every two weeks (from 24th July to 3rd November) from the same tree and analysed. The average weight of the apples at each date was as follows :- (1) 24th Jaly, 21.5 ; (2) 7 t h August, 34.0 ; (3) 23rd August, 46.0; (4) 7th September, 50.2 ; (5) 21st September, 60.3 ; (6) 4th Octo- ber, 68.7; (7) 18th October, 75.3; and (8) 3rd November, 76.5 grams. The percentage cornposition of the apples at the different dates was :- Invert Cellulose Nitrogenous Starch. Saccharose. sugar. Acidity. substance. matter. Adz. 1. 4.8 1.1 6.4 0.5 4.4 - 0.4 2. 4.8 1.2 6.8 0.5 3.1 0.6 0.4 3. 4.9 1.2 8.3 0-4 3.2 0.5 0.4 4.5.8 2.3 8.3 0.4 2-8 0.3 0.3 5. 3.8 2.5 8.3 0.3 2.8 0.3 0.3 6. 3.3 3.2 8.2 0.2 2.7 0.3 0.2 7. 2.1 3.7 8.6 0 2 2.6 0-4 0.3 8. 0 8 2.9 9.4 0.2 - 0.3 0-2 The apples were green until September 7, at which date the pips began to become coloured. The chief change is in the starch, which, as ripening proceeds, becomes converted into what seems to be a mixture of saccharose, glucose, and levulose. It is possible that a portion of the saccharosu had migrated from the leaves, but it is probable that some of it is furtlished by the starch. The same disap- pearance of the accnmulated starch, and, coincidently, an increase of saccharose and invert sugar was also observed in apples allowed to ripen after being taken from the tree. N. H. M.116 ABSTRACTS OF CHEMICAL PAPERS. Nitrification of Prairie Soilg.By J. DUMONT and J. CROCKE- TELLE (Compt. rend., 117, 670-6731 .-Boussingault, and more recently BrBal, have shown that prairie soils contain comparatively small amounts of nitrates, so that the enormous amount of organic nitrogen becomks very slowly available for Vegetation. It seemed likely that the slow nitrification is due to insufficient alkalinity. The anthors accordingly instituted experiments in which two different soils (containing respectirely 6.84 and 5.76 per cent. of humus) were exposed for Chree o r four weeks, after being treated with various amounts (0.1 to 1.0 per cent.) of potassium carbonate, chloride, and snlphate, and sodium carbonate (each alone) ; check experiments were made in which nothing was added.At the conclusion of the experi- ments the soils were extracted, and the nitric acid estimated. Similar experiments were made in which arable soils (containing 2.9 and 1.08 per cent. of humus) were treated with the various salts, and exposed for 15 days. The results of the experiments show that with the rich soils an addition of 0.2 to 0.3 per cent. of potassium carbonate increases nitrification, whilst larger quantities are injurious. Potassium sulph- ate (0.7 to 0.8 per cent.) gave rise to increased nitrification. Potassium chloride had only a slight effect, the nitric nitrogen per cent. being raised from 0.008 per cent. t o 0.01 per cent. with 0.025 to 0.3 per cent. of the aalt. Sodium carbonate had no beneficial effect, nitrification being lessened when more than 0.15 per cent. was applied to the soil.I n the case of the experiments with arable soils, in which only one amount of each salt w;t8 applied (0.2 per cent.), the best result was obtained with potassium sulphate. It remains to be ascertained what amount of the salt gives the best results. ’ N. H. 31. Comparative Experiments with various Phosphates. Bg 0. KELLNER, Y. KOZAI, P. MORI, and M. NAGAOKA (Landw. Versuchs- Stat., 43,1--14).-Experiments have already been made on the effect of different phosphates on irrigated soil (ibid., 41, 305). The results now given were obtained on ordinary arable land, consisting, like the irrigated soil, of sand mixed with volcanic ashes, rich in easily de- composable aluminium silicates, iron, and humus, but containing very little lime.The manures employed were double Ruyerphosphate (with 47-84 total and 43.65 per cent. of phosphoric acid, soluble in water), precipitated calcium phosphate (with 29.35 total phosphoric acid), basic slag (with 21.73 per cent. of phosphoric acid), steamed bone meal (with phosphoric acid, 23.06 ; nitrogen, 3.87 ; and fat, 1.33 per cent.), crude bone meal, freed from fat (phosphoric acid, 19.70; nitrogen, 4.74 ; and fat, 1.93 per cent.), crude crushed bone (phos- phoric acid, 21.66 ; nitrogen, 4.61 ; and fat, 14-07 per cent.) and bone ash (containing 30.465 per cent. of phosphoric acid). The experi- ments were conducted in Wagner’s zinc cylinders, 60 cm. in diameter, and 1 m. deep. Calcium carbonate (1000 kilos. per hectare), potassium sulphate (200 kilos.per hectare) and ammonium sulphate (containing 50 kilos. of nitrogen per hectare) were mixed with the soil as well as the phosphates, which were each applied in twoANALYTICAL OHEMISTRY. 