摘要:

PHYSIOLOGICAL CHEMISTRY. 111 Physiological C h em is t ry. Absorption of Dextrose in the Small Intestine, and the Effects of Drugs on the Process. Ey FRIEDRICH VON SCANZONI (Zeit. Biol., 1896, 33, 462-474).-Ethereal oils, oil of mustard, alcohol, pepper, and orexin have, in certain concentrations, a favour able influence on the absorption of dextrose ir, the intestine, as in the stomach. I n the stomach, the absorption may be increased fivefold, but this is not nearly so well marked in the intestine; the rise is only a few degrees per cent., for the intestine is already, in normal circum- stances, the ideal place for dextrose absorption. The dose necessary t o stimulate the intestine is smaller ; for instance, oil of mustard (1 i n 200) has no harmful effect on the stomach and stimulates the absorption process there, but it is harmful t o the intestine. W.D. H. Absorption of Peptone in the Small Intestine, and the Effect of Drugs on the Process. By ERNST FARNSTEINER (Zed. Biol., 1896, 33, 475-488).-A 1 per cent. aqueous solution of peptone was introduced through a fistula into the ileum in a dog, and after 15 minutes, 63 per cent., on the average, was absorbed. Addition of 5 per cent. alcohol raised this figure to 72-74; oil of mustard (1 : 1500-5000) t o 72-73 ; oil of cinnamon (1 : 500) to 69. The effect of these drugs is not so marked as in the stomach. Bitters like quassia have no constant action. Mucilages hinder absorption ; 2 per cent. of starch brings the absorption down t o 21-25 per cent. W. D. H. Changes in Cane Sugar in the Alimentary Canal.By HEINRICH KGBNER (Zeit. Bid, 1896, 33, 404-40’7).-1nversion of cane sugar does not occur in the stomach, nor in artificial gastric digestion. The statement often made to the contrary is owing (I) t o dextrose being present from the remains of the previous meal ; (2) t o the ingestion of sugar which had previously been partly inverted ; and (3j to the fact that in pathological cases, especially if there is a transudation of serum into the stomach, inversion may occur. Inversion begins in the small intestine; cane sugar is, however, resistant, and may be found in small amounts quite low down the intestine. Absorption of cane sugar occurs most rapidly in the stomach and duodenum. W. D. H. Iron in the Animal Organism. By WINFIELD S. HALL (Chenz.Cent?.., 1896, i, 970; from Du Bois Reymond’s A~chiv, 1896, 49-83).- Carniferrin was added to food free from iron, and given t o white mice ; the tissues being examined microchemically by the ammonium sulphide method, and control experiments made on mice that had had no carni- ferrin. The whole animals were also incinerated, and the iron estimated in the ash. In those fed only on food free from iron, there was112 ABSTRACTS OF CHEMICAL PAPERS. R loss of 40 per cent. in the total iron of the body in three weeks. In those fed on carniferrin, the red corpuscles increased in number, and absorption of the iron was found to occur chiefly in the duodenum, and to a less extent in the jejunum. Storage of iron occurred in the spleen, and to a less extent in tha liver.The liver, large intestine, and kidney appear also to excrete iron. W. D. H. The Value of Rhamnose in the Normal and Diabetic Organism. By LUDWIG LINDEMANN and RICHARD MAY (C‘hem. Centr., 1896, i, 932-933 from Bezctsch. Arch. Klin. Med., 56, 283-294).-1n a healthy man, about 8 per cent. of the rhamnose given was recovered in the urine ; in a diabetic patient, 11.7 per cent. in the urine and 4#4 per cent. in the fEces was recovered ; there was a simultaneous excretion of dextrose, but the nitrogenous output was diminished from 17 to 14.8 grams per diem. Rhamnose acts, therefore, as a proteid- sparing food. W. D. H. The Proteids of Leuczemic Urine. By RUDOLF KOLISCH and RICHARD BURL~N (Chern. Centr., 1836, i, 972-973, from Zeits. Klin. Med., 29, 374-38O).-Albumosuria is not a constant feature in IeucEmia ; when present, i t probably originates from the decompo- sition of leucocytes, the increase in alloxuric substances in the urine supporting this view.The principal new point made out in the case described is the occurrence of Lilienfeld’s histon in the urine. W. D. H. - Luciferase, or the Light-producing Enzyme of Animals and Plants. By RAPHAEL DUBOIS (Compt. Bend., 1896, 123, 653-654). -The author is of opinion that the active agent in the production of light by certain animals and plants is a substance having the genera,l characters of an enzyme, to which he therefore gives the name luci- feiqase, and that it is not the result of slow oxidation. The lumini- ferous organs of the glow-worm, and the eggs contained in the ovaries of the female, give with tincture of guaiaciim, a fine, blue coloration, as does also the lurninons mucus from the surface of dead fish after treatment with chloroform water and filtration.A. C. C. Analyses of Human, Cows’, and Mares’ Milk. By WILLIAN CAMERER snd FRIEDRICH SOLDNER (Zeit. Biol., 1896, 33, 635-568. Compare Abstr., 1896, ii, 378).-A very large number of analyses of human, cows’, and mares’ milk are given; in the case of human milk, the different dates of lactation are stated. The paper is chiefly com- posed of tables of results, which cannot be conveniently shortened, and do not appear t o show any new points of interest. W. D. H. Constancy of the Freezing Points of Milk and other Organic Liquids. By J. WINTER (Bull. SOC. Chem., 1896, [3], 15, 162--163).-The author finds that his observations (Abstr., 1896,ii,199) have been to some extent anticipated by Beckmann.PHYSIOLOGICAL CHEMISTRY. 113 Excretion of Calcium in Diabetes. By EEXST TENBAUM (Zeit. Biol., 1896,33, 379--403).-The increased amount, both of liquid and solid nutriment taken by diabetics, accounts, in large measure, for the increase in the volume of urine and amount of nitrogen excreted. When such increase occurs, the quantity of calcium salts in the urine increases also in a proportionate way. The large output of calcium appears to be dependent solely on the increased nutriment taken. Calcium and proteid are so closely associated that this is what would be expected. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8977205111

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Chemistry of Vegetable Physiology and Agriculture. 113 The Changes which take place in Milk, either Spontaneously, or during Culinary Processes. By ANTOINE B~CHAYP (Bull. Xoc. China., 1896, [3], 15, 96).-An historical sketch of the development of the germ theory of fermentation of organic solutions. M. W. T. Putrefaction of Albumin. By OSKAR EMMERLIXG (Beg.., 1896, 29, 272 1--2726).-1n these experiments, pure proteids were treated with pure cultivations of micro-organisms. Wheat paste freed from starch by treatment with malt and repeated washing with water, and from fatty substances by washing with alcohol and ether, was mixed with calcium carbonate, potassium phosphate, and mag- nesium sulphate, and placed in the Koch steam steriliser for 3 days, it was then mixed with the Pg*oteus and kept in an incubator at 3 7 O ; after 4 days, gas began to be evolved, which consisted of 46 per cent.GO,, 38 per cent. H, and 16 per cent. N. After 14 days, the process was stopped, and the strongly alkaline liquid distilled in a cur- rent of steam. The distilkcte consisted of phenols and volatile bases, from which trimethy lamine was isolated and identified. The 9.esidue contained the non-volatile bases, and the acids as their caIcium salts; in the former, betaine was present, and was isolated by means of its aurochloride (m. p. 227'). The acids were separated by the frsc- tional precipitation of their silver salts, formic, acetic, and butyric acids being identified. 11. Behaviour of Egg albumin with S ~ ? ~ y l o c o c c u s pyogeqzes aui'eus.The decomposition products, isolated in the same wa,y, were found to be, in the distillate, phenol, indole, and scatole, and in the wsidue, voh- tile, formic, acetic, propionic, butyric, and traces of higher fatty acids ; non-volatile, oxalic and succinic acids. Betaine and trimethyl- amine were also present. I. Behaviour of wheat gluten with Proteus vulgai-is. J. F. T. A New Bacillus which forms Butyric Acid from Glycerol, By OSKAR EMMERLING (Bey., 1896, 29, 2726-2727).-This bacillus, for which the author proposes the name Bacillus boocopicus, is isolated from cow-excrement by Fritz's method. It is very similar to B. subtilis, and grows well on gelatin. With beef broth, it does not form indole. With glycerol, a t 36', in the presence of calcium114 ABSTRACTS OF CHEMICAL PAPERS.carbonate, methylic alcohol, acetic acid, butyric acid, and traces of formic and succinic acids are produced; 6 grams of alcohol, 4.5 grams of acetic acid, and 7 grams of normal butgric acid being obtained from 600 grams of glycerol. From grape sugar, ethylic alcohol and lactic acid are produced. J. F. T. The Cause of Poisoning by Curtains containing Arsenic. By OSKAR EMMERLING (Bey., 1896,29, 2728).-As the result of a large number of experiments conducted with different bacilli and micrococci, the author states that in no case is hydrogen arsenide evolved from fabrics containing arsenic by their means. It is, therefore, highly improbable that poisoning from woollen stuffs containing arsenic is due to hydrogen arsenide, evolved by the action of a micro-organism.J. F. T. Denitrifying Bacteria and the Loss of Nitrogen caused by them. By R. BURRI and ALBERT STUTZER (Ann Agvorz., 1896, 22, 491-494; from Centr. Bact. Par., 1895, 1, 2 Abt., 257, 350, 392 and 422).-From horse-dung, two bacteria were isolated, which together, but not singly, decomposed nitrites with liberation of free nitrogen. The one was identified as Bacterizcm coli cornm.une, whilst the other is new, and is designated B. denitrificans I. Another variety, B. de?zit$cuns 11, , which alone liberates nitrogen from nitrates and nitrites, was isolated from old straw. This micro-organism throve in artificial solutions as well as in nitrate-broth, and destroyed the nitrate in the same length of time. B. coli with B.denit. I., however, caused no turbidity in the artificial solution in a week, and did not decompose the nitrate in the least., in absence of complex nitrogen compounds, The destruction of nitrates (in both) is checked when the amount of nitrate present exceeds 0.5-0.6 per cent. This holds both for B. coli with B. denit. I. and for B. derzit. 11. This has nothing to do with the production of nitrite (which is not poisonous, as the author formerly supposed), but to excessive alkalinity. I n the presence of 0*06--0*07 per cent. of phosphoric acid the fermentation produced by B. coli with B. denit. I . was checked, whilst B. denit. 11. remained active in presence of 0.14 per cent. of phosphoric acid. Quantitative experiments with B. denit. 11. in artificial solutions, showed that 22.2, 20.3 and 20.6 per cent.of the nitrogen of the nitrates remains, and is probably in the form of proteids. On one occasion, 79.5, on another 82.7, per cent. was evolved as gas. Neither carbonic anhydride nor nitrous oxide could be detected. I n the complete absence of oxygen, R. denit. I. with B. coli reduce llitrates completely, but without evolution of nitrogen, the nitrate being almost entirely converted into nitrite. With very limited access of air, B. denit. I. will develop sufficiently to give rise (in conjunction with B. coli) to evolution of free nitrogen; whilst with abundant aeration the evolution of nitrogen is normal. fi. denit. 11. decomposes nitrates normally in compIete absence of air, whilst with aeration, the fermentation is hindered or completely stopped.N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 115 Origin of Trimethylamine, and the Spontaneous Develop- ment of Heat in Hops. By JOHANNES BEHRENS (Ried. Centr., 1896, 25, 713-714 ; from Dev Bieybyauer, 1896, 578--579).-Whilst, according to Griesmayer and Greshoff, trimethylamiiie is a constituent of hops, the author was unable to detect its presence either in fresh hops, or in hops which had been kept in the dry state. I n presence of water, however, hops acquire a very repulsive odour, in which that of trimethylamine can readily be detected. This change, and the rise of temperature which accompanies it, is due to a bacterium (BccciZZus IupuZipei-da) which resembles Flugge's B. fEuopl'escens putibus both morphologically and physiologically.The nitrogenous substances of the hops which are utilised by the bacillus are proteids, choline, ammonia, and asparagine, whilst malic and citnric acids, &c., supply carbon. The tannin present in the hops does not seem to be changed by the bacillus. The antiseptic nature of hops prevents the develop- ment of other micro-organisms. N. H. J. M. Action of Phenylquinolines and Phosphines on Lower Organisms. By A. J. F. HERMAXN TAPPEINER (Chern. Centr., 1896, i, 1010-1011 ; from Deutsch. ATC~,. Klin. Ned., 56, 369--380).-Those organisms (Infusoria, Amcebz, Turbellaridae) on which quinine works strongly are even more readily killed by phenylyuinolines and phos- phines ; those (yeasts, bacteria) on which quinine has but little action are less affected by the compounds in question.Of the phenylquino- lines, the /3-compound acts most strongly, the a-compound least so. W. D. H. Vegetation in Respired Air. By LOUIS MANGIN (Bied. Centv., 1896, 25, 689-690 ; from Jour. Agric. p a t . , 1896, i, 491-493)- Equal quantities of seeds and tubers were placed, with equal amounts of water, in each of a series of receivers through which air was drawn by means of a pump. The apparatus was so constructed that a small quantity of air could be withdrawn for analysis. As the air became richer in carbonic anhydride and poorer in oxygen, growth was con- siderably retarded. Whilst linseed absorbed 3.29 per cent. of oxygen, and produced 1.44 per cent. of carbonic anhydride in an atmosphere containing 1 to 3 per cent. of carbonic anhydride, the amounts were 1.45 and 1-04 per cent.when 2 t o 6 per cent. of carbonic anhydride was present. I n the case of peas) the amount of substance produced diminished from 53.5 to 42.5 grams when the percentage of carbonic anhydride rose from 1-3 to 2-5 per cent. There was, moreover, a change in the nature of the oxidation process indicated by an increase in the quotients CO,/O,. With linseed, for instance, this was 0.51 in an atmosphere containing 1-3 per cent. of carbonic anhydride, and 0-74 when the percentage was 3-5 N. H. J. M. Production of Vegetable Proteids. By TAMAS KOSUT~NY (LcLncEw.-Veysucl~s.-Stcct., 1896, 48, 13-32), The object of the author's experiments was to throw light on the question whether assimilation, and the process of reduction which it involves, influences the produc- tion of proteids from asparagine. Assuming that amides are formed116 ABSTRACTS OF CHEMICAL PAPERS. from proteids as secondary products of oxidation in germinating seeds, it seemed likely that, in developed plants, proteids might be formed from amides in the process of deoxidation under the influence of light.Comparative experiments were made in which the one half of a number of leaves of Riptwia suuvtcge were cut during the day (between 2 and 3 p.m.), the remaining halves being separated from the plants in the night, and analysed. The percentage of total nitrogen .diminished as the season advanced. I n the 1894 experiments, the difference was about 0.25 per cent. (from 21st June t o the end of August), but in 1895, with a longer interval, the percentage diminished from 5.314 (on May 8) to 1.25 a t the end of October.As regards variations in composition during day and night, the total nitrogen was somewhat higher during the night than in the day time (102*37:100), but the non-proteid nitrogen is much less by night than by day (45 : 100). The leaves contain rather more ammonia but less nitric acid in the night than in the day time. Since, in the night, oxidation prevails in the plant, it is probable that the conver- aion of nitrates into proteids is greatest in the night. No asparagine, or similar substance, could be detected in the leaves cut off in the night. It is concluded that, whilst the crude substances which produce proteids are chiefly taken up by tihe plant in the day time, their actual conver- sion into proteids takes place more in the night than in the day.The leaves contain on the average 1.10 per cent. more water in the night than in the day time. Leaves cut in the day time contain the most sugar, thohe cut in the night the most free acids. The percentage of ash increased, somewhat irregularly, from 9-43 on May 8 to 19.93 on October 23. N. H. J. M. Effect of Nitrogen on Root Formation. By HERMANN MULLER (Bied. Cerzti',, 1896, 25, 595-597 ; from Jcclwesbei.. Vei-sucl~s-stat. Wzdensweil., 1895,- 4, 48).-Water-culture experiments were made in which half of the roots of a number of plants were immersed in nutritive solutions free from nitrogen, the other half in solutions con- taining nitrogen. The plants selected were vetches, maize, sunflower, and beans, &c.I n presence of nitrogen, the root-development was greatly increased. It is concluded that proteids are formed in the roots, and not in the leaves only; otherwise, it must be assumed that the proteids migrated t o the roots directly supplied with nitrogen, and not t o those (of the same plants) growing in solutions free from nitrogen. N. H. J. M. The Physiological Significance of Lecithin in Plants. By JULIUS STOKLASA (Bey., 1896, 29, 2761--2771).-The important part which is played by phosphoric acid in plant physiology has led the author to determine the proportion of lecithin occurring in certain vegetable organs ; the paper forms a summary of the analytical results and the conclusions which they suggest. Seeds which are rich in albumin contain also a greater proportion of lecithin, whilst oily seeds, those, for instance, of B~ccssiccc oleyacecb, Xinccpis arvensis, and Beta vulgaris, are poor in lecithin ; germination of the last-named is not accompanied by decomposition of lecithin, but in the case of PisuwVEGETdE1,Z PHYSIOLOGY AND AGRICULTVRE. 11 7 sc&imrn this process involves reduction in the percentage of the sub- stance in question.I n the fruit of maize, 74 per cent. of the total quantity of lecithin is found in the embryo and scutellum, only 26 per cent. occurring in the endosperm ; from this fact, the author concludes that the lecithin in the scutellum, and especially in the embryo, under the influence of radiant energy, serves t o elaborate chlorophyll in the early stages of plant life.Development of the leaf is also associated with the production of lecithin, which increases with the multiplication of chlorophyll granules ; this increase is in some may related t o the assimilation of carbonic anhydride, and it appears probable to the author that lecithin arises in the granules themselves as a product of assimilation. Moreover, analyses show that vine leaves, when allowed to grow for 10 days in darkness, contain only one-third as much leci- thin as similar, but unprotected, leaves from the same plant collected a t the same time of day (4 o’clock). ChZoroZecithin*is an amorphous, greenish-black substance with metallic lustre, which has been isolated from freshly-gathered, unpressed grabs leaves ; its behnviour towards baryta indicates the presence of choline, glycer ylphosphoric acid, and chlorophyllan groups, and, in this respect, it resembles Hoppe-Seyler’s chlorophyllan, differing from that substance, however, in the amount of phosphorus present, for whilst chlorophyllan contains only 1.38 per cent., chlorolecithin contains 3.37 per cent.Thus the author has traced an intimate connection between lecithin and chlorophyll, and maintains that, not only does the former sub- stance actually occur in chlorophyll granules, but that phosphorus is a constituent of chlorophyll, and that without this element the elaboration of chlorophyll and the development of chlorophyll granules is impossible. Examination of apple-blossom has shown that the pedicel is engaged in transmitting lecithin from the leaf to the flower. The petals are richest in lecithin previous to fertilisation, acting as storage vessels, which become rapidly depleted of lecithin when the fruit is formetl. The pollen contains 6 per cent.of lecithin, and, Zacharias having shown that nuclei’n occurs in this product, it is noteworthy that animal spermatozoa, also contain lecithin and nuclein. Coexistence of Laccase and Tyrosinase in certain Fungi. By GABRIEL BERTRAND (Compt. rend., 1896, 123, 463-465).-An extract of various species of BussuZa obtained by plasmolysis with washed chloroform or ether, has much more active oxidising properties than extracts prepared by the methods previously described. It also acts on tyrosin, in additioo to having the oxidising properties of laccase, and it would seem that both ferments are present in the extract, This is confirmed by the fact that, when the extract is heated at YO”, the power of affecting tyrosin disappears, whilst the extract still attacks the substances that are oxidised by laccase.When an extract of Russzck~ delica in aqueous chloroform is mixed mithexcess of alcohol, a precipi- tate is formed, and the liquid does not attack tyrosin, but oxidises phenols and amines in the same manner as laccase. The precipitate, TvhcJn purified by suspension in chloroform and reprecipitation by alcohol, yields *. This is not a chlorinated derivative of lecithin, as its name would seem t o imply 31. 0. F. -[EDITORS]. VOL, LXXII. ii. 9118 ABSTRACTS Ol!’ CHEAIICAL PAPERS. an aqueous solution which has practically no action on phenols and amines, but rapidly oxidises tyrosin.I t follows that laccase and tyro- sinaee coexist in the juice of many species of fungi (compare Abstr., 1896, ii, 61, 268, 571). By EDMUND 0. TON LIPPMANX (Rei-., 1896, 29, 2645--2654).-0f the nitrogenous com- pounds present in beet-juice, the following have been already obtained and more 01- less carefully characterised : asparagine, glutamine, betai’ne and choline, leucine and tyrosine, glutamic or pyroglutamic acid, citrazinic acid, lecithin, and logumin. The author has already pointed out (Abstr., 1888, and Zeit. f. Ruben- zzlck. 7?zd., 38, 68) that,, besides lecithin, the cell-substance contains other phosphorus compounds, which may be extracted by means of alkalis, and are probably closely related to the nucleins, and, further, that their decomposition products, the xanthine-compounds, may be obtained from the molasses by fractional precipitation with phospho- tungstic acid.H e has now succeeded in isolating a considerable number of nitrogenous substances in the following manner. The dilute solution of the decomposition products was neutralised and precipit,ated wit’h !end acetate, phosphotungstic acid, or mercuric nitrate, and the precipitates formed were then decomposed, in order to liberato the contained bases, which were subsequentlyfractionally precipitated by means of phosphotungstic acid, mercuric nitrate, mercuric chloride, Ce-c. The following substances were isolated and completely characterised : xanthine, guanine, hypoxanthine! adenine, cnrnine (rarely observed in plants), arginine, guanidine, allanto’in, and possibly vicin.The investi- gation is complicated by the occurrence of the decomposition products of these substances. The recurrence of vicin, a glucoside, in the above product of alkaline hydrolysis is not impossible, as woulci a t first sight appear, as Drenk- mann has described a glucoside ( 2 e i t . f . Rubenxuck. Incl., 46, 478) which is o n l j slon-ly decomposed by strong alkali a t high temperatures, C. H. B. Nitrogenous Constituents of Beet-Juice. A. L. The Maximum of Plant Production. Ey ADOLF NAYER (Lmzdtu. T’e?-suchs.-Stcd, lS96, 48, 6 l--’iG).--The maximum production of the various agricultural plants, as grown in ordinary agricultural practice, was previously shown (ibicl., 1892, 40, 205) to be 7000-8000 kilos.per hectare in Northern Europe, although by very heavy manur- ing twice that amount, or more, could be obtained. With regard t o the question whether the limft of production depends on the amount of sunlight or on the amount of carbonic anhydride in the air, the results of Dehkrain’s experiments on sugar beet (Abstr., 1890, 406), in which a greater yield was obtained under the influence of farmyard manure, as compared with minernls, seem to point t o the production of carbonic anhydride from the organic manure as the cause of the increaqed yield, espe.=ially as the soil t o which minerals were ap- plied was shown to be poor in carbonic anhydride. (Dehdrain attributed the greater yield on the dung-plot to the direct assimilation of organic matter.) I n 1893 and 1894, the author made experiments with sugar lxet (on plots of 0.25 are) in which plants received (1) farmyard manureVEGETABLE PHYSIOLOGY AS 1) AGRICULTC‘RE.119 (1 20,000 kilograms per hectare), (2) minerale,and (3)mineralsinconjunc- tion with cai-bonic anhydride (liberated on the spot from 10 per cent. dex- trose solution and yeast). ‘I’hz results indicated t h a t the highest yield of sugar beet can be obtained a i t h exclusively mineral manure, when sufficiently watered, as well as with farmyard manure. It is not pos- sible to explain D e h h i n ’ s results, as the plan of the experiments is not fully given; but i t seems likely t h a t the beneficial effect of the farmyard manure must, at any rate, be largely due to the increased water-capacity of the soil.Nutritive Value of Horse-chestnuts. By PAUL GAY (Ani2. Agroiz., 1896, 22, 401-423).-The horse-chestnuts employed in the experiments had the following percentage conipoeit4ion. Crude Ether N-free Crude Water. protcin. estract. extract. cellulose. A&. 38.93 4.81 4.64 46.19 3 66 1.77 Two lots of sheep were fed with lucei ne (500 grams), peas (5CO gramhj, with the addit ion of mangolds and horse-cheatnuts respectively, given i n such quantity t h a t the amount of dry matter of each was the same. The increase of liye weight was much greater in the case of the sheep fed with chestnuts than with those fed with roots. On reversing the foods, tlie same result was again cbtained. It is concluded that raw chestnuts a r e about three times as nutritive as mangolds.The valne of chestnuts is considerably increased by cooking. I n experiments with COWS, in which 5 kilos. of chestnuts per head per day mere givetl, i t mas found t h a t no effect was produced either on the taste or compo- sition of the milk, and the milk had no injurious effect on calves. The yield of milk Wac, however, considernhly diminished (from 15 to 12 kilos. per day). This is mcribed to deficiency of water in the food, in which case the remedy would be easy. Pigs dcclined to eat chestnuts in nny quantity, and left more than half the faod with which they wers mixed. Molasses as Food for Cows. By ~ J G U S T STELLWAAG ( B i d . Centr., 1896, 25, 718-719 ; from Zeit. ZcmlLv. Kei*. Bnyem, 1895, 778). --Pour cows were fed f o r a week with chaff (two-thirds hay and one- third straw, 20 kilos.), fresh brewers’ grains (20 kilos.), malt germs (2 kilos.), and crushed barley (4 kilos. per 1000 kilos.live weight). For two of the cows, the same feeding was continued four weeks longer ; whilst the other two, instead of tlie barley, had molasses mixed with an equal weight of palm cake (3 kilos.). During the next four weeks, the food OF the two sets of corns was reversed. The composition of the molasses food resembled that of the bai ley, bnt contained ~omewhat less csrbohydrtites and rather more fat. The cows consumed the whole of the molasses mixture ( ~ h i c h was mixed with the brewers’ grains), and did not suffer from indigestion. There was no change, either in the amount of milk or in the percentage of fat, during the experiments.N. H. J. &I. N. H. J. M. N. I€. J. 11. Recent Progress in Soil Examination. By EUGEXE w. HILGARD (Rep. Jgi i c . E J ~ er. Stat. . t ? d . fo,. 1894-5, 23--32).--d number of Calif( rnian ar?d H waiian scils were analjsed, emilloying Dyer’s120 ABSTRACTS O F CHEMICAL PAPERS. citric acid extraction method, and the results obtained agreed exceed- ingly well with vegetation experiments. With regard t o the recognition of ‘cnitrogen hunger” in soils, the author recommends separation and analysis of the humus. The more nitrogenous the humus is, the less carbon will be oxidised by the limited amount of oxygen present in the soil, It mas previously concluded that a soil in which the humus contained less than 2.5 per cent.of nitrogen would be benefited by nitrogenous manure, notwith- st’anding that the soil itself contained as much as 0.17 per cent. of nitrogen. This opinion was confirmed by a vegetation experiment, which clearly showed that available nitrogen was deficient. The amount of lime present in the soil is, however, of great importance in this connection. With a deficiency of lime, soils would show ‘( nitro- gen hunger,” even when the humus contained more than 2.5 per cent. of nitrogen, whilst in calcareous soil, a low percentage of nitrogen might suffice. The author thinks that the examination of humus, in conjunction with Dyer’s method for mineral constituents, will eventually furnish a means of readily ascertaining the wants of soils, although the vegetation tests (in pots or in the field) will have the last word.By ST. SMORAWSKI and H. JACOBSON (Bied. Centr., 1896, 25, 580-581 ; from B1atte.l. f. Zuckers-iibe~buczc, 1896, 3, 193-201).-Basic slag and mineral and bone superphosphates respectively (sbout 1 per cent.) were mixed with soil, and the phosphoric acid soluble in water and in citrate solution mas determined, The soil was then put into beakers, moistened with water, and left to dry, being occasionally stirred. The phosphoric acid was again determined as before. This was repeated several times at intervals of 4 t o 8 weeks. The results indicate that the phosphoric acid originally soluble in water is very rapidly converted into the citrate-soluble form, but this has no effect on its value as manure.The citrate-soluble phosphate seems to undergo no further change. The alleged inferiority of basic slag is, therefore, unfounded. Hineral and bone superphosphates containing the same percentage of phosphoric acid have equal value as manures. Assirnilability of Nitric and Ammoniacal Nitrogen by Plants. By AIME PAGXOUL (Ann. Agron., 1S96, 22, 4%-490).- Mangolds, Cumelincc, clover, and oats were grown in sterilised sand, (1 ) without any manure, (2) with sodium phosphate and potassium nitrate, and (3) with sodium phosphate, potassium chloride, and ammonium sulphate ; as compared with nitrate, ammonium sulphate gave two or three times as much dry produce in each case. The unmanured plants were quite free from nitrates. The plants which received nitrate con- tained 0.35 to 0.75 per cent.of nitrogen as nitrates (in the dry substance), whilst those which received ammonium sulphate contained much less, but still quite appreciable amounts (0,017 to 0.150 per cent.). Nitrogen in the form of ammonia was found in the plants manured both with nitrate and with ammonium sulphate, but in much smaller quantitythan nitric nitrogen. The results indicate that,under the N. H. J. 35. Behaviour of Superphosphate and Basic Slag in Soil. N. H. J. 3%.ASALTTICAL CHEMISTRY. 121 conditions of the experiments, nitrogen was directly assimilated in the form of ammonia, aucl in greater quantity than in the form of nitrates. Nitrogen as nitrates was determined in the plants as follows: After drying the subst.ance a t 105", a small quantity (0.2 gram) mws boiled with a little water, and, when cold, treated with a few drops of lead acetate solut,ion, and about a gram of animal charzoal. After an hour, it was filtered and diluted to 50 C.C.; of this solution, 5 C.C. was evaporated to dryness, well stirred with a few drops of phenol dissolved in sulphuric acid (1 : 7), and treated with ammonia. The yellow colour thus produced, if nitrates were present, was compared with that of a standard solution of ammonium picrate (N = 1 per million), by pouring the two solutions into two similar tubes, each holding 50 C.C. and divided into C.C. The solution to be tested is diluted until it has the same tint as 50 C.C. of the standard solution, and its volume V (in c.c.) read. The miount of nitrogen in milligrams per cent. = v.10000 2ooo =tip7. Ammonia was determined by distilling the fresh substance (10 grams) with water (50 c.c.), magnesia (0.5 gram), paraffin (0.5 gram), and a few pieces of pumice, using a spiral condenser ; the distillate, which is collected in a flask containing a few drops of very dilute sulphuric acid, is diluted to 50 C.C. and treated with Nessler solution, employing, for comparison, a solution of ammonium sulphate (N = 1 per million). The Agricultural Value of Deteriorated Phosphatic Manures. By JULES JOFFHE (Bull. SOC. Chinz., 1896,; [ 31, 15, 42-46).-Millot has proved that the deterioration of phosphatic manures is due t o the formation of an insoluble ferric phosphate. To determine the relative values of superphosphate, tricalcium phosphate, and the ferric phos- phate obtained from a sample of manure containing very little tricalciam phosphate, from which all the soluble phosphate had been removed, crops of mustard were grown in plots which differed only with regard to the nature of the phosphate present. N. H. J. M. The results were as follows. Plot without fertiliser.. ...................... 100 Plot with ferric phosphate from deterio- rated superphosphate ..................... 167 Plot with tricslcium phosphate ............ Plot with superphosphate .................. 360 280 M. W. T.

