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PHYSIOLOGlCAL CHEXISTRP. 51 P h ys i o l o g i c a1 C h e m i 8 t r y . Simple Form of Gas Pump. By L. HILL (J. Physiol., 1894, 17, 353--355).-This is a modification of the mercurial pump suitable for the examination of small quantities of blood. Its con- struction is figured. W. D. H. Heat Value of Nutritive Substances. By F. STOHMANN (Zeif. Biol., 1894, 31, 3 6 6 3 9 1 ) .-In addition, to certain generalisations contrasting animal and plant life and their mode of nutrition, and the products they give rise to, the chief part of the present paper con- tains tables of the elementary composition and heat value of the most important animal and vegetable protejids, albuminoids, derivatives of these such as urea, and the amido-acids, animal and vegetable fats and carbohydrates. Heat Production in the Chick before and after Hatching.By M. S. PEMBBEY, M. H. GORDON, and R. WARREN (J. Physioi., 1894, 17, 331-34S).-Up to the 20th or 21st day of incubation, the Berthelot's apparatus was used. W. D. H. 5-252 ABSTRACTS OF OHEMICAL PAPERS. chick responds to changes of external temperature like a cold-blooded animal; then there is an intermediate stage when no response is ob- t,ained, and when the chick is hatched it responds like a warm- blooded animal. The method used was a modification of Haldane's apparatus. W. D. H. Bldod Coagulation. By L. LILIENFELD (Zeit. phy&oZ. Chern., 1894,20,89-165 ; compare Abstr., 1894, ii, 22).--In this paper, in ad- dition to a historical account of the question, a full description of experiments and theories is given, part, of which has appeared in several preliminary communications. The active agent in coagula - tion is regarded as a nucleo-albuminous substance, named nucleo- histon ; it is considered to originate from leucocytes, especially from their nuclei, and from platelets.The nnclein in this substance hastens, whilst the histon hinders, coagulation; the separation intonuclein and histon can be effected by lime water or baryta water. Nuclein alone. and calcium chloride alone, do not cause coagulation in solutions of Hammarsten's fibrinogen; but i f acetic acid is added to a solution of fibrinogen, a substance is precipitated which is coagulated by nuclein with calcium salts, or by calcium salts alone. This substance is termed thrombosin ; and fibrin is regarded as a calcium compouud of thrombosin.The constituent of fibrinogen which remains in solution when thrombosin is precipitated by acetic acid, is like peptone in some of its properties, particularly in its hindering influence on coagulttion. Nuclein, or rather nucleic acid, acts just like acetic acid, precipitating free thrombosin from fibrinogen (not a nucleic acid compound of thrombosin). This holds both for intravascular aud extra-vascular coagulation ; nucleic acid first splits up the fibrinogen molecule, and then one of its components, thrombosin, unites with a calcium salt to form fibrin. The fibrin-ferment is described as a globulin which is a product and not the cause of coagulation. W. D. H. Glucase. By F. ROHNAXN (Ber., 1894, 27, 3251--3253).-1'he author, in conjunction with Bial, has recognised the presence of an enzyme in blood-serum and lymph, which has the power of trans- forming starch into glucose (Abstr., 1893, i, 187).He now states that the enzyme affects glycogen in a similar manner. Bial has already shown (Abstr., lE93, ii, 333, 581) that blood-serum trans- forms dexti-in and maltsose into glucose. Tho author finds that by the action of saliva on starch paste, isonialtose, maltose, and dextrin are formed, together with a small amount of glucose ; whilst by the action of pancreatic juice and intestinal juice (succzis entericus) on starch paste, a larger quantitj of glucose is formed but not so large as that resulting from the action of blood-serum. Following, however, the velocity of the liquefication of starch paste and of the increase in the cupric reducing power, it is found that pancreatic juice acts more powerfully than saliva, the latter, however, liquefies starch paste more rapidly than blood-serum.Furthermore, saliva and pancreatic juice bring about a quicker rise of the cupric reducing power of the transformation products to a maximum, b u t this is lower than theFHY SIOLOQICAL CHEMISTRY. 53 maximum attained by the actron of blood-serum over a considerably longer period. According to the author, the simplest explanation of these results is that saliva, pancreatic juice, intestinal juice, and blood-serum contain both diastase (maltase) and glucase, the former being present in largest, amount in the pancreas, and in the smallest in the blood, and rice rers$ as regards glucase.By allowing fresh yeast cells to remain over alcohol, whereby the glucase is destroyed, the aqueous extract no longer acts on maltose but only on saccharose. Invertase and diastase can thus be prepared free from glucase. A. R. L. Action of Calcium and other Salts on the Animal Organism. B v H. WEISKE (%a'/. Biol., 1894, 31, 421--448).-A number of rabbits were fed r?n oats, a diet which is acid and poor in calcium, and the observations showed that they lost weight ; a comparison being made with other animals who received in addition calcium carbonate, calcium sulphate, strontium carbonate, or magnesium carbonate. At thc end of the research the composition of their bodies, and especially of the skeleton, was examined. The salts administered correct the acidity and harmfulness of the oats ; calcium carkonate having the best effect, both as regards the general condition of the animals and the amount of calcium in the skeleton.The bones show also that strontium and magnesium can replace part of the calcium. The urine and feces also show evidence of the different salts administered. W. D. H. Calcareous Concretions in the Brain. By F. B. MALLORY (J. Patliol. and Bacterial., 1 894, 3, llO-l17).-These not uncommon deposits are due to the calcareous infiltration of colloid material (hyaline of v. Recklinghausen) which 1s deposited in the blood vessels. In the larger vessels, the middle coat is earliest and most affected. W. D. H. Salivary Glands of the Leech. By J. M. CROOCKEWIT (T{jdsclii*.&. hTed. Dierk Vereen., 1894, 896--'312).-It is the secretion of these glands which prevents the coagulation of the blood. Most of the present papel. is anatomical. Some observations of a chemical nature seem to indicate that the substance to which the secretion owes the activity alluded to above is a nucleo-albumin. W. LENZ (Zeit. Biol., 1594,31,392--399).-The ox in different states of development furnished the material for the research. The calcium in the liver cells of the calf is about 79 per cent. greater than in thc f nlly-grown animal. The foetal period shows two maxima, namely, i n the fifth and tenth months ; at these times, there is 45 per cent. more calcium than in the adult ; the minima also appear to be two occurring in foetuses o€ 20-30 and 60-i0 cm.long respectively. The amount of calcium varies inversely with that of the iron during the foetal period ; they are described as antagonistic. Sex and pregnancy make no difference, W. D. H. Calcium in the Liver Cells of the Ox. By F. KR~GER W. I). H.54 ABSTRACTS OF CHEMICAL PAPERS. Percentage of Sulphur and Phosphorus in the Hepatic and Splenic Cells at different Ages. By F. KR~GER, F. SZTMKIEWICZ, L. V. LINGEN, and H. WALTER (Zeit. Biol., 1894, 31, 400-412).- The amount of sulphur in the liver cells of oxen remains fairly con- stant throughout life, and i n different individuals of the same age varies within certain narrow limits. Phosphorus is more variable ; the foetal cells are richest, and during foetal life the percentage is fairly constant; it is less in the calf, less still in the grown ox.Sex makes no difference. With regard to the spleen, again sulphur varies but little, being, however, rather less abundant in calves than in the foetal and full- grown periods. Phosphorus is most abundant in foetuses between 30 and 60 cm. long, sinks at birth, rises suddenly after birth, and is lowest of all in the grown animal. During the foetal period, the sulphur in the splenic cells is about 16 per cent. higher than in the liver cells ; after birth, the two are about equal, and in grown cattle the splenic cells are a.bout 9 per cent. richer in sulphur than t'he liver cells. Foetuses of 30-60 cm. length have 39 per cent. more phosphorus in the splenic than in the liver cells. I n foetuses of 80-90 cm. length, the amount of phos- phorus is about the same in the two varieties of cells; whilst in foetuses of 90-100 cm.length, the liver cells contain 16 per cent. more phosphorus than the splenic cells. After birth, the splenic cells again contain more phosphorus by 25 per cent. than the liver cells ; in grown cattle, there is an approximate equality, although the total amount of phosphorus is less than in calves and foetuses. I n adult men, the liver cells contain 2.41 of sulphur, 1.28 of phos- phorus, and 0.077 of iron per cent. In the liver of new-born children, the numbers are respectively 3.56, 1.54, and 0.314. The adult man and ox are in this connection very much alike. In fatty degeneration of the liver, the numbers were 2.18, 0.87, and 0.176, that is, sulphur and phosphorus fall, whilst iron rises.By A. WROBLEWSKI (Inaug. Diss., Bern, 1894).-The mean of analyses of the casein of human milk gives C, 45.01; H, 7.31; N, 15.07; P, 0.8; S, 4 7 ; 0, 27-11 per cent. It differs from the casein of cow's milk in solubility, and in the fact that on peptic digestion it yields no residue of nuclein. Phosphorus in Digestion Products of Casein. By W. v. MORACZEWSKI (Zeit. pliysiol. Chem., 1894, 20, 28--51).-A series of five experiments show that the arnonnt of phosphorus in the nuclein left after the digestion of casein by artificial gastric juice is variable, and that all the phosphorus of the casein is not in the form of iiuclein ; from 6 t o 60 per cent. of the phosphorus is present in this form. The casein of human milk contains phosphorus but no nuclein (compare Wroblewski, preceding abstract).IV. D. H. Egg-shells of Echidna and other Vertebrates. By R. NEU- MEISTER ( Z e i t . Biol., 1894, 31,413--4'20).-The egg-shells of Echidna aczde[rfa ( E . hystrix) consist of a keratin-like substance containing Sex has zio influence. W. D. H. Case'in of Human Milk. W. D. H.PHTSIOLOQICAL CHEMISTRY. 55 5 per cent. of sulphur. It is, however, digested neither by gastric nor by pancreatic juice ; some other keratins are similarly resistant. I n invertebrates, the organic basis of egg-shells is chitin or some other skeletin. Keratin appears to be only present in the egg-shells and membranes of vertebrate animals. I n the frog only has mucin been described. The eggs of some birds and reptiles are briefly referred fo in this connection.Calcium carbonate is the principal inorganic constituent. W. D. H. Acidity of Urine. By V. LIEBLEIN (Zeit. physiol. Chem., 1894, 20, 52-€%).-This gives a, long and critical account of the various methods, chemical and colorimetric, by means of which the acidity of urine, and the various factors of which it is made up, can be deter- mined. The following general conclusion is drawn, that by the estimation of phosphoric acid in the form oE diphosphate alone, can a trustworthy measure of the acidity of urine be obtained. W. D. H. Ethereal Hydrogen Sulphates in Urine. By J. E~GER (Chem. Uentr., 1894, i, 873; from PhLarm. Zeit. f. Russland, 23, 149-151).- The ethereal hydrogen sulphates in the urine are increased in most diseases of the liver ; the liver, under normal circumstances, prob- ably oxidiees aromatic substances. I n intestinal catarrh and in kidney diseases (especially chronic ones), these constituents of the urine are also increased.By disinfection of the alimentary canal and rapid removal of its contents, the ethereal hydrogen sulphates are diminished. a- and p-naphthol, hydrochloric acid, hydrogen phos- phate, and sulphuric acid cause an increase; quinine nitrate and lactic acid, a decrease in these sulphates. Calomel produces the latter result when it causes purgation also. Potassium iodide, arsenic, ipecacuanha, digitalis, tvallaria, Adonis vernalis, opium, morphine, codeine, and bismuth salicylate have no effect. W. D. H. Hzematoporphyrin in Normal Urine. By A. E. GARROD ( J .Physiol., 1894, 17, 349-352) .-Renewed research confirms the author's previous conclusion that haematoporphyrin is a scanty but uormal constituent of urine. 20 C.C. of a 10 per cent. solution of sodium hydroxide are added to every 100 C.C. oc" urine ; the precipi- tated phosphates are collected and washed with water. The precipi- tate is dissolyed in rectified spirit and acidified with hydrochloric acid ; the solution shows the bands of acid hsematoporphyrin. Am- monia is then added to precipitate the phosphates, and acetic acid to redissolve them ; chloroform then extracts haematoporphyrin com- pletely, and shows the bands of the alkaline pigment. W. D. H. Pigmentation of Uric acid Crystals Deposited from Urine. By A. E. GAHROD (J. Pathol. and Bacterial., 1894, 3, 100--106).-0f the true urinary pigments which exist ready formed in urine, only the normal yellow pigment (urochrome) and uroerythrin appear to possess the property of colouring uric acid crystals deposited from flieir solutions.The yellow pigment being a constant constituent of56 ABSTRACTS OF CHEMICAL PAPERS. urine always furnishes the ground tint of the crystals, and plays the more important part in determiniog their form, the whetst,one or canoe shape being specially the one produced. I n the majority of instances, uric acid crystals wliich are spontaneously and rapidly deposited from urine, contain uroerythrin also, to which they owe their red colour when seen in bulk. I t is, however, never the sole colouri2g matter in these sediments, and varieties of tint are due to differences in admixture of it with urochrome.The minute quantity OF iron present in the ci-ystals is a, constituent of neither pigment. Urobilin and hamatoporphyrin take no part in the coloratioii of t h e crystals, but other pigments occasion~lly present in urine may share in the coloration, such as the brown products caused by the action of mineral acids, the oxidation products of phenol-derivatives, and the pigments of the bile. W. I). H. Percentage of Iron in the Liver in Aukylostomiasis. By B, R ~ K L ( J . Put hsl. and Bucteriol., 1894, 3, I 07-109) .-The percentage of iron in liver and spleen in five cases of disease, due to the presence of the worm Azd-ylostoma duodenale, is given. The interest of such an investigation arises from the fact that the symptoms produced a r e very like those of pernicious anamia.Average 1. 2. 3. 4. 5. percentage. Liver .. .. trace 0.26 0.2068 0.0123 0.0228 0.100 Spleen. . . 0.04 3.28 - 0.0592 0.071 0.862 The average percentage of iron in the liver is less than in other diseases, and much less than in pernicious anEmia ; thus : aukylos- tomiasis, 0.1 ; other diseases, 0.12 ; pernicious anamia, 0.7. The iron in the spleen is scarcely affected. The intense anamia associated with the disease is simply due t o loss of blood from the intestine, and is not cansed by any toxic snb- stance causing blood destruction in the liver. W. D. H. Piperazine as a Solvent of Uric acid Stones in Urine. By J. FAWCETT (Brit. dled. J., 1894, ii, 1426).-An aqueous solution of piperazine dissolves uric acid stones, but a solution of this substance in urine of the strength of 1 in 1000, which is above that usually found in the urine after takiDg the drug internally, has no eEect whate per, W.D. H. Physiological Actian of certain Pyridine, Naphthalene, and Quinoline Derivatives. By R. COHX (Ber., 12394, 27, 2904-2919 ; Zeit. phyhiol. Chem., 1894, 20, 210-218 ; compare Abstr., 1893, ii, 544) .-In rabbits, quinaldine is entirely destroyed in the organism. In dogs, this is probably the case also, but the examination of the urine was more difficult, and the result somewhat uncertain. 1-Methyl- quinoline is in dogs entirely destroyed in the body. 3-Methylquinoline is changed into the corresponding quinolhe-3-carboxylic acid in small measure (7 per cent.) ; the rest is destroyed.W. D. H.VEGETABLE PHYSIOLOGY AND XGRIGULTURE. 57 Action of Drugs cn the Heart of Daphnia. By J. W, PICKER- IKG (J. Physiol., 1894, 17, 356--359).--The hcart of Daphnia can be easily observed with the microscope in the intact animal. The heart of each animal has an individual rhythm which, if external circum- stances are unvaried, remains constant. Atropine sulphate, in doses oE0-3 milligram, increases the cardiac frequency ; but after 5t period of from 20 to 30 minutes the heart becomes irregular, and, finally, stops in diastole and its irritability is lost. Muscarine nitrate, in large doses, has practically no effect on the heart, although it causes violent intestinal action, and, finally, loss of general irritability. Veratrine, in doses of 2 milligrams, does not seriously impair the cardiac- rhythm; its depressing action is removable by he& Caffejine causes? in small doses, increase of force and frequency; in large doses, tonic contraction and systolic stoppage ; theobromine and xanthine have no effect. W. D. H. Pharmacological Investigation of Manaca Roots. By J. BRXBDL (Zeit. Biol., 1894, 31, 251--292).-The substances separated were manacin, C2?H33N2O10, rnumcei~t, CI5H2,N2O9, 8 fluorescent sub- stance identical with the aesculetin of Zwenger (Annulen, 90, 63), valeric acid, and a material resembling humons substance. Lenardson (Inaug. Dim., DoiFut, lS94), who has worked at the same plant, gives the formula f o r manacin as CISH2,N,O5. Manacin is convertible into manace'in by the action of certain micro-organisms. In addition to botanical details, the bnlk of the research refers to the phjsiological actions of manacin, the most marked of which is a stimulating action of the motor end plates and of secreting glands. Manacein causes very similar results. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8956805051

出版商:RSC    

年代:1895

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOQY AND AQRIGULTURE. 57 Chemistry of Vegetable Physiology and Agriculture. Bactericidal Action of Light and Air. By R. F. D’SRCY and W. B, HARDY (J. Physiol., 1894, 17, 390-393).-Marshall Ward haa sliowc that the bactericidal power of light is a pecuiiar property of light of short wave length, and is a t its maximum at the violet end of the blue. This is only manifested in the presence of oxygen, and Wiirstei- (Bey., 1886,19, 3201) has shomii that “active oxygen ” is produced when evaporation takes place in direct sunlight. The present experi- ments show that when the spectrum of a powerful arc light i s allowed to fall on a moist surface in the presence of st delicate indi- cator, oxidation occurs, and t,he action commences at the blue end of the green, and continues through the blue, violet, and ultra-violet regions; in other words, the action is confined to a portion of the hpectrum which corresponds with the region of activity i n Ward’s experiments.IV. D. H.58 ABSTRACTS OF CHEMIOAL PAPERS. Effect of Sunlight on Tetanus Cultures. By F. F. WESBROOK (J. PathoZ. and Bacterial., 1894, 3, 70-77) .-The experiments con- firm other observers in the conclusion that oxygen is a necessary factor in the destruction of bacteria by light. Without oxygen sun- light is powerless. Moreover, the oxygen in the contained air shows diminution during the exposure of cultures. W. D. H. Thermophilic Bacteria. By A. MACFADYEX and F. R. BLAXALL (J. Yathol. and BacterioZ., 1894, 3, 87-99).-The paper gives an account of bacteria which flourish at a high temperature in manures, in the causation of spontaneous combustion, &c.It is difficult to believe that they are merely freaks which only develop when a bacte- riologist appears on the scerie with an incubator. Their wide distri- 'bution, their good growth at these high temperatures, and their active fermentative properties, all point to their fulfilling some useful function i n the economy of nature. W. D. H. Antiseptic Action of Phenyl-substituted Fatty Acids. By J. P. LAWS (J. Phpiol., 1894, 17, 360-.363).-Phenylbutyric acid re- strains the growth of anthrax bacilli when present in the proportion of 1 to 2500; it kills the sporeless bacilli in 30 minutes in a solution of 1 to 1000, and in 10 minutes in a solution of 1 to 700. The following table compares its action with related substances.Phenol. Phcnylacetic Phenylpro- Phcnylbutyric 1 1 acid. 1 pionic acid. I acid. I I I Restraining power.. 1-700 - 1.-1900 1-2500 Killing power.. , . . . I 1-200 I 1-450 1 1-600 I 1-1000 Length of exposure. 45 mins. 30 mins. 30 mins. 30 mins. Antiseptic power thug increases with molecular weight ; in the fatty acid series itself, the converse holds good (Duggan, Amer. Chem. J., 7, 62). W. D. H. Assimilation of Free Nitrogen by Algm. By A. KOCH and P. K.OSSOWITSCH (Bot. Zeit., 1893, 51, 321-325) .-The authors' experi- ments were as follows. Pure, ignited sand with nutritive salts (including calcium nitrate) was put into a number of Erlenmeyer flasks (60 grams of sand to each); in two experiments, sugar (0.05 gram) was added. The sand was seeded with algse from a chalk heap, the flasks closed, and a slow current of purified air passed through There was an arrangement for absorbing any ammonia which might be evolved.Three flasks were kept dark, and three near it window for nearly 3+ months. In the flasks kept dark (and conse- quently free from algse), there was no gain of nitrogen, whilst there was a distinct gain in the other flasks in which algp developed-the greeter the dedopment of algae, the greater the fixation. - N. H. J. M.VEGETABLE PHYSIOLOGY AND AQRICULTURE. 59 I Cystococcus, Phormidium, soil bacteria 1 2 -6 2 -6 2 -6 2 *6 and mould Cystococcus and bacteria .............. I Stichococczu and bacteria.. ............ i Nostoc, large round algte, Scenedesmus i and soil bacteria Fixation of Free Nitrogen by Algae.By P. KOSSOWITSCH (Bot. Zeit., 1894, 52, 9?-116).--’E’rank (Be?.. d. hot. Ges., 1889, 34), and Schlooaing and Laurent (Abstr., 1892, 1021; 1893, ii, 363) have shown that soil bearing a growth of green or bluish-green algze gained nitrogen from the free nitrogen of the air, and the results were confirmed by Koch and Kossowitsch (preceding abstract) ; but the question whether the soil bacteria took any part in the fixation remained undecided. In the present paper, results are described which were obtained by using (1) pure cultivations of algae, and (2) impure cultivations with soil bacteria. As in the previous experiments (Zoc. cit.), thin layers of pure sand were employed with nutritive matter, which had to be varied according to the requirements of the algs.Thus, whilst Stichococcus prefers the phosphate, KH2P0,, Cystococcus preferR K2HP0,. The addition of sugar was favourable to some forms, but had no effect on others. In the first series of experiments, which comprised 18 flasks seeded with Cystococcz~s, there mas no fixation of nitrogen, either with or without sugar. The algae grew well so long as they mere supplied with nitrate, but no longer. In the other experiments, the sand was seeded with mixtures of algae and bacteria, obtained partly from the chalk heap (Zoc. cit.) and partly from arable soil, the experiments being conducted similarly to those with Cystococcus. There were five pairs of experiments, the one of each pair having sugar, the other none.In 1 and 2, a pure cultiva- tion of Cystococcus and a soil eyfract were employed for seeding; 3 and 4 were. seeded from the silica employed in isolating Cystococcus ; 5 and 6 from a sand culture of Xtichococcus, which had proved to contain soil bacteria; 7 and 8 were seeded from a thick, gelatinous skin which had formed on sand seeded a year before from the algae of the chalk heap ; 9 and 10 were seeded from a mixture of algae and bacteria from arable soil, which resembled the mixture used for 8 and 9. The following are the results obtained, 7.1 I 9.5 I 3.1 I 8-1 2.3 ? 2 -7 i ? I 19.1 N O . Of erpts. 1 Nitrogen (milligrams). At commence- ment. Ai. conclusion. Without With sugar. 1 sugar. I 3,4 5 , 6 7,8 9,lO The results of both series of experiments show that neither Cpto-60 ABSTRACTS OF CHEMICAL PAPERS. coccus nor S~ichococcus have the power of fixing nitrogen.Both i n the author’s and in Schloesing and Lament’s experiments, the greatest amouiit of fixation was observed when Nosioc was present. It is possible that Nostoc and some other alge have the power of fixing nitrogen, but as yet there is no evidence of fixation by algae in absence of bacteria, and the aiithor is inclined to the opinion that it is t h e bacteria which assimilates free nitrogen. The evidence in favour of this view is the beneficial effect of sugar in Experiments 3 and 4. In the first series, with pure cultivations of Cystococcus, there was no fixation either with or without sugar. In Experiments 3 and 4 of the second series (see table), there mas without sugar scarcely any fixation, with sugar considerable fixation, indicating that not the Cystococcm, but the bacteria, fixed nitrogen.With mixed alga: and bacteria, there was considerable fixation, both with and without sugar. The conclusion drawn is that here some alga, especially the geIatinous ones, take the place of sugar in supplying nutriment to the bacteria. This theory would account for the fact that similar soils exposed to and screened from light gain and do not gain respectively. In the first case alga develop, in the second case no alga are found, and without the carbonaceous food for the bacteria, fixation cannot take place. It was observed that the gelatinous substance of the algs was full of bacteria. There is, therefore, a symbiotic rela- tion between soil bacteria and certain alga? similar to that of the Legunzinosce and the nodule bacteria.Berthelot (Abstr., 1893, ii, 429) and Gautier and Drouin (ibid., 1888, 746 and 871) showed that the fixation of nitrogen in soils depends on the presence of organic matter. N. H. J. 11. Assirnilability of Potassium in Poor Sandy Soils by the Action of Nitrates. By P. PICHARD (Compt. rend., 1894,119,471- 473).-1t was previously shown (Abstr., 1893, ii, 548) that newly- formed nitrates are the most readily assimilated. The results of experiments now described show that the potash of siliceous rocks is rendered available by nitrification, or by the application of nitrates. Tobacco was grown in the white sand of Bollene; in the first series the sand was manured with the nitrates of sodium, calcium, and magnesium, and with superphosphate ; in the second, with organic nitrogen and the phosphates of sodium, calcium, and magnesium ; whilst in the third series potassium was applied as nitrate, sulphate, and phosphate, nitrogen being present as nitrate, and in cake.The most striking results were obt’ained with the first series, in which no potash was applied. There was 5.6 grams of potassium present, in- soluble in aqua regia ; of this, 0*66,3-21, and 0.48 gram was assimilated by the tobacco manured respectively with calcium, sodium, and mag- nesium nitrates. In the second series (nitrogen applied in organic form), there was active nitrification ; of 5.6 grams of potash, insoluble in aqua regia, the plants took up from 1 to 3 grams, the greatest amount being assimilated under the influence of calcium carbonate.It is concluded that potassium is absorbed by plants in the form of nitrate. The sandy soils of Bretagne, with plenty of organic nitrogen,VEGETABLE PHYSIOLOGY AND AORlCULTURE. 61 giire immensely increased yields of roots when treated with chalk and lime, especially when gypsum is a-dded. Taking into account the assirnilability of potassinm in the form of silicate under the influence of nitrates, the total potash of soils should be determined, as well as the potash dissolved by acids. Effect of Chlorides on Vegetation and on the Amount of Starch in Potatoes, By J. SCHULTE (Bied. Centr., 1894, 23, 706-707; from 2CIagdeb. Zeii., 1894, KO. 244).-FieId experiments mere made in which peas, rye, and barley were grown without manure, and with calcium, magnesium, and sodium chlorides, magnesium and calcium sulphate respectively (450 cwt.per acre). Potatoes mere grown withoat and with the same minerals, farmyard manure being applied in each case as well. The results, showing yield of grain and of potatoes, percentage and yield of starch in potatoes per hlorpen, are given in a table. The figures show that the employment of chlorine compounds in the potassium salts* bave no injurious effect at all, and that the magnesium chloride plot gave in most cases the highest yields, and, in the case of potatoes, much the greatest yield of starch. Effect of the Degree of Ripeness and of Manures on the Physical and Chemical Properties of Barley Meal.By C. KRAUS and A. STELIWAAG ( B i e d . Centy., 1894, 23, 667-670; from Zeits. Zandw. VET. Bay ern, 1894,1&-171) .-Lower Franconian barley was grown without manure, and with sodium nitrate (120 kilos. per hectare), and Chevalier barley without manure, and with guano (300 and 500 kilos.). The ears were examined at three or fonr periods of ripeness ; the dry matter, flintiness, starch, proteids, and weight of grains per thousand being determined. The flintiness increased with the ripeness of the grain, and was not influenced in the case of Chevalier barley by the difference in manuring. As regards chemical composition, this is improved by ripening, the quantity of starch increasing whilst the nitrogen diminished. Tile best compositeion is not obtained as a rule until the grain is yellow- ripe.Generally speaking, heavy manuring gives better yields if the crop is not laid ; in this case, light grains rich in nitrogen are pro- duced. With increased percentage of nitrogen, the grains are more flinty. N. H. J. 31. Nutritive Value of Cocoa. By H. CCHN (Zeit. p7~ysi0l. Ckem., 1894, 20, 1--2i).--Tbe constituents of cocoa were separated by methods which are described, and their amount estimated. The beans and powdered cocoas of commerce mere used ; the former con- tained 48-50 per cent. of fat’, and 10.8 of proteid ; the latter, :$2-33 per cent. of fat, 13.8 of proteid, and 12 of starch. Experiments in relation to its nutritive value wcre carried out in the usual way ; the fat was found to be well digested, but the proteid not, nearly 50 per cent. of the latter being mused.Secondary Products containing Nitrogen formed during Combustion in Air. By L. LLOSVAY DE: NBGY ILOSVA (BLLZI. bfOc. N. H. J. M. N. H. J. M. W. D. H. * According to the text : there is no reference to potassium salts in the table.62 ABSTRACTS OF CHEMICAL PAPERS. Chim., 1894, [S], 11, 272-280).-The author has estimated the amount of ammonia and of nitrogen oxides formed during the corn- bustion of some fuels. The following table gives the results, calculated in grams, of product per kilo. of fuel. Total Niti*ogen as Nitrogen as combined nitrogen oxides. ammonia. nitrogen. Gram. Gram. Gram. Charcoal dried at 120". ....... 0.1190 0*6$81 0.7671 Charcoal heated a t 600" for 2 hours .................... 0.1279 0.3679 0.4958 Charcoal heated at 900" for 2 hours ....................0.0229 0.0229 Coke heated a t 600" for 2 hours 0.1756 0.1289 0.3045 Coal-gas.. .................. 0.0771 0-0052 0.0823 ............ 0.0147 Carboric oxide.. 0.0147 - Volume for volume, hydrogen and coal-gas produced the same weight of ammonia, and almost the same weight of nitrogen oxides. Carbonic oxide, on the other hand, produces less than half as much nitrogen oxide, and, of course, no ammonia. The ammonia formed during the coinbustion of coke or charcoal is probably only a pro- duct of the decomposition of these substances. Coal yields a much larger proportion of ammonia, of which a large part is produced during the destructive distillation antecedent to the true combustion of the coal. Prom these figures (basing his calculations on the amount of coal mined each year, which he takes as 390,000,000 tons), the author calculates the quantity of combined nitrogen (assimilable by plant life) formed annually by the combustion of fuel to be 299,000 tons. Lawes and Gilbert calculated the combined nitrogen taken up annually by the soil to be 1,000,000,000 tons, whilst Boussingault's figure ma,kes it 164,000,000 tons. The author thinks that his own total is probably largely increased by the nitrogen oxides produced during storms, by the amount of ammonia produced from thc burning of coal being larger than t,he figure 0.7671, which he used, and froxi other sources, but that the figure of 1,000,000,000 tons is largely in Hydrogen .................. 0.3286 0.0236 0.3522 excess of that actually absorbed by the soil. L. 1'. T.