117 quantities, 50 and 100 to 100 and 200 kilos. per hectare. There were 48 cylinders, six without phosphate and six with each manure (three with the smaller and three with the larger amount). Barley was first sown. After the plants were cut and the stubble mixed with the soil, millet was sown, next wheat, and lastly buckwheat. The total dry substance, and the amount of phosphoric acid removed from the various cylinders is given i n tables. The larger amounts of manures gave in every case higher yields than the smal!er, but as they did not in every case hat-e their full effect, the results obtained with the smaller quantities are the more suitable for comparison.Taking first into coiisideration the effect on the first growth (barley), super- phosphate gave the highest yield of dry produce, which contained 21.5 per cent. of the total phosphoric acid applied. The next most e5cacions manure was steamed bone meal, of which 16.6 per cent. of the total phosphoric acid applied was found in the produce. Then precipated calcium phosphate, crude bone meal free from fat, crude crushed bone, basic slag, and, lastly, bone ash. The produce obtained under the influence of these manures contained respectively 13.8,12.4, 12.6, 13.1, and 5.0 of the total phosphoric acid applied. It is note- worthy that the high percentage o€ fat in the crushed bone (14.07) did not hinder the utilisation of the phosphates. As regards the effect of the manures on the subsequent growth (millet, wheat, and buckwheat), there was a decided but different effect in each case. The results, which are shown i n a curve, indicate a great similarity in the after-effect of the superphosphate, the steamed bone meal, and the precipitated phosphate and also the basic slag, all of which were chiefly utilised by the first two growths. The slight effect produced by the superphosphate and the precipitated phos- phate in the after-growths was due to their diminished solubility in contact with the soil, but better results were expected with basic slag. Both the crude bone meal and the crushed bone, which had but little influence on the first crop, had rery considerable effect on the succeed- ing crops, and their action would probably have continued long. Of the different bone manures applied, the crude crushed bones gave the greatest total yield ; next the bone meal freed from fat ; and lastly, the steamed bone meal. The results show that, under the prerailing climatological conditions, fat also acts in unlocking the calcium phosphate, although more slowly than the nitrogenous matter. Bone ash becomes gradually and uniformly available for the roots. It is not suitable for damp rich soils. N. H. M.

ISSN:0368-1769    

DOI:10.1039/CA8946605108

出版商:RSC    

年代:1894

数据来源: RSC

摘要:

ANALYTICAL OHEMISTRY. Analytical Chemistry. 117 An Automatic Extractor. By W. D. HORNE (Chem. News, 68, 450).-The following arrangement is devised to effect the delivery of a definite quantity of water iu portions of equal volume at regular intervals. A bottle of the desired capacity is fitted with a stopper,11s ABSTRACTS OF CHEMICAL PAPERS. bored with two holes, each carrying an open tube; the tubes pass just through the stopper internally, but externally one of them is short and straight, and terminates with a constricted orifice, whilst the other is bent twice atright angles, and extends down the whole height of the bottle outside. I n use, the bottle is filled with water, stoppered, and inverted, and water can then be caused to escape from the short tube at any desired rate by regulating the supply of air admitted through the other tube. This regulated water supply drops into a receptacle suspended below the bottle, and provided with an adjust- able inverted siphon inside, by which any required volume of water can be automatically drawn off at a time, and utilised for washing a precipitate or other purpose.D. A. L. Lunge’s Gas Tables. By A. LWOFF (Zeit. anpq. Chem., 1893, 443-44.5) .-In Lunge’s original tables, a correction for pressure down to 710 mm. is given. The author has now also corrected the volumes for pressures varying from 680 to 710 mm. L. DE K. Indicators for Titrations with Standard Sulphide Solutions. By P. WILL~ANS ( Chew News, 68, 23G).-The author has compared the delicacy of the following reagents when used as indicators for titrations with standard sulphide solutions :-I.A solution of sodium tartrate, treated with a small quantity of caustic soda and lead acetate, and heated until clear. 11. A solution of potassium nitroprusside, saturated with soda, evaporated nearly to crystallising, and treated with 4 parts of alcohol, and fiItered. With the first reagent 0*0000245 gram, with the second 0.0000982 gram of sodium sulphide in 1 C.C. may be detected. D. A. L. Estimation of Dissolved Oxygen in Water. By C. &l. TAN DEVENTER and B. H. JUHGENS (Chem. Centr., 1893, ii, 546; from Muandbl. natuurw., 18, 72) .-The method described depends on the fact that when iodine is set free from potassium iodide by means of free nitrous acid, nitric oxide is formed, but that if dissolved oxygen is present, the latter combines with the nitric oxide, forming NOz or N203, which in presence of acid liberates a fresh quantity of iodine.Note by Abstmctor.-The method is almost exactly identical with that described by Thresh (Trans., 1890, 185), with the modification that instead of carrying out the titzation in a current of coal gas, the liquid to be tested is covered with a layer of petroleum. H. G. C . Estimation of Nitrogen in Coal Gas. By L. LANG (Chem. Centr., 1893, ii, 773 ; from J. f. Gasbel., 493-494).-20 C.C. of the sample of gas is measured in the Bunte’s burette, mixed with 125 C.C. of air, and exploded in ti Hempel’s pipette. Carbonic anhydride and oxygen are now absorbed as usual, and the remaining nitrogen is measured. Any excess over the amount of nitrogen present in the air is supposed to Lave been present in the gas. L.DE K.ANALYTICAL OEEMISTRY. 