ISSN:0368-1769    

DOI:10.1039/CA8977205113

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

ASALTTICAL CHEMISTRY. An a 1 y t i c a1 Chemistry. 121 Methods of Rock Analysis. By MAX DITTRIGH (Ziittl~. Badisch. yeol. Lmzdesnnst., 1894, 3, 75--105).-The methods are essentially those usually adopted, t h e material being first fused with sodium and potassium carbonates ; several small variations are described in detail. %. J. 8.122 ABSTRACTS O F CHEMICAL PAPERS. Estimation of the Three Halogens, Chlorine, Bromine, and Iodine, in Mixtures of their Binary Compounds. By A. A. BENNETT and 1;. A. PLACEWAY (J. Anter. C'henz. SOC., 1896, 18, 688-692). --Two grams of the mixed salts is dissolved in 150 C.C. of water; 50 C.C. of a 20 per cent. solution of iron alum is add.ed, and the iodine is expelled by distillation; this, as usual, is condensed in an apparatus containing 35 C.C.of SO per cent. potassium iodide and titrated. The bromine is then liberated by adding 35 C.C. of a saturated solution of potassium permanganate and distilling, in the usual way, in to potas- sium iodide solution, when i t sets free an equivalent quantity of iodine. S f t e r reducing the excess of permanganate with sulphuric acid and ferrous sulphate, the chlorine is precipitated with silver nitrate. IJ. DE K. Action of Bromine on Metallic Chlorides and a Method for the Estimation of both Halogens in the pres2nce of one another. By FRITZ BLAU (.110mtsl2., 1896, 17, 547-566).-The author has taken the experimental numbers obtained by Berthelot (Abstr., lSSl, 342 ; 1883, S ; 1885, 632) in his experiments on the amount of chlorine liberated by the action OF bromine on different chlorides, and from these has calculated the affinity constant li' by means of the equation Kz = ( A - ') (I' - ') where A = the number of C2 equivalents of chloride originally present, B = those of bromine, and C =t the (necessarily equal) number of equivalents of bromide and chlorine produced in the reaction.The results thus obtained are roughly of the same magnitude, and differ completely from those based on Humpidge's data (Abdx., 1884, 1245). This divergence can probably be accounted for by the inaptitude of the indirect method for the estimation of chlorine and bromine when one of these is present in a large excess. The author has carried out experiments on t h e action of bromine on concentrated sodium chloride solutions, I n making the experiments, a measured quantity of a solution of pure sodium chloride was placed in a stoppered flask, and a weighed quantity of pure bromine, contained in a small, thin-walled bulb, dropped in; on shaking, the bulb was broken, and the flask was placed in the dark a t a constant temperature for several hours.The excess of bromine and the liberated chlorine were then quickly removed by a rapid current of air which had been filtered through cotton ~ ~ o o l , and as soon a s the last trace of bromine was thus removed, the amounts of sodium bromide and chloride in the solution were estimated. Exact analytical results were obtained by using a modification of Berglund's method (Abstr., 1885, 836) for the estimation of bromide and chloride in the presence of one another.For this purpose, the bromine was set free by means of potassium perrnanganate and potassium hydrogen sulphate ; and the solution clPtilled in a vacuum a t the ordinary temperature in a special appa- ratus, the bromine being collected in aqueous potash. The hypo- bromite thus formed was converted into bromide, and the liquid treated exactly as before, the bromine in the second distillate being estimated by means of iodine. The residues in the two distillation flasks were united, and the amount of chloride c'mt.zined in them estimated.ANALYTICAL CHENISTRY. 123 The author finds that at 12-13' K=272*67, and a t 16-17' K = 246.08. Care was taken t o show that no secondary actions took place, a s the solution formed was quite neutral. It was also proved expe- rimentally that the current of air always removed the two halogens in the same proportion, so that the equilibrium was not disturbed.J. J. S. Jacobsen and Brunn's Method for the Purification by means of Iodine of Hydrogen Sulphide containing Arsenic.., By ZDENKO H. SKRAUP (Clien~. Ceizty., 1896, i, 469 ; from Zeit. Oste~r. Apoth.-V. 34, '72--'76).-1n testing the efficiency of this method (Jacohsen, Abstr., 188'7, SSS), which is based on the facts that hydrogen nraenide and dry iodine form arsenic tri-iodide, whilst hydrogen sul- phide and iodine clo not react i n the absence of water, the gas, after washing with water and subsequent drying by means of calcium chlo- ride, was passed over dry i )dine, then into sodium hydroxide solution (2) and then into warm nitric acid.The residue obtained on evaporating the nitric acid was treated with sulphuric acid and submitted t o Marsh's test. Slow passage of the gas through the apparatus was found to effect either a complete removal of arsenic cr to leave only slight traces, but unsatisfactory results mere obtained when a more rapid current was employed. By GEORG LUXGE (J. d m r . Chem. Soc., 1896, 18, 685-686).-A final reply to Gladdiiig (Abstr., 1895, ii, 291, and 1896, ii, 622). Experiments conducted on behalf of the author have again shown that, when precipitating a sulphate with barium chloride solution, the latter may be added either quickly and in moderate excess, or run in from a burette at the rate of one drop per second without any sensible difference in the result.Estimation of Sulphides in Calcium Carbide. E. TV. W. Estimation of Sulphur in Pyrites. L. DE I<. By FREDERICK J. POPE (J. Amer. Chem. Soc., 1896, 18, 740-'741).-A weighed quantity of the sample is jntroclucecl into a dry Erlenmeyer flask pro- vided with a stop-cock funnel and a delivery tube leading to a 10 02. wash-bottle, which is in turn connected with a smaller one ; both are partially filled with a standard solution of leacl acetate, the total value of which is, of course, accurately known. The calcium carbide is first decomposed by water until no more acetylene is evolved, and excess of dilute sulphuric acid is then introduced and the mixture boiled; hjdrogen sulphide is evolved, and precipitates part of the lead as sul- phide. The excess of lead is then estimated by the author's method Estimation of Sulphur in Ores.By J. H. STANSBIE (Chenz. il7ews, 1896, 74, 189). LUCIEN L. DE KONIKCK (?%id,, 2%i).-stansbie sug- gests the use of nitric acid and bromine for the oxidation of sulphur in ores, whilst de Koninck points to a similar application of the same re- agents by himself years ago. Estimation of Sulphuric Acid or of Barium. By JAMES EDNUNDS (Chew&. News, 1896, 74, 1 S7-18S).-For the proposed method, there (this vol., ii, 125). L. DE K. D. A. L.1.24 ABSTRACTS O F CHEMICAL PAPERS. are required decinormal and centinormal soIutions of barium nitrate, potassium chromate, silver nitrate, sodium chloride, ancl potassium sulphnte, centinormal solutions of potassium thiocyanate and calcium sulphate, and a decinornial solution of ferric sulpfmte.The latter is made by oxidising a solution of ferrous sulphate by boiling with nitiic acid, then boiling with a large excess of sulphuric acid to expel the nitric acid, and making up t o the strength of a decinormal solution of iron in about a quinquenormal sulphuric acid. The calcium and potassium sulphate solutions serve for tests and controls. I n use, 10 C.C. of the decinormal solutions of barium nitrate, potassium chromate, and silver nitrate are added successively to 70 C.C. of the liquid under examination, contained in a tall 200 C.C. stoppered bottle, shaking vigorously for one minute after each addition. The mixture is preferably allowed to subside, or may be filtered, ancl 20 C.C. of the clear liquid is mixed with a measwed excess of decinormal soclium chloride, and titrated back with centinormal silver nitrate, using potassium chromate as indicator.From the data obtained, the content of sulphuric acid is calculated. The liquid tested should have the strength of a centinormal solution ; if stronger, it should be diluted, if weaker, concentrated, or the centinormal reagents employed throughout. Moreorer, as a preliminary, substances precipitating barium or chromates, or reducing the latter, also ammonia, S.C., must be eliminated, and any haloids present must be estimated, for which purpose the thiocyanate and ferric sulphate are provided. I n estimat ing barium, the 70 C.C. of liquid under examination being of suitable strength, is first shaken with 10 C.C. of decinormal potassium sulphate, then the excess of sulphuric acid is estimated in the above manner.D. A. L. [Estimation of Nitric and Ammoniacal Nitrogen in Plants.] By AmE PSGNOUL (Ann. Ay7*., 1896, 22, 485--490).-See this vol., ii, 120. Wet Method for Estimating Carbon and Nitrogen in Organic Compounds. By PAUL FEITSCH (Awzaclen, 1896, 294, 79-88).- The derivatives of isoquinoline described by the author (Abstr,, 1895, i, 624) were annlysed by a new method, which combines Messinger’s process for estimating carbon (Abstr., 1889, 80; lS90, 1467) with Kruger’s modification of Kjeldahl’s method for determining nitrogen (Abstr., 1894, ii, 258). The substance t o be analysed is oxidised by means of potassium dichromate and concentrated sulphuric acid in a small distilling flask through which a current of purified air is passing.The gas produced is then passed into a heated combustion tube 36 cm. in length, con- taining a mixture of granulated copper oxide and lead chromate between two copper spirals. After being dried with calcium chloride, the carbonic anhydride is absorbed by potash. The residue in the flask is transferred to a larger distilling flask, connected with a Liebig’s con- denser, and the ammonia liberated on treatment with caustic soda is determined in the ordinary manner. Figures illustrate the form of apparatus employed, and analytical details me described in the paper. &I. 0. F.ANALYTICAL CHEJIISTKT. 125 Analysis of Mortars. By WILLIAM J. DIBDIN and ROBERT GRIM- WOOD (Annlyst, 1896, 21, 197--204).-The authors have analysed a large number of limestones, bricks, and mortars, and have tabulated the results.I n estimating lime and sandy matter in mortars, it must be remem- bered that, in practice, the mortars are made by volume m d not by weight. The best plan, therefore, is t o prepare a mortar according t o the particular specification and to analyse this side by side with the inspected sample, allowing, of course, for difference in moisture, &c. The authors also give convenient factors for reducing the weights t o volumes. Earthy matter is estimated by treating the sample with dilute hydrochloric acid and repeatedly decanting from the heavy sandy matter; the earthy matter is then filtered, dried, and weighed. The filtrate contains the soluble silica, calcium, &c., which are then estimated a3 usual.Froin the amount of the former, a very fair idea as to the By ~ ~ J R I C E LUCAS (Bull. s'oc. Chim., 1896, [3], 15, 39--42).-The author describes a method for estimating very small quantities of lead in alloys, SLc. The lead and copper are separated by electrolysis, using a current of 0.3 ampkre and 2 volts. ; the lead,which is deposited on the positive pole in the form of peroxide, is, after washing, drying, and weighing, redissolved in 1 C.C. of the nitric acid containing nitrous acid, obtained by the electro- lysis of nitric acid. The solution is rendered neutral with caustic soda and diluted so that 50 C.C. of water contains about 1 milligram of lead ; five drops of ammonium sulphide is now added, and the colour of the liquid compared with that of solutions containing the same quantity of sodium nitrate and ammonium sulpbide, t'o which cliff erent qiiantities of a standard solution of lead nitrate have been added.Sodium carbonate and neutral salts have a considerable effect on the colour of the leacl sulphide, consequently great care must be taken t o keep the conditions exactly the same in the different solutions. quantity of added cement may be obtained. L. DE K. Colorimetric Estimation of Lead. 11. W. T. Volumetric Estimation of Lead. By FREDERICK J. POPE (J. Arne?.. Chenz. Soc., 1896, 18, 737-740).-The lead should be in the form of acetate. Lead sulphide (galena) is first converted into sul- phate by the action of mixed nitric and sulphuric acids, and after removing the free acid, i t is dissolved in ammoniurii acetate ; the lead is now precipitated by adding an excess of standard solution of potassium dichrornate, and the lead chromate is filtered off.The excess of chromate is then estimated by adding an excess of standard arsenious acid solution and a little dilute sulphuric acid, stirring until the yellow colour has completely disappeared or changed t o a faint green; after adding a slight excess of sodium hydrogen carbonate, the excess of arsenious tLcid is titrated with standard solution of iodine. The calculation will be easily understood. The test andyses are Estimation of Iron and Aluminium Oxides in Phosphate Rock. By THOMIAS S. GLADDIKG (J. A n z e ~ . Chem. Soc., 1896, 18, remarkably accurate. L. DE K.126 ABSTRACTS OF CHEMICAL PAPERS. 717 --721 ; 721-724).--Four grams of the finely-ground sample is heated for half-an-hour with 30 C.C.of dilute hydrochIoric acid (1-1). This will leave any iron pyrites undissolved. After filtering, the iron is fully oxidiscd with nitric acid, and the liquid made up to a definite bulk. An aliquot part of the solution, representing, say, one gram, is nentralisecl with ammonia and well cooled; more ammonia is then added until a permanent precipitate has formed, and this is again dissolved by cautiously adding hydrochloric acid. 15 C.C. of ammonium acetate (made by neutralking 30 per cent. acetic acid with ammonia) and 5 C.C. of acetic acid are placed in a beaker, and the ~ h o q hate soln- tion is slowly added, with constant stirring.After keeping it a t 60" for about an hour, the precipitate is collected and washed with a 10 per cent. ammonium acetate solution, redissolved in a fern C.C. of hot hydrochloric acid (1-4), and one gram of animonium phosphate is added. Ammonia is added until the liquid is turbid, then hydro- chloric acid until the precipitate just redissolve9, and the liquid is again pourecl into 15 C.C. of ammonium acetate and 5 C.C. of acetic acid. The precipitate formed is treated again in the same way, when a product is obtained free from calcium and consisting of normal aluminium phosphate with normal iron phosphate. The two are weighed together, and the iron phosphate is estimated volumetric- ally. I n another method, the solution is made as debailed above, but instead of using ammonium acetate, it is run into a solution of potassium hydroxide (500 grams per litre), and heated at 70" for about a n hour.From the filtrate, the aluminium is recovered by first adding ammonium phosphate, then hydrochloric acid in slight excess, and precipitating the aluminium phosphate from this solution by means of acid ammonium acetate in the way already described. The iron may be estimated in the precipitate produced by the potash. L. DE K. By ADOLF JOLLES ( l l l o n t ~ ~ ~ I ~ . , 1896, 17, 677-696).-The first method described is as follows. A suitable quantity of the blood is evapo- rated to dryness, the residue strongly ignited, and then dissolved by fusing it with perfectly anhydrous potassium hydrogen sulphate, about 1 gram of the latter being used for each C.C.of blood originally taken ; the operation is best conducted in a platinum crucible, but one of good Berlin porcelain may be used. The contents of the crucible are then rinsed with hot water into a beaker, poured into a flask, treated with dilute sulphuric acid and pure zinc (the amount of iron in which has been previously estimated; about 1 gram of zinc is used for every 1-2 C.C. of blood taken), boiled until all the zinc has dissolved (the gask being closed with a Bunsen valve), and the amount of iron finally t'itrated with N/50 or N/lOO permanganate. I n 10 samples of the blood of one and the same pig, the amount of iron found, per 1,000 grams of the blood, varied from 0.662 to 0.687 ; in the blood of eight different pigs, i t varied between 0.549 and 0.948.A. second method is to evaporate the strongly ignited residue from 3-5 grams of the blood several times with strong hydrochloric acid Estimation of the Iron in Blood for Clinical Purposes,ANALYTICAL CHEJIISTRI’. 127 on the water bath, dissolve the residue in waier, and precipitate in the cold with a solution of nitroso-P-naphthol (1-2 grams of the pure crystnllised substance in 100 C.C. of 50 per cent. acetic acid), using about 5 C.C. of the solution per 3 grams of blood taken. The very bulky precipitate is collected, washed with small quantities of 50 per ceiit. acetic acid, dried at looo and finally ignited, the residual ferric oxide being weighed. The whole operation requires about 45 minutes, and the results agree well with those obtained by the first method.A third colorimetric method is recommended for clinical purposes. It requires two similar Nessler cylinders, graduated up to 15 c.c., ant1 furnished with taps near the bottom ; also a ferric solution, for pur- poses of compqrison, made by fusing 0.0358 grams of pure ferric. oxide with 50 grams of anhydrous potassium hydrogen sulpbate, dissolving the product in water and making up t o 500 C.C. 0.05 C.C. of blood is measured in a capillary pipette, rinsed out into a crucible, and evaporated t o dryness ; the residue is st’rongly ignited and fused with 0.1 gram of potassium hydrogen sulphate, and the cooled mass is rinsed with hot water into one of the cylinders and diluted to the 10 C.C. mark, whilst in the other cylinder 1 C.C. of the ferric solu- tion is placecl, and diluted to 10 C.C.To each cylinder is then added 1 C.C. of dilute hydrochloric acid (1 : 3), and 4 C.C. of ammonium thiocyanate solution (7.5 grams per litre), and the liquid is run out from the more deeply-coloured solution until the tint is seen to be the same on looking down through the t v o solutions. In this way, the amount of iron in the blood can be calculated, the specific gravity of the blood being also determined, if required, by Hammerschlag’s method (Zeii‘sclw. klin. Med., 20, 244)’ which requires only a single drop of blood. The percentage amount varied, in 10 adult men, between 0.526 and 0-720 ; in one anzmic inan, it was only 0.441, and in an anzmic woninn, 0.433. The results by this method agree well with those obtained by the other two methods, and 10-15 minutes suffice for making the experiment. Volumetric Estimation of Molybdenum and of Vanadium, 8 y CARL FRIEDHEIM (Bey., 1896, 29, 2981--2985).--Mainly a reply to Gooch and Fairbanks’s criticisms (this vol., ii, 76), on the method previously described by the author and Enler (Abstr., 1895, ii, 535).The author shows that as good results can be obtained by his simpler method (Toc. cit.) as by Gooch and Fairbanks’s more complex one, provided the mixtnre is not heated too rapidly, so that no hydrogen iodide may be evolved before the air in the flask has become replaced by iodine vapoar. The heating need only be continucd until the liquid becomes clear green ; further heating, RS recommended by Gooch and Fairbanks, is useless, Solubility of Bismuth Sulphide in Sodium Sulphide ; Estimation of Small Amounts of Bismuth in Anti-Friction Alloys.By THOMAS B. STILLMAN (J. A w e r . Clrem. Xoc., 1896, 18, 683--684).-The author has found that bismuth sulphide is sensibly soluble in solution of sodium sulphide (sp. gr. 1.06) a t the boiling temperature. If, when analysing an alloy coiitainiiig but a few per cent.. of bismuth, the neutralised solution is boiled as usual with C. F. B. J. J. S.128 ASSTKACTS OF CHEMICAL PAPERS. 75 C.C. of the sodium sulphide, the loss in bismuth will be very greatg whilst fractions of a per cent. may escape detection altogether. L. DE K. Estimation of Ethylene in the Presence of Benzene Vapour. By FRITZ HABER and H. OECHELH~USER (Beg.., 1896, 29, 2700-2705).-Ethylene is completely absorbed by bromine water, as Tread- well and Stokes have stated, although this is denied by Winkler. Benzene, too, is almost entirely removed by this treatment, but in a purely mechanical manner ; no chemical action takes place, for bromine vapour mixed with benzene vapour can be exposed to diffused light for 2 minutes without any loss of bromine occurring. It is thug possible t3 estimate the amount of ethylene by absorbing with a measured quantity of bromine water of known strength, and determining the residual bromine; this was done by treating the bromine water, while still in the burette, with potassium iodide, and subsequently titrating with thiosulphate. The bromine water was sucked into the (Bunte) burette through the lower tap, and its volume measured in the burette itself, the volume between the lowest graduation and the stop-cock having been previously determined. I n this way, the Cnrlsrulie coal- gas was found to contain 3.85 per cent. of ethylene ; the contraction, after treatment with bromine water and the addition of potassium iodide, was 4.4 per cent. ; the difference is, of course, benzene. C. F. B. Limiting the Explosive Proportions of Acetylene and Detecting and Measuring the Gas in the Air. By FRANK CLOWES (Chem. News, 1896, 74, 188).-The author’s determinations show that the limits of explosiveness of mixtures of acetylene and air are reached with 3 and 82 per cent. of the former gas; from 22 per cent. upwards, the burning is accompanied by t’he separation of carbon. The corresponding limits for hydrogen are 5 and 72, for methane, 5 and 13. Even in quantities far below the explosive limit, acetylene binges the author’s standard hydrogen flame a yellowish green, and gives a well-defined, pale bluish “cap,” which with a hydrogen flame 10 mm. high, attains a height of 17, 19, 28, and 48 mm. for 0.25, 0.5, 1, and 2 per cent. of acetylene respectively, whereas 2.5 and 2.75 per cent. of that gas give caps 56 and 79 mm., in height over a 5 mm. hydrogen flame. D. A. L.

ISSN:0368-1769    

DOI:10.1039/CA8977205121

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

General and Physical Chemistry. Stereo-chemical Spectrometric Researches, I. By JULIUS W. BRUHL (Zeit. physikal. C'hem., 1896, 21, 385-413; Bey., 1896, 29, 2902--2913).-The author has determined the molecular refraction and dispersion in the case of a number OF stereoisomeric compounds. I n the case of those compounds which could not be examined in the liquid state, solutions were prepared, and it was observed that, in order to obtain the best resnlts, the solvent should have a refraction and dispersion as nearly as possible equal to those of the compound itself." The compounds examined were : (I) monobromo-+-butyleiie, dimethyl- acetylene hydrobromide ; a-tolane dichloride, p-tolane dichloride ; syn- anisaldoxime, anti-anisaldoxime ; a-ben zilmonoxime, P-ben zilmonoxi me ; a-nitroformald ehyde-h ydrazone, /I-nitrof ormal d eh y de-h y drazone ; and (11) cinnamic acid, allocinnamic acid, cinnamylideneacetic acid, alloein- namylideneacetic acid ; methylic cinnamate, meth ylic allocinnamate, ethylic cinnamnte, ethylic allocinnamate ; anti- and syn-metadibromo- diazobenzene cyanide. The compounds may be divided into two classes, as indicated, in the first of which the refraction and dispersion are equal, or nearly so, the differences being ususlly within the experi- mental errors ; these compounds include baloids, oximes, and hydra- zones.I n the second class, which includes acids, ethereal salts, and diazo-compounds, the values of the spectro-constants do not agree, and in this heterospectric class, it is noteworthy that, in every case, the higher melting, less soluble compound has the greater refraction and dispersion. In all cases, the observed numbers are considerably higher than the values calculated from the chemical composition ; this is probably due to the elevating influence of the ethyleae-phenyl unions.Similar results had been obtained by Walden (Abstr., 1896, ii, 633) in the case of the fumarates and maleates, but the author considers that further research is necessary before deciding whether the differ- ences in the heterospectric compounds are due to a real difference of constitution. L. M. J. Changes of Rotation in the Passage from Acid to Lactone, By W. ALBERDA VAN EKENSTEIN, W. P. JORISSEN, and L. THEODORUS REICHER (Zeit physikal. Chem., 1896, 21, 383--384).-The rotations of a number of acids and of the corresponding lactoues mere determined, and the numbers obtained are given in the accompanying table, the values for the molecular rotation being divided by lo3.(Trans., 1896, 1056.) * This was observed by Perkin to obtain also in the case of the magnetic rotation. VOL. LXXII. 11. 10130 ABSTRACTS OF CREMICAL PAPERS. 1011. Lactone. I Mol. rotation of I DifY. Acid. Ribonic ............... Gluconic ( d ) ......... Mannonic ( d and I). .. Saccharinic ........... Isosaccharinic ...... Saccharic ............ Maiinosaccharic ..... a-Rhamnohexonic ... a-Glucoheptonic.. .... Gulonic (d and I) . . , + 0.2" +1-3" to +1%" + 2.0" - 1.1" - 1'1" + 2.6" + 0.2" 3-1'3" + 1.6" k 2 . 7 " ~ - 3 '0" + 11" to 12'1" -9.5" t o -9'8" +15 2" + 10'2" + 7 '3" t o 8.0" + 35.1"- 35.6" + 16.3" - 11.2" 79.9" I 3 '2" 10'8" to 9-2" 11 -7' 16.3" 11.3" 35.2" 15'0" 12.6" ' 9'9" to 10'6" I L.M. J. Spectrum of Chlorophyll. By ALEXANDRE L. ETARD (Con@. rend., 1896, 123, 824--828).-Knowledge of chlorophyll can only be extended by examination of large quantities of a chlorophyll of definite chemical composition. As a matter of fact, chlorophylls are compara- tively stable compounds, and can be treated with ordinary reagents for the purpose of elucidating their chemical structure. l n spectroscopic examinations, it is essential that the chlorophyll be a definite chemical species, dissolved in definite proportion in a given solvent, and examined in a layer of definite thickness. The author gives drawings of the spectra of a-medicagophyll, C28H45N04, dissolved in carbon bisulphide and in alcohol of 90°, and of a-borragophyll, C,,H,,NO,,, in the same solvents, the concentrations in each case being 1 : 400, 1 : 1000, 1 : 10000.Mere variations in the thickness or concentration of the solution examined are sufficient to cause one chlorophyll to be taken for another. I n solutions of 1 : 10000, only the principal orange band remains visible. I n carbon bisulphide, the bands are displaced towards the red as com- pared with the alcoholic solution, but they are particularly well-defined. The spectra of medicagophyll from lucerne and borragophyll from borage are distinctly different in the number and position of the bands ; the former shows three bands between the general absorption a t the red and violet ends, the latter five.C. H. B. Chemical Action of the Rontgen Rays. By ALEXANDER VON HEMPTINNE (Zeit. physikal. Chem., 1896, 21, 493--496).-The electric conductivities of a number of salt solutions were determined, and no alteration was found to occur when the solutions were placed in the path of the Rontgen rays. I n the case of solutions sensitive to light, such as silver nitrate in alcohol, and mercuric chloride with ammonium oxalate, the results obtained were doubtful, the effect, if any, of the rays baing extremely small. The radiation was also found to have no effect on the velocity of hydrolysis of ethylic acetate, from which the author concludes that the Rontgen rays do not influence ionisation. A mixture of hydrogen and chlorine was not affected, and negative results were like-GENERAL AND PHYSICAL CHEMISTEY.131 wise obtained with a mixture of chlorine and carbonic oxide, so that their chemical activity appears to be very slight. Action of Metals and their Salts on Rontgen Rays. By JOHN H. GLADSTONE and WALTER HIBBERT (Chem. News, 1896, 74, 235).- The authors find that all metals transmit the Rontgen rays more or less, lithium being almost absolutely transparent, gold practically opaque, and there is every gradation between these two extremes ; the order of absorption of the rays is that of the atomic weights, but the absorption increases more rapidly than the atomic weights. Metallic salts show absorption analogous to that of the metal ; in fact, the absorption of a dry salt is the sum of the absorptions of its constituents.In solutions, the absorption seems to be that of the salt itself plus that of the solvent. D. A. L. By A. E. TAYLOR (J. Pihysical Chem., 1896, 1, 1-20 and 81--90).-The author has continued the work of Bancroft (Abstr., 1894, ii, 4) on single-liquid polarisable cells, with especial reference to the effect of the negative ion on the potential difference between an electrode and the electrolyte in which i t is immersed. The results confirm Bancroft’s conclusion that, with mercury as’ one pole of the combination, the influence of the negative ion of the salt solution is appreciable, but concentration has no effect on the electromotive force of the cell. It has been shown by Gouy and others, on measuring single potential differences by means of the change of the surface tension of mercury, that an error might be introduced in some cases where there was the possibility of the formation of complex mercury salts.If dropping mercury electrodes do not always give correct results, the solution pressure of a metal is independent of the nature of the negative ion. In every case where the electromotive force of a cell appears to vary with the negative ion, the possibility of complex salts is present. The author concludes that the potential difference between a metal and an electrolyte is not a function of the negative ion of the salt solution, and that in certain cases dropping mercury electrodes do not give correct values for the single potential differences By MARCEL DELBPINE (Compt. Fend., 1896, 123, 888--89l).-The author has determined the heats of saturation of hexamethylenetetramine by hydrochloric, sulphuric, nitric, and acetic acids, and the heats of dissolution of the hydro- chloride, of the three sulphates, and of the two nitrates.For the heats of saturation (I mol. each of acid and base in 1 litre), the following numbers are given. L. M. J. Irreversible Cells. measured by that method. K. c. Hexamethylenetetramine Salts. CaZ. Cal. &HCl 1-13 +HNO, 1.15 HC1 -2.13 HNO, 2-1 9 3H2S04 2.11 4C2H402 0.53 +H2S04 3-51 C2H402 0.81 H2S04 4-10 2C,H402 1-06 The addition of the second half equivalent of acid, therefore, pro- The resultspoint to the slight dissocia- 2HC1 2.32 2HN0, 8.37 duces less heat than the first. 10-2132 ABSTRACTS OF CHEMICAL PAPERS.tion of the neutral salt in solution, of the base and its crystallised salts are given. The following heats of dissolution C,H,,N, cry st. + 4.80 Cal. C,H,,N,,HNO, - 5.5 Cal. C,H1,N4,HC1 - 3-94 ,, C6H,,N4,2HN0, - 14.26 ,, C,H,,N,,H,SO, - 1.60 ,, C6H,,N4,H2S0, + H2O - 4.71 9, from which the following heats of formation are calculated, solid + HNO, solid = CGH12N4,HN03 solid + 19.09 Gal. ,, +2HNO, ,, =C6H12N,,2HN0, ,> +34'63 ,, ,, +&H2S04 ?, =C,H12N4,&H2S04 + 16-09 97 = C6H1,N4,H2804 + 26.11 ,, C,H,,N,,H,SO, ,, + H,O llquld =C6H12N4,H2S04,H20 + 3.11 ,, 'GH12*4 ,, + HCl gas =C6H,,N4,HCl solid +28*17 ,, in solution, the acetate apparently being more dissociated. C6H12N4 U6H12N4 C6H12N4 C6H12N4 ?, + H,S04 7: The hydrochloride, nitrate, and sulphate are about equally stable A.C. C. Heat of Formation of Selenic Acid and Selenates. By RENB METZNER (Compt. vend., 1896, 123, 998--1000).-The heat of neutralisation of selenic acid by sodium hydroxide was found to be + 31.19 Cal., whilst the action of selenic acid on the normal selenate absorbs - 0.70 Ca.1. Thomsen found + 30.39 Cal. and -096 Cal. respectively, and the corresponding numbers obtained by the author with potassium hydroxide were + 31.31 Cal. and - 1.24 Cal. The heat of neutralisation of the acid by barium oxide is +36.92 Cal., by lead oxide, +19*81 Gal.; and by silver oxide, +18*35 Cal., these values being obtained by double decomposition. The hydrate, Se0,,2H20, was obtained by concentrating the acid under atmospheric pressure at a temperature below 210°, and puri- fying the first crystals by melting and recry stallisation ; the monhydrate, H,Se04, was prepared in a similar way, but the evaporation was in a vacuum.The calorimetric measurements gave the following results. H2Se04 H2Se0, liq. + Aq = SeO, ,, ,, + 16.80 ,, sol. + Aq = SeO, diss. develops + 13.35Cal. SeO,,ZH,O sol. + Aq = SeO, ,, 9 , + 7.45 9 , Se0,,2H20 liq. + Aq = SeO, ,, 9 ) + 12.02 ,, hence the heat of fusion of H,Se04 is - 3.45 Cal., and of Se0,,2H20, - 4.75 Gal. and H,SeO, sol. and H20 sol. = SeO3,2H2O sol, develops +4.55 Cal. Combining these results with Thornsen's determinations, it follows that SeO, sol. + 0 + H20 = H,Se04 diss. develops + 19-86 Cal. {sea, >, +O+H,O= H,SeO, liq. ,, + 3.06 ,, Se+O,+H,O =H2Se0, diss. ,, + 76-66 ,, =H2Se04 liy.,, + 59.86 ,, = H2Se04 diss. ,, + 145.66 ,, [Ez;;ip =H,Se04 liq. ,, + 128.86 ,, All the values, except those for hydration, are lower than the corresponding values for sulphuric acid. Cryoscopic Researches. By KARL AUWEBS and K. ORTON (Zeit. physikcd. Chem., 1896, 21, 337-377).--In order to further attest the C. H. B.GENERAL AND PHYSICAL CHEMISTRY. 133 validity of the rules deduced by Auwers (Abstr., 1896, ii, 293), the authors have determined the cryoscopic behaviour of a large number of substituted phenols and also of oxyazo-compounds. The first set of experiments was on the effect of ortho-substituents on various para- phenolic compounds. The aldehyde-group has the most powerful “ abnormalising” influence; the cyanogen and methylic carboxy-groups are nearly alike in their effects.Nitro-groups have the strongest “normalising” effect, whilst of the halogens, iodine has the most marked influence. The cryoscopic behaviour of the orthohydroxyazo- compounds leads the authors to the conclusion that these compounds are not phenols, but hydrazones of orthoquinone. The researches were then extended to the derivatives oE benzoic acid, but here the influence of the substituent is less marked, as almost all the compounds examined are abnormal, the variations from normal value increasing with the concentration. L. M. J. Abnormal Freezing Point Depressions. By GUIDO BODLANDER (Zed. physikal. Chrn., 1896,21, 378-382).-1n the experiments made by Cliamician and Garelli on the formation of solid solutions in the case of anthracene and salicylic acid in benzoic acid, the concentration of the salicylic acid in the solid solution was compared with that in the m*igimZ solution, whereas the author points out that comparison should have been made with the solution with which the crystals were in equilibrium; on making this correction, he finds that the ratio is not constant, but varies from 0.68 to 1-0s.Similarly, in the experi- ments with benzene, phenol, and benzil, the ratio of the concentration of the phenol in the solid and liquid solutions varies from 0.309 to 0.198, increasing with dilution. If the molecular weight in the solid phase is calculated from thesenumbers, it is found to be smaller than that in the liquid, and on the assumption that the solid contains simple molecules, and the liquid simple and double molecules, the author cal- culates the dissociation of the €atter; the results appear to be in accordance with the laws of mass action, but the author does not con- sider that this must necessarily be the true explanation of them. L.31. J. Compressibility of certain Gases at 0” and under nearly Atmospheric Pressure. By ANATOLE LEDUC (Compt. Tend., 1896, 123, 743--745).-The author has determined the compressibility of five gases at pressures ranging from 35 cm. to 113 cm. of mercury, adopting Mariotte’s method. The apparatus consisted of a manometer similar to that used by Regnault in the determination of the expan- sion of gases at constant pressure, with the addition, however, of a third tube, by means of which mercury could be admitted at will with- out introducing air bubbles.The gas was cooled by immersing the apparatus in a bath of ice-cold water, the temperature of which was accurately observed. Owing to the dight variations of pressure, the author substitutes A(P - Po) for E in Regnault’s expression, n ZT representing the departure of a gas from Mariotte’s law. Expressing134 ABSTRACTS OF CHEMICAL PAPERS. the pressure in centimetres, and taking Po= 76, the following values of the coefficient A are given. A = lOZ*lO--G, a number which is higher than that obtained by Regnault. Carbonic anhydride. Nitrous oxide. Rydrogen chloride. At 0", A=120*10-6 (between 76 cm. and A = 11*10-5 (approx.). 120 cm.). At 15", A = 107.10-6 (between 76 cm. and 120 cm.). Ammonia. Sdphurous anhydride.A = 323~10-~. The following coefficients of expansion of gaseous ammonia between At Oo, A=243-10-6 (between 76 cm. and 130 cm.). A t 14O, A = 190.10-6. 0' and 14" are given. Const. press. of 115 cm. ........................ 0.00404 Const. press. of 76 cm. ........................ 0.00389 A. C. C. Potential Energy and Virial of Molecular Forces. By G. BAK~ER (Zeit. physikal. Chem., 1896, 21, 497--506).-By considera- tion of the potential energy in a liquid, the author deduces that the ratio between the heat of vaporisation and the difference between the liquid and gaseous densities is proportional to the square of the diameter of the molecules, and hence, under certain conditions, the latter may be compared. New Method of Determining the Specific Gravity of Liquids.By RONAN ZALOZIECKI (Zeit. angw. Chern., 1896, 552-556). -The principle of the method has already been taken advantage of by Boyle and by Babinet to compare the specific gravities of two different liquids. The author's apparatus consists essentially of a long U-tube, one of the arms of which is calibrated, whilst a stop-cock, a little above the bend, separates it from the bend and the other arm. If the sp. gr. of an aqueous solution is required, the uncalibrated limb is filled with a liquid of low sp. gr., and immiscible with water, such as light petroleum, which answers very well. The aqueous liquid is run into the calibrated tube to a fixed height,, and, by opening the tap, the two liquids are brought into contact. The apparatus is plunged for some time in water at 15", and the difference in the height of the two columns is then recorded in mm.For instance, if the column of aqueous liquid measures 602 mm. (= 500 mm. + 2 mm. allowance for effect of capillarity in a tube 5 mm. broad), its sp. gr. is found by multiplying the difference by 2, adding 1000, and multiplying this by the sp, gr. of the light petroleum. The apparatus may, of course, be used for petroleum, oils, &c. ; in this case, water is used in the uncali- Solution and Fusion. By WILDER D. EANCROFT (J. Physical Chem., 1896, 1, 137--148).-The author discusses the question whether solubility and fusion curves are always identical, or ever so. It is evident that solubility curves cannot in all cases be fusion curves, as the temperature of the experiment is above the fusion temperature of either of the components in many cases.Even where this is not the case, the L. M. J. brated limb instead of light petroleum. L. DE K.GENERAL AND PHYSICAI, CHEMISTRY. 135 author holds that there is a distinction between a fusion curve and a solubility curve, The approximation formula? for the change of concen- tration with the temperahre have the same form for both curves ex- cept that the heat of fusion enters into one, and the heat of dissolution into the other. Since these two quantities are not identical, it follows that there is a radical distinction between the two curves. The partial pressure of the solvent is always less than its vapour pressure as a pure liquid at the same temperature ; it is therefore possible for the vapour pressure of the dissolved substance (solute) to be greater or less than its vapour pressure in the pure state, depending on conditions with which we are not yet familiar.Even when two liquids are miscible in all proportions (consolute), it appears that each may still have a definite solubility one in the other. Some Abnormal Cases of Solubility, By HENRI L. LE CHATELIER (Compt. rend., 1896,123, 746-749).-When certain metallic sulphates are added in increasing quantities to sodium sulphate, the curve representing the melting points of the various mixtures is differ- ent in character from those plotted by the author for the mixtures of salts previously examined (comp. Abstr., 1894, ii, 272, 307). In the case of the sulphates of calcium and magnesium, the following numeri- cal results are given, 875" being the melting point of sodium sulphate.Concentration ... 0 1 3 5 7.5 10 20 30 40 Temperature ..... 875" 884" 900" 912" 923" 930" 941" 938" 923' H. C. Na,SO, + CaS04- 46 51 54 57 67 75 100 912" 905" 925" 950" 1040" 1130" (1350"). Na2S0, + MgS04- Concentration ... 0 5 15 30 35 42 48 50 55 Temperature ..... 875" 870" 830" 740" 690" 655" 675" 700" 730" 67 70 75 80 100. 800" 795" 870" 925" 1170". The effect of the addition, therefore, of the first small proportion of these two sulphates is either to raise the melting point of the mixture, or at least to produce no appreciable lowering. It is probable that this abnormal behaviour is due t o the isomorphism of sodium sulphate with the double sulphates formed. When certain fused mixtures of the above sulphates are allowed t o solidify, the mass remains transparent even to the point of complete solidification, owing to the formation of crystals which are all of the same nature.The curves representing the melting points of mixtures of sodium sulphate with increasing propor- tions of the sulphates of calcium, barium, lead, magnesium, and cadmium consist of three parts, the first corresponding with the formation of isomorphous crystals containing the two constituents in varying propor- tions, the second t o the formation of definite double sulphates, and the third to the crystallisation of the added sulphate itself. A. C. C. Precipitation of Salts. By H. A. BATHRICK (J. Physical Chem., 1896, 1, 157--169).-Bancroft has shown that the solubility of salts in alcohol can be represented by an equation of the form (x + A ) y'& = C', where x and y denote respectively the quantities of alcohol and of salt136 ABSTRACTS OF CHEMICAL PAPERS.in a constant quantity of water. The author finds by direct experiment that this equation holds for the solubilities of salts in aqueous alcohol and in acetone. The factor rz is apparently independent of the tempera- ture. The term A is a function of the salt, the solvent, and the tem- perature. If x is expressed in reacting weights, the product of A into the reacting weight is independent of the nature of the substance de- noted by x. H. C. By HENRI LESCCEUR (Compt. rend., 1896, 123, 81 1--813).-The author discusses the precise significance of the colour changes of certain indicators.He points out that the formation of a blue colour with litmus indicates the presencenf excess of alkali, and not neutrality. When an alkali is added t o a solution of n salt of an insoluble oxide in presence of litmus, the change to blue takes place, not when all the free acid has been neutralised, but after all the oxide has been precipitated and the alkali is in excess. I n many cases, the colour of the litmus changes continu- ously from red to blue. The behaviour of litmus with alum and other salts clearly shows that the red colour indicates neutrality as well as acidity. I n the case of phenolphthalein, the production of the red colour indi- cates, not the passage from acidity to alkalinity, but from neutrality to alkalinity.Helianthin (Poirrier's orange No. 3) is colourless in neutral or alka- line solutions, and red in presence of acids, This indicator, therefore, shows the passage from neutrality to acidity. The author considers that a really neutral substance is one with which phenolphthalein and helianthin both remain colourless, whilst litmus remains red. The Neutrality of Salts and Coloured Indicators. C. H. B. Speed of Etherification, as compared with Theory. By ROBERT B. WARDER (J. Physicul Chem., l896,1,149---156).--The theory of mass action is applied to Lichty's experiments (Abstr., 1896, ii, 557) on the speed of etherification, in which equivalent weights of ethylic alcohol and the several chloracetic acids were made to react for definite intervals at 80". Numbers are given proportional to the co- efficient of speed, as obtained by integration between the limits of suc- cessive determinations.They show the same general features for each acid; a steady decrease in the early stages is followed by a moderate increase, then by a rapid fall. Further experiments are needed to determine the cause of the secondary influences indicated before the actual constants can be determined and in order to trace the effect of successive atoms of chlorine in acetic acid. Catalytic Hydrolysis by Metals. By BOIIUSLAV RAYMAN and OTTOKAR &ULC (Zed. phgsikal. Clbenz., 1896, 21, 481-492).-The effect of temperature on the inversion of sugar by pure water was first studied, a platinum flask provided with a reflux platinum condenser being employed.At GO", no change occurred in 50 hours ; at SOo, the rotation fell from + 11-56' to + 0.31" in 58 hours, and at 100" reached - 3.42" in 25 hours, Rotation/time curves are constructed in each case, from which it is seen that the velocity of inversion is at first H. C.GENERAL AND PHYSICAL CHEMISTRY. 137 small, then increases, and again diminishes towards the close of the reaction. I n glass vessels, the velocity is considerably less, and the effect of metals other than platinum was, therefore, investigated by the use of similar copper and silver flasks, when the rate of inversion was found to be slightly less than in the platinum vessel and less in the copper than in the silver flask, The solution in the copper flask became slightly acid and turbid owing to traces of finely-divided copper.The effect of finely-divided metals of the platinum group mas investi- gated, hard glass flasks being used, and curves are given as before. An increase of velocity was obtained in each case, except that of iridium, the accelerative effect of palladium being extraordinarily great. The effect is probably due partly to a specific action of the metal and partly to acids formed by oxidation. The decomposition of glucose and fructose by water was therefore investigated, but found to be of a very complicated nature. Absorption, Water in Colloids, especially in the Hydro- gel of Silicic Acid. By JACOBUS M. VAN BEMMELEN (Zeit. ccnorg. Chem., 1896, 13, 233-356).--In continuation of his researches on the composition and properties of inorganic oxides in the colloidal state (Abstr., 1894, ii, 191), the author has examined the conditions under which the absorption and elimination of water by the hydrogel of silicic acid take place at constant temperature. The process is a gradual and a continuous one, the elimination of water taking place, however, with greater digculty the more nearly the substance ap- proaches the anhydrous condition.The hydrogel appears to form an intermediate stage in the passage from the liquid to the solid condition during the separation of a dissolved colloidal substance from a solvent. This separation commences with the formation OF the hydrosol, the solution usually remaining clear, but the dissolved substance exer- cising little or no influence on the osmotic pressure, boiling point, freezing point, or electrical conductivity.Solutions of colloids in this condition contain molecular groups which do not follow the laws which hold for crystalloids in solution, and determinations of the molecular weights of colloids in solution by the customary methods are therefore valueless. The formation of the hydrogel is indicated by the coagulation that occurs. It may be assumed that the semi- liquid particles of the colloid arrange themselves with the water molecules to form a cell-like structure of definite form, and that these cells hang together at certain points, so forming a network. The water is then retained, partly by the cells themselves, and partly in the interstices between the cells. The author shows that the general behaviour of the hydrogel of silicic acid is in keeping with these views. H. C. By G. BAKKER (Zeit. physikccl. Chenz., 1896’21, 507--508).-The paper contains a more rigid proof of the conclusions obtained in the author’s previous paper (this vol., ii, 17) which involved certain tacit assumptions. By KARL SEUBERT (Zeit. ccnoyg. Chem., 1896, 13, 229-232).-The author regards tho result of Morley’s L. M. J. Theory of Corresponding States. L. M. J. Unit of Atomic Weights.138 ABSTRACTS OF CHEMICAL PAPERS. determination of the ratio 0 : H = 15,879 : 1 as probably correct to within 0.06 per cent. It may, therefore, now be regarded as proven that the atomic weight of oxygen (H= 1) is, for practical purposes, about 15.88. The use of this number, and the retention of the atomic weight of hydrogen as the unit, is advocated in place of the practice of fixing the atomic weight of oxygen as 16. The Discovery of New Elements during the last Quarter of a Century, and Questions relating thereto. By CLEMENS WINKLER (Ber., 1897, 30, 6-21).-This paper is the report of a lec- ture delivered before the German Chemical Society, and traces the history of those elements which have been discovered during the last quarter of a century, A New Stirrer. By HERMANN SCHULTZE (Bev., 1896,29, 2883).-- This consists of a glass rod, to one end of which two glass balls are hung by pieces of platinum-iridium wire. When the rod is rotated by a turbine, the balls fly asunder, stirring the liquid in which they are immersed. C. F. B. H. C. M. 0. F.