ISSN:0368-1769    

DOI:10.1039/CA8956805057

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年代:1895

数据来源: RSC

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62 ABSTRACTS OF CHEMICAL PAPERS. An aly t i c a1 C h e m i s t r y. Estimation of Chlorine in Urine. By E. BGDTKER (Zeit, physiol. Clzem., 1894, 20, 193--202).---Mohr’s method gives too high results, as the urine contains substances which hinder the end reaction, probably by dissolving silver chromate. To incinerate the urine first is a tedious process, and results as good are obtained by the following method, the principle of which is t o perform the reverseANfiY TICAL CHEMISTRY. 63 of what is usually done, namely, to estimate silver by means of sodium chloride. The urine is first made strongly acid with nitric acid, and excess of silver solution added; in the presence of nitric acid, and absence of bromides, iodides, and thiocyanates, silver chloride is alone precipitated. By careful neutralisation of the fiItrate with a feeble alkali, soch as magnesia, a liquid is obtained in which the excess of silver can be estimated by titration with sodium, chloride.W. D. H. Sodium Thiosulphate for Standardising Iodine Solutions. By C. MEINEKE (Chem. Zeit., 1894, 18, 33-34).-Sodium thio- sulphate may be completely freed from adhering moisture by trent- ing the powdered substance, first with 96 per cent. alcohol, aid then removing the excess of the latter by washing with ether. The ether is finally completely expelled by a current of dry air. The product is absolutely free from mechanically adhering water, and, if satisfactory in other respects, constitutes a valuable reagent for ascertaining the strength of iodine solutions. By F.JOHNSON (Chem. Xews, 1894, 70, 212).-One gram of pyrites is treated in a flask with 25 C.C. of nitric acid ; after a quarter of an hour, 1.5 grams of potassium chlorate is added, the whole warmed for a quarter of an hour, mid then evaporated to dryness ; 20 C.C. of hydrochloric acid is added aiid boiled off, and another 20 C.C. added and half boiled off, the residue is diluted with 50 C.C. of water, filtered, and washed. The solution is then made up to 200 c.c., heated with 1.5 grams of sodium hypophosphite, slight excess of barium chloride added, and after three hours the clear liquid is decanted on to a filter, whilst the precipitate is treated with 1 C.C. of hydrochloric acid and 100 C.C. of boiling water, being filtered after five minutes. Indole as a Test for Nitrites. By 0.BUJRID (Chem. Zeit., 1894, 18: 364).-1ndole gives a very delicate and beautiful reaction with traces of nitrites in water analyses. I t is best to use a diluted alco- holic: solution containing about 0.1-0.2 gram of indole per litre. Ten C.C. of the sample of water is mixed with a few drops of hydro- chloric acid, and heated to 70-80". A few drops of the reagent is now added, when, if nitrite is present, a beautiful red coloration is obtained, which in a few minutes will get somewhat darker. The author thinks that the reaction may also be utilised quantitativelv. L. DE K. L. DE I(. Estimation of Sulphur in Pyrites. D. A. L. Estimation of Carbonates and Caustic Alkalis in Mixtures. By P. L. ASLANOGLOU (Chem. News, 1894, 70, 166--167).-Titrating total alkalinity with N/10 sulphuric acid, with methyl-orange as indi- cator, and then the alkalinity due to hydroxide with phenophthalein as indicator, gives erroneous results. Therefore, in place of the second titration, the author suggests estimating the carbonic anhydride in a Schrotter's apparatus, using methyl-orange to indicate the end of the action; he has obtained good results.Hydrochloric acid, or nitric64 ABSTRAOTS OF OHEMIOAL PAPERS. acid distilled from urea nitrate, and not sulphuric, should bo used f o r expelling the carbonic anhydride. Estimation of Carbonates and Causticz Alkalis in Mixtures. By C. A. SEYLER (Chern. New$, 1894, 70, 187--188).--Phenol- phthalein, although not to be highly recommended as an indicantor for the estimation of carbonates in presence of hydroxides, is capable of giving accurate results if precautions are taken to prevent any loss of carbonic anhydride (compare preceding abstract).Triammonium Orthophosphate and the Detection of Mag- nesium. By P. SCHOTTLANDER (Zeit. anorg. Chem., 1894, 7, 343- 344) ,-When examining a solution for magnesium with ammoniunk phosphate, a precipitate of triammonium orthophosphate is sometimes obtained having the appearance of magnesium ammonium phosphate, and may thus lead to errors ; this precipitate is especially liable to occur in the prcsence of much ammonium chloride and strong ammonia. Triammonium orthophosphate, (NH&POI + 3H20, is obtained by adding ammonium chloride to an ammonium phosphate solution, warming the mixture at 60°, and then adding ammonia.It crjs- tallises from the solution, on cooling, in long, four-sided prisms, and gradually evolves ammonia when exposed to the air. Estimation of the Heavy Metals by Titration with Sodium Sulphide. By G. NEUMANN (Monatsh., 1894, 15, 495-504).-The neutral solntion of the metal to be estimated is first precipitated with a known excess of fitandard alkali sulphide, and the solution containing the suspended sulphide or hydroxide is rendered clear, if necessary, by the addition of sodium chloride solution. An aliquot part of t h e solution is then filtercd off, or removed by means of a pipette, and the excess of sulphide indirectly determined in i t ; this is best done by boiling with a known excess of N/10 sulphuric acid and afterward8 determining the unused acid by titration with N/lO potassium hydroxide. This indirect process is necessary, because the alkali sulphide destroys the colour of litmus and of phenolphthale'in. The estimation of the amounts of metal in the following salts by this method gave excellent results :-alum, chrome alum, silver sulphate, copper sulphate, cobalt sulphate, cadmium gulphate, lead nitrate, manganese sulphate, nickel sulphate, ferrous sulphate, ferrous ammo- ainm sulphate, ferric chloride. D. A. L. D. A. L. E. C. R. G. T. M. Colorimetric Estimation of Picric acid in its Compounds with Organic Bases. By L. Ku~usow (Zeit. physiol. Chm., 1894, 20, 166-169) .-Ptomaines are readily separated from mixtures by the addition of picric acid ; the compound can be weighed, bat the method here recommended is to estimate the picric acid colorimetric- ally, either by the spectrophotometer, or, more readily, by the use of Eoppe-Seyler's doable pipette (Abstr., 1893, 1264). W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8956805062

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年代:1895

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General and P h y s i c a l Chemistry. Refractome tric Researches. By J. F. E 1.1 KMAX (12ec. T~az.. Chl'm., 1894, 12, 157--197).-1n continuation of his refractomctric observations (Abstr., 1893. ii, l j , the nut,hor has measured the mole- enlar refractions and dispersions of a large number of organic com- pounds. He finds generally that in any series of homologous compounds there is a regular change i n both the refraction and dis- persion with risiug molecular weight if the highel- members of the series are alone considered, but that this rule never holds for the initial members of the series. As a typical example the following series may be quoted. (A - 1)WV. Difference for CH2. Water - ................ 5 83 Met h y 1 ic a1 co h ol ....... 1 '2 . 93 7.10 E t b ylic alcohol .........20-54 7.61 Hep tylic alcohol. ....... 58-39 5 x 7.57 Cetylic alcohol ......... 226.76 9 x 7.59 The mean vdues obtained for the refraction of the CH,group fi-om a. large number of observations with different compounds, and using Gladdone's formula, are for the lines Ha, Hs, and for a ray of infinite wave-lenglh A (calculated by means of' Cauchy's formula) p = 7.889 u = 7.754 d = 7.590, and for the dispersion 0 - a: = 0.1353. The variations in the numbers actually obtained bay observation fi*om these mean values all lie within the limits allowable for error of experiment. H. C. By P. WALDEN (Zeit. physikal. Chem , 1894, 15, 196-208).-The author determined the optical rotation of solntioiis of a-bromocamphosulphonic acid and some of its salts, at various dilutions and constant temperature (20*5"), employing for the purpose the apparatus of Schmidt and Hiinsch.I n the case of the free acid, an increase in dilution from 2, = 2.08 to v = 120 was ac- companied by a decrease in the molecular rotation of from 287" to 870", so that the undissociated molecule possesses a somewhat greater rotatory power than the dissociated molecule. In thc experiments w i t h salts of lithium, sodium, potassium, beryllium, magnesium, zinc, and bai-ium, dilution has in most cases a similai- effect, whilst at equal dilution (also approximately equal dissociation) the moleculsr rota- tions weye approximately equal as seen in the table. Optical Rotation of Ions. a. H. Li. Na. E. T1. Be. Mg. Zn. Ba. 30 + 273" 5275" 272" 273" 273" 274" 268" 272" 272" The rotation is hence dependent on the number of active ions, and VOL.LXVIII. ii. 6 120 + 270 271. 270 269 271 271 270 270 26966 ABSTRACTS OF CHEMICAL PAPERS. at complete dissociation, in equimolecular solutions, the rotations of different, salts containing the same active acid ion are equal. In aqueous acetone solution (93 per cent. acetone), a much higher nnmber (343") was obtained at v = 30. The morphine and quinidine salts gave molecular rotations of -100" and + 1CiU8" respectively. The algebraic sum OF the molecular rotations of the constituents being - 100" and +996"; the molecular rotation of an electrolyte of two active ions appears to be equal to the algebraic sum of their molecular rotations. L. M. J. Development of the Latent Photographic Image by Alkali Peroxides.By G. A. LE ROY (Compt. .rend., 119, 5573.- Aqueous solutions of alkali peroxides, or a solution of hydrogen per- oxide made strongly alkaline, can develop the latent image formed when emulsions of silver bromide or silver chloride in gelatin are exposed to light, the intensity of reduction being sensibly proportional to the quantity of light acting on the emulsion. The developing power of the alkali peroxides is, however, much below that of the substances usually employed as developers by photographers. The image, which consists of a mixture of metallic silver and silver oxides, is considerably reduced in intensity when placed in solutions of a1 kali thiosulphates or thiocyanates. (Zeit. physikal. Chem., 15, 323-326).-The author considers the light emitted during crystallisation to be in all probability electrical, and due to the union of electrified ions; for fhis reason, it should be most marked in the sudden crystallisation of strongly dissociated compounds, and the following experiments, suitable also for lecture PurPoseE, are described.A glass cylinder is half filled with a warm saturated, sodium chloride sdution, and into it is poured an equal quantity of hydrochloric acid sp. gr. 1.12, and the solutions mixed by a glass rod, when a bluish-green light fills the whole cylinder. Or the two liquids having been carefully poured in, the cylinder is strongly shaken, when a flash of light occurs. Alcohol may also be used in place of the acid, and similar effects may be obtained by the use of potassium chloride or bromide instead of the sodium salts.The former compound with alcohol gave a most marked effect, the light being stronger and greener than that obtained with sodium chloride. L. M. J. Some Voltaic Combinations with a Fused Electrolyte and a Gaseous Depolariser, By J. W. SWAN (PTOC. Roy. XOC., 1894, 56, 56-64).-The author describes a number of different cells of the Upward type, with a fused electi-olyte and a gaseous depolariser. The electrolyte used was either the molten chlorides of sodium and potassium mixed, or chloride of lead. The cathode was always molten lead, and the anode carbon, chlorine being used as the depolariser. As a general conclusion, it was found that it is necessar.y that the surlace of the carbon pole on which the cathion is deposited be alter- xately exposed to the action of the gas and the electrolyte.The research, proves that it is possible to form pyro-batteries of the Upward type,, C. H. B. Light emitted during Crystallisation. By E. BANDROWSKGENERAL AND PHYSICAL CHEMISTRY. 67 although it is extremely difficult to realise the conditions required for effective action. H. C. Polarisation. I. Solid Cathodes. By J. SOSZKOWSKI (Zeit. physikal. Chem., 1894,15, 267--504).-For the polarising E.M.F., the author employed a Gulch thermopile of 50 elements, capable of yielding a pressure up to 3.5 volts ; a Leclanchh cell, and four standard Clarke cells being employed for its determination. The cathode ex- amined was immersed in a N/10 solution of sulphuric acid, and the polarisation determined by the measurement of the E.M.F.obtained from this cathode connected with a calomel element, that is, practi- cally, the chain, cathode, NllO sulphuric acid, potassium chloride solution, mercury. Experiments on the effect OE the dnration of the current mere made with cathodes of polished and platinised platinum, polished silver and mercury, and the polarisation reached its maximum constant value in from two to three minutes (polished platinum 15 minutes). The effect of the current strength on the polarisation was obtained by the addition of external resistances. With a platinised platinum cathode of 2 square cm. area and an E.M.F. of 3.3 volts, the polarisation decreased to a minimum of -180 volts when 700 ohms had been added, further addition having no effect.A similar decrease was obtained by the addition of internal resistance, that is, snbatitution of LeclancM cells for the thermopile. The influence of the size of the cathode was investigated by the use of mercury electrodes of respectively 1 and 2 square cm., and although for low E.M.F.s the smaller cathode gave markedly greater polarisa- tion, a t 3.3 volts the values were almost identical. The nature of the surface was then altered and platinum electrodes (1) polished, (2) platinised, (3) platinised and heated to redness, (4) covered with scratches, were em$oyed, Very different values for the polarisation were obtained, the highest values being obtained with (4) and lowest with (2). The platinised cathode also gave the curve of polarisation, polarising E.M.F., approximately a straight line of inclination tan-' $.I n no case does a maximum value occur, and the differences the author considers to be due to different occluding powers of the sur- faces. Similar experiments were performed with silver cathodes with entirely similar results, the differences between the differently pre- pared silrer cathodes being, however, not as great as with the platinum electrodes. L. M. J. Polarisation. 11. Liquid Cathodes. By J. ROSZKOWSKI ( Z e i f . physikal. Chem., 1894,15,305-322 ; see preceding abstract) .-Liquid cathodes consisting of mercury and amalgams of lead, zinc (1 per cent.) and copper (0.053 per cent.), were employed, and curves embodying the relations of polarisation to polarieing force are given.In the cases of the zinc and lead amalgams, the curves are at first parallel t o the axis of abscissae, after which, like the other curves, they become approximately straight lines of inclination tan-; 0.62, and no indication of a maximum is apparent. A cathode of Wood's alloy was examined in both the solid and the liquid state, 6-2(j. 8 ABSTRACTS OF CHEMICAL PAPERS. the effect of increase of temperature being first determined by experi- ments on mercui-y. With an E.M.F. of above 3 volts the effect of tem- perature became constant, namely, an increase of polarisahon of about 0.0@03 rolt per degree. I n the experiments with Wood's alloy, no chsnge in the polarisation was observed at the point of fusion or solidification. The curves obtained for both solid and liquid also were almost identical, and closely resembled those previously obtained, being at, first parallel to the axis of abscissE.Hence in this case the nature of the siirface has but little effect on the polarisation, which, if the E.M.F. is above a certain value, is approximately a linear function of the polarising force. L. M. J. Influence of Electrolytes on the Conductivity of Acetic acid. By A. J. WAKEMAN (&it. physiknl. Ghein., 1894, 15, 159- 182).-The conductivity was deteimined in the case of mixtures of acetic acid with varying quantities of cyanacetic, propionic, succinic, glycollic, and hydrochloric acids, and from the results the value of k was obtained. The conductivity was then calcnlated on the assump- tion that two solutions in which tbe concentration of the ions are equal do not, alter on mixing, and hence that the effect of the addition of the solution of the second acid to the acetic acid solution may be regarded as (1) the abstraction of water from, or addition to, the latter until the two solutions become isohydric; (2) admixture of these iso- hydric solutions.The calculated values of the conductivity and of k obtained thus are compared with the observed values, and in most cases the agreement is very satisfactory. In the case of acetic and glycollic acids, concordance is only good when the former acid is in considerable excess. In all cases, as would be expected, the effect of strong acids is very much more marked than that of weak, the addition of %Qb cyanacetic or iTi:G5 of hydrochloric acid being very noticeable.The conductivity of hydrogen chloride dissolved in acetic acid was also determined, but, owing to the great resistance, only with approximate accuracy. Curves expressing the results are also given. Thermoelectric Properties of Salt Solutions. By G. F. EMERY (Pi.0~. Roy. SOC., 1894, 55, 356--373).--If a circuit is formed of two substances, one a metallic wire and the other a, sdution, and the junctions between the metal and the liquid are at different tempern- tures, an E.M.F. is developed in the circuit, which varies in magnitude nearly in proportion to the differcnce of temperature between the junc- tions, and, in comparison with the ordinary thermo-electromotive forces in metallic circuits, is very considerable. The author has made experiments to find out how the E.M.F.vaiies with variations both in the strength and in the nature of the solution. The results show that both have considerable influence on the magnitude of the E.M.F. The E.M.F. per lo, in terms of lO-*volt as unity, 8, varies con- siderably with the concentration of the solution, and cui'ves are plotted whose ordinates are equal to 8, and abscissae are the corre- spondiug concentrations in gram molecules per li tre of volume. For zero concentration, the curves all appear to start from somewhere about 0 = 8.6 at an angle to the axes, and then, as concentration L. 31. J.GENERAL AND PEYSICAL GELEMISTRY. 69 increases, the curves bend round nmre or less sliarply until t,hey arc' nearly parallel t o the axes of concentration.For some salts, 0 increases with increasing concentration, whilst foi. others it decreases, so that for thermoelectrical purposes we may divide salts into positive a i d negative, according as tile value of 8 for the solution is greater 01. less than its apparent value for pure water. The final value for 0 in ;b solution appears to be due to the superposing of it salt effect on that. due to the water itself. A few experiments were niade on the thermoelectric force gene- rated in a purely liquid circuit, that is, in a circuit composed of t w o kinds of liquid, the junctions being a t different teniperat,ures. Expe- riments are also described, which lead to the conclusion that the thermoelectric forces at the junctions of metals and solutions are part of a system of reversible thermodynamic phenomena. H.C. Method for Determining ths Thermal Condiuctivity of Xetals, with Applications to Copper, Silver, Gold, and Platinum. By J. H. GRAY (Pwc. R o y . SOL'., 1894, 56, 199-203). -One end oE a given length of wire is kept, a t a constant, known temperature. The rise of temperature of tlie other end of the mire is noted every minute, and, i f proper precautions are taken to prevent loss by radiation from the sides, the data are obtaiiiecl for calculating t8 he thermal conductivity. Several qualities of copper were tested, as well as pure gold, silver, arid platinum. The values for the mean thermal conductivity in C.G.S. units, between the temperatures 10" and 97", are given below. Couductivitfg. Copper, Specimen 1. .............0.9594 7 , ,, 2 . . ............ 0.88838 3 , ,, 3 . . ............ 0.8612 ,? ,, 4 (very iiiil)ue) 03497 7, 3 , 5 ,, 9 7 0.5198 Silver (pure) ................... 0.9625: Gold ..................... 0.7464 Platinum (pure) ................ 0.186 1 Diameter. 2.00 miii. 2.11 ,, 3-09 ,, 2.04 ,, 2.04 ,, 2.02 ,, 2-00 ,, 2.00 7, Experiments to find out if there is any relation between the electrical and thermal conductivities confirmed what has been found by previous investigators, that if une metd is a better conductor f o r heat it is also a. better conductor f a r electricity. The results did not, however, prore that the ratios were always the same, although i n some cases they agreed rery closely. Specific Heats of Gases at Constant Volume. Parts I1 and 111. Carbonic Anhydride.By J. JOLY (PKK. Roy. XOC., 1894, 55, 390-391 ; 392-393) .-The specific heat of carbonic anhydride at constant volume is given in terms of its variation with density p, f o r the mean specific heat between 12" and loo", as The following empirical equation expresses the line p = 0.124, ca.lcu- lated into a line of rariation of specific heat with ternperat,nre. H. C. C, = 0.1650 + 0.6165,~ + 0*3400$.70 ABSTRACTS OF CHENICAL PAPERS. C, = a + 2 b (100 - t ) + 3c(100 - t)2, where t is the initial temperature oE the experiment, and a = 0~19020000 b = 0*00006750 c = 0*00000182 H. C. Law of Corresponding Boiling Points. By G. W. A. KAHL- BAUM and C. G. v. WIRKNER (Ber., 1894, 27, 3366--3374).-A reply to Diihring's criticism (this vol., ii, 37). Atomic and Molecular Solution Volumes.By J. TRAURE (Ber., 1894, 27, 3173-3178).-1f m is the molecular weight of ;I substance dissolved in water, aq the amount of water which holds unit moleciilar weight of the substance in solution, d the density of the solution, and 6 the density of the water, the constant, m + aq Vfn = ~ - a s ( , d 6" is called by the aathor the molecular solution volume, and the corre- sponding constant for the atom ra the atomic solution volume. The densities of soluiions of a, number of compounds of some 50 elements have been determined, and a number of relationships between atomic and molecular solution volumes have been discovered. A summary of the chief results i8 given in this paper. The elements hydrogen, lithium, sodium, silver, and univalent copper, gold, and silver have equal atomic solution volumes. In the series sodium, potassium, rubidium, and cesium, the atomic solution volumes increase by about 10 units with every rise in atomic weight.The atomic solution volume of rnbidium is equal to that of am- monium. The thalliixm compounds hcve somewhat greater molecular solution volumes than the corresponding potassium compounds. The elements calcium, strontium, and lead have equal atomic solu- tion volumes, as have also the elements zinc and magnesium, barium and cadmium, bivalent iron and manganese, bivalent copper and nickel. Cobalt has a greater solution volume than nickel, and beryl- lium hag the highest solution volume of any of the bivalent elements. Equal solution volumes were also noticed in the following cases.Platinum, palladium, and iridium ; aluminium and tervalent iron ; molybdenum and tungsten in moljbdates and tungstatea ; chlorine and bromine in chlorates and bromates ; chlorine and manganese in perchlorates and permanganates ; nitrogen and vanadium in nitrates and vanadates ; carbon and silicon in carbonates and silicates. The green chromium compounds have a smaller molecular solution volume than the violet. Iodates have a smaller solution volume than cblorates and bromates, but iodides have a greater volume than bromides, and bromides a greater Folume than chlorides. The atomic solution volume of fluorine is smaller than that of chlorine. An increase in atomic solution volume with rising atomic weight is observed also in the series : oxygen, sulphur, selenium, tellurium ; nitrogen, phosphorus, arsenic, antimony ; silicon, titanium, zirconium.GENERAL AND PHYSICAL CHEMISTRY.71 The molecular solution volume is in ererg case an additive function, Water of crystallisation does not appear to be present in any of the dissolved salts. An atom may change its solution volume with change of valency. This property the author proposes to indicate by the term “polysterism.” It follows from this property that there is a direct relationship between valency and atomic volume. H. C. The Critical State. By K. WESENDONCK (Zeit. physiknl. Chew., 1894,15, 26?-266).-The author describes some of the appearances observable in carbonic anhydride at the critical state, and points out that at 31.7” nebulosity is observable and inhomogeneity exists so that the true critical point must be higher than this; further researches are therefoiae desirable.L. 31. J. Freezing Points of Concentrated Solutions. By R. ABEGG (Zeit. physikal. Chem., 1894, 15, 209-260).-The lowering of the freezing point was first determined in aqueous solution at concentra- tions up to 5 gram molecules per litre ; the compounds examined being chiefly the lower alcohols, acids, and ethereal salts. The osmotic work was calculated according to both Arrhenius’ and Raoult’s formula, and the results shown graphically against concentration as abscissm The curves are usually convex to the axis of abscissse, and in those calcu- lated according to Arrhenius’ formula the inclination increases with the molecular weight, the Raoult curves being less divergent.The hydroxyl group usually tends to make the curve steeper, the reversc obtaining for the carboxyl group. A downward bending can be explained by the formation of aggregates, and this occurs with those compounds where Ramsay’s and Shield’s experiments indicated association. A number of ethereal salts were also examined in acetic acid and benzene solutions, and the results recorded graphically. whilst by interpolation the molecular osmotic work ( n - / n ) was obtained at a number of concentrations. Although the curves are not straight lines, a first approximation can be obtained by use of the formula r/n = A + Bn. In the case of mixtures, the osmotic pressure is greater than the sum of the osmotic pressures of the components separately, and this follows theoretically from the author’s results, thus: r1 = An1 + Bn12, r2 = An2 + B2n2; n- = A(n, + + B1nl + B2n2 (nl + Q, that is, n- = T, + r2 + (B, + B,)(~Z~?L~).n, + n2 The osmotic prcssures for mixtures of cane sugar and methglic alcohol, glycerol and ethylic alcohol, acetic acid and ethylic alcohol and glycerol and cane sugar in aqueous solutions were calculated, the values for A and B being obtained from the previous experiments. The agreement with the observed values was very satisfactory, and best for the calculations according to Raonlt’s method. L. 31. J. Solubility of Double Compounds. Ey R. BERI~ESD (Zeit. physikal. Chew,., 1894, 15, 183-195; see also Abstr., 1892, 1047, 1385).-The solubility relations of a mixture of picric acid and aathracene, which unite to form a double compound, were determined.72 ABSTRACTS OF CHEMICAL PAPERS.Antlwacene (total), 2' . . . Picric acid (total) . . , . . . Anthracene (free), u I . . . Picric acid (free), z2. . , . Picrate,tt ... .. , . .. . . .. The compounds were pnrified as completely as possible, ficely pow- dered, and added to 120 C.C. of 99.5 per cent. alcohol, the vessel being kept! in circular motion at a temperature of 25" f o r eight days, after which quantities of the solution mere withdrawn, and the coii- stituents estimated. Eleven experiments are recorded ; in the first, the solution was saturated with nnthracene solely ; in the last, witb picric acid only ; in the sixth, the anthrnctene picrate was first obtained in excess. The difference between the anthracene i n the first and sixth experiments gave the quantity present in the latter as picrate, a similar calculation being possible for the picric acid from the sixth and twelfth experiments.The quantities of picrate so calculated were respectively 0.137 gram and 0.105 gram, and the mean value 0.121 gram was employed. The composition of the solution calcn- lated thus is given in the following table. 0 -1% 0 -190 0 -306 0 '215 0 '228 0 *2RG - 1'017 2.071 2.673 3.233 3.469 - 0'176 0.176 0.176 0.176 0.183 - 0.999 2.032 2.623 3.166 3'401 - O'C32 0.069 0.089 1 0.119 0.121 Antli~acene (tohi), v . . . Picric acid (total) . . . . . . Anthracene (free), u1 . . . Pic& acid (frec), ? t 2 . . . , 0 a202 0 -180 1 0.162 0.151 0.149 - 3 -994 5 *OS7 5 'SF3 6.727 7 *511 7 -432 0.149 0.127 1 0'200 0.098 0.696 - 3 926 5'775 6.659 7'443 - The values hence obtained for q u 2 j t ~ , vary only from 4-7 to 5.7, o r within the experimental limits, Graphical Representation of Heterogeneous Systems.By H. W. B. ROOZEBOOM (Zeit.physikaZ. Chem., 1894, 15, 145--158).-The author gives graphical representations of the equilibrium of systems consisting of from 1 to 4 substames. In the latter case, the edges of a regular tetrahedron are taken as axes, the coordinates of any point being measured parallel to sides of the figure. The influence of tem- perature and pressure must be expressed by a series of such tetra- hedra. I n the selection of the componeota, the following must be observed, (1) they should be the least possible; (2) they must be capable of entering into the system in varying proportions ; (3) they must be in actual equilibrium under the conditions of the experiment- Substitution systenis, as for instance KC1 + I = KI + C1, may be considered by deriving the equilibrium from that of the system of the three simple components.Similai-ly a double decomposition is obtainable from the tetrahedron of the four simple components, whilst a decomposition with apparently five components is also re- ducible to that of four. L. M. J. L. M. J. Picrate,?! . .. .. .. .. . . .. 1 0.121 I Principles of a New System of the Elements. By J. TRAUIIU (BeT., 1894, 27, 3179--3181).-The author has shown (this vol., 0.121 0.121. - iP r- INCRGANlC CHEMLSTRY. i a ii, 70) that certain simple relationships exist between the atomic volumes of similar elements. I n place of regarding the properties of the elements as functions of their atomic masses, he proposes an arrangement in which the atomic volumes are the determining f:tctors. Similar elements then appear in groups having equal atomic roluiiies, or i n which there are equsl differences between the atomic volumes of allied elements. H. C. Lecture Experiments : Ethyl Ether. By F. B~IANDST~TKI: (( 'hem. Cenfr., 1894, i, 1145-1146 ; from Zeit. physilin1.-Chem. Unterr., 7, 183--185).-The heaviness of ether vaponr is easily shown by tabrill? a small bottle half full of ether and closiiig it with a cork carrying two glass tubes; the one tube bent a t right angles, and passing just through the cork, the other tube bent into an S-form, and having one end passing through the cork to just above the sur- face of the ether, the other and outside end being 6-8 cm. below the surface of the ether. The ether vapour will pass out of the lower end of this bent tube, and may be burnt. If two bottles, fitted in a similar way, are joined by a piece of rubber tubing, the size O E the ether flziiie may be regnlsted by raising or loweriiig one of the bottles. The lowering of temperature produced by the evaporation of ether is sliown as follows. A strong test-tube is fitted with a cork carrj- ing a thermometer aud two glass tubes, the one reaching nearly t o the bottom of the test-tube, the other just passing through the cork. The test-tube is charged with about 5 C.C. of water and 7 C.C. of ether, and a current of air passed through it. I n a few minutes a temperature of -7" to -8" is obtained, and the liquid solidifies. E. C. R.

ISSN:0368-1769    

DOI:10.1039/CA8956805065

出版商:RSC    

年代:1895

数据来源: RSC

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INCROANlC CHEMLSTRY. P r- i a I n o r g a n i c C h e m i s t r y. Artificial Ice. By A. C. CHRISTOMAXOP (b’er., 1894, 27, 3431- 3437).-Ice produced from the water supply of Athens was fonncl to be separable into transparent and opaque portions. A detailed analysis showed very plainly that of these two varieties the former only was fit for consumption, being almost pure ; the impurities of the original water were divided in various proportions between the opaque ice and the small amount. of water that did not freeze. 31. 0. F. Concentration and Distillation of Hydrogen Peroxide. By R. WOLFFEXSTEIN (Bey., 1894, 27, 3307-3.312) .-Hydrogen peroxide is relatively stable when heated, provided that the solution is free from alkaline compounds, from derivatii*es of the heavy metals, aiid from solids of every kind, even those that are chemically indifferent. Commercial hydrogen peroxide, 3 per cent., can be concentrated on the xater bath in an ordinary dish at i s 0 until it contains 47.7 per cent.The yield is 61.8 per cent., the loss is due to volatilisation, and74 ABSTRACTS OF CHENICAL PAPERS. not to decomposition, for, by the use of a beaker instead of a dish, .the yield is 56 per cent. of solution, containing 64.7 per cent, of hydrogen peroxide. These solutions may be concentrated by distillation under reduced pressure, either directly or, preferably, after extraction with ether, to remove alumina. After repeated fractionation, almost pure (99.1 per cent.) hydrogen peroxide was obtained. It boils at 14-85" (68 mm.), is a colonrless, syrupy liquid, does not readily moisten the containing vessel, is volatile in air, and irritates the skin, producing white marks which remain during several hours.It is strongly acid, and, when ueutralified with alkali and distilled, the distillate readily reddens litmus. The preparation of large quantities of the pure per- oxide is best accomplished by concentrating the commercial solution on the water bath until it contains about 20 per cent. ; it is then evaporated under reduced pressure (68 mm.) until it contains 50-55 per cent., extracted with ether, and finally fractionated in a vacuum. The percentage of peroxide in the various solutions was determined by titration with potassium permanganate solution. The author is unable to confirm Schilow's statement, that a solution of peroxide containing 50 per cent.can be prepared by treating the commercial product (3 per cent.) with soda and extracting with ether. The hydrates HzOz + HzO and H20, + 2H20 haye also been pre- pared; they are liquid a t -20°, but solidify in a mixture of solid carbonic anhydride and ether. J. B. T. Bye-products formed from the interaction of Ozone and Ammonia. By L. ILOSVAY DE NAGY ILOSVA (Bey., 1894, 27, 3500 -3503).-Carius, who has previously investigated this subject, found that animonium nitrite and hydrogen peroxide were first produced, these then reacted further forming ammonium nitrate and water. The author gives a detailed account of his experiments, which are partly original and partly a repetition of Carius'. Ozone is readily absorbed by aqueous ammonia (2-20 per cent.) with formation of nitrite and nitrate.The action is more energetic as the concentration of the ammonia increases ; whichever substance was in excess nitrate and nitrite were formed. Dry ozone and dry ammonia do not react at ordinary temperatures. Hydrogen peroxide could not be detected under any circumstances ; the reagents employed for its recognition were titanium dioxide in concen hated sulphuric acid solution, and chromic anhydride and ether. J. B. T. Formation of Hydrazine from Inorganic Compounds. By P. DUDEN (Bsr., 1894, 27, 3498-3499).-Hydrazine is formed by the reduction of recently -prepared potassium dinitrososnlphonate, K2S03Nz02, with sodium amalgam at O", and is separated by treatment with benzaldehyde.Zinc dust and ammonium hjdroxide or soda may also be used as the reducing agent ; other substances which act in alkaline solution cause the formation of hydroxylamine, ammonia, and potassium hyponitrite in varying quantity, and the yield of hydrazine is consequently much diminished. J. B. T.IKORGANIO OHEMISTRY. 75 Salts of Dinitrososulphonic acid. By A. HANTZSCH (Rer., 1894, 27, 3264--3273).-The author considers that the salts of this acid probably have the symmetrical formula O< N*oR I rather than the NSO,R asymmetrical one NO*N(OR).SO,R, proposed b y Raschig. Two isomeric potassium salts have been described. One of these gives a precipitate with barium chloride which is insoluble in water, but which dissolves in hydrochloric acid to form a solution which remains clear for a short time, but then deposits barium sulphate (Pelouze), whilst the other was only once obtained by Raschig, and gives no precipitate with barium chloride, although, on the addition of hydrochloric acid, an immediate precipitate of barium sulphate is formed.The author has succeeded in obtaining this second salt, but has been unable to prepare that described by Pelouze. Concen- trated solutions of this salt give with barium chloride a precipitate of the barium potassium salt, which is soluble in a large amount of water. The silver potassium salt is a white mass, which decomposes at 83" with evolution of red fumes. A. H. Action of Hydrogen Phosphide on Potassammonium and Sodammonium. By. A. JOANN~S (Compt. rend., 119, 557-559).- When hydrogen phosphide is passed into a solution of potassam- monium in liquefied ammonia, the gas is absorbed and hydrogen is evolved, a liquid being formed which does not mix with the ammonia, although not quite insoluble in it.When the action is complete, and the excess of ammonia is allowed to volatilise, potassium hydro- gen phosphide or potassium phosphine, PH& is obtained in slender, white needles. When heated, i t is converted into potassium phos- phide, PK3, with evolution of hydrogen phosphide, and water also decomposes it with evolution of hydrogen phosphide. Sodammonium behaves similarly, the quantity of hydrogen libe- rated corresponding with the formation of the compound PH2Na. The liquid solidifies when slowly cooled. I€, however, the tube is kept at 0" and the ammonia is allowed to escape, a considerable quantity is retained by the phosphide, and the liquid does not solidify. No definite compound of the phosphide and ammonia seems to be formed, and a further quantity of the latter is evolved when the liquid is allowed to acquire the ordinary temperature.If it is heated at 65", still more ammonia is liberated, and the residue solidifies, and has the composition PH,Na. It decomposes in the same manner as the potassium compound. When nitrous oxide is allowed to act on these derivatives of phos- phine, a volume of nitrogen is liberated equal to the volume of nitrous oxide employed, and the action is therefore quite different from that between nitrous oxide and the amides. C. H. B. Crystallised Products formed in the Deacon Process. By A. ARZRUNI and E. SCHUTZ (Zeit. d l y s t . Min., 1894, 23, 529-535).- The authors give the results of the investigation of a series of cry- stallised products formed during the Deacon process of making chlorine, and presented to the collection of the Aix-la-C hapelle76 ABSTRACTS OF CHEMICAL PAPERS. Technical School by the director of t h e Rhenania Chemical Works a t Stolberg. The following three compounds are described ciytallo- gray h icall y and c h e mica1 1 y . 1. Cu(Fe2)2As401i, triclinic. 2. Fe2(As03)2, monoclinic. 3. Fe2(As03)2 + 10H20, rhombic. B. H. 13.