119 Adulteration of Basic Slag. By E. WRAMPELMEYER (Landzu. Verszcchs-Stat., 43, 183-190) .--Natural phosphorite is sometimes coloured so as to resemble basic slag ; finely powdered coal is some- times added for this purpose. The following methods for detecting adulteration are given:-(1) Estimation of loss on ignition in a Rossler furnace. The loss in old samples of basic slag is slight, whilst with fresh samples there is a gain owing to oxidation. (2) Estimation of substance soluble in warm water after ignition. (3) Determination of sp. gr. Basic slag has a sp. gr. = 1.9 or higher, whilst all the other phosphates examined varied from 1.1 to 1%.( 5 ) Estimation of phosphoric acid soluble in citric acid (Loges’ method) and in ammonium citrate (Petermann’s method). Results of examination of various phosphates show that the microscopic ex- amination and sp. gr. done are generally sufficient for ascerta,ining whether the slag is genuine or not. In t w o cases, however, the microscopic examination, solubility in water, citric acid, and ammon- ium citrate indicated genuine slag, whilst the low sp. gr. and the high loss on ignition clearly pointed to adulteration. The suspected sample should always first be examined with a microscope, then, if necessary, the loss ou ignition and sp. gr. and solubility in water deteymined, lastly, if any doubt remains, the solubility determined by Loges’ and Petermann’s methods.N. H. 31. Estimation of Carbon in Steel. By R. LORENZ ( Z e i f . angw. Chem., 1893, 635--637).-The author, in reply to de Koninck, states that, fusion with lead chromate in a current of oxygen a t a white heat (Abstr., 1893, ii, 491) causes the complete oxidation of the carbon, and doubts whether the same satisfactory result could be obtained by the use of borax or microcosmic salt, even when mixed with copper oxide. L. DE K. Volumetric Estimation of Silver. By G. DENIG~S (Compt. rend., 117, 1078--1081).-The reaction between silver nitrate and potassium cyanide, with formation of silver potassium cyanide, qroceeds regn- lady in presence of ammonia, and the end reaction IS made very sensitive by adding a, small quantity of potassium iodide to the liquid.The result is not affected by considerable variations in the proportion of ammonia, or by the presence of alkali hydroxides, carbonates, chlorides, bromides, phosphates, &c. It is, therefore, not only a very accurate process for the estimation of hydrocyanic acid or cyanides, but, by using a standard solution of potassium cyanide, it can be employed for the estimation of any silver compound what- ever. A solution of about 10grams of potassium cyanide perlitre is used, and will remain unchanged for many days, its stability, especially in hot solutions, being increased by the presence of excess of alkdi. The quantity of substance taken for analysis should contain about one-thousandth of a gram equivalent of silver, and is dissolved in 10 C.C. of ammonia solution and 5 C.C.of water, with the aid of heat if necessary. The ferrocyanide, bromide, and iodide will not dissolve until the standard cjanide solution is added. The phosphate, arsen-120 ABSTRAOTS OF CHEM‘IC,AL PAPERS. ate, chromate, oxide, and sulphide should be dissolved in nitric acid and then mixed with excess of ammonia. I n all cases the liquid con- taining a slight excess of ammonia is mixed with 20 C.C. of standard cjanide solution, about 100 C.C. of water, and a small quantity of potassium iodide solution, and decinormal silver nitrate solution is added gradually with constant agitation until a slight, permanent turbidity is produced. The difference between the volume of silver solution required and that required for the 20 C.C. of standard cyanide solution alone, gives the quantity of silver present in the substance.This process is available for the volumeti-ic estimation of precipi- tates of silver chloride ; the direct estimation of chlorides in liquids of animal origin ; the determination of the xantho-uric compounds i n urine by precipitation with ammoniacal silver nitrate solution, and estimation of the excess of silver in the filtered liquid ; estimation of potassium iodide by precipitation with ammoniacal silver nitrate solu- tion; and estimation of all substances such as acetylenes, arsenic hydride, antimony hgdride, aldehydes, carbonic oxide, &c., which are capable of altering the strength of alcoholic, ammoniacal, or acid solutions of silver salts. C. H. B. Electrolytic Analyses.By F. R~DORFF (Zeit. angw. Chem., 450 -453).-The author, in reply to Classen, objects to the processes given in that chemist’s work, and thinks his own methods are more accurate (compare Abstr., 1893, ii, 93-95). L. DE I(. Volumetric Estimation of Copper with Sodium Sulphide. By A. BORNTR~GER (Zeii. angw. Chem., 1893, 517--524).-The author prepares the sodium sulphide solution by dissolving 40 grams of the commercial sulphide in 1 litre of water. This solution is standardised by means of a solution containing 69.278 grams of crystal- L e d copper sulphate per litre. 