ISSN:0368-1769    

DOI:10.1039/CA8977205129

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

133 0 r g ani c Chemistry. Theory of the Pyrogenic Reactions of Aliphatic Hydro- carbons. By FRITZ HABER (Be?.., 1896, 29, 2691-2700).- Berthelot's theory, with its assumption of a limiting equilibrium, and Lewes' theory of the luminosity of flame, are criticised, and, in part, rejected. These investigators obtained abnormal results because they experimented with paraffins containing only one or two atoms of carbon in the molecnle. The author has experimented with hexane, and also with trimethylethylene, acetylene, and benzene. To avoid secondary reactions, the gas was exposed for a few seconds only t o the high temperature ; this mas attained by passing it in a current through a heated tube. At a temperature of 600-SOO', neither carbon nor an appreciable quantity of hydrogen was liberated; what happens is a shifting of a hydrogen atom, with formation of an olefine and either methane or ethane, the latter, if formed a t all, being always formed in smaller amount.Thus hexane yields amylene and methane. Trimethylethylene also yields methane, but it yields ethylene in addi- tion, although this requires a complete change in the arrangement of the atoms of carbon. Long ago, too, Thorpe and Young (A?zncderz, 1873, 165, 1) noticed that the distillation of paraffin yields no hydrogen, but lower hydrocarbons ; in this case, however, of approximately equal molecular weight. I n the case of the paraffins, then, the union between carbon and carbon is more easily dissolved than that between carbon and hydrogen. The opposite is the case with aromatic hydro- carbons ; benzene, for instance, yields diphenyl and hydrogen.It decomposes, however, much less easily than hexane. I n addition to the products mentioned above, hexane yields a littIe benzene; this, however, is obtained equally from trimethylethylene, and is doubtless formed by a secondary reaction from the acetylene first produced. At 900-1000", the reaction is quite different; coke, tar, and hydrogen are formed, and methane is the only paraffin to be found, ethylene the only olefine ; ethylene and hydrogen therefore do not unite to form ethane a t this temperature. Acetylene (at 800') yields but a little ethylene with much hydrogen; a great part of the gas is unchanged. Incidentally, it is shown how the results of a gas analysis, including an explosion of the residual gas after absorption, may be utilised to infer the presence or absence in the gas of ring compounds with the composition C,L H,,,, such as trimethylene. The results of such analyses lead one to assume the presence of such hydrocarbons in coal-gas.Methane alone is entirely stable. C. F. B. Limiting the Explosive Proportions of Acetylene, and Detecting and Measuring the Gas in Air. By FRANK CLOWES. (Cliem. News, 1896, '74, 188. By ~S~ARCELLIN BERTIIELOT and GUSTAVE ANDRE (Conzpt. rend., 1896, 123, See this vol. ii, 128.) Decomposition of Sugars under the Influence of Acids. VOL. LSSII. i 1134 ABSTRACTS OF CREMICAL PAPERS. 567--580).-The authors have investigated more especially the forma- tion of carbonic anhydride, humic, levulinic, and formic acids by the action of dilute mineral acids on various sugars.Phosphoric acid was preferred to hydrochloric or sulphuric acid, because it does not volatilise with steam and exerts no oxidising action on the sugars. Some of the experiments were made a t looo, in sealed tubes from which the air had been removed; others in flasks a t the ordinary pressure, sometimes with a reflux condenser, sometimes with an ordi- nary condenser so that the volatile products were removed as fast as they were formed. The substances estimated, as a rule, were glucose, carbonic anhydride, carbonic oxide, formic acid, humic acid, which was dried and weighed a t loo", levulinic acid, which was estimated by the method of coefficients of distribution between water and ether (Ann.Chirn. Phys., 18'72, [4], 26, 396 and 433), furfuraldehyde, and water. Glucose, when heated in sealed tubes a t 100" with about five times its weight of phosphoric acid and six times its weight of water, yields carbonic anhydride and carbonic oxide in small quantity, and formic, levulinic, and humic acids. Even after 115 hours, 12 per cent. of the glucose remains unchanged, and the phenomena indicate that a large part, at least, of the glucose is first changed into glucosan, which then undergoes decomposition. The quantity of formic acid is higher than corresponds with the quantity of leviilinic acid, but part of it is formed at the same time as the humic acid. Direct experiments show that there is a considerable and variable difference between the rittes of formation of the levulinic and humic acids.The carbonic oxide results mainly from secondary decomposition of the formic acid, but part of it is formed by the action of the acid on the glucose. Direct experiments show that the levulinic acid yields neither carbonic oxide nor humic acid. The greater part of the carbonic anhydride is pro- duced in the earlier stages of the decomposition, and results chiefly from the direct action of the acid on the glucose, although a small quantity is formed by the prolonged action of acids on levulinic acid. I n flasks a t the ordinary pressure, there is an increase in the propor- tion of carbonic anhydride, and this is not due to oxidation, since the same result is obtained in an atmosphere of hydrogen; furfuralde- hyde is also formed.As in the experiments with tubes, there is no fixed relation between the formic acid and humic acid; there also seems to be evidence of the formation of a small quantity of acetic acid. The proportion of volatile acids formed seems to be greatest when sulphuric acid is used, but the proportion of humic acid shows no similar variation. The higher proportion of carbonic anhydride formed during distillation cannot be attributed t o decomposition of levulinic acid. The isomerides of glucose, galactose, levulose, and maltose behave in a similar way, and when distilled with acids yield a notable pro- portion of carbonic anhydride, and also a small quantity of furfur- aldehyde. As Tollens and Grote have observed, the production of humic acid from leviilose is more rapid than in the case of the other sugars, but all the other changes are also more rapid with levuloso than with the others. The moI'0 concentrated the acids, the greater is the proportion ofORGANIC CHEMISTRY.135 humic acid formed. The complicated nature of the reaction is LL natural result of the complicated constitution of the glucoses; the production of formic acid, for example, may be attributed t o the splitting off of the last aldehydic molecule of the generatrix of the glucose. C. H. B. Arabinose. By MARCELLIN BERTHELOT and GUSTAVE ANDR~ (Compt. 9*encZ., 1896, 123, 625-631).--The authors have studied the action of water and acids on arabinose and on furfuraldehyde under various experimental conditions. No furf uraldehyde was formed when dilute aqueous solution of arabinose was distilled a t loo", but when heated with water for 5 hours a t 200°, almost one-half of the theoretical yield of f urfuraldehyde was obtained.Three experiments are described in which arabinose was heated in sealed tubes with (1) saturated aqueous hydrochloric acid, (2) 25 times its weight of 12.3 per cent. hydrochloric acid, and (3) dilute aqueous phosphoric acid. Of the products formed, namely, carbonic anhydride, carbonic oxide, formic acid, furfuraldehyde, organic acids, and huinic matters, about 92 per cent. of the carbon of t'he arabinose taken appeared as humic matter, and in no case was more than a trace of furfuraldehyde obtained, the latter being decomposed and polymerised under the conditions of experiment. Gum arabic, when heated in a sealed tube at 100" with concentrated aqueous hydrochloric acid, gave similar results, but with more dilute hydrochloric acid a larger propor- tion of carbonic anhydride was formed.When arabinose (5 grams) was slomiy distilled with dilute aqueous phosphoric acid, for 590 hours, the evaporated water being replaced from time to time, i t yielded 0,2999 gram of carbonic anhydride, and 1,9632 gram of furfuraldehyde. It is remarked in conclusion that when arabinose is submitted to the action of dilute acids, three classes of reactions occur simultaneously. (1) The formation of furfuraldehyde, which marks a distinction between the pentoses and hexoses. (2) The formation of humic acid, more especially in sealed tubes. (3) The formation of carbonic anhydride, more marked under conditions of slow distillation, a decomposition common to the pentoses and the hexoses.By SIEGMUND GABRIEL and CARL VON HIRSCH (Bw., 1896, 29, 2747--2751).-The autliors have succeeded in preparing this base, which had previously only been ob- tained in aqueous solution, by distilling P-propylamine hydrobromide with 33 per cent. aqueous potash, and fractionating the distillate. Lo- ally lamine, CHMe:CH*NH, is R colourless, mobile liquid, which fumes i n the air, has the characteristic odour of the anlines, is very hygro- scopic, and is miscible with water; it boils a t 66-67" (751 mm.pressure), has a sp. gr. 0,812 at 16", and burns with a luminous flame. The base readily undergoes change when its solution in water is heated. I n addition to the salt with bismuth iodide, which has been previously described, it was only possible to obtain the pkctizeocldo~~ide, which is an orange red, crystalline powder.I t acts as a poison, and exerts n reniark- able specific action on the so-called papillary part of the kidneys, in this respect resembling vinylamine. It reacts in the normal manner with -,hloroform and potash, and with nitrous acid, but does not undergo the A. C. U. Isoallylamine (1-Aminopropylene). 4 2136 ABSTRACTS OF CHEMICAL PAPERS. thiocarbimide reaction. With carbon bisulphide, it forms Pp-methpl- p-mercaptothiazoline (Hirsch, Abstr., 1890, 859) ; this substance melts a t 95-97', and not a t 82' as stated by Hirsch. The base readily unites with the halogen acids, forming the corresponding substituted propylamine.P-CT~loi.o~i.o~~Zcl?r7inepici*ate melts a t 158". /3-.Ioclo~n*opy lamine hyclriodicle is a crystalline powder. The picwde melts a t 150". Sulphurous acid converts the base into p methyltaurine, C,H9NO:,S. The base is accompanied by a poZymer*ide, (C,H,N),, which boils a t 143-145", and has the normal vapour density corresponding with the above formula. A. H. Action of Sodium on Acetaldehyde. By PAUL C. FREER (Anna- Zen, 1896, 293, 326-338. Compare Abstr., 1894, i, 65).-The produc- tion of sodium acetone, CH,:CMe.ONa, by the action of metallic sodium on a dilute xylene solution of acetone (Zoc. cit.), suggested the possibility of obtaining the sodium derivative of vinylic alcohol, CH,:CH* ONa, by treating acetaldehyde with the metal.Acetaldehyde is vigorously attacked by sodium, hydrogen being liberated and a crystalline sub- stance formed, but, owing to the unstable character of this product, it is necessary to study the action in presence of benzoic chloride, which gives rise to a solid benzoyl derivative of an aldehydo-aldol. Aldelydo ccltlol henxoate, OBz*CHMe*UH,* CH<$>CHMe, is pre- pared by heating ether, acetaldehyde, and benzoic chloride with metallic sodium in a reflux apparatus, from which air is excluded by means of a current of hydrogen ; after 24 hours, the ethereal liquid is treated successively with water and dilute potash, being finally dried with calcium chloride, and allowed to evaporate. The substance crystal- lises from petroleum in colourless, transparent prisms, and melts a t 86-87"; when heated with water in sealed tubes at looo, benzoic acid, aldol, and acetaldehyde are produced, whilst distillation gives rise to benzoic acid, crotonaldehyde, and acetaldehyde.Although insoluble in cold, dilute caustic potash, it dissolves on heating the liquid, which then becomes yellow owing to the production of alde- hyde-resin ; the substance is indifferent towards bromine, phenylhy- drazine, and cold, aqueous potassium permnnganate. The production of a benzoate by the action of sodium on acetaldehyde in presence of benzoic chloride may be explained in two msys-either aldehyde, under the influence of sodium, is condensed to aldol, the sodium derivative of which is then produced, and combines with benzoic chloride, or the sodium derivative of acetaldehyde is first produced, undergoing condensation with more aldehyde to form the sodium derivative of aldehydo-aldol, which yields the benzoate in presence of benzoic chloride.The latter explanation is the more probable, owing to the fact that the action of sodium on aldol gives rise to a derivative which is not identical with the initial product of the action of the metal on acetaldehyde. As the syrup from which aldehydo-aldol benzoate separates in the first instance undergoes decomposition when kept, depositing ben- zoic acid, it must be examined without delay. A solution of bromide in chloroform acts on it immediately, without liberatingORGANIC CHENISTRY. 137 hydrogen bromide, and benzoic acid is formed, along with an oily substance containing lminine ; phenylhydrazine gives rise to benzo- phenylhydrazicle, and a resinous phenylhydrszone ; the readiness with which hydrolysis takes place suggesting the presence of an oxygen ether (compare Nef, Abstr., 1893, i, 629), which is probably aldol benzoate. This view is confirmed by the fact that the original syimp, when distilled, yields benzoic and crotonic acids, acetaldehyde, croton- aldehyde, and a small quantity of isocrotoiialdehyde ; moreover, when sodium acts on aldol in presence of benzoic chloride, hydrogen is liberated, and the oily product is identical with the syrup which remains after separating aldehydo-aldol benzoate.Action of Aqueous Potassium Hydroxide and Carbonate on Isobutaldehyde. By MAXIMILIAN BRAUCHBAR (Monatsh., 1896, 17, 637-647.Compare Fossek, Abstr., 1882, 1279, and especially Fmnke, Abstr., 1896, i, 404.)-When isobutaldehyde is allowed to remain for 2 weeks in a closed vessel at the ordinary temperature, in contact with an equal volume of aqueous potassium hydroxide (containing 92 grams KOH per litre), it is largely converted into di-isobutalde- hyde, some isobutyric acid being also formed. If the mixture is allowed to remain for 5 weeks, the main product is Fossek's "di- isopropylglycol, " melting a t 52", but some di-isobutaldehyde is still obtained; the glycol is formed from the di-ieobutaldehyde, a part of which is reduced to the glycol at the expense of another part, which becomes oxidised t o isobutyric acid. Di-isobutddehy de may be ob- tained unmixed with other substances, and in much better yield, by using potassium carbonate instead of the hydroxide ; isobutaldehydc is allowed to remain for six weeks in contact with an equal volume of a saturated solution of the carbonate. Di-isobutaldehyde is obtained as a liquid, but it crystallises when kept, and then melts a t 90-92".At 218", its vapour is completely dissociated into that of isobutaldehyde ; as a consequence of this easy dissociation, i t is largely decomposed when distilled, even under diminished pressure ; it boils between 90" and 120' under a pressure of about 16 mm. It yields a monncetyl dei*ivcctive as a pale yellowish oil boiling at 136-139" under 18 mm. pressure; also a monoxime as a colourless, viscid oil boiling at 140° under 16 mm. pressure. It is reduced by sodium amalgam and dilute sulphuric acid to di-isopropyl glycol CHMe,.CH(0H) CMe; CH,* OH, and oxidation with per- manganate converts i t into Fossek's acid, C,H,,O,[=CHMe,*CH(OH)*CMe,*COOH], melting a t 92", together with some di-isopropyl ketone. These re- actions of di-isobutaldehyde lead to the adoption of the formula CHMe,*CH(OH)*CMe,*CHO for it ; i t is formed from isobutaldehyde by an aldol condensation. M. 0. F. C. F. B. Action of Alcoholic Soda on Isobutaldehyde. By ADOLF FRANKE (NomtsA., 1896, 17, 672-676).-Contrary to Urbain's state- ment (Abstr , 1896, i, 590), isobutaldehyde, when heated with 5 per cent, alcoholic soda without cooling, yields a glycol, CIHMe,*,~H(OH)*CMe,*CH,*OH,138 ABSTRACTS O F CHEMICAL PAPERS. biit not one of the three products he enumerates.At - 20°, the pro- duct is di-isobutaldehyde (compzre Brauchbar, preceding abstract) J the oxime of this snbstsnce, when heated with acetic anhydride for 9 hours a t 120°, yields the ucetyl derivative oE R n i t d e , CHMe,.O€T(OAc).C~e~*CN, as an oil which boils a t 112' under 16 nim. pressure, and vields the acid, CHMe,. CH(OH)* Cllle,. C'OOH, when hyd/olysed with ataeous potash: c. F. B. Hydrazidoacetic Acid, By WILHELM TRAUBE and E. HOFFA (Be?.., 1896, 29, 2729-2730) -1sonitraminacetic acid, on reduction with sodium amalgam a t 0' in slightly acid solution, yields hydrazidoacetic acid; this cannot be separated in the ordinary way by extraction with benzaldehydc, bnt on employing salicylaldehyde in its place. the condensation product readily separates as a white, crystalline pre- cipitate.This orthohydroxybenzylidenehydrszido-acetic acid is, when pure, a colourless compound, becoming, however, brown when exposed t o the air; it is readily soluble in alcohol and ether. It exists in two stereoisomeric forms, melting a t 78' and 105' respectively. On removal of salicylaldehyde, free hyld~ccxidocccetic ncicl is produced, forming colourless crystals, melting a t 145'. It is very soluble in water, scarcely soluble in alcohol and ether. The hgdroioclicle, NH,*NH* CH,* COOH,HT, melts a t 156". Electrolysis of Potassium Xanthate in Aqueous Solution. By J. F. CARL SCHALL (Chenz. Celztr., 1596, i, 588 ; from Zeits. Elektyo- techn. u. Elektrochenzie, 2, 475-476.) -By the electrolysis of potassium xnnthate in concentrated aqueous solution, e t l q l i c 6is-dithiocccybontcte, S,(CS*OEt),, is formed by the union of the anions EtO*GSS.It separates at first as a yellow oil, which subsequently solidifies t o a crystalline mass. The process is analogous to the formation of acetyl and benzoyl bisulphides by the electrolysis of the potassium salts of thioacetic and thiobenzoic acids respectively, as observed by Bunge Methylenecarbamide. By BERNHARD TOLLENS (Bey., 1896, 29, 2751-2752).-Goldschmidt, in 8 recent paper on the action of for- maldehyde on carbamide (this vol., i9 22) has omitted to refer to the papers of Holzor (Bey., 17, 659 ; 18, 3302), and Liidy (Abstr., 1889, 1059), on the same subject. J. F. T. (Bey., 1870, 3, 297). E. w. w. A. H. Asymmetric Nitrogen, V. Imides of Tartaric Acid and of Benzoyltartaric Acid.By ALBERT LADENBURG (Bey., 1896, 29, 2710--2719).-Further facts are brought forward in support of the theory of the asymmetric nitrogen atom. The t,wo benzylmalimides of Giustiniani can either be structural- or stereo-isomerides. The former supposition seems improbable, from the fact that such isomerism has never as yet been observed in the case of inactive. acids. Preparations of the imides of dibasic acids, such as succinic acid, inactive malic acid, meso-tartxric acid, and racemic acid showed that they existed in one form only, The occurrence of two isomeric benzylmalimides is, then, a further instance in support of the theory of the asymmetric nitrogen atom,ORGANIC CHEMISTRY. 139 and can be explained in the same way as in the case of isoconiine* Other substituted malimides are in the course of investigation.Substituted imides of tartaric acid are best prepared by heating the bitartrate of a primary amine above its melting point. Tartcci.naetJ~?llimide, I >NMe, from the bitartrate of methylamine (m.p. 1 70°), crystallises from alcohol in colourlegs, rhombic needles, melts at 1'78", and has a rotation [a]= = 193.69O. A second sub- stance of the same composition is obtained on evaporating the mother liquor; this melts a t 152"-153", but was subsequently found t o he a mixture of the methylimides of cl- and 1.-tartaric acid, and not a n homogeneous substance. OH* CH* CO OH. CH. CO - OH* CH* CO OH* CH* (20 (I'wttcre t hjglimide, 1 >N.Et, prepared in the same way as the methylimide, melts at 171-174", and has a rotation of [.ID = The corresponding derivatives of benzoyltartaric acid are prepared by the action of benzoic chloride on the tartarirnide.By the action of benzoic chloride on tartarmethylimide, only a very small quantity of the mono-benzoyl compound is produced, the chief product being diben- xo~lltccrtccr~aetl~~linlzide, which crystalllies from alcohol in colourless prisms containing alcohol of crystallisation, and having the formula 4C,9H,,N0,,3C,HG0 ; it melts at 68'. On heating, the alcohol is rapidly given off, and two isomeric compounds are formed, the proportions of which depend on the temperature of decomposition. On heating at 100' for 1-2 hours, a-di6enxoylta~tccr~azeth~Zin~ide is produced, melting at 56", and this, at the ordinary temperature, passes slowly into the P-compound.P-DibenxoyZtccrtal.naetJ~~Z~r~a~~e is best formed by heating the com- pound containing alcohol of crystallisation a t 60" for 6-10 hours ; it melts a t 106°-1070, and at that temperature passes into the a-com- pound. The optical rotation for the a-component is 183.9, and for the p- 1SS*S, the difference being only very slight. It is, therefore, highly probable that these compounds are stereo-isomerides, and their occur- rence can only be explained by the assumption of an asymmetric nitrogen atom. The author concludes with a brief summary of his ideas as to the nature and function of the asymmetric nitrogen atom. H e no longer supposes that it is possible t o obtain optically active nitrogen com- pounds containing no asymmetric carbon atom, but understands by an asymmetric nitrogen atom, an atom serving to modify the activity produced by the asymmetric carbon atom, as is seen in the cases of isoconiine, the benzylmalimides and the dibenzoyltartarmethylimides. H e further defines an asymmetric nitrogen atom as such that two of its valencies must form a ring compound, whilst the third is otherwise combined. Such a ring must, however, possess neither symmetry nor pseudo-symmetry, and must, theref ore, be optically active, The capability of the third nitrogen bond to take up two, and perhaps in many rings four positions of equilibrium, causes s tereoisomerism.165-166'. J. F. T,140 ABSTRACTS OF CHEMICAL PAPERS. Imides of Racemic Acid. By HERMANN WENDE (Be?.., 1896, 29, 2719--2721).-The imides of racemic acid are prepared by heating the biracemate of the corresponding alkylamine above its melting point.The methylimide from methylamins birncenzrbte (m. p. 180') melts a t 157--158O,and crystallises from alcohol in lustrous needles. Ethylamine biracenzccte melts at 142-143', and, on heating, passes into the ethyl- ccmide, melting at 179'. The popylamine salt melts at 147', and the popglimide crystal Iises in glistening needles. Aniline bimcemate separates when molecular quantities of racemic acid and aniline are mixed ; the crystals containJl mol. H,O and melt and decompose at 173' ; thephnylimide melts a t 235-236'. Benzylamine biracemate melts a t 178'. The benzylimide formed from this crystallises from glacial acetic acid in leaflets melting at 168'.Ethereal Phosphopalladates and their Ammoniacal Deriva- tives. By E. FINCK (Compt. rend., 1896, 123, 603--604).--Ethylic- phosphopcdludate, P,(OEt),PdCI,, forms red, prismatic crystals, insoluble in water, but soluble in alcohol. It is obtained by placing phospho- palldic chloride and absolute alcohol in separate dishes under a bell jar, which also encloses a dish containing quick lime. Methylicphospho- pulladate is strictly analogous to it in composition and is obtained in a similar way; it crystallises in white, prismatic needles, soluble in alcohol, benzene, and ether. When treated with ammonia in presence of water or benzene, ethylic phosphopalladite yields colourless crystals of the composition P(OEt),PdCl2,2NH3, whilst in presence of alcohol the product is P(OEt),PdN2H,,2HC1 + P( OEt),NH3PdN,H,,2HC1.The methyl derivative yields analogous compounds under the same conditions. Ethylic phosphopalladate, when evaporated with aqiieous ammonia, yields white, deliquescent crystals of the compound P,O( OEt) ,PdNH,,HCl, whilst the methyl derivative yields the compound P2( OMe)6N213[4, 2 HCL [P P2( OMe),PdN,H,, 2HCl-J. When heated with paratoluidine and alcohol, ethylic phosphopalladite yields white, prismatic crystals of the compound P( EtO),C7H,N,PdC12 ; an analogous methyl derivative is obtained in the same way. Pyri- dine, under similar conditions, yields the compounds J. F. T. P(OEt),C,NH,,PdCl, and P(OMe),C,NH5,PdC12. C. H. B. Constitution of Vinaconic [Trimethylenedicarboxylic] Acid.By RICEARD MARBURG (Annulen, 1896, 294, 89-134. Compare Abstr., 1895, i, 171).-The main facts which lead the author to support the view of W. H. Perkin, jun., who regards vinaconic acid as trimethylenedicarboxylic acid, have been already described (loc. cit.) ; the present paper contains an amplified record of the experimental details. Ethylic y-chlorisosuccinute, CH,Cl*CH,* CMe(COOEt),, obtained from ethylic sodioisosiiccinate and ethylenic chloride, boils at 127-1 28' under a pressure of 9 mm. ; not more than 10 per cen . of this salt is produced, and a certain amount of ethylic symmetrical a-dimethyl-ORGANIC CHEMISTRY. 141 adipindicarboxylate [hexane-2 : 2 : 4 : 4-tetracarboxylate] is also formed (compare Abstr., 1894, i, 441.) When ethylic y-chlorisosuccinate is heated at 260-270°, it yields ethylic a-methylbutyrolactonecarboxylate (compare Abstr., 1895, i, 171).The barium salt of a-methylbutyro- lactonecarboxylic acid contains 4H20, the calcium salt, 1H,O , whilst the silver salt is anhydrous. Barium hydroxyethylisosuccinate contttias 3H,O, and the silver salt crystallises from water. a-Methylbutyrolactone is obtained on heating the lactonecarboxylic acid at 140°, carbonic anhydride being eliminated ; this substance is also produced on hydrolysing y-phenoxyet hyl-a-methylacetic acid (Trans., 1896, 173). The bcm'um, cc~lcium, and silver salts of a-methyl- y-hydroxybutyric acid are anhydrous. Methylvinnconic (1 -rnethyltrr.imethylene-2 : 2-ilicarboxylic) acid, CHMe I \ C( COOH) ,, CH,--/ the ethylic salt of which is produced when ethylic sodiomalonnte is treated with propylenic bromide (Abstr., 1895, i, 172), crystallises from benzene in lustrous needles, and melts at 113.5"; the ba~ium salt contains 2H,O, the hydrogen b a ~ i u m salt 3H,O, and the ccclciunz salt 5H20, whilst the silvep and hydrogen silver salts are anhydrous, and crystallise from water, Methylvinaconic acid is quite distinct from allylmalonic acid.y-BTomopro~yl~nccZonic m i d , CHMeBr. CH,. CH(COOH)2: is obtained by the action of hydrobromic acid on methylvinaconic acid, and when crystallised from chloroform, melts a t 107*5" ; it is identical with the acid produced on treating allylmalonic acid with the same agent, and boiling water converts it into the y-methyl-a-butyrolactonecarboxylic (valerolactonecarboxylic) acid, obtained by Hjelt from the hydrogen bromide additive compound of allylmalonic acid.The by-omine additive compound of methylvinaconic acid, C4H&( GOOH),, crystallises from chloroform in needles, and melts and decomposes at 130-1 31" ; the bromine additive compound of allylmalonic acid melts at 124.5'. Methylvinaconic acid is very readily attacked by concentrated nitric acid, and after 10-20 hours two molecular pro- portions of carbonic anhydride are eliminated ; vinaconic acid, on the other hand, yields no gas during the first 5 days, the quantity eliminated after 20 days representing less than a tenth part of one molecular proportion. a , * CHMe, CH,,--/ 1 ; 2-Met~~yltrinzethylenecarboxylic acid, I \CH* COOH, is obtained along with valerolactone on submitting methylvinaconic acid to dry distillation above 140"; it is a colourless, limpid liquid, having the odour of butyric acid, and boils at 190-191" under a pressure of 745 mm.It remains liquid a t - 18", and has the sp. gr. = 1.030 at 0°/4" and 1.015 at 18"/4'. The calcium salt contains l$H20, the barium salt 2H20 ; the silvei* salt is also crystalline, Methyltrimethylenecar- boxylic acid is distinct from ethylidenepropionic and allylacetic acids. M. 0. F,142 ABSTRACTS OF CHEMICAL PAPERS. Mesitylene from Acetone. By VICTOR MEYER and W. MOLZ (B~T., 1896, 29, 2831-2833). (Compare Abstr., 1896, i, 547.)-The fractions of mesitylene of high-boiling point prepared from acetone do not yield any appreciable quantity of monoketones when treated with acetic chloride and aluminium chloride ; it is improbable, there- fore, that they contain hemimellithene.The observation made by Lucas and Sohn t h a t a small quantity of hemimellithenecarboxylic acid is produced by the carboxylntion of mesitylene, is doubtless to be explained by the occurrence of isomeric change similar to that which obtains when symmetrical durene is treated in the same way. A . L. Constitution of the Nitroso-derivatives of the Two Secondary Ethylidenanilines. By ALEXANDER EIBNER (Bey., 1896, 29, 2977- 2981).-The two isomeric ethylidenanilines described by von Miller and Plij?hl (Abstr., 1894, i, 410) both yield nitroso-derivatives, which are sulphur-yellow powders, soluble in hot alcohol and in benzenes ; on the addition of ether t o these soiutions, the compounds are obtained in bright yellow, glistening crystals.The nitroso-compound from the base obtained by'Fckstein melts at 161", and is sparingly soluble in hot alcohol, but insoluble in ether ; that from the author's base melts at 120°, is readily soluble in hot alcohol and only sparingly so in ether. Both compoundB, when reduced with tin and hydrochloric acid, yield the same products, namely, tetrahydroyuinaldine and paraphenylene- diamine. NO*NPh*CHMe*CH,*CH:N*C,H,*NO [N :NO = 1 : 41 for the two nitroso-compounds. On adding ferric chloride to a solution of the hydrochlorides of tetra- h ydroquinaldine and paraphen ylenediamene in molecular proportion, a beautiful green coloration is produced, which turns to blue on the addition of water.Other secondary Schiff's bases can yield similar nitroso-compounds- for example, Sender's propylidenaniline (Abstr., 1892, 1189) and the base from orthotoluidine and acetaldehyde. This reaction agrees with the formula J. J. S. Orthophenylenebiguanide. By RUDOLF ZIEQELBAUER (Monatsh., 1896, 17, 648--666).-Monamines, NH,R or NHR,, simply combine with dicyanodiamide, C,H,N,, yielding substituted biguauides, C,H,RN, or C,H,R,N,. Orthophenylenediamine hydrochloride, how- ever, when it is heated with dicyanodiamide, in molecular proportion, in alcoholic solution for 7 hours a t 1 0 5 O , reacts with evolution of ammonia,. The product formed, however, has still the properties of a biguanide, and the constitution C,H,<NH, NH*C(NH) C(NB)>NH must be assigned to it.The author concludes that this and other reactions of dicyanodiamide are best explained by adopting the formula CN*NH* C(NH).NH, for that substance. Ort?zophenyZene6iguccnicle, C,H,N,,H,O, crystallises in yellowish, nac- reous plates, and melts and decomposes a t 242"(uncorr.). The following salts were prepared : nitrate, (CsHgN,),,5HN0, + 3H,O (&ths of the nitric acid can be titrated with baryta) ; ?uyhmhZoride, C,H,N,,HCl; pTcctinocldoi-ide, CsH,N,,Pt,CI, + 2H,O, ora~ge-yellow, darkens aboveORGANIC CHEMISTRY. 143 260°, but is still unmelted at 300" ; szcZpluttes, O,H,N,,H,SO, + 4H20 and (UsH9N,),,H,S0, + H,O, the latter brownish in colour ; clhi*onzate, U,H,N,,H,Cr,O,, yellow ; fe~i.ocyccnicle (C,H,N,),,H,FeC,N, + 3H20), yellowish. A red cobnlt and a chocolat e-brown nickel derivative, (C,H,N,),Co + 34H,O and (C,H,N,),Ni, were also prepared ; such metallic derivatives are obtained by mixing a solution of a salt of the biguanide with a salt of the metal in question, pouring the mixture into a large quantity of hot, dilute alkali hydroxide, and allowing the whole to cool.By PAUL JACOB- -The reduction of benzene azoaniso'il, OMe*C,H,*N,Ph, and benzene- azoveratrole, C6H,(O&lIe),*N,Ph [(OMe), = 3 : 41, have been studied, only cthylic ethers having been previously examined. The reduction and subsequent operations were carried out just as in the case of benzene- azophenetoil (Abstr., 1896, i, 23). Benzeneazoanisoyl behaves like the last substance, yielding the ortho- and para-semidine bases, OMe*C,H,(NH,)*NHPh [OMe:NH,:NHPh= 1 : 4 : 31 C.F. B. Reduction Products from Azo-compounds. SON, M. JAENICKE and FRIEDRICH MEYER (Bey., 1896,29, 2680-2690). and OMe*CGH;NH*C,H,*NH,, in addition to the bases anisidine and aniline, which result from a division of the molecule ; the quantitative relations are also similar. Benzeneazoveratrole also undergoes a similar reduction, but the action could not be studied quantitatively, for the niain reaction is accompanied by another, which results in the removal of one methoxyl group, and the formation of a benzidine base, NH,. C,H,( OMe) C,H,*NH,. 2-AnzitLo-5-nzetl~ox~cli~i~esayZami~~e (orthosemidine base) melts a t 73') and yields a c a d o n bisulphide derivative, C,,H,,N,SO, melting at 208' ; a yellow snlicylidene derivative, C,,H,,N,O,, me1 ting at 132' and oxidised by mercuric oxide to a scclicylic derivative, C,,H1,N20,,:melting at 123' ; with formic acid, a met?Lenyl derivative, OMe*C,H,:<Fz>CH, melting a t 77" ; and with benzil, a stilbccxoniuna bccse, N- CPh NPh(OH):bPh ' OMe*C,H,< melting at 163-1 65".4-Anzido-4'-metlioxydip?~enylcm~ne (parasemi- dine base) melts a t 102". Benzeneazoveratrole was prepared froin crystallised guaiacol by diazotising the latter, and boiling the sodium salt of the product,benzene- azognaiacol, with alcoholic methylic iodide; it is red, and melts at 44.5-45". 2-Anaido-4 : 5 - c L i ~ z e t l ~ o r c ~ c l i p l ~ e ~ a ~ l ~ ~ ~ ~ i n e (orthosemidine base) has a pale violet colour, and melts at 151' ; its rnet?Len?/l derivcctivs melts at 106-107'* 4 : 4'-0ic~mido-2-nzetl~oxytli~j?~e.n~l (benzidine base), is pale pink, and melts at 104'.Incidentally, the acetyl derivative of amidoveratrole, C,H,( OMe),*NHAc, was prepared ; it is silver-grey, and melts at 132.5-133'. G2(,nincolclis-ccxo6enxene, OMe*C,H,(OH) (N,Ph),, is obtained at the same time as benzene-azoveratrole ; it is dark grey with a vioIet sheen,144 ABSTRACTS OF CHEMICAL PAPERS. and melts a t 150-155". 