ISSN:0368-1769    

DOI:10.1039/CA8956805073

出版商:RSC    

年代:1895

数据来源: RSC

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76 ABSTRACTS OF CHEMICAL PAPERS. Mineralogic a1 Chemistry. Fresh Discoveries of Gypsum Crystals. By G. SIAATS (Ber., 1894, 27, ~181--3182).-Fully-dereloped crptals were found near Crone on the Brabe (? in Posen), in a clay associated with lignite; the clay contained lime, magnesia, alumina, and iron. Swallow-tail twins were seldom found, but intersect'ion twins were common. C.. J?. B. Lindesite and Pyrrhoarsenite. By L. J. IGELSTR~~X (Zed. Ewpt. Miu., 1854, 23, 590-593).-1. Lindesite is the name gi.ven to a, new mineral found in the parish of Linde, Orebro, Sweden. The minerirl is of a brownish-red colour, and has a hardness of about 6 . Analysis gave the following results. &On. Fe203. dl,03. MnO. CaO. MgO. Na20. H20. Total. 48.37 21-92 2.47 10.97 5-76 5-49 6.12 0.90 1OO.OCO The formula is 3R0,SiOz,R203,Si02.The mineral consequently ap- 2. Pyi.1.hoal.senite.-This mineral was discovered by the. author in The author has proaches acmite and rhodonite in composition. 1886, and analysed subsequeiitly by A. G. H6gbom. now analysed it himself with the following result,s. As20j. MnO. FeO. cao. MqO. Total. 51-88 28.38 trace 13.55 3-33 99.14 B, H. B. P h y s i o l o g i c a l C h e m i s t r y . Influence of Xntra-venous Injection of Dextrose on the Blood- gases. By V. HARLEY (PTOC. Boy. SOC., 1894, 56,148-154).-The experiments were made on dogs. Samples (30 C.C. in each) were collected before, an hour after, and 3-5 hours after the injection. There is a diminution in both carbonic anhydride and in oxygen after the injection. The lessening of carbonic anhydride supports the view that lactic acid derived from the sugar displaces the caybonicPHYSIOLOGICAL CHEMCSTRY.77 anhydride in its combinations as sodium salt. The lessening of oxygen is very marked, and the explanation is not at present foi-th- coming. W. .I). H. Contents of the Healthy Stomach. By A. L. GILLESPIE (Rep. of Lab. R. C. Y., Edin., 1894, 5, 43-50; from Edin. N e d . J., 1$93).- The following conclusions are drawn from the examination of the contents of the healthy stomach. (1) Free hydrochloric acid is secreted immediately the food enters; but this combines with pro- tejid, so that salivary action is not impeded during this first stage. The free acid does not appear in the stomach contents till from half- an-hour t o two or three hours after the meal is taken: the time varies according to the composition of the meal.Hydrochloric acid combined with prote'id is less antiseptic than the free acid. The in- organic salts, especially the chlorides, and the total proteids per cent. in solution fall dnring the progress of digestion. Albumin (probably mucin, sic) increases, albumoses remain stationary, and peptone diminishes. Physiological text-books are stated to be in error concerning the a,mount of acid ; the following numbers are derived from the present observations . Tot8al acidity from . . . . . . Combined acidity from . . 0.073 ,, 0.324 ,, Free acidity from . . . . . . . ,, Oa108 to 0.36 per cent. 0.018 ,, 0.09 The causes of variation are the time after the ingestion of a. meaI and the character of the food taken.The free hydrochloric acid is seldom over 0.09 per cent. after a pi-otejid meal, but i t may rise to 0.162 or 0.27 after a meal chiefly carbohydrate in nature. W. D. H. Analysis of Gastric Contents. By A. L. GILLESPIE (Bq. of Lab. R. C. P., Edin., 1894, 5, 56-70; from I?iternat. $feed. Mag., October, 1893) ,-A description of certain methods for examinina the gastric contents, with some modifications in the direction of simplifying them. W. I). H. Action of Acids and Alkalis on the Gastric Secretion. BY A. L. GILLESPIE (Rep. of Lab. R. c. P., Edin., 1894, 5, 213-244).- An examination of the gastric contents after the administration of acids and alkalis i n various forms of dyspepsia supports the well-known therapeutic doctrine that, if giveu before food, acids diminish and alkalis increase the acidity of the gastric juice.By A. L. G~LLESPIE (Rep. ,$ Lab. 12. 0. P., Edin., 1894, 5, 20-26 ; from J. Anat. and Physiol., 27, 195).-The properties of the compounds formed between proteid matter and hydrochloric acid are i n part described, aud certain theo- vetical suggestions made concerning the mode of digestion of proteids in the stomach. W. D. H. Gastric Digestion of Proteids. W. D. H.18 ABSTRAOTS OF CBEMICAL PAPERS, Influence of Fats on the Assimilation of Proteids. By R. LAAS (Zeit. physiol. Chem., 1894,20,233-248) .-The admixture of fat with proteid food increases the nutritive value of the latter, more nitrogenous matter being assimilated. Fats, however, unlike carbo-- hydrates, do not lessen the putrefactive changes in proteid in the alimentary canal.W. D. H. Metabolism. By I. MUNK (PJliiger’s Archiv, 1894, 58, 309-408). -This is a series of five papers, all relating to various important points in connection with nutrition, The methods employed are as a rule similar to those generally used in metabolism experiments, rtud the experiments and results are discussed with great fulness. The first series of experiments, performed on dogs, show the great sparing influence on proteids exerted by gelatin. I n a mixed diet, fully five- sixths of the proteid may be replaced by gelatin. The second set of experiments relates to the loss of material during the condition of inanition in a dog. They take into account not only the loss of organic material, but also of the inorganic salts, and cannot be explained otherwise than that the bones share in the wasting as well as the softer tissues.The third section discusses certain points of detail in connection with the sparing influence of carbohydrates on profeids, with special refereme to putrefactive changes, as evidenced by ethereal hydrogen sulphates in the urine. The fourth discusses the influence on metabolism of the division of the food into rations, and leads to the important practical con- clusion that in man the food should be divided into at least three meals in order to make the best use of the nutriment administered. The fifth and last section treats of a variety of points, chiefly criti- cising certain recent researches. Among these, those of Hirschfeld and others stand especially prominent, in which it has been stated that a smaller nitrogenous intake is compatible with healthy equilibrium than was formerly supposed to be the case.This is a very important consideration, as diet tables for soldiers, convicts, &c., may have to be considerably altered with economical advantage if Hirschfeld is right. The present paper, however, lends no support to Hirsch- feld’s ideas. It ia admitted that there are considerable personal variations from the normal standard (Voit : 118 grams prote’id, 36 grams fat, and 500 grams carbohydrate per diem). This normal must not be slavishly followed in individual cases, but expresses an average, from which, however, the variations after all are not very great ; hence it should form the basis for the construction of average diets for large numbers of people.Influence of Carbonic Anhydride and Oxygen on Blood Coagulation. By A. E. WRIGHT (Proc. Roy. SOC., 1894, 55, 279- 294).-The method used consisted in determining, by means of sam- ples of blood withdi~awn into capillary tubes, the alterations in t h e coagulability of the blood by altering the gaseous intake of living animals (dogs and rabbits). Increase of carbonic anhydride increases the rate of coagulation. The same is true f o r human blood in cases of W. D. H.PHYSIOLOGICAL CHEMISTRY. 79 Immophilia. Diminution of the carbonic anhydride decreases the coagulability to the original normal. Decrease and increase of oxygen cause respectively decrease and increase of coa,gulability.W. D. H. Disappearance of Leucocytes from Blood after Peptone Injection. By D. BRGCE (Proc. Roy. SOC., 1894, 55, 29%-299j.- Injection of peptone solution into the circulation of rabbits does not cause a destruction of lencocytes, but merely a withdrawal of them ilito various organs, notably the lungs and spleen. W. I). H. Changes in Liver Cells. By T. L. BRUNTON and S. DEL~PLNE (Proc. Roy. Soc., 1894, 55, 424438).-Various drugs were given t o rabbits, and the effect on the liver cells noted. The compounds studied may be subdivided into three groups: (1) stimulating or excito-secretory, with pilocarpine for a type ; (2) neutral ; and (3) depresso-secretory, with atropine for a type. To thc Grst group belong toluene, benzene, sodium iodide, pilocarpine, chrysophanic acid, ammonium chloride, metntolylenediamine, and nitric acid ; to the second, aniline and phenol ; to the third, phenol, atropine, and ammonia. The following caused marked increase in glycogen :- sodium iodide, metatolylenediamiiie, chrysophanic acid, toluene (?), ammonium chloride (Y).The following did not do so, sometimes even causing a diminution of hepatic glycogen :-nitric acid, pilocarpine, benzene, and ammonium chloride (?). The following caused a marked diminution in the “free iron” in the liver:-sodium iodide, toluene, metatolylenediamine. The following cause4 a dimi- nution of the “ free iron,” but in a less marked degree :-ammo- nium chloride, nitric acid, pilocarpine, benzene (in the fed liver) ; in the fasting liver, berzene causes a doubtful increase of iron.Ammonia causes a diminution of glycogen and an increase of iron. Atropine causes a slight diminution of glycogen and little change in the iron. W. D. H. Chemical Stimulation of Sensory Nerves. By P. GRCTZNER (PJliiger’s Archiv, 1894, 58, 69-104).-1t is well known from previous researches that the chemical stimulation of nervous structures produces different effects from other forms of stimulation. The present experiments confirm this statement, and are concerned with sensory nerves. The experiments fall into three categories- (1) on taste, (2) on reflex respiratory effects in animals, and (3) on pain in man. The chief results from the last of these three sets of experiments, which are given with greatest fulness, may be sum- marised as follows :-A wound in the finger having been made, solu- tions of various agents were applied to the exposed nerves, and the time at which pain was noticed, and the kind of pain experienced were noted.It was foand that the pain reaction time for sodium iodide mas 5 , for an equivalent solution of sodium bromide 10, and of sodium chloride 50 seconds. The halogens themselves act in the reverse order, chlorine being the strongest stimulant. With potas- sium compounds, the chloride has the most, and the iodide the least intense action. Potassium hydroxide is stronger than sodium80 ABSTRACTS (JF CHEBlICAL PAPERS. hydroxide, a.nd ammonia, which has no action on motor nerves, is stronger than either. Ammoniuin chloride acts more strongly thxn sodium chloride, which is nearly inactive, but rather less strongly than potassium chloride.Cxsium chloride is stronger still. Rubi- dium chloride acts about the same as polassium chloride. The chlorides of calcium, strontium, and barium show no great difference ; all give a burning sensation, the chloride of calcium being strongest and quickest in its action. The chlorides of zinc, cadmium, and mercury act in the order named, but less strongly and less quickly than those of the alkaline earths. With regard to acids, thgre was found a pretty constant agreement between the acidity or avidity of the acids and their physiological action on sensory nerves ; nitric and hydrochloric acids coming first, -then sulphuric, and then, a t a long interval, phosphoric. Of the monhydric alcohols the lowest act most feebly; the cor- responding fatty acids act in the reverse direction.Glycerol, which is such a strong stimulus for motor nerves, has practically no action on sensory nerves. W. D. H. Chemical Stimulation of Ciliated Epithelium. By G. WEIS- ZAND (Pjliiger’s Archiu, 1894, 58, 105-132) .-Ciliated epithelium from the frog’s oesophagus was used ; it was examined microscopic- ally in solutions of various substances. Sodium fluoride acts most harmfully; then in order of molecular weight and harmful action come the iodide, bromide, and chloride. The potassium compounds of the halogens act similarly, although in a less degree ; they are shi-onger stimuli of nerves. Ammonium chloride acts more feebly than potassium chloride. The chlorides of potassium. rubidinm, and czsium arrange themselves in their harmful action in the order of their eynivalent weights ; the chlorides of calcium, strontium, and barium in the opposite order, the last named even stimulating ciliary activity.Potassium chlorate is intensely more harmful than the chloride. Of the halogens themselves, iodine is the most, and chlorine the least harmful. The alkalis first stimulate then lessen ciliary activity ; this is most marked with sodium hydroxide, then potassium hydroxide, ammonia coming last. Calcium, strontium, and barium hydroxides are stimu- lating, especially the firstl named. Small equivalent quantities of acids heighten a t first the activity of the epithelium, and then destroy it. I n this direction phosphoric acid is weakest, then hydrochloric, and then sulphuric.The fatty acids act harmfxlly in the order of their molecular weights, except that formic acid acts more strongly than acetic. On the whole, the action of these chemical substances is similar to their action on motor nerves. W. D. H. Rennet and similar Ferments. By R. PETERS (Preisschift, &stock, 1894).-Bg means of rennet, not only is the natural or artificial solution of caseinogen precipitnble, but also solutions of csse’ia, or boiled whey-proteid, arbd vnrious otber prote’ids of animalPHYSIOLOGICAL CHEMISTRY. $1 p. c. 2'7.356 3 -84 2.366 0.220 0-830 0'660 0.336 20.10 nncl vegetable origin under certain conditions, of which the presence of calcium hydroxide is the most important. The precipitated prote'id can be dissolved, and is again precipitable by the ferment. Part of the prote'id, however, always remains in solution, due to splitting of the proteid molecule, as Hammarsten showed.Ferments similar in their action are found in different parts of the vegctablc kingdom. IV. D. H. By L. VAUDIN (J. Pliarm., 1894, [ 5 ] , 30, 337-339).-The following table gives the analytical results ob- tained: Colostrum of the COW. p. c. 22-47 1-36 1.023 0.271 0.791 0.605 9'0% 0'264 --- Solids (dried at 95") .... As11 (soluble) .......... .. (insoluble) ........ Calcium phosphate ..... Yrotei'ds .............. Acidity (as P?O,) ...... Butter. ............... Lactose. ............ Just before calving. -- p. c . 27 -615 1 -30 1 5 2 0 '278 0 '809 0 -622 23 -705 0 *348 1. p. c. 24 '49 6 *38 2 .I7 0 -250 0 9339 0 -630 0 a272 -- 14 -91 - Just nfter calving.I Five 2. 1 3. ---- I 1'. z 24.14 2 '43 2 -86 0 *190 1.02 0 *87 17 -6s 0 -28 -- p. c. 14-37 5 -1s 4 '07 0.21; 0 -51 0 -38 4 3.5 0 -16 The lactose and butter are low before, and increase regularly after, calving. The ash o r salts and prote'ids are very high before calving, decreasing afterwards, but the ratio between them changes. The composition of the salts also varies, sulphates being present during and imniediately after parturition, but not in normal milk. By A. L. GILLESPIE (Rep. of Lab. R. C. P. Edin., 1854, 5, 51--35).-About 20 different kinds of dropsical fluid were examined, and albuinoses were found in nearly every specimen, peptone in a few, in addition to the prote'ids usually described. W. D. H.Noto By Abstractor.-These results are of but little value, as the albumin and globulin present were first removed by heat, an agency which would, of course, lead to the formation of these products of y roteoly sis . Ethylic Sulphide in Dog's Urine. By J. J. ABEL (Zeit. physiol. L. T. T. Albumoses in Serous Effusions. Chem ., 1894, 20, 253--279).--l)og's urine, which has been treated with milk of lime or free alkalis, yields a volatile substance which is absorbed by concentrated sulyhuric acid, from which it can he. agaiit liberated by neutralisation. It was identified as ethylic sulphide. The compound with mercuric chloride melts at 119O, not at 90" as formerly stated. With nitro-sulphuric acid, it gives a deep green coloration. On oxidation with potassium permanganate in strong sul- VOL.LXV'IXI. ii. 782 ABSTRACTS OF CHEMICAL PAPERS. phuric acid solution, ethylic culphide yields acetic and sulphuric acids, and not the sulphone. Carbohydrates of Normal Urine. By K. BAISCH (Zeit. pliysiol. Chem., 1894, 20, 249-252 ; compare Abstr., 1893, ii, 542; 1894, ii, 393). -The carbohydrates of normal urine are three in number : d-glucose, animal gum, and a third which in former communications was not identified. The present research shows that this is probably isomaltose, a substance formed during digestive processes ; i t agrees with isomaltose in the following properties : reduction of E’ehling’s solution, non-fermentability with yeast, dextro-rotatiou, crystalline form, solubilities and melting point of its osazone. W. D.H. W. D. H. Albuminuria. By F. D. BOYD (Rep. of Lab. R. C. P. E d i n . , 1894, 5, 79-84, 85-87, 88--102).-The total protejids were estimated by boiling, the albumin by boiling after removal of the globulin by half saturation with ammonium sulphate, the globulin by difference. Both protejids are generally present; the proportion varies so much that it is not possible to diagnose the variety of kidney disease present by means of it. Even in amyloid degeneration, the globulin may not be in excess. In the albuminuria of pregnancy, the globulin is present i n larger amount than in other forms of albuminuria. In the albuminuria of heart disease, the globulin is usually more abundant than in chronic interstitial nephritis. I n acute nephritis, without haematuria, the two proteids are about equal; but when blood is present the globulin is proportionally more abundant.Four cases of Bright’s disease are recorded in which serum albumin was present, but serum globulin absent, or present only in the merest traces; and one case where globulin and albumoses were present, but albumin absent. In no case did the proteid quotient bear any relation to that of the blood. The amount of protejid is often greater than that found in transudations. From these con- siderations, the presence of proteid in the urine is considered to be due to secretion rather than transudation, and there is some evidence that the lower the state of nutrition of the renal epithelium the greater is the amount of globulin allowed to pass. Some observations are recorded that confirm Posner’s (T7i.1.ch.o~’~ Archi?;, 79, 318) observations.The urine secreted by the Mal- pighian tufts is by many physiologists regarded as albuminous. The albumin is considered t o be re-absorbed as the urine passes along the renal tubules in the normal condition. Posner took pieces of the kidney and plunged them into boiliug water for two or t.hree minutes ; sections were then prepared. Where albuminuria had been present, the microscope revealed coagulated masses of protejid in the capsule chambers and tubules, but when the healthy kidney, either of man or animals, was examined no such evidence of albumin was ever found. W. D. Is. Haemoglobinuria. By A. L. GILLESPIE ( R e p . of Lab. R. C. P., B d i n . , 1894, 5, 192-198 ; from E d i n . &led. J., June, 1892).-Glinical details of a case of paroxysmal haemoglobinuria are given ; the chiefVEGETABLE PHYSIOLOGY AND AGRICULTURE. 83 point of chemical interest is the observation that on one occasion the pigment present was not oxyhaemoglobin or metha?moglobin, as is usually the case, but acid haematin ; aim, at any rate, no reduction occurred on the addition of ammonium sulphide. The spectra of acid hzmatin and of methzmoglobin are, however, so similar that this evidence can hardly be regarded as conclusive since no meabui-e- ments of the absorption bands are given. w. D. H. Alcaptonuria. By H. V. OGDES ( Z e i t . physiol. Ohem.., 1894, 20, 280-286).-A case of this disease is described. It agrees in all im- portant points with those previously described by Baumann, Wolkow, .:md Embden. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8956805076

出版商:RSC    

年代:1895

数据来源: RSC

摘要:

Organic Chemistry. Liquid Ethane and Propane. By A. HAINLEN (Annulen, 1894, 282, 229-245) .-A detailed account of the experiments of which the ’results have already been published by L: Meyer (this vol., i, 1). A. H. Preparation of the Paraffins. By F. KLUGE (A~~nalen, 1894, 282, 214-228) .-A detailed account of the experiments of which the results have already been published by L. Meyer (this vol., i, 2). A. H. Formation of Dicarbon Compounds from Carbon Bisulph- ide at Low Temperatures. By V. MEYER (Bey., 1894, 27,3160- 3161) .-When carbon bisulphide is chlorinated at 20-40°, the carbon tetrachloride formed is found to contain perchlorethylene and perchlorethane. &I. 0. F. New Class of Compounds of the Inactive Hydrocarbons. By J. A. WANKLYN and W. J. COOPER (Chem. News, 1894, 70, 211-212J-The authors find that hydrocarbons from Russian kerosene produce a reduction in temperahwe when mixed with acetic acid, and regard it as indicating combination, and, moreover, the products begin to distil at a lower temperature than would be the case if they were only mixtures of their components.D. A. L. Ferric Thiocyanate. By L. ANDREWS (Chem. News, 1894, 70, 165-166) .-Spectroscopic examination of solutions of ferric thio- cyanatein amylic alcohol distilled from phosphoric acid, and in absolute ethylic alcohol, show that the absorbent power of such solutions diminishes more rapidly than the concentration ; and inasmuch as the molecular conductivity of such solutions is found to diminish, with increasing dilution, in about the same ratio as the reciprocal of the absorption coefficient, the falling off of the colour cannot be due to electrolytic dissociation ; and, as hydrolysis is out of the question in the present case, neither Magnanini’s nor Ostwald’s theory seems capable of fully explaining the behaviour of ferric thiocyanate in solution.Compared with aqueous solutions, a solution containing 0-0625 milligram of ferric thiocyanate per C.C. of amylic alcohol transmitted 48 per cent. of light of wave-length 587, about the same amount as an aqueous solution containing 0.247 milligram per C.C. D. A. L. Linalol and Licareol. By P. BARBIER (Bull. SOC. Chim., 1894, [3], 11, 261).--Referring to Bouchardat’s paper (Abstr., 1893, i, 54$), the author claims priority of discovery (Abstr., 1892, 1236) of the tendency of acetic anhydride to cause the conversion of the alcohola VOL.LXVIII. i. !?78 ABSTRACTS OF CHEMICAL PAPERS. of this class into isomerides. and licareol. L. T. T. He also denies the identity of linalol Constitution of Rhodinol from Oil of Pelargonium. By P. BARBIER and L. BoTJVEAUr,T (Compt. rend., 1894, 119, 334-33'7).- The principal constituent of oil of pelargonium is a somewhat oily liquid with a strong odour of roses ; it boils at 115-116" under a pressure of 10 mm. ; sp. gr. at 0" = 0.8866; rotatory power of a column 20 cm. long -12" 28'. When heated at 150-160" with a large excess of acetic anhydride, it yields (together with a small quantity of a hydrocarbon which boils at 60-80" under a pres- sure of 10 mm.) an acetate which boils at 120" under a pressure of 10 mm., and has a somewhat agreeable odour; sp.gr. at 0" = 0,9158. This acetate combines with one molecular proportion of bromine. When hydrolysed, the liberatled alcohol has its original boiling point, but its odour has become weaker, the sp. gr. has fallen to 0.8825, and the rotatory power of a column 200 mm. long has fallen t o -7" 13'. Phenylic isocyanate acts on the alcohol as a dehydrating agent, and yields only diphenylcarbamide. This rhodinol from pelargonium is a primary alcohol, and when carefully oxidised yields an aldehyde containing the same number of carbon &toms. The yield is, however, somewhat small, a large quantity of condensation products of high boiling point being formed at the same time. The aldehyde has a mixed odour of peppermint and lemon, and boils at 105-108", but cannot be separated from the excess of alcohol that always accompanies it.It yields a liquid oxime boiling at 140-150°, and this is converted by acetic anhydride into a nitrile, Cl0Hj[,,N, which boils at 112-113" under a pressure of 11 mm., and combines with one molecular proportion of bromine. The aldehyde has the composXon CloHI6O. The products of the oxidation of rhodinol contain an acid, C,oH,,02, which boils at 149-150" under a pressure of 10 mm., and combines with one molecular proportion of bromine. More energetic oxidation yields acetone and an acid, C7H120,, which boils without decomposing above 300" under the ordinary pressure and at 250" under a pressure of 10 mm. It is a bibasic acid, and does not combine with bromine; when boiled with aniline, it yields an anilide which crystallises in slender, colourless needles melting at 206-207", somewhat soluble in alcohol, especially on heating, but only slightly soluble in ether.When boiled with acetic anhydride, the acid yields a very viscous anhydride, C7Hlo03, which boils at 180" in a vacuum. This new bibasic acid is a-methyladipic acid; attempts to prepare it syn- thetically were unsuccessful. The rhodinol of oil of pelargoiiium differs from its isomerides, lemonol (geraaiol) aiid licarhodol, with which it has hitherto been confounded, in that it does not readily lose water with formation of a terpeie, &id is not attacked by hydrochloric acid i n the cold. More- over, the hydrochloride, when heated with potassium acetate, yields rhodinol acetate, whereas the hydrochlorides of its isomerides yield a terpene.It is a primary alcohol with a ringconstitution, but with only one ethylenic fuaction. C. H. B.ORGANIO OHEMISTRY. 79 Syntheses in the Sugar Group. By E. FISCHER (Ber., 1894, 27, 3189--3232).--This paper is a compilation of the work accom- plished by the author and his collaborators, together with the more im- portant researches of other chemists in the same domain since the year 1891. It thus forms a continuation of the paper on the same theme (Abstr., 1890, 1223) which the author deiiT-ered as a lecture before the German Chemical Society. The first section deals with experi- mental methods, and in the next section the present aspect of the sugar group is discussed, the known aldoses and ketoses being tabulated together with the mono- and di-basic acids and polyhydric alcohols derived from them.The autlioib then deals with the stereo- chemistry of the sugar group, and from this leads up to the con- figuration of the sugars and allied compounds. He then describes s nomenclature which expresses the configuration of these compounds in a, more concise manner, thus glucose is denoted “ hexose + - + + ” or ‘‘ hexapentoZaZ + - + +.” These formula do not, however, represent, as did those of van% HOE, the influence of a single asymmetrical carbon atom on the optical properties of the molecule, but only the position of one subsfituent to the right or left side of the configuration formulae (compare Abstr., 1891, 1173 and 1444).The last two sections are under the following headings : “ Influence of Configuration on Chemical and Physical Properties ” and “ Im- portance of Stereochemical Results in regard to Physiology.’’ The papers quoted have all appeared in this Journal, principally as abstracts ; their collation has, however, enabled the author t o draw some most important and suggestive deductions. By J. WEISSBERG (Bied. Centr., 1894, 23, 715 ; from Oester.-Uugar. Zeits. Zuclcer.ind. ZL. Landw., 22, 153-155) .-Ignited magnesia is about 300 times less soluble in 10 per cent. sugar solution than lime, and is less soluble in boiling sugar fiolutions than in cold solutions. Inas- much as magnesia is so sparingly soluble i n pure sugar solutions, and much more soluble in sugar-lime solntions, itl was thought possible to prepare a magnesia sucrate, or, at least, a lime-magnesia sucrate; neither compound could, however, be obtained.Beetroot juice (100 c.c.) WAS treated with milk of lime in the usual manner with addition of ignited magnesia (1 gram). After the first saturation, a, few C.C. of milk of lime and some milk of magnesia were added to the juice, which mas then saturated a second time. The filtered solution yielded an ash containing CaO, 0.351 giwn; NgO, 0.021 gram; or about 1 7 times as much lime as magnesia. Limestone containing 2 or 3 per cent. of magnesium carbonate would, therefore, have no appreciably injurious effect on the compo- sition of the products, since magnesia is so slightly soluble in sugar juice. N. H.J. M. A. R. L. Amount of Magnesia and Lime in Sugar Juice. Iodide of Starch Reaction. By C. MEINEKE (Chein. Zeit., 1S94, 18, 157--163).-An aqueous solution of iodine may be added to a solution of starch until the liquid is decidedly yellowish, without developing any blue colour. The smallest amonnt of potassium iodide, 9 2a0 ABSTRAOTS OF CHEMICAL PAPERS. however, is sufficient to give the reaction. This seems a t first a con- firmation of Mylius's statement, that iodide of starch contains potas- sium or hydrogen iodide as .an essential constituent ; but the author's investigat,ion proves that the presence of a soluble iodide is not at all necessary for obtaining the blue compound. The author has tabulated the results of a large number of experiments, showing that the com- pound is also formed, more or less completely, in the presence of other salts such as potassium, sodium, ammonium, calcium, and barium chloride ; potassium, sodium, ammonium, and magnesium sulphate ; Maltol.By H. KmAw and M. BAZLEN (Bey., 1894, 27, 3115- 3120 ; compare J. Brand, Abstr., 1894, i, 270).-Maltol forms charac- teristic metallic salts. The z i m salt separates in colourless needles which retain water ; the copper salt is anhydrous. The calcium salt crystallises in silky needles containing 5Hz0 ; it becomes yellow in contact with air or in a vacuum, owing to loss of water. The lead, barium, cadmium, potassium, and ananzonizm salts are also crystalline. Benzoylmaltol, CsH5O2*OBz, is colourless and neutral ; it melts at Oxidation of maltol with potassium permanganate gives rise solely to acetic acid and carbonic anhydride, the same products being formed on treating the aqueous solution with silver oxide.Maltol is not acted on by hydriodic or sulphuric acids, and no change occurs when the solution in alcohol or acetic acid is saturated with hydrogen chloride. Bromine has no action on maltol dissolved in chloroform, but the aqueous solution yields a syrupy acid which loses bromine very readily. It is clear from these observations that the constitutional formula suggested for maltol (Zoc. cit.) must be considerably modified, and the authors prefer to regard it as a methylpyromeconic acid. Nitrogenous Compound prepared from Fungus-cellulose." By E. WINTERSTEIN (Ber., 1894, 27, 3113-3115 ; compare Abstr., 1894, ii, 425).-The author has already shown that the cellulose ob- tained from various fungi contains a considerable quantity of nitro- genous constituents which are not of a prote'id nature.Further investigation has shown that when the fungus-cellulose is heated with hydrochloric acid, it yields glucosamine hydrochloride, identical with the product obtained in a similar manner from chitine (Abstr., 1885, 53 ; 1886, 329). Whether the constituent which gives rise to the formation of glucosamine is identical with chitine has not yet been ascertained. H. G. C. potassium alum ; potassium and sodium biborate. L. DE I(. 115-116". M. 0. F. Action of Halogen Xydracids on Formaldehyde in presence of Alcohols. By L. HEKRI- (Compt. rend., 1894, 119, 425-426),- The reaction recently described by Fame (this vol., i, 14) was pre- viously observed by the author (Bull. Acad.Sci, Beige, [3], 25, 439), and also by P. Henry (Abstr., 1892, 27) ; the former investigated the action of hydrobromic and hydriodic acids as well as that of hydro- chloric acid. C. H. B.ORGANIC CHEIIISTRY. 81 Chloro-formoxime. By R. ScnoLr, (Ber., 1894,27,2816-2822). -This substance, which has recently been described by Nef (this VO~., i, lo), was obtained by the author in 1892, having been regarded as the dihydrochloride of fulniinic acid. The observations of Nef are fully con firmed. 31. 0. F. Cause of the Transformation of Ethylic a-Bromacetoacetate into Ethylic y-Bromacetoacetate. By A. HANTZSCH ( B e r . , 1894, 27, 3168-3169 ; compare Abstr., 1894, i, 227).-This remarkable intra-molecular change is due to the agency of traces of hydrogen bromide, and is checked by the presence of moisture.M. 0. F. Free Acids from Beeswax. By T. MARIE (Conzpt. rend., 1894, 119, 428--631).-The free acid present in beeswax mas regarded by Brodie as a single substance; but Schalfesew and Nafzger have shown that it is a mixture. The author finds that the separation of the acids cannot readily be effected by Heintz's method of fractional precipitation with metallic acetates, bat is easily attained by means of fractional crystallisation from methylic alcohol, provided all organic substances except the acid's are first removed. The wax is extracted with boiling methylic alcohol, and, after the greater part of the solvent has been distilled off, the cooled and crys- tallised residue is pressed in order to remove the ole'ic compounds and the colouring matters.The cake is melted, mashed several times with boiling water, decolorised with charcoal, and filtered through paper ; it is, then heated with lime and potash-lime until evolution of hydro- gen ceases, in order to destroy myricin. The powdered mass is next suspended in water, heated to boiling, and saturated with dilute hydrochloric acid, the calcium salts which precipitate being col- lected, washed, dried, and treated with boiling alcohol and benzene t@ remove neutral substances. The acids are then liberated, and, after crystallisation from methylic alcohol, melt at 79-80'. The mixture of acids is well triturated with 30 times its weight of msthylic alcohol, heated carefully to boiling, and filtered at 60".The filtrate contains chiefly cerotic acid, which crystallises on cooling. This treatment is repeated with successively diminishing volumes of alcohol until the residue melts at 78". The dissolved product will fhen melt at 76". A single crystallisation from ethylic alcohol raises this melting point to 7'7.5". Crude cerotic acid has beerr described as a single substance, but in reality it contains from 30 to 40 per cent. of analogous acids. The author is investigating the properties of the pure acids and its salts. C. H. 13. Constitution of Ricinoleic and Ricinostearolic acids. BV A. G. GOLDSOHEL ( B e r . , 1894, 27, 313.1-3129; compare J. Ba&ch, Abstr., 1894, i, 170).-Ricinostearolic acid, when treated with concentrated sulphuric acid, yields ketohydroxy- atearic acid, C6H13*CH(OH)*CH,*CH,*CO*[ CH2],*COOH. The latter gives with bydroxylamine, ketoximehydroxystearic acid, CGH13.C H (0 H) CH2.C i C [ C H,] 7.C 0 OH, CGH13*CH (OH) *CH,*CH,*C (MOH) [ CH,] 7*COOH,82 ABSTRACTS OF CHEMICAL PAPERS.and this acid is converted by phosphorus pentachloride into an oil, which, whm heated with fuming hydrochloric acid at 180-200', > 0, amidocaprylic acid, a-hexyl- YHz'CH(C6His) co yields ydecalactme, CH2 - trimethylenimine, C,H,,*CH<CHz>CH,, and azela'ic acid. Ketohydrozystearic acid forms silky crystals, and melts at 8 6 8 5 ' . The barium and s i h e r salts are colourless, and the ethylic salt melts at 54.5" ; the acetyl derivative is a yellow oil.The phenythydrazide is foTmed when the acid is heated with phenylhydrazine at 150'. Ketozimehyd~ozystearic acid is an oil which is decomposed into hydroxylamine and ketoxystearic acid by dilute mineral acids. On heating it with alcoholic ammonia and adding hydrochloric acid, the product exhibits the characteristic reaction of pyrroline derivatives. The hydrochloiide of a-hexyltrimethylenimine is hygroscopic, and yields the yellow platinochloritle, melts at 172", and its hydrochloride at 147'. Turkey-red Oil. By P. JCILLARD (BUZZ. SOC. Cl~im., 1894, [3], 11, 2SO-286) .-This is a continnation of the author's previous work (Abstr., 1892, 819, and 1893, i, 455) on the action of sulphuric acid on castor-oil and on ricinoleic acid. Diricinic acid, 0 (CnH3z*COOH)p, is a bibasic acid.It is a thick, oily liquid, soluble in alcohol in all proportions, whilst its ethylic and methylic saits are but sparingly soluble in alcohol. Ricinoricinic acid, OH~C17H32~C0*O*C17H3z*COOH, best prepared by heating ricinoleic acid at 1 7 0 - B O O , is the first mem- ber of the series of polymerides of ricinoleic acid, and is a monobasic acid. Di h y drox yst e u w w Lpli uric acid, S OaH*C i7H3s ( OH) *C 0 OH, closely resembles ricinosulphuric acid in properties. Diliydrozystearic acid, ClaH3604, is very soluble in alcohol and ether, sparingly in light petroleum, and melts at 66-68". A solid acid, C36H;oO;, was obtained, melting a t 70-73', which appears to be a molecular com- pound of dihydroxystearic acid with ricinoleic acid. Isoricinoleic acid, C118H3t03, is an oily liquid, soluble in alcohol and in light petroleum, and appears to be a ketonic acid.Action of Thionyl Chloride on Organic Acids and Aldox- imes. By C. MOCREU (Compt. T e d . , 1894, 119, 337-340).--See this vol., ii, 43. NH Amidocaprylic acid, NH2* [ C H2] ?*C 0 OH, M. 0. F. L. T. T. Preparation of Thiodiglycollic acid. By J. M. LOV~N (Ber., 1894, 27, 3059-3060) .-An improved method of preparation. 95 grams of crystallised chloracetic acid is placed in a large beaker, and a solution, heated to 35', of 145 grams of crystallised sodium carbonate in 50 C.C. of water is added. 45 grams of sodium hydroxide is dissolved in water, so that th2 solution has a volume of 100 c.c., one half is saturated with hydrogen sulphide, and then the two halves are added simultaneously to the solution in the beaker, which is meanwhile shaken or stirred.The pasty mass is allowed to standORGANIC OHEMISTRY. a3 for three hours ; 110 grams of strong sulphuric acid is then added, carefully, but without cooling, and the hot solution is filtered, and allowed to cool. After six hours, the crystals of crude thiodiglycollic acid are collected and dried; they weigh about 70 grams, aDd con- tain 10-15 per cent. of sodium hydrogen sulphate. The crude crystals are dissolved in hot water (50 C.C. for every 70 grams), and the solution is filtered ; on cooling, 53 grams of very pure thiodigly- collic acid is deposited. The mother liquor horn the crude crystals, evaporated until it weighs 270 grams, is cooled to 40°, and then filtered, The filtrate, on further cooling, yields crystals of thiodiglycollic acid ; these are purified by recrystallisation from the mother liquor of the first crop of pure crystals, and then weigh 10 grams.63 grams of the pure acid are thus obtained from 95 grams of chloracetic acid, a, yield which is 84 per cent. of the theoretical. C. F. B. By H. W. BOLAM (Ber., 1894, 27, 3061-3062) .-When ethylic dicarboxyghita- conate (1 mol.) is boiled with 10 per cent. aqueous barium hydroxide (4 mols.), it is partly hydrolysed, malonic and another acid, 0 H* C H:C (C 0 0 H)z ( ? ) , being formed, The barium salt of the latter acid resembles that prepared by Ruhemann and Norell (Trans., 1891, 749) from etliylic amidoethy lenedicarboxylate. C. F. B. Leucine from Pancreatic Digestion.By R. COHK (Zeit. physiol. Chem., 1894, 20, 203-209) .-The present research brings forward evidence to show that the leucine obtained in a pancreatic digestion of prote'id matter is not a single substance, but a mixture of several isomeric substances. W. D. H. Hydrolysis of Ethylic Dicarboxyglutaconate. Derivatives of Dimethylalloxan. By W. TECHOW (Ber., 1894, 27, 3082-3089) .-DimethyldiaZuvic acid, C 0 < ~ ~ ~ : ~ CH*OH, is best obtained by the action of sodium amalgam on a thick magma of amalic acid (tetramethylalloxantin) and water, the whole being well shaken and cooled. The product is poured into hot dilute hydro- chloric acid, and filtered, the whole series of reactions beicg carried out quickly, as the acid is very soon reddened by the air, especially when moist.The acid forms compact prisms, reddens at loo", melts and decomposes at 170", and reduces silver and copper solutions in the cold. The potassiunt salt, C6H7N,04K, forms voluminous flakes, which soon assume a deep blue colour in the air, and the barizcnz salt, CIzH14N408Ba + 2H20, forms microscopic crystals. Dicldorodimetli ylbarbituvic acid, CO:(NMe*C0)2:CC1,, is readily ob- tained by the action of phosphorus pentachloride on amalic acid at 180" ; it crystallises from alcohol in delicate, white needles or well- developed prisms, melts a t 157" (uncorr.), and on long continued boiling with water loses hydrogen chloride, with formation of dimethylalloxan. When treated with sodium amalgam, it is con-84 ABSTRACTS OF CHEMICAL PAPERS.verted into the dimethylbarbituric acid, already described by Mulder (Abstr., 1879, 618). Dimet1tyl.r;ioluric acid, CO:(NMe*CO),:C:N*OH, is prepared by the action of hydroxylamine hydrochloride on di- methylalloxan, and forms hard, well-developed crysta.ls melting at 124". It is strongly acid, liberating carbonic anhydride from carbon- ates. The potassium salt, C6H6N,04k', forms a deep bluish-violet, flocculent, crystalline mass, the amnzonium salt, C6H6N304NH, + H,O, deep red crystals, which change to pale red on beating, and the barium salt, C12H12N608Ba + H,O, a heavy, red precipitate. When added in small quantities to hot concentrated nitric acid, it is con- verted into dinzethyl.rzitrobarbituric acid, CO:(NMe*CO),:CH*NO,, which separates from acetone as a white, microcrystalline mass, melting at 148"; the sodium salt, CsH6N306Na + 4H20, crystalhes in slender, yellow prisms.The ammonium salt of dimethylthionztric acid, CO:( NMe*C 0) ,:CH*NH*S03NH, + 2H20, is obtained by saturating a concentrated solution of ammonia with sulphurous anhydride and warming with solid ammonium carbonate and dimethylalloxan, and separates, on cooling, i n fascicular aggre- gates of slender, lustrous needles; the water of crystalliRation is evolved at 105", the salt simultaneously assuming a red colour, and, on further heating, it decomposes completely at 180". On adding barium chloride t o its solution, the barium salt, C6H7N306SBa, separates in silky crystals. The free acid is an amorphous mass, which is readily soluble in water, has strongly acid properties, and, on boiling in aqueous solution, is converted into sulphuric acid and dimethyluramil, C0:(NMe*C0),:CH*NH2.The latter compound is also obtained by the reduction of dimethylvioluric acid or of di- methylnitrobarbituric acid, but is besk prepared by boiling ammonium dimethylfhionurate with fuming hydrochloric acid, diluting with water, and neutralising with ammonium carbonate. Dimethyluramil then separates in snow-white, silky flakes, which melt and decompose at about 'LOOo, and, on exposure to the air in the moist condition, quickly become dark red. It reduces silver and copper solutions, is decom- posed by alkalis, even by ammonium carbonate, but unites with acids t o form unstable salts ; the hydrochloride forms small, hard crystals, which lose hydrogen chloride in a vacuum, and the platinochloride, ( C6H9~303),,HzPtC16, crystallises in yellow prisms. Dimeth ylpseudouric acid, C 0: (NMe*CO),:C H*NH*C 0*NH2, is pre- pared by the action of a concentrated solution of potassium cyanate on dimethyluramil.T t forms small, white crystals, reddens at loo", melts and completely decomposes a t 210°, and reduces silver soh- tions. The potussiuin salt, C7H,N40kK + H,O, is crystalline, and the copper salt, (C7H9N404),Cu + 2H20, is a pale green precipitate, which loses its water of crystallisation at 1 0 5 O , the colour changing simul- taneously to yellowish-brown. Action of Iodine and Potassium Hydroxide on Uric Acid. By E. BRYK (Monatsh., 1894, 15, 519--529).-Kreidl has described a method for the estimation of uric acid by treating it with potassium H.G. C.ORGIAKIC CHENISTRY. 85 Iiydroxide and iodine, and subsequently titrating with thiosulphate (Abstr., 1893, ii, 55s). The author finds that the action of iodine on R solution of uric acid, to which potassium hydroxide has been pre- viously added, depends on the proportion in which the substances are present and also on the temperature. If only a small excess of potassium hydroxide is employed, say i n the proportion of 2.25 mols. t o 1.3 atoms of iodine and 1 mol. of uric acid, and the mixture is kept cool, a yellow insoluble substance separates. This on analysis gave the numbers C = 28.37-26.86, H = 4.39-3-71, N = 28.53- 29-19, and on solution in potash or sulphuric acid and subsequent reprecipitation with water gave uric acid.When a similar mixture is warmed, potassium urate, carbonic anhydride, and ammonia are formed. The employment of a hrger proportion of potassium hydrox- ide, say 4 mols. to 2 atoms of iodine and 1 mol. of uric acid, gives rise t o allantoin and carbonic anhydride; the yield of the former is good (40-50 per cent.). G. T. 31. Polymeric E thoxy sulphone t hylene sulp hinic Lac t on e . By G. WALTER (Ber., 1894, 27, 3043-3045).-When an aqueous solu- tion of free ethoxysulphonethylenesulphinic acid is evaporated to dryness, there is formed, in addition to the lactone soluble in water, already described (Abstr., 1893, i, 459), an insoluble poly- meric modification, which has, however, the same melting point and chemical properties as the soluble variety.It can be converted into the latter by hydrolysing it with baryta water, liberating the free acid from the barium salt so obtained, and evaporating the solu- tion of this acid. C. F. B. Some Derivatives of Ethoxymethylsulphone. By G. WALTER (Bey., 1894, 27, 3045-3049; compare Abstr., 1893, i, 459).- Ethoxymethylsulphone, OH*C2Hp*S02*CH1, on treatment with phos- phorus pentachloride, yields chlorethylme thylsulphone, which melts at 8.5-9". When this is tredted with ammonia, there are formed, besides ammonium chloride, the hydrochlorides of primary and secondary metli y lszclphou et hylamine, NH2* C2H& 02*CH3 and NH(C2H4*S0,-CH3)2. The first hydrochloride forms deliquescent prisms, and the corresponding orange platinoclzloride melts and de- composes at 220-221".The second hydrochloyide melts at 202-203", the orange platiwocldoride at 1 59-160°, and the benzoyl-dericative at 131"; the free base forms stable crystals. If ethoxymethylsulphone is allowed to remain with cold, strong, siilphuric acid, and the mixture then added to a magma of water, ice, and barium carbonate, barizcm methylsi~lplphonethyle~ze sulphate, Ba(SOI*C2H4*S02*CH3), + H20, is formed. This is readily hydrolysed, by boiling with water, yielding barium sulphate, sulphiiric acid and ethoxymethylsulphone ; am- monia converts it into the amines described above. C. F. B.86 ABSTRACTS OF CHEMIOAL PAPERS. Action of Sulphuric Acid on Bromothiophen. By A. TORT. and R. SCHULTZ (Ber., 1894, 27, 2834-2839 ; compare Abstr., 1894, i, 117 and 276).-In addition to the results already described (Zoc.cit.), it is found that slightly fuming sulphuric acid converts tri- bromothiophen into tetrabromothiophen, the sulphonic acids of dibromo- and tribromothiophen being also formed in small quantities. If fuming acid is employed, perbromodithienyl and tetrabromothiopheu are formed. M. 0. F. Synthesis of Metachlorotoluene and of Symmetrical Chloro- xylene from Ethylic Acetoacetate. By A. KLAGES and E. KKOEVENAGEL (Ber., 1894, 27, 3019-3025 ; compare this vol., i, 48). -Dih~drometac7~lo~otoZueize [Me : H2 : C1 = 1 : 2 : 3 : 51 is prepared by the action of phosphoric chloride on 3-mebhyl-AZ-keto-tetrahydro- benzene ; the intermediate methyltrihjdrodichlorohenzene could not be isolated, it is a highly refractive liquid with an aromatic odour, boils at 78-80" (25 mm.), at 160-170" under atmospheric pressure, and is volatile with steam, some of the compound being decomposed.The yield is 60 per cent. of the ketone employed. The ketone is re- generated by the action of sulphuric acid (95 per cent.), a tertiary alcohol being first formed which is either identical with the ketone or is converted into it by intramolecular rearrangement. The dibromide is unstable and could not be purified; on warming alone or with quinoline, hydrogen bromide is eliminated and metachloro- toluene is formed. 2 : 3 : 5-Dihydl.ochZol.o-xyZene [Me : Me = 1 : 31 is prepared in a similar manner to the toluene derivative from 3 : 5-dimethyl-A2-keto-tetra- hgdrobenzene, which it closely resembles ; it boils a t 78-80" (15 mm.), and a t 176-178" under ordinary pressures with little decomposition, darkens on exposure to air, and regenerates the ketone on treatment with sulphuric acid.The yield is 70 per cent. of the ketono em- ployed. The dibromide is unstable and is readily converted into symmetricd chloro-xyZene, a highly refractive mobile liquid boiling at 190-191" ; its vapour rapidly attacks the skin. The sulphonic acid crystallises in lustrous plates, is readily soluble in water, and melts at 65-68'. The sodium and barium salts crystallise in plates. The sulphonic chloride and the sulphonamide crystallise in colourless needles melting at 48-49" and 189-190" respectively. The position of the sulphonic p o u p has not been determined. Mercuric Phenoxides and Naphthoxides.By E. DESESQUELLE (Bull. SOC. Chim., 1894, [3], 11, 263-269) .-Mercuric p-naphthoxide chloria'e, ClHg*O*CloH7, obtained by shaking together aqueous solu- tions of mercuric chloride and potassium p-naphthoxide, crystallises in colourless prisms soluble in alcohol, insoluble in water. For medical purposes, the author proposes for this substance the name P-sublimo- naphthol. Nercuyic ,%rtaphthoxide, Hg( 0*C,0H7)2, forms microscopic: crystals, almost insoluble in the usual solvents but slightly soluble in boiling phenol. Acetic acid acts on it with development of heat, yielding mercuric p-naphthoxide acetate as a white, crptalline sub- stance, soluble in alcohol, almost insoluble in water. J. B. T.ORGANIC CHEMISTRY. 87 Jfercuric phenoxide chloride forms colourless crystals melting about 210", soluble in phenol or in a boiling alcoholic or aqueous solution of phenol.Merczwic phenoxide hydyoxide, OH-Hg*OPh, is formed when a large excess of potassium phenoxide is employed, and crystallises in stellar groups of prisms. With acetic acid, this compound yields qizercuric pheiioxide acetate, crystallising in colourless prisms. The author has not been able to obtain the derivative Hg(OPh),. L. T. T. New Colour Reaction of Iridol. By E. NICKEL (Chem. Zeif., 1894, 18, 531).-When a solution of iridol (Abstr., 1894, i, 48) in aqueous alcohol is warmed with a solution of mercuric chloride (2 parts) and sodium nitrite (1 part) in water (40 parts), a beautiful, violet coloration, having a bluish tinge, is developed. This reaction was previously described by the au thor as characteristic of vanillin, and, indeed, there is no essential difference between the colorations produced by the two substances.A. R. L. Thioaniline (m. p. lOS0), and.& new Isomeride. By K. A. HOF- NAX" (Bw., 1894, 27, 2807-2816).-The author has shown that Merz and Weith's thioaniline is orthodiamidophenylic sulphide, S( CsH4.NH2), ; orthodiamidophenylic bisulphide is also formed when aniline is heated with sulphur, and may be converted into ortho- diarnidophenylic sulphide by the addition of lead oxide to its solution in boiling aniline. Pnradiamido~?ieizylic subhide is prepared by heating a mixture of aniline, aniline hydrochloride, and sulphur for 6-7 hours at 175" ; it crystallises from boiling water in colourless, lustrous plates, which melt at 85.5".The hydrochloride yields an emerald-green solution when heated with fuming sulphuric acid for half an hour at .loo". On adding lead peroxide to the solution in alcoholic hydrochloric acid, a green coloration is produced, changing to deep blue. The benzoyl derivative melts a t 234", and the diacetyl derivative at 185"; the corresponding derirstives from orthodiamidophenylic sul phide melt at 255" and 213-215" respectively. Pa~.adiamidophe~aylic bisd@hide, C12Hl,N,S,, is associated with the foregoing compound. It forms colourless needles, and melts a t 80" ; the diacety Z deriva,tive melts a t 205" ; it yields paradiamidophenylic sulphide when sti*ongly heated. The solution of the hydt.ocltloride i n alcohol is coloured deep cherry-red by lead peroxide, and the colour- less solution i n strong sulphiiric acid becomes violet when heated. Sulphur is precipitated when hydrogen sulphide is passed through a solution of the hydrochloride in dilute hydrochloric acid, nmido- phenyl mercaptan remaining dissolved.When paradiamidophenylic bisulphide is diazotised, decomposed in alcoholic solution with copper powder, and saturated with hydrogen sulphide, thiophenol is pro- duced, and parabromothiophenol is formed on displacing the amido- group with bromine. Suggested Non-existence of Isopropyleneparamidophenol, By A. MICHAELIS and K. LUXEMBOURG (Be,.., 1894, 27, 3005-3009). -Haegele's work on this compound has been repeated, and his M. 0. F.88 ABSTRACTS OF CHEMICAL PAPERS. results are confirmed as regards its formation from pure acetone; it melts at 172-174", is slowly hydrolysed by boiling with water, and more readily with dilute acids (compare Hantzsch and Freese, Abstr., 1894, i, 572, and this vol., i, 24).The calcium hypochlorite reaction is a delicate test f o r pararnidophenol; the acetate reacts more readily than the hydrochloride ; the dilute hypochlorite solution should be added gradually, as the violet colour is destroyed by excess of it. Chlorides of Hydroximic Acids and their Products of Change, By A. WERNER (Ber., 1894, 27, 2846-2850).-001.thonitrobenz?~ydr- oximic chloride, NOz*CsH4*CC1:NOH, is formed when dry chlorine is passed into a solution of orthonitrobenzaldoxime in chloroform ; it melts at 92-94'. The ?)zeta-derivative melts at 94-95', and thepara- compound at 115-117".Orthom'trobenzsn ylamidozime, N02*C6H4.C (NH,) :NOH, is obtained by warnling the acid chloride with alcoholic ammonia. It forms bright yellow needles, which contain 1H20 ; the substance loses water at SO", and melts at 141-142". The para-derivative melts at J. B. T. 165-167". when metanitrobenzhydroximic chloride is warmed with concentrated aqueous potash. It melts at 183-183". The para-compound melts a t 197-198'. Orthonitrobenzenylpiperidoxirne, NO2*C6H,*C (C,NH,,) :NOH, is ob- tained by mixing ethereal solutions of piperidine and ortho- nitrobenzhydroximic chloride. It melts at 132-133", and th.e wzeta-derivative melts at 159-160". The para-compound melts a t 166-1 67'. M. 0. El. Action of Amidoacetal on Orthonitrobenzoic Chloride and Paranitrabenzoic Chloride.By W. LOB (Ber., 1894, 27,3093- 3097).- Orthonitrobenzo ylamidoncetal: is obtained in a manner analogous to the benzoyl derivative (Abstr., 1893, i, 300), and ci-ystallises from ether on the addition of light petro- leum in stellate groups of colourless needles melting at 70-71". On treatment with cold fuming hydrochloric acid, it is converted into os-thonitroh~pul'aldeh yde, N02*C6H,*CO*NH*CH,*CH0, an amorphous, pale yellow substance, which softem at 90°, decomposes at a higher temperature, and reduces Fehling's solution. It could not be directly converted into the corresponding orthonitrohippuric acid, but the latter was obtained by the action of orthonitrobenzoic chloride and alkali on glycocine ; it crystallises from hot water in long, narrow plates melt- ing at 188", and gives crystalline precipitates with silver and lead salts.01-thamidobenzoy Zamidoace ta 1, NH2* c6H4* C 0 *NH* CHz* CH (OE t) 2, is prepared by the reduction of the nitro-compound with zinc dust and acetic acid in alcoholic solution, and crystallises from light petroleum coctaiining a little ether, in druses of colourless needles, melting at NOz*C,H,* CO*NH*CH,*CH( OE t ) 2 ,ORGANIC OHEMISTRY. 8 9 80-81". By the action of concentratled hydrochloric acid, not only are both the ethyl groups eliminated, but also the elements of water, with formation of the an12 ydrids of orthcr11tidohippuraldehyde, a white, amorphous compound, which decomposes at 300" withoiit previously melting; it has the empirical formula C,H8N20, but is probably a pol ymeride.Pamnitrobenzoylamidoacetal is prepared in a similar way to, and closely resembles the ortho-derivative ; it melts at 82", and, with hydrochloric acid, yields paraniti-ohippuraldehyde, which forms colour- less, amorphous flakes, softens at loo", and reduces Fehling's solution. Like the ortho-compound, it cannot be converted into the correspond- i n g acid, which was prepared from paranitrobenzoic chloride and glycocine, and forms colourless prisms melting at 129". When paranitrobenzoylamidoacetal is treated with reducing agents, it does not, like the ortho-derivative, yield the amido-compound, but is converted into the azoxy- or azo-derivative according to the strength of the reducing agent employed. Parazoxybenzoylanz.idoacetn1, ON,[ C,H,*CO*NH*CH,*CH(OEt),],, is obtained by the action of zinc dusb and acetic acid in the cold, and crystallises in pale red plates melting at 182".Parazobenzoylamidoacetal, N2* [ CsHd*C O*NH* CH2-CH( OEt),],, is formed if the eolution is boiled with zinc dust and acetic acid; it crystallises in long, narrow, carmine-red plates, melting at 202.5". H. G. C. Derivatives of Amidoaldehyde. By H. HELLER (Be,.., 1894,27, 3097 -3102) .- E. Fischer has already shown that amidoacetal com- bines with aldehydes and acid chlorides, and that the products are resolved by the action of hydrochloric acid into the corresponding derivatives of amidoaldehyde. The author, in the present paper, describes a, number of these derivatives. Yaramethozy bemy lideneantidoacetal, O&fe-C6H4*CH:N-CH2*CH( OE t)2, is obtained by the action of amidoacetal on anisaldehyde, and forms a coloarless oil having a bluish fluorescence, and boiling at 190" (corr.) under 12 mm.pressure. It yields salts, of which the oxalate, melting at 138", is the most stable. On reduction with sodium in alcoholic solution, it yields paramethoxybenzylamidoacetal, OMe*C&t4*CH2*NH*CH2*CH(OEt),, which is a colourless, slightIy fluorescent liquid boiling at 187" (coi-r.} under 12 mm. pressure ; its oxalate crystallises in colourless needles melting at 174". Paramethoxybenzylamidoaldehyde, OMe*C,H,*CH,*NH*CH*CHO, is obtained in the form of the hydl-ochloride by the action of hydro- chloric acid on the foregoing compound at 50" ; it crystallises with iH20, reduces Fehling's solution strongly, and with alkalis yields the free aldehyde, which is amorphous.The phenylhydrazone hydro- chloride crystallises from alcohol in lustrous, colourless plates which become brown a t 150" ; it is converted by alkalis into the oily free pheny lhydrazone. Anisy lamidoacetal, OMw C6H4* CO*NH CH2*C H (OEt ),, is prepared90 ABSTRAOTS OF CITEXIGAL PAPERS. by the action of auisic chloride on a cooled ethereal solution of amidoacetal, the hyd?.ochZoride separating out in lustrous, white plates which are converted into the free base by alkalis ; the latter forms yellowish, prismatic needles melting at 60-61". With hydrochloric acid, it yields paramethoxyhil,puraldehllde, OMe* CsH,*C 0 - C H2*CH0, the hydrochloride of which separates out in colourless cube-shaped crystals melting at 128" with decomposition.The free aldehyde forms amorphous flakes and reduces Fehling's solution strongly. The phenylhydrazone c r p talliscs in colourless needles, which soon become reddish, and on heating turn brown and then melt at 126"; the oxime crystallises in slender, white needles, and melts and de- composes at 1-63". By the action of bromine, the aldehyde is con- verted into metabronzopnramethoxyhippuric acid, C,,,H,,O,NBr, which forms slender, white needles and melts at 161-162" ; its silver salt crystallises from hot water in stellate groups of needles. When strongly heated with concentrated hydrochloric acid, it is converted into metabromanisic acid. Ortli oh ydroxy benz yliden eamidoacetal, OH*C,H,*CH:N*C H2* CH (OE t)2, obtained by the act'ion of salicylaldehyde on amidoacetal, crystal- lises in yellow tablets melting at 32', and boils at 188" (corr.) under 15 mm.pressure. Orthohydroxybenzoylamidoacetal is prepared by heating mothylic salicylate with amidoacetal at 120", and crystallises from light petroleum in yellowish, rhombic plates melting at 54". By the action of strong hydrochloric acid, it is converted into the hydrochloride of orthohydroxyh+puraldeh yde, OH*C,H**CO*NHCH,*CHO,HCI, which forms white tablets, and melts at 150" with decomposition. The free aldehyde has only been obtained as a syrup with strongly reducing properties ; its phenylhydrazone crystallises in pale yellow needles, and melts and decomposes at 134" ; the oxima forms needles melting at 142'.(Be?-., 1894, 27, 3102-3105).-Phthalyldiamidoacetal, H. G. C. Phthalyl Compounds of Amidoacetal. By W. ALEXANDER C,H,[ CO*NH* CH,*CH (OE t)2] 2, is obtained by the action of phthalic chloride on amidoacetal i n ethereal solution, and separates, on the addition of light petroleum, in colourless needles melting at 90', and decomposing rather above 100". The corresponding a!dehyde is formed by the action on it of hydro- chloric acid, the hydrochloride being thus obtained as a syrup which reduces Fehlitig's solution. By the action of alcoholic potash, phthalyl- diamidoacet a I is converted into ortho benzo ytarrdoacetalcar box y 2ic acid, COOH*C,H,.CO*NH*CH,*CH( OEL)~, which separates on the addition of light pet.roleum to its ethereal solution in stellate groups of colonr- less needles containing 1H,O ; it melts and decomposes at about 100°.TerephthalyldiarvLidoacetal is prepared in a manner analogous to the phthalyl-derivative, and cry s t a k e s i n flat needles or plates melt- ing at 165". The corresponding aldehyde, C,H,( CO*NH*CH,*CHO),, is a bulky, white powder which only dissolves in concentrated hydro-ORGANIC UHEMISTRY. 91 chloric acid and alkalis ; its phenylhydrnzone forms yellow flakes. TerephtlzaZ?lldianzidoacetic acid, Cs~l(C!O*N~*CHO.COOH)a, is ob- tained by the action of bromine on the aldehyde, and crystallises from hot water in needles which melt at 240" with evolution of gas; the silver salt is a curdy precipitate which may be recrystallised from hot water, and the copper salt an insoluble, crystalline precipitate, which is blue when moist, but becomes green on drying.The acid may be more conveniently prepared by acting on glycocine with terephthalic chloride according to Baumann's method. Ilsophthalyldiamidoacetal, obtained in the same manner as its isomerides, melts at 75" ; the corresponding aldehyde closely re- sembles the terephthalyl derivative, but cannot readily be converted into isophthalyldiamidoacefic acid, which was therefore obtained from glycocine and isophthalic chloride ; it forms colourless cubes, and melts with decomposition at about 210'. Aromatic Nitro-derivatives. By V. METER (Ber., 1894, 27, :3153--3159).-Triiiitrobenzoic chloride [COCl : (NO2), = 1 : 2 : 4 : 61 is produced on heating trinitrobenzoic acid with a mixture of the oxychloride and pentachloridc of phosphorus. It displays re- markable stability in presence of water, being only slightly decom- posed when boiled with it for an hour (compare Sudborough, Trans., 1894, 1030).The solution of trinitrobenzoic acid in alkali (1 mol.) is colourless, and yields a colourless silver salt with silver nitrate; but if excess of alkali is employed, a deep orange-red liquid is formed. On adding acid to this solution, unchanged trinitrobenzoic acid is thrown down; this behaviour is comparable with the development of a deep red coloration exhibited by trinitrobenzene in presence of alkali. A small quantity of 1 : 3 : 5-dinitrobenzoic acid dissolved i n dilute alkali forms a colourless solution, becoming deep violet when excess of strong alkali is added.After a few minutes, the Iiquid loses colonr, and on remaining for two hours a further change occurs, and a stable, magenta coloration is developed. The author criticises the conclusions drawn by Nef regarding the constitution of salts of the nitro-paraffins (this vol., i, 3). Reduction of Paradimethylamidobenzoic acid and Par- amidobenzoic acid. By A. EINHORN and A. MEYENBERG (Ber., 1894, 27, 2829-28.34 ; compare Abstr., 1894, i, 591).