20 C.C. of the solution is mixed with a little ammonia, and titrated in the cold with the alkaline sulphide until a drop of the supernatant liquid gives no coloration with acetic acid and potassium ferrocyanide.The process may be nsed i n presence of zinc. The copper solution is rendered alkaline with ammonia, and any iron oxide is filtered off. The addition of the sulphide may at first also precipitate a little of the zinc, but this rapidly redissolves a3 long as a trace of copper is present. The process may be recom- mended for the assay of brass, commercial copper sulphate, and a variety of copper sulphate disinfectants. L. DE K. Separation of Lead from Copper by Electrolysis. By H. NISSENSON (Zeit. angw. Chem., 1893, 646).-The author states that Kiidorff is wrong in supposing that the electrolytic separation of copper from lead is only successful when the lead is present in minute quantity, and proceeds as follows :-1 gram of copper ore is dissolved in 30 C.C.of nitric acid of 1.4 sp. gr., diluted to 180 C.C. and electro- lysed carefully according t o Classen’s directions. An accurate estima- tion of the copper is obtained, even in the case of ores containing 12 per cent. of lead to 20 per cent. of copper. L. DE K.ANALYTICAL CHEMISTRY. 121. Electrolytic Separation of Metals of the Second Group. By S. C. SCHMUCKER (Reif. anorg. Cliem., 5, 199-210).-The author adds to the solution an excess of bromine to ensure the highest degree of oxidation ; tartaric acid is next added, and then an excess of ammonia. The solution, after being put into a platinum dish, is now electrolysed as usual, the strength and duration of the current varying somewhat according to the nature of the metallic salts. For instance, in the separation of copper from tin, the solution containing about 0.1 gram of each metal in 175 C.C.of liquid was exposed to the galvanic action for 17 hours, the current yielding 0.4 C.C. of electro- lytic gas per minute. The copper was completely recovered, and perfectly pure. The tartaric acid method has proved successful in the separation of copper from arsenic, antimony, and tin ; cadmium from antimony ; cadmium from tin ; cadmium from arsenic ; cadmium from arsenic, antimony, and tin ; bismuth from arsenic ; bismuth from antimony ; bismuth from tin ; bismuth from arsenic, antimony, and tin ; mercury from tin ; mercury from arsenic ; mercury from antimony ; mercury from arsenic, antimony, and tin. The author has not, as yet, tried any experiments with lead when mixed with tin, arsenic, or antimony.L. DE I(. Estimation of Manganese Oxides by means of Hydrogen Peroxide. By H. C. JONES (Compt. rend., 117, 781-7,93).--The method described by Carnot (Abstr., 1893, ii, 427) is only a special case o€ the general method described by the author (Amer. Chein. J., 12, 275), which is applicable also to the higher oxides of lead. C. H. B. Detection of Nitronaphthalene in Mineral Oils. By N. LEONARD (Chem. News, 68, 29f).-a-Nitronaphthalene is added to mineral oils to remove the fluorescence, and may be detected by geiitlg warming and agitating the oil with zinc dnst and hydrochloric acid ; the characteristic odour of a-naphthylamine will indicate the previous existence of the nitro-derivative ; this may be confirmed by the blue precipitate, quickly changing to purple, obtained when ferric chloride is added to a portion of the acid aqueous solution of the aruine pre- viously neutralised with ammonia ; also by the production of a yellow colour, changing to crimson with hydrochloric acid, when another portion of this liquid is rendered alkaline with soda, extracted with ether, the ether evaporated from the extract, and the residue dissolved in a small quantity of alcohol and treated with a drop of a solution of sodium nitrite and acidified with acetic acid.D. A. L. Estimation of Cresol or Xglenol. By F. KEPPLER (Chem. Ceiztr., 1893, ii, 892-893 ; from Arch. Hygiene, 18, 51-66).-A mix- ture of potassium bromide and bromate is added to the solution con- taining the cresol. After adding a sufficiency of sulphuric acid, the liquid is filtered through glass wool, and an aliquot part of the filtrate is titrated, as usual, by means of potassium iodide and sodium thiosulphate with starch as indicator.L. DE K.122 ABSTRACTS OF CHEMICAL PAPERS. Checking Fehling’s Solution. By A. BORNTRXGER (Zeit. angw. Chem., 1893, 600-601).-The author has come to the conclusion that the standard solution of invert sugar used to check the Fehling solu- tion should be prepared at the ordinary temperature. Pure saccha- rose is easily prepared by precipitating a filtered, concentrated solution of sugar candy with alcohol and drying the precipitate. 19. grams of this product is dissolved in dilute hydrochloric acid con- taining 4.5 per cent. of HCl in a 100 C.C. flask. After standing over night, 25 C.C. is pipetted off, coloured with a little litmus, exactly neutralised with alkali, and made up to 1 Zitre.This solution con- Sugar in the Blood. By F. SCHESCK (P’iiger’s Archiv, 55, 203-211) .