6eii2xe.iaeicxogwcciclcoZ, obtained as mentioned above, forms red prisms, melting a t 70.5-71-5" Uramides, Urethanes, and Oxamethanes of Parapheny- lenediamine and Metaphenylenediainine. By HUGO SCHIFF ant1 ADRIANO OSTROGOVICH (A.rz.rraZen, 1896, 293, 371-388. Compare Abstr., 1894, i, 236, 333).-The derivatives of paraphenylenediamine have been already described (Zoc.cit.), and the paper contains a tabular representation of their rela tionship ; a description of the metaphenylenediamine derivatives appears for the first time. Acetylmetaphenylenediamine 7, yd~ochZoi*ide, HCI,NH,* C,H,*NH Ac, is obtained by heating metaphenylenediamine clihyclrochloride and sodium acetate in molecular proportion with water ; it forms a reddish, crystalline mass, having no definite melting point, and softens a t 194". il~etc~cetccmitlo~l~erL?lZcn1.bnIrnicZe, NHAc*C,,H.,*NZI*CONH,, is pro- duced on mixing cold, Concentrated, aqueous solutions of acetyl- metaphenylenediamine hydrochloride and potassium cyanate ; it crystallises in reddish needles, and melts a t 225". Metaphenylene- carbamide, C,H,<NH>CO, is also produced in small quantity, and the same substance is obtained when acetamidophenylcarbamide is submitted to frequent recrystallieation.Meta~~iidop~~enylcccr6ccnzicle hpcl~och lovide, HC 1, NH,* C,H, N H CO NH,, is formed when a very concentrated solution of acetamidophenyl- carbamide is boiled with hydrochloric acid for 10 minutes; it crystallises from dilute alcohol in lustrous scales, and melts at Metamidop?LenyZoxcLnzic acid, NIX,* C,H,*NH- CO- COOH, has been already described by Klusemann (this Journal, 1875, 269) and melts a t 225" ; the hyd?*ochZos.ide cry stallises in needles and decomposes above 300", whilst the potassiunt salt crystallises in yellow scales, and decom- poses about 270". The acetyl derivative melts at 125", and begins t o decompose a t 130".U~.amido~l~enyZoxnmic acid, NH,* CO-NH C,H, * NH* COO COOH, is obtained by heating potassium amidophenyloxamate with carbamide at 130", and also from amidophenyloxamic acid and potassium cyanate; it crystallises from water in small needles, and melts at 230'. Metccp~~enyleneclioxanaic acid, C6H,(NH* COO COOH),, is obtained by heating alcoholic acetylmetaphenylenediamine with ethylic oxalate in a reflux apparatus ; it separates from alcohol in crystalline aggregates, and melts, decomposing, at 240". &-Substituted Derivatives of Hydantoin. By ENRICO QUENDA (Chent. Centr., 1896, i, '701 ; from Ann. China. E I c c ~ m . , 23, 61-64). -Methylglycocine and monoparatolylcarbamide, when heated at 1 35-1 40°, yield diparatolylcarbamide and y-paratolyl-P-met~yZ~~~c~c6n- toin, the former being insoluble in water.The latter, which gives Weyl's reaction, melts a t 112-113", is soluble in water, and easily so in alcohol. Similarly, monorthotolylcarbamide and methyl-glycocine form diorthotolylcarbamide, which melts a t 250", and y-o&otoZyl- P-methylhydantoin. The latter, which was neither obtained in a crystal- line form, nor analysed, does not give Weyl's reaction. C. F. E. N H 281-282" M. 0. F. E. W. \V,ORGANIC: CHEMISTRP. 3 45 Derivatives of Paramidophenol. By VICTOR WIRTHS (A~.c?L. PT~cci*nz., 1896, 234, 680--634.)-The entry of a dibasic acid radicle into the amido-group of an amidophenol may be effected by heating the latter with an acid anhydride or amide in an oil-bath or over a free flame, Phthalylparamidophenol has already been obtained by this method (Piutti, Abstr., 1886, 1026).~ u ~ ~ i ~ z ~ ~ i ~ c 1 . ~ ~ ? ? 2 . i c Z o ~ J ~ e ~ z o l , OH*C,H,.N: (C0)2:C2H,, from succinic an- hydride and paramidophenol, crys tallises in needles, melts at 270°, and is insoluble in all the usual solvents, except alcohol and glacial acetic acid. OxcclyIpal.anticlop~~eno~, OH*C,K,*N< I , may be prepared by heating either oxalic acid or oxamide with paramidophenol ; it crys- tallises in needles, does not melt a t 350", and sublimes when sharply heated, being a t the same time partly decomposed. The derivatives under consideration can also be prepared by heating paramidophenol with ethereal salts in a sealed tube a t 160". The foregoing oxalyl derivative has been obtained in this way.With diethylic tartrate, 2 molecules of amidophenol enter into the reaction, y i el ding tccrt 7 *onyldipiemn uiclopJLeno I, OH* C,H,*NH* CO*CH(OH) *CH(OH)*CO.NH*C,H,* OH, which crystallises in reddish needles, melts and decomposes at 282O, and dissolves in glacial acetic acid and alcohol. Sztccin~I~~,n~~ct?~i.isidine, OMe. C,H,*N: (CO),: C,H,! prepared by melting succinic anhydride with anisidine, crystallises in needles, melts a t 162", and dissolves in hot water and alcohol. Succinylparaphenetidine melts at 158' (Piutti, Chenz. Zeit., 1896, 20, 54). LSuccinyZdipava- phel.zetidine, OEt.C6H,*NH* CO-C,H; CO *NH* C,H,* OEt, crystallises in needles, melts at 2 5 8 O , and is insoluble in water. By heating anisidine or phenetidine with ethereal salts in tubes at 150-160", the following have been prepared.O.caIll~cci.nnisi~ii2e, OMe*C,H4*N<?O which crystallises in needles, melts a t 115", and dissolves in water and alcohol, OzccZyZlli,as~cc~~i~i- dine, C,O,( NH* C,H,* OMe),, crystallises in needles, melts at 260", and is insoluble in water. O i r : e , n I ~ ~ 2 ~ c c ~ c ~ T ~ e n e t i d i . r z e crystallises in six-sided tablets, melts a t 110", and dissolves in hot water, alcohol, and glacial acetic acid . Tm .tsm iy Id i$n m? his iclii be cry s t a1 li ses in large? 1 us t ro u s lamin=, melts at 259", and dissolves freely in alcohol and hot glacial acetic acid, but only sparingly in ether, chloroform, and benzene. I'tur- t i . o s z y Z ~ 1 i ~ ) c t ~ . { i 2 i ~ e ~ ~ e t ~ ( ~ ~ ~ ~ e forms large laminz, melts a t 271", and resembles the preceding compound in solubility.By heating such substituted amidophenols as have been described above with acid chlorides, compounds containiug acid radicles sub- stituted in the hydroxyl of the phenol are obtainable. The following instances are cited ; the compounds are best crystallised from glacial acetic acid. ~'~itT~ccT?/I2~cct.c,ni~zicl opheny I ic benxocc te , OBz*C,H,*N:(CO),: C6H, ; needles, melting a t 256". 1'~~tl~aZyZp~~1.~~7)aicZ02~henyZic butyrcte ; needles, melting a t 156'. 1 ' 7 ~ t l ~ c c Z ? / Z ~ ~ c c r r ~ c ~ ~ ~ ~ i ~ o ~ J ~ e ~ a ~ l i c propionate ; needles, melting at 168". P7~the~~~~1)~~~~~c~~iicZopJ~en~Zic acetate ; needles, melting a t 2 2 6 O . co CO co'146 ABSTRACTS OF CHEMICAL PAPERS.~ u c c i n y l ~ a s ~ a . n ~ ~ ~ o ~ ? ~ e n ~ Z ~ c benzoate, OBz* CGH;N: (CO),: C,H, ; needles, melting at 2 1 5". S~~cci~zylpcc1.ccrniclop?~e?zy lie p?*opioizate ; needles, me1 tin g a t 1 7 8 O . A. G. B. Action of Phthalic and Succinic Chlorides on Compounds of the Type R*NH,. By BRONISLAW PAWLEWSKI (Be?.., 1896, 29, 2679. Compare Abstr., 1895, i, 414). -By heating orthamido- benzoic acid with phthalic chloride, ~)J~t?~cckaizilo~t~oca~box?/lic acid, UO<!3>C:N* C,H,* COOH, is obtained ; it melts and decomposes at 241-242'. Parani traniline and succinic chloride yield pale yellowish * - CH,* CO CH,* CO succiny~cc1.ci~~~t~.o~T~e~zyliinide, I >No CGH,*N 0,, melting at 175". C F. B. Aromatic Chlorophosphines and their Derivatives. By C. A.AUGUST MICHAELTS (Anncclen, 1896,293, 261-325 ; 294, 1-55. Com- pare Abstr., 1894, i, 586; this vol., i, 49).-[With HUBERT GLAUBITZ.] -ParatoZy lcyanophosphine, CGH,Me P (CN), , obtained from para t olyl- chlorophosphine and silver cyanide, is a bright yellow, viscous liquid, which boils at 145' under a pressure of 50 mm. ; paratol~ltl~ioe~ano- phosphine, C,H,Me*P(SCN),, is a reddish-yellow liquid, which boils a t 237-240" under a pressure of 40 mm. PlmzyZic pccrntoly~TLosp?~oIzate, C,H,Me*PO(OPh),, is obtained from tolyloxychlorophosphine and phenol (2 mols.), the mixture being heated at 120-130"; it is a colourless, viscous liquid, which exhibits feeble, blue fluorescence, and boils above 360". The chloride, C,H,Me*PO(OPh)Cl, is produced when one-half the quantity of phenol is employed ; it is a white, crystalline mass, which melts at 5 5 O , and boils above 360" without undergoing decomposition. Silver phenylic pnrcctol~lpl~o~~?~onute and pheng I ic parat o lylphospho n arnicle , C ,; H,Me P 0 (0 P h ) - NH, , have a1 s o been prepared, and the latter substance crystallises from ether and melts a t 115-1 16".The pT~enyZhyclvccxicZe of monophenylic paratolyl- phosphonate crystallises in small, white needles, and melts a t 173-174"; thepiperidide is a yellow oil. Paratolglic pn?.atol?l~?iosp~ionate, C,H,Me*PO(O*C,H,Me),, is a viscous liquid which boils above 360' ; the cldoi.ide melts at 60", and boils above 360" without undergoing change. P'henylenic pa/ratol~~)?~ospr~onate, C,,H,Rle*PO:O,:U,H,, melts a t Sl", forming a feebly fluorescent liquid which boils above 360" ; the chZor*ide is a colourless, viscuous liquid, which does not decompose when distilled above 360".Pccratol~~hos~~?~o~zdiaii~irle,C!,H,Me PO(NH,),, cry stallises in colourless, lustrous leaflets, and melts a t 176" ; this substance is not formed when tolyloxychlorophosphine is treated with ammonium carbonate, a com- pound being produced which melts a t 74", and is probably an isonzeride of paratolylphosphonic acid (m. p. 189"), as it yields this product when treated with boiling water. The diccnilide, C,H,Me*PO(NHPh),,crystal- lises in small, nacreous needles, and melts a t 209". The toluidide forms slender, snow-white needles, and melts a t 237", and the ?iionotoluiclitle, C,~,nle*PO(OH).NH*C,W,~~e, is a white powder which melts a t 208"; the plierqZlqcli.axide forms slender needles, and melts at 17 1".ORGANIC CHEMISTRY.144 d n i l i ~ i e - n - t o l ? / ~ l ~ o s ~ ~ l ~ o n i c acid, C1,H,Me*PO(OH)*NHPh, is obtained as chloride along with the foregoing anilide when tolyloxychlorophos- phine is heated with aniline hydrochloride ; it is a white powder, which melts a t 150°, and is decomposed when dissolved in alcohol or glacial acetic acid. The copper salt is a bright blue powder; the phenylic salt melts a t 59', forming a very viscous, highly-refractive oil, which boils at 283" under a pressure of 48 mm. [With E . PIPER . ] --Nitmpamt ol y lphospho nic cccid, NO,*C,H,Me * PO( OH),, is obtained by heating paratolylphosphonic acid with fuming nitric acid for 2 hours in a reflux apparatus ; it crystallises in aggregates of pale yellow needles, and melts at 191'.The barium salt forms yellowish leaflets, and contains 2H,O, and the calcium salt contains lH,O; the lead, coppei', and silver salts are anhydrous, and the ethylic salt is liquid. ~initropccrato~y&hosphonic acid is obtained by heating the phosphonic acid with a mixture of concentrated and fuming nitric acids for 3 hour8 on the water bath ; it crystallises from water in yellowish leaflets, and melts a t 251". The barium salt contains 2H,O, and the lead salt is anhydrous. Anaidopn~~cctol?~&l~osphonic m i d is formed on reducing the nitro- derivative with tin and hydrochloric acid, and crystallises from alcohol in lustrous needles ; it rapidly darkens in the atmosphere, and melts indefinitely at 270-290'.The silver and lead salts are amorphous, and the ethylic salt is a yellow liquid. The action of nitrous acid in presence of hydrochloric acid gives rise ultimately to trichlorotolu- quinone, along with a substance which is probably tartronic acid. Parabenzophosphonic acid, COOH*C,H,*PO(OH),, was obtained by Michaelis and Paneck on oxidising paratolylphosphonic acid with potas- sium permanganate. The hydrogen CCI lciunz and hydi-ogen bnrizcin salts are anhydrous, and the copper salt is a bright blue, crystalline sub- stance, containing 1 hH,O. The dihydrogen ethylic salt crystallises in long, colourless needles, and melts at 78"; the hydrogen silver etlqlic salt forms snow-white crystals. The rnorzccrnide crystallises in small needles, melting above 300', and forms the silver salt, which is a white powder very sensitive to light.The anilide separates from alcohol in small, white crystals, and melts at 242'. [ With MORITZ G . M IETR I NG. ] -Pcwcctoly~di?ne thylph o s$t, i?ze ox icle, C,H,Me*Yl\le20, is obtained by suspending paratolyldimethylphos- phine (Czimatis, Abstr., 1883, 57) in much water, and adding a slight excess of mercuric oxide; it is a hygroscopic, crystalline mass, and melts at 95". The nitro-derivative forms yellow prisms, melting a t 175", and yields a ntei.cu~*icllloi.ide, which crystallises from water in slender, white needles, and melts a t 127". Dimethy&r~ospl~ine-o~i~e~~c~~ccben%o~c cccicl, COOH* C,H,*PMe,o,. is produced on oxidising paratolyldimethylphosphine oxide with potassium permnnganate ; it separates from alcohol and ether in colourless crys- tals, melts at 240°, and boils above 360' under a pressure of 15 mm. The mer~uricldoi~icle crystallises in beautiful white needles, and melts a t 154", the aurochlokle forms colourless, rhorubic plates, and the ybtinochloride crystallises in colourless plates, and melts at 234".The cwzmoniwm salt melts and decomposes a t 212", the silver salt forms148 ABSTRACTS OF CHEMICAL PAPERS. colourless crystals, and the copper salt is a bluish-green powder. The chZm-icZe is a liquid, and, when treated with aniline, yields the unilide, which crystallises from alcohol in nacreous leaflets, and melts at 235O. by the action of silver oxide on the I~ydrochZoi~ide of the ethylic salt, C,H,Me*PMe,Cl*CH,* COOEt, which is formed by the action of ethylic chloracetate on tolyldimethylphosphine, separating as a hygroscopic crystalline powder, which melts at 153' ; the platinochlokde of the ethylic salt forms slender, yellowish-red needles, and melts at 200".The betcc'ine itself melts at gO6', and the hydrochloyide a t 172O, whilst the pkct,tinochZoYide crystallises from hot water in small needles, and melts a t 220'. ~oZ~Zdiethy~?~osplLine oxide, c,H,Me* PEt20, forms hygroscopic crys- tals, and melts at '74" ; the mercu~icldo~~ide contains lH,?, and melts at 135". The nityo-derivative is an oil, forming a wLercui*zchZwicle, which melts at 105". Diet7~~lpl~os~)~~i~2e-oxide-pct,~.ct,benxoic acid, COOK. C,H,*PEt,O, is an oil which distils under a pressure of 15 mm. without undergoing change; the anilicle crystallises in leaflets, and melts at 198', and the nze~cu~*icl~Zoricle-icZe at 134'.The betake is a hygroscopic mass, and yields a plct,tinochZos.ide, which crystallises from hot water in yellow needles, and melts at 157"; the ethylic salt of the betai'ne is a liquid, forming the hgdrochloride, which melts a t 96". [With LUIS DA ROCHA ScHMIDT.1-Orthotolylchlorophosphine is a colourless, highly-refractive liquid, having a sp. gr. = 1.3067 a t 18*5', and boils at 244'. O ~ ~ t ~ ~ ~ t ~ l ~ Z t e t ~ ~ ~ t , ~ ~ ~ o r o p ~ ~ o ~ ~ l ~ i ~ ~ e , C,H,Me*PCl,, is a white, crystalline substance, and melts at 63 -66'. C,H,Me*POCl,, is obtained from the tetrachloride by means of sulphurous anhydride, and forms a colourless liquid having a sp.gr. = 1.3877 a t 18.5', and boils at 273". O?.tl2otoZ~Zp~os~~ine oxide, C,H,Me*PO,, crystallises from benzene in short prisms. Ammonium orthotolylphosphinite is a crystalline salt, becoming brown on exposure to air, and the bcci-iunz salt contains 1H,O ; the coppe?. and Zeccd salts are anhydrous, and the cmilide crystallises in white needles, and melts at 234". CI~Zos.ol.tl~otoZ?/lrLos~r~o?2~c ncid [Me :P : C1= 1 : 2 : 41 is produced by the action of chlorine on orthotolylphosphonic acid, and separates from dilute alcohol in small crystals, melting at 305'; the s i l v e ~ salt is amorphous. L ) ~ c ~ ~ Z O ~ O ~ ~ ~ ? ~ O ~ O Z ~ Z ~ ~ O S ~ ~ ~ O ~ ~ ~ C acid crystallises in slender needles, and melts at 240' ; the silvei- salt is a white powder.O i ~ t h ~ t ~ Z ? / l o ~ ? / ~ l ~ l ~ ~ ~ p l ~ [With E. P~~~~.]--Nit~~~-~rtl~otoZyZ~~,kospl~opzic acid, [Me : P :NO,= 1 : 2 : 41, is obtained more readily than the para-compound, being formed when a solution of the phosphonic acid in fuming nitric acid is evaporated on the water batli; it crystallises froin water in pale yellow needles, and melts at 174'. A?~LicZortlLotoZ~Zpl~osp?~onic acid, obtained by reducing the nitro-com- The barium and culcizcrn salts are anhydrous.ORGANIC! CHEMISTRY. 149 pound, crystallises in needles which quickly become brown, and softens a t 280--300°, above which temperature it decomposes ; the bcwium salt is a reddish-brown powder, sparingly soluble in water, and the culciuni salt is also moderately soluble.Oi.tl~obe92xopl~ospl~orLic ncicl, obtained by oxidising orthotolylphos- phonic acid with potassium permanganate, separates from mster in small crystals, melting a t 172" ; when gently heated in small quantity, i t sublimes for the most part without undergoing change. The silvei- salt is a white substance, which is sensitive to light ; the cldoricle melts a t 54' O~~t~~otolyldiet7zylp~~ospl~ine, C,H,Me-PEt,, is a mobile, colourless liquid of penetrating odour, and boils at 263'. The methioclicle crystal- lises from water in colourless needles, and melts at 98' ; the ethiodide crystallises from alcohol, and melts a t 162'. [With ?vILLIAM B E R G H E G G E R . ] - ~ ~ e t U t O ~ y ~ c ~ ~ ~ O ? ' O ~ ? ~ O S p ~ ~ ~ ~ Z e iS prepared by heating small quantities of 1 : 3-mercuryditolyl (Abstr., 1895, i, 368) with phosphorus trichloride (10 parts) in sealed tubes a t 200" for 12 hours; i t is a dense, colourless liquid, which boils a t 235", and has a sp.gr. = 1.282 at 22'. DIetcctolyltets.ucldo~ophosphine is a viscous oil, which becomes crystal- line below 0'. MetutolyloxyclJos.ophospJhae boils a t 275', and has a sp. gr. = 1.3533 at 18'. A i m ~ z o n i u m metatolylphosphinite cry stallises in lustreless, white needles, and the potussium salt is deliquescent ; the bccrium salt forms stellar aggregates of needles, and the p/~enyZiiydi*uxine salt, cryst'al- lising in ysllow needles, melts and decomposes at 131". Metatolylphosphorzic CLC~CZ, C,H,Mc*PO(OH),, crystallises from water in lustreless, white needles, and melts at 116-117".The hydrogen potussium salt forms white needles, and the tdhyclrogen potussium salt, white leaflets ; the buyiuna, siluev, and ?~ydi*ogen silves. salts are an- hydrous. ChlorometcctolylphospT~onic ncid [Me : P : C1= 1 : 3 : 41 is formed when a stream of chlorine is passed into an aqueous solution of metatolylphos- phonic acid for 20 minutes; it crystallises from water in small, white .needles, and melts a t 176". The silvei. salt is a white powder, and resists the action of light. [Me:P :C1, = 1 : 3 : 2 : 4 :5], is obtained by prolonged action of the halogen, and crystallises in needles or leaflets, melting at 220'; when heated above this tempera- ture, it ;Fields 1 : 2 : 4 : 5-trichlorotoluene, and is, therefore, identical with trichlorotolylphosphinic acid described by Michaelis and Lange (this Journal, 1876, i, 392).Bromometatolylphospkonic cccicl [Me : P : Br = 1 : 3 : 43 crystallises from water in white needles, and melts a t 198' ; the silver salt is amorphous. Metu6enxop~zospl~onic ucid is obtained by oxidising metatolylphos- phonic acid, and crystallibes from alcohol in small, white needles, melt- ing at 245-246"; the silves., Zeud, and bcwiunz salts are anhydrous, and the chloride is a white, crystalline substance, which melts a t 61', and boils at 360'. [With MORITZ L~~~~~~~~~~].-Pcc~ethyZphenyZchZoroph,osphine (ethyl- 6en~enechZoi~op~osphine), C,H,Et*PC12, is prepared from ethylben- VOL. LXXII. i. ?t1 Trichlorotolylphosphonic acid150 ABSTRACTS O F CHEMICAL PAPERS zene, phosphorus trichloride and aluminium chloride, and forms a colonrless, highly-refractive liquid, which boils at 250-252", and has a sp.gr. = 1.227 at 17". Ethyl6enxenetet~nchloropT~os~~~i~~e is obtained by the action of chlorine on the foregoing substance, and forms a white, crystalline mass, melt- ing at 5 1'. Ethylbenxeneoxychloyo~liosphine is a colourless liquid which boils at 294O, and has a sp. gr. = 1-29 a t 1 6 O . Ethylbenzenephosphinous ucid, C,H,Et *PHO*OH, is produced when the chlorophosphine is treated with water, and the liquid evaporated ; it separates in crystals, and 'melts at 63-64'. The ccnanaonium salt forms lustrous, quadratic leaflets, and the bcwium salt is a crystal- line powder containing 1H,O ; the copper salt is a biuish-grten, crystal- line powder, and the phenylhydraxins salt separates from hot water in lustrous, yellowish-white leaflets, and melts a t 133".Et?Lylbenxenephosphonic acid crystallises from water in slender, lustrous needles, and melts a t 164" ; the hydyogen ccnmzonium salt crystallises with difficulty, and the hydyogen phenylhychccxine and trihyd~ogen potccs- sium salts crystallise from water. The bcwium salt forms lustrous needles, and contains 3H,O ; the copper salt is greenish-white, and con- tains 1H,O, and the silver salt is a white, crystalline powder. Ethyl- benzenephosphinic acid is immediately oxidised by potassium perman- ganate, in alkaline solution, yielding benzophosphinic acid, carbonic anhydride, and water. Phosphino-ethylbenzene, C,H,Et*PO,, is obtained by dissolving ethyl- benzene-phosphinic acid in benzene and heating the solution with ethyl- benzeneoxychlorophosphine on the water bath in a reflux apparatus ; it is exceedingly hygroscopic, and forms small, white crystals, which melt at 68".Di-ethglbenzenephosphonic mid, (C,H,Et ),PO: OH, is a b ye-produc t in the preparation of ethylbenzenephosphinous acid, and is isolated in the form of the coppe~ salt ; the silvey salt is amorphous. Ethgl benxenephosphine, C,H,E t *PH,, is a trans parent, highly -ref rac- tive liquid which boils at 200" ; the plcctinochloride is a golden yellow, crystalline powder, and the Ihydriodide separates from water in lustrous, white crystals, melting a t 118". Ethylberzxenediethy~~osp~~ine, C6H,Et *YEt,, is a colourless, highly- refractive liquid, having a penetrating odour ; it boils a t 268-270", and has a sp.gr. = 0.929 a t 17". The pbtinochloride is reddish- white, and the methiodide crystallises in long, white needles, and melts a t 135"; the ethiodide forms white needles, and when heated is resolved into its components without undergoing fusion. EthyZbenzenepho~phinop~e~yl~h~drcczone, C,H,Et P:N*NHPh, is ob- tained by the action of ethylbenzenechlorophosphine on phenylhydrazine dissolved in ether ; it is a white crystalline powder, and melts at 139". [With FRITZ ROTHE and R. USTER] . - ~ - C u m y ~ c h ~ o r o ~ ~ o ~ p ~ i C,H,Me,*PCl, [Me, : PCI, = 1 : 2 : 4 : 51, obtained from pcumene, phosphorus trichloride, and aluminium chloride, is a colourless, highly- refractive liquid, which boils at 280", and has a sp.gr. = 1.2356 a t 20" ; it is also produced when the mercury derivative corresponding with symmetrical brorno-+-cumene (Abstr., 1895, i, 368) is heated with phosphorus trichloride in sealed tubes at 230-240". $-CumyZtetra-ORGANIC CHEMISTRY. 151 chlorophosphine, C6H2Me,*I?C1,, is a greenish-white crystalline mass, and melts at 75'. $-CumyZoxychlorophosph~ne, C6H2Me,*POCI,, is crystalline and colourless ; it melts a t 63", and boils at 307-3308". IC/-Cumylp~~o,~z)~~inous acid, C,H,Ne,*PHO*OH, is produced by the action of water on the chlorophosphine, and crystallises from alcohol in rhombic leaflets ; it melts at 128', and undergoes no change when exposed to the air. The potassium, l e d , and coppey salts are anhy- drous, and the bcc~ium salt contains 3H20 ; the phenyzhydruzine salt crystallises in small white needles, and melts at 180'.$-Cunaylphosphonic m i d , C6H,Me,*PO(OH),, is obtained by the action of water on the tetrachloro- and oxychloro-phosphines, and crystallises from water in white needles ; it melts at 212', and is spnringly soluble in cold water. The hydi*ogen potccssium, hydqaogen burium, and silvev salts are anhydrous ; the hpdi-ogen nickel salt, with 4H,O, crystallises in lustrous, green leaflets. The pJ2enyZic salt melts at 62*5O, and boils above 360"; the diunilide, C6H,Me,*PO(NHPh),, crystallises from dilute acohol in lustrous needles, and melts a t 197". Ti+anilido-$-cumyZ- phosphonium chloride, C6H2Me,*(NHPh),C1, obtained by heating q-cumyl- tetrachlorophosphine with aniline hydrochloride at 170-180", melts at 247"; the bomide, iodide, and nitrute melt at 259O, 220', and 224-225' respectively, whilst thelqdroxide, which is indifferent towards litmus, melts a t 203.5'. The phenylhydmxide of $-cumylphosphinic acid, C,H,Me,*PO(N,H,Ph),, crystallises in small, lustrous needles, and melts at 208' ; it reduces Fehling's solution when heated.ChZoro-$-cumylphosphnic acid [Me, : P : C1 = 1 : 2 : 4 : 5 : 61 is produced when chlorine is passed into a solution of IC/-cumylphosphonic 'acid dissolved in glacial acetic acid, and crystallises in white, lustrous needles, melting at 235' ; when treated with fuming nitric acid a t low tempera- tures, it yields nitrochloro-$-cumylphosphonic acid, the hot acid con- ver t in g it into dini t roc hloro-+-cumene.The hydrogen phenylhydraxirze salt crystallises from alcohol in small needles, and melts at 197.5'. 6 : 3-Cl~Zo~*onitro-$-cumyZphosphonic cccid crystallises from water in long, lustrous, pale yellow needles, and, when slowly heated, melts and decomposes at 227-228'. 3 : 6-Dinit?.o-$-cun~yZp~osp~~onic acid forms small, white needles, and decomposes a t 239' when slowly heated ; if the temperature is raised rapidly, the nitro-acids explode. The hydrogen phenylhydrccxine and hydrogen uniline salts of the dinitro- acid melt and decompose at 240' and 273" respectively, the copper salt crystallises in greenish needles containing lH,O, and the silver and hydrogen s i l v e ~ salts crystallise from water. xylophosphonic mid, COOH*C,H,Me,*PO(OH), [= 1 : 2 : 4 :5], ob- tained by oxidising IC/-cumylphosphonic acid in. alkaline solution with potassium permanganate, melts at 258', and, when heated above this temperature, yields metaphosphoric and xylenecarboxylic acids.The silver salt is sensitive to light. (COOH),C,H,Me*PO(OH'), [? = 1 : 4 : 3 : 61, is produced when the oxidation with permanganate is performed under modified conditions ; it is a yellowish, hygroscopic powder, which melts at 185-190' ; the silver salt is colourless. Di-$-cumyZphosplmnic acid, (C,H,Me,),PO.OK, is obtained on treat- ing with water the residue from the preparation of $-cumylchloro- Me2hyZphtl~ulophosphonic acid, m 2152 ABSTRACTS OF CHEMICAL PAPERS, phosphine after extraction with light petroleum. It forms highly refractive crystals, belonging to the monoclinic system, the axial ratios being a : b : c = 0.96 : 1 : 0.983 ; /3 = 113'.The acid melts nt 202-203', and is converted at 240-250" into t,!r-cumene and phosphino-$J-cumene, C,H,,PO,, a white, crystalline powder, which melts at SO'. The potassium salt of di-$-cumylphosphonic acid contains 1 H,O, and the ammonium salt 2H20 ; the bcc~ium, Z e d , silvei., cobalt, nickel, and copper salts are anhydrous, but the two last-named contain 10H20 when crys- tallised from aqueous ether. Dixylophosphonic acid, (COOH*C6H2~~e,)2PO*OH, is produced on oxidising di $-cumylphosphonic acid with potassium permangannte ; it melts at l85', and the silver salt is not altered by exposure to light. +-Cumylphosphine, C,H,,*PH,, which is obtained when an alcoholic solution of pcumylphosphinous acid is submitted to distillation in an atmosphere of carbonic anhydride, has a very disagreeable odour, and boils at 214- 218' ; it is rapidly oxidised on exposure to air, $-cumylphosphinous acid being produced.Thepkutinochloride is yellow, and the diethyl derivative has a penetrating odour, boils at 274-275', and yields a red, crystalline pkcctinochloride ; methyldietl~yk-t,!r-cumylphos- phonium iodide crystallises from water in lustrous, rhombic plates, and melts at 160'. Diphenoxy-$-cumyZphosphine, C,H,,*P(OPh),, obtained by the action of +-cumylchlorophosphine on sodium phenoxide suspended in ether, is a viscous, colourless liquid, having a sp. gr. = 1.144 at 1 5 O , and the refractive index = 1.5085 ; it boils at 283' under a pressure of 40 mm.Boiling water converts it into phenol and +-cumylphosphinous acid. Diethoxy-+-cumylphogphine, C,H,,*P!OEt),, is a colourless liquid, having the odour of the thiocarbimides ; it has a sp. gr. = 1.048 at 15', the refractive index = 1,505, and it boils at 232-233' under a pressure of 100 mm. [With BERNHARD H~c~~a.]-~esitykch~orophosp~ine, C,H,Me,*PCI,, [Me, : PCl,= 1 : 3 : 5 : 41, is prepared from mesitylene, phosphorus trichloride, and aluminium chloride, and crystallises in transparent plates a centimetre in length ; it melts at 35-37'', forming a highly- refractive, colourless liquid, which boils at 273-275', and has a sp. gr. = 1 -205 at 15'. Mesityltetrachlorophosphine, C,H,Me,*PCl,, melts at 70". Mesityloxychlorophosphine, C,H,Me,*POC12, forms large, trans- parent crystals ; it melts at 92-93'? and boils above 360'.Mesitylphosphinous acid, C6H2Me,*PHO*OH, crystallises from water in lustrous needles, and melts a t 147' ; the potassium, ummonium, cal- cium, and copper salts me crystalline and anhydrous. The phenyl- hydraxine salt melts and decomposes at 132", and the aniline salt crystalliaes in long, yellowish needles ; the barium salt contains 6H,O, and crystallises in long needles, which rapidly effloresce on exposure. Mesitylphosphmic acid, C,H,Me,*PO(OH),, crystallises from dilute alcohol in long, colourless needles, and melts at 167'; the hydrogen ammonium and silver salts are anhydrous, whilst the burium salt con- tains 1 H,O, and the nickel shlt 8H,O. is produced when the phosphonic acid is heated with benzene and the oxychlorophosphine in a reflux apparatus at 40'; i t separates Phosphinomesitylene, C,H,Me,-PO,,ORGANIC CHEMISTRP.I53 from chloroform in small crystals, and melts and decomposes at P-Xylophosp?bonic w i d , COOH*C,H2Me,*PO(OH),, is obtained on oxidising mesitylphosphonic acid with potassium permanganate ; it is amorphous, and melts a t 245', yielding metaphosphoric and mesitylenic acids at higher temperatures. The silver salt is decomposed by light,. Methy Zisoplbthulophosphonic acid, (C 0 OH),C,H,Me PO (OH), , is also formed during oxidation, and is very hygroscopic ; it sinters a t 215' and melts at 255', yielding metaphosphoric and uvitic acids when heated above this temperature. Mesitglp?hosphine, C,H,Me,*PH,, is produced on submitting mesityl- phosphinous acid to dry distillation in an atmosphere of carbonic anhydride; it forms colourless needles which melt a t 40°, and under a pressure of 25 mm.it boils at 125'. Theplatinochloride forms orange crystals, and the diethyl derivative boils at 170', and forms an orange plcctinochloride ; naesitylmethyldiethylp?~osphoniu~ iodide cry stallises in colourless, lustrous needles, and melts, decomposing, at 125'. The p?LenyZhydraxone, C,H,,P:N*NHPh, crystallises in small, lustrous needles, and melts at 135'. [With OSWALD M ~ ~ ~ ~ . ] - ~ " u m ? j ~ c h ~ o r . o p ~ ~ ~ ~ p ? ~ ~ ~ ~ e , C H C,H,* Pel,, is obtained from cumene, phosphorus trichloride, and aluminium chloride ; it is a colourless liquid which boils at 268-270°, and has a sp. gr.= 1 ~ 1 9 0 a t 12'. Cunzyltetr.ccc?Llorophos23hine, CHMe,* C,H,*PC14, is a white, crystalline mass which melts at 53-55". Cumyloxychlor.op?~os- phine, CHMe,*C,H,*POCl,, melts at 35', and boils at 183' under a pressure of 35 mm. Ctmylphosphinous cccid, CHMe,* C,H,*PHO* OH, is a viscous oil, which dissolves sparingly in water; the bcyium salt contains 1H,O, the phenyl- Aydraxine salt melts a t 16l0, and the hydrogenphenylhydruxine salt at 135'. CunzyZphosphonic acid, CHMe,. C,H,*PO(OH),, produced on decom- posing the tetrachloride with water, crystallises from cymene in lustrous prisms, melting a t 139' ; the barium and silver salts are anhy- drous, and the phen@~di~a,uine salt crystallises in pale yellow leaflets, and melts a t 172'. HydroxyisopropyZphenyZphosphonic acid, OH* CMe,* c,H,*Po(oH)2, obtained by oxidising cumylphosphonic acid with potassium perman- ganate, separates as an oil from the aqueous solution ; at 105-120°, the acid loses water, yielding phenylallylphosphonic acid, a white powder which melts at 250'.Dicumylphosphonic acid, (CHMe,*C,H,),Po*oH, is a bye-product in the preparation of cumylphosphonic acid, and remains after removing the latter by means of light petroleum ; it is a white powder, which becomes brown when heated, but does not melt. The copper and aluminium salts are anhydrous. Cymylchloro;u?Losplzine, C,H,MePra*PC1,, boils at 275-278" ; the tetrachlorophosphine is a viscous liquid. CymyZphosphinous acid is liquid, and the barium salt contains 1H,O. Cymylphosphonic acid is also liquid, aud the hydvogem silver and silvev salts are decomposed by light ; the phenylliydraxine salt crystallises from alcohol, and melts at 156".Cuirzyldieth~lp~oshine boils at 260--270'. M. 0. F. 2 15-21 GO. The silver salt resists the action of light. C,H,* C,H,*PO(OH),,154 ABSTRACTS OF CHEMICAL PAPERS. Behaviour and Oxidation of Tetriodoterephthalic Acid and Tri-iododiamidobenzoic Acid. By JACOB LUTJENS (Bey., 1896, 29, 2833-2839).-1t is well-known that, whilst orthoiodobenzoic acid readily yields an iodoso-derivative on oxidation, the isomeric meta- and para-acids fail to do so. This difference in behaviour is pos- sibly connected with the fact that, on occasion, the orthoiodoso-acid acts as a compound having a structure C6H4<!(gE1>0, which the isomeric acids are unable to assume.On this supposition, diorthoiodobenzoic acid on oxidation should yield only a moniodoso-derivative, and in like manner tetriodoterephthalic acid should yield a di-iodoso-acid. 2 : 4 : 6-Triiodo-3 : 5-diamidobenxoic acid is formed when a solution of dimetamidobenzoic acid in sulphuric acid is treated with one of iodine and iodic acid in caustic soda. It crystallises from hot, dilute alcohol in grey, felted needles. Attempts t o eliminate its amido-groups were unsuccessful. The author describes briefly the following salts of tetriodotere- phthalic acid : The ccclcizcm salt, C6I4(COO)~Ca + 2H,O ; the strontium salt, C61,(C00),Sr + 8H,O ; the barium salt, C61,(COO),Ba + 4H,O; the rnugneszurn salt, C,I,(COO),Mg + 6H,O, and the cadmium salt, C6T,(COO),Cd + 4H,O, are readily soluble in water ; the coppe~ salt, C6I4(coo)~cu 4 3H,O, forms blue-green crystals, and is sparingly soluble in water ; the methylic salt, C,I,(COOMe),, crystallises in white needles, melting at 310-3312', the ethylic salt, C,I,(COOEt),, melts at 262*5", and the propylic salt, C,I,( COOPr),, a t 2 39".The chloride, C6T4(COCl),, crys- fallises from chloroform, and melts a t 2'79'; the properties of the latter are in accordance with those of other diortho-substituted benzoic acids, the substance being characterised by its excessive stability towards alkalis and hot water. ~ ~ - ~ o d o s o d ~ - ~ o d o t e r e p ~ ~ t h c ~ l ~ c acid, C6T,( <!