-Yaradimethyla~nido- co - hexah ydrobenzoic acid, CJIlo<NHMe2> 0, is obtained, in associa- tion with hexahydrobenzoic acid, by the reduction with sodium of paradimethylamidobenzoic acid dissolved in amylic alcohol. The acid liquefies at 99-loo", resolidifies at 130°, and finally melts at 218-220" ; i t contains 2+H20.It is a neutral substance, and forms a bright blue coppel- salt ; the platinochloride melts at 232". H. G. C. M. 0. F. #-.A VV- Pnramidohexah ydrabenzoic acid, C6H10<NH,>0, is formed on reducing with sodium paramidobenzoic acid- dissolved in amylic alcohol, hexahydrobenzoic and valeric acids being formed simulta-92 ABSTRACTS OF CHEMIOAL PAPERS. neonsly. acid crystallises in small, white plates which melt at 303-;304". On adding the aqueous solution to absolute alcohol, the If. 0. F. Isomeric Paramethylenedihydrobenzoic acids. By A. EIN- HORN and R. WILLSTATER (Ber., 1894, 27, 2823-2829; compare Abstr., 1894, i, 523) .-In addition to Az> 4-paramethylenedihydro- benzoic acid, and the acid obtained by Einhorn and Friedlander on hg drolysing the methiodides of ethylic r-ecgonine and Z-ecgonine, there exists a third acid, CsH802, which remains liquid a t -20".It is prepared by heating A 2* 4-paramethylenedihydrobenzoic acid with alcoholic potash for 48 hours in a reflux apparatus; it boils at 160" (20 mm.), and the amide melts a t 90". The cr,ptalline acid (m. p. 55-56') described by Einhorn and Friedlander is also formed when A 2s 4-paramethylenedihydrobenzoic acid is boiled with alcoholic potash for 12 hours ; the amide melts at 101-102". This acid and paramethylenedihydrobenzoic acid, on reduction, yield the same 1 : 4-ethylcyclopentanecarboxylic acid. I t is not yet clear whether the liquid acid just described is struc- turally different from the substance obtained by Einhorn and Fried- lander, or whether the isomerism is geometrical in character.M. 0. F. Bismuth Salts. By B. FISCHICR and B. GR~~TZNER (Arch. Pharnz., 1894, 232, 460-466 ; compare Abstr., 1894, i, 416).-The authors prepared basic bismuth salts by heating freshly precipi- tated bismuth hydroxide with the respective acids. Basic bismuth pal-acresotate, C7H70*C00*Bi0, and the metacresotate both form needles similar in all respects to tho salicylate. No definite basic salts could be obtained from anisic, benzoic, or cinnamic acids. Tho tartrate, C4H40,,2Bi(OH)2, forms an amorphous, electrical, white powder. Attempts to prepare the basic nitrate by the action of the calculated quantity of a 5 per cent. alcoholic solution of nitric acid on freshly precipitated bismuth hrdroxide were sometimes suc- cessful and sometimes not.The authors were unable to find out the conditions necessary to ensure a successful result. Hydroxy-derivatives of Phenylbutyric acid. By F. KOPISCH (Bey., 1894, 27, 3109-3113).-In the course of their synthesis of phenylte trose, Fischer and Stewart (Abstr., 1892, 1U7) obtained several hydroxy-derivatives of phenylbutyric acid ; the anthor has subjected these to a further examination in order, if possible, to separate them into optically active compounds. In this he has been unsuccessful ; but a number of interesting derivatives have been obtained which are described in the present paper. Barium phenyltrihydrozybutyrate, (C,,Hl10s)2Ba, is obtained by the action of boiling baryta water on the lactone, and forms slender needles.The strychnine salt, CzlH22N20,,CIoH,z05 + H20, crystallises in microscopic needles or plates, loses its water of cryatallisation at 93", and becomes yellow at 105". Nitrophenyltrihydrozybutyrolactone is obtained by the action of nitric acid of sp. gr. 1.5 on the lactone of the trihydroxy-acid, and crystallises in slender, colourless needles melting at 185" with slight evolution of gas; on boiling with alkalis L. T. T.ORGANIC CHEMISTRY. 93 it first dissolves, after which a crystalline, yellow precipitate sud- denly separates. Phenylamidodihydroxybutyrk anhydride, prepared b y boiling phenylbromhydroxybutyrolactone with ammonia for a short time, forms well-developed, colourless prisms which have a neutral reaction, become brown at 200°, and melt at 215".It is not altered by boiling with alkalis or heating with phenylhydrazine, and it is therefore uncertain whether it is a lactone or a lactam. Phenylbromo- dih ydroxy b ut yranilide, 0 Ha C HP h* C HBr* C H( 0 H)* C 0 NHP h, obtained by heating t'he bromolactone with aniline at loo", crystallises in slender needles melting at 167-168" (uncorr.), and the phenyl- hydrazide, obtained by the action of phenylhydrazine in the cold, forms microscopic, rhombus-shaped plates melting and decomposing a t 168-169". If the bromolactone is warmed with phenylhydrazine, it is converted into phenylhyd?-oa y benzy lh ydrox ypyraiolid&e,- which has , and crystal- probably the constitution CO< CR(OH)*FH*CHPhOH NH-NPh lises in spherical aggregates of colourless needles melting at 208".When the bromolactone is reduced with sodium amalgam, it yields two products having the composition C10H1003 and C10H:1002 respec- tively. The former is probably a phenylhydroxybutyrolactone, and may be a stereoisomeride of the compound described under the same name by Biedermann (Abstr., 1892, 471). It crystallises from ether in colourless needles, melts at 124-126", and gives a white crystal- line precipitate with phenylhydrazine in ethereal solution. The second compound, separated by means of its solubility in light petro- leum, crystallises in large, colourless needles melting a t 87-88", and behaves towards phenylhydrazine in the same manner as the previous compound. Its constitution is unknown. €I. G. C. The Law of Etherification of Aromatic Acids.By V. MEYER and J. J. SUDUOROUCH (Ber., 1894, 27, 3146-3153 ; compare Abstr., 1894, i, 463) .-The nitrophthalic acids behave similarly to substi- tuted benzoic acids as regards the formation of ethereal salts. Dinitrophtbalic acid [NO, : COOH : COOH : NO2 = 1 : 2 : 3 : 41 gives no ethereal salt, whilst the acid [NO2 : COOH : COOH : NO, = 1 : 3 : 4 : 5 ) yields monalkylic salts. 1 : 2 : 6-Dinitrobenzoic acid gives no ethereal salt. Tetrachlorophthalic acid, however, yields small quantities of the normal methylic salt, but as the behaviour of 2 : 4 : 6-trichloro- benzoic acid is normal, the authors conclude that the normal methylic salt is analogous in structure to phthalylic chloride, and cannot, fherefore, be regarded as a true ethereal salt. Both 2 : 4 : 5- and 3 : 4 : 5-trichlorobenzoic acids yield an ethylic salt.2 : 4 : 6-Tri- chlorobenzoic acid was prepared from trichloraniline instead of tri- bromaniline. M. 0. F. Introduction of Acid Radicles into Ethylic Benzoylacetate. By A. B~CRNHARD (Annalen, 1894, 282, 153--191).-When ethylic cuprobenzoylacetate is treated with benzoic chloride, three su bsti tu- tion compounds are produced. Ethy tic dibenzoylncetate, or ethylic a-benzopl-P- hydroxycinnamate, O H C P h: C Bx*C OOE t, has been pre- VOL. LXVIII. i. h94 ABSTRAOTS OF OHEMICAL PAPERS. viously described (Trans., 1891, lOOO), and is converted by bromine into ethylic bromodibeazoylacetate. The copper compound crystal- lises from alcohol in needles melting at 221'. Ethyl ic a - beitzoyl-p)- bemozycimamate, OBz-C P h: CBrC OOE t, con- stitutes about one-hlf of the neutral products formed by the above reaction.It ciytallises from ether in thick prisms, melts a t 9B0, and is readily soluble in hot alcohol, &C. It gives no coloration with ferric chloride, and is only slowly decomposed by warming with aqueous soda. When treated with sodium ethoxide, it yields ethylic benzoate, together with ethylic a-benzoyl-P-hydroxycinnamate. A similar change is produced by phenylhydrazine, benzoylhydrazine being formed. Bromine also acts in a somewhat, similar manner, benzoic bromicle and eth$?ic a-bronzodibenzoylacetate, CBrBz,*COOEt, being produced. The latter crystallises in elongated tablets, and melts at 109-110'. The same bromo-compound is formed directly by the action of bromine on ethylic dibenzoylacetate and ethylic a- benzoyl-/3-acetoxycinnamate. The remainder of the neutral oil referred to above probably consists of etkylic p- Benzoxyisocinnamate, OBz-CPh:CH*COOEt, although this has not yet been isolated from it in the pure state.Benzoic chloride reacts in a precisely similar manner with ethylic sodiobenzoylacetate, the action being in both cases exactly analogous to that of benzoic chloride on ethylic acetoacetate (Nef, Abstr., 1894, i, 628). When ethylic cuprobeuzoylacetate is treated with two-thirds of the calculated amount of acetic chloride, the product consists of ethylic p-acetoxyisocinnamate, and a smell amount of ethylic benzoyl- acetoacetate, together with some regenerated ethylic benzoylacetate. Ethylic ben zoylacetoacet ate (e thylic a-benzoyl-p- hydroxycrotonate), OH*CMe:CBz*COOEt, has been previously described by Bonn6 (this Journal, 1887, ii, 437).Etkylic /I-acetoayisocimzamate, OAc*CPh:CH*COOEt, is a neutral substance, and crystallises in long needles melting a t 27-28'. It reacts with sodium ethoxide in alcoholic solution to form ethylic acetate and ethylic sodiobenzoylacetate, and behaves in a similar manner with phenylhydrazine, acetylphenylhydrazine being produced. Ethylic a-beiazo~l-/3-acetozycl.otolzate, OAc.C'Me:CBz*COOEt, is ob- tained by the action of acetic chloride on the copper compound of ethylic benzoylacetoacetate as a neutral, unstable, brown oil, which is readily decomposed by dilute soda, gives a red coloration with alcoholic ferric chloride when left f o r a few minutes in contact with it, and reacts with sodium ethoxide to form ethjlic acetate and ethylic sodiobenzoylacetoacetate.Ethylic chloroformste reacts with the sodium and copper com- pounds of ethylic benzoylacetate to form ethylic benzoylmalonate and ethylic /3-carbetlioxyisocinnamate, a small amount of ethylic dibenzoylsuccinate (Perkin, jun., Trans., 1883, 263) being also formed in the second case. Etiiylic BemoyhzaZonate, OH*CPh:C(COOEf),, is a yellowish oil,ORQANIC CHEJIISTRY. 95 which boils at 192-193" under a pressure of 13 mm. It has strongly acid properties, dissolves in sodium carbonate, and gires a red coloration wihh alcoholic ferric chloride immediately. When distilled with steam, it decomposes quantitatively into ethylic benzoyl- acetate, carbonic anhydride, and alcohol.Sodium ethoxide, in alcoholic solution, produces the sodium derivatire, which is a fine, white powder, and reacts with copper acetate yielding the coppey dei*ivntive, which crystallises in dark green needles melting at, 180". Ethylic carbethoxy.isoci?znamate, C 0 OE t *O *CPh:C H* COOEt, is a neutral, viscid, yellow oil, which boils at 200-202" under a pressure of 15 mm. It gives no coloration with ferric chloride until the mixture has stood for a considerable time. With sodium ethoxide, it forms ethylic carbonate and ethylic sodiobenzoylacetate, and reacts with phenylhydrazine in an analogous manner, ethylic benzoylacetate, ethylic carbazinate, and 1 : 3-diphenylpyrazolone (m. p. 135") having been isolated from the product.It is noteworthy that almost equal quantities of the neutral and acid products are formed by the action of ethylic chlorolormate on ethylic sodiobenzoylacetate, whilst with the corresponding derivative of ethylic acetoacetate, the neutral compound is the chief product. The action of acid anhydyides 0% ethylic benzoylacetate proceeds in a manner very similar to that of the acid chlorides, as will be seen from the following summary of the products obtained. (1) Acetic anhydride yields ethylic benzoylacetoacetfate (20-30 per cent.), a mix- ture of ethylic P-acetoxy isocinnamate, and ethylic a-benzoyl-p-acetoxF- crotonate (20 per cent.), acetophenone (15 per cent.): acetic acid, ethylic acetate, and ethylic benzoylacetate (18-32 per cent.). (2) Benzoic anhydride yields ethylic dibenzoylacetate (50 per cent.), small amounts of tribenzoylmethane and ethylic dehydrobenzoyl- acetate, ethylic benzoate, benzoic acid, and possilnly ethylic P-benz- oxyisocinnamate.Acetic anhydride also acts on ethylic oxalacetate to1 form ethylic p-acetoxyfitmarate, which is a neutral oil, gives no coloration with ferric chloride, and reacts with phenylhydrazine to form acetylphenyl- hydrazine. The author is of opinion that the difference in behaviour towards alkalis of the two forms of tribenzoylmethane and dibenzoylacetone may be due to physical causes, and is not necessarily to be ascribed to a difference in chemical constitution (compare Claisen, Abstr., 1894, i, 192). Two formulaa are possible for the derivatives of the P-ketonic acids which contain two acid radicles such as ethylic dibenzoylacetoacetate, CAcBz,*COOEt and 0BzGMe:CBvCOOEt.Both formule equally express the neutral character of the compound; if the former of the two formulse were correct, the same substance should be obtained by the action of acetic chloride on ethy lic dibenzoylacetate, and of benzoic chloride on e tbylic benzoylacetoacetate, whereas, according to the second formula, two different compounds should be produced. Experiment shows that the latter is what actually occurs, ethylia h 296 ABSTRACTS OF OEEMIOAL PAPERS. a-benzoyl-P-acetoxycinnamate and ethylic a-beneoyl-P-benzoxycroton- ate respectively being formed. The same view is further confirmed by the fact that sodium ethoxide, phenylhydrazine, and bromine always replace that acid radicle which has been last introduced.I f this formula be accepted, there are still two stereoisomeric con- figurations possible, but at present it is impossible to decide between them with any approach to certainty. A. H. Vinyltriphenylsulphone (Triphenylsulphonethane). By R. OTTO (Ber., 1894, 27, 3055--3058).-When monochlorethylene di- chloride is warmed with sodium benzenesulphinate in alcoholic solu- tion, i t yields, not a trisulphone, but the disulphone, CzH4( S02Ph),, sodium sulphate and benzenesulphonate being simultaneously formed. When warmed with sodium phenyl mercaptide, NaSPh, in alcoholic solution, however, it yields uinyltrithiophenyl (tritTLiophenylethane), SPh*CH,*CH(SPh),. This is an oil having an odour resembling that of lemons ; when oxidised with permnnganate, it yields ethylene- diphenylsulphone and a benzenesulphonate, but, if care is taken to avoid a rise of temperature, uinylts.iphenylsulpho}~e (triphenylsulphon- ethane), S02Ph*CH2*CH( SO2Ph),, is formed.This is insoluble in water; it is readily hydrolysed by aqueous soda, apparently with formation of glycollic aldehyde. C. F. B. Indigo. By C. J. VAN LOOKEREN and P. J. VAN DER VEEN (Landw. Versucks-Stat., 1894, 43, 401-426) .-The authors have prepared indican from the leaves of plants belonging to the species Indigofera, and their results are identical with those obtained by Schunck in his experiments with Isatis tinctoria (woad). The sugar, which the authors obtained as a syrup by hydrolysing their indican, was dextro-rotatory, reduced Fehling’s solution, gave a brown colora- tion with alkalis, and was probably identical with ordinary gluccse (dextrose). The so-called indigo-gluten is probably a mixture of nitrogenous decomposition products of indican, with a certain amount of the enzyme (rendered inactive) which determines the hydrolysis of indican.Schunck’s oxindicanin gives a red precipitate when warmed with Millon’s reagent. Experiments are next de- scribed which point to the existence of an enzyme as the hydrolyst of indican, thus the hydrolysis of indican proceeds under conditions which exclude the presence of micro-organisms. The quality of the indigo-blue is affected by continuing the lixiviation process too long, which is done in practice, and the cause of this may be the action of bacteria.If the so-called fermentation is protracted, the indigo-blue contains a larger proportion of calcium salts and more indigo-gluten. According to the authors, the usual practice is to employ water at a temperature of 27.5” for the fermentation ; better results are obtained by digesting with water at an init#ial temperature of 5 9 , the digestion (fermentation) being continued for about seven hours at a temperature of about 28”. The authors find that in the manu- facture of indigo-blue, equivalent quantities of lime, potash, or soda may be used instead of ammonia. A. R. L.ORGANIC CHEMISTRY. 97 Parahydrazidodiphenyl, By H. MGLLER (Ber., 2894, 27, 3105-3108).--Parah ydrazi'dodiphenyl, C12Hg*NH*NH2, is prepared by diazotising paramidodiphenyl and reducing the diazo-compound with tin and hydrochloric acid, the Jydrochloricle thus formed being decom- posed by alkali and the free base extracted with ether ; after crystal- lisation from hot alcohol, it forms lustrous, colourless plates, melts at 135-136" (uncorr.), and quickly oxidises in the air, especially when moist.The hydrochloride, sulpha.te, and nitrate all wystallise in colourless plates, and are sparingly soluble in cold water. The acetyl derivative, ClzHg*N2H2Ac, crystallises in colourless plates melting at 203", and the thiocarbamide, Cl2Hg*N2H2CS*NHPh, in colourless needles melting at 182" ; the latter dissolves in concentrated sulphuric acid with a deep blue colour. Parahydrazidodiphenyl readily combines with aldehydes and ketones, including the sugars, but the compounds obtained from the latter do not cryst,allise well, and are, therefore, of no use for the recognition or isolation of the sugars.Acetonehydrazolaed~henyl, C12Hg*NH*N:CMe2, is crystalline, melts at 86-87", and yields an indole when heated at 180" with zinc chloride. Acetophenoneh ydrazone- diphenyZ, C12H,*NH*N:CMePh, forms colourless plates melting a t 148", and benzylidir~ehydrazidodipl~enyl, ClzHS*NH*N:CHPh, crystal- lises in yellowish needles meltiiig at 153". Arabinosehydrazonedi- pheny 1, C12H9*NH*N:C5H1004, is obtained with difficulty in nodular aggregates of slender crystals, and melts, when quickly heated, at 138-140", with decomposition. The xylose derivative has similar properties. Glucosehy druzoiied ipheny 1, C12Hg*NH*N: C8HI2O5, forms very slender crystals, melts at 143-1441' with evolution of gas, and, on heating with an excess of the hydrazine, yields the osazone.Galuctosehydrazonediphenyl crystallises in stellate groups of colour- less needles melting and decomposing at 157-158". Stereoisomeric Paraphenylhexahydrobenzoic acids. By B. RASSOW (Annalen, 2894, 282, 139--153).-ParaphenyEhexahydroben- zoic acid, C6Hl,.Ph-COOH, may be prepared by reducing paradiphenyl- carboxylic acid with sodium and boiling amylic alcohol, or by treating the same acid with sodium amalgam in alkaline solution, whereby it is converted into a mixture of tetrahydro-acids, acting on these with hydi-obromic acid, and finally reducing the hydrobromides thus obtained by means of sodium amalgam. The crude hexahydro-acid melts at 190-195"; but on crystallisation yields an acid, which melts at 202", together with a portion of lower melting point, from which an acid, melting a t 113", may be isolated in small quantity by extracting with boiling water, filtering, and adding potassium permanganate to the solution in sodium carbonate until a permanent coloration is produced.Paraphenylhexahydrobanzoic acid (m. p. 202') crystallises from dilute acetic acid or ether in lustrous plates. The silver salt is insoluble in water, the sodium and ammonium aalts sparingly soluble, and the potassium salt readily soluble. A solution of the ammonium salt gives white, insoluble precipitates with barium chloride, calcium chloride, zinc sulphate, and mercuric chloride, whilst the magnesium H.G. C.98 ABSTRACTS OF OBEMICAL PAPERS. salt dissolves in hot water. The mcthylic salt, prepared by treating the chloride with methylic alcohol, forms tabular crystals, and melts at 28-30". On oxidation with potassium permanganate, the hexa- hydro-acid is converted into a hydroxy-acid, which probably has the formula OH*C6H,Ph*COOH. It forms a honey-like mass, with an ill- defined melting point of about 145'. This hydroxy-acid loses a molecule of water when boiled with water, a tetrahyd?-ophen?lZbeiazoic acid being formed, which melts at 158", and, since it is not altered by boiling with aqueous soda, is probably a AlD2-acid. It at once decolorises alkaline potassium permanganate, and com bines with bromine. The silver salt of the hydroxy-acid also loses a molecule of water when boiled with water, yielding the salt of the tetrahydro- acid.More thorough oxidation converts the hexahy dro-acid into benzoic acid, Isoparaphenylheanhydrobenzoic acid (m. p. 113') is best obtained by heating the acid of higher melting point with fuming hydrochloric acid at 170-180". It forms lustrous needles, and dissolves in about 1000 parts of boiling water. The silver salt blackens when heated in contact with the solution from which it has been obtained, and is somewhat soluble in hot water. The sodium, potassium, and ainmonizcm salts are all readily soluble in water, and the calcium salt moderately so. When the iso-acid is heated with fuming hydrochloric acid, it is partially reconverted into the acid of higher melting point, the same state of equilibrium being reached from either acid, that of higher melting point constituting about 90 per cent.of the mixture, The iso-acid is also converted into benzoic acid by oxidation. The paper is prefaced by a note by Baeyer, in which he points out that it has been found impossible to obtain stereoisomeric forms of tetrahydro-a- and [3-naphthoic acids, and that this result, although, as it is negative, it cannot be considered decisive, is in favour of the view that the valencies of the 6 hydrogen atoms of the benzene ring are perfectly symmetrically arranged. The results described in the foregoing paper show that in the closely related hexahydrophenylbenzoic acid the differences between the properties of the two stereoisomerides are quite well marked.A. H. Tetramethyldiamidodiphenylmethane. By J. PINNOW (Bey., 1894, 27, 3161--3167).-The action of nitrous acid on tetramethyl- diamidodiphenylmethane converts it into a mononitro-derivative, which melts a t 87-88'. The further action of nitrous acid gives rise to a &nitro-derivatire, which crystnllises in slender, red needles, and melts at 123-124". An isomeride is produced when a mixture of nitric and sulphuric acids is added to the solution of tetramethyl- diamidodiphenylmethane in concentrated sulphuric acid ; it crysta.llises from glacial acetic acid in red prisms, which melt at 191.5" (uncorr.). This compound yields tetraineth y ltetramidodiphenylmethane when re- duced with tin and hydrochloric acid ; the base crystallises in colour- less needles, which melt at 142" (uncorr.).The action of nitric acid on tetramethyldiamidodiphenylmethane in glacial acetic acid solution 1 eads to the formation of nitibosamines and nitramido-derivatives ;ORGANIC CHEMISTRY. 99 di?nethyldinitrosanaiaoa~p~enyl~nethane is prod uced on adding sodium nitrite to the solution of the base in hydrochloric acid (sp. gr. 1.19). It crystallises in slender, pale yellow needles, which melt a t 101.5". A condensation product of tetramethyldiainicloclipheiiylmethane with formaldehyde appears to be formed when a mixture of dimethylaniline (10 grams), formaldehyde solution (10 grams), and glacial acetic acid (15 grams) is boiled for eight hours; it has the composition With diazobenzenesulphonic acid, tetrametbyldiarnidodiphenyl- methane yields a colouring matter, which, on reduction with tin and hydrochloric acid, is resolved into paramidodimethylaniline and par- Constitution of the Alkali Compounds of Phenolphthalein.By E. HJELT (Chem. Zeit., 1894, 18, 3).--According to Armstrong (Proc., 1893, 58), the coloured salts of the phthale'ins assume a quinono'id structure ; this view presupposes, for example, in the case of phenolphthaleyn, that the phthalide ring (lactone ring) is readily disrupted by alkalis. The author's experiments indicate, however, that the hydrolysis of the phihalide ring, CoH,< :?> 0, proceeds much more slowly in the case of phthalide and of meconine than in the case of the aliphatic lactones (Henry, Abstr., 1892,1S03). According to it in minutes), the following values were the formula Ac = found; for phthalide, Ac = 0.0674 (A = 10.1) ; and for meconine, Ac = 0.0298 (A = 11.2).The hydroxy-acid corresponding with phenolphthalein is unknown, and is probably incapable of existence. (Cl*&N2) 2. amidobenzenesulphonic acid. 31. 0. F. a: (A - x)t A. R. L. Synthesis and Constitution of Vulpic acid. By J. VOLHARD (Armalen, 1894, 282, l-Zl).-According to Spiegeel (Abstr., 1881, 97, 173, 1036; 1882, 1076), vulpic acid is the motiomethylic salt of the bibasic pnlvic acid, which is converted by alkalis into dibenzyl- glycollic acid, OH*C(CH,Ph),*COOH, a diketonic acid, symmetrical diphenylketipic acid, C 0 OH* CHPh-C 0 G O CHPhGOOH, being formed as an intermediate product. I n order to prepare vulpic acid synthetically, the author starts from benzylic cyanide, which is converted by ethylic oxalate and sodium ethoxide in alcoholic solution into the cliuitrile of dipheiyE- ketipic acid, CN*CHPh*CO*CO*CHPh*CN.This substance crystal- Iises from amylic alcohol in olive-green, lustrous scales, and melts and decomposes at 270". When hydrolysed with 60 per cent. sul- phuric acid, the nitrile is converted into pulvic acid dilactone (70 per cent.), and pulvic acid (14-18 per cent.), a small amount of other products of unknown nature being also formed. When the dilactone is treated with a solution of potash in methylic alcohol and the solution acidified, vulpic acid is obtained, identical with that x>reDared from Evernia vulpina. * Piperidifis vullpate f o r i s long, thin, yellow n.eed1es melting at 139-142".100 ABSTRAOTS OF OHEMIOAL PAPERS.The pulvic acid prepared from the dilactone is also identical in every respect with that obtained by Spiegel. It crystallises with lC2H,0 in yellowish-red, rhombic prisms, which have the axial ratio 0.5835 : 1 : 0.4337. Nonohromopuivic acid, C,,H,,BrO, cry stallises in radial groups of yellow tablets, melts at 208-209", and forms a crystalline ba?.ium sult. , is con- CO*$!HPh 0-co tained among the products of hydrolysis of the dinitrile. It forms small needles, and melts at 231-233". It follows from this synthesis that pulvic acid is the anhydride of diphenylketipic acid, but it is at present impossible to decide between the formulae Dibenzylozalylcarboxylic acid lactone, CHPh:C < C P h < ~ ~ ~ > C : C P h * C O O H and O< C:CPh*COOH I C:CPh*COOH A.H. Pulvamio acids and Ethereal Salts of Pulvic acid. By R. SCHENCK (Annalen, 1894, 282, 21-44 ; compare the foregoing abstract) .-Pulvamic acid has previously been described by Spiegel (Abstr., 1881, 1076). The ammonium salt melts at 218", and the potassium salt crystallises in slender needles with 5Hz0, whilst the zirzc and silver salts are insoluble and amorphous. It appears to be impossible to displace a second hydroxyl-group in the molecule by the amido-group. Pulvomethylainic acid, CleH,,04N, is obtained by the action of methyl- amine on the dilsctone. It crystallises in quadratic plates, and melts at 237'. The barium salt is sparingly soluble in water. Pulvanilic acid, C24H,0aN, forms com- pact crystals, and melts at 187-188".The ammonium salt melts a t 1.53" ; the potassium salt forms yellow crystals with 2HE,0. Pulv-a- naphthylamic acid crystallises in iridescenh, reddish-yellow plates, and melts a t 211-212". The ammonium salt melts at 208O, and the barium salt crystallises from alcohol in slender needles. Pulvo-p- naphth ylamic acid forms druses of large, reddish-yellow crystals, and melts at 292". The ammonium salt melts indefinitely a t about 182". Putv- dimethylamic acid crystallises in small prisms, and melts at 211", its dimethylamine salt melting at 210". The acid is quite analogous to pulvamic and pulvrnethy lamic acids. Pulvopiperidinic acid is very unstable, and melts at from 150" to 160". Its piperidine salt melts at 199-220". The metallic salts aro decomposed by boiling with water, piperidine being formed.Pwlvvhy dmxamic acid is obtained by heating the dilactone with hydroxylamine hydrochloride, sodium acetate, and acetic anhydride. It crystallises in quadratic plates, and melts at 194O, with evolution of carbonic anhydride; the acid is bibasic to baryts water. Its monaniline salt forms plates melting a t 163-164". Pzclrop7~enylhydrazinic acid melts at 201-202", and forms The metlzylamine salt melts at 214". The barium salt forms a crystalline powder. Methylaniline and diphenylamine do not yield amic acids.ORGANIC CHEMISTRY. 101 a, phenylhydrazine saZt, which is more readily soluble in alcohol, and melts at the same temperature. The ammonium salt forms pale yellow, slender needles, and melts a t 187-188".The mon-ethereal salts of pulvic acid may be obtained by the action of potash and an alcohol on the dilactone, or by that of an alkylic iodide on the hydrogen silver salt. The normal ethereal salts form compounds with 1 mol. water and 1 mol. piperidine. The following have been prepared. M. p. of piperidine M. p. compound. Methylic vulpate.. ...... 141" 147-148" Ethylic vnlpate ......... 138-139 152-153 Methylic ethylpulvate.. .. 150-151 151 Propylic vulpate ........ 95-96 149 Methylic propylpulvate . . 121-122 126 Propylpulvic acid. ...... 134 - Ammonia reacts with the normal ethereal salts to form an amide and phenylacetic acid. The amide, CIoH8O2N2, crystallises in bronze- coloured plates, and melts at 247.5". When boiled with dilute hydro- chloric acid, it yields cyanophenylpyrnvic acid (compare the following abstract).A. H. Derivatives of Diphenylketipodinitrile. By J. VOLHARD and F. HENKE (Annalen, 1894, 282, 45-84; compare the two preceding abstracts).-The hydrolysis of the dinitrile occur8 in several stages. Dip hen y lke tipamidonitrile, CN*CPh:C (OH) C (OH) :C PhG O*NH2, is obtained by treating the dinitrile in the cold with concentrated sulphuric acid. It forms pale yellow needles containing 1 mol. C2He0, and melts and decomposes at 199-200"; it gives a brownish- red coloration with alcoholic ferric chloride. When boiled with aqueous sodium carbonate, the nitrile is decomposed into benzglic cyanide and hydroxyphenylmaleinimide, CloH7N03, which is described later on. Diphenyl ketiparnidonitrilesuly honk acid, CI8Hl3O3N2*SO3H, is ob- tained by warming a solution of the dinitrile in sulphuric acid on the water bath.It forms microscopic, flat needles, and does not melt below 300". The sodium and barium salts are both crystalline. No diamido-compound was observed among the products of hydrol- ysis of the dinitrile, but a small amount of pulvamic acid (com- pare the preceding abstract) is formed. Thig substance can also be readily obtained by boiling the amidonitrile with hydrochloric acid. The methylic salt forms almost colourless, compact crystals melting at, 216-217". When t h i s salt is hydrolysed, pulvic acid, and not an isomeride of vulpic acid, is formed. The dinitrile readily dissolves in alcoholic potash, forming tt potassium saZt, C18H,202N2K2 + 2C2H60, which crystallises in colour- less plates.The sodium salt may be prepared in a similar manner, The dinitrile also appears to form an unstable compound with 1 mol. HCl. The monacetate, CN*CPh:C(OAc)*C (OH):cPh.CN, is obtained by the action of a mixture of acetic acid and acetic anhydride;102 ABSTRACTS OF CHEMICAL PAPERS. i t crystallises in lustrous needles, and melts at 208-209.5". It is insoluble in water, but dissolves in aqueous alkalis, the sodi?cm salt crystallising with 3H20 in scarlet needles. The nzethylic salt, prepared from the amorphous red silver salt, crystallises in lustrous, yellow needles, and melts at 229-231". When heated with aqueous ammonia at loo", the acetate yields benzylic cyanide and phenylacetamide, together with oxalic and oxamic acids.Acetic and benzoic chlorides act on the sodium and silver salts, but only reproduce the monacetate. The cliacetate is formed when the dinitrile is treated with pure acetic anhydride, and forms gregish- green needles melting at 177-179". It is insoluble in water and alkalis, and combines with 1 mol. of alcohol to form a compoultd, which can be recrystallised from toluene, and melts at 191-191.5". Methylic alcohol forms a similar C O ~ ~ p t n d , which crystallises in colourless granules, and melts and decomposes at 196". The compound with amylic alcohol crys tallises in very slender needles. Acetic chloride reacts with the dinitrile to yield the monacetate together with the anonacetate of the lactone of the semi-hydrolysed dinitrile, C( OAc)*v:CPh*CN co-0 CPh< This crystallises in canary-yellow needles, and melts at 141-142".The corresponding benzoate crystallises in slender, yellowish needles, melting at 168-168.5". The monobenzoate of the dinitrile is also formed in dark, orange-red granules, melting at 220-224", which dissolve in alkalis. Phosphorixs oxyc hloride converts the , corresponding dinitrile into a chloro-derhathe, CPh< in composition with the lactone compounds described above. It crystallises in long, greyish-green needles, and melts at 161-1 62". It is insoluble in water and aqueous alkalis, but dissolves in alcoholic potash, and yields a crystalline bai-iz~rn salt. When heated with sodium acetate and alcohol, it loses chlorine, forming a Izydroxy- compound of the formula CI8Hl1O&, which crystallises in matted, reddish-yellow needles, and melts a t 193-194". When heated with acetic anhydride, this is converted into the acetate of the semi-lactone already described.Dilute alcoholic ammonia at 100" converts the dinitrile into au iso- C C1* f: : C Ph*CN co-0 cyaizop~eny123yrzLz'amide, C(OH)<Cph--&o, C (NH) *NH which crystallises in red needles, and does n o t melt below 280". It dissolves in alkalis, and forms crystalline sodizcm and barium salts. Arnylic nitrite con- verts it into a nitro-derivatiee, C,,H,N,O,*NO,, which melts and decomposes at 246". When heated with dilute hydrochloric acid, it is very readily converted into Fvyd~oxyphenylmalei'nimide, which is best prepared by heating the amidonitrile or its sulphonicORQANlC OHEMISTRY. 103 acid with aqueous sodium carbonate.It crystallises in lustrous, yellow scales, melts at 216-218", gives a green coloration with ferric chloride, and forms salts with one equivalent of metal. The ethylic salt crystallises in long, lustrous needles, resembling the salts of uranium in appearance, and melting at 128-130". This substance is isomeric with the ethylic phenylcynnopyruvnte described by Erlenmeyer, jun. (Annalen, 1892, 271, 172). The latter compound, on hydrolysis, yields a substance which was described by Erlenmeyer as phenyl- cyanopyruvic acid, but which is identical with hydroxyphenglmaleiin- imide. This substance cannot have the constitntion ascribed t o it by Erlenmeyer, as, when its silver salt is treated with ethylic iodide, it yields t,he yellow ethereal salt described above, and not the original colourlem ethylic phenylcyanopyruvate, C N*CPh*CO*COOEt, by the hydrolysis of which it was obtained. It is, moreover, con- verted by ammonia into the phenylamidomaleinimide described below.Acetic anhydride converts hydroxyphenylmale'inimide into the acetate, CloH,N20,Ac, which ci*yst,allises in long, white needles melting a t 134-135". Etl~oxyp7tenyl~taleiia-be?azoyl.imide, C19H,,04N, prepared by treating the yellow ethylic salt with benzoic chloride, crystallises in yellowish needles with a greenish fluorescence, and melts at 105-106"- The isomeric be?zzovt-derivat izie obtained from Erlenmeyer's ethylic phenylcy anopyruvaie crystallises in colourless prisms, and melts at Co--NH is obtained by the CPh*bOy PJLe?aylamidomalei;nimide, NHz*C< 102-103"._ - ~ -~ actioii of alcoholic ammonia on ethoxyphenylmale'inimide, and has also been obtained from the chloro-semilactone described above, and from the neutral ethereal salts of pulvic acid, a proof that it contains no cyanogen group. It crystallises in thin, golden-yello w, lustrous plates, and melts at 248-2419'. The corresponding piperidide, C1,H1,02N2, is formed when ethoxyphenylmale'inimide is heated with piperidine, and crystallises in orange-coloured needles melting at 155-156.5". co-? is formed when CPh* CO' Ethoxypheizylmnteic anhydride, C(0Et) < the imide is warmed with aqueous sodium carbonate. I t crystallises in transparent, prismatic needles, and melts at 97-98". The free acid corresponding with the anhydride cannot Be obtained, but its salts are formed by dissolving the anhydride in boiling alkalis or alcoholic ammonia.The ammonium saZt, C12H1005(NH&, melts at 144-146", and the sodium and barium salts are both crystalline. Fuming hydriodic acid a t 165" converts the anhydride into phenyl- succinic acid, which is a ciytalline powder melting at 160-161" (stated by Spiegel as 167"). The formation of pheiiylarnidomaleinimide from the ethereal salts of pulvic acid can best be explained by adopting Spiegel's view, that this acid is a hydroxy-lactone. A. H. Thio-derivatives of p-Naphthol. By R. HENRIQUES (Ber., 1894, 27, 2993-300S).-By the a.ction of sulphur chloride on p-naphthol in104 ABSTRACTS OF GHEMIOAL PAPERS. chloroform solution, di-P-hydroxydinaphthylic sulpphide, S (CIoH6*OH),, is formed ; it is sparingly soluble in chloroform and in carbon bisul- phide, and separates in long, silky needles, or in colourless, trans- parent, highly lustrous, round crystals, and melts at 211".With con- centrated sulphuric acid, a bl-aish-green coloration is produced ; with diazo-derivatives, sulphur is eliminated, and the ordinary azo-naph- tho1 dyes are produced; the sulphur is not, however, removed by treatment with silver salts. The molecular weight was determined by the boiling point method. The compound is identical with that (m. p. 21pO) prepared by Dahl and Go. by heating P-naphthol, sulphur, and lead oxide at 180-200', and with the compound (m. p. 210') obtained by Lange (Abstr., 1888, 375) by heating naphthol with sulphur in alkaline solution, and to which he errone- ously gives the formula S2(CloH,*OH)2.The Zead salt, C20H12S02Pb, is yellow and amorphous ; the acetyl derivative, S(C10H~*OA~)2, crys- tallises in colourless needles. and melts at 193". S:? *CloH6*OH S:S*CloH6*OH Or Dithiodi- P-It ydroxydinaphthylic biszclphide, 0 H*CloH6*S*S*s*S CloH6* 0 H, is formed, together with the sulphide, from which it is separated by means of its greater solubility in carbon bisulphide, and is deposited in large, sulphur-coloured crystals, melting at 141"; the yield is 15 per cent. of the naphthol employed. The compound is also formed by heating dihydroxydinaph thylic bisulphide (see below) with sulphur in alkaline solution; it is decomposed by silver salts, silver sulphide being precipitated, and dissolves in alkalis with an intense, yellow colour.The Eead salt, C2,H12S402Pb, is orange colonred ; the acetyl derivative, C20H12S,02Ac2, crystallises in pale yellow needles, melting at 164". Di-P-h ydroxydinaphthylic bisdphi'de, S2(CloH6*OH),, is separated by means of its lead salt from the chloroform mother liquors obtained in the preparation of the preceding dithio-compound and sulphide ; it readily dissolves in all organic solvents, in alkali carbonates, and in borax solutions, and crystallises in yellow needles, melting a t 166" ; it is decomposed by silver salts. The lead salt, CZoHl2S2O2Pb, is orange colonred ; the acetyl derivative resembles that of the preceding com- pound, and melts at 194". Dithiodih y droxydinaph thylic bisulphide and dih ydroxydinaphth ylic bisulphide give with potassium ferricyanide pale yellow, sparingly soluble ferricyanides ; dihydroxydinaphthylic sulphide, in the same circumstances, is oxidised to dehy~rodioxydi~aphthylic sulphide, C,H12S02, which is deposited in large, red crystals, melting at 155".The compound contains no hydroxyl, it dissolves in concentrated sulphuric acid with a dark blue colour, and readily reacts with hydroxylamine, although the products could not be isolated. The phercylhydrazide, S (CloH6*N2HPh),, crystallises in brick-red needles, melting at 184'. 2sodihydroxydinaphthylic sulphide is prepared by the reduction of tihe preceding compound with zinc dust and glacial acetic acid; it crystallises in long, pale yellow needles, melts at l52", is readilyORGAN10 OHEMISTRY.105 soluble, and is easily converted into dihydroxydinaphthylic sulphide by heating with alkalis. With potassium ferricyanide, the dehydro- derivative ir;l regenerated ; by the action of diazo-compounds, azo- naphthols are formed and sulphur eliminated. The silver salt is colourless ; the lead salt, C2,H,,S02Pb, resembles that of the isomeric compound ; the acetyl derivatice is crystalline, and melts at Dinaphthy lenethiophen, C2,,HI2S, is prepared by the action of con- centrated sulphuric acid on isodihydroxydinaphthylic sulphide at loo", the sulphrtte dissolving with a blue-green colour, and evolution of sulphurous anhydride ; the compound crystitllises fronr glacial acetic acid in yellow needles, melts at Z47", is neutral, and boils without decomposing ; the coloration produced with sulphuric acid is similar to that of the original sulphide.The yield is 60 per cent. of the sulphide employed. Dihydroxydinaphthylic sulphide gives no thio- phen derivative. The author discusses in detail the oonstitution of dehydrod-ioxydinaphthylic sulphide and of isodihydroxydinaphthylic sulphide ; the former, although generally resembling the quinones, differs from them in its behaviour towards phenylhydrazine and reducing agents ; he considers that the two dihydroxydinaphthylic sulphides are stereoisomeric, 147-148". ylOH6'S*ylOHS 9R ~10H6*s0Cl0H6 OH OH OH Iso- (syn-) sulphide (m. p. 152'). Normal (anti-) sulphide (m. p. 211'). this is in complete accord with their behaviour, and, if correct, is the first example of simple stereoisomeric sulphur compounds.The dehydro-derivative and the thiophen probably have the formulae C,Hs<,>CloHs [s : 0 = 1 : 21 and ~ ~ o ~ ~ - ~ ~ o ~ s respectively. S \/ S J. B. T. Preparation of 1 : 2-Naphthaquinone. By K. LAGODZINSKI and D. HARDINE (Ber., 1894, 27, 3075--3076).-An improvement of the method of Stenhouse and Groves (this Jourual, 1877, ii, 52). Fifty grams of %naphthol is dissolved in a solution of 14 grams of sodium hydroxide in 500 C.C. of water. The whole is tben placed in a 3-litre vessel, diluted with 1 litre of water, and stirred with 25 grams of sodium nitrite ; a large lump of ice (about 500 grams) is then added, and the stirring continued while 700 C.C. of 10 per cent. sulphuric acid is gradually added. After 2-3 hours, the precipitate is col- lected on a calico filter and washed with water until the washings have only a feebly acid reaction.It is then placed in a 14-litre flask, 300 C.C. of 10 per cent. sodium hydroxide added, and the whole diluted with water to 1,200 c.c., and warmed for a time on the water bath. Hydrogen sulphide is passed through the warm solation until white crystals of nmidonaphthol begin to separate. These are col- lected on a porcelain funnel, washed with water, treated with 700 C.C.106 ABSTRACTS OF CHEMICAL PAPERS. of 5 per cent. sulphuric acid previously warmed to 70-80". and filtered through a folded filter ; the residual sulphur is washed with another 700 C.C. of the acid, and the united filtrates are cooled with a large lump of ice and oxidised with potassium dichromate.The 1 : %naphthoquinone, which then separates out in orange-yellow needles, is carefully washed until free from sulphuric acid. The yield is 47.5 grams, 86.6 per cent. of the theoretical. By C. BOTTINGER (Ohem. Zeif,, 1894, 18, 483-484) .-Dz'chloracet-a-na~hthnlide is prepared by moderately warming a mixture of dichloracetic acid and a-naphthyl- amine; it separates from ether in colourless crystals, and melts at 164'. Gl?lceric-a-naphthal~de is obtained by warming a-naphthyl- amine with an alcoholic solutiou of glyceric acid ; it is crystalline, and melts at 137"; a secondary product (m. p . 