-The following method of estimating sugar in the blood is recommended : 50 C.C. of blood is mixed with 50 C.C. of water ; to this, 100 C.C. of 2 per cent. hydrochloric acid and then 100 C.C. of 5 per cent. mercuric chloride are added. The mixture is filtered, and the filtrate decomposed with hydrogen sulphide. This is again fil- tered, 150 C.C. of the filtrate taken, and air passed through it to get rid of the hydrogen sulphide: it is concentrated to 100 c.c., and then titration is performed by Knapp’s method. The mercuric chloride appears to give as good results as the more expensive iodide.When the blood coagulates, the disappearance of sugar is very great ; i t may be 25 per cent. If kept uncoagulated by an oxalate, the loss is insignificant. If blood is acidified, the loss is practically nil. W. I). H Use of Methylene-blue for the Detection and Estimation of Sugar in Urine. By N. WENDER (Chenz. Ceizt,r., 1893, ii, 670-671 ; fr6m Pharm. Post., 26, 393--397).--.Ihl obserred that methylene- blue is decolorised, by reduction to the leuco-compound, by invert sugar, dextrose, dextrin, &c., whilst it is not acted on by cane sugar. Urea, uric acid, and the inorganic salts in urine are without action on methylene-blue ; creatinine decolorises it with tolerable rapidity ; creatine, after boiling for some time, and albumin, when it is present to the extent of some tenths of a per cent.Animal gum and glycuronic acid may also decolorise methylene-blue ; concentrated alkalis decolorise it rapidly with separation of the free base, but dilute alkalis do not produce any effect. All normal urines in the undiluted state decolorise alkaline methylene-blue solutions on heat- ing; 1 C.C. normal undiluted urine decolorises 1 C.C. of methylene- blue solution (1 : 1000). To decolorise the same amount of methyl- ene-blue, about 4.5 C.C. of 10 times diluted normal urine is required, whilst only 1 C.C. of a similarly diluted diabetic urine, containing 0.5 per cent. of sugar,.produces the same effect. In order to detect the presence of sugar in urine, the following method is adopted : 5 or 10 C.C.of the urine is diluted to 10 times its volume ; 1 C.C. of this solution i5 then treated with 1 C.C. of aqueous methylene-blue solution (1 : 1000) and 1 C.C. of normal potash, diIuted with abmt 2 C.C. of water, and boiled over a naked flame for a minute. I n the presence of 0.5 per cent. of sugar, total decolorisation takes place. If the coloration remains, the urine may be considered as not diabetic. tains 0.5 per cent of invert sugar. L. DE K.ANALYTICAL OHEMISTRY. 123 Quantitative experiments showed that 1 mol. of methylene-blue is reduced by 1 mol. of dextrose. 1 C.C. of methylene-blue solution, 1 : 1000 = 0.001 gram methylene-blue would be reduced by 0.005 gram of dextrose. The decolorising power of a normal urine, therefore, corresponds with that of a 0.11 per cent.solution of dextrose. If p is the percentage of sugar in the urine which has to be debermined, ZI the dilution factor, c the number of C.C. of the methylene-blue s o h - tion required, then p = 0.05 v/c. The determination of sugar in urine is carried out in the following manner. If sugar is found by the qualitative test, the urine is diluted according t o its specific gravity. Sp. gr. . . . . . 1*027-1.025 1.025-1*030 1*030-1*038 The volume of the diluted urine which is required to exactly de- colorise 0.001 gram of mcthylene-blue is then determined, several titrations being made. 1 C.C. of methylene-blue solution and 1 C.C. of normal potash are put into a test tube, and the urine run in gradually from a burette, the liquid being boiled once or twice.This process is repeated until the exact amount of urine required has been found. The results obtained by the author fall between those givcn by the polarisation method and by the reduction of Fehling’s solution. 0 wing to the great dilution of the urine, the disturbing influence of the other constituents of urine which are capable of reducing methyl- ene-blue is scarcely perceptible. Estimation of Saccharose in Mixtures of Maltose, Isomalt- ose, Dextrin, and in Worts. By J. JAIS (Chem. Centr., 1853, ii, 893-894 ; Zeit. ges. Brauw., 16,;349--351).-The author has carefully investigated ,Meissl’s inversion method, and has found that it is per- Glycogen. By S. FRXNKEL (P’liiger’s Archiv, 55, 378-379) and J. WEIDENBAUM (ibid., 380-391 ; compare Abstr., 1893, i, 186).-1n reply to Weidenbaum’s criticisms on the trichloracetic acid method of estimating glycogen, the author reaffirms his position, and charges his critic with error, suggesting that he used impure preparations of trichloracetic acid.To this, Weidenbaum replies by publishing analyses of his trichlor- acetic acid and a, number of fresh experiments in which his former conclusions that Frankel’s glycogen contains nitrogen, and that the glycogen is only imperfectly extracted from the tissues by the use of the acid, is fully confirmed. By W. GULEWITSCH (P’iiger’s Arcliiu, 55, 392-393) and by C. PFL~GER (ibid., 394-401 ; compare Abstr., 1993, ii, 601). -Gulewitsch points out that Pfliiger was not the first to suggest a method for overcoming the difEculties often experienced in the use of Briicke’s reagent for the estlimation of glycogen.This and certain small points of detail in the methods suggested furnish matter for the polemical portions of the two papers here under review. (50 times) (100 times) (200 times) A . H. fec tly trust worthy. L. DE I(. W. D. H. Glycogen. W. D. H.124 ABSTRACTS OF CHEMIOAL PAPERS. Estimation of the Acidity of Vinegar. By L. VANINO ( Z e i f . angw. Chem., 1893, 676-677).