(:Fl>O),, is produced when tetriodoterephthalic acid is warmed with a large excess of fuming nitric acid, and is most readily purified by means of its sodium salt.It is a a lemon-yellow powder insoluble in the ordinary media, and has very feeble acid poperties, being precipitated from solutions of its salts by carbonic anhydride. A. L. Addition of Hydrogen Cyanide to Unsaturated Carboxylic Acids, By JULIUS BREDT and J. KALLEN (Annalen, 1896, 293, 338--371).--Ethylic cyamobenxyZmcdonate, CN* CHPh- CH(COOEt),, is prepared by cautiously adding 33 per cent. hydrochloric acid to an alcoholic solution of ethylic benzylidenemalonate mixed with aqueous potassium cyanide, the liquid being well cooled during the operation ; it crystallises in needles melting at 48*5', and yields phenylcyanopro- pionic acid when hydrolysed with baryta. Plmaylcycmopropionic m i d , CN *CHPh*CH,*COOH, is obtained by heating alcoholic ethylic benzylidenemalonate with aqueous potassium cyanide on the water bath, and crystallises from dilute alcohol inORGANIC CHEMISTRY.155 slender needles, melting a t 150' ; the ethylic salt is produced when half the quantity of potassium cyanide and a much larger proportion of alcohol are employed, and forms a colourless liquid, which boils a t 176' under a pressure of 16 mm. The ccclcium and bcc~iuuna salts crystallise in needles containing 3H,O, and the silvey salt is a white, amorphous powder. When phenylcyanopropionic acid is hydrolysed with potash, phenylsuccinic acid is produced ; the anhydride melts a t 150' (compare Spiegel, Annalen, 1883, 219, 30). Ethglic P-cyccnobutyvate, CN* CHMe* CH, COOEt, is obtained on h c at ing ethylic ethylidenemalonate, dissolved in alcohol, with aqueous potassium cyanide for 7 hours at 60"; it is a colourless, mobile liquid having a pleasant odour, and boils a t 105-106", under a pressure of 14 mm.Hydrolysis with baryta converts it into pyrotartaric acid, ~ ~ d v o e c ~ c c n t o ~ c c c t o ~ ~ t v ~ ~ e , CN* C,,H,,O,, is produced when alantolactone (Abstr., 1895, i, 555) is dissolved in alcohol and heated with aqueous potassium cyanide for 12 hours in a reflux apparatus ; it crystallises in silvery scales, and melts at 132'. Hydroalantolic acid nitrile, CN* C,,H,,(OH)*COOH, is obtained in the form of the sodiunz salt, when the lactone is treated with alcoholic sodium ethoxide ; the salt crystallises in stout needles, and yields the lactone when treated with acids.The bc.wiuna and calcium salts are anhy- drous, and the silvey salt is amorphous. The C L ' I I L ~ ' ~ ~ ~ , NH,* CH,. C,?H,,O,, obtained on reducing hydroalantolactonitrile by adding sodium to the boiling solution in absolute alcohol, crystallises from dilute alcohol in aggregates of needles; it melts and decomposes at 1'71", and the plcctinocldovide is a bright yellow substance insoluble in ether and water. Ngd~~onlccntoZcccto~~ecc~i.boxglic acid, C,,H,,O,* COOH, is f ormed when bydroalantolactonitrile is heated on the water bath with alcoholic potash so long as ammonia is liberated ; it crystallises from dilute alcohol in colourless, prismatic needles, melts at 137", and boils a t 250" under a pressure of 14 mm. The sodium, bccvium, and ccclcium salts are anhydrous, and the silvey salt crystallises from boiling water.Ssl ts of hydroalantodicarboxylic acid, OH-C!,H21(COOH),, are obtained by hydrolysing the foregoing lactonic acid with alkalis, but on acidifying the solution, separation of the lactone takes place; the sodium salt is very hygroscopic, and crystallises in small needles insoluble in alcohol. The bccviuna and calcium salts dissolve with difficulty in water, and the lead salt is an amorphous powder insoluble in cold and hot water. 0i.tl~ohydvoxypl~enyZsuccinic acid, OH* C6H,* CH(COOH)*CH,* COOH, is produced on heating an alcoholic solution of coumarin with aqueous potassium cyanide for 6 hours in a reflux apraratus ; when rapidly heated, it melts a t 150", water being eliminated and the anhydride produced, this change taking place at 135' when that temperature is maintained for a considerable period.The aqueous solution develops a violet coloration with ferric chloride ; the cc~lcium and bcwiunt salts are anhydrous. The ~cnlyclvide melts a t 134", and boils at 200' under a pressure of 14 mm, a portion undergoing decomposition ; the ncetgl derivative of the anhydride crystallises from a mixture of chloroform and ether, and melts a t 90'. 31. 0. F.156 ABSTRACTS OF CHEMICAL PAPERS. Condensation of Tannins with Formaldehyde. By C . EMANUEL MERCK (Chem. Centr., 1896, i, 560; from Ber. ii. d. Jahr., 1895, 14-1 9).-By treating plant extracts with formaldehyde in presence of hydrochloric acid, the tannins are easily withdrawn in the form of condensation products, which are named tannofowns.Z'cmno- forma, CH,( C,,H,O,),, prepared by the condensation of tannin with forni- aldehyde, is a reddish-white powder which decomposes a t 230'. It is soluble in alcohol and in dilute alkalis, with the latter forming a yellow or brownish-red solution, from which it is precipitated by acids. In warm, concentrated sulphuric acid, i t clissolves, with production of a brown colour, and on further heating this turns green and then blue. With alcohol, either the green or the blue solution becomes fiist blue and then wine-red. Q u e i ~ c i t ~ ~ . l z ~ a o f o ~ ~ ~ ~ z , CH2(C14131307)2 + H,O, prepared from oak bark tannin and formaldehyde, is a reddish-yellow powder, which blackens at 275'; it is insoluble in water, ammonia, and sodium hydroxide, and the brown colour of its solution in concentrated sulphuric acid is not affected by alcohol.Quebrccchitunnofown, CH2(C,,H,,0,),0 or OH,( C,,H,,O,),O. Xlm f c m ~ tannoform, CH,(C,H1,O7)O, prepared from Rhat'any tannin and formaldehyde with elimination of 4 molecules of water, is a yellowish-brown powder ; its brownish-red solution in concentrated sulphuric acid rapidly tnrns red. JQr~obalccns tannofos*m, prepared from nijrobalan tannin and formaldehyde, is a yellowish-brown powder with properties similar t o those of tannoform, but its solution in con- centrated sulphuric acid, on warming, becomes first green and then black. Like myroloalaii tannin itself, it contains a litlle gallic acid and a considerable quantity of ellagic acid. This tannoform is an excellent protective against decubitus and hypericli,osis, and its effect is very different from that of tannin.E. W. W. Oxidation of Diacetylcitraconfluorescein. By JOHN T. HEWITT and FRANK G. POPE (Bei.., 1896, 29, 2824--2827).-The ethers of citra- confluoresceyn do not yield fluorone compounds when treated with alkaline potassium permanganate solution, owing to the readiness with which they suffer hydrolysis. Diacetylcitraconfluorescein, however, is oxi- dised by a hot solution of chromic acid in glacial acetic acid, yielding a com,pound difficult to purify, but which doubtless has the constitution O < ~ ~ ~ ~ ~ ~ ~ > C ( O H ) * C O O H . It is readily soluble in sodium hy- droxide, yielding a yellow solution ; this darkens on heating, and, if an acid is then added, the hydrox~~uol.o?zecc~~box~Zic ucicl, O<cGH3(oH)>C*COOH --C,H,O' [C:OH:0=1:3:6; C:O:O=1:3:6], is obtained in brown flocks. This acid, if moist, dissolves somewhat readily in acetone, and is deposited from it as a heavy, brown, crystal- line powder; it is very sparingly soluble in dry organic solvents, but dissolves readily in alkalis, and shows no tendency to form a lactone, hence the hydroxyl-group is in the para-position relatively to the carbon atom of the pyrone nucleus.The c~nznzoniun2 salt of the acid yields characteristic red precipitates with various metallic salts, that produced by silver nitrate having the composition C,,H,O,Ag. A. L.ORGANIC CHEMISTRY. 157 The Colour Base (C15HllN)z from Benzylphthalimidine.By SIEGMUND GABRIEL and ROBERT STELZNER (Bey., 1896, 29, 2743-2746. Compare Abstr., 1888, 143).-This substance, the molecular formula and constitution of which hare not yet been ascertained, is con- verted by nitric acid into nitrobenzylidenephthaliniidine (Abstr., 1885, 903, 1231). Chlorine converts the Lase into P-clichloyo-a-cleoxybeia- x d i ~ z o r t l ~ o c ~ ~ ~ ~ 6 0 x ~ Z ~ ~ ~ ~ i c l e , CPhCl,. CO*C,H,* CO*NH,, which can also be obtained by the action of chlorine on deoxybenzoincarboxylamide. It crystsllises in stellate groups of flat prisms, and melts, with evolu- tion of gas, a t 197". The chloro-compound is reduced by hydriodic acid and phosphorus to benzylphthalimidine. When it is heated a t 140" with acetic and hydrochloric acids, benzilorthocarboxylic acid is produced.When the chloro-compound is dissolved in normal alkali and the solutioii gently warmed, crystals of dihydrodiphthalyldiimide (A bstr., 1893, i, 372) are deposited. Concentrated potash (33 per cent.) converts it in the cold into a substance of the formula Ul5Hl,NO2, which is also formed as a bye-product in the reduction of nitrobenzyl- idenephthalide (Abstr., 1888, 143). Finally, the chloro-compound is decomposed, with evolution of ammonia and formation of benzoic and phthalic acids when it is boiled with 10 per cent. potash. Constitution of the Colour Bases of the Triphenylmethane Series. By HUGO WEIL (Rer., 1896, 29, 2677--2678).--A reply to von Georgievics (Abstr., 1896, i, 441, 690), upholding the author's previous statements (ibid., 565).An interesting statement, made in support of the alleged stability of magenta in presence of alkalis, is that, from a solution of rosaniline carbonate (prepared by passing car- bonic anhydride into a suspension of rosaniline in water), sodium chloride precipitates rosaniline hydrochloride, whilst the now colourless solution is alkaline from the presence of sodium carbonate. A. H. C. F. B. Hydroxy-derivatives of Tetramethyldiamidotriphenylme- thane. By EEMIL VOTO~EK (Cltem. Cent,.., 1896, i, 544; from List9 Chem, 1895, 221--237).-The author obtained crystalline leuco-bases of dyes by the condensation of Michler's ketone with various phenols, namely, phenol, catechol, resorcinol, quinol, and pyrogallol. By oxidation of these bases, dichroic solutions of dyes a t e obtained, whilst the ncetyl derivatives on oxidation yield green dyes which turn violet or blue on addition of alkalis.With para-amidophenol, no condensation could be effected. E. w. w. History of Madder Dyestuffs. By CARL T. LIEBERMAN and SIEGFRIED FRIEDLANDER (Ber., 1896, 29, 2851-2854). - Runge (Monogi.. cles Iii*ctpps und d e i . Xyuppj5o&stofe, 1835) maintained that the madder dyes, obtained by Robiquet and Colin, &c., were impure substances, but regarded his o\Fn madder-red and madder-purple as chemical entities. The authors have examined samples of cloth coloured with Runge's dyes, and find that, whilst his madder red was pure purpurin, his madder-purple was impure, although rich in alizarin. Samples of madder-dyeing from various localities were examined, and the results show that those from Avignon contained the largest proportion of alizarin, although contaminated with much purpurin.158 ABSTRACTS OF CHEMICAL PAPERS.The authors point out that the high proportion of alizarin in the French dyes accounts for the ease with which Robiquet and Colin achieved the isolation of pure alizarin. A. L. Pinene. By J. C. W. FERDINAND TIEMANN and FRIEDRICH W. SEMMLER (Beis., 1896, 29, 3027-3034).-The authors now claim to have established the formula CH- CH,- ‘C for the constitu- tion of pinene, having traced the demolition of the hydrocarbon through the following phases. /CH,-CH \CMe2* CHMe/ CH, 00 CMe,*CHMe. 1. Pinonic acid, COOH*CH,* CH< 2. Isoketocamphoric acid, COOH*CH,~CH(CH,*COOH)*CMe,*CMeO. 3.Isocamphoronic acid, COOH* CH,* CH(CH,* COOH)*CMe,* COOH. 4. Hydroxyisocamphoronic acid (salts), COOH. CH,* CH[CH( OH)*COOH]*CMe,* COOH. 5. Isocamphoranic acid, COOH*CH,* CH<CM,, CH(CO0H) co>O, or COO CH-COOH CH,--CH*CMe,* COOH. 6. Dimetbyltricarballylic acid, COOH* CH(CH,*COOH)*CMe,* GOOH, and 7. Hydroxytrimethylsuccinic acid, COOH* CMe(OH)* CMe,*COOH. The widely different conclusion regarding the structure of pinene t o which von Baeyer has been led, is attributed to the employment by that investigator of more vigorous agents in breaking down the mole- cule, leading t o pinonic acid, C,,H,O,, pinoy lformic acid, ClOHl4O5, pink acid, C,H1,O,, and norpic acid, C8H,,0,. The existence of a picean ring (this vol., i, 83) in the two last-named substances is not regarded by the authors as evidence of the presence of this complex in pinonic acid, because the behaviour of pinonic and pinoylformic acids towards oxidising agents differs widely from that of pinic and norpic acids ; moreover, the production of isoketocamphoronic acid, COOH- C H,*iCH(CH,* COOH) CMe,.CMeO, from pinonic acid is difficult to reconcile with the formula COOH* CH,* CH<c,grz>CH* CMeO for the latter substance. Von Baeyer regards isoketocamphoronic acid as having the constitution COOH. CH,* CH( COOH)*CMe; CH,* CMeO, representing isocamphoronic acid by the expression COOH- CH(CH,* COOH)*CMe,*CH,*COOH, but this is scarcely consisteut with the glutaric character of the sub- stance, and with its conversion into terpenylic acid, which is analogous t o the transformation of a-dimethylglutaric acid into 7-isocaprolactone. The authors prefer to regard pinoylformic acid as having the consti- tution GOOH- CH,* CH< I this being in agreement with the production of isoketocamphoronic acid when it is treated I I CH,- CO CMe,*CH* COOH,ORGANIC CHEMISTRY.159 with sodium hypochlorite. When dimethyltricarballylic acid, COOH*CH(CH; COOH). CMe,* COOH, is heated with bromine, the \ Y lactonic acid, C O O € € * C H < ~ ~ ~ o o ~ ~ > O , is formed, and this, when fused with caustic potash, yields oxalic and us-dimethylsuccinic acids. M. 0. F. Condensation Products of Cyclic Ketones : Syntheses in the Terpene Series. By OTTO WALLACH (Bey., 1896, 29, 2955-2966. Compare Abstr., 1896, i, 572).-The synthetical pulegone, C,,H,,O, obtained by condensation of methylcyclohexenone with acetone (loc.cit.), is separated from bye.products by converting it into the semi- ca~bc~zone, which forms two modifications, melting below 100" and at 144", respectively ; the ketone regenerated from these derivatives boils at 94-95' under a pressure of 14 mm., and under atmospheric pressure a t 214-215". The sp. gr. = 0.9123, and the refractive index nD = 1.46732, both a t 20". Representing natural or parapulegone by the formula CMe2: C<co-cH,, 'H2*UH2>CHMe, the structure of the syn- thetical ketone will be either t h a t of pseudopulegone, CH --CH, COMe- CH: C<cH2. CHMe>CH2, 0 C O L C H or of orthopulegone, CMe,: C<CHMe. CH,2>CH2 ; the odour of the new ketone is scarcely distinguishable from that of the natural pro- duct, but in chemical properties they are widely different.Pulegol, C,,H17* OH, is obtained by treating pulegone in ethereal or alcoholic solution with sodium ; it is a viscous liquid, having the odour of terpineol, and boils a t 103-104" under a pressure of 15 mm., and under atmospheric pressure at 215". The sp. gr. = 0.912, and the re- fractive index, nD = 1.4792 a t 20". When the warm alcohol is treated with phosphoric anhydride, the tepyene, CIOHIG, is prodiiced ; this boils a t 173-175", and a t 18" has the sp. gr. = 0.823, and. the refractive index nD = 1.4601. The bemqliclene compound of synthetical pulegone is a yellowish, friable mass, and melts at 83-84", Synthetical pulegone is not the sole product of the action of acetone on methylcyclohexenone.A conzpotcncZ, C',,H,,O, is also formed, and the same substance is obtained when mesitylic oxide is employed; it boils at 179-183" in a vacuum. [With DORRANCE]. - Benzylidenemethylhexenone (loc. c k ) con- denses with acetone t o form the benzylidene compound of synthetical pulegone. BenxyMexcLhg~i.oi,2etcctolu~c~~~~e, CH,Ph* C',H,Me*NH,, is obtained by reducing the oxime of benzylidenemethylhexenone (m. p. 109-llO"), in alcoholic solution, with sodium ; it readily absorbs carbonic anhy- dride, and boils a t 235-245'. The Iqcl~ochlos.ide is solid, the curbc~nzicle crystallises in needles and melts a t 185", and the acetgl de~ivat~ive a t 168". Benxylnaet~~lI~exunoZ (benxylhexuhydi*onz etaweso I>, CH2Ph* C,H,Me* OH, is formed when benzylidenemethylhexenone is reduced in alcoholic solution with sodium ; it crystallises from methylic alcohol in beautiful,160 ABSTRACTS OF CHEMICAL PAPERS. colourless needles, and melts a t 97".Phosphoric anhydride converts it into ~ ~ e x c ~ h y ~ , ~ ~ o r n e t ~ ~ g l ~ ~ o ~ e n e , C14HlS, which boils a t 128" under a pressure of 14 mrn. ; at 20" it has the sp. gr. = 0.99 and its refractive index n,, = 1.5455. I CH,* CH, CO-CH, Biscgclopentenepentanone, I >C : C< I , isobtained by CH; CH, CH, CH, treating pentanone with a conchxaced solution 6f sochum ethoxide ; it boils at 117-119" under a pressure of 12 mm., under atmospheric pressure at 253-254". It has the sp. gr. = 1.0176, and the refractive index nD = 1,52095, both at 20"; the oxirne melts a t 123-124'. The substance is capable of further condensation with benzaldehyde and pentanone under the influence of sodium ethoxide or hydrochloric acid.%cvc lodipentenepentunone. LCH,*dH, GO-C = C-- CH, CH; I CH, >' ' '<cH, AH,*AH,- CH, >CH, is a bye-produccin tge preparatioi of t i e foiegoiig compound, and is separated by means of the volatility of the latter in an atmosphere of steam; it crystallises from methylic alcohol in yellowish needles or leaflets, melts at 76-77", and boils a t 190" under a pressure of 12 mm. It does not yield an oxime. CH,* CHMe CH,* CHMe CHMe- CH, CH,* CHMe, is a condensation product of methyl-3-pentanone-1. It is colourless and without odour, and boils at 127" under a pressure of 13 mm.The oxime melts a t 94", and the alcohol, obtained by reduction with sodium, boils at 121" under a pressure of 13 mm. &scyclohexenehexnone, C,,H,,P, is obtained from the cyclic hexenone and sodium ethoxide ; it is volatile in steam, and forms yellow crystals. The oxinze melts at 146-148". Biscgc lonze t Thy llhexenerne t hy Ihexunone, C,,H,,O , is obtained f rorn methylhexenone and sodium ethoxide, and also by withdrawing the elements of halogen hydride from the compounds C,,H,,ClO, and U,,H,,BrO, produced from methylhexenone and halogen hydride. It boils a t 143-144" nnder a pressure of 10 mm. ; its sp. gr. = 0.9635, and its refractive index nD = 1.4955 a t 20". The oxime melts at 152'. [With OTTO M. Ru~~~].-&scgclanzethylpentenewaeth~Zpe?atanone, I >C:C< I , or I >c:c< I CH,---CO CH,* CH, CH,-- CH, GO-CH, M.0. F. French Oil of Roses. By JUSTIN DUPONT and JACQUES GUERLAIN (Gompt. rend., 1896, 123, 700-702).-The authors have made a pre- liminary examination of two samples of French oil of roses distilled during the years 1895 and 1896. These samples differ considerably from the Bulgarian (Turkish) oil in their general characters, and possess a very much more fragrant smell. The following numbers are given. French, French, Bulgarian 1895. 1896. (average). Sp. gr. 30'/15" ..........., ......... ... 0.8225 0.8407 0.8650 Rotation a t 30' (100 mm. tube). . . - 6" 45' .- 8' 3' - 3' 30' Percentage of stearoptene ... ... . .. 35 26 66013ORGANIC CHEMISTRY. 161 The stearoptene was separated completely from both of the above samples, and melted at 38" in the first case and at 33" in the second.By a series of fractional crystallisations, two products were obtained from it, the one melting a t about 39", the other a t about 24' ; this confirms Bertram's statement that two solid hydrocarbons exist in rose oil, melting a t 20" and 40" respectively, and is opposed to the observations of Markownikoff and lieformatsky (Abstr., 1893, i, 662; comp. also Abstr., 1894, i, 253). The two oils from which the stearoptene had been removed produced rotations of - 10" 30' and - 10°42' respectively. The oils mere heated for 1 hour with alcoholic potash, and the insoluble portion was separated and frac- tionated under a pressure of 20 mm. Four fractions were obtained, boiling at 110-120", 120-125", 125-150', and 15O-1SO0.From the first fraction, an optically inactive liquid mas obtained boiling at 114-115' (20 mm.), having a sp. gr.=0*8859, and possessing the odour of geraniol. It is therefore probably geraniol. From the alkaline liquid obtained in the hydrolysis of the oil, a syrupy acid having a powerful and characteristic smell was obtained by acidifying with sulphuric acid and extracting with ether. This will be studied. The above results point to the presence in the French oil of roses of a powerful lsvo-rotatory ethereal salt which is hydrolysed on prolonged boiling with water. The hydrolysis of this salt in the preparation of the Turkish oil is thought by the author to account for the diminished fragrance of that oil as compared with the products they have examined, which were obtained by one distillation only.A. 0. C. Camphor. By J. C. W. FERDINAND TIEMANN (Beg*., 1896, 29, 3006-3026. Compare Abstr., 1895, i, 426, 675, 678).-a-Camphole- nonitrile, C"* CH2-CH< , is most conveniently prepared by heating camphoroxime (500 parts) with 25 per cent. sulphuric acid (1500-2000 parts) in a reflux apparatus for 15 minutes, the source of heat being removed as soon as action commences; it boils at 226 -2274 and in a decimetre tube a = + 7.5'. When hydrogen chloride is passed into an alcoholic solution of the nitrile, a-campho- lenic acid is produced, along with a certain quantity of isoamido- camphor. CH2- t H CMe2*CMe CH2- FH a-Campholenamidoxim e, NOH: C(NH2)*CH2*CH< first C1Sle;CMe' obtained by Goldschmidt and Zurrer, is produced when arcampholeno- nitrile is heated with aqueous hydroxylamine during several days under pressure; it crystallises in white needles melting at 102', and the hydrochloride melts at 181".CH2- CH a-Camphylamine, NH,* CH,. CH,* CH< I I 3 was obtained by CMe;CMe Goldschmidt and Schulhoff on reducing alcogolic a-campholenonitrile with sodium; it boils at 111-112° under a pressure of 25 mm., and at 194-196' under atmospheric pressure. I n a decimetre tube, a= + 6 O ,162 ABSTRACTS OF' CHEMICAL PAPERS. a-Campholenamide (Abstr., 1895, i, 676) crystallises in lustrous leaflets on adding petroleum to the solution in benzene; dissolved in alcohol, it has [ a ] D = - 4.06'. Although warm, dilute sulphuric acid converts the amide into the sulphate of isoamidocamphor, incautious treatment with the acid gives rise t o dihydrocampholenolactone, with elimination of ammonia.CH2- CH a-Campholenic acid, COOH. CH2* CH< 11 is obtained on CMe;CMe' hydrolysing the nitrile o r the amide with &oholic potash, and is identical with the product formed when P-dibromocamphor is heated with dilute alcohol and sodium amalgam. Prepared from this source, i t has been known as hydroxycamphor, and its formation from P-dibromocamphor leads the author to regard the latter as having the constitution CH-CH,-----CBr PHBr co \ ; when this is reduced, hydroxy- \CMe2*CMe/ \ CH,---CO camphor, CH/-CH,-C*OH, is first formed, passing imme- diately into dihydrocampholenolac t one or a-campholenic acid.a-Cam- pholenic acid boils g t 236O, and, in a decimetre tube, a= + 9' 37', the calcium salt crystallises from alcohol in white needles; the ethylic salt boils at 222--224O, and, in a decimetre tube, a = + 10' 20'. \CMe2*CMe/ a-Dihydroxydihydrocampholenic acid, CH2- CH*OH I CMe,*CMe*OH COOH*CH,* CH< (compare Abstr., 1895, i, 676), was first obtained by Wallach on oxidising crude campholenic acid with potassium permanganate (Abstr., 1892, 1237) ; it is more conveniently prepared, however, by oxidising an ice-cold solution of sodium a-campholenate with 2 per cent, potassium permanganate, added to the liquid during 2 hours. The acid crystallises from water or chloroform, and melts at 144' ; it has [.ID= 58.03'. ca,-yo . 1- Pinonic acid, COOH*CH,*fiU' i n nmJuced along with a-dihydroxydihydrocampholenic acid when a-campholenic acid is oxidised, and is also formed when a-dihydrouydib ydrocampholenic acid is submitted t o dry distillation, water being eliminated, a change which probably involves the formation of an intermediate product =c- -CH I containing the ethylenic oxide group I >0, which undergoes atomic rearrangement into $he residue, ZCH* CO.I-Phonic acid sepa- rates from water in tetragonal crystals, and melts at 98-99', forming a colourless, viscous oil, which boils a t 178-180' under a pressure of 12 mm. ; it has [ u ] ~ = - 21.4'. The o x i m forms white needles, and melts at 147', and the semicuvbccxone crystallises from alcohol, and melts at 2.32'. The acid yields bromoform or carbon tetrabromide under the influence of alkali hypobromite, but the action proceeds with greater difficulty than in the case of inactive pinonic acid ; con-ORGANIC CHEMISTRY.163 centrated sulphuric acid converts Z:pinonic acid into methoethyl- heptanonolide, and the substance obtained from this source appears to be optically active. I n all other properties, I-pinonic acid agrees with the inactive substance obtained from pinene. Isoketocamphoric acid, COMe. CMe,. CH(CH,* COOH),, is obtained alike from a-dihydroxgdihydrocampholenic and E-pinonic acids by the oxidising action of chromic acid; it separates from ether in large, lustrous crystals, melts a t 128-129' (Abstr., 1895, i, 478), and is optically inactive. The oxime crystallises in needles, and melts at 185-186', and the semiccwbaxone at 187'.Isocamphoronic acid, COOH. CMe,* CH(CH,* COOH),, first obtained by Kachler on oxidising camphor with nitric acid, and subsequently by Kachler and Spitzer on oxidising the mixture of products obtained when P-dihromocamphor is reduced with sodium amalgam, is prepared from a-dihydroxydihy drocampholenic and I-pinonic acids by allowing chromic acid to act more vigorously on the substances than is per- mitted when isoketocamphoric acid is required ; in order to separate the acid from terpenylic and terebic acids, it is precipitated with cupric acetate. Isocamphoronic acid melts a t 166-167" ; its ethylic salt boils at 195-200' under a pressure of 36 mm. According to the above expression, isocamphoronic acid contains a double glutaric acid groupiag of the atoms, and, in consequence, yields an anhydride with great difficulty ; prolonged treatment with boiling acetic chloride yields an mhydro-acid which dissolves readily in chloroform, and is so rapidly converted into isocamphoronic acid under the influence of water that it has not been found possible to purify it.The constitution which von Baeyer ascribes to isocamphoronic acid (this vol., i, 82) is not in accordance with this observation; the con- version of the substance into terpenylic acid, which the author has shown to take place under the influence of concentrated sulphuric acid (this vol., i, 91, 158), agrees with the behaviour of a-dimethylglutaric acid when treated with the same agent, y-isocaprolactone being formed. Moreover, the ready conversion of camphor into carvacrol, para- cymene, and metacymene, and, further, the production of trimethyl- succinic acid or its anhydride (1) when camphoronic acid is submitted t o dry distillation, (2) on oxidising camphoric acid with chromic acid (3) on heating trimethylpentanonedioic-acid, COOH- CHMe*CMe,* CO* COOH, and (4) by the ultimate oxidation of camphoric acid with potassium permanganate, indicates the presence in the camphor molecule of one carbon atom to which two methyl groups are attached, and a second carbon atom combined with one methyl group ; furthermore, these two carbon atoms are united directly with one another, becoming separatc d when carvacrol or cymene is"produced from camphor.v M. 0. F. Crystallographic Properties of Substituted Camphors. By JULES MINGUIN (Conzpt.Tend., 1896, 122, 1548-1550).-Dezti*ogyrnte benzylidenecamphor forms rhombic prisms of 11 1' 45' in which b = 1000 and h = 801 *6. The faces observed are m p g3 b* el e2 eh. The crystals being most commonly formed of p rn g3 63 a1 el. Sometimes el and a1 are abnormally developed and p and on disappear. No hemihedral faces a r e observed.164 ABSTRACTS OF CHEMICAT, PAPERS. Lc~vogyi~nte ben,yyl.ide,.~eccc~~~pr~o~ has precisely the same form and likewise shows no hemihedral faces. Bcccemic bennx?lZidenecccmpl~o9. forms monoclinic prisms of 11 9' lo', the inclination of the axes being 25", whilst 6 = 1000 and h = 996.7. The general form is 21 m h1 bl d l , the face 11 being highly developed. AnisyZidenectcmpho~ forms rhombic prisins of 114" 15', b= 1000 h = 297.4.The faces observed are m g1 g3 ccI el e ) b!, 6; being excessively developed, whilst cc1 e1 ef g1 are very small. Me thyllsc6 I ic y Zide necanaph o T . -l'h 0 or t h 0- d e r i vn t i ve of the preceding (para) compound forms monoclinic prisms of 93" lo', the inclina- tion being 23" 13', and 6 = 1000, h = 852.9. The general form is p m g1 cc1 hl e2, the face 91 being very small, whilst h1 is always strongly developed. Ethy~sceZicyZideneccc~~~?~~~~ forms monoclinic prisms of 103' 8', the in- clination being 26", and for b= 1000, h=879*6. The common faces are p m g1 h1 el 63, and of these d g1 hl are not always present. The substitution of more or less complex rxdicles in the CH, groyp of camphor lowers the symmetry, Amongst those that crystallise in the rhombic system, the angles of the prisms do not greatly differ, and in the zone rn there is always an angle of about 160' corresponding with a face g,, The molecdar grouping seems to remain the same, and the ratio of the linear dimensions of the primary form is the most variable element.Racemic benzylidenecamphor and the methyl- and ethyl-salicylidenecamphors differ but little in the zone ph, and the angles of inclination of the prisms are nearly the same. Orthomethplsalicylidenecamphor has less symmetry than the para- isomeride. C. H. B. Dammar Resin. By G. GLTMMANN (A?& Phcwm., 1896, 234, 584 -589).-The resin was extracted in a large Soxhlet apparatus with absolute alcohol, and the alcoholic extract was poured into dis- tilled water, whereon a pure white substance separated; a bitter principle remained dissolved in the water.The pure resin separated i n this way melts a t 100" and dissolves in ether, absolute alcohol, chloroform, benzene, carbon bisulphide, and sulphuric acid ; when destructively distilled it yields a product containing phenolic com- pounds; the ethereal oil obtained by distilling the resin with steam boils at 82', and smells of pepper. DummuroZic m i d , OH*C,,H~70,(COOH),, is obtained by shaking the ethereal solution of the pure resin with a solution of potash (1 : 1000) and precipitating the acid by hydrochloric acid ; it is freely soluble in alcohol, ether, chloroform, benzene, aniline, phenol, sulphuric acid, acetic acid, and carbon bisulphide ; light petro- leum dissolves it very sparingly.The coppel. and potassium salts were analysed, also an cccetgl and a bennxoyl derivative, which appear t o war- rant the above formula for the acid. The ethereal solution from which the acid has been extracted contains a-clamrnurresen, C,,H170, which melts at 65", and dissolves in alcohol, ether, chloroform, sulphuric acid, and carbon bisulphide. The portion of the crude resin insoluble in absolute alcohol is only soluble in chloroform, and constitutes ~-dccrnmc6r+*esen. It melts at ZOO". TheORGANIC CHEMISTRY. 165 following is the percentage composition of the dammar resin examined by the author. Dammarolic acid .............................. 33.0 Water .......................................... 2.5 Ash ............................................3.5 Impurities.. ..................................... 8.0 a-Dammar-resen .............................. 40 . 0 p-Dammar-resen .............................. 22.5 Loss .(ethereal oil, bitter principle). ........ 0.5 A. G. B. Guaiacum Resin. By OSCAR G. DOEBNER and ED. LUCKER ( A ~ c h . Plzcc~m., 1896, 234, 590--610).-The following analysis was made by precipitating the alcoholic solution of the resin with alcoholic potash, which throws down potassium guaiaretate, evaporating the filtrate, dissolving the residue in water, precipitating the guaiaconic and guaiacic acids with hydrochloric acid, and separating them by means of ether, in which the former is soluble. Soluble in alcohol Insoluble in alcohol * Containing :- Ash .............. Gum.. ............Fer cent. Guaiaretic acid., ............. 11.15 Guaiaconic acid ............ 50.00 Guaiacic acid @-resin) ... 11 *75 Residue * ..................... 24.96 {Loss ........................... 3.14 Per cent. ...................................... 2'10 ................................... 9'64 Guaiaretic acid was prepared according to the recipe of Hlasiwetz (Annnlen, 1859, 112, 182 ; 1861, 119, 206 ; 1864,130, 346). It forms white, lustrous laminse and melts at 86'. Analyses of the acid are in accord with the formula C2,,H2*04, not C,,H,,O,; the benxoyl deriva- tive, C,,H2,04Bz, forms nearlycolourless crystals and melts a t 131'. Dry distillation of the acid yields guaiacol, pyroguaiacin, and tiglic aldehyde. Guaiaconic acid (Hndelich, J. pi. Chna., 1862, 87, 321) is a white, amorphous powder and melts a t 74-76". Analyses indicate the formula C20H2405, not C,,H,,O,, for the acid, and since the acid is insoluble in alkali carbonates it cannot contain a free carboxyl group.The dibenxoyl derivative melts at 81-83', and the dincetyll derivative at 61-63'. By destructively distilling the acid, tiglic aldehyde, guaiacol, and pyroguaiacin are obtained, and by fusing it with potash, protocatechuic acid, together with small quantities of volatile fatty acids and phenolic compounds. Guaiacic acid (Hndelich's p-resin; Zoc. cit.) mas not obtained in a pure condition ; the benxoyl derivative, C,,H,,Bz,07,~ is a white, crystal- line powder and melts at 155-158'. By dry distillation of the acid, tiglic aldehyde and creosol were isolated.'' Guaiacum oil " (guccjakol) is prepared by boiling guaiacum resin with sodium carbonate solution, filtering from the resin, which separates on cooling, saturating the filtrate with carbonic anhydride, again filtering, and extracting with ether. The oil is left when the VOL. LXXII. i. n166 ABSTRACTS OF CHEMICAL PAPERS. ether is evaporated; it is somewhat freely soluble in water, and freely in alcohol and ether. By acidifying the alkaline solution after it has been extracted with ether, '' gucciacuna yellow," C,,H2,0i, is pre- cipitated, and may be crystizllised in yellow octahedra, which melt t: 115' and dissolve in strong sulphuric acid with a cornflower-blue colour. A. G. B. By OSCAR G. DOEBNER ( A d z . Pl~cwrn., 1896, 234, 610-613).