214') was also isolated in small amount. Pyruvic acid reacts with a-naphthylamine in alcoholic solution, forming p y.l.uvic-a-naphthaZide, which melts at 148-149'.a-Naphthylamine hydrogen tartrate melts and decomposes at 180" ; tartaric-ol-naphthalide crystallises in long, white needles, and melts a t 210", and a-naphthylamine citrate crystallises in four-sided tablets, and melts at 146". The citrate and tartratepf a-naphthylamine have a burning taste. A. R. L. a-Dinaphthalidocitric acid. By C. BOTTINGER (Chem. Zeit., 1894, 18, 672) .-Of the two theoretically possible modifications of a-di- naphthalidocitric acid, one is obtained, together with other products, by heating a pulverised mixture of citric acid and a-naphthylamine at 140"; it crystallises from boiling alcohol in white needles, and melts at 187-188". If dissolved in nitric acid of sp. gr. 1-48, a yellow nitro-compound is formed, which yields intensely reddish- yellow alkali salts.When the acid is treated with acetic anhydride, a ye1lo-r compound is obtained, which is insoluble in soda and is probably an anhy dro-compound. The silver salt of a-dinapbthalido- citric acid is a white precipitate, insoluble in water, and very stable. C. F. B. Derivatives of a-Naphth ylamine. A. R. L. 1 : 2-Amidonaphtholsulphonic acids. By M. B~NIGER (Bey., 1894,27, 3050-3054) .-1 : 2 : 2'-Nitrosodihydroxpaphthalene, when heated with sodium hydrogen sulphite and hydrochloric acid, yields, by a reaction already described (Abstr., 1894, i, 199), 1 : 2 : 2'-amido- dihydro~ynap~~thalene-4-szllp~onic acid ; this can be oxidised with nitrous acid to 2'-hydrozy-l : 2-nap hthapuinone-4-szL~honic acid, and this, with aniline, yields 2 : 2'-dih y d ? .o . r y . 4 - a n i l i d o n a p ~ t ~ ~ ~ ~ i ~ ~ 1 : 2 : 3-Nitrosohydroxynaphthalenesulphonic acid and 1 : 2 : 2'-nitroso- hydroxy naphthalenesulphonic acid undergo an analogous series of reactions. C. I?. B. Nomenclature of Cyclic Derivatives of Naphthalene. By C. GRAEBE (Ber., 1894, 27, 3066--3068).-1t is proposed that when, in compounds of the type of carbazole or ant,hracene, one phenylene group is replaced by naphthylene, the term "Naphtha-" (orORGANIC CHEMISTRY. 107 '' Naphth- ") should be prefixed to the name of the parent substance ; and that when both the phenylene groups are replaced by two naph- thylene groups, the term " Dinaphtho " should be prefixed. Thns the compound C10H6<_0- > C,H, would be termed naphf7zozanfhon~, co the compound c&6<-0_ co >C diiiapht7~oxa?z,thone.C. F. B. 1 : 2-Dihydroxynaphtho-3 : 4-Acridone. By K. LAGODZIXSKI bud D. HARDJNE (Ber., 1894,27, 3066-3075).-When 1 : 2-naphtha- quinone is dissolved in acetic acid and the solution warmed with snthranilic acid, 3-hydroxynnphthaquinone-4-nnilz'do-orthocarbo~~lic x i d , C,oH,0(OH):N*C6H4*COOH [O : OH : N = 1 : 2 : 41, is formed. This crystallises in dark red plates with ft metnllic lustre, and melts at 270-271" ; it yields no anhydride (acridone), but is hydrolysed by dilute mineral acids to 2-hydroxynaphthaquinone and anthranilic: acid. If a solution of anthranilic acid in water and alcohol is warmed with aqueous potassium 1 : %naphthaquinone-4-sulphonate, 1 : 2-nap7i- thapzciizone-4-anthralzilz'c acid, CloH,J12*NH*C6H,-COOH [O, : NH = 1 : 2 : 41, isomeric with the preceding compound, is formed.This crystallises in dark red needles, and melts at 252" ; its methylic sai't forms brilliant, dark red crystals, which melt at 1 8 6 O . When heated with strong sulphuric acid at 200", it yields 1 : Z-izap7~thapzci?zone- co 3 : $-acridone, CloH,O2< HN> C6H4, which crystallises in reddish- yellow needles, and melts above 400". With ortbophcnylenediamine it yields a dark yellow aaine, which melts a t 276", and it can be readily hydrolysed to Eiydroxynaphthaquinone and anthranilic acid. When suspended in acetic acid and reduced with sulphurous an- hydride, it yields brown, crystalline 1 : 2-dihydrozy-3 : 4-naphthac~i- done, C,,H,(OH),< - >C6H,; this is not, like alizarin, a stable sub- stance, nor does it dye with mordants ; it bas rather the properties of a qninol-derivative, being oxidisable with extreme readiness to the. corresponding quinone ; its yellow diacetyl derivative melts at 280".C. I?. B. co IhH Dihydrophenonaphthacridine and Phenonaphthacridine. By M. SCH~PFF (Ber., 1894, 27, 2840-2845 ; compare Abstr., 1894, i, 41) .-Dihyd~opheizoiaaphthacridine, ClOH6<,,"> C6H4, has been already described as phenonaphthacridine (Zoc. cif.) ; the acetyl derivative melts at 181-181.5". Phenonaphtliacridine, cIoH6<& ->CSH,, is obtained by oxidising the dihydro-derivative with silver nitrate ; it melts at 225-226". The hydrochZoride and the nitrate crystallise in dark needles; the platinochloride forms minute, violet needles, and the picrate separates in brown needles.The ethyl derivative crystallises from alcohol in dark needles. CH CH108 ABSTRACTS OF UHEMICAL PAPERS. When phenonaphthacridone is reduced with sodium amalgam, the foregoing substance is formed in association with a red substance, which does not melt below 360". If reduction is effected bv means of zinc dust and acetic acid, the ~ ~ d r o ~ ~ d i h y d r o ~ ~ ~ n o n a ~ ~ c10H6 <NH CH(oH)>C6HA, which melts at 345", is formed. It yield8 brown solutions with sulphuric acid and alcoholic potash, and is not dissolved by aqueous alkali. Reddish-brown fumes are evolved when the substance is heated, and a brown sublimate is formed, exhibiting the violet colour reaction of phenonaphthacridine with sulphuric acid.M. 0. I?. Analyses of Cotton Dyed with Alizarin. By C. LIEBEI~MANN and P. MICHAELIS (Ber., 1894, 27, 3009--3019).-This work was undertaken in order t o ascertain whether the theory of dyes advanced by Liebermann (Abstr., 1893, i, 370) is in accord with the facts so far as regards the relative proportions of base and dye present in the cloth. The theory has so far derived no support from the authors' observations. Technically prepared samples of Turkey red, Bordeaux, and dark madder violet were examined, a detailed description of the analytical methods is given, and the results are tabulated. Specimens of cloth practically identical in appearance may contain totally different compounds ; for example, the relative proportions of alumi- nium and tin in an aluminium-calcium-tin " lake," vary greatly, an d the metals do not replace each other in atomic proportions. These results, and the somewhat contradictory analyses of other observers, are probably due to the presence of uncombined mordant i n the cloth, which should, therefore, always be dyed to the deepest possible shade before being used for analysis.J. B. T. Some Points in Stereochemistry. By A. COMBES (Bull. SOC. Chirn., 1894, [3], 11, 261-263).--8 criticism of Bouveault's recent paper (Abstr., 1894, i, 421). The author disputes (a) the novelty, and ( b ) the correctness of some of Bouveault's theories as to the relation between rotatory activity, and the constitution and stereoisomerism of cyclic compounds. L. T. T. Action of Camphoric Anhydride on Benzene in Presence of Aluminium Chloride. Bey E.BURCKER and C. STABIL (Compt. Tend., 1894,119, 426-428).-The action of camphoric anhydride on benzene in presence of aluminium chloride, yields, as chief product, phenylcamphoric acid (Abstr., 1891, 324), and two others, which the authors have isolated. One of these, pkenylcamphoric anhydride, C,6H1e02, is formed in quantity depending on the temperature, and is separated from the acid by means of i t u greater solubility in benzene. It is a yellowish, syriipy liquid, which does not crystallise even aEter remaining in a vacuum for three months. The other product is formed when the action is violent and the substances remain in contact for a long time. It is a diphenyl com- pound, which has the composition CL2HU02, and crystallises in reddish-yellow masses from benzene, in which it dissolves moreORGANIC CHEMISTRY.109 readily than phenylcamphoric acid. CHPr<CH2-C0 T-T2*cH2> C Ph*C OPh. It may have the constitutioii C. H. B. Natural Resins, By M. BAMBERGER (Hmzatsh., 1894, 15, 505-518 ; compare Abstr., 1832, 204) .-The resin from Pinus Znricio (Poir), which melts at about loo", is resolved, on digestion with ether, into an a-modification (80 per cent.), which is soluble in ether, and a @-modification (20per cent.), which is insoluble i n ether. The a-yesin is a reddish-white, amorphous powder, which is soluble in dilute potash, benzene, and toluene, and dissolves in concentrated sulphurio acid, forming a, reddish solution ; its methoxyl number is 33.The /%resin is a reddish-white powder, also ,soluble in dilute potash, but insoluble i n benzene and toluene; i t has a methoxyl number 62, and gives at first a green, and later a violet, coloration when hydrochloric acid is added to its alcoholic solution. When an excess of potash is added to an alcoholic solution of the a-resin, or of the crude resin, a, colourless, crystalline, potassiuni compound is formed. A cold aqueous solution of the latter, when treated with hydrochloric acid, gives a powdery precipitate of pinoresinob, CleHleOs, which gradually separates from its alcoholic solution in drusy masses, melts at 80-go", contains two methoxyl groups, takes up 2 atoms of iodine, and farnishea the following derivatives. The potassium saEt, CIsH160,K2 + 4H20, is very soluble in water and methylic alcohol, but is insoluble in ethylic alcohol ; the calciwm salt, CIRHl6O6Ca, is a white, insoluble precipitate ; the diucety Z-deriaa- five, Cl,Hl6o6i&, crystallises in slender, white needles, and melts at 164" ; the dibenzoyl-derivative, C19H1606B~2? crystshes in short prisms, and melts at 160".On treatment with methylic iodide, the potassium salt is converted into dimethylpinoresinol, C18H1606Me2, which crystd- lises in scales and melts a t 94". The forniula for pinoresinol must, therefore, be 'C16Hl,02(0H)2(OMe),. The caffeic and ferulic acids found in an earlier investigation (Zoc. cit.) are, in all probability, present in the resin in an uncombined state. Scammony Resin. By H. SPIRGATIS (Arc7~. Pharnt., 1894, 232, 482--486).-A reply to Poleck (Abstr., 1894, i, 471), maintaining the correctness of his former work, and especially c4 tha arialgses and proposed formula of barium scamrnonate.Gaultherin, a New Glucoside from Betula Lenta. By A. SCHNEEGANS and J E. GE~~OCK (Arch. Phnrm., 1894, 232, 437- 444!).-1n 1844, W. Procter, jun., announced (Amer. J. Pharm., N.S., 15, 249) the existence, in the bark of BetuZa Zeizta, of a glucoside, to which he gave the name gaultherin ; he did not, however, obtain i t in the pure state, and the authors have therefore re- examined the Betula Zenta bark. I n extracting the bark, i t was found that even with 94 per cent. alcohol partial hydrolysis of the glucoside took place, the odour of methylic salicylate becoming apparent. By using for extraction a solution of lead acetate (15 per cent.of the weight of the bark) in strong alcohol, this decomposition was pre- G. T. M. L. T. T. YOL. m v m . i. i110 ABSTRACTS OF OHEMICAL PAPERS. vented. Quultlierin, C,,H,,O, + HZO, crystallises in coloui-Iess needles, which are easily soluble in glacial acetic acid and in alcohol, slowly but freely in water, and almost insoluble in ether, chlorofornl, benzene, and acetone. The aqueous solution does not affect iron salts, nor does it affect Fehling's solution in the cold, but at 100" cupyous oxide is at once precipitated. Strong sulphuric acid dissolves the glucoside, forming a pale red solution, which rapidly darkens and de- composes. Wheii the dry glucoside is heated, the odour of methglic salicylate becomes apparent at about loo", and the substance blackens and decomposes at 120".Theaqueous solution has a bitter taste and is lerorotator,y. The glucoside is decomposed bg mineral acids, by alkalis, or by heating the aqueous solution at 130-140", yielding carb0hydrat.e and methylic salicy late. L. T. T, Crystalline Constituents of True Coto Bark. By 0. HESSE (AnnuZen, 1894, 282, 191-207 ; compare Abstr., 1894, i, 380).-The coto bark employed by Jobst and Hesse (Abstr., 1880,325) was derived from Bolivia, whilst riowadays the term has been extended t o include varieties from Venezuela and Brazil. The following results were obtained with the bark from Bolivia. Cotoin extracted from this bark is identical with that obtained from other va-rieties. Bensoylcotoih is formed by the direct action of benzoic anhydride, and crystallises in compact lustrous prisms, melting at 110-112".It gives a brownish-red coloration with ferric chloride. Dibenzoykotoin is best prepared by the action of beuzoic chloride on coto'in, and cryst'allises in concentric groups of small needles, melting at 134-135". Hydrocotoin only yields one benzoyl-derivative, which crystallises in white needles, melts at 113", and gives no coloration with ferric chloride. The substance known as dicoto'in has the formula C?5H2006, and not C44H34O11 as formerly supposed. The cryoscopic determination of the molecular waight, however, gives the number 214, instead of 416, as required by the above formula. This is explained by the fact that dicoto'in is in reality a mixture of coto'in with a, substance which has the composition and moleculnr weight corresponding with the formula C11H602, and may be obtained from dicoto'in by adding ferric chloride to its alcoholic solution and evaporating.The iron compound of coto'in is thus formed, whilst the new substance crystal- lises out in long needles. It separates from light petroleum in colourless, strongly lustrous plates, melts at 60-6 I", and volatilises at a higher temperature. It does not contain the hydroxy-group, and gives no colora.tion with ferric chloride. With phenylbydrazine, it forms a compound of the formula C,,H22N40, which crystallises in colourless needles, melting at 194". In all its properties, i t bears a, very close resemblance to phenylcoumalin ; as, however, the latter melts at 68", the identit,y of the two cannot be considered as proved.Psendodicotoin, C25H2007, is also a mixture of cotoh with a sub- stance of the formula CIIH,Os, which the author terms hydrozy- phenylcoumaZin ; this crystallises from light petroleum in colour- less plates or white needles, and melts at 61". Acetic anhydride con- verts it into acetoxyphenylcoumalin, CIIHTACOS, which crystallises inORGANIC CHEMISTRY. 111 Instrous needles and melts at 65". With phenglhydrazine, it foi*ms a caompound, C23H22N402, crystallising in flat needles arid melting at 193". When treated with aqueous potash, it is converted into ~3-pher;ylcozimalic acid, CllH1003, which crystallises from acetic acid jn prisms or plates and melts at 207". The melting point is, how- ever, uncertain, as the acid passes gradually into its lactone, which melts at 221".The paracoto'in obtained from the specimens in question agreed in properties with that previously described. The author contirms the occurrence of piperonylic acid among the products obtained by fusing paracoto'in with potash (Ciamician and Silber, Abstr., 1894, i, 51). A. H. Properties of the Dihydroquinolines, and the Constitution of Ring Systems containing Nitrogen. By G. CI~nii CIAN (Ber., 1894, 27, 3077--3081).-1t has already been shown by Ferratini (Abstr., 1893, i, 602) that the trimethyldihydroquinolirie obtained by the action of methvlic iodide on 2'-methylindole, which has one of the .I CMe :yH CHMe-EH has NMe*CHMe. Or CsH4<NMe-CMe, following formulse, C6H4< properties which strongly resemble those of the indoles, although it may be readily converted into quinoline derivatives.The author finds further that wheu the hydriodide of dihydrotriniethylquinoline is heated, it loses methylic iodide and is converted into trimethyl- indole, the yield of the latter being very satisfactory. The action is analogous to that which takes place when the hydriodides of tertiary bases are heated, methylic iodide and the corresponding secondary base being obtained. The great similarity in the properties of the two series is readily explained by the above formuloe of the dihydroquinoline derivatives and the usual formula of the indole ring, the former being " nuclear " homologues of the latter. Bamberger's centric formulae with a quinquavalentl nitrogen atom do not, howerer, afford a ready explana- tion of the analogy.Ethereal Salts and Betahes of Quinolinesulphonic acids. By A. CLAUS and J. STEINITZ (Annalen, 1894, 282, 130-138 ; com- pare the ne,xt abstract) .-Meth ylic quinoline-l-sulphonate, H. G. C. is obtained by the action of methylic iodide on the silver salt at 8 5 O , and crystallises in colourless, lustrous prisms melting at 96". It gradu- ally decomposes when kept, with formation, of the free acid and ~1 volatile oil, which bas not yet been analgsed ; this decomposition proceeds much more rapidly at 100". The benzylic salt crystallises in splendid, six-sided tablets and prisms, which have a diamond lustre, and melt a t 84". When heated a t 200", i t decomposes with formation of the free acid and an oil, which has the empirical formula Cl4Hl3.These two salts and the ethylic salt do not appear to form a meth- iodide, and it has therefore been found impossible to prepare the cor- responding be taines.112 ABSTRACTS OF CHEMICAL PAPERS. auinoline-4-su223honic acid methylbetnigte, C9NH,MeS02, is readily formed, and crysttnllises in yellowish prisms, which can be heated to :360" without undergoing any change. It dissolves in alkalis, but cannot be recovered, either free or in the form of a salt, by acidi- fying the solution. The betake, moreover, does not combine with alkylic iodides. Similar results were obtained with gzcinoline-3-sulpholtic acid methyl- betaine, which may be prepared from the silver salt and methylic iodide at 100". The systematic investigation of this action has shown that many of the monobromo-derivatives of the 4- and 3-sulphonic acids only yield ethereal salts when their salts are heated with methylic iodide, whilst others, such as the 3-bromo- and 3-chloro-4-sulphonic acids only yield betaines.A. H. Alkyl Derivatives of Quinaldine-p-carboxylic acid. By A. CLAW and J. STEINITZ (Annalen, 1894, 282, 107-130; compare Abstr., 1893, i, 728). - Ethylic quinaldine-p-carboxylate meth- iodide, C,NH6Me*COOEt,MeI, has been described by Hantzsch (Abst,r., 1886, 369). The methochloride crystallises in long, colourless needles, melting a t 1 5 8 O . The behaviour of these compounds towards alkalis has already been described by Hnntzsch. The authors find that the insoluble amorphons yellow substance finally obtained has the composition ClaNHrd02:CH,, but it is probably a poly meride.Xthylic quiitaldirLecarbozylate ethiodide is formed with considerable difficulty, and cryst,allises in groups of plates which melt and decom- pose at 236". The ethochloride forms well-developed prisms, and melfs at 146" ; its platinochlo?-ide, (C~3H,302N,EtC1)J?tC14, crystallises i n compact, red prisms, and melts and decomposes at 238". Eth ylic ethylidenequi~~aldi~tiurn-~-carBoxylate, Cl~NHI3O2:CHMe, is obtained as an amorphous, yellowish-red mass, which has not been ;malysed, by the action of alkalis on the ethiodide. It is completely soluble in ether, and does not undergo polymerisation to an insoluble compound when kept. On treatment with hydrochloric acid, i t yields the ethochloride melting at 146".The silver suEt of qninaldine- /3-carboxylic acid is a micro-crystalline powder, and when treated with methylic iodide yields the wzethylic salt of the acid. This suh- stance can also be obtained by synthesis from methylic acetoacetate and orthamidobenzaldehyde, and by the action of methylic iodide on quinaldinecarboxylic acid ; in the latter case, the direct product is the hydriodide of the methylic salt. The methylic salt forms colourless needles, melting at 72". The following additive compounds and ethereal salts of quinaldine- /3-carboxylic acid have also been prepared. From the methylic salt, the methiodide, vitreous, yellow prisms, melting at 200" ; the metho- chzoride, colourless, vitreous prisms, melting a t 157" ; the ethiodide, lemon-yellow plates, melting at 210" ; the ethocliloride, colourless, vitreous needles, melting at 150" ; and the ethobromide, granular crystals, melting at 154'. From the ethylic salt, the ethobromide, granular crystals, melting at 21i". The p ~ o p y l i c salt forms colourless,0 R Q A N 1 C C HEN I ST H Y. 113 vitreous prisins, and melts at 51" ; the p o p y l i c methiodide golden- yellow needles, melting at 186" ; the benzylio salt forms colourless prisms, melting at 82O.and the beutylic methiodide flat, golden-yellow needles, melting at 176". The methylic methochloride and iodide, when treated with alkalis, yield a yellow, amorphous substance which behaves in a similar nittnner to the corresponding derivative of the ethylic salt. It is a yellow powder, nielts and decomposes a t 182", and has the formula of methylic ~ ~ i e t h .r J l e r z e ~ z c i i a c c l d ~ ~ z i ~ ~ ~ i a - ~ - c a l . ~ l a t e , C9NH5Me(C0 OMe) :CH2, of which i t is probably a polymeride. Quinaldine-IJ-carboxylic acid cliff ers from the ymrboxglic acids of the quinoline series in two important respects. It forms no direct additive compounds with halogen alkgls without at the same time being converted into an ethereal salt, and the additive compounds of the ethereal salts do not yield the corresponding beta'ine when treated with alkalis. Quinald,ine-p-carboxylic acid rnethochloyide can, however, be readily obtained by heating the methochloride of one of the ethereal salts with fuming hydrochloric acid. I t forms short, vitreous prisms, and melts with decomposition at 230".The corresponding betazne forms thick, monosymmetric prisms containing 2H20, which are lost at loo", the anhydrous compound melting at 144". It has an intensely bitter taste, and is readily decomposed with formation of a violet colouring matter. It unites readily with methylic and ethylic iodides to form compounds which are in every respect identical with the methylic methiodide and ethylic meihiodide already described. This behaviour confirms the view expressed by Claus and Buttner (Abstr., 1893, i, 731) as to the course of the analogous reaction with cc-phenyl- cinchoninic acid. The betajine dissolves i n alkalis, forming a salt which could not be isolated, and does not form an oxinic acid. A. H. 4' - Orthohydroxyphenylquinoline and 4' - Metahydroxy- phenylquinoline.By €3. BESTHORN, E. BANZHAF, and G. J A E Q L ~ (Ber., 1894, 27, 3035-3043) .-Orthoet?coxymeto~henone was prepared from ethylic ethglsalicylate by Tahara's method (Abstr., 1892, 844) ; it melts at 43", and boils at 243-244". It was converted, by the same method as sthat used in the case of the para-compound (Abstr., 1894, i, 344), into orthoethox!ybeuzoylacetmze, 0 Et*C6H4*CO*CH20C Me0 ; this melts at 56", and forms a sodium salt, whicb, when warmed with aniline and acetic acid, yields a yellow nnilide, OEt.C6H**C0.CH,*CMe:NPh. When the latter is heated at 50" with sulphnric acid monohydrate, several reactions take place, and as B result of one of t,hese some 4'- orthoet hozypheny Epuina 1 diizesulphonic a c i d , 0 E t C6H3 (S 0,H) CloNH8, is formed, and crystallises in tiny, white needles.When this is boiled with hydrobromic acid, it is converted into 4'-orthoh yduoxypheizyl- ifl114 ABSTRACTS OF OEEMICAL PAPERS. quinaEdiiLe, OH*C6H4*CI,,H8N, which melts at; about 187-188" ; alld its sodium salt. when heated with benzaldehydc and zinc chloride at, .200", yields a benzylidene compound, OEt*C6H3( S03H)-C,,H6N:CHPh. If the latter is oxidised with permanganste, and the product heated with 11 ydrobi-omi c acid, ye1 low is h-red 4'-orthoh ydmzypli e n ylq uinaldinic acid, OH*CsHl*CgNH5*COOH, is formed ; this melts and decomposes a t 243-245", and, when heated at 950', yields 4'-ol.t?iohyd?.ox~~?lenyi qicinoline, OH*CRH4*CgNHG, identical with the " quinolinephenol " ob- tained by Koenigs from apocinchene (Abstr., 1893, i, 377).Bletanzethoxyacetophenone was prepared like the para-compound (Abstr., 1894, i, 344) ; it boils a t 239-24l". 1Cfetanzethoallbelzzoyl- cicetone was obtained as an oil, its nizilide as yellow needles melting a t 89-85". This anilide yields a sulphonic acid, the barium salt of which forms a benzylidene compound. From the latter 4'-metuhydroxy- p ~ ~ e ~ z y l q u i ~ a a l ~ i ~ z i c acid can be obtained ; this melts and decomposes at about 235", yielding 4'-metahydroxyphen?llquinoZine, identical with the Py-S-/3-phenolquinoline OE Koeniga and Nef (Abstr., 1887, 599). Paramethoxy-a-phenylcinchoninic acid, Parahydroxycin- choninic acid, and Parahydroxy- a-phenylcinchonine. By 3. CLAUS and G.BRANDT (AniznZen, 1894, 282, 85-107).-3-iMethozy-L - yheitylcinchonirric acid methiodide, OMe*CgNHIPh*COOH,MeI, is oh- tnined by heating a-pheriylquininic acid with methylic iodide a t 1:35-136", and forms aggregates of small, reddish-yellow needles, rnelting at 216". The methochloyide is prepared by triturating the methiodide with moist silver chloride, and is a hygroscopic mass, which crystallises from alcohol in small needles, melting at 195". The corresponding betazne is formed when the methiodide is treated with moist silver oxide, aild crystallises with 1H20 in yellow, vitreous prisms, which become anhydrous at 100" and melt a t 218". The betaine is also formed when the aqueous solutions of the metho- (ahloride and iodide are boiled, and when these substances are treated with alkalis.The further action of alkali produces a quaternary ammonium hydroxide of the formula OMe*CgNH4Ph*COOH,MeOH, from which the original betaine, or one of its salts, can readily be regFined 1)s acidi6cation of its solution. This substance, probably owing to the presence of the phenylic group, is much more stable than the corresponding derivative of quininic or cinchcninic acid, and does not form an oxinic acid. It was found impossible to prepare an ethobromide of the acid. ?'he sodium salt of methoxyphenglcinchoni~iic acid forms slender, \-ellow needles, containing 6H20, whilst the copper salt is a light green precipitate. The hydrochloride, Cl,H1&N + 3HC1, crystallises from concentrated hydrochloric acid in lemon-yellow, vitreous needles, and loses 2HCZ at 100".3-H~dro~~~cinchoizilzic acid qnethiodide, OH*CgNR~*COOH,MeI, is formed from its componeuts with considerable difficulty, and c r p - ta,llises from alcohol in splendid, orange-yellow, vitreous prisms, melting at 302". Its solution in water readily decomposes, with formation of resinous compounds. The methochZoride may be pre- pared 1,s the action of silver chloride, but is hest obtained by heating C. F. B.ORQASIC CHEMISTRY. 115 the methochloride oE quininic acid with fuming hydrochloric acid at 2SO", this being a reaction capable of general application to this class of substances. The corresponding betaiite is formed by the action of water, alkalis, or silver oxide on the foregoing compounds, and crystallises with 1H,O in large tablets or prisms, which lose their water at 100" and melt at 304".The product of the action of alkalis on the betaine, methyl- q~Linoliiii~~ml~ydrOxicleca~.boxylic acid, has not been isolated. Its soln- tion is stable in the air, so that the presence of the free hydroxy- group has the same influence on the stability of the compound as has the phenylic group in the case of methoxyphenylcinchoninic acid. 3-Hydrox?l-3'-p7Le?2yZcir~c~oni?z~c acid, OH-C,NH,Ph*COOH, may be prepared, by Dobner's method, from parahydrmyaniline, pyruvic acid, and benzaldehyde, and forms small, vitreous plates and needles, which decompose at 693-300". Its alkaline solutions become dark brown on exposure to the air. The copper and silver salts are amorphous precipitates. The methocldo&le is prepared by the action of hydro- chloric acid at 230-235" on the methochloride of methoxyphenyl- ciiichoninic acid, and forms greenish-yellow, lustrous plates, melting a t 248".The rnethiodide can only be obtained with great difficulty from its components and is very unstable. The betazne forms almost, colourless, grariixlar crystals, and me1 ts at 243". The alkaline sol u- tions of the betaine are somewhat unstable, but no compound of the nature of an oxinic acid is formed, resinous matter being gradually produced. The solubility of the substituted cinchoninic acids is shown in the following table. 100 grams of the boiling saturated solution contains It forms flat, green crystals, and melts at 295". Paramethoxycincho~iinic acid . . . . , . . . . . Paramethoxy-a-phenylcinchoniuic acid .. . 2.22 ,, Paraliydroxycincho~iinic acid. . . . . . . . . . . Parahydroxy-a-phenjlcinchoninic acid . . . 0.44 ,, 1.24 grams. 0.28 gram. A number of ethereal salts have also been prepared by the action of an alkylic iodide on the silver salt of the acid. Methylic salts. Ethylic salt. &I. p. M. p. 2'- Pheny lcinchoninic acid . . . . . . . . . . . . 3-Methoxycinchoninic acid . . , . . . . . . . . 3-Hydroxy-2'-phenylcinchoninic acid , . 148 - 61 " 8.5 - - 3-Methoxy-2'-phenylcinchoninic acid . . 111 105" These salts readily undergo decomposition when heated, the free acid being formed, together with a terpene-like substance, the nat,ure of which has not yet been determined. A. H Pure Dextrorotatory Coniine. By A. LADEXBCRG (Ber., 1894, 27, 3063-3066).--Coniine was prepared synthetically i n the same way as before, but on a larger scale ; YO grams of inactive coiiiine, boiling at 165-169", were obtained.This mas treated with dextro-116 ABSTRACTS OF CHEXICAL PAPERS. rotatory tartaric acid, as before, when tJlie salt of dextrorotatory coniine crystallised out. l'his was. however, now recrystallised three times, after which it yielded a coniine, boiIing a t 167.7" (corr.), and with sp. gr. = 0.8438 and specific rotation [ a ] , = +18*3", both a t 23". The difference between this and the earlier numbers is attributed to the presence of isoconiiiie in the sample then investigated. c. I?. B. Nicotine (Metanicotine). By A. PINNER (Bey.: 1894,27,28tji- 2869 ; compare Abstr., 1894, i, 388).-When the additive compound of benzoic chloride and nicotine is heated with strong hpdrochloric acid at loo", benzoic acid and nicotine are formed, whilst, if boiled with sodium ethoxide, hydrogen chloride is eliminated and benzoyl- metanicotine is produced.dcetylmetanicotine is obtained by heating nicotine with acetic anhydride for 10-12 hours at 170" ; it is hydro- lysed only with difficulty, yielding metanicotine. When metanicotine is heated with a strong solut.ion of barium hydroxide for 10-12 hours at 170°, mehhylamine is formed, together with a base, CgH9N, of which the picrate melts a t 151". The action of bromine on metanicotine gives rise to the compound, CloH,,Br2N2,2HBr,Br2, crystallising in reddish-yellow needles, which melt at 170". On adding dilute caustic soda to the hydrobromide of metanicotine bromide, monobroiriometanicotine, C:10H13BrNZ7 separates in the form of an oil; the picrate melts at 190".Reduction with hydrochloric acid and zinc dust gives rise to the foi*mation of meta- nicotine. The optical activity of cotinine, dibromocotinine, and dibromoti- conine has been determined. The first-named has [a],, = --56", whilst dibromocotinine has [a]= = + 95.5", and dibromoticonine has [a],, = +13*6"; the determinations were made at 20". Derivatives of Caffeine. By L. CRAMER (Ber., 1894, 27, 3089- 3092).-~~~ethyZamidocu~ez~e7 C8H,N402*NHMe, is readily obtained in 8 similar manner to amidocaffe'ine by heating chlorocaffe'ine with methyIaminc and alcohol a t 100"; it crystallises from hot w a t e r in slender, colourless needles, melts a t 310-315", simultaneously be- coming brown.The picrnte crystallises in yellow plates. EthyE- amnidocc@eiize, C8HgNr02*NHEt, is prepared in a similar manner, and also forms slender needles, melting at 226-230" with partial sub- limation. Hydrusidocafleine, CsH,N40,*N,Hs, prepared by boiling chlorocaffelne with an aqueous solution of hydrazine hydrate, crystallises in slender, colourless needles, melting and completely decomposing a t 240". It reduces Fehling's solution on warming, and yields a hyd~ochloridt., which crystallises well and dissolves readily in warm water. With benzaldebyde, the hydrazine compound forms benzylideneh?j~razido- cufezue, CRH,Na02*N2H:C€IPh ; this crystallises in slender needles, melting at 270" to a brown liquid.On treafment with nitrous acid, it is converted into azirnidoccr$eiwe, CRHSN402N3, which forms colour- less needles, sparingly soluble in water, and rapidly becomes red in the air when moist. Anilidocqffeine, C8H9N4O2*NHPh, crystallises from alcohol in colour- M. 0. F.ORGANIC CHEMISTRY. 117 less needles, melting at about 260" and decomposing at a slightly higher temperature ; the hydrochloride, C,,Hl5N,O2,HCl, also crystal- lises in needles, which are dissociated by water. Nitrosonnilido- cafei'ne, C8N,H90,*NPh.N0, decomposes at about 225" and gives Liebermann's reaction. BenzoyZaitilidocu$e~~~e, CBN,Hg02*NPhBz, is obtained by boiling anilidocaflk'ine with beneoic chloride, and, after cryatallisation from alcohol, melts at 225". By the action of alcoholic potash on anilidocaff eine at 120", it is converted into atdidocaffeidine, the sulphate of which crystallises well ; the action of hydrochloric ;wid and potassium ch1orat)e converts it into chloranil and dimethyl- alloxan.Pamtoluidocafeine melts at 270-275", orthotoluidocaffeine a t 230", and metaxylidocafeine at 210-212". Thebaine. By M. FREUND (Ber., 1894, 27, 2961-2963).- Thebenine is not isomeric with thebaine as Hesse thought, but con- tains hgdroxyl in place of methoxyl, its mzethiodide, C,H2,NOsI, is crystalline, melts at 210", and is resolved into trimethylamine and thebenoZ, CIJIlrO, on fusion with alkalis. Thebenol melts at 186", and by distillation with zinc dust, or reduction with hydriodic acid and phosphorue, yields a hydrocarbon which melts at 135O, and is perhaps an ethylphenanthrene.Thebenine ethiodide when fused with alkalis yields thebenol and iiiethyldiet'nylaniine, proving that thebenine is a secondary base. Thebaine is a tertiary base, but its relationship to thebenine pre- cludes the presence in it of the group NMe2. When treated with alkalis, its rnethiodide yields tetramethylethylenediamine, not tri- methylamine, as Roser stated ; it is probable that dimethylhydroxy- ethylamine, which is closely related t o morphine, is formed as intermediate product. The production of the ethylene base resembles that of tetrethylethylenediamine from triethylaminethylene iodide as observed by Ladenburg. The following provisional formuloe are given for thebaine, thebenine, and thebenol respectively H. G.C. > CH,. W J. B. T. Opium Alkaloids. By 0. HESSS (Annulen, 1894, 282, 208- 824).-When crude laudanine (Annalen, Supp1.-Bd., 8, 272) is - con- verted into the hydrochloride and this is recrystallised from water, the mother liquor is found to contain an alkaloid, Zaudanidine, C20&5N04, which is isomeric with laudanine, but differs from it in being optically active ([a],-, = -87.8"). The new alkaloid melts at 177" (laudanine melts at ltiti"), but in other properties closely resembles its isomeride. The hydi*ochZoride is much more readily soluble in water than that of laudanine. The hydriodide is sparingly soluble, and the platinochlo- ride is a brownish-yellow, amorphous mass. The hydrogen oxalate forms small, white needles. Acetic anhydride converts it into acetyl- Zazidanidine, which crystallises with 1H20, melts at about 9 8 O , and dissolves in dilute aqueous potash and soda, but not in ammonia.It118 ABSTRAOTS OF GHEMIOAL PAPERS. seems probable that laudanine consists of two optically opposed con- stituents, of which landanidine is one, but this question is being further investigated . A. H. Benzoylquinine. By A. WUNSCH (Compt. WWZ., 1894, 119, 407-%09).-Schiitzenberger obtained benzoylquinine by the action of benzoic chloride on the alkaloid, and described it as a resinous and uncrystallisable substance. The author prepares i t by adding grad unlly, with frequent agitation, 60 parts of pure, well-dried, and finely-powdered quinine t o 100 parts of benzoic chloride, heated on a water bath. The product, after cooling, is treated with several times its volume of'cold yater, which rapidly dissolves the benzoyl- quinine hydrochloride, but only very slowly attacks the excess of benzoic chloride.The base is purified by precipitation with ammonia and crystallisation from aqueous ether. It forms very distinct, highly refractive, colourless prisms of the composition Benzoylquinine is insoluble in water, and the crystals remain unchanged even in contact with boiling water, but it dissolves readily in alcohol, benzene, chloroform, light petroleum, and carbon bisulphide, atnd also in ether, especially if i t contains water. I t crystallises from all the solvents except alcohol, and the crystals, which are anhydrous, melt at 139", but decompose at a higher tem- perature. Benzoylquinine is distinguished from quinine benzoate by its insolubility in water and its resistance t o the action of potassium hydroxide.Like quinine, it ~7ields a green coloration with chlorine water and ammonia, and the dilute aqueous solutions of its salts are fluorescent. It is neutral to both phenolphthalek and litmus, and even the basic salts are acid to litmus. It forms two series of salts, namely, basic salts, which contain 1 mol. of the base and 1 mol. of a mouobasic acid, and normal su*Zts, which contain twice as much acid. The basic salts are very stable, and are insoluble, or almost insoluble, in water. They are usually hydrated, and effloresce rapidly. The normal salts are partially decomposed by water. The basic hydrochloride crystallises from alcohol in acicular prisms containing + mol.H,O, and is very soluble in alcohol ; the normal hydrochtovide crystallises from absolute alco- hol in small, square prisms, which contain 1 mol. EtOH, absorb moisture rapidly from the air, and dissolve in all proportions in water and alcohol. The basic salicylate cry stallises from dilute alco- hol in anhydrous lamellae ; the basic tartrate forms brilliant needles containing 9H20 ; the basic succinate forms colourless prisms, which contain 8H20, and effloresce very rapidly. 4$1).-This paper is a continuation of the author's previous work (H. Kunz, Abstr., 1887, 980). Methylemetonium hydroxide (loc. cit.) has now been obtained as a golden-yellow, amorphous powder. Its solution is very strongly alkaline, and absorbs carbonic anhydride C.H. B. Emetine. By H. KUNZ-KRAUSE (Arch. P h ~ m . , 1894, 232,466--ORQANlU UHERIISTRP. 119 frum the air. The carbonate is an amorphous powder, softening a t 120", and melting with evolution of carbonic anhydride at 256-160". EthyZemetoniu.nz iodide, C30H4,~N205E tI, cryst allises in white needles ; the hydroxide resembles the methyl base. Both these derivatives are quaternary ammonium bases. In the preparation of emetine, a colozir base, containing both nitro- gen and sulphur, was found among theresidues. The authors believe this to be an acetyl derivative of emetine, and by heating emetine with other acids, and with acetic and benzoic anhydrides, &c., they have obtained derivatives apparently analogous to it. This reaction is being farther studied. When ometine is heated with hydriodic acid, 4 mols. of inethylic iodide are eliminated. Emetine therefore contains four methoxyl groups and almost certainly one hydrosyl group. The constitution of emetine may, therefore, be represented by the formula Cz,H,,N,(OMe)4*OH, aud the nucleus C,,H,,N probably contains one OF more tertiary butyl- toluene groups. The author maintains the correctness of the above formula against Paul and Cownley's contention (Abstr., 1894, i, 155, and Pharnt. J. Truus., 1894, [ 3 ] , 54, l l l ) , that emetine is a mixture of two alkaloids, CI5&NO2 and C,rH20N0,, and calls attention t o the fact that each of these formule contains an uneven number of valencies. Both methylemetiue and the colour base resemble curare in their physiological action, producing paralysis of the motory system and then death. L. T. T. Identity of Cytisine and Ulexine. By A. PARTHEIL (ATc~L, Pharm., 232, 486--488).-The author maintains his claim to priority in proving the identity of these two alkaloids. The Products of Hydrolysis of Convolvulin, and its Com- position. By H. J. TATERNE (Rec. Trav. Chim., 1894,13,187-217).- Convolvulin, extracted by alcohol from jalap-root coming from Vera Crux, was hydrolysed by dissolving it in baryta water, removing the barium with sulphuric acid, and boiling the solution with 8 per cent. of free sulphuric acid. The,re were formed a Folntile acid (methylethylacetic), a crystalline acid (hydroxypentadecylic) not volatile with steam, and a sugar which could not be obtained in the crystalline form, but which the author is nevertheless inclined to regard as glucose. MethyZethyZucetic acid, CHMeEtCOOH, is identical with the sub- stance obtained by Pagenstcoher (Abstr., 1879, 455), except that i t is optically active, having specific rotation [a]= = + 17" 30'. Hydrozy- pentadecylic acid, CHMeEt.CH(OH)*C,H1,*COOH, mei ts at 50.S" when pure; its methylic salt melts at 35", and boils at 606-208" under 15 mm. pressnre. When it is heated with phosphorus pentachloride and the product reduced with hydriodic acid and phosphorus, n peizta- decyEic acid, Cl5HWO2, is obtained ; this melts at 48", and is isomeric, therefore, with the normal acid, which melts at 51"; it boils at 206"120 ABSTRAOTS OF OHEMIOAL PAPERS. under 14 mm. pressure. When the hydroxy-acid is oxidised with nitric acid, i t yields methylethylacetic acid, and au acid, C10HIA04, which melts at 116", and boils at 235" under 13 mm., and at 294" under 100 mm. pressure ; this acid is isomeric with sebacic acid, which melts at 133-133.5" Possibly, convolvulin has the formula C32H62016: and its hydrolysis may then be represented by the equation C32H62016 + H2O = 2c6Hno6 + c5E100, + C,6H&,. C . F. B. Two Cactus Alkaloids. By A. HEFFTER (Ber., 1894, 27, 2975- 2979) .-Anhaline, CloH17N0, is extracted from Anhalonizlnz .fissuratuwz ; it crystallises in colourless, stellate prisms, and melts at 115". The solution in concentrated sulphuric acid is colourless, even when warmed, but becomes green on the addition of a drop of nitric acid. The most characteristic reaction is the production of a yellow colour with nitric acid, changing to orange-red with potash. The sulphate, (C10H17N0)2,H2SO~ + 2H20, crystallises in colourless, lustrous plates, and melts at 197". The hydrochloride, CloHl7NO,HC1, crystallises in slender, hygroscopic plates. The oxalate is anhydrous and resembles the snlphate. The yield of alkaloid was very small, only 0.2 gram from 1 kilo. of the dry plant. Pellotine, C13H21N03, so called from the Mexican name " pellote," of Anhalonium Williamsi, crystallises in colourless, transparent, an- hydrous plates, and melts at 110". The yield is 0.89 per cent. of the fresh plant. It dissolves in sulphuric acid with a slight yellow oolour, changing to deep red with nitric acid. The phospkotungstate and yhosphornolybdate are voluminous, the former white, the latter lemon colonred. The potassiomemuric iodide crystallises in pale yellow prisms ; the potassiocadmizcm iodide in colourless, rectangular plates; thepotassiobisrnzcth iodide is amorphous at first, but changes to needles ; the iodopotassium iodide crystallises in slender needles. The picrate crystallises in stellate prisms. The platinochloride is de- posited in golden-yellow crystals ; the h ydrochZoride, ClaH2,NO3,HC1, in rhombic prisms. The oxalate crystallises in needles. The meth- iodide, ClaH21N03,MeI + H20, is deposited i n colourless prisms melt- ing at 198". The methochloride, CI,H2,,N03,MeCI, crystallises in slender, colourless needles melting at 226". Determinations by Zeisel's method show that pellotine contains two methoxy-groups. By the action of hydrochloric acid at loo", methylic chloride is eliminated and a base formed in small quantity, which yields a PZatinochEoride crystallising in orange-red prisms. J. B. T.