-The author strongly recommends the process originally worked out by Baumann and Kux. 10 grams of the sample of vinegar is mixed with a solution of 4 grams of potassium iodide and 0.8 gram of potassium iodate and introduced by means of a pipette into the bottom part of an ordinary specimen tube, inside which is sealed a small glass cylinder, which contains the alkaline solution of hydrogen peroxide.After standing for at least two hours, the glass is connected with the author's apparatus (Abstr., 1891, 615), which is easier to manipulate than Wagner's azotometer used in Kux's experiments. The two solntions are mixed and the liberated oxygen is finally read off with the usual precautions. The acetic acid is calculated from the volume of gas at N.T.P., or Kux's tables may be used. L. DE K. Estimation of Malic acid. By C. MICKO (Chem. News, 68,286). -To facilitate the separation of malic acid in wines by means of lead acetate, the author evaporates 100 C.C. of wine, or 50 C.C. of cider, to a few c.c., sets aside for an hour with 4 or 5 C.C. of binormal sulph- uric acid, then, while agitating continuously, gradually mixes in 50 C.C.of strong alcohol and 50 C.C. of ether. After 6 to 10 hours, filtering and washing with ether-alcohol ensue, and the ether and alcohol are subsequently expelled by distillation over a water bath, but finishing off in a vacuum. Chlorides are removed from the residue by cooling it to 50" or 60" and adding the smallest possiLle excess of freshly prepared silver sulphate and filtering. The filtrate is neutralised with potassium carbonate, evaporated to a small volume, and is ready to be further treated for the separation of malic acid. Butter Testing. By E. SPAETH (Zeit. angui. Chem., 1893, 513-515).-The author uses a kind of weighing flask, the lid and bottom of which are trebly perforated. The bottom, inside, is covered with asbestos.A glass boat, filled one-third with pieces of pumice the size of a pea, is introduced, and the whole is dried for an hour at 105". The boat is taken out and placed on the balance pan alongside the weighing flask, and weighed. An average lot of butter, weighing about 10 grams, is now put into the boat, and the whole is again weighed. The boat is now placed first on an open water bath for half an hour, then inside am air bath for about two hours at 100". After cooling, it is put inside the weighing bottle, the whole is re- weighed, aud the loss represents the water. The fat is estimated by placing the whole apparatus inside a Soxhlet tube, and extracting the fat with ether in the usual manner. The Ralt may be estimated by digesting the insoluble residue in water rind estimating the chlorine with silver nitrate.The test analyses Butter Analysis. By C. VIOLLETTE (Compt. TtXd., 117,856-8%). -The weight in it vacuum of 1 C.C. of butter at 100" varies from 0.86320 to 0.86425 gram, whilst for margarine the corresponding vdues are 0.85766-0.85865 gram. The density of a mixture of butter D. A. L. show the process to be handy and accurate. L. DE K.ANALYTICAL CREIIISTRY. 125 and margarine is exactly the mean of the densities of its constituents. When cows are fed chiefly on hay, the density of the butter is about 0.86320, whilst if the food consists of grains, pulp, cake, and meal, with very little hay, the density of the butter is about 0 86425. Out of 150 samples of butter, two only, derived from cows highly fed with grains, meal, and cake, gave densities a$ high as 0-86.530 and 0.86540 respectively, whilst one, derived from a cow fed on straw and hay, had a density of 0 86277. The anthor has therefore constructed a densimeter, giving all the densities at 100" comprised between those of pure butter on the one hand and margarine on the other, each unit in the fourth decimal place corresponding to a length of 1.4 mm.on the scale. The butter to be examined is heated in a cylindrical copper vessel by means of steam. For practical purposes, a series of smaller densinieters is used, which allow first of an approximate, and, afterwards, of a more accurate, classification of the butters under examination. Experi- ments must be made from time to time with avei-age butters from the same district, and from animals fed on various diets.In doubtful cases the butter must be analysed. C. H. B. Analysis of Lard. By C. A. NEUFELD (Chem. Centr., 1893, ii, 778; from Awh. Hygiene, 17).-The author comes to the conclusion that neither Hubl's test, nor the silver reaction, are of much use in Estimation of Beef Fat in Lard. By W. I?. K. STOCK (Analyst, 19, 2--7).-The author's process is based on the slight solubility of beef stearin in ether at 13". The requisites are : six 25 C.C. graduated test-mixers fitted with glass stoppers ; ether of 0.720 specific gravity ; a set of mixtures of pure lard melting at 34-45" with 5, 10, 15, and 20 per cent. of beef stearin melting at 56" ; a second set of mixtures of pure lard melting at 39-40" with beef fat melting at 50".The melting point of the sample is taken by the capillary tube method 24 hours after the tube has been filled. Suppose the melting point to be at 34", 3 C.C. of the melted fat is run into one of the test- mixers and dissolved in 21 C.C. of ether, then placed in water at 20-25". 