-Tiglic aldehyde (5 parts), guaiacol and creosol (9 parts, comprised of I mol. of each) were dissolved in glacial acetic acid, strong hydrochloric acid (2 parts) was added, and the mixture heated for 30 minutes on the water bath; the liquid mas then poured into strong hydrochloric acid (250 c.c.), heated for 15 minutes, and finally poured intocold water.The brown resin which separated has the formula C2,H2*04, and is therefore isomeric with guaiaretic acid (see preceding abstract) ; from its forma- tion, the constitution CHMe: CMe* CH [C,H,Me( OMe)( 0 H)] *C,H,( OMe) *OH may be ascribed to it. It is insoluble in water, soluble in alcohol, and dissolves in strong sulphuric acid with a cherry-red colour. A similar resin, of the empirical formula of guaiaconic acid, was obtained by the condensation of tiglic aldehyde with a mixture of guaiacol (1 mol.) and pyrogallol dimethyl ether (I mol.).It does not give a blue coloration with oxidising agents. Finally, a resin, C2,H,,0,, has been prepared from pyrogallol dimethyl ether (2 mols.) and tiglic aldehyde, which dissolves in strong sulphuric acid with a red colour. The view that certain resins may be regarded as condensation pro- ducts of aldehydes with phenols is upheld by these experiments. Synthesis of the Acids of Guaiacum Resin. A. G. B. Guaiacurn Blue. By OSCAR G. DOEBNER (Awl&. PJLrwrn., 1896, 234, GI 4--620).-After enumerating the oxidising agents which are capable of producing guaiacum blue, the author points out that the colouring matter is an oxidation product OF guaiaconic acid, and is best prepared by shaking 100 C.C.of a solution of this acid (10 grams) in 96 per cent, alcohol (I litre) with a solution of ferric chloride (10 grams) in water (3 litres). The blue flocks which separate are rapidly filtered off, washed with cold water, and dried over calcium chloride in a vacuum protected from light. By subsequently washing with benzene, any unaftered guaiaconic acid may be removed. The blue powder thus prepared has the formula C2,H2,06 or C2,HF206, the former being more in accord with its formation from guaiaconic acid than the latter is. It appears that the colour of the blue compound is dependent on the oxygen which it contains in excess of that in the parent guaiaconic acid, this oxygen being in much the same condition as that in which the second atom of oxygen exists in hydrogen peroxide; thus, a number of oxidising agents will bleach the colouring matter, themselves suffering reduction. The blue loses oxygen and is bleached a t 100'.Its solutions in glacial acetic acid and in alcohol are deep blue, but they very rapidly lose oxygen, becoming colourless. This oxygen is probably not eliminated in the form of ozone, since,ORGANIC CHEMISTRY. 167 when it is set free by a dilute acid, it does not liberate iodine from potassium iodide; this is also the case with the oxygen liberated from hydrogen peroxide by a dilute acid. Regarding guaiaconic acid as consisting of a condensation product of tiglic aldehyde, guaiacol, and pyrogallol dimethyl ether, the author constructs a formula for the blue which is built on the lines of that for ccerulignone, the oxidation product of pyrogallol dimethyl ether.In the well-known tests which depend on the formation of guaiacum blue, it is better to use guaiaconic acid itself than to use guaiacum. A, G. B. The Action of Formaldehyde on Aloin. By C. EMANUEL MERCK (Chem. Centy., 1896, i, 561 ; from Bey. ii. d. Jcch~., 1895, 21-23). -By the action of formaldehyde and concentrated sulphuric acid on alo'in, a condensation product, CH,:C17Hl,07, is obtained as an amorphous, tasteless powder, which, on heating above 260', becomes black. It dissolves in dilute sodium hydroxide solution, forming a yellow solution, from which it is reprecipitated by acids. It forms a yellow solution in concentrated sulphuric acid, and a reddish-yellow solution in concentrated nitric acid.Bitter Principles contained in the Leaves of Leucodendron concinnum. By C. EMANUEL MERCK (Chem. Cent?'., 1896, i, 561; from Ber. ii. d. Jahi*., 1895, 3--7).-From the leaves of this plant, which is native to the Cape and of the order of Pyotecccetz, a glucoside ZeucogZycoclkz, C,7H,201, or C,iH44010, may be obtained as a bitter, white powder, by evaporating the alcoholic extract and repeatedly dissolving the residue in alcohol and precipitating with ether. It has a specific rotatory power [a], = - 40.25" and is decomposed by water. By the action of 2 per cent. sulphuric acid a t loo', a brown oil is produced, which, when treated with acetic anhydride, yields white cry- stals and an almost colourless liquid. From this liquid, which reduces Fehling's solution, a phenylglucosa,zone melting a t 181-1 92' can be obtained (&galactose or glucose 2).By further evaporation of the alcoholic extract, a second bitter principle, Zeucochin, may be isolated, which is possibly identical with proteacin, obtained by Meiring Beck from the same plant. Leucodrin, C15Hl,0s, has a specific rotatory power, [a], = - 15-45', and crystalliscs in white prisms which are very sparingly soluble in water, and only slightly so in cold alcohol. OctcccetyZZeucon'.l.ia, C,,H,O,Ac,, which melts at 188-190", is formed by the action of acetic anhydride on leucodrin. (Compare Hesse, Abstr., 1896, i, 495). E. W. W. A Crystalline Bitter Principle contained in Plumiera acuti- folia. By C. EMANUEL MERCK (Chent.CentY., 1896, i, 561 ; from Bey. ii. d. Jdw., 1855, 11-1 3).-This substance, C57H1,O3, + 2H,O, ob- tained by evaporation of the alcoholic extract, melts at 157-158' and forms a colourlesa solution in concentrated sulphuric acid, which, on warming, turns yellow, reddish-yellow, brownish-red, or black. Its solution in concentrated nitric acid is also colourless, but becomes yellow on warming, and, similarly, the solution in sodium hydroxide turns yellow on boiling. This substance cannot be identical with plumieride, which has beeen isolated by Boorsma. E. w. w. E. W. W.168 ABSTRACTS OF CHEMICAL PAPERS. Compounds contained in Radix imperatoriae ostruthium. By C. EMANUEL MERCK (Chenz. Centy., 1896, i, 561 ; from Be?*. ii. c2. Jcch., 1895, S--lo).-In the taproot of this plant three substances have already been found, namely, peucedanin, oxypeucedanin, which the author regards as a homogeneous compound in opposition to the views of Hlasiwetz and Weidel, and ostruthin.The author has obtained a new substance osthin C,,H,,05 which crystallises from dilute alcohol in slender, yellow needles, melts at 199--200°, and is insoluble in water. I n concentrated sulphuric acid, it forms a yellow solution, which, on warming, becomes dark red. I t s solutions in alkalis and ammonia are also yellow. Biacetylosthin, Cl,Hl,0,Ac2 melts at 183-186O. Monoacetylosthin melts at about 171-1 80". I n the original paper, a table of the melting points, solubilities, &c., of these four plant substances is given. E. W. W. Synthesis of Pyridine Compounds from Ethereal Salts of Ketonic Acids and Ethylic Cyanacetate in Presence of Ammonia or Amines.By ICILIO GUARESCHI (Chem. Centr., 1896, i, 601-603 ; from Estr. Mem. Reccle Accncl. Sci. Tovino, ii, %).-By the action of ammonia on homologues of ethylic acetoacetate, an ethereal salt of an amido-acid, NH,*CMe:CMe*COOEt, and an amide of a p- ketonic acid, COMe-UHMe-CO *NH,, are formed. But in the presence of ammonia, or an amine, the cyanacetamide first produced reacts with the P-ketonic acid amide to form a pyridine derivative, the condensa- tion taking place with ease a t the ordinary temperature. I n this way, ethylacetoacetamide and ethylic cyanacetate form an ammonium salt, NH4*N<FE:gFG) >CMe, from which hydrochloric acid liberates an acid compound of a similar constitution, or more probably possessing a.composition represented by the formula, The author has found that the ieactions take place directly between cyanacetamide and &ketonic acid amides or ethereal salts of ketonic acids, and similarly also between ketonic acid amides and ethylic cyan- acetate. The new compounds thus formed have acid properties, yield dyes and, with ferric chloride, give a bluish-violet coloration or precipi- tate. Those derived from ethylic acetoacetate, and containing the group - CH,* C(OH)=, form precipitates with copper sulphnte and acetate, and become coloured by the action of potassium nitrite or of bromine water, whilst those containing the substituted group, - CHMe*C(OH)=, do not give these reactiocs. To all these new substances, the author gives formulz analogous to (I), representing them as up'-dihydropyridine derivatives, and re- garding them also as derived from glutaconimide, When an amine is employed instead of ammonia, the resulting com- pounds contain an alkyl group directly united to nitrogen, and as these also have acid properties, this acidity cannot be ascribed to the presenceORGANIC CHEMISTRY.169 of an imide group, but the presence of a hydroxyl group must be assumed as in the formula, N h f e < ~ ~ ~ ~ ~ $ > C M e (11). Similarly, the compound obtained from methylamine and ethylic methylaceto- acetate is to be regarded as containing a hydroxyl group, since it forms R silver compound, and with ferric chloride gives a coloration, although this is very fugitive.Its formula is therefore written, The constitution of the compounds which do not contain substituted imide groups the author prefers, for the present, to write in accord- ance with the formula (11) rather than with the formula 3-Cyccno-6-I~~d.i~ox~-4-~netl~yl-5-etl~~/l-A3~~-di~~ydi~opy~iCone (Formula (I)), prepared from ethylacetoacetamide, ammonia, and ethylic cyanace- tate, melts at 234-235", and is slightly soluble in cold water. The ammonium and the copper salts, (C,H,N,O,),Cu and C,H,CuN,O,, have been analysed, and the sodium and magnesium salts prepared. 3-Cyano-6-?~~d~ox?/-4-nzetl~yl-A316-dilayd?'opy?'idone or cyanonaethylylutcc- conimide, N<:f)i$gj>CMe, is obtained by the action of ethylic acetoacetate, ammonia, and ethylic cyanacetate ; at 295", it becomes brown, and is charred at 300-304"; it yields a bromine derivative, which is decomposed by water or alcohol.By means of this reaction, the author proved that acetoacetamide is formed by the action of ammonia on ethylic acetoacetate. The ammonium, sodium, barium, silver, copper, and copper ammonium salts were analysed. The author was unable to determine whether the cyanodihydropyridinecarboxylic acid prepared by Held from ammonia and ethylic cyanacetate is identi- cal with this compound. 3-Cyc~no-6-7~yclroxy- 1 -naeth yl-A3~5-dihydropyriclolze or cyanomethylgluta- connzethylinzide (Formula (11)), prepared from ethylic acetoacetate, methylamine, and ethylic cyanacetate, melts a t about 285", and its silver salt was analysed. The 1-ethyl compound or cyanomethyZglutccconethyL imide, which melts at about 242", and the 1-ally1 compound or cyuno- ~~zetlaylglutcccoiaallylimicle, which melts at 222", may be obtained by similar reactions.3-Cfyccno-6-7~ydro~?/-4-nzet~~yZ-5-et~yl-A3~ F-l -dihyd~-opyridone, or methy Z- cyano~zethy~g~utc6co~a~nz~de, prepared from methylacetoacetamide, ammonia, and ethylic cyanacetate, melts at 270-272'. The ammo- nium, sodium, silver ,barium, and copper salts were analysed. 3-Cyuno- 6-hyd~oxy-l : 4 : 5-t~imethyZ-A3~5-di~ayd~~p~3~2'done (Formula (111)), pre- pared from ethylic methylacetoacetate, methylamine, and ethylic cyan- acetate, melts a t 264-265O. With ferric chloride, it first gives a colorntion,andisthenoxidisedtoacompound which meltsat 235". Amido- 6ensoylacefunaicle, NH,* CPh:CH* CO *NH,, which melts at 164-1 65",and cyunophenylglutccconimide, which melts at 280-282", are obtained by the interaction of ethylic benzoylacetate, ammonia, and ethylic cyanacetate.E. w. w.170 ABSTRACTS OF CHEMICAL PAPERS. Stereochemistry in the Piperidine Series, By CARL D. HAT~RIES (Be?.., 1896, 29, 2730--2731).-1t has been already stated that vinyl- diacetonamidoxime, on reduction with zinc and alcoholic hydrochloric acid, yields paramidotrimethylpiperidine. Further investigation showed that this oxime, on treatment with sodium and boiling amylic alcohol. was reduced to an isomeric paramidotrimethylpiperidine, the two amines being easily identified by means of their hydrochlorides, that of the former being generally oily, whilst that of the latter is a fine, crystalline solid.On treating the two bases with nitric acid, two hydroxyalkylamines (hydroxytrimethylpiperidines) are produced, the first being the compound (m. p. 123') obtained by E. Fisher from vinyldiacetonamiiie by direct reduction, the second a compound melting at 160-161". Both these compounds are also produced by the reduc- tion of vinyldiacetonamine (oxytrimethyltetrahydropyridine) with sodium amalgam, and can be separated by fractional crystallisation. The former (m, p. 123') is, however, not a homogeneous substance, but is a mixture of the base melting at 160-161', with a new hydroxytrimethylpiperidine melting at 137-1 38', the two being easily separated by means of their hydrochlorides. Both the compound melting at 160-161', and the mixture (m. p.123') pass, on treatment with sodium amyloxide, into the stable compound melting at 137-138'. This subject will be treated more fully in a paper to be published in the Anncclen. J. F. T. Diphenylindone. By ADOLF DAHL (Be?*., 1896, 29, 2839-2842. Compare Abstr., 1896, i, 146).-When diphenylindone is heated with hydriodic acid and phosphorus during 6 hours at 150-160°, tw$en$- p'opccne, CHPh,. CHMePh, is produced. It distils unaltered a t 365', solidifying t'o a hard, white mass ; no crystalline derivative could be obtained. Triphernyllactic ncid is formed when diphenylindone is fused with potash at a moderate temperature. It crystallises from glacial acetic acid in yellowish crystals resembling those of common salt, and melts a t 189'. Methyl& triphenylacrylc~te occurs in the bye-products obtained in the preparation of diphenylindone (Zoc. cit.).It crystallises from light petroleum in yellow needles, melting at 136O, and yields triphenyl- acrylic acid on hydrolysis. - A. L. Quinolineoxyquinolines. By PAUL COHN (Monatsl~., 1 S9 6, 17, 667-671).-When 2'-chloroquinoline is heated with excess of 1-hydroxyyuinoline, a reaction takes place, the evolution of hydrogen chloride being violent at 165'. The product, C,NH,* O*C,NH,, crystal- lises in yellow needles, and melts at 175" (uncorr,). The yellowish Tylcl~o- chloride, C,,H,,N20,HCl, which is decomposed by water, the yellow pZutinochZo~*ide, C,,H,,N,O,H,PtCl,, and the brownish-yello w 21cclZccdio- chZo?ide, Cl8Hl2N2O,€I,PdC1, + H20, were also prepared.2'-Chloroquinoline also reacts with 3-hydroxyquinoline, but less readily. The product, isomeric with that described above, crystallises in yellowish needles, and melts at 120' ; the yellow plcctinocldoricle, C,8H,,N,0,H,PtCl,, was also prepared and analysed. Its constitution has not yet been definitely ascertained. C. F. B.ORGANIC CHEMISTRY. 171 The Isorosindulines. By OTTO FISCHER and EDLJARD HEPP (Bey., 1896, 29, 2752--2'760).-The authors propose to retain the name isorosinduline in the sense in which they have previously (Annalen, 272, 306) employed it, and to apply the term pseudorosinduline to the compounds called isorosindulines by Kehrmann (Annnlen, 290, 3 47). They have examined the isorosinduline prepared by Nietzki and Otto (Abstr., 188S, S43) from quinonedichlorodiimide and phenyl- P-naphthylamine, in order to ascertain in what respects it is analogous to the safranines.action of nitrosodiphenylamine on P-naphthylphenylamine. The hydro- clZZoi~%Ze crystallises in long, flat prisms with a copper-red lustre, The nitmte crystallises well in thick prisms, which have a metallic lustre. The base also forms crystals, which have a coppery lustre. It melts a t 169-171', and imparts a blue colour to sulphuric acid. Concentrated hydrochloric acid at 230-240' converts the base into iso?~osindone, ~O:C,H3<Sph>CloH, This substance is best prepared from nitroso- phenol and P-naphthylphenylamine, and is a weak base, the h~d~oclzloride of which dissociates in aqueous solution. The free base crystallises in prisms, which have a dark bronze lustre, and, melt at 223-224'.With ferric chloride, the hydrochloride forms a characteristic double snlt, crystallising in golden yellow needles. -7- ,I\ - /lydyoxyiso?.osindone, 0: C,H7(0H)<Nph>C10HG, is formed when isorosindone is boiled with concentrated alcoholic potash ; it crystallises in red needles, which have a bronze lustre. The potccssiunla scclt is readily soluble in water, sparingly in potash. iMethoxyisos.osindone crystallises in needles, which melt a t 2 74', and have a greenish lustre. by the action of aniline and its hydrochloride on isorosinduline in alcoholic solution. The hycZi*oclZZovide crystallises in prisms, with a greenish lustre. The free base forms brownish-red needles, which have a bluish lustre and melt a t 151-152'.Pheny~c6ccnil~c~oisoros~n- dziline is formed when isorosinduline is heated at 150-160° with aniline and aniline hydrochloride, and crystallises with 1 molecule of benzene in needles which have a dark bronze lustre. Anilicloisorosin- cloize is formed when anilidoisorosinduline is heated with hydrochloric acid at 160-170"; i t crystallises in lustrous needles, with a bronze lustre. Ethylisos.osindzclil?,e, NH:C,H,<&>Cl,H6, is obtained by the reaction of quinonedichlorodiimide and P-naphthylethylamine. The hyd~*ochlo~icZe forms short, flat, red prisms ; the nnitmte is less soluble than the hydrochloride, and crystallises in dark needles, which have a bronze lustre. Etlkylisoyosindone forms slender, brownish-red needles, and melts at 178' ; the hydrochlos.itZe crptallises in dark brown prisms.172 ABSTflACTS O F CHEMICAL PAPERS.Isorosinduline is converted by the action of nitrous acid into n diazo-compound. When this solution is treated with alcohol, nitrogen is evolved, and phenylnaphthophenazoiiium chloride is produced identical with the substance formed when rosinduline itself is treated in a similar manner. When the diazo-solution is treated with alcohol, and then, after a time, with a large excess of ammonia, rosinduline is formed, so that by this reaction the isorosinduline can be converted into rosincluline. A. €3. Azonium Compounds from Aposafranine, Rosinduline, and their Isomerides. By FRIEDRICH KEHRMANN and W. SCHAPOSCHNI- KOFF (Be?.., 1896, 29, 2967-2972. Compare this vol., i, 107.)-In consequence of Fischer and Hepp's publication (preceding abstract), the authors describe the following compounds which they have pre- pared. An additive compound of phenylphenazonium chloride and ferric chloride, C,,H,3N,Cl,FeC13, was prepared by the method previously described.If prepared from pure aposafranine, i t crystallises readily from its acetic acid solution, otherwise a black, tarry mass is obtained ; the crystals are light reddish-brown, thick needles, and melt at 186'. It is readily soluble in water, and in boiling alcohol and acetic acid, but practically insoluble in a saturated ferric chloride solution, in 23 per cent. hydrochloric acid, and in ether. PJLen~l~lLencLxoniunz nitmte, C,,H,,N,*NO,, was prepared from a cold, aqueous solution of the ferric chloride compound ; this was rendered slightly alkaline by adding cold, dilute ammonium carbonate solution drop by drop, filtered into a few drops of dilute nitric acid, and then saturated with pure sodium nitrate.After the lapse of several days, the nitrate separated in reddish-brown crystals. It crystallises from alcohol in thick cubes, melts at 192O, and is readily soluble in water and alcohol. Phenylnaphthophenazonium chloride forms an additive compound with ferric chloride, which can be obtained by deamidating either rosinduline or Nietzki and Otto's isorosinduline, and has already been described. PJ~en?lZncc~J~t?~op~,encLxon~u~ n i t m t e , C,,H1,N2*N03, recrystallised from alcohol, forms orange-yellow plates, melts a t 225O, and is moderately soluble in cold water.PJ~eoayliZcc2~J~tJ~opJ~enaxoniunz plcctinoclJovicZe (C,,H,,N,),PtCl,, is a brick-red, crystalline powder, practically insoluble in water. Pl~ennyZ?zcc2~J~tlrop~e~zccxoniurn diclwonznte, (C,,~i5N,),Cr,07, is also a red, crystalline powder which is insoluble in water. The iodide, C,,H,,N,T, crystallises from alcohol in black plates. J. J. S. Some Phenyltriazoles. BY ASTRID CLEVE (Be?.., 1896, 29, 2671--2677).-This paper has been published earlier than mas originally intended on account of the work done on the same subject by Young (Trans., 1895, 1063). The oxytriazoles that Widman has prepared (Abstr., 1 S9 6, i, 629) by treating a-acidylphenylsemicarba- zides with dilute alkalins hydroxides, were converted into chlorotria- zoles by heating them for 3-5 hours a t 150" in a sealed tube with the calculated quantity of phosphoric chloride, together with a littleORGANIC CHEMISTRY.173 phosphorus oxychloride. The chlorotriazoles were then reduced to triazoles by heating them for about 3 hours at 150-160" in a sealed tube with excess of concentrated hydriodic acid (sp. gr. lm'7)and a little i,ed phosphorus. The triazoles are weak bases ; the chlorotriazoles, on the other hand. sel2orn form hvdrochlorides. .I N = CC1 CPh:N 3-C'l~lo~o-1 :5-diphenyZ-l: 2 : .i-triaxoZe, XPh< I , melts at 96' ; the reddish-yellow platinochloi-icle decomposes at 195". 1 : 5-Diphenyl- triazole melts at 91', its yellowish-white pici*ate at 139' ; the platino- chloride crystallises with 4H,O (and also with 3H,O + 2HCl1). 3 : 1 : 5-Methoxy/clip?~e,zyZt~ic~xoZe was prepared by treating the hydroxy- triazole in alcoholic solution with sodium methoxide and methylic iodide ; it melts at 88', and has basic properties.3-C?~Zo~o-l-pl~enp!- 5-isopopplt~inxoZe melts at 56", the tviazole itself at 58'. ~-C?L~O~*O-~- p l ~ e ~ z ~ l - 5 - ~ ~ o p ~ l t r i c ~ x o Z e and the corresponding ti*iaxole were obtained as oils; the yellowish-white pic~ccte of the latter melts at 128-130', and the platinocl~loride crystallises with 4H,O. 3-Cldo~o-5-butyl- pl~eiayllt~iaxole and the corresponding triazole are also oils. C. F. B. Asymmetric Nitrogen (IV.) Isoconiine. By ALBERT LADENBURG (Bey., 1896, 29, 2706--2709).-The existence of isconiine having been called in question, the author now brings forward a series of experi- ments, showing that it is in reality a homogeneous substance, and not a mixture of d- an6 s*-coniine.The platinochloride of the compounds, produced by the distillation of d-coniine hydrochloride with zinc dust, behaves differently from the platinochloride of a mixture of d- and s*-coniine ; in the former case, a crystalline residue remains after treatment with a mixture of alcohol and ether, whilst in the latter the platinochloride entirely dissolves. 'This insoluble residue, which is the platinochloride of isoconiine, must therefore be free from d- and s--coniine. Similarly, the rotation of benzoylisoconiine is very different from that of the benzoyl compound of a mixture of d- and r-coniine. Finally, no pure cl-coniine (rotatory power 18.3') could be isolated from isoconiine, which would be the case were it a mixture of cl- and ?*-coniine.J. F. T. Tropinic Acid. By GIACOMO L. CIAXICIAN and PAUL G. SILBER (Bei-. , 1896, 29, 2975-2976. Compare Abstr., 1896, i, 513).-The authors state that the aurochloride of the base, previously described by them as obtained by the action of hydriodic acid and phosphorus on tropinic acid, has proved not to be identical with a-methylpyrolidine auro- chloride, as was at first thought possible. The base is probably a trialkylamine, obtained by the complete decomposition of the tropinic acid molecule. J. J. S. Attempts to Determine the Constitution of Tropanine and Granatanine Bases by Cryoscopic Methods. By FELICE GAEELLI (Be?.., 1896, 29, 2972-2975. Compare Abstr., 1894, i, 157; 1895, ii, 205).-The author has previously shown that similarly-constituted174 ABSTRACTS OF CHEMICAL PAPERS.substances can form solutions, which, on cooling, yield abnormal results for the depression of the freezing point. This phenomenon can be made use of in solving questions as to the constitution of different compounds. As regards tropanine and granatanine, the author is able t o show tha.t their cryoscopic behaviour agrees with the constitutions already deduced from chemical considerations. Both are to be re- garded as containing two nuclei, like naphthalene, the two rings, however, being joined respectively in the para- and meta-positions in the two compounds. Normal freezing point depressians were obtained with the two com- pounds in benzene and also in diphenyl solutions, but abnormal results in naphthalene solutions.Special precautions were taken on account of the readiness with which the bases combine with water and carbonic anhydride. J. J. S. Alkaloids contained in the Seeds of Blue and White Lupines. By SHERMANN Dams (Chew,. Centv., 1896, i, 708-709 ; from Apoth. Zeit., 11, 94-95).-A comparison of the alkaloids obtained from the seeds of Lupinus angustifolius and L. ccZbus, respectively, led to the following conclusions. The composition of these compounds or Zupcc- wines is represented by the formula, C,,H,,N,O, ascribed to them by Siebert (Abstr., 1892, 223), and by Soldaini (Abstr., 1896, i, 193). The lupanine from L. ulbus described by Soldaini as deliquescent is identical with the liquid lupanine from the same plant, and also with the liquid alkaloid obtained by Siebert from L.nngust~olius. The identity of these compounds was proved by comparison of nu- merous salts, both chemically and crystallographically. This alkaloid, which the author names clext~olzq~nnine, can in reality be readily obtained in a crystalline form, separating from light petroleum in colourless needles, which melt a t 44", and whose aqueous solution is dextroyotatory. Soldaini's solid lupanine from 1;. Q Z ~ U S , which melts a t 99' and is optically inactive, has a composition represented by the formula Cl5H,*N2O, or C,,H,,N,O,. By converting it into thiocyanate, it may be separated into two components, dextro- and laevo-Iupanine respec- tively. The free bases obtained from these salts form colourless noedles which melt at 44', and re-form the original inactive lupanine when mixed in equal parts.The dextro-component is identical with the dextro-lupanine obtained from blue and white lupines. None of the groups OH, OMe, CO, or COH, is present in lupanines. By the action of bromine on dextrolupanine hydrochloride in alcoholic solution, two new bases, C,H1,NO and C7HllN0, are obtained, each of which contains a hydroxyl group. The constitution of lupanine is, therefore? probably represented by the foymula C,Hl,N*O*C7Hl,N. E. w. w. The Alkaloids of Corydalis. (By ERNST A. SCHMIDT (Arcl~. Yharn2., 1896, 234, 489-491. Compare the following abstract).-- Corydaline and corybulbine behave towards iodine in a similar manner to canadine (Abstr., 1894, i, 479).The details of the experiments are given in the following abstract. A. H.ORGANIC CHEMISTRY. 175 The Alkaloids of Corydalis Cava. By H. ZIEGENBEIN (Arch. Pharna., 1896, 234, 482-53'7. Compare the preceding abstract).-The alkaloids were obtained from Corydalis cava by the method described by Freund and Josephi (Abstr., 1894, i, 100). The author finds that the formula of corydaline is most probably C,,H,;NO,, in agreement with Freund and Josephi, whereas Dobbie and Lauder (Trans., 1892, 605) have proposed the formula C,,H,,NO,. The hydrochloride could not be obtained crystalline. The hydrobromide and hydriodide are white when pure, but become yellow when exposed t o the air. The nitrate crystallises in lustrous tablets melting at 198". The auro- chloride, ( C,,H,7N0,,HC1),, AuCl,, crystallises in very characteristic rosettes of needles melting a t 207".A compound of the normal formula could not be obtained. Hemipinic acid was obtained by the oxidation of the alkaloid, the result previously published by Dobbie and Lauder (Trans., 1594, 57) being thus confirmed. When corydaline is treated with iodine and alcphol, it is converted into cZel~~d~oco~~ydc~Zi.lze hychiodide, C,,H,,NO,,HI, 4 atoms of hydro- gen being removed from the molecule. This substance crystallises with 2H,O and forms lustrous, pale yellow needles, The corresponding iuycli*ochZoi*ide, C,,H,,NO,,I€Cl + 4H,O, crystallises in yellow plates and prisms. The c~u~ocldo~~ide has the normal formula and melts a t 21 9". The pZcctinochZoi*icZe crystallises in long needles containing 6H,O. The It,ycZvobTonaide crystallises in yellowish-brown needles, and softens a t 126O, melting at a slightly higher temperature. The hyds*oyen stcZ2Accte separates from hot water in yellow, prismatic crystals. When the hydriodide is treated with chloroform and caustic soda, an additive compound, C,,H,,NO,,CHCl,, is formed, which crystallises from chloroform in almost colourless tablets, melts at 162-163", and does not lose weight a t 100". A compound with acetone was pre- pared in a similar manner but could nok be obtained crystalline. This substance serves as a convenient source for the salts of the base, since it is readily decomposed by dilute acids, acetone and the corresponding salt of the base being produced. Dehydrocorydaline also appears to form a hydropolysulphide when its hydriodide is treated with yellow ammonium sulphide. The free base has been obtained in yellow crystals but only in extremely small quantity. When dehydrocory- daline is reduced, it is converted into a base which has the composition and melting point of corydaline and also gives many of the same reactions ; it, however, forms a normal ntwochloride, 0,,H,7N0,,HAuCl, + 4H,O, which crystallises in slender, pale yellow prisms. Dehydrocorydaline, like coi-ydaline itself, contains four methoxy-groups, and therefore has the formula C,,H,,N(OMe),. Bulbocapnine is not acted on by iodine in a similar manner to cory- daline. The methiodide melts at 235-240", whereas Freund a n d Josephi give the melting point 257". When treated with acetic anhydride, the alkaloid is converted into the tiicccetyl derivative, which crystallises in white needles and yields a crystalline IqcZi*ocl~Zo~*ide and ~~Zati~zocJ~lo~~icle which appear to have abnormal composit,ions. The iaitmte crystallises in yellow needles. C18H13N (OAC)31176 ABSTRACTS OF CHEMICAL PAPERS. Corycavine melts at 216-217" (214-215', Freund and Josephi). It appears to have the formula C,,H2,NOG, and not C,,H,,NO, as stated by Freund and Josephi ; t h i s also agrees with the composition of its salts. The Iqclvochloi*icZe, C2,H2,NOG,HC1, crystallises in compact needles and the pZcttinoc?~lo~ieZe, (C2,H2:,N06),,H2PtCI, + 3H,O, in pale yellow granules. The I~ph*ochlo~ide crystallises in yellowish prisms, and the plccti~aocl~lo~~icle crystallises with 3H,O. Iodine acts on the base as it does on corydaline, but the product has not been obtained in sufficient quantity for analysis. The alkaloid does not appear to be affected by iodine. Corybulbine, C,,H,NO,, melts at 238-240". A. H. Erythrophle'ine. By ERICH HARNACK (As-cli. PIiccs*sn., 1896, 234, 561--570).-The author has recently examined a sample of '' Eythro- p!le%a ?~ycl~oc?~lo&um" prepared by E. Merck, which yields a base differing in several important points from that previously investigated (Harnack and Zabrocki, Avc?~. expev. Path. Phcwm., 15). The question whether the alkaloid was in each case obtained from a parent bark of the same species (Erptl~s*ophleunz.deunz guineense) remains unsettled. The commercial hydrochloride is a fine, bright yellow, amorphous powder which is hygroscopic, and gradually agglomerates to a dry, solid mass when kept; it dissolves freely in cold water, and the solution has a tendency to froth. The base itself is precipitated by alkalis from the solution of the hydrochloride ; it is freely soluble in alcohol and ether, soluble in amylic alcohol and ethylic acetate, and insoluble in light petroleum ; its crystallisation has not been accom- plished. The platinochlosdcle and the bismuthoiodicle are described and were annlysed, but a decision could not be made between the formulz C,,H,,N07 and C,,H,,N07 for the base. When the hydrochloride of the base is heated with hydrochloric acid (38 per cent.) in a reflux apparatus, i t undergoes hydrolysis, form- ing e?ytlwoplLZeic cccicl, C27H,,O8 or C,7Hi2OS, and methylamine ; the acid is not decidedly crystalline. Serum-albumin Crystals. By A. MICHEL (Chenz. cent^. , 1896, i, 757-758, from Yes4. physiol. med. Ges. TVu~zbu~g, 29, No. 3, and Cent?*. med. Wiss., 1896, 152--153).-The crystals were prepared from horse's blood serum. An equal volume of saturated solution of ammo- nium sulphate is added to the serum, and the globulin which is thus precipitated is filtered off. To the filtrate, ammonium sulphate solution is added until it just gets cloudy. The crystals of albumin sink, and are purified by repeatedly dissolving them in water and precipitating by ammonium sulphate ; they are doubly-refracting, hexa- gonal prisms about a centimetre long ; they are coagulated by heat at 51--53'without change of form, but their doublerefraction and solubility in water is lost. They contain C, 53.1 ; H, 7.1 ; N, 15.9 ; S, 1.9 ; 0, 22, and ash, 0.22 per cent. The specific rotation is about - 61". AUGUST G~RBER adds a note that, among other animals, the blood- serum of the rabbit was the only one that yielded crystals. Crystals are best obtained from horse's serum, in which the amount of globulin is small. W. D. H. A. G. B.