ISSN:0368-1769    

DOI:10.1039/CA8956800077

出版商:RSC    

年代:1895

数据来源: RSC

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VEGETABLE PHYSIOLOGY AND AGRICULTURE. 83 Chemistry of Vegetable Physiology and Agriculture. Dialysis of Beer Yeast. By E. O~rarus (Compt. rend., 119, 479-480).--9 solution of beer yeast in pure water, or in a solution of sugar, is allowed to diffuse through parchment-paper into a solu- tion of sugar in boiled water; after 15 to 20 minutes, the sugar in the latter solution is inverted, although no cellules, but only some inicrozymes, can be detected in it. It is only after two or three hours that small, isolated yeast cellules are observed in the sugar solution, and only after 11 or 12 hours that chains of cells can be detected. It follows that beer yeast secretes a dialysable substance, and that inversion of the sugar takes place without actual contact with the yeast cells. The medium is first modified by the zymase, and only after this alteration constitutes a nidus favourable to the development of cells.Nitrifying Ferment. By G. TOT~OMEI (Staz. Sper. Agrar., 1894, 26, 246--263).-Affer giving a short historical sketch of the subject of nitrification, the author describes his own experiments, which were mostly on the lines of those of previous investigators. It is con- cluded that nitrification is due to a micro-organism, that moisture is indispensable, that slight alkalinity is favourable, and that light, the chemically active rays, is prejudicial to the development of the organisms. Nitrification proceeds much more rapidly in porous than in compact substances, and is assisted by small quantities of ozone, Vaiaiations of temperature hinder nitrification.C. H. B. N. H. J. M. Glutarnine in the Green Parts of Plants. By E. SCHULZE (Zeit. physiol. Chewt,., 1894, 20, 327-334) .-It has been previously shown that in the families Caryophyllaceae and Pilices no asparafrine is found. I t was therefore expected that glutamine occurred instead. The correctness of this hypothesis is shown by the experiments re- corded in the present paper ; further experiments show that glutamine is formed in the leaves. W. D. H. 7-284 ABSTRACTS OF CHEMICAL PAPERS. Crystalline Nitrogenous Compounds in Seedlings. By E. SCHULZE (Zeit. physioZ. Chem., 1894, 20, 306-326) .-This is mainly a review of previoiis work. Different seedlings yield to analytical processes different nitrogenous crystalline pyoducts. Thus, in L?qxhhs Zuteus, asparagine, phenylalanine, nmidovnleric acid, arginine, choline, and xanthine-like substances are found ; in C'icczt~bita pepo, glutamine, asparagine, leucine, tyrosine, arginine, choline, vernine, and xanthine- like substances ; in Vicia sativa, asparagine, ph enylalanine, leucine, amidovaleric acid, guanidine, choline, and beta'ine. This does not indicate that in plant metabolism the proteid molecule breaks down in different ways, it being contended that the disintegrative metabolism of prote'id is qualitatively the same, but varies quantitatively. This is supported by experiments on plants of the same kind, only of different ages. It may also be that in some plants certain varieties of nitrogenous crystalline compounds are used more in nourishing the tissues, whilst in other plants other compounds are more advan- tageous, and so are used up first. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8956805083

出版商:RSC    

年代:1895

数据来源: RSC

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84 ABSTRACTS OF CHEMICAL PAPERS. A n a l y t i c a l Chemistry. Thioacetic acid as a Substitute for Hydrogen Sulphide in Qualitative Analysis. By R. SCHIFE' and N. P. TARUGI (Be?.., 1894, 27, 343'7-3439) .-Excellent results may be obtained by employing thioacetic acid instead of a current of hydrogen sulphide in qualita- tive analysis. About 2 C.C. of a 30 per cent. solution of ammonium thioacetate is simply added to the solution, made acid with hydro- chloric acid in the usual way, and the liquid boiled. The reactions given by the metals appear to be identical with those obtained with hydrogen eulphide, but the time required for precipitation is greatly lessened. The only products of decomposition of the acid in the presence of hydrochloric acid are ammonium chloride, acetic acid, and hydrogen sulphide, so that the separation of the metals remaining uiiprecipitated is not interfered with.The reagent has been used for some time, and with great success, in the laboratories of the University of Pisa. A. H. New Applications of Alkalimetry and Acidimetry. By E'. HUNUESHAGEN (Chem. Zeit., 1894, 18, 505-506, 547) .-&timation of the Hardness of Water.-The reagents wanted are a, solution of 3.786 grams of sodium carbonate in 1 litre of water and dilute nitric or hydrochloric acid of corresponding strength. 200 C.C. of the sample i s titrated directly with this acid, tincture of cochinelle serving as indicator. Each C.C. of acid shows 1" of temporary hardness (German scale). The permanent hardness is estimated as follows. 200 C.C.of the sample is mixed with a moderate excess of the sodium carbonate solution, evaporated to dryness, and the residue, after being moistened with a little water, is once more evaporated and heated to about 200". It is now dissolved in a little water, the liquidANALYTICAL CHEMISTRY. 83 filtered, and the insoluble matter washed with about 50 C.C. of water. The filtrate is then titrated as before. The Dumber of C.C. of acid deducted from the C.C. of added soda represents the permanent hardness. The total hardness may be estimated directly by using the resulting liquid from the estimation of the temporary hardness for the determination of the permanent hardness. Volumetric Estimation of Phosphoric acid by Titraliizg the Ye1 low Precip*tate.-The liquid should not contain more than 0.05 gram of phosphoric anhydride.If free hydrochloric or sulphnric acid is present, the phosphate is precipitated with a little ammonia and at once redissolved in nitric acid. After adding some ammonium nitrate and a little ammonium sulphate, the liquid is heated, prccipi- tated with a slight excess of molybdatc solution, and the precipitate collected and washed with a 1 per cent. solution of potassium nitrate, iuitil the filtrate is practically neutral. The filter is then put back into the beaker, from 10 to 50 C.C. of water is added, and, after adding a few drops of 1 per cent. solution of phenolphthaleln, the mixture is t itraked with normal alkali uutil the precipitate has all dissolved, and the liquid turned permanently red. It is advisable t o add a slight excess of the alkali, and then to tiirate back with normal acid.1 O.C. of normal alkali = 0*003077 gram of phosphoric anhydride. Acidimetric Estimation of I',urhgstic acid.-T he acid is separated in the usual manner, without troubling about any silica which may be present. The precipitate, after being washed, first by decantation, xiid then on the filter, with a 5-10 per cent. solution of potassium nitrate, is mixed with water, heated to boiling, and dissolved in excess of normal soda. The excess of alkali is titrated back with normal acid, phenolphthaleln serving as indicator; 1 C.C. of normal alkali = 0.116 gram of tungstic anhydride. L. DE K. Estimation of small Quantities of Chlorine in Fats. By R. BENEDIKT and H. ZIKES (Chem. Zeit., 1894,18, 640--641).-A tube, made of hard glass, 100-110 cm.long and 11-12 mm. wide, is drawn out funnel shaped at one end and bent at an angle of 45" upwards. The funnel is provided with a doubly perforated india-rubber cork, through which passes a narrow bent tube for admitting air or carbonic anhydride, whilst the other hole admits a tube connected with a calibrated 100 C.C. reservoir containing the oil. The tube is made ready for use by introducing in the middle two separate 15-20 cm. layers of lime held together by plugs of asbestos. The empty space between the bend and the first plug of asbestos is tilled up with broken pieces of porcelain. The tube is now laid in the combustion f timace, which must extend slightly beyond the second layer of lime. The other opening is closed with a cork through which passes a bent tube connected with a test-tube to collect any t a r ; another narrow tube carries off the gases, which iiiust be lighted, and which indicate the progress of the combustion.When the lime is red hot, the oil is very slowly admitted, n very slow current of carbonic anhydride being also passed through. When, after 3 to 5 hours, about 25-30 grams of oil has entered the tube, the supply is stopped, and, when the flame has gone out, the tube is86 ABSTRACTS OF CHEMICAL PAPERS. allowed to cool; it is then emptied, and the contents examined for chlorine in the usual manner, The test analyses are very satis- Estimation of Organic Nitrogen by Stock’s Method. By C. E. ZAY (Xtaz. Spw. Agrar., 1894, 26, 22--31).-The nitrogen of several substances was determined by Kjeldahl’s method (employing 20 C.C.of sulphnric acid containing 200 grams of phosphoric an- hydride per litre) and by Stock’s modification--using manganese dioxide (5 grams) with (1) sulphuric acid alone, and (2) with sulphuric acid containing phosphoric anhydride (20 C.C. per litre). Concordant results were obtained, and the employment of manganese dioxide effected a very great saving of time in the decomposition process. factory. L. DE K. N. H. J. 31. Volumetric Estimation of Nitric acid. By D. MONN~ER and H. AURIOL (Chem. Centr., 1894, 24, 1095-1096; from Arch. sci. phys., Genive, 31, 352--358).-The process is based on the well- known principle that nitrates are reduced by nascent hydrogen. Sodium amalgam, prepared by adding 1 part of sodium to 100 parts of hot mercury, is allowed to act on the solution of the nitrate in the presence of tartaric acid.The hydrogen is collected and measured, and a check experiment is made with the same amount of amalgam without the nitrate. The difference of hydrogen evolved is the measure for calculating the amount of nitric acid. L. DE I(. Genuineness of Basic Slag. By E’. SESTINI (Staz. Spey. 4 g ~ a r . , 1894, 26, 57--62).-Sorne samples of slag which the author had occasion to examine contained about 16 per cent. of total phosphoric anhydride and 4.4 to 5.8 per cent. soluble in dilute acetic acid (1 : 2), whilst the sp. gr., the amounts of water and of lime were about the same as are found in the case of normal slag. The results ob- tained indicate that the small amount of soluble phosphoric acid is not due to adulteration, but is connected with the amounts of ferric and ferrous oxide and alumina (about 3 per cent.) soluble in the same dilute acetic acid.After discussing Wrampelmeyer’s methods for the examination of basic slag (Abstr., 1894, ii, 119), the author points out that it is sometimes more difficult than was supposed to distinguish between an adulterated slag and one which owes its sparing solubility to its mode of production. The amount of ferrous oxide which a slag con- tains is of interest, as it does not occur in natural phosphates, and the different portions which can be separated from each other by levigation should be examined. N. H. J. 31. Estimation of Carbon in Steel.By H. KOCH (Chem. Zeit., 1894,18, 485).-Air contained in a gasometer is first passed through a washbottle filled with sulphuric acid, then through two bottles con- taining solid potash ; then cornea an empty bottle, and, finally, one filled with sulphuric acid. The purified air then passes through the lower tube of the combustion flask, where it removes t,he carbonic anhydride and any hydrocarbons formed during the process, andANALYTICAL CHEMISTRY. 87 it escapes through the upper tube. The gases are dried in a calcium chloride tube and comuletely burnt by passing them through a, combustion tube contiin- ing red hot copper oxide. The re- sulting carbonic anhydride is first dried by passing it over calcium chlo- ride and phosphoric anhydride, and then absorbed in a weighed potash apparatus to which is sealed a tube containing phosphoric anhydride.When required for the analysis of steel, the apparatus and combustion tube must first be completely freed from any carbonic acid or carbonaceous matter ; the copper oxide is therefo1.e heated to redness, a cnrrent of puri- fied air being transmitted for some time. Into the flask is introduced 8 granis of chromic acid and 120 C.C. of dilute sulphuric acid (4 : S) and the mixture boiled out. Afterwards 2 grams of the steel borings is intro- duced into the flask, the apparatus is coiinected with the combustion tube, and the operation conducted as usual. It will be noticed that the apparatus P i 4mi 4. , I V , I I I I I I i 3 0 m 1 I I I I I 16c.m 2 2 m Height of flask, 30 cm.Contents, 250 C.C. Width of ground neck, 4 cm. consists of two essential parig the flask proper and a cooling contri- vance. L. DE K. Sodium Cobalt Nitrite as a Reagent for Potassium. By J. VAN EYK (Chem. Centr., 1894, i, 1162; from Nederl. Tijdsch. Piiarrn.: 6, 1:36--139).-The sodium cobalt nitrite is prepared b y adding 100 C.C. of a 60 per cent. solution of sodium nitrite to a solution of cobalt nitrate (30 grams) iii water (60 grams). After the evolution of nitric oxide has ceased, the mixture is filtered, and the saltl pre- cipitated with alcohol. By means of this salt, potassium can be detected when diluted to the extent of 1 : 10000. Ammonium salts are also precipitated by the reagent, but not until the concentration reaches 1 in 2000. E. C. R. Assay of Nitre. By A.HELLICH (Chem. Zeit., 1894, 18, 485- 486) .-The author has noticed that commercial nitre often contains perceptible quantities of perchlorates, and consequently should be tested for this impurity. Its presence, which is difficult to account for, has until now been ignored in the various schemes for nitre analysis. L. DE K. Estimation of Mercury in the Presence of Iodine. By FRANGOIS (J. Pharm., 1894, [S], 30, 249--254).-The estimation of mercury when combined in any form with iodine is easily effected by electrolysis. The salt need not be dissolved, but merely placed in the88 ABSTRACTS OF CHEMICAL PAPERS. clectrolysing vessel with the electrolyte. The latter may be dilute sulphuric mid, but the author finds the best electroljte €or this purpose to be formed by dissolving 20 grams of pure ammonium nitrate in concentrated pure ammonia, and making up with the latter to 100 C.C.The electrolysis is carried out in a platinum crucible of which the bottom is connected with the negative pole of the battery (two Bunseii cells). The positive pole is formed by a platinum yod, of which only about 1 mm. dips into the liquid. The mercury is deposifed on the bottom of the crucible. When the action is finished, the solution is removed with a pipette, and the mercury is washed first with water and finally with alcohol, dried, and weighed with the crucible. The iodine in the solution is reduced with sulphurous acid, and estimated as silver iodide. This process may also be used for estimating mercury in the presence of bromine or chlorine. L.T. T. Qualitative Separation of Chromium from Iron and Alumi- nium. By R. B. RIGGS (Amer. J. Xci., 1894, 287, 409--411).-The mixed hydroxides or basic acetates containing about 0.1 gram of each metal are digested in 100 C.C. of water to which 10 C.C. of hydrogen peroxide and 1 gram of sodium hydroxide has been added, until effervescence ceases. After filtering off the iron, the liquid is slightly acidified with acetic acid, and the aluminium precipitated by am- monia. If the filtrate is yellow, this is a sure sign of the presence of chromium, which may, however, be confirmed, for instance, by the well-known hydrogen peroxide test. L. DE K. Apparatus for the Assay of Pyrolusite by Bunsen’s Process. By C. ULLMANN (Chew. Zeit., 1894, 18, 487).-A beaker filled with the requisite amount of solution of potassium iodide is placed on a block of wood of about the same height.In the beaker is placed a special apparatus to collect the chlorine, a kind of upright glass cou- denser, the inner tube of which is drawn out like a pipette, and the top of which is provided with a stopcock and funnel. The tube is filled by drawing out the air through the funnel and then closing the stopcock. The flask containing the sample and R sufficiency of hydro- chloric acid is now connected with a doubly-bent delivery tube pro- vided with a bulb. Heat is applied, and after the bulk of the air has coilected in the apparatus, the chlorine enters, and is, of course, rapidly absorbed by thepotassium iodide. When all the chlorine has been boiled off, the stopcock is opened, and the beaker is placed on the table.After rinsing the apparatus and delivering tube, the liberated iodine is titrated as usual with thiosulphate. L. DIE K. Standardising Potassium Permanganate. By Miss C. F. ROBERTS (Amel.. J. Sci., 1894, 286, 290 --292).-The author recom- mends standardising potassium permanganate by means of a solution of ferrous chloride, made by dissolving a known quantity of electro- 1s tically - prepared metallic iron. About 10 grams of iron ammonium sulphate is dissolved in 150 C.C.ANALYTICAL CHEMISTRY. 89 of water, 5 C.C. of a satuiaated solution of potassium oxalate is added, and the whole is then heated with a sufficiency of ammonium oxalate niitil a clear solution is obtained. This solution is then decomposed in a beaker between two platinum electrodes, the iron being depo- sited on a weighed piece of platinum foil of a size convenient to bc inserted in a rather large weighing bottle.After about 16 hours with a current of 2 amperes, a sufficient amount of metal will have precipi- tated, when it is washed and dried in t.he usual way. Estimation of Iron in the Ash of Vegetable or Animal Matter. By M. RIPPER (Chem. Zeit., 1894,18,133-134).-The ash is dissolved in strong hydrochloric acid, the solution mixed with a few C.C. of hydrogen peroxide, and evaporated to di-yness on the water bath ; the residue is then just moistened with a few drops of hydi*ochloric acid, dissolved in about 20 C.C. of water, and transferred to a beaker. About 1.5 grams of potassium iodide is added, the beaker covered with a watch glass, and heated for 10 minut'es at 60" ; the liberated iodine is then titrated in the usual manner with N/100 sodium thio- sulphate.The process, which hitherto has only been used for the estimakion of fairly large quantities of iron, only occupies one or two hours, and compares favourably with the gravimetric methods. Electrolytic Separation of Iron and Cobalt from Zinc. By G. VORTMANN (Claem. Ccntr., 1894, i, 877 ; see Abstr., 1894, ii, 34).- In separating iron from zinc by the electrolysis of an alkaline tartrate solution, only a single accumulator, giving a current of 0.07-0.1 ampBre, should be used instead of the two formerly recommended ; it then becomes unnecessary to rsdissolve the iron, since it is deposited free from zinc.The electrolysis should be conimenced in the cold, but towards the end a temperature of 50-60" promotes tahe deposition. The cathode (a disc of platinum, silver, or silvered copper, 50 mm. in diameter) should be from time to time replaced by a new one, and the operation continued as long as any gain in weight takes place. After the removal of the iron from the solution, the zinc is deposited by using two accumulators in series, with an E.M.J?. of 4 volts. Cobalt is also better separated from zinc in an alkaline tartrate solution by using 2 volts than by 4. Addition of potassium iodide diminishes the deposition of cobaltic oxide on the anode, but as this cannot be completely prevented the anode must likewise be weighed. The operation is performed as for iron, but with a warm solution.Separation of Arsenic, Tin, or Antimony from Lead, Copper, Silver, Cadmium, Cobalt, Nickel, &c. By P. JAXXASCH (Uer., 1894, 27, 3335-3336).-Elernents, such as arsenic and tin, the chlo- rides of which are comparatively volatile, may be separated from other metals by dissolving the mixture in nitric acid or aqua regia in a special glass vessel, evaporating, and heating the residue at a suit- able temperature in a current of dry hydrogen chloride, the vessel being placed in a nickel air bath, which can be heated up to 450" ; L. DE K. L. DE K. M. J. 8.90 ABSTRACTS OF CHEBIICAL PAPERS. the more volatile chlcrides distil over, and are collected. the apparatus were given in a previcus paper (Abstr., 1894, ii, 330).Action of Organic Matters on Potassium Permanganate. By A. ZEGA (Chem. Zeit., 1894, 18, 2--3).--The author has proved that t,rustworthy, compa'rable results in the titration of organic matters contained in potable waters may be obtained by operating in the following manner. 50 C.C. of the sample is put into a 100 C.C. flask, mixed with 5 C.C. of the usual permanganate solution, 5 C.C. of dilute sulphuric acid (1 : 2) added, and the mixture heated f o r 20 minutes on a water bath ; the excess of permanganate is then titrated back by oxalic acid. The process is particularly useful when the water contains volatile organic matters. The standard permanganate is checked under the Details of C. F. B. same conditions. L. DE K. Analysis of Petroleums. By A. RICHE and G.HALPHEN (J. Pha~m., 1894, [ 5 ] , 30, 289-300).-The object of this work was to end methods for distingixishing (a) between petroleums of Russian and American origin, and ( b ) between crude oils, and mixtures of refined and residual oils. As a rule, the &ussian oils contain less volatile oils and are denser than the American ; €or fractions of the same boiling point, Russian oils are generally denser than American, the mean sp. gr. of t,he fraction 140-160°, for example, being, f o r Russian oils 0.782, and for American 0.755. The refractive indices vary directly with the sp. gr., and so for fractions of the same boiling point are higher for Russian than for American oils. Russian oils are generally poorer in light oils and richer in heavy oils than American, whilst the latter are richer in solid paraffins, and are often rendered turbid by cold from separation of these substances.The American petroleums are generally almost exclusively composed of saturated hydrocarbons, whilst the heavier portions of the Russian oils generally contain hydrocarbons of the CllHsn series. None of these differences are, however, sufficiently certain to form satisfactory bases for analysis. The authors have found the best test to be the solubility of the oils in a mixture of equal volumes of chloroform and alcohol. 4 grams of the refined petroleum t o be tested (of which the density at 15" has already been determined) is introduced into a flask, and the alcohol-chloroform mixture gradually added from a burette until the liquid, which is at first rendered turbid, again becomes clear; the quantity of solution required is then noted.The fractions chosen should be those of about sp. gr. 0.800 to 0.830, as at these densities the difference is most marked. Thus, for sp. gr. 0.820 American refined oils required from 8 to 11 C.C. of the alcohol-chloroform f o r solution, mihe mean being 9.5 c.c., whilst for Russian oils the numbers were 4-3 to 4.8 c.c., giving a mean of 4 5 C.C. F o r crude oils, a much larger amount of solvent is required; Russian crude oils of sp. gr. 0.851 to 0.877 requiring about 15 c.c., whilst refined oils of the same sp. gr. or mixtures of refined oils with about 10 per cent. of residuals, only required from 4 to 5 C.C. WithANALYTICAL OHEMISTRT. 91 Amel-ican crnde oils, of which the sp.gr. varies from 0.788 to 0.822, the solvent required also amounts to about 15 c.c., whilst with the same oils refined, or mixtures of refined with residuals, from 5 to 7 C.C. only are required. A few of the very light American crude oils (of about 0.785 sp. gr.) require much less of the solvent. F~dl tables and curves of solubility are given in the paper, and a special form of burette for keeping the alcohol-chloroform out of contact with the air is described. L. T. T. Assay of Ethereal Oils. By J. KLIMOXT (Chem. Zeit., 1894, 18, 641-642 ; 672--673).-The author's process is based on the fact that ethereal oils react strongly with bromine, whilst paraffin oil gives scarcely any reaction. For the assay of oil of turpentine, for instance, the following reagents are required.Solution of bromine in chloi~oform of about 1 per cent. strength ; pure chloroform, treated with strong sulphuric acid, washed, and redistilled ; pure tnrpent'ine, made by first washing oil of turpentine with aqueous soda, and after- wards collecting the fraction distilling over at 168-170'. 0.5 C.C. of this is put into a, stoppered 20 C.C. flask and accurately weighed; chloroform is then poured in up to the mark, and the solution put into ;t little burette. 10 C.C. of the bromine solution is introduced into another little flask, and the turpentine solution slowly added until the colonr of the bromine has entirely disappeared. If now a sus- pected sample of turpentine is at once treated in the same way as the pure specimen, its lesser bromine-decolorising power will indi- cate a more or less marked adulteration.The author has tabulated the results of experiments with almost every known ethereal oil, including 9 specimens of refined turpentine and 11 of inferior brands ; also experiments with adulterants, such as resin oil and petroleum. The figures given are not bromine numbers, but represent the equivalent amount of turpentine. L. DE K. Detection of Methylated Spirit in Tinctures, &c. By A. ASHBY (Analyst, 19, 261-271) .-The author has sat,isfied himself that, of the numerous methods proposed, the test with sodium nitro- prusside in the presence of ammonia is the best. The red colour will appear within 10 or 15 minutes. The constituent the reaction is chiefly due to has yet to be ascertained.When examining alcoholic liquids free from solid matter, the test may be applied directly by mixing the sample with an equal bulk of it 1 per cent. solution of sodium nitroprusside and adding a few drops of ammonia; but in the case of officinal tinctures, 25 C.C. of the sample is distilled, and the first 5 C.C. which pass over tested. Ethereal solutions are distilled to dryness, and successive portions of the distil- late are tested; if, however, the sample is very weak in spirit, it is best to add 2 or 3 C.C. of' strong, pure alcohol to the distillate before applying the test. If the not very probable presence of a sulphide be suspected, it is best to add some fixed alkali before distilling. Gravimetric Estimation of Sugar by means of Alkaline Copper Solutions.By L. GRUNHUT (Chew,. Zeit., 1894,18,447- L. DE K.92 ABSTRACTS OF CHEMICAL PAPERS. 448) .-Owing to the great difliculty of completely oxidising cuprous oxide, the results obtained by weighing the copper oxide are often much too low ; weighing as cuprous oxide on a filter has also its dis- advantages. The author strongly recommends the process wherein the cuproEs oxide is collected on a, weighed asbestos filter contained in a glass tube. After first igniting in a current of air to burn off organic matters, the oxide is reduced in a current of dry hydrogen and the residual metal finally weighed. L. DE K. Gravimetric Estimation of Glucose. By F. GAUD (Compf. rend., 119, 478-479).-50 C.C. of the freshly-prepared alkaline copper solution is mixed with an equal volume of water, boiled for :L few minutes in a porcelain dish, and then placed on a water bath, the water in which is boiling; 25 C.C.of the sugar solution, contain- ing about 1 per cent. of glucose, is then added all at once. Re- duction under these circumstances takes place below loo", a con- dition which is essential to prevent the destructive action of the alkali on the glucose. After 10 minutes, reduction being complete, the liquid, which should have a deep blue colour, is decanted off, and the precipitate is washed with boiled water until the washings are no longer alkaline to phenolphthalein. The precipitate is then transferred to a sp. gr. bottle holding 20 to 25 c.c., the capacity of which a t 0" is known, and the bottle is filled up to the mark with boiled water and weighed at a temperature t .Let P be the weight of the liquid and precipitate, the total volumc of which is equal to the capacity of the flask at the temperature f , that is t o say, Vt = V,[1 + 3P(t - to)]. The sp. gr. of dried cuprous oxide is A = 5.881, and the sp. gr., d, of water at the temperature t is known ; then the weight p of cuprous oxide is given by the expres- sion P - V t d p = - 1 - d / A . To obtain perfect results, the weight P should be reduced to a vacuum. The change in the sp. gr. of cuprous oxide caused by ordinary changes of temperature is too small to affect the result. The weight of cuprous oxide is not strictly proportional to thc weight of glucose present, and it is necessary t o prepare a table showing the relation between various values of the two numbers.' h e author obtained the following results. Cuprous oxide. Glucose. Cuprous oxide. Glucose. Milligram& Milligrams. Milligranis. Milligrams. 10 5.413 100 46.22 20 9-761 200 91.047 30 14.197 300 138.842 50 23.036 400 188.928 C. H. B. Modification of the Copper Test for Glucose. By ALLEIN and E'. GAUD (J. Phurm., 1894, [ 5 ] , 30, 305--307).-The authors findANALTTICAL OHPhlISTRY. 93 (this vol., i, 123) that the free potash 01’ soda in Fehling solution causes the decomposition of a part of the glucose to be estimated, and thus causes the lorn results known to be obtained by that method. The following solution gives results free from this error. 8.7916 grams of pure (electrically deposited) copper is dissolved in 93 grams of sulphuric acid, the solution is diluted with its own volume of water, and the whole made up to 1000 C.C.with strong ammonia. A deep blue solution is thus obtained, which is perfectly stable, and of which 10 C.C. corresponds with 0.05 gram of glucose. The estimation is con- ducted in a flask fitted with a triple-bored cork to admit the end of the burette containing the glucose solution and tubes for passing a current of hydrogen. 10 C.C. of the amraonio-copper solution and 10 C.C. of ammonia are introduced into the flask on a, water bath, and heated to about 80°, amd the liquid containing the glucose is then added drop by drop until the solution becomes colourless. If desired, the solution may be reoxidised (by substituting a stream of air for that of hydrogen as long as the reproduced blue colour deepens) and a second estimation be then performed, The cuprous oxide dis- solving in the ammonia to a clear, colourless solution, renders the end of the reaction very sharp and exact.Note.--No reference is made to the earlier processes of Pavy and others, in which ammoniacal copper solutions are employed.-EDrroRs. Estimation of Crystallisable Sugar in Raw Sugars. By M, KARCZ (Clzem. Centr., 1894, 17, 845-846 ; from Zeit. Zuck. Ind., 23, 21--24).-Thirty or fifty grams of the sample is mixed in a dish with an equal weight of absolute glycerol, and placed for some time iii a desiccator. The glycerol soon dissolves the adhering syrup, but leaves the crystals intact. After pouring the glycerol into a giass funnel filled with cotton wool, and provided with a cover containing a calciiim chloride tube, an aliquot part of the filtrate is examined in the polariscope.The polarisation deducted from that of the original raw sugar gives the amount of crystallisable cane sugar in the sample. L. DE K. Estimation of Cane Sugar in Beer Wort. By K. AMTHOR (Chern. Centr., 1894, i, 932-933 ; from Zeit. Nahi-uiiy.smittelunters. Hygiene, 8, 80--81).-A criticism of Jais’ process (Abstr., 1894, ii, 123). Whereas Jais, in estimating the nialtose and inverted sugar, boils for only two minutes, the reduction tables are constructed for an ebulIition of four minutes, which yields higher results. Moreover, the hydrochloric acid used attacks constituents of the wort other t.han cane sugar, and augments their reducing power.(Chein. Zeit., 1694, 18, 748).--Twenty to thirty grams of the sample is rubbed with 250 C.C. of water, and mixed with excess of a soluticli of iodine in potassium iodide ; the starch combines with the iodine, and forms a corn paratively heavy compound, which settles long before any appreciable quantity of yeast has gone down. The milky liquid is syphoned off, and the iodide of starch repeatedly lixiviated L. T. T. M. J. S. Estimation of Starch in Compressed Yeast. By F. FILSINC~E~;94 ABSTRACTS OF CHEMICAL PAPERS, with water until all the yeast cells have been removed. The starch is finally collected on a weighed filter, dried at 105", and weighed. The iodine is practically expelled during the heating. In calculating the percentage, it must be remembered that commercial potato starch generally contains 15 per cent.of water. The test analyses are very satisfactory. When, however, the amount of starch is below 10 per cent., the results will be somewhat too low. L. DE K. Estimation of Carbohydrates. By E. SCHULZE (Chem. Zeit., 1694,18,527-528) .-The author points out that if carbohydrates, on boiling with dilute sulphuric acid, yield other products besides dextrose, the action of the acid should not be unduly prolonged. If a mixture of carbohydrates be inverted, it is almost impossible to get a good result, as some of them may already have become largely decomposed before the inversion of the others is anything like com- plete. L. DE K. Separation of Uric acid, Adenine, and Hypoxanthine.By M. KR~GEK. (Zeit. physiol. Chenz., 1894, 20, 170--175).-1n a hot solution containing the three substances, copper sulphate and sodium thiosulphate precipitate only adenine and hypoxanthine. I n a cold solution of these two substances, the same reagents precipitate adenine only. W. D. H. Estimation of Xmthine-like Substances in Urine, By M. KR~GER and C. WULYF (Zeit. physiol. Chem., 1894, 20, 176-185).- The new name alloxuric substances is suggested for those of the uric acid group. The alloxuric bases which occur i n small quantities in urine are xanthine, guanine, hypoxanthine, carnine, paraxanthine, and heteroxanthine ; a specific reagent for their precipitation is a mixture of copper sulphate with sodium hydrogen sulphite, but it also precipi- tates uric acid.100 C.C. of urine is precipitated with 10 C.C. of these reagents, and the precipitate allowed t o collect for two hours. Uric acid is separately determined in another sample of urine. The absolute amount of the nitrogen in this precipitate varies from 2.6 to 8 milligrams per 100 C.C. of urine, the average being 4.53. The proportion of uric acid nitrogen to the nitrogen of the allox- uric bases varies from 2.1 : 1 t o 7.6 : 1. The mean of 19 analyses gives 3-82 : 1. The average uric acid nitrogen in the 24 hours is 0.2333 gram ; and of nitrogen in alloxuric bases, 0.0481 gram. Estimation of Acidity in Milk. By &I. SCHAPFER (Staz. Sper. Agrar., 1894, 26, 164-167 ; from Bent. BZGttey j". Landw.).-The apparatus used in the method described, which is a modification of the Soxhlet-Henkel method, consists of two cylindrical bulbs connected by a naryow graduated tube.The lower bulb holds just 50 c.c., and is provided at its lower end with a small bulb, holding 2 C.C. The upper of the two large bulbs is of about the same size 8s the lower, and is stoppered. I n making a determination, 3 C.C. of phenolphthale'in aolutiori is poured into the apparatus (filling the W. D. H.ANALYT tCAL CHEMISTRY. 95 lowest poi*tion of the apparatus), then the milk to be examined, until i t reaches the 50 C.C. mark, and lastly, 4 normal soda solution (2-2-5 c.c.). The apparatus is then corked, and the contents mixed. More soda is gradually added until alkalinity is produced, The amount of alkali added is read off in the narrow tube. I n mixing the alkali, the apparatus niust not be shaken (as froth would be pro- duced), but so inclined that the liquid runs into the upper bulb.The method is of use in ascertaining whethei. milk is sufficiently free from acid to keep. It will probably also be of use in test,ing milk intended for cheese-making, and will furnish evidence of milk having been more or less skimmed (since milk slways becomes more acid when left at rest), and the presence of such milk as an adult era11 t. N. H. J. &I. Soxhlet’s Areometric Estimation of Fat in Milk. By H. TIXPE (Chem. Zeit., 1894, 18, 392-394) .-This deservedly popular process has one great inconvenience, namely, that the ether sometimes refuses to properly separate from the alkaline solution, so that only a small amouiit can be drawn off.The author now recommends that the sample zf milk should first, be diluted with three volumes of water. The ethereal layer then separates with the greatest ease. L. DE K. Loss of Total Solids in Milk on Keeping. By E. J. BWAK (Analyst, 19, 241--244).-The author accidentally noticed that milk placed in the usual weighing dishes will, if not soon evaporated, yield a residue which may be as much as 1 per cent. too low. If imme- diately before evaporation the milk is cnref ully neutralised with K/lO soda, the loss will not be so great, owing to tho formation of a stable lactate. Contrary to Bell’s statement, the author fhds lactic acid to be sensibly volatile in the preseace of water. The results of several experiments are tabulated, and show the disproportion between the acidity and the loss in total solids.L. DE I(. Periodic Estimation of Volatile Fatty Acids in the Butter produced during a Year. By L. CAMTONI and L. CARCANO ( S t a ~ . Sper. Agrar., 1894, 26,131-137) .-With the view of ascertaining the causes of the variations in the amount of volatile fatty acids in butter, samples of butter from three dairies were examined weekly for a year. The results, which are given in tables, do not show any great differ- ences or regularity. This is, perhaps, due to the fact that in the Lombardy dairies calving does not take place at definite periods, and a kind of compensation may thus take place between conditions which raise and lower respectively the amount of volatile fatty acids. A table is also given showing the results of experiments with Zeiss’ butter-refractometer as well as the vol;tt.ile fatty acids.Modification of the Reichert-Meissl Butter Process. By C. BGXTE (Clzem. Zeit., 1894, 18, 204--206).-The author criticises the sulphuric acid process lately proposed by Kreiss and modified by N. H. J. M.96 ABSTRACTS OF CHEMICAL PAPER& others, and has finally adopted the following plan. 5 grains of hutter-fat is introduced into an Erlenmeyer litre flask, and heated for H time in a drying oven at 100"; 10 C.C. of sulphuric acid (sp. gr. 1-8;%5) is added, and the mixture well agitated until all the fat has dissolved. The flask is now put into water at 30-32" for 10 minutes ; 150 C.C. of water is added, and then strong solution of potassium permanganate until the liquid acquires a transitory pink colour.'l'he liquid is then subjected to the usual distillation and titration. L. DE K. Estimation of Lecithin in Plants. By I!!. SCHULZS (Zeit. physiol. Chem., 1894, 20,225-232, 252).-A critical reply to v. Bitto in reference to his method (Abstr., 1894, ii, 402). Analysis of India-rubber Wares. By R. HENRKJUES (C7Leu). Zeit., 1894, 18, 411412, 441-444; compare Abstr., 1892, ii, 399). -The author gives further instructions for the analysis of rubber wares. Adulteration with fatty matter or fatty surrogate (falctis) may be detected by treating a weighed quantity of the sample with alcoliolic soda, as previously described, and noticing the loss in weight. If the sample contains much added mineral matter, it is best to first treat i t with moderately strong acid before boiling with the alkali ; as the latter dissolves small quantities of rubber, a correction must be made by deducting from the weight of the surrogate a quantity cor- responding with 2.5 per cent. of the rubber actually found ; soluble sulphur is, of course, allowed for. Asphalt, whether true bitumen or the artificial product, is another adulterant. In the absence of surrogate, 1 grnm of the finely-divided sample is soaked for an hour in 30 C.C. of nitrobenzene. The insoluble mass is thrown upon a filter, gently pressed with a small pestle, and further washed with another 30 C.C. of the solvent; the mass is then transferred by means of a wash- bottle to a porcelain dish and boiled with water until all odour of nitrobenzene has disappeared; it is then dried and weighed. As rubber is not altogether insoluble in nitrobenzene, a correction must be made by deducting 2.5 per cent. from the asphalt for true rubber dissolved ; soluble sulphur must also be allowed for. If the sample contains also oil surrogate, this muat be first removed by treatment with alkali, in which asphalt is practically insoluble. The process becomes still more complicated if, besides asphalt, lamp-black is also present ; this withstands the action of all ordinary solvents, and re- mains in consequence with the rubber. The author has found that in pure rubber there is a fairly constant atomic relation between the hydro- gen and the carbon, which may be taken as 16 : 10. The residue containing the rubber + thelamp-black is therefore submitted t o an organic combustion, and any excess of carbon put down to lamp- black. The test analyses given by the author are remarkably satisfactory cousidering the nature of the analysis. The procass does not, as get, W. D. H. provide for i\r host of other possible adulterants. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA8956805084