3 C.C. of each of the first set of mixtures is dissolved in exactly the same way. The five tubes are then cooled down to 13" and allowed to remain at that temperature (particularly towards the last) for 24 hours. The apparent volume of deposit in each tube is then noted, and this will give an immediate clue as to the condition of the sample. The ether is poured ofi from the tubes as far as possible, and 10 C.C. of fresh ether at 13" is added in each case.The stoppers are inserted, the tubes well shaken, and after the deposit has settled the operation is repeated. The whole contents of the tubes are now transferred to weighed shallow beakers. The ether is carefully r n n off, and the deposits are dried for 15 minutes at 10" The beakers are cooled and weighed and the standard weight nearest to that of the sample is used as the factor by which to calculate the beef fat. For samples with a higher meltiug point, the second set of testing for small quantities of adulterants. L. DE K. VOL. LXYI. ii. 111-26 ABSTRACTS OF CHEMICAL PAPERS. mixtures should be used. The actual presence of beef fat must he proved by the microscope. For this purpose, a few particles of the dry residue are placed on a slide, moistened with alcohol, and covered.Very moderate pressure should be applied to the cover, and the slide viewed with a 1-inch objective and the C eye-piece. The presence of beef stearin may often be recognised by the naked eye. As regards pure lard, the author is eiiabled to state that no sample melting below 39" gives more than 0.011 gram of ether-washed deposit. A sample melting at 45.8" gave, however, 0.146 gram of deposit. This shows the necessity of having the two sets of standard mixtures and carrying out the analysis by a strict comparison test. Direct experiment has shown that neither cotton oil, palm-nut-kernel oil, nor cocoa-nut. oil, interferes with the deposition of the crystals of beef stearin. L. DE K. Furfuraldehyde as a Test for Sesame Oil. By V. VILLAVECCHTA and G.FABRIS ( Z e d . angw. Qhem., 1893, 505--306).-The authors recommend the following method for the detection of sesame oil. 0.1 C.C. of a 2 per cent. alcohqlic solution of furfuraldehyde is put. into a test g1a.s and mixed with. 10 C.C. of the sample of oil ant1 10 C.C. of hydrochloric acid (sp. gr. 1-19>. After shaking for half a mirute, the mixture is left to itself. If less than 1 per cent. of sesame oil is present, the acid liquid will become carmine-red. In the absence of sesame oil the acid layer will be either colourless or of a dirty-yellow colour. The test may also be carried out as follows :- 0.1 C.C. of the furfuraldehyde solution is put into a test glass, mixed with 10 C.C. of oil and 1 C.C. of hydrochloric acid. gfter thorough shaking, 10 C.C.of chloroform is added to dissolve the oil. I n presence of sesame oil, tbe acid layer will present a fine carmine-red colour, and in its absence there will be either no colour at all or only a trace of green. By saponifying sesame oil with bttrium hydroxide and treating the alcoholic extract of the soap with light petroleum, the authors have Estimation of Alkaloi'ds by Hulsebosch's Process. By F. LIEONIGH (Chenz. Centr., 1893, ii, 890-8'31 ; from Pharrn. Centr. HuZZe, 34, 591--593).-The author rejects the process as being utterly untrustworthy, but suggests a few possible improvements in the apparatus, and also recommends liberating the alkdo'ids by Detection of Piperazine in Urine. By BIESENTHAL (Chem. Centr., 1893, ii, 624-625 ; from Therap. Monakh., 1893, 356).- Korig found (Therap.Monatsh., 1893, 117) that in two cases the addition of picric acid to the urine, after administering piperazine, produced precipitates, which he regarded as albumin. The author considers that these were due to piperazine itself, since this substance, even when diluted 1 : 20,000 with water, gives a distinct precipitate with picric acid and passes through the organism witbout change. vsually piperazine shows itself in the urine 3-4 hours after having succeeded in isolating the chromogenic principle. L. DE K. means of lime instead of by sodium hydroxide. L. DE K.ANALYTICAL CHEMISTRY. 137 been taken ; the precipitate produced in such urine with picric acid has the characteristic crystalline form of piperazine picrate, and cannot, be mistaken for albumin picrate.The piperazine urine gives none of the reactions of albumin. The identity of the precipitate with piperazine pic'iate wax further shown by decomposing i t with hydro- chloric acid, removiug the picric acid by agitation with ether, and detecting the piperazine by means of a solution of potassium bismuth iodide. The presence of piperazine could even be detected in the urine itself by the use of this reagent. In order to detect albumin along with piperazine in urine, acetic acid may be employed ; this coagulates the albumin on heating, and the coagulum does not redissolve, whereas the precipitate of piperazine picrate disappears on heating and reappears on cooling. Test for Coca'ine. By SCHAERGES (Chem. Centr., 1893, ii, 888; from Schweix.Woch. Pharm., 31, 341--343).