ISSN:0368-1769    

DOI:10.1039/CA8977200133

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年代:1897

数据来源: RSC

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138 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Nascent Hydrogen. By R. FRANCHOT (J. Physicccl Chern., 1896, 1, 75--80).-Ferric sulphate was reduced in an electrolytic cell, using platinum as the cathode, and pure zinc, cadmium, or copper as the anode. As, on analysis, it was found that the reduction at the anode was equal to or even greater than that at the cathode, it became evident that zinc, cadmium, and copper reduce ferric sulphate directly. This was further confirmed by adding zinc, cadmium, and copper, to different portions of a carefully neutralised solution of ferric sulphate, when in all three cases considerable quantities of ferrous iron were formed. It appears, therefore, that, in the reduction of ferric salts in acid solutions by metals, there is a direct reduction by the metal and an indirect reduction due to the action of the acid on the metal.Action of Sulphuric Acid on Iodine and Iodic Acid. By PAUL CHRI~TIPN (Compt. ?*end., 1896, 123, 814--1316).-When iodic acid is dissolved in sulphuric acid a t ZOOo, there is slight decomposition, and the crystals that separate on cooling are yellowish, but if some fuming nitric acid is added to the hot liquid, the crystals are white. They retain small quantities of sulphuric acid when dried on porcelain, but, if powdered and again dried, they contain 99.6 per cent. of iodic anhydride; this has not previously been obtained in a crystalline form. When the solution of iodic acid in sulphuric acid is heated at 250-260°, oxygen and iodine are liberated, and a yellow, amorphous precipitate is formed which is instantly decomposed by water into iodine, iodic acid, and sulphuric acid.With prolonged heating, the liquid becomes black, and then, with extreme slowness, it deposits yellow crystals, which can also be obtained by dissolving iodine in a H. C.INORGANIC CHEMISTRY. 139 hot solution of iodic acid in sulphuric acid. These crystals are decom- posed by water in the same way as the amorphous products. The ratio of iodine t o oxygen is 5.291, and of free iodine to iodine present as iodic acid 1.506. The crystals seem to have the composition 2S03,H,0,2T,0, ; they are decomposed by water in accordance with the equations 3120, + H,O = 2I,O, + 2HI and 1205 + lOHI = 61, + 5H,O, the final result being 51,0, = 3I,O, + 21,. Ogier found that the action of ozone on iodine converts it into a yellow powder, which is decomposed by water in the same way as the compounds described by the author.C. H. B. Ozone and Phosphorescence. By MARIUS OTTO (Compt. rend,, 1896, 123, 1005--100'7).-Whilst ozonised air was being aspirated with a water pump, it was observed that the water became luminous, and retained its luminosity for five or six seconds. Flasks filled with the issuing water were, in fact, distinctly luminous. It was found that, when water is shaken with ozonised oxygen, the phenomenon of luminescence can be reproduced five or six times and then ceases, but is observed again with the same quantity of gas if a fresh quantity of water is introduced. Increase or reduction of pres- sure has no appreciable effect on the luminosity.With alcohol of 90°, the luminescence is feebler but more persistent ; with benzene, it is very feeble, and the ozone is completely absorbed or decomposed. Thiophen yields abundant luminous vapours, and is the only com- pound t h a t showed this peculiar phenomenon. With milk, the phos- phorescence is much more intense than with ordinary water, and with urine, it was more intense than with any other compound examined. On the other hand, water carefully freed from organic matter showed no phosphorescence, even with highly concentrated ozone, and it follows that the phosphorescence observed with ordinary water is due to the action of the ozone on the vegetable or animal matter present in it. C. H. B. Action of some Hydrogen Compounds on Thionyl Chloride.By J. ADOLPHE BESSON (Compt. rend., 1896, 123, 884-8S6).-Alu- minium bromide reacts vigorously with thionyl chloride, the solution, when cooled, depositing crystalline double compounds of aluminium chloride and bromide with thionyl chloride ; on distilling this under reduced pressure, thionyl bromide, solidifying at - 52', is obtained, but the yield is much smaller than is obtained by the method pre- viously described by the autbor (Abstr., 1896, ii, 358). Hydrogen iodide reacts vigorously with thionyl chloride, according to the equation 2SOC1, + 4HI = 4HC1+ 21, + SO, + S, even when cooled by a freezing mixture. Hydrogen sulphide reacts slowly with thionyl chloride, accord- ing to the equation 2SOC1, + 2H2S = 4HC1+ SO, + 3S, when cooled in a mixture of ice and salt, whilst at higher temperatures the main action is represented by the equation 2SOC1, + H,S = S,C1, + SO,+ 2HC1.Gaseous hydrogen phosphide a t ordinary temperatures causes an evolu- tion of hydrogen chloride, t b e liquid, after some time, forming two140 ABSTRACTS OF CHEMICAL PAPERS. layem, the upper of which, on distillation under reduced pressure, yields, first, thionyl chloride, then phosphoryl chloride, and, finally, thiophosphoryl chloride, PSCl, ; a syrupy liquid from which no definite compound can be obtained remains in the retort. The lower layer is viscous, and contains chlorine, sulphur, phosphorus, oxygen, and hydrogen. It yielded no definite results on analysis. A. C. C. Densities of Nitrogen, Oxygen, and Argon, and the Composi- tion of Atmospheric Air..By ANATOLE LEDUC (Compt. rend., 1896, 123, 805-807).-The author's determination of the density of nitro- gen prepared by chemical methods gives 0.9671 as compared with air. Oxygen obtained by electrolysis of a solution of potassium hydroxide gives the number 1.10523, which is slightly lower than that previously given. The density of argon calculated from the density of air, and the constant proportion (0.0119) of argon in it, is 1.376, or 19% with reference t o hydrogen. The weight of a litre of oxygen at 0" and normal atmospheric pres- sure is 1.4293 grams ; of nitrogen, 1,2507 grams; and of argon, 1.780 grams. The composition of air by weight is, nitrogen, 75.5 ; oxygen, 23.2 ; argon, 1.3 ; and, by volume, nitrogen, 78.06 ; oxygen, 21.0 ; and argon, 0.94.C. H. B. Presence of Nitrites in the Air. By GEORGE DEFBEN (Chena. News, 1896, 74, 240--241).-Continuing these investigations (com- pare this vol., ii, 94), air tightly corked up for 12 to 24 hours in large bottles of over 8 litres capacity along with 100 C.C. of water, and occa- sionally shaken, yielded up all its nitrites to the water. Determi- nations made in this way showed that the presence of human beings in a room increases the proportion of nitrites in the air, and confirmed the similar effect of burning gas already noticed. Air from the lungs blown through water gave no evidence of nitrites ; this, however, is not considered conclusive evidence of the absence of nitrites in expired air, inasmuch as air that yields nitrites when exposed over water, does not yield them when bubbled through ivater, this being attributed to the oxidation of the nitrites to nitrates by the large preponderance of oxygen in the gaseous mixture.Like previous investigators, the author finds the proportion of nitrites and nitrates in the air increased by thunderstorms, and reduced, by washing out, by rainstorms. D. A. L. Transformations of Pyrophosphoric Acid. By MARCELLIN BERTHELOT and CUSTAVE ANDRB (Compt. rend., 1896,123,776-782).- A solution of pyrophosphoric acid containing 15.6 grams of phosphoric anhydride per litre was prepared by the action of hydrogen sulphide on lead pyrophosphate, and was allowed to remain a t the ordinary tempe- rature, the proportion of pyrophosphoric acid being determined from time t o time (this vol., ii, 158).Titrations with tropeolin and phenol- phthalein showed that the solution contained no metaphosphoric acid, and that none of the latter was formed during the course of the experi- ments. One series of the experiments gave the following results.INORGANIC CHEMISTRY. 141 Days ........................ 2 5 10 19 52 89 110 121 Percentage of pyrophos- phoric acid remaining 91 87 83 76.5 69.5 58 49.5 43.1. The conversion of pyrophosphoric into orthophosphoric acid pro- ceeds continuously, but is very much slower than the hydration of metaphosphoric acid. Experiments with a solution of half the con- centration gave similar results, and showed that the rate of change increases with the concentration. Similar results were obtained with pyrophosphoric acid prepared by the action of hydrochloric acid on silver pyrophospha t e.I n order to ascertain whether pyrophosphoric acid can be obtained by the direct dehydration of the ortho-acid, some of the latter was heated and weighed from time to time, and when the ratio of phos- phoric anhydride to water was 1 : 1.55, the product contained 56.4 per cent. of the phosphorus as pyrophosphoric acid, 29.8 per cent. as the ortho-acid, and 13.8 as the meta-acid. It follows that some metaphos- phoric acid is formed even before all the ortho-acid has been converted into the ppro-acid, and, during the heating, a condition of equilibrium is established between the three acids. When the beating is carried further, the phenomena become very complex, owing to the polymeri- sation of the rneta-acid.During the heating, there is a notable vola- tilisation of the solid matter, which, however, only becomes distinct when the meta-acid begins to form. C. H. B. Effect of the Presence of Boric Acid in Glass and Enamels. By L. GRENET (Compt. ?*end., 1896, 123, 891-$93).--When boric acid is added to glass and enamels, it increases their toughness and fusibility, and modifies their coefficient of expansion, sometimes increasing and at other times diminishing it. When increasing quantities of boric acid are added to glass, the coefficient of expansion at first diminishes and then increases, finally approaching that of boric acid itself. Tables are given showing the coefficients of expansion of mixture8 of the oxides of sodium, lithium, zinc, and lead, as also of white glass and bottle glass, with increasing quantities of boric acid.The amount of boric acid that can be added to glass without causing devitrification, on the one hand, or the separation of the added boric acid, on the other, depends on the nature of the metallic oxides and the proportion of silica contained in the glass, as well as on the rapidity with which the latter is cooled. A. C. C. Combustion of Illuminating Gas on Cooled Surfaces. By FRITZ HABER and A. WEBER (Bey., 1896,29,3000-3006).-According to Lewes (Abstr., 1892, 407), appreciable quantities of unburnt gas arise from the combustion of illuminating gas on cooled surfaces ; the authors, however, consider that this result is due to an insufficiency of oxygen, and have, therefore, repeated the investigation.They state the results of numerous experiments carried out with a Tech gas-burner and with various forms of gas-stove, and appear to arrive a t the same conclusion as Lewes. An explanation of the presence of unburnt gas is put forward in the paper. M. 0. F.142 ABSTRACTS OF CHEMICAL PAPERS. The Development of the Soda Manufacture and Allied Indus- tries in the last 25 Years. By ROBERT W. HASENCLEVER (Bey., 1896, 29, 2861--2877).-This period stretches roughly from the development of the ammonia-soda process to the realisation of an electrolytical method for the preparation of soda. The paper under review contains very brief notices of the more important innovations during this period, and gives references to sources where details of the methods introduced may be found .SzcZphzc~ic Acid manzcfactu~~e,--Pyrites is still the chief source of the sulphur. The German ore, the consumption of which has remained fairly constant, contains zinc, and this is recovered from the roasted ore by an electrolytical method. Spanish ore is more and more imported into Germany; 1 ton of it yields 610 kilos. of iron oxides, 34 kilos. of copper, 294 gram8 of silver, and ga gram of gold. Some works are erecting blast-furnacesfor smelting the iron oxides, which they find a diffi- culty in selling. A successful method of utilising zinc blonde for the manufacture of sulphuric acid has also been worked out. I n the con- struction of the leaden chambers, of the acid pumps, and of other appa- ratus, great advances have been made, the chemist having called in the engineer to his aid.Lunge, guided by some of his researches, has even proposed to substitute earthenware towers with perforated plates for the leaden chambers. The chamber acid is still concentrated at first in leaden pans, the final concentration being carried out, as a rule, in platinum vessels on the Continent, whilst in England glass vessels are still largely used. Lunge has patented a method by means of which a concentrated acid is made, by cooling it to about -20°, to yield crystals of H,SO,, a weaker acid beng left behind. Sulphuric anhydride is now made on the large scale, and cheaply; the best way is to obtain a solution of sulphurous anhydride by passing through water the gases given off from the furnaces in which pyrites is roasted, to heat this solution, and pass a mixture of the evolved gas with air under increased pressure over platinised asbestos.Hydrochloric Acid and Chlorine.-On the Continent, where the am- monia-soda process has almost entirely replaced the old Leblanc process, the price of hydrochloric acid has risen greatly, and certain branches of industry that depended on it have had to be given up. I n England, however, no great rise in price has taken place, so that, in this country, chlorine is still largely made by the Weldon process, although the Deacon process has of late begun to find a wider development ; the latter process is now the one chiefly used on the Continent. One of its defects is, that the conversion of the hydrogen chloride is not complete, and a weak solution of this gas is obtained as a bye-product ; the use of sulphuric acid has been introduced to regenerate the gas from this solution.The ammonia-soda manufacturers have made many attempts to obtain chlorine from the bye-products formed in that process. The only method which has been attended with any measure of success is that of Mond, who freezes out the ammonium chloride from the solution of it obtained in working the ammonia-soda process, volatilises it in vertical cast-iron retorts lined with thin tiles, passes the vapour into vertical wrought-iron cylinders packed with balls of magnesia (containing a little kaolin and calcium chloride) heated to a temperature of 300°, and drives out theINORGANIC CHEMISTRY. 143 ammonia by means of the gases resulting from the calcination of sodium hydrogen carbonate ; these gases contain no oxygen, and being heated by passing first through a regenerator, they raise the temperature of the magnesia decomposer to 600".Air is then passed into the decomposers at this temperature, and a gas containing 18-20 per cent. by volume of chlorine is obtained ; finally, the decomposers are cooled to 350" by a current of cold air, and ammonium chloride vapour is then again intro- duced. As regards the chemical reactions involved, the ammonium chloride vapour reacts with the magnesia, yielding magnesium chloride, together with ammonia and water, which pass on, The magnesium chloride is then decomposed by the oxygen of the air, chlorine being formed and magnesia regenerated.Mond is, however, not extending this process as rapidly as he would otherwise have done, on account of the in- troductionof electrolytical methods for the preparation of chlorine. In the manufacture of bleaching powder, mechanical methods have been largely introduced; lime, fed in at one end of a system of pipes, is made t o travel through these by an endless screw, meeting a current of chlorine as it does so, and is delivered as bleaching powder at the other end of the system. Xoda.--In Germany, France, Austria, and England, 13, 16, 36, and 50 per cent. respectively of the total output is still manufactured by the old Leblanc method ; in this method, the chief advance consists in the introduction of mechanical furnaces, in place of working the charges by hand.Hargreaves has developed a method by which sodium sul- phate is made directly, without the intervention of sulphuric acid, by the action of sulphurous anhydride, steam, and air on salt in iron cylin- ders; the products are sodium sulphate and hydrochloric acid. This process is worked to some extent in England, and also at one or two works in France and Germany. The recovery of the sulphur from the waste of the Leblanc process was at one time effected by letting the waste stand with water in tanks through which air was blown, and then decomposing the resulting extract with hydrochloric acid, when sulphur mas precipitated. This process, due to Schaffner and Mond, is now less used, on account of the rise in price of hydrochloric acid, Chance has worked out a process in which the soda waste is treated in cylinders with the gases obtained by burning limestone ; hydrogen sulphide is formed, and this is burned t o sulphur and water in a Claw furnace, whilst the calcium carbonate remaining in the cylinders is used for making cement.This method is worked in England, but not very widely. I n the ammonia-soda process, the chief advances have been in the increase of the output of an installation, and in diminishing the loss of ammonia. C. F. B. Lithium Nitride. By ANTOINE GUNTZ (Compt. r e d . , 1896, 123, 9 95-9 9'7). -Lithium combines with nitrogen with incandescence when heated in a stream of the gas, but the product is impure, because the dish holding the lithium is attacked. Iron, nickel, silver, platinum, rock crystal, and graphite are all acted on somewhat readily.A much purer product is obtained by heating the lithium very gently in an iron dish in a very slow current of nitrogen, but in this case some of the lithium may remain uncombined. It is very important t o take account of impurities in calculating the results of the thermochemical144 ABSTRACTS O F CHEMICAL PAPERS. measurements. When this allowance is made, the product has the composition Li,N, and the reaction Li,N + mH,O liq. = 3LiOH diss. + NH, diss. develops + 131.1 Cal., and hence 3Li sol. + N gas = Li,N sol. develops + 49.5 Cal. This value is lower than the heat of combination of lithium with hydrogen ( + 21.6 Cal. for Li), and, as a matter of fact, the nitride is decomposed somewhat easily when heated in hydrogen.On the other hand, the hydride seems to be decomposed when heated in nitrogen, but what really happens is that the hydride dissociates and the nitrogen then combines with the liberated lithium. C. H. B. Beryllium Oxide. By PAUL LEBEAU (Compt. Tend., 1896,123, 81 8-82 1) .-Pure beryllium oxide, prepared by the method previously described (Abstr., 1896 ii, 168), fuses in the electric arc, and, on cool- ing, forms a white, crystalline mass, slightly harder than rubies. On the surface, there are often small, detached hexagons, resulting from condensation of vapour of the oxide, which, therefore, is somewhat volatile in the arc. The sp. gr. of the oxide dried at 440" is 3.012 at O", and that of the fused oxide 3.025 a t 0" ; it follows, therefore, that no appreciable polymerisation takes place at a high temperature.The fused oxide is not attacked by gaseous hydracids at a red heat, but concen- trated acids dissolve it slowly, and in this respect it differs from alu- mina. I n sulphuric acid, i t swells up and yields a dense crystalline powder of anhydrous beryllium sulphate, which dissolves very slowly in boiling water. The oxide dried at 440" is attacked by fluorine when heated, but not by other halogens or by members of the sulphur and nitrogen gronps. I n the electric furnace, it is reduced by carbon, silicon, or boron and with the latter yields a crystallised boride mixed with carbon boride and a beryllium borocarbide. Potassium, sodium, and aluminium have no action on the oxide at 'high temperatures, and it is not reduced hy magnesium, even at the boiling'point of this metal.C. H. B. Earths of the Yttria Group in Monazite Sands. By PAUL SCH~TZENBERGER and 0. BOUDOUARD (Cmpt. Tend., 1896,123,782-788, Compnre Abstr., 1896, ii, 475).-The authors have fractionated the earths of the yttria group obtained from monazite sands, by means of fractional crystallisations of the sulphates and fractional decompo- sition of the nitrates. They find that after the former method has yielded an oxide of constant molecular weight, the latter allows it t o be still further fractiFnated. Details of the fractionations are given ; the extremes of the molecular weights of the oxides are 91.25 and 148, but both the extremes and all the intermediate fractions give the same spark spectrum, consisting chiefly of two bands a t h618-614, and X602--595.5, with further bands at X499-497.5 and h481.5-480.These spectra seem to be identical with that of yttria, but the high equivalent of some of the fractions of oxides show that they are not identical with yttria. CJ. H. B. The Alleged N e w Element, Lucium. By WILLIAM CROOKES ; (Chem. News, 1896, 74, 259).-Careful physical and chemical examina-1NORGANIC CHEMISTRY. 145 tions, revealed the fact that P. Barriere's lucium was nothing but Reduction of Permanganic Acid by Manganese Dioxide. By HARMON N. MORSE (Bey., 1897, 30, 48-50. Compare Abstr., 1896, ii, 475)-The results already described (Zoc. c i t . ) are again enumerated (compare Hirtz and Meyer, this vol., ii, 93). In the spontaneous liberation of oxygen due to precipitated manganese dioxide, the author recognises a tendency to the production of substances forming a impure yttrium.D. A 1,. homologous series Mnb,5MnO,, Mn0,l OMnO,, MnO, 1 5Mn0,, diff e&g by 5Mn0,. " I n pre4nce of nitric acid, lead peroxide and permanganic acid both lose oxygen in accordance with the equation 2HNn0, + 3Pb0, = H,O + 2Mn0, + 3Pb0 + 30,. M. 0. F. By LEVAT (Compt. Tend., 1896, 123, 945).-Steel tempered in a solution of phenol possesses greater hardness, elasticity, and flexibility than when tern- pered in water. A. C. C. Ey VICTOR THOMAS (Compt. rend., 1896, 123, 943--945).-The author has deter- mined the amount of nitric oxide absorbed by known weights of ferrous bromide dissolved in known volumes of water at loo, and at 15-16'.A t the lower temperature, two experiments gave results agreeing with the formation of a compound of the formula 3Fe,Br4,bN0. A t the higher temperature, the absorption corresponded with the formation of B compound of the formula Fe,Br,,NO. These results are confirma- tory of those obtained by Gay with ferrous sulphate and chloride, who found that, below 12*5", 3 atoms of iron united with 2 mole- cules of nitric oxide, whilst above that temperature 2 atoms of the metal united with 1 molecule of the gas. I n a future communica- tion, the author will describe a crystalline compound obtained by the union of nitric oxide with ferrous bromide in ethereal solution. The Tempering of Steel in a Solution of Phenol. Absorption of Nitric Oxide by Ferrous Bromide.A. C. C. Crystallised Magnesium Chromite. By EM. DUFA u (Cofizpt. rend., 1896, 123, 886--888).-When a mixture of chromium sesqui- oxide (150 grams) and magnesium oxide (40 grams) is heated in the electric furnace with an arc of 50 volts and 300 ampkres, normal magnesium chromite, MgCr,O, is formed which can easily be obtained as a dark green, crystalline powder. The crystals, which are octa- hedral, have a sp. gr. = 4.6 a t 20°, are harder than quartz, and have no action on polarised light. They are readily attacked by sulphuric acid, slowly by hydrochloric and hydrofluoric acids, and are not acted on by boiling nitric acid, Chlorine, bromine, iodine, and sulphur have no marked action on the compound, and it is oxidised only with great difficulty, even when heated to redness in oxygen or when fused with potassium chlorate or nitrate.Under the conditions of the experi- ment, no basic chromites were formed. Molybdenum Iodide. By hf. GUICHABD (Conzpt. vend., 1896, 123, 82 1--823).-When molybdenum chloride, obtained by the direct VOL. LXXII. ii. 11 A. C . C.146 ABSTRACTS OF CHEMICAL PAPERS. action of chlorine on the metal, is heated in a current of hydrogen iodide, a considerable quantity of iodine is liberated and a brown, amorphous di-iodide, MoI,, is formed, of sp. gr. 4.3 ; i t is insoluble in water and alcohol. When heated in a vacuum up to the melting point of glass, it is not decomposed, but when heated in air, iodine is liberated and an oxide is formed which, a t a higher temperature, is converted into molybdic anhydride. Hydrogen reduces the iodide a t 500°, and the change is very rapid at an incipient red heat. Chlorine decom- poses it below 240°, and bromine behaves similarly. In oxygen at 350°, there is vigorous incandescence, with liberation of iodine and formation of molybdic anhydride. Sulphur readily converts the iodide into a black sulphide, but nitrogen is without action a t the softening point of glass. Water decomposes it very slightly a t the ordinary temperature, and a little more rapidly at 700", whilst in superheated steam, hydrogen is liberated as well as hydrogen iodide, probably as a result of the decomposition of the steam by an oxide, MOO, formed as the first product of the action of the steam on the iodide. Hydrogen sulphide converts the iodide into sulphide, and sulphuric and nitric acids oxidise i t slowly in the cold and more rapidly on heating. Aqueous potash acts 06 it slowly a t the ordinary temperature. - C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA8977205138

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

146 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Artificial Pirssonite : Simultaneous Production of Northu- pite, Gaylussite, and Pirssonite. By AUGUST B. DE SUHULTEN (Compt. rend., 1896, 123, 1023--1025).-Bright, limpid crystals of the new mineral, pirssonite (this vol., ii, 48), have been artificially produced by adding excess of calcium chloride to a solution of sodium carbonate and heating the mixture on the water bath for 12 hours. The minute crystals are orthorhombic, and are tabular parallel to 6 (OlO), but do not show the hemimorphism which is so characteristic of the natural mineral ; they have the optical characters of pirssonite. The com- position is CaC0,,Na,C0,,2H20; sp. gr. 2.349. A t loo', there is no change, but at 130°, most of the water is lost. When placed in water, the crystals soon become dull, and after a time are decomposed into calcium and sodium carbonates.The new mineral, northupite, has already been artificially prepared by the author (Abstr., 1896, ii, 610). Northupite, pirssonite, and gaylussite all occur together a t Borax Lake, California, and they have been prepared simultaneously by heating for some hours on the water bath a mixture of 150 grams of sodium chIoride, 50 gsalus of sodium carbonate, 6 grams of calcium chloride, and 10 grams of mag- nesium chloride in 550 C.C. of water. By this method, octahedra of northupite and delicate needles of gaylussite are obtained, and, as the solution is concentrated, pirssonite is formed at the expense of the gay- lussite. Rhombohedra1 ciystals of the double salt MgC0,Na,C03 (Abstr., 1896, ii, 610) are also formed a t the same time, and it is predicted that this will be found as a natural mineral at Borax Lake.L. J. S.MINERALOGICAL CHEMISTRY. 147 Anhydrite in Ontario. By W. NICOT, (Canadicm Hecod Sci., 1896, '7, 61).-Anhydrite occurs in considerable quantity a t the Foxton phosphate mine, township of Loughborough, Co. Frontenac. It is associated with gypsum, calcite, and pyroxene, and resembles pink fluorite in appearance. Analysis gave Loss on CaO. so,. co,. SiO,. Fe,O,. ignition. Total. 41.71 57.47 0.286 0.151 0,065 0-26 99.942 L. J. S. Valleite, a new Orthorhombic Amphibole. By GIUSEPPE CES~RO (Bull. Acad. 2%. Belg., 1896, [3], 32, 536-545. Compare Abstr., 1896, ii, 481).-This mineral occurs with the violet tremolite (hexagonite) of Edwards, St,.Lawrence Co., N. Y. ; it closely resembles anthophyllite in appearance, but differs from it in its optical cha- racters and in containing only a small amount of iron. The indistinct crystals are flattened parallel to (100) and have a perfect lamellar cleavage in this direction ; other cleavages are (OlO), (021), and, less distinct, (110), ( O l l ) , (031), and (001). The prism angle is 54" 30'; a : b : c = 0.515 : 1 : 0.255. The plane of the optic axes is (010) and the acute negative bisectrix is perpendicular t o (100) ; 2E = 90" 28'. H = 4.5 ; sp. gr. 2.88. It is easily fusible to a white, nearly opaque, bead. Analysis by Renard gave SiO,. MgO. CaO. Fe,O,. MnO. K20. H,O. Total. 58.02 27.99 5.04 1.28 2.88 0.89 3.13 99.23 This agrees with the metasilicate formula, RO,SiO,.The Garnet Group, By H. SCIINERR (Zeit. K~yst. Mi%., 1896,' 27, 431-432 ; from Inccug.-Biss., ib%iachen, 1894).-Several analyses are given of the lime-garnets associated with the serpentine masses of the Eastern Alps; some of these have been quoted by Weinschenk (this vol., ii, 106). The following are of garnets from the Rothenkopf, Zillerthal, Tyrol : I, light red ; 11, cherry-red ; 111, dark brown. L. J. S. SiO,. A1,03. Fe,O,. FeO. MnO. CaO. Total. I. 37.18 14.03 13.73 2.54 trace 32.73 10021 11. 36-75 6-90 21.38 2-17 trace 32.55 99.75 111. 37.52 13.29 13.01 1.71 0.54 34.01 100*08 As in the garnets of the Gross-Venediger, the dark brown shows the more marked optical anomalies, whilst the cherry-red is almost iso- tropic.From the analyses, it is seen that there is no connection between colour and chemical composition, and that the darker garnets (aplome) are not richer in ferric oxide than the lighter (essonite), as is sometimes supposed. L. J. S. [Action of Hydrochloric Acid on Titaniferous Augite.] By E. LORD (Zeits. Kryst. Min., 1896, 27, 431 ; from 1naug.-Biss., Heidel- berg, 1894).-In a dissertation on the basalts of the Pichtelgebirge the following analyses of the zoned titaniferous augite from the limburgite of the Kaiserstuhl, Baden, are given ; these were made with the object of seeing whether, by the action of hydrochloric acid, a separation into parts containing titanium and free from titanium could be effected. The bulk analysis of the augite is given under I ; I1 gives the com- 11- 2148 ABSTRACTS OF CHEMICAL PAPERS.position of the portion (57 per cent. of the whole) which went into solution when the powdered mineral was digested for 12 hours with hot, concentrated hydrochloric acid ; and I11 gives the composition of the insoluble portion. SiO,. TiO,. AI,O,. Fe,O:,. FeO. MgO. CaO. Nw,O. K,O. Total. I. 43.85 3.14 6.19 6.99 3.70 11.89 22.44 1.50 0.50 100.20 11. 43.41 3.19 6.92 7.04 3.38 11.64 22.54 1.50 0.50 100.12 111. 44.30 3.09 5.46 6.85 4.04 12.75 22.34 [1.17] 100.00 After digesting for 4 days, 82.44 per cent. was dissolved; and with dilute acid (1 : l), 43.77 mas dissolved after 12 hours. In both these cases, the composition of the soluble and insoluble portions is, as before, much the same as that of the original nugite, so that no separa- tion can be effected by these means.Endomorphic Alterations of Granitic Magma in Contact with Limestone. By ALFRED LACROIX (Compt. ?*end., 1896, 123, 1021--1023).-At the peak of Braceil, in Orlu, AriBge, the granite of QuCrigut is in contact with a thick, sedimentary series consisting of schists with thick bands of limestone. Fragments of the schist and limestone are enclosed in the granite, and these rocks have been largely absorbed by the granitic magma. The granite in contact with the ex- tensively corroded limestone has undergone considerable alterations’; it becomes progressively more basic, by loss of quartz and felspar, and development of hornblende and mica, and lastly olivine, and passes to hornblende granite, quartz-diorite, mica-diorite, hornblendite, and, finally, to hornblende-peridotite, this being an almost complete series of granular eruptive rocks.Sometimes enstatite is developed, and norites, with or without olivine, result. The plagioclases, oligoclase to anorthite, are zoned and much corroded, indicating great variations in the composition of the magma, By CH. BOUCHARD and ALEXANDRE DESGREZ (Con@. rend., 1896, 123, 969-970).-The gas from the mineral waters of Bagnoles de l’Orne contains carbonic anhydride, 5.0 ; nitrogen, 90.5 ; argon, 4.5 ; helium, traces= 100.00. No carbonic anhydride is found in the mineral waters of Cauterets. -- L. J. S. L. J. S. Gas from the Mineral Waters of- Bagnoles de l’Orne. C. H. B. Mineral Water of Kralitz. By FR. FAKTOR (Verlh. wiihwf. V&., R~iinn, 1896 (1895), 34, 366-368).-The baths of Kralitz, near Pross- nitz, in Moravia, have been known sirice 1825. The water has a tem- perature of ; sp. gr. = 1,00544 a t 16.5”; on standing, it becomes turbid, and deposits ferric oxide, silica, and organic matter. Analysis gave, in 1,000,000 parts :-FeO, 18.526 ; CaO, 158.400 ; MgO, 41.656 ; K,O, 32-118 ; Nrt,O, 44.961 ; SiO,,. 15.600 ; SO,, 36.382 ; P,O,, 0.260 ; C1, 50.763 ; GO,, in bicarbonates, 330.1 10 ; GO,, free, 9.073 ; total solids (dried a t lSO’), 562.029. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8977205146

出版商:RSC    

年代:1897

数据来源: RSC

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PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. 149 Mercury Air Pump for the Estimation of Blood-GaseR. By FRIEDRICH NEESEN (Zeit. phpiol. Chem., 1896,22, 478--482).-This is a modification of the mercurial air pump, the details of which are fully explained, and illustrated by a diagram. The special advantage claimed for it is rapidity of action. By FERDINAND KLUG (Pfiiiger’s Archin, 1896, 65, 330-342).-A large number of albuminous substances were sub- jected to the action of gastric juice prepared from the dog, pig, and ox, and the results compared. Differences between the three juices occur; but the main result is that alkali-albumin and casein are best digested, after these follow serum-albumin, syntonin, serum-globulin, fibrin and legurnin; whilst boiled egg-albumin and dry meat powder are the least easily digestible.The yield of anti-albumose is greatest with alkali-albumin and plant-casein ; then follow serum-globulin, synton- in, serum-albumin, and casein. The yield of hemi-albumose is greatest with casein, both animal and vegetable ; serum-albumin, syntonin, gluten, and gluten-fibrin also yield a relatively large amoinnt of hemi- albumose ; serum-globulin, fibrin, boiled egg-white, legurnin, and raw flesh yield relatively little. On the other hand, serum-globulin and syntonin yield the most peptone ; egg-albumin, casein, serum-albu- min, and fibrin follow in the order named. The absolutely greatest quantity of proteid is dissolved by pepsin in the presence of hydrochIoric and lactic acids ; phosphoric, nitric, acetic acids follow, and then, at a distance, sulphuric and citric acids.The optimum concentration differs with the different acids ; thus it is 0.6 for hydrochloric, 8.0 for lactic, 6.0 for phosphoric and acetic, 0.8 for nitric, 0.6 for sulphuric, and 8.0 for citric acid. The relative propor- tion of hemi- and anti-products differs considerably with the various acids, a fact which is against the supposition that the hemi- and anti- group exist preformed in the albuminous molecule. By HUGO WINTERNITZ (Zeit. pgsiol. Chem., 1896, 22, 449--477).-The .blood of the fmtus, and of the new-born animal, is much richer in hzemoglobin and total solids than t h a t of the adult animal, but shortly after birth this large pro- portion begins to diminish. The experiments recorded were made 011 dogs, cats, and rabbits, the hzemoglobin being estimated by the Hoppe- Seyler double pipette.By MAURICE HANRIOT ( C o ~ p t . Tend., 1896, 123, 753-755. Compare Abstr., 1892, 742).-The ob- ject of this inve:stigation was t o determine the manner in which reserve f a t passes into the circulation and is utilised by the organism. In his experiments, the author, instead of employing the natural fats, makes use of an aqueous emulsion of monobutyrin as a test for the pre- mnce of a hydrolysing enzyme, on account of the greater ease with whieh W. D. H. Gastric Digestion. Another series of tables gives the effects of different acids. W. D. H. The Blood of New-born Animals. W. D. H. A New Enzyme in the Blood.150 ABSTRACTS OF CHEMICAL PAPERS. it is capable of undergoing saponification. Mono butyrin is readily saponified by blood serum in neutral or slightly alkaline solutions, but the action is considerably retarded by the presence of the liberated acid if this be left unneutralised.Using equal quantities of butyrin, the acidity in a given time is directly proportionad to the amount of serum employed; moreover, the activity of the latter is destroyed when it is heated to 90°, it being then unable to produce butyric acid in the test solution. The amount of saponification taking place with various proportions of butyrin and serum in different times was determined by observing the quantity of a standard solution of sodium carbonate necessary to neutralise the liberated butyric acid ; and the results are given in a table.The active enzyme, for which the name Zipme is suggested, is also capable of acting, though much more slowly, on the natural oils and fats. Lipuse is very stable, and appears to be as active in the serum a t the end of eight days as at the beginning. In a future communication, the author proposes to show the invariable presence of lipase, both in plants and animals, whenever there is a reserve of fat to be utilised. By FR. N. SCHULZ (PJiigey’s Archiv., 1896, 85, 299-307).-The experiments were made on rabbits, pigeons, and dogs. The fat was estimated by extraction with ether after preliminary artificial gastric digestion. Inanition was found to cause a rise of from 30 to 100 per cent. in the amount of fat in the blood, as compared with that in normal animals.By B. MOORE and D. P. ROCKWOOP (S. Phpiol., 1897, 21, 58-84).-The emulsibility of free fatty acids, and their solubility in bile, have been known for many years, but the extent of such solubility has not been ascertained, and the bearing of these facts on fat absorption has not attracted much attention. The present research attacks both these points. I n connection with the first, the solubility determinations show : (1) that palmitic and stearic acids are practically insoluble i n ox bile at 38-40°, whilst 4 per cent. of oleic acid is easily soluble a t that temperature. Hence the solu- bility of mixed fatty acids is probably due to an action of oleic acid in aiding the solution of the others. (2) Of the mixed fatty acids of lard, beef suet, and mutton suet, lard acids are most, and mutton suet acids least, soluble, the solubilities for the three sets being 3.5, 2.5, and 2 per cent.respectively in ox bile, 5, 5, and 1 in pig’s bile ; and 6, 5.5, and 2 in dog’s bile. (3) The solubility of the fatty acids in bile is only in part due to bile-salts. Strong solutions of the bile-salts dissolve fatty acids much more feebly than the bile itself. Mere removal of the pseudomucin from bile diminishes its solvent action. A solution of pseudomucin alone, however, does not dissolve fatty acids. (4) On cooling the solution of fatty acids in bile below 40°, much of the dissolved acids separates out. The power of the bile to dissolve fatty acids is not impaired by repeating the process ; the formation of a true emulsion was never observed.The intestinal contents of the dog dissolve fatty acids in a way very similar t o bile. Pancreatic juice and bile together decompose and dissolve fat; pancreatic juice alone decomposes, but does not A. c. c. Fat in the Blood during Hunger. W. D. H. Absorption of Fats.PHYSIOLOGICAL CHEMISTRY. 151 dissolve it, whilst bile alone has no action. A large number of experi- ments were made on the reaction of the intestinal contents in different animals, and the results and conclusions drawn therefrom may be summarised as follows. The way in which fat is absorbed varies in different species of animals, and certainly it is not always absorbed as dissolved fatty acids. Most, however, if not all, of the fat is absorbed in soluble form by the epithelial cells, either as fatty acid or soap.When fatty acids are dissolved in bile or the mixed intestinal juices, the reaction of the solution is acid. Intestinal contents, theref ore, which are alkaline to litmus cannot contain free fatty acids in solution. In white rats, the reaction is alkaline to litmus along nearly the whole small intestine, and usually the whole way, and, in the dog, the same is usually the case for the lower part of the ileum. Yet lacteals filled with white emulsion are seen proceeding from these parts. Here, probably, the fat is absorbed as soap. In the greater part of the dog’s small intestine, the reaction is acid to litmus, but alkaline to methyl-orange. The acidity to litmus is due to organic, probably dissolved fatty, acids, but the alkalinity to methyl-ora.nge indicates that there is an excess of alkali above that required to combine with inorganic acids, and that this excess is com- bined with weak acids, probably with fatty acids in the form of soaps.Munk objected to the view that any considerable amount of fat is absorbed as soap, on two grounds: (1) the acid reaction of the intestinal contents ; (2) the enormous quantity of alkali which mould be necessary to saponify all the fat in even an ordinary meal. The first objection falls to the ground when one considers that the acidity is due to organic acids ; and the second may be met by the suggestion that a small amount of alkali could act as the mere carrier of an indefinitely large quantity of fat, provided that, in the splitting up of soap into fatty acid and alkali which occurs in the epithelial cells, the alkali makes its way, as is probable, back to the intestine, rather than into the blood-stream. Histologists are unanimous that fat does not enter the epithelium in the particulate form of an emulsion; fat granules have never been observed in the striated border of these cells.Emulsification usually occurs, it is true, and this is obviously useful for the exposure of a large surface of fat to the action of the intestinal fluids; but fat absorption, as shown by the lacteals,. proceeds alike whether any piece of gut contains emulsion or clear fluid. By E. BOGDANOFF (P$iigep*’s Archiv., 1896, 65, 81--89).-Dormeyer’s discovery (Abstr., 1895, ii, 540), that simple extraction of muscular tissue with ether is not sufficient to remove all the fat, is confirmed.By prolonged extraction with ether after the removal of the fat which is easily removable, a fat is obtained charac- terised, like butter fat, by a high percentage of volatile fatty acids. From the wsult of microscopical examination of the muscular tissue, which had been treated with osmic acid a t different stages after ether extraction, the conclusion is drawn that the second fat is a constituent of the muscle-plasma. W. D. H. The Fat of Flesh. W. D. H.I52 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Animd Fats. By CARL AMTHOR and JULIUS ZINK (Zeit. anal. Chem., 1897,36,1-17).-The authors, having special facilities for obtaining genuine specimens of the fat of various wild and domesticated animals, have made numerous estimations of specific gravity, melting and solidifying points, iodine and saponification numbers, both of the fats themselves and of the fatty acids, as well as the Hehner and Reichert values, the acetyl number (according to Benedikt and Ulzer), and the free acidity when fresh and after a lapse of time. The animals selected were the elk, red deer, fallow deer, chamois, roebuck, badger, wild boar, dog, fox, wild and domestic cat, pine marten, pole cat, hare, tame and wild rabbit, tame and wild duck and goose, and the last, after two years’ captivity, domestic fowl, turkey, black cock, dove, and starling.The first five are distinguished from the others by high specific gravity and low iodine number, the iodine number of chamois fat being the lowest yet recorded. The fat of the wild boar, hare, wild rabbit, and black cock exhibits the pro- perty of drying to a varnish when exposed to the air in a thin layer ; the fat of the domestic pig and rabbit does not dry.Comparing the fat of wild with that of domestic animals, the former always shows a higher iodine absorption and generally a higher acidity in the fresh state ; in the case of the wild goose kept in captivity for two years, the iodine number had fallen to that of the domestic goose. Besides the above numerical values, observations of colour, consistency, odour, &c., are recorded. M. J. 8. Muscular Work and Glycogen. By FRIEDRICH SCHENCK (PJiigeY’s A?*chiv., 1896, 65, 326--328).-A further criticism of Seegen’s work. (Comp Abstr., 1896, ii, 48). By AN.MEDVEDEFF (P’iigeiJs Archiv., 1896, 65, 249-271).-The principal experiments recorded were made with salicylaldehyde and extracts of animal organs. Under certain circumstances, the amount of oxidation is proportional to the square of the concentration of the oxidation ferment (or active proteid), and inversely proportional t o the square root of the concentration of the salicylaldehyde. Physiological oxidation processes belong to the class of what Schmiedeberg terms ‘ synthetic oxidations.’ W. D. H. Oxidation in the Tissues. W. D. H. Influence of Calcium Salts on Fibrin Formation. By OLOF HAMMARSTEN (Zeit. phgsiol. Chem., 1896, 22, 333-395).-A very com- plete and critical article on the recent theories that have been advanced concerning the part played by calcium salts in the process of blood- coagulation, the points of difference between the theorists being tested by carefully-devised experiments.The view of Alex. Schmidt, that calcium salts do not qualitatively act differently from other neutral salts like sodium chloride, is not correct. Schmidt admits that the calcium salts are quantitatively more active than other salts, but Arthus and Pages are undoubtedly right in attributing to calcium salts a specific action; and the removal of such salts by the addition of alkali oxalates inhibits coagulation, because the plasma is thereby decalcified. The use of the term decalcification is not abso-PHYSIOLOGICAL CHEMISTRY. 153 lutely correct, for the calcium which is in intimate union with fibrinogen is not influenced by the oxalate.The question then arises what is the specific action of calcium salts? Are they of use in the formation of fibrin ferment, or do they act, as in the formation of casein in milk, by precipitating the proteid which has been subjected t o the action of the ferment 1 The analogy drawn by Arthus between casein formation and fibrin formation only holds good in part, for calcium salts are not essential for the fermentative change of fibrinogen into fibrin ; provided fibrin ferment is present in sufficient amount, fibrin is formed typically and abundmtly from solu- tions of fibrinogen, whether calcium salts have been removed by an oxalate or not. Pekelharing is right when he assumes that the specific action of calcium salts is in the genesis of fibrin ferment, or, to adopt a new nomenclature, in the change of prothrombin (zymogen or percursor of tibrin ferment) into thrombin (the ferment itself).Fibrin is certainly iiot a calcium compound of fibrinogen ; both contain the same amount of calcium. Lilienfeld’s thrombin, a substance he considered he had split off from fibrinogen by the action of acids like acetic or nucleic acid, and which he further supposed combined with calcium t o form fibrin, does not exist. It is nothing but fibrinogen itself partially precipitated by the acid employed. NOTE BY ABSTRACTOR.-NO reference is made in this paper to a preliminary note by E. A. Schiifer (I’roc. plqsiol. s’oc., 1895, 18), who arrived a t much the same results on most points. Ringer (Pmcti- tione?., 24, 81) has also shown, in connection with cardiac muscle, that soluble oxalates do not produce absolute decalcification.Fate of Cholesterol in the Animal Organism. By STANISLAS BONDZYNSKI and V. HUMNICKI (2eit.physioZ. Cliem., 1896,22, 396-410). -In man, the cholesterol of the bile leaves the body in the fzces as a new substance coprosteyol ; this has the formula C27H4S0, and from an examination of its derivatives (see this vol., i, 183), appears to be di- hydrocholesterol. I n dogs, cholesterol is found in the faces as such. In horses, the material found is named hippocopyosteyol, C2;H,,0, or C27H5G0’ ITf. D. H. Behaviour of Formanilide in the Animal Organism. By FRIEDRICH KARL KLEINE (Zeit. physiol. Chenz., 1806, 22, 327- 332).- The urine of animalsfed on a diet mixed with fornianilide mas exam- ined ; in dogs, small doses of the drug are almost entirely destroyed in the metabolic process ; large doses lead to the appearance of ortho- hydroxycarbanil in the urine.This same substance was found by Jaffe after the administration of acetanilide. It is produced by oxida- tion and a subsequent loss of water, W. D. H. C,H,-NH-COH + 0, = OH*C~H~*NH*COOH = C,H~<:>UOH + H,O. In rabbits, the substance found in the urine is amidophenol. W. D. H. Ingestion and Excretion of Iron in Health. By RALPH STOCKMAN and E. D. W. GREIG (J. Phpiol, 1897, 21, 55--57).-The iron meta-154 ABSTRACTS OF CHEMICAL PAPERS. bolism of the body, so far as regards intake and output,is extremely small, an examination of the ingesta and egesta in four series of observations made on three healthy adults showing in the first and fourth observations that the intake and output were almost equal, amounting to 6.2 and 6.3 milligrams in one case, and 3.5 and 3.7 milligrams in the other. I n the other two series, the iron excreted on the three days of the analysis was much greater than the amount ingested, but at other times the balance must be reversed, or the equilibrium of health would not be maintained. Concerning internal iron-metabolism, which must be considerable if blood corpuscles are broken down in such large numbers as is commonly supposed, little or nothing is known. The greater part of the iron is apparently not excreted, but retained in store by the liver for future use. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8977205149