-A few centigrams of the alkalo'id is dissolved in a drop of water and a drop of sulphuric acid. On adding to the colourless solution a drop of a solution of potassium chromate, or dichromate, a rapidly-vanishing precipitate is obtained. On warming, the liqnid turns green and gives fumes re- sembling those of benzoic acid. Cocaiine is disfinguished from morphine by its insolnbility in cold solutions of fixed alkalis. A. H. L. DE K. Detection of '' Saccharin " in Wines and Beers. .Gy E. SPAETH (Zeit. angw. Chem, 1893, 579--581).-To detect saccharin in wines or cordials, the sample is mixed with purified sand, evaporated to about 10-20 c.c., acidified with a few C.C. of phosphoric acid, and extracted, at a gentle heat, with a mixture of equal parts of ether and light petroleum (b.p. 60"). After filtering through asbestos, the mass is again extracted until the tiltrate measures about 200-250 C.C. After distilling off the solvent, the residue is taken up with a very weak solution of sodiiim carbonate and tasted. A sweet taste points to the presence of " saccharin," the amount of which may be ascertained as usual by a fusion with nitre and an estimation of the sulphate so produced. When applying the process to beers, the bitter principles of the hops must be first removed by adding a few crystals of copper Reaction of Indoles. By A. ANGELI (Gazzetta, 23, ii, 202--3 03). -On melting a trace of an indole or indolecarboxylic acid with dehydrated oxalic acid in a test tube, a beautiful coloration is pro- duced, and can be dissolved in acetic acid.Indole and its aliphatic derivatives give a magenta colour, whilst a-phenylindole yields a violet colouring matter. nitrate. The liquid need not be filtered. L. DE K. W. J. P. Process for the Full Analysis of Root Crops. By A. v. ASB~TH (Chem. Zeit., 17, 725--726).-The author recommends the following process for the analysis of potatoes :--The substance is cut into thin dices, and about 8 grams of the sample is dried, first at 50°, and then at 110". If the The loss reprebentis-the moistuie.128 ABSTRACTS OF CHEMICAL PAPERS. temperature is raised too rapidly, the starch gelatinises, and is then very difficult to dry. The dried substance is incinerated, and the mineral matter weighed. E’or the estimation of the other con- stituents, about five potatoes are cut up, partially dried a t 50°, reduced to powder, and then finely ground; tlie flour is then sub- jected to analysis.The remaining moisture is determined by drying at 110”, and the total nitrogen is determined by Kjehldahl’s process as modified by the author. [The substance is boiled with sulphuric acid and copper sulphate, potassium permanganate being only used in extreme cases ; the liquid is distilled with aqueous soda containing Rochelle salt, and the ammonia is then titrated.-ABsT~ACTO~.] The fatty matter is estimated by exhausting 10 grams of the flour with ether in a Soxhlet’s tube, the residue being exposed to the air until all the ether has gone off. About 2 grams of it is taken for the estimation of the starch and dextrin by the author’s baryta method (Abstr., 1887, 868), but it is necessary to redetermine the moisture and make due correction for any alteration.The minor constituents are estimated by triturating 5 grams of the flour with cold water, and collecting the insoluble mass on a weighed filter. After drying, a portion of it is used for a nitrogen estimation (in- soluble proteids). The solution is evaporated on the water bath, and the residue finally dried for three hours over sulphnric acid in a vacuum ; this gives the total soluble matter; it is then treated with water, and any proteid matter which has coagulated is collected on a weighed filter, dried, and weighed. The filtrate is concentrated to a syrup and mixed with twice its volume of alcohol. The precipitate is washed with alcohol, dissolved in water, and titrated by means of baryta, which gives the dextrin. The alcoholic solution is evaporated in a platinum dish. and the re- sidue, after drying in a vacuum, is weighed ; this gives the sugar and amido-acids. The siigar may be estimated by Fehling’s solution, and the amido-acids are then taken by difference; they may, however, also be estimated directly by deducting from the total nitrogen the nitrogen due to the prote’ids, and calculating the difference to asparagine, which contains 21.97 per cent. of nitrogen. By taking the sum of the soluble prote’id, dextrin, and asparagine, and deducting this from the matter soluble in water, the difference gives the colour- ing matters and gummy substances. In conclusion, the author gives the details of an analysis of a variety of red potato, popularly known as the Zulu-King. Not a trace of sugar was found. As the iesult is very favourable, the cultivation of this crop on the large scale is much to be recom- mended. L. DE K. The Ferrocyanide Test for Urine. By J. P. HARPLUS (Chtm. Centr., 1893, ii, 496 ; from Centr. klin. Med., 14, 577).-See this vol., ii, 107. Estimation of Protei’ds and Extractives in Cow’s and Human By I. MUM (Virchow’s Archiz., 134, 519--540).-See thls Milk. vol., ii, 106.

ISSN:0368-1769    

DOI:10.1039/CA8946605117

出版商:RSC    

年代:1894

数据来源: RSC