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

154 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Alcoholic Fermentation without Yeast Cells. By EDUARD BUCHNER (Ber., 1897, 30, 117--124).-When brewery yeast, to which no starch has been added, is ground with quartz sand and kieselguhr, moistened with water and pressed, the liquid which is obtained has the power of producing the feymentation of sugar, although it appears to be quite free from yeast cells. It has a sp. gr. of 1.0416, contains about 10 per cent, of residue, and gelatinises when boiled. This liquid produces alcoholic fermentation in solutions of cane-sugar, maltose, glucose, and fructose, but does not ferment either lactose or mannitol. Fermentation continued in many cases for two weeks, even at the tem- perature of O", and was not stopped by filtration of the liquid through a Berkefeldt filter. Plate cultures showed that in some cases small numbers of micro-organisms were present, but yeast cells were in no case detected.The author gives the name xymcse to the substance which produces the fermentation. This appears to be a proteid, since the fermentative power of the solution is practically destroyed when it is heated for an hour at 40-50" and the coagulated albumin filtered off. The dried precipitate produced by alcohol does not yield any ferment to water. A. H. Effect of Ammonium Nitrate on Aspergillus niger. By CHARLES TANRET (Compt. rend., 1896, 123, 948-95O).-When Aspr- gillus niger is sown in Raulin's solution, the spores germinate in less than 24 hours, forming a mycelium which soon produces black conidia.When, however, the ammonium nitrate in the nutrient solution is in- creased from 0-25 per cent. t o 0.5 or 0.75 per cent., the spores, at a temperature of 30-40" produce a mycelium, which grows rapidly but does not fructify. At a temperature of 20-22O, even 1 gram of ammonium nitrate per 100 C.C. of solution does not prevent the forma- tion of conidia. During the growth of the aspergillus in the mycelial state, both citric acid and nitric acid are formed in the solution, andVEGETABLE PHYSI0LOC:Y AND AGRICULTURE. 155 starch appears in the tissue of the mould. When grown in Raulin’s solution, no starch is elaborated. Behaviour of Bacteria, towards Chemical Re-agents. By THEODOR PAUL and BERNHAED KROKIG (Zeit. p7LysikuZ. Chem., 1896,21, 41 4-450).-1n order to determine quantitatively the effects of various acids, bases, oxidising agents, and metallic salts on bacteria, the num- bers of colonies were counted after similarly-prepared cultivations were treated with the respective compounds.The bacteria employed in the experiments were Stc~plzyZococcus pyogenes c~u~’eus, and the spores of the anthrax germ, B a c i l l u s ccnthrc~is, and numerous experiments were per- formed with each compound examined. The authors obtained the following results. The salts of mercury, gold, and silver exert a specific poisonous effect, strongest in the case of the mercury com- pounds; platinum salts have little action, if any. I n metallic salt solutions in which the metal is present as a complex ion, the disinfect- ing action is extremely small; it is, however, not only dependent on the number of the metallic ions, but also on the anion and the non-dis- sociated part.The effect of mercuric chloride is greatly decreased by the addition of sodium chloride, or other chlorides, but is not affected by other salts, such as sodium nitrate, The acids only act as disin- fectants in concentrations of the gram molecular weight per litre, and exhibit a specific action which is not proportional to the concentration of the hydrogen ions. The weak organic acids, however, appear to act according to the degree of dissociation. Lithium, sodium, and potassium hydroxides have almost equal effects, but the action of ammonium hydroxide is very slight. Of the oxidising agents, nitric acid, chromic acid, chloric acid, and permanganic acid act in the order stated, which is also that of their oxidising powers as determined electrically (Abstr., 1893, ii, 58).The halogens have also a specific action, which is most powerful in the case of chlorine. Phenol acts better in a 5 per cent. solution than at higher concentrations, and the effect is increased by the addition of metallic salts, most noticeably sodium chloride ; it is, however, diminished by dissolution in alcohol, and in the most favour- able conditions is not nearly as great as that of mercuric chloride, which appears to be the strongest disinfectant examined. I n absolute alcohol, however, even this compound, like other salts, has little or no effect, but acts best in a solution containing water and alcohol in proportions which vary with the different compounds.Chemistry of the Membranes of Lichens and of Fungi. By F. ESCOMBE (Zeit, physiol. Chem., 1896, 22, 288-306. Compare Win- terstein, Abstr., 1894, ii, 425 ; 1S95, i, 80, 199, 323,493). The hyphen- membranes of Cetrccria idandiccc, after the extraction of fats, oils, colouring matter, astringent substances, lichenin, &c., consists mainly of an insoluble anhydride of galactose, which the author terms para- galactan ; on oxidation, it yields mucic acid. Lichenin on hydrolysis yields, apparently, only galactose (compare E. Fischer), and is, there- fore, probably a galactan. No chitin, or related substance, and no cellulose could be detected, The membrane of PeZtigercc cccnincc contains no cellulose, but apparently a small amount of chitin.Evermia pru- nastre was also investigated, the algae cells contain cellulose, and the hyphen-membrane a substance which, on treatment with potassium A. C. C. L. M. J.156 ABSTRACTS OF CHEMICAL PAPERS. hydroxide, becomes gelatinous. sclerotium of Claviceps pu~puy'ecc which could not be identified. A substance was obtained from the J. J. 8. Crystalline Nitrogenous Compounds in Seedlings. By ERNST SCHULZE (Zeit. pl~ysiol. Clzem., 1896, 22, 411-434. Compare Abstr., 1895, ii, 84).--Cornpletme details for the isolation of the different arnido- acids are given, Seedlings of Pkea excelsa, grown in sand in a dark room, contain asparagine with a little glutamine, whilst in the open, in good soil, no asparagine, but a considerable amount of glutamine, can be obtained.Etiolated seedlings of Lupi7aus albus, of 24 weeks' growth, yielded phenylalanine, amidovaleric acid, and asparagine, but apparently no leucine. Arginine could not be isolated from the cotyledons of the same seedlings. Normal green seedlings gave a quantity of leucine and amidovaleric acid, b u t only a little asparagine, and apparently no phenylalanine. Green seedlings of Lupinus Zuteus gave leucine, a small quantity of asparaghe, and a fair amount of arganine. Etiolated seedlings of Lupinus angustifolius L. yielded leucine and amidovaleric acid, and the presence of small quantities of phenyl- alanine and arginine was also indicated. Nitrogenous Compounds derived from the Proteid Sub- stances of certain Conifers.By ERNST SCHULZE (Zeit. physiol. Chem., 1896, 22, 435-448. Compare Abstr., 1895, ii, 84).-Etiolated seedlings of Picea excelsa contain arginine, together with smaller yuan- tities of asparagine and glutamine ; normal green seedlings, however, contain arginine and glutamine, but no asparagine. The seedlings of Abies pectinata contain even more arginine, but little or no glutamine and asparagine. Seedlings of Pinus sylveshis contain arginine and asparagine, with a little glutamine. Analyses of the Juice of Different Varieties of Goose- berries, Currants, and Strawberries, By ALBERT EINECKE (Landw. Yersuchs.-Stat., 1896, 48, 131-160. Compare Abstr., 1895, ii, 366.)-The. analyses include invert and cane-sugar, acid, extract, nitrogenous matter, crude ash, phosphoric acid, and potash. The sp. gr. of the juice was also determined. The results are given in per- centages in the berries, The variations in the amounts of important constituents in the different varieties are, as a rule, not considerable, and it is not at present possible to ascertain by analysis to what variety cz sample belongs. Comparing the produce of 1894 and of the dry season of 1895, it was found that, whilst gooseberries were richer in juice in 1894, the currants contained more juice in 1895. The juice of both fruits was richer in constituents in 1895 than in 1894 (except nitrogen in currants). With regard to the influence of manures on the com- position of the juice, no effect was observed in the case of goose- berries and currants. In the case of strawberries, there was an increase of valuable constituents under the influence of manure, whilst the percentage of nitrogen was lowered; of ash constituents the amount of potash was increased, whilst that of phosphoric acid was diminished, by manuring. J. J. S. J. J. 8. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8977205154

出版商:RSC    

年代:1897

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 157 Analytical Chemistry. Estimation of Sulphur in the Gases Produced by the Com- bustion of Petroleum. By RICHARD KISSLINQ (Chenz. Zeit., 1896, 20, 199).-A small lamp, with a reservoir capable of holding about 100 grams of oil, is fitted with a lamp-glass made of hardened glass the top of which is drawn out and bent so that it may be connected with a series of absorbing tubes. By means of a current of air, the products of combustion are first passed through a U-tube 200 mm. long filled with glass beads moistened with a 5 per cent. solution of potassium permanganate. The gases then again pass through a nitrogen bulb also filled with permanganate solution, and finally through an empty bulb. When the combustion is over, the tubes are rinsed, the liquid cleared by boiling with hydro- chloric acid, and the sulphuric acid estimated with barium chloride in the usual manner.The air in the room should, of course, be free from Estimation of Ammoniacal Nitrogen in Artificial Manures. By 0. BOTTCHER (Chem. Zeit., 1896, 20, 151--152).-The author has proved by a large number of experiments that ammoniacal salts con- tained in manures are completely decomposed by boiling with water and calcined magnesia. Boiling with aqueous soda is, therefore, un- necessary, and is often the cause of finding too high a percentage of ammonia, due t o decomposition of the nitrogenous organic matter. The magnesia should, however, be free from carbonate-if not, the any sulphurous vapours. L. DE K. resultrs will be untrustworthy. L. DE K.A New Method of Estimating Phosphorus in Phosphor- Bronze. By FELIX OETTEL (Chem. Zeit., 1896, 20, 19--20).-From 3 to 10 grams of the sample in turnings or filings is digested with nitric acid, and the oxide of tin collected, slightly washed, dried, and ignited in a porcelain crucible; it is then mixed with about thrice its weight of potassium cyanide and fused for a few minutes at a red heat. I n this way, the oxide is reduced to metallic tin, and the melt con- tains, besides potassium cyanide and cyanate, all the phosphorus as potassium phosphate. The melt is boiled with water, filtered, the cyanogen compounds removed by boiling with hydrochloric acid, and the traces of tin or copper which have again passed into solution are precipitated by a current of hydrogen sulphide and the whole filtered.The filtrate is concentrated to a small bulk, the last traces of the hydrogen sulphide are decomposed by adding a little bromine water, and the phosphoric acid is finally precipitated by adding ammonia magnesium mixture. The test-analyses are satisfactory ; the presence Critical Examination of Methods for the Estimation of Phosphoric Acid. By C. MEINEKE (Chem. Zeit., 1896,20, 108-113). -The author has long ago proposed to ignite the yellow phospho- molybdate precipitate before weighing it ; the latest investigation shows that it contains 3.944 per cent. of phosphoric anhydride. The precipitation of phosphoric acid by means of molybdate solu- of arsenic does not interfere. L. DE K.158 ABSTRACTS OF CHEMICAL PAPERS. tion is not influenced by the presence of an excess of ammonium chloride.The magnesium pyrophosphate obtained when the magnesium method of precipitating phosphoric acid is employed, is not the stable compound which it was formerly believed to be, but contains what may be regarded as free phosphoric acid, which volatilises at a very high temperature. The author thinks the precipitate should be first ignited in the ordinary way and then at a much stronger heat; the By LOUIS CAMPREDON (Compt. vend., 1896, 123, 1000-1 OO3).-When very finely-powdered coal-ash is heated with concentrated hydrochloric acid for 15 or 20 hours, the whole of the phosphorus does not dissolve, and the propor- tion that remains in the residue is greater the higher the temperature to which the ash has been heated.It often amounts to 10 per cent., and may amount to as much as 25 per cent. of the total phosphorus present. I n order to get the whole of the phosphorus into solution, the ash must be heated with five times its weight of a mixture of equal parts of potassium and sodium carbonates. Estimation of Readily-Soluble Phosphoric Acid in Basic Slags. By MAX GERLACH and MAX PASSON (Chem. Zeit., 1896,20, 87--88).-The authors have shown that the active ingredient of Wagner's solution is the free citric acid, and that the large amount of ammonium citrate may be safely reduced to one-tenth. At a tempera- ture of 17*5",a 3 hours' treatment does not yield more soluble phosphoric acid than half-an-hour's extraction. This does not, however, imply that the undissolved phosphate is really insoluble ; treatment with fresh quantities of solution will gradually dissolve it completely. Phosphoric Acid : Estimation of Pyrophosphoric Acid.loss then observed represents the free acid. L. DE K. Estimation of Phosphorus in CoaJ Ash. C. H. B. L. DE K. By BIARCELLIN P. E. BERTHELOT and GUSTAVE ANDR~ (Compt. rend., 1896, 123, 773-776).-The method described is available in presence of orthophosphoric acid, but is not generally applicable in presence of mstaphosphoric acid. The solution is precipitated with a mixture of magnesium chloride and ammonium chloride and acetate in presence of a considerable excess of acetic acid, and the liquid is heated on a water bath for 3 to 4 hours, in order t o enwm complete precipitation. The pyrophosphate thus obtained contains a somewhat variable pro- portion of magnesium, and therefore it is washed, dissolved in dilute nitric acid, boiled for about an hour, and the orthophosphate into which it is converted is then precipitated in the usual way.The magnesium pyrophosphate is comparatively stable, even when boiled with dilute acetic acid, but it is obvious that the boiling should not be too prolonged. When orthophosphoric acid is also present, the filtrate from the precipitated pyrophosphate is concentrated and mixed with ammonia, which precipitates the phosphoric acid in the usual form. C. H. 13.ANALYTICAL CHEMISTRY. 159 Volumetric Estimation of Arsenic. By EMERICH SZARVASY (Rev., 1896, 29, 2900-2902).-The arsenic is precipitated in the usual way as sulphide, the precipitate being collected by filtration through a plug of asbestos placed in a combustion tube.After being washed with alcohol and ether, and carefully dried in a currenta of warm air, it is heated in a stream of oxygen. The arsenious anhydride which condenses in the cold part of the tube is dissolved in aqueous soda, and estimated by means of iodine solution. A. H. Volumetric Estimation of Boric Acid. By MAX HONIG and GUSTAV SPITZ (Zeit. angw. Chem., 1896, 549-552).--The authors titrate the free acid with standard alkali in the presence of a sufficiency of glycerol, using phenolphthalein as indicator. As soon as the liquid turns red, more glycerol is added, and should this destroy the colour, more soda is run in. When dealing with Sorates or mixtures of the same with alkali carbonates, a little methyl-orange is first added and then a slight excess of hydrochloric acid.After boiling, using a reflux condenser, the liquid is cooled, carefully neutralised, and the boric acid estimated as directed above. Insoluble borates are boiled with excess of normal acid and then treated in the same way. When the acid has to be estimated in the presence of silica-for instance, in enamels-the sample is fused with potassium sodium carbon- ate, the melt boiled with water, and the liquid mixed with ammonium chloride in quantity sufficient to nearly neutralise the alkali used. After boiling for some time, an ammoniacal solution of zinc oxide is added to complete the precipitation of the silica, and when the ammonia has been entirely driven off, the liquid is filtered and the precipitate washed with hot water.A drop of methyl-orange is next added to the filtrate, then a slight excess of normal hydrochloric acid, and after boiling the mixture is treated as before. Another process worked o u t by the authors is based on the follow- ing principles. Native insoluble borates, when made into an impalpable powder, are completely decomposed by boiling with solution of sodium hydrogen carbonate, passing carbonic anhydride through the boiling liquid. The solution, which then contains sodium tetraborate, and, of course, also alkali carbonate, is mixed with ammonium nitrate, and the carbonic acid quantitatively precipitated by silver nitrate, without throwing down any boric acid. When the liquid is now mixed with excess of ammonium chloride and distilled in a current of steam, the distillate contains an amount of free ammonia equivalent to the sodium in the tetraborate.From the amount of soda, the quantity of boric acid can readily be calculated. The results obtained by the second method agree fairly well with those obtained by the first process. L. DE K. [NOTE BY ABSTRACTOR.]-T~~ titration of boric acid by means of glycerol, alkali, and phenolphthalein has been described by Thomson (Abstr., 1894, ii, 28); 30 per cent. of glycerol by volume was found to be always sufficient. Estimation of Sodium Carbonate, Silicate, and Borate in Soap. By WM. WALTKE (Chem. Zeit., 1896, 20, 20-2l).-FIom160 ABSTRACTS OF CHEMICAL PAPERS. 5 to 10 grams of the soap, previously cut up small, is treated with boiling alcohol, and the insoluble portion is dissolved in hot water, filtered, evaporated t o dryness, and the residue dried until the weight is constant.I n an aliquot part of this residue, the carbonic anhydride is estimated in a Geissler's apparatus, and from the result the amount of sodium carbonate is calculated. The remainder is then treated with hydrochloric acid and the silica separated in the usual manner ; in the filtrate from the silica, the whole of the sodium is present as chloride. This is now estimated volumetrically, and from the total thus found, the amount corresponding with the silicate and carbonate of sodium is subtracted; from the difference, the amount of sodium present as borate can be calculated. When the salts are present in fair proportions, the results obtained by the process are quite satisfactory.L. DE K. New Method of Estimating Potassium. By PAUL L~SCHE (Chenz. Zeit., 1896,20, 38-39. Reply by H. HAEFCKE, ibid., 88-89).- This process is intended for the analysis of crude potassium compounds containing an approximately known amount of potassium. Fifty grams of the sample is boiled with 150 C.C. of water and 10 C.C. of strong hydrochloric acid, and, when cold, diluted to 200 C.C. ; 10 C.C. of the filtrate is then mixed with a sufficiency of platinic chloride solution, evaporated to dryness, and the residue broken up and repeatedly extracted with 96 per cent. alcohol to remove any sodium platinochloride. The insoluble matter is collected on a weighed filter, dried at 120", and then washed with a 10 per cent.solution of ammonium chloride at 30" to remove the sulphates ; the ammonium chloride in turn is removed from the insoluble residue of potassium platinochloride by washing with alcohol, and the filter and constants dried a t 120-1 30". HAEFCKE sharply criticises the process, and does not hesitate to The test-analyses are satisfactory. reject the method as being quite untrustworthy. L. DE K. Estimation of Potassium at the Stassfurt Works. By ALBERT ATTERBERG (Chern. Zeit., 1896, 20, 131. By RUDOLF RUER, ibid., 270, and by EMIL BAUER, ibid., 270).-ATTERBERO states that the chemists at the Stassfurt potash works use a process which gives results sometimes 2 per cent. in excess of the truth, and attributes this to the incomplete washing of the precipitated platinochloride.This should not be put on to the filter until completelyexhausted with alcohol in the dish, and shodd be well broken up with a glass rod. RUER also complains about the process giving results which are too high, amounting t o about + a per cent.; and proposes to lower the factor 0.3056 to 0.304 so as to counterbalance the error, BAUER prefers to avoid the weighing on a filter, and to redissolve the precipitate in boiling water. The liquid is then evaporated in a weighed platinum dish, and the residue dried at 120". L. DE K. Estimation of Potassium at the Works at Leopoldshall, Stassfurt. By TIETJENS and APEL (Chem. Zeit., 1896, 20, 202-203). -The authors, in reply t o Atterberg (preceding abstracts), suggestANALYTICAL CHEMISTRY. 161 that the difference in the percentage of potassium found may possibly be E imation of Potassium as Potassium Platinochloride.By HEI-. ICH PRECHT (Chem. Zeit., 1896, 20, 209).-A reply to Atterberg (prcr ding abstracts), The author recommends treating the platino- chloride residue with commercial absolute alcohol instead of spirits of wine ; contrary to theory, the sodium platir,ochloride is more readily soluble in the former liquid, whilst the potassium salt is practically Analysis of Commercial Copper by Electrolysis. By A. HOLLARD (Compt. TB'YL~., 1896, 123, 1003--11)05).-Ten grams of the copper is placed in water and 15 C.C. of concentrated sulphuric acid, and 40 C.C. of nitric acid of 36" B is added. Towards the close of the reaction, the liquid is gently heated.Antimony sometimes separates, but, if the quantity is small, it does not interfere with the estimation of the copper; if large, it is separated by filtration, dis- solved in aqua regia containing a high proportion of nitric acid, evaporated to dryness, dissolved in dilute hydrochloric acid containing tartaric acid, and added subsequently to the liquid from which the copper has been removed, and in which the antimony is to be estimated. The copper solution is diluted to about 350 c.c., Luckow's electrodes (cone and spiral) are introduced, the base of the spiral being about 6 mm. below the base of the cone, which should be completely covered by the liquid, and a current of about 0.3 ampere is allowed t o pass until all the copper is precipitated.The firmly adherent deposit on the cone contains the copper and the silver. Part, but not all, of any lead that may be present will be deposited on the spiral as peroxide. When more or less than 10 grams of copper is taken, the best quantities of sulphuric and nitric acid respectively are, for 1 gram, 1 C.C. and 30 c.c.; for 3 grams, 6 C.C. and 33 C.C. ; for 5 grams, 10 C.C. and 35 C.C. ; for 20 grams, 20 C.C. and 60 C.C. The estimations of the other constituents of the copper will be described subsequently. C. H. B. Nessler's Reaction as a Test for Mercury or Iodides. By GBORGES DENIGBS (Chem. Zeit., 1896, 20, 70).--Detection of Merczq. The solution, measuring about 2 c.c., is mixed with 2 C.C. of ammonia, and potassium iodide is added in quantity just sufficient to redissolve the precipitate. On adding aqueous potash, the characteristic brown colour will appear, Detection of Iodine.-The solution is, if necessary, precipitated with ammonium sulphide, and the filtrate boiled to expel the excess of the reagent.Ammonia and aqueous soda are first added t o it, and then a solution of mercuric chloride, when the well-known coloration will be Estimation of Mercury Salts by means of Sodium Dioxide. By BL C. SCHUYTEN (Chenz. Zed., 1896,20, 239).-The process is based on the remarkable fact that sodium dioxide, which possesses such strong oxidising properties, is yet capable of reducing mercury com- pounds t o the metallic state. due to the samples having absorbed moisture. IJ. DE K. insoluble. L. DE E. produced.L. DE K. VOL. LXXII. ii. 12162 ABSTRACTS OF CHEMICAL PAPERS. The mercury compound, soluble or insoluble,is mixed with a suficiency of water contained in a porcelain basin fitted with an inverted funnel , the stem of which is bent a t right angles. Sodium dioxide is intro- duced in small portions at a time, as long as a precipitate is formed and after putting on the funnel the whole is gently heated until vapours begin to condense in the neck of the funnel. When cold, the funnel is rinsed, and the metallic mercury is collected on a weighed filter, and dried in a desiccator. The process is not applicable to the native By ERNST HINTZ and HERMANN WEBER (Zeit. anal. Chem., 1897, 36, 27--31).-The separa- tion of thoria from the oxides of the cerium and yttrium metals is based on the solubility of thorium oxalate in ammonium oxalate, and its reprecipitation from this solutionon the addition of hydrochloricacid.I n opposition to Glaser (Chem. Zeit., l896,20,613),the authors find that thorium oxalate dissolved in a hot concentrated solution of ammonium oxalate is not precipitated on diluting and cooling. The hydrochloric acid solution of 1 gram of the substance, freed from silica by evapora- tion, and from heavy metals by hydrogen sulphide, is diluted to 200 C.C. and precipitated hot by 1 gram of oxalic acid. After remaining for two days, the precipitate is collected, washed, and digested for several hours on the water bath with 60 C.C. of a solution (saturated cold) of ammo- nium oxalate. The mixture is diluted to 300 c.c., and allowed to remain cold tor two days, then filtered, and the filtrate heated with 5 C.C.of concentrated hydrochloric acid, whereby the thorium oxalate is com- pletely precipitated. The residue left undissolved by the ammonium oxalate is repeatedly digested with fresh portions of oxalate solution, and the filtrates treated as before. The thorium oxalate is then washed and ignited. I t is, however, not yet quite free from cerium and yttrium. It is therefore redissolved, either by boiling with hydrochloric acid or by fusion with potassium hydrogen sulphate, precipitated with ammo- nia, dissolved in hydrochloric acid, and, after evaporation to expel excess of mid, its feetjly acidified solution (diluted to 300 c.c.) is boiled with 3-4 grams of thiosiilphate. The filtrate is precipitated by am- monia, the wanhed precipitate dissolved in hydrochloric acid, the solution evaporated, then taken up with a little water, and the boiling solution treated with a hot concentrated solution of ammonium oxalate.Water is added, aud the mixture allowed to remain long in the cold. The precipitate consists of the oxalates of the cerium and yttrium metals, and the weight of the oxides is deducted from that of the im- pure thoria. I n some cases of very impure thorites, it is necessary to ignite the oxalates left undissolved by ammonium oxalate, and, after bringing them into solution as chlorides in feebly acidifiedwater, toapply the thio- sulphate method for the precipitation of the thoria present ; but as the precipitation of thoria by this means is imperfect, the filtrate also requires to be treated by the ammonium oxalate separation method.(Compare Abstr., 1896, ii, 677.) M. J. S. Use of Nitroso-/3-Naphthol in Inorganic Analysis, By ROBERT BURGASS (Zeit. angw. CAem., 1896,596-601).-This reagent, first intro- sulphids. L. DE K. Estimation of Thorium in Thorite.ANALYTICAL CHEMISTRY 163 duced by von Knorre for the separation of cobalt and nickel (Abstr., 1893, ii, 500), has been tried by the author for the separation of other metals. He finds that copper, cobalt, and iron are completely precipi- tated ; silver, tin, bismuth but partially, and these should, therefore, be removed before adding the nitrosonaphthol. Mercury, nickel, chro- mium, manganese, lead, zinc, aluminium, cadmium, magnesium, calcium, beryllium, antimony, and arsenic remain in solution.I n presence of excess of iron, any phosphoric acid will also be carried down ; molybdic or titanic acid interferes with the accurate estimation By HUGO AMSEL (Zeit. angw. Chem., 1896, 613--61S).-The author thinks that, if the sample is free from the carbonates and sulphates of barium, calcium, and lead, it may be passed as commercially pure. If a quantitative analysis has to be made, the best plan is t o boil about 0.5 gram of the compound with a 10 per cent, solutionof aqueous potash for some time; hydrochloric or nitric acid is then added in slight excess, and any insoluble matter, such as barium sulphate, is collected and weighed. The filtrate is mixed with excess of sodium carbonate, and heated, with addition of bromine ; the precipitate contains calcium carbonate and lead carbonate (the latter being partially converted into dioxide), whilst the filtrate contains sodium chromate and sulphate.The details Separation of Tungsten and Titanium. By ED. DEFACQZ (Compt. vend., 1896, 123, 823-824).-A mixture of 8 parts of potas- sium nitrate and 2 parts of potassium carbonate, heated a t its melting point, completely dissolves tungstic anhydride in 8 or 10 minutes, whether the anhydride has previously been strongly heated or not. Netallic tungsten is likewise dissolved. On the other hand, the fused mixture does not dissolve either titanium oxide or metallic tit.anium. The substance to be analysed is heated to dull redness for 20 to 30 minutes with 7 to 8 times its weight of the mixture of nitrate and car- bonate specified,and,after cooling, the product is treated with water and evaporated to dryness.The residue is first extracted with water and then washed with water containing ammonium nitrate, in order t o pre- vent the titminm oxide from passing through the filter. The insoluble residue is dried, strongly heated, and afterwards fused with potassium hydrogen sulphate, the titanium being estimated in the usual way. The tungsten in the solution is precipitated as mercurous tungstate. Comniercial Prussian Blue. By ERNEST J. PARRY and JOHN HENRY COSTE (Armlyst, 1896, 21, 225--230).-The authors have examined a large number of samples of commercial Prussian blue, and tabulated the results. The chief point in the analysis is the estimation of the total iron, and the nitrogen ; the latter by Kjeldahl’s process.The factors for converting these into Prussian blue are respectively 3.03 and 4.4. I n properly manufactured samples, the results obtained from these estimations ought to agree, but there may be occasionally either excess of ironor of nitrogen in the form of alkali or even of aluminium of the cobalt or copper. L. DE I(. Assay of Chrome Yellow and Chrome Red. present no novel features. L. DE K. C. H. B.164 ABSTRACTS OF CHEMICAL PAPERS. ferrocyanide. Commercial blue may be passed as sufficiently pure if it contains 30 per cent of total iron and 20 per cent. of nitrogen. When boiled with sulphuric acid, it should become colourless in a By F. W. JONES and F. A.WILLCOX (Cl~em. News, lS96,74,283).-The method is based on the solu- bility of mercury fulminate in acetone saturated with gaseous ammonia. A tared filter paper is placed iIt a funnel to the neck of which has been fitted a piece of rubber tubing provided with a clip. The paper is moistened with a solution of ammonia in acetone ; the finely- powdered cap composition is weighed off directly on to the filter paper, covered with the solution of ammonia in acetone, and the whole allowed to remain for 3 or 4 hours. It is then washed repeatedly with the same solution until the washings give no coloration with amme niurn sulphide, and afterwards washed with acetone until the washings give no residue on evaporation ; it is then dried, and weighed ; the loss gives the amount of mercury fulminate.The paper and contents are again put in the funnel, washed with water until free from potassium chlorate, dried, and weighed; the further loss in weight gives the amount of potassium chlorate, and by deducting the weight of the filter paper from the last weighing, the amount of the antimony sul- phide is obtained. By C. EMANUEL MERCK (Chem. Zed., 1896, 20, 228).-By means of molybdic acid, i t is possible to detect the presence of 0.2 per cent. of methylic alcohol, or 0.02 per cent. of ethylic alcohol, in the absence, of course, of any organic matter capable of interfering with the test. This is best carried out by dissolving molybdic acid in sulphuric acid at 60°, and pouring the hot solution gently into the liquid to be tested, when a blue ring will form at the surface of contact.On shaking, the colour disappears, but returns on adding more of the reagent, few minutes without any charring. L. DE K. Analysis of “Cap Composition.” D. A. L. Molybdic Acid, a Reagent for Alcohol. L. DE K. Estimation of Alcohol by Means of the Ebullioscope; In- fluence of Extractive Matters. By FRANZ FREYER ( Z e d . angw. Chern., 1896, 654-659).-The principle of the instrument (of which there are several varieties) is based on the difference between the boiling point of pure water and that of the spirit to be tested ; a table is then referred t o for the alcoholic strength of the sample. The author points out that in the presence of much extractive matter the results are untrustworthy, as the alcohol may then be found several per cents.too high. A new table allowing for extractive matter Detection of Caramel in Wine, and its Possible Confusion with Coal-tar colours. By A. J. DA CRUZ MAGALRAES (Compt. rend., 1896, 123, 896--897).-A sample of port wine examined by the author gave reactions pointing to the presence of a coal-tar colouring matter, although it was known that only caramel made from cane- sugar had been added. Further exeriments showed that caramel pre- pared from cane-sugar differs considerably from caramel made from is given. L. DE K.ANALYTICAL CHIENISTRY. 165 glucose, in that it behaves with certain reagents exactly like a coal-tar colour. Thus, when treated with basic lead acetate and then shaken with amylic alcohol, the former caramel communicated an orange-yellow colour to the solvent, whilst with the glucose caramel no coloration occurred.Ether, when shaken with a solution of the former, acquired a n orange yellow colour, whilst with the latter no colour was ex- tracted. Mordanted wool was dyed orange by the former, yellow by the latter. Genuine wine, t o which no caramel had been added, did not give these reactions. Simple and Convenient Extraction Apparatus for. the Analysis of Food Stuffs. By J. IT,. BEESON (J. A m e ~ . Cliena. Soc., 1896, 18, 744-’745).-A modification of the Johnston extractor. The extraction tube, which is rather short, has a funnel stopper, and is so constructed that the sample may be weighed and dried in the same before extraction, After placing the tube in a Stutzer tube, the extraction with ether, kc., proceeds as usual, the returning drops of liquid being allowed to fall through the funnel tube on to the centre of Reformation of the Present Methods of Analysis of Food Stuffs.By F. JOSEF GNIG (Larndzo. Versucla-Stat., 1896,443, Sl-110). -Owing to the probable difference in nutritive value of the pentosans and bexosans, it is desirable, if possible, to estimate separately the amounts of these two groups in food stuffs. Experiments were first made in which rye grain and straw, and pea corn and straw, were treated with 1.25 per cent. sulphuric acid and 1.25 per cent. caustic potash. Both solutions dissolved more or less of the pentosans, and even 0.3 per cent. potash dissolved some, but i n no case was the solution complete, Superheated water dissolved the pentosans in rye flour and straw almost completely as well as the starch.When, therefore, starch is estimated by first dissolving with superheated water and subsequent inversion, results are obtained which are more or less too high, since the dissolved pentosans reduce Fehling’s solution as well as the hexoses. To obtain more correct results for starch, it is therefore proposed (when superheated water is employed) to ferment the inverted solution with beer-yeast, and toestimate the carbonic anhydride o r the alcohol produced. The method is, however, not perfect, owing to the production of hexoses from the cell-membrane. Pentosans seem to accompany the hexosans in all parts of plants. The following amounts of pentosans were found in starch from different sources : potato-starch, 1.25 ; maize-starcb, 2-04 ; rice-starch, 1.40, and wheat-starch, 1.05 per cent.Estimation of starch as maltose after treatment with diastase gave results which were too high, although less of the pentosans was dis- solved than when superheated water was employed. The fermentation method would give better results. The usual process of food stuff analysis has two faults, the use of too dilute acid and the use of too strong alkali. The acid is not strong enough to dissolve all the hemicellulose, whilst the alkali dis- solves, besides fat and proteids, lignin, which should be either determined along with cellulose or else separately. With regard to alkali, it was A. C. C. the sample, so as to avoid loss of tlic latter. L. DE K.166 ABSTRACTS OF CHEMICAL PAPERS.found that 0.5 per cent. soda solution dissolved almost the whole of the nitrogenous matter of the food, leaving a residue of crude fibrs containing much the same amount of nitrogen as when 1.25 per cent. potash was used. The use of the more dilute alkali has the advantage t h a t the lignin present is less attacked, and may therefore be estimated separate1 y. Experiments with different strengths of acid are still in progress, but the results so far obtained indicate that, whilst less than 1 2 per cent. hydrochloric acid is insufficient t o dissolve the whole of the pento- sans, better results may be obtained by heating under pressure with more dilute acid. Formaldehyde as a Reducing Agent. Estimation of Formaldehyde. By BRUNO GRUTZNER (ATCIA.PIAccT~., 189 6, 234, 634-640) .-To estimate potassium chlorate, the aqueous solution (about 2 per cent.) may be mixed with formalin (35 per cent. aqueous solution of formaldehyde-5 grams) nitric acid ( 5 C.C. ; strength not named) and excess of silver nitrate solution. The mixture is heated on the water bath for half-an-hour, and the precipitated silver chloride then estimated by any of the usual methods. Potassium bromate mpy be estimated on precisely similar lines, save that the heating must be continued for 2-24 hours in order to complete the action. Iodates are not reduced by this method, and perchlorates only partially ; periodates are reduced to iodates. By mixing a measured volume of a formalin solution with an excess of potassium chlorate, adding a measured excess of NjlO silver nitrate solution, heating the mixture in the water bath until further heating produces no turbidity in the clear liquid above the settled precipitate, and titrating the excess of silver nitrate solution with potassium thiocyanate in the usual manner, the strength of the formalin solution may be determined. One molecule of silver nitrate corresponds with three of formaldehyde. Estimation of Formaldehyde.By GYSEERT ROMIJN (Zeit. ccizal. Chiem., 1897, 36, 18--24).-Besides reviewing the methods of Legler (Abstr., 1883,1035) and of Brochet and Cambier (Abstr., 1895, i, 325) the author proposes two new ones, the first depending on oxidation by iodine in alkaline solution, and the second on the combination of form- aldehyde with potassium cyanide, and he has studied their suitability for estimating formaldehyde both when occurring alone and when mixed with other substances of an aldehydic character, such as acetaldehyde, acetone, and benzaldehyde.A solution of formalin was used for the experiments. With the pnre substance, all four methods gave prac- tically identical results (37.38-31.9 per cent.), but owing to the want OF sensitiveness of litmus i n solutions containing hexamethylenatetra- mine, Legler’s method requires the use of much stronger solutions than the other three, and is altogether of inferior accuracy. The operations in the new methods are as follows. To a quantity of the solution containing about 15 milligrams of formaldehyde, there is added 25 C.C. of a N/10 iodine solution, and so much strong soda solution that the mixture becomes pale yellow.After 10 minutes, a small excess of hydrochloric acid is added, and the free iodine is titrated N. H. J. M. A. G. 13.ANALYTICAT, CHEAIISTHY 167 with thiosulphate. Two atoms of iodine are consumed by 1 molecule of formaldehyde. With the pure substance, the results are perfectly concordant, and the great convenience of the method renders it the most advantageous of the four. It cannot, however, be used in the presence of the other aldehydes, and in the case of acetone, which, as shown by Kramer and Messinger, forms iodoform with quantitative completeness, the two substances are estimated jointly. The reaction with potassium cyanide consists in the combination of the two substances in molecular proportion.Somewhat more than this amount of cyanide (in a solution containing about 6 grams per litre) is therefore added, and the mixture is poured into an excess of a N/10 solution of silver nitrate containing so much free nitric acid that the mixture remains acid. The excess of cyanide separates as silver cyanide, and the unprecipitated silver is titrated with ammonium thiocyanate (Volhard’s process). In the presence of acetaldehyde, the aldehydecyanide mixture must be immediately added to the silver nitrate or the results obtained will be too high, but acetone and benzaldehyde are without influence, even if half-an-hour elapses at this stage. Legler’s method seems not to be affected by the presence of theabove three foreign substances, but the hydroxylamine method cannot be used in pre- sence of any of them.Polarimetric Estimation of Tartaric Acid. By ALBERT COLSON (BUZZ. Chim Xoc. [ 3 I, l5,158).-The author experimented with solutions of tartaric acid of different strengths, made just alkaline with ethylenediamine. In the absence of impurities, and for solutions containing not more than 100 grams of tartaric acid per litre, the con- centration could be directly determined from the observed rotation. I n the presence of a substance such as citric acid, it mas found that an error was introduced which increased with the amount of the second substance present. The observations could, however, be corrected by means of an empirical equation involving the density of a solution containing the same amount of ethylenediamine tartarate, and the density of the solution under observation.By HEINRICH FRESENIUS (Zek c m d . Chem., 1897, 36, 31--32).-The author, having made numerous com- parisons of the methods of Gerber and Babcock (Abstr., 1891, 508) with the gravimetric process of extracting the milk, previously dried on sand, by ether, and weighing the residue obtained from the ethereal extract, finds that the results of the three methods agree satisfactorily. Gerber’s process consists in mixing 10 C.C. of sulphuric acid (sp. gr. 1.82-1+33) with 1 C.C. of amylic alcohol and adding 11 C.C. of the milk. The flask is then closed by a caoutchouc stopper, well shaken, and then revolved for 3 minutes in Gerber’s centrifugal machine. The fat collects in a graduated portion of the special-shaped vessel, and the reading gives the percentage at once. Method of Establishing the Purity of Butter by Deter- mining the Specific Gravity.By RAOUL BRULL~ (Bied. Centr., 1896, 25, 638 ; from Xilchzeif., 1896, 297, and JOUT~Z. Agyic., 7 March, 1896).-The failure of sp. gr. determinations of butter fat as a means M. J. S. M. W. T. Estimation of Fat in Milk. M. J. S.168 ABSTRACTS OF CHEMICAL PAPERS. of ascertaining the purity of butter, is attributed to the presence o water, colouring matter, &c. The following method is recommended for obtaining the f a t in a pure state. The butter (100-500 grams) is melted, the fat separated as far as possible, violently shaken for some minutes with finely powdered calcium chloride (5-6 per cent,) and powdered animal charcoal (4 per cent.), and filtered.The fat, which is now colourless and quite dry, has a sp. gr. of 0.S655 a t loo", whilst oleomargarin has a sp. gr. =0*8600, and the addition of 10 per cent. of margarin lowers the sp. gr. of butter fat by 0*00055. Separation of Trimethylamine from Ammonia. N. H. J. M. By HERMANN FLECK (J. Amer. Chem. Xoc., 1896, 18, 670--672).-The mixed hydro- chlorides are repeatedly extracted with boiling absolute alcohol, which is then distilled off in a 750 C.C. distilling flask. Excess of aqueous soda is added to the residue, and the gases given off on boiling are passed into a large volume of water; litmus is added, and the liquid is neutra- lised exactly with dilute sulphuric acid. The whole is now evaporated to dryness, and the residue extracted with 1 litre of cold, absolute alcohol, which dissolves the trimethylamine sulphate, leaving the ammonium compound undissolved. The alcohol is distilled off, and the residue transferred to a weighed dish and dried until the weight is constant, L. DE K. Colour Reactions of Brucine ; Detection of Nitrites in Presence of Sulphites. By P. PICHARD (Compt. ?*end., 1896, 123, 590--592).-Brucine in presence of hydrochloric acid and a trace of a nitrite yields, in 5 minutes or less, a vermilion red coloration which changes to pale yellow; this reaction is capable of detecting 1 part of nitrous acid in 640,000 parts of water. A nitrate under the same conditions gives no coloration. Chlorine and hypochlorous acid give no coloration with free brucine, but an intense vermilion coloration with the nitrate, chloride, acetate, and sulphate, especially the latter. The presence of sulphites or sulphurous acid very materially reduces the sensitiveness and accuracy of the ordinary reactions for the detection and estimation of nitrous acid, and hence they cannot well be applied t o soils which have been treated with calcium sulphate, and may in consequence contain lower sulphur compounds; this applies also, of course, to water that has percolated through such soils. On the other hand, the presence of 1 part of sulphurous acid in 2060 parts of water reduces the sensitiveness of the brucine test only to one-half, so that 1 part of nitrous acid in 329,000 paarts of water can still be detected. This reaction should be used for the detection of nitrites in soils or drainage waters which may also contain sulphites. In either case, sulphides must first be removed if they are present ; this is best done by agitating the solution with finely divided lead sulphate. C. H. B. By MELCHIOR KUBLI ( A ~ c h . Pharm., 1896, 234, 570-585).-A reply to 0. Hesse (Abstr., 1896, ii, 550). A. G. B. Testing Quinine Sulphate.

ISSN:0368-1769    

DOI:10.1039/CA8977205157

出版商:RSC    

年代:1897

数据来源: RSC