出版商:RSC    

年代:1895

数据来源: RSC

摘要:

97 General and Physical Chemistry. Indices of Refraction of Solutions of Sulphur and Phos- phorus in Carbon Disulphide. By V. BERGHOFF (Zeit. physikal. Chem., 1894, 15, 422-436) .-The indices of refraction of solutions of sulphur in carbon bisulphide for sodium l i g h t were determined ab two different temperatures, 3.5" niid 22.7". The results are contained in the following table, the first column of which gives the concen- tmtions of the sollitions as the number of pwtr by weight of sulphur contained in 100 parts of carbon bisulphide. 1a3.j. q?:z.p Diff. for 1". itlj cal. 0 1.64143 1 *62522 8443 1.63172 5 1.65153 1.63668 7735 1.64264 10 1,66175 1.64704 7662 1.65294 15 1.671iO 1.65772 '7281 1.66335 20 1.68105 2.66643 7 647 1.67232 25 1.69073 1.67564 7s 60 1.65169 Solutions of phosphorus in carbon bisul phide were examined only at 20 7".The numbers obtained were as follows, Conc. ?Zr'o.;. 0 1.62697 5 1.64012 10 1.65226 15 1.66517 20 1-67628 25 1.68646 ( u - l)/d, but not for (n? - l)/d(n? + 2). have little or no influence on the values of ( R ! - I)/(.?. Tho sulphur solutions give constant vdiies for the expression Tempcraturc appears t o H. C. Saturated Hydrocarbons containing the Active Amy1 Radicle. By Miss I. WELT (Coinpt. y e i d . , 11.9: 743-747).-Ethy1- ainyl, propylsniyl, isobutylamyl, and diamyl were prepared by the action of sodium on mixtures of the appropriate alkylic iodides. When necessary, corrections were iiiade for the small quantities of allcglic iodides present in the hydrocarbon. The rotatory powers are as follows. LON temperatnrr.High temperature. r-JL- 7 c;--- 7 t . [alu. CUID. Hthylamyl.. . . . 17" + 6.23 t o + 6.43 60" + 6.09 Propylarnyl . . . 16 + 6-44 54 + 6-23 Tsobutylamyl .. 20 + 5.88 51 + 5.66 Diamyl.. .. . . .. 21 +12*08 7s + 12-06 VOL. LXVIII. i i 8 - Diainyl . . , . .. . 17 +11.95 __98 ABSTRACTS OF CHEMICAL PAPERS. All the hydrocarbons are dextrogyrate, and the rotatory power is only slightly affected by the temperatwe, although it tends to diminish. I n the case of t'he hydrocarbons containing one asymmetric carbon, the rotatory power passes through a maximum, the exact position of which is not yet determined, alt,hough the calculated maximum corresponds with pentylsmyl. The rotatory power of diamyl is nearly double that of the hydrocarbons containing only one amyl group, which is in agreement with the views of Guye and Gautier.C. H. B. Attempts to Resolve Unsaturated Compounds into Optically Active Constituents. By A. LE BEL (Bull. SOC. Chim., 1894, [3], 11, 292-295) .-The fact that the naturally occurring ethylene deriva- tives are optically inactive has tended hitherto to divert inquiry from the possibility of theii? activity. It is quite feasible, however, that by substituting sufficiently heavy groups for two of the hyrdro- gen atoms in the ethylene molecule the latter might be caused to suffer sufficient deformation to gire rise to such activity. A some- what analogous case occurs in the series of diamine platinochlorid es, the crystalline forms of which undergo modification as the molecular weight increases, this modification being probably due to internal stereometric rearrangement of the molecules.The results of experiment, however, fail to confirm any such sup- position. Both allylic alcohol and ammonium a-crotonate (from 0-hydroxybutyric acid) fail to show any signs of differentiation into optically active modifications when used as culture-media for moulds. Male'ic and fumaric acids also yield practically inactive products. Mesaconic and citraconic acids at first seemed to give decisive evidence in favour of the theory, as the former yielded a dextro- gyrate, the latter a laevogyrate, product when subjected to the above- mentioned process. In one experiment, 400 grams of citraconic acid i n weak aqueous solution (0.2 per cent.) yielded a product, the methylic salt of which proved to be distinctly laevogyrate.As, horn- ever, the activity was found to reside in the least volatile portion, it was probably due t o an impurity, and on repenting the experiment with slight modificatioiis on a larger quantity (1400 grams), the impurity was isolated as a liquid which boiled at about 140", and gave rise to a, rotation of -10" pel' 10 cin. It proved on analysis to be methylic nzethylnzntate, COOMe*CHMe*CH(OH)*C OOMe, formed by hydration of the citraconate. The more volatile portion was also active, but proved on analFsis to consist of a mixture of the citraco- nate and methylmalate. The results of the experiments with mesa- conic and citraconic acids must, therefore, also be taken LLS negative, and the molecules of the simpler of the ethylene derivatives, at all events, must continue to be represented by plane formulz.JN. w. Rotatory Powers of Disubstituted Alkylic Tartrates. By P. FREUNDLEK (Bd. Snc. Chinz., 1894, [3], 11, 305-3 17).-See this vol., i, 173.GENERAL AND PHYSICAL CHEMISTRY. 99 Determination of the Molecular Weight of Liquids. Bg P. A. GUYE (Comnpt. rend., 1894, 119, 852-S54).-The ratio of the molecular refraction to the critical coefficient (absolute critical tem- peraAnre divided by the critical pressure) should theoretically be about 1.8. On the other hand, the quantityf given by the equation where p , and T, are the critical pressure and absolute critical tem- perature, and p and T any other pressure and corresponding tempcra- ture, should have the value 2.8 to 3.1 if the molecule in the liquid state is of the same weight as the molecule at the critical point, or the value 3.2 to 4.1 if polymerisation has taken place.The author has calculated the values of the above two quantities for a number of liquid hydrocarbons, and comes to thg conclusion that these have the same moleculaib weight in the liquid as in the gaseous state. Scientific Electro-chemistry of the Present, and Technical Electro-chemistry of the Future. By W. OSTWALD (Zeit. physikal. Ciiem., 1894,15,409-42l).-A popular address to the German Electro- technical Association. The author deals with the modern theories of electro-chemistry, and points to technical improvements for the future, more particularly in the construction of secondary batteries, and the direct conversion of the energy of burning coal into electricity.Thermoelectric Properties of Pure Metals. By I(. NOLL (Ann. Phys. Chem., 1894, [2], 53, 874--911).-Owing to considerable dif- ferences between the observations of different workers on the thermo- electric properties of metals, the author redetermines the electromotive force for various combinations, employing metals in as high a state of purity as was obtainable. In the first series of experiments, the second metal was in all cases mercury, and the temperatures of the junctions 100" and 0". The EMF. was determined by Du Bois Raymond's modification of Poggendorf's methods, Clarke cells being employed as the source of the constant E.M.F. The results of these researches (expressed in microvolts) are contained in the following table, + values indicating a current from mercury to metal at the hot junction.H. C. H. C. Bismuth.. ..... - 67054 Nickel ........ -1664.2 Cobalt ........ -1522.3 Nickel silver. .. - 1085.2 Platinum.. .... + 4.59 Aluminium.. .. + 362.4 Magnesium.. .. + 391.89 Tin. .......... + 396.03 Lead ......... + 402.5 Brass. ........ + 443.31 Carbon rod.. .... Silver .......... Gold ........... Copper.. ....... Zinc ........... Cadmium ....... Carbon filament . Iron.. .......... Piano wire ...... Antimony. ...... + 662.88 + 710.25 + 71335 + 725.58 + 692.71 + 875.09 + 1452 + 1601.4 + 1732.3 + 3379-6 I n many cases the effect of small quantities of impurity was very Thus platinum gave values as high as +593*88, and copper great. 8-2100 ABSTRACTS OF CHEMICAL PAPERS.as low as +684*29 when the metals were not chemically pure. The state of aggregation had also a marked effect i n some cases, for instance, silver (710.25 ; 671*51), zinc (692.71 ; 335*2), iron, brass, nickel. The second series of experiments was performed at varioiis temperatures between 217" and O", a number of experiments being made in each case. From the results? the value for 100--Oo was calculated, good agreement with the observed value being in all cases obtained. The junctions were in some cases formed with mercury, in others with copper. The electromotive force is given according to Gaugain by formula E = (tl - tz)(Z, f c(tl + t z ) ) . The values for b and c are deduced from two experiments, and the results calculated by their aid compared with tbe observations.The agreement is per- dc fectly satisfactory. The value 2 = b f ct is then calculated, and as this can be expressed as b =fs (kz - k,) t, where 16, and 16, are the constants for the different metals of the junction, the numbers are referred to lead for which 7; = 0. The valnes thus obtained for the thermoelectric power -- are compared with those of other observers. The difference in the result may be explained by the effect of impurities which, as is evident from the numbers, produce considerable variations. L. hl. J. da dt Conductivity of Aqueous Solutions of Carbonic Anhydride. By W. E'. KNOX (Ann. Phys. Chem., 1894, Cd], 54, 44-571.- Kohlrausch's method was employed for the determination of the conductivity, and a number of experiments at varying pressures were made, the results being recorded for both rising and falling pres- sures.As the temperature was not constant, varying to the extent of about a degree, the results were reduced to coristant temperature by useof the formula = ;t + 7.:- cQ ct , where Q is the quantity of dk sk 8k aQ dk I sk carbonic anhydride dissolved. This reduced to J; = F; -- T~ . d t 4- sQ . dt. The value for the latter term is found to be -0.0169 a t m'st 155 and -0.0099 at 18", and for the former 0.0300 and 0.0257 for the same temperatures, which are those to which the results are reduced. Tables are then given of the reduced numbers, corrections being also made for the condnctivity of pure water. If rn is the equivalent (6COJ content per litre, then kl l/& should be approximately constant.The value for this expression is determined, a variation of from 121 t o 139 being observed a t 12.5", and of from 144 t o 159 at 18" ; the value form, however, varying between 0.002 and 0.2. If also the value for the most dilute solution is neglected, the numbers a t 18" oiily vary between 147 and 144. The time taken to saturate water by passing a stream of carbonic anhydride through it was also observed, together with the time required to free it from the gas by a current of air. In the latter case the curve of decrease of saturation is approximately logarithmic. The author points out that the increase in conductivity of pure wat'erGENERAL AND PHYSICAL CEEMISTRY. 101 when exposed to the air is probably due to thc solution of carbonic anhydride (compare ,4bstr., 1894, ii, 375).By W. LOUGUININE (Compf. m2d., 1894, 119, 601--604) .-The alcohols were carefully purified, and precautions were taken to exclude moistura at every stage of the operations. The method adopted was similar to that of Regnanlk, but only 100 C.C. of liquid was employed. The differences between the author’s results and those of previous observers, is probably due to the care taken to exclnde moisture. In the case of isopropylic alcohol and isobutylic alcohol, it was assumed that the specific heat of the liquid is the same as f o r the correspond- ing normal alcohol, and that the specific heat of dimethylethgl- carbinol is the same RS that of fermentation amylic alcohol. The results are as follows, the determinations being made under a pressure of 54.5-755 nim.L. M. J . Heat of Vaporisation of Saturated Fatty Alcohols. Ethylic alcohol ............... 201.42 cal. Isopropylic alcohol. ........... 159.72 ,, Isobutylic alcohol ............. 136.16 .. Diniethyle thylcarbinol. ........ 110.37 , . Normal propylic alcohol ....... 164.07 ,, Normal butylic alcohol ........ 138.18 ,, Amylic alcohol (fermentation). . 118.15 ,, C. H. B. Trouton’s Law and the Saturated Fatty Alcohols. By W. T,OCGUINIXE (Compt. y e i d . , 1694, 119, 645-647) .-Trouton’s law, that the product of the moleculai. weights of substances into their latent heats of vaporisation, divided by their boiling points in absolute temperature, is a constant qnantity, holds good for the saturated alcohols of tbe fatty series (compare preceding Abstract).MY Ethjlic alcohol ............... 46 78.3” 201.42 26.37 51. t. 9.. T?’ Propylic alcohol.. ............. 60 96.96 164.07 26-61 Isopropylic alcohol ............. -60 S2.19 159.72 26-98 Eutylic alcohol ................ 74 116.48 138.18 26% Isobutylic alcohol .............. 74 107.67 136.16 26.47 Amylic alcohol (feimicnt:ttion). .. St; 130.06 118.15 25.iY Dimethylethylcarbiiiol .......... 85 103.08 110.37 25-90 The boiling points correspond with n pressure of about 750 mni. ancl the mean value of the constant is 26.34. Schiff’s results with ethereal salts of the acetic series give about 21,nnd for the hydrocarbons of the benzene series about 20. The results of Berthelot and O@&r with formic ancl acetic acids give different values, but in these cases the vnpoiir is not normal.If, however, the values for normal vapour are taken, the constant beconies 25.9 for acetic acid. It follows that the MY value of the constmt r remairis practically constant for a given 1 + t series of compounds, although it varies from cne series to another. Tronton’s empirical law is therefore capable of wide and important102 ABSTRAOTS OF CHEMICAL PAPERS. application, and makes it possible t,o calculate the latent heats of vapori- sation of a whole series of compounds, if the ralue for one of them is known. C. H. B. Heat of Combustion of Glycogen. By P. STOHJIANN and R. SCHMIDT (J. p. Chem., 1894, [Z], 50, 385--387).-The glycogen employed was extracted from the liver of a rabbit by means of water, no alkali being used.After purification by precipitation with alcohol in the presence of hydrochloric acid and potassium mercury iodide, it was dried, extracted with ether to remove a small amount of fat, and then again dried at 120". Ignition was ensured by the addition of a small piece of collodion. The following table shows the results obtained, compared with the corresponding data for cellulose and starch . Heat of combustion. 7 r-,--h----. Per gm. cal. Per gm. mol. Cal. Glycogen. ....... 4 190.6 6 78-9 Cellulose ........ 4185.4 678-0 S farch .......... 41 82.5 677.5 The heat of formation of glycogen is therefore 230.1 Cal. Thermochemistry of the Isomeric Acids of the Composition C,H,O, and CSH8O3. By F. STOHMANN and H. LANGBEIN ( J . pr. Cham., 1894, [ 21, 50, 388-400) .-The following table contains the heats of combustion and formation of a number of these acids, com- pared with their electrical conductivity, as determined by Ostwald and others. A.H, Heat of Heat of Electrical combustion. formation. conductivity. Cal. Cal. k. Hydroxybenzoic acid [ortho] ... 727.1 137.9 0.102 > .. [meta].. .. 726% 138.4 0.0087 99 ,, [para] . 725.9 139.1 0.00286 3, ,) [ 1 : 3 :2].. 879.3 148.7 0.1 018 9 ) ,, [l: 5: 21.. 880.1 147.9 0.00841 Hjdroxytoluic acid [COOH : Me : OH = 1 : 2 : 61.. 883.4 144.6 0.106 ,, [l : 4 : 2 j . . 878.4 149.9 0.06S4 Nandelic acid.. .............. 890.9 137.1 0.041 7 Phenoxyacetic acid.. .......... 903.3 124.7 0.0756 Orthohydroxymethylbenzoic acid [COOH : CH2*OH = 1 : 21.. .. 887% 142.2 0.015 Phthalide..74.3 - .................. 884.7 It appears that both heat of combustion and electrical conductivity are greatest for the ortho-acids and least for the para-acids. Taking the heat of combustion of benzoic acid as 771.7, and of the toluic acids as 929.4 (ortho), 929.1 (meta), and 927.4 (para), it follows that the substitution of hydroxyl f o r hydrogen in benzoic acid Auisic &id [OMe : COOH = 1 : 41 895.2 132.8 0.0032GENERAL AND PHYSICAL CHE3lISTRY. 103 diminishes the hcnt of conilmstion hy 44% (ortho), 45.1 (meta), and 45.8 (para) Cal., whilst in the toliiic acid series the numbers vary from 46-49.8 Cal. The substitution of inethyl for hydrogen, on the other hand, increases the heat of formation by the following amounts. Benzoic acid, ortho ............157.7 Cnl. ............ 9 : nietn 157.4 ,, 7 9 para.. 135.7 ,, Salicylic acid, Me = 6 . . ........ 156.3 ,, 9 9 Me = 3 . . ........ 152.2 ,, 7 Jfe = 5 . . 153.0 ?, 7 , lvIe = 4.. 151.3 ,, ............ ........ ........ 'rhc substitution of inethyl for hydrogen, Iiowever, gives rise t o different yesults, according as this hydrogen atom is combined with carbon, uitrogen, or oxygen. The same relations hold with the group CH,*COOH, so that it may be concluded that a carbon atom which combines with a nitrogen atom requires an amount of energy equal to 10-12 Cal., and one which coinbines with an oxygen atom 15-20 Cal. more than one which combines with another carbon atom. The actual values obtained \\-ere CH:,. CI&.COOH. With C ............... 156.6 Gal.150.9 Cal. ,, N .............. 166.6 ,, 169.7 ,, ,, 0 . . ............ 171.7 ,, i7o.a ,, By means of these iiuiiibers, the heats of foriiiation of the varions acids can be approximately calculated from those of the simpler acids from which i'hey are derived by substitution. A. H. Mercuric Sulphates. By 1%. Vaiiil:~ (Compf. Tend., 1894, 119, 684-687) .--The heat of dissolution of mercuric snlphate in dilute sulphuric acid is +4*35 Cal. at 16.5", and +4.90 Cal. at 14". Neasureinent of the heat developed by the action of hydrochloric acid on mei*curic sulphate, snl pliuric acid on mercuric chloride, hydrocyanic acid on mercuric sulphate and sulphuric acid on mer- curic cyanide, sulphuric acid and sodium chloride on mercuric sul- phate, and other similar reactions gim, as a mean value HgO ppt.+ H,SO, dil. = HgSOr dim HgO ppt. + H,S04 liq. nnhyd. = HgSO, + H,O liq. ....................... develops + 2.6 Cal. sol. + H,O liq ..................... ,, + 19.6 ,, HgO ppt. + SO, solid = HgSOI solid.. 9 , + 40.1 9 , solid ............................. ,) +166-1 y 7 Hg liq. + S solid + O4 gqs = HgSO4 The dissolution of basic niercuric sulphate in dilute sulphuric acid develops +9.1 Cal., and reactions similar t o those employed in the case of the normal sulphate give the following resuit.104 ABSTRACTS OF UHEMICAL PAPERS. 3Hg0 ppt.. + H2S02 dil. = ;3HgO,SO3 sol. + H20 liq ..................... develops +13*38 Ca1- HgSOd SO]. + 28gO l)pt. = 3HgO,SO3 solid ............................. 9 , +10*78 ,, The action of a 1arge quantity OF water on n o ~ ~ x a l merciuric snlphate does not r t d t in its complete conversion into tlle basic sulpliate, owing to the siniultaiieons formation of an acid suiphate.with development of heat. The niasinium thermal disturbance COY- responds with the formation of a solution containing sulphuric acftI, and saturaked with the basic snlphnte. Sulphuric acid is completely displaced from mercuric sulpliate by even very dilute hydrocpnic acid, and is also disp!ncecl alruost, if not quite, completely by hydro- chloric acid. C. H. R. Relation between the Vapour Pressures of a Substance in the Solid and Liquid State. BJ- A. PONSOT (Conapt. rend., 1894, 119, 791-794).-l'he nnthor has formerly shown that for ice and water RT log F - -= ELK(Ttl t,, - T) - (C, - C f P and f being the nipour tcmioiis at T, 7,, the latent heat of fusion a t To, the temperatui.e of the triple point., C, and C, the specific heats of water and of icc.Tliis relationship is now shown to hold good in the cases of benzene and acetic acid. H. C. The Absorption Coefficients of Carbonic Anhydride and Hydrogen Sulphide in Water at the Freezing Point. By K. PWTZ and H. HOLW (Am. Phys. Chent., 1894, [2], 54, 150-138).-- If a current of gas be passed through pounded ice, the temperature sinks to that of the frcezing point of a saturated aqueous solution of tlte gas, which may be calculated by the usual foymnlae. For carbonic anhydride and hydrogen sulphide, the authors find the depressions to be respectively 0.156'' and 0.302", the calculated numbers being 0-158 and 0.377. The absorption coelffcieiits were then determined, both at zero and at the freezing point of the solution.The method consisted in passing a streairi of tlie gas through (or addition of solid carbonic. anhydride to) the water contained in a flask ; finding the quantity of gas contained by weighings, a n d correcting f o r that above the liqiiid by measurement of maiionietric pressure. Corrections are made f 0 1 small quantities of foreign gases unavoidably present. For carbonic anhydride a t O", they obtained the value 1.7308, and a t -0.15" 1-7375. whilst hydrogcii sulphide gare tlie value g o = 4.6'796. Buiiseii found a d u e no = 1.796i f o r the former gas, but this was obtaitied by extrapolation, tkie lowest observed temperature being 4.4'.Henrich obtained the value 1.7326 (Abstr., 1892, 1044). The value 4.6796 also is considerably higher than that found by Schonfeld and Carius for the same gas; this the authors consider is due to the fact that these obseryms did not use completely saturated solutions. L. 35. J.GENERAL AND PHYSICAL CHEMISTRY. 105 New Reaction Illustrating the Phenomenon of Dissociation. By A. GUNS (C'laenz. iVTcz(;~c, 1894, 70, 223--224j.-When nmn~or~ia (sp. gr. O*SSO) is added, drop by drop, t o cz soltition containing 0.2 gram of zinc sulphate in 5 C.C. of water, until i t is 1 or 2 drops in excess of tlie qnant,ity rcquirecl to re-dissolve tlie precipitate, aiid 10 or 12 drops of a 10 per cent. solution of sodium phosphate and 5 C.C. of water are also added, a perfectly bright solution is obtained, whiclr on heating acquires a turbidity that increases to a thick curdy pre- cipitate in the boiling liquid ; the mixture, however, regaii;s its ori- ginal brightness and freedom from any precipitate on cooling.The operation may be repeated ninny times if loss of ammoilia is avoided. When the excess of ammonia is removed by drawing air throug11 the cold solution, it precipitate is obtained which contains ammonia ; whereas the precipitate obtained from the boiling solution does not contain ainmonia ; hence the formation of the precipitate in t h e latter case appears to be due to dissociation. Experimental Proof of the Laws of Van't Hoff, Arrhenius, and Ostwald for Dilute SOlLltiOnS. By 31. WILDERMANN ( Z e i f . physiknl. C h e m , 1194, 15, 33'7-%'7).-The freezing points of very dilute solutions have been determined with great care and every pre- caution to secure the highest attainable degree of accuracy.Rxperi- ments with the non-electroly tes cane-sugar., carbamide arid alcohol show that these in the most dilute solutions give results in perfect. accordance with 1-an't HOE'S well known fnrrnnla for t'he molecn1;w reduction 0.03 T'/zc, if for zu the d u e 80 Cal. is taken. The electro- lytes, snlphuric acid, potassium chloride, di- and tri-chloracetic acid, aiid orthonitrobenzoic acid all give reductions of the freezing point of water which are in accordance with the view that these substances have undei.gone electrolytic dissociation to the degree ind icatecl by the conductivity measurements of the corresponding solutions.The dissociation calculated f r m i the freezing points is, however, somew bat smaller than that calculated from the conductivities, which may in part be accounted for bj- the presence of higlier non-dissociated and dissociated molecules in the solution (coinp. Abstr., 1893, ii, 509). The accuracy attained in these experinleiits is sufficient, to enable cczlcnlations to be made of the affinity coefficients from Ostwdd's law of dilution in the cases of dichloracetic acid and orthonitrobenzoic acid. The calculated value is practically independent of the dilution in each case, but is somewhat smaller than that obtained from the conductivity. H. C. D. A. L. Determination of the Freezing Point of Water. By 11. WILDERJIAXN (Zez?. physikal.Chem., 1894, 15, 358--364).-1n deter- mining the freezing point of water or of very dilute aqueous solu- tions, a n error is introduced, owing to the fact that from snch solutions the ice separates out, in fine crystals which cake round the bulb of the thermometer, this occurring before the thermometer indicates the temperature of the solution. The layer. oE ice being a bad conductor, an error is introduced of 0~0015--0~0017" in the temperature registered as the freezing point. To obviate this, the author allows the solution106 ABSTRAO'L'S OF CHEMICAL PAPERS. u ncler examination to partially solidify before the thermometer, which has been previously cooled below the melting point to be observed, is introduced. The ice does not crystallise oiit round the bulb under tliese circumstances, and the mercury rises to the true melting poiut.Freezing of Sulphuric acid Solutions. By R. PICTET (COW@ r e d . , 1894, 119, 642-645) .--Four series of experiments were made with mixtures containing increasing proportions of either water 01. sulphuric acid. The results of all the series were found to agree, provided that congelation was allowei! to tske place very slowly and the temperature of the cold chamber was kept as high as was con- sistent with the freezing of the liquid ; if these precautions aye not observed, the results are not concordant. The curve of the tempera- tures of crystallisation cuts the zero line five times, but the points of maxima and minima do not correspond with definite hydrates except in the case of the decahydrate H2S04,10H20, which freezes at - 88".The liquid contains more sulphuric acid than the crystals when the freezing point, falls on a descending part of tbe curve, but the reverse is the case when i t falls on an ascending part of the curve. Whilst at the points of maxima and minima the liquid and the crystals have the same composition. The results are given in the following fable. H. C. Percentage of Formula. sulphuric acid. Sp. gr. Freezing point. 100*00 84-48 73.08 57.65 47.57 40.50 35.25 33.1 1 31-21 29.52 28.00 26-63 25.39 23-22 21.40 17-88 9.82 6-77 5-16 1.78 0.54 1.842 1.777 1.650 1.476 1.376 1.311 1.268 1.249 1.233 1.219 1.207 1.196 1.187 1.170 2.157 1-129 1.067 1.045 1-032 1.007 1.001 + 10.5" + 3.3 - 70 -40 - 50 - 65 - 88 - 75 -5.5 -4s - 40 -34 - 26.5 - 19 -17 - 8.E; - 3.5 + 2.5 + 4.5 + 0.5 0.00 C.H. E. Pressure of Solution as a Means of Determining the Tempe- rature of Change. By J. VERSCHAFPELT (Zeit. physikal. Chem., 1894, 15, 437-456).-Prom the analogy between the process of vaporisation and that of solution, Nernst concludes that substances have a certain solution pressure analogous to their vapour pressure.GENERAL AND PHYSICAL CHENISTRY. 107 Since in many cases a change in the composition of a substance, as for example in a salt containing water of crystallisation, is indicated by an abrupt change in the vapour pressure, a change in composition should also be indicated by a change in the pressare of solution. This method is applied to an examination of the decomposition of crystallised sodium sulphate.Na2S04,10H20 Na2S04 + 10HzO, the behaviour of the salt towards mixtures of amylic alcohol and water at different temperatures being observed. The temperature of change is found to be 32*74", corresponding with the temperature of maximum solubility. From the results obtained, the value of Van't Hoff's coefficient i for water dissolved in amylic alcohol is calculated. This calculation points to a complex molecule of at least (HZO)P. Correct Formulae for Osmotic Pressure ; Change of Solubility, Melting and Boiling Points; Heats of Solution and Dilution in Dissolved Dissociated Substances. By J. J. VAN LAAR (Zeit. physikal. Chern., 1894,15,4.57-497) .-Thermodynamical calculations not suitable for abstracting. Rate of Hydrolysis of some Ethereal Salts. By R.LOWENHERZ (Zeit. physikal. Chem., 1894, 15, 389--396).-A continuation oE the work of De Hemptinne (Abstr., 1894, ii, 274), the chief result of whose investigations was that fhe nature of the alcohol was of little influeuce, that of the acid of great influence,on the rate of hydrolysis of etliereal salts. I n order to study the influence of the alcohol, the acetates of glycerol and phenol were examined. The influence of the acid was studied by taking ethereal salts of formic, mono-, di- and tzi-chlorncetic, and benzoic acids, arid also ethylic iodide. The results fully confirm De Hemptinne's coiiclusions. The ratio of the constants of the velocity equation in the case of the greatest variation for the akohols (methylic alcohol and phenol) is only about 2 to 1, but the greatest variation for the acids (formic and benzoic acids) is about 3700 to 1.H. C. H. C. H. C. Position of Magnesium in the Genetic System of the Ele- ments ; Atomic Volumes ; Allotropes and Isomsrides. By C. T. BLANSHARD (Chem. News, 1894, 70, 235, 271-272, %95--296).-1t is pointed out that the atomic volume, tohe analysis of the spectrum, t.he volume heat (sp. ht. x sp. gr.) suggest the classification of magnesium with calcium, strontium and barium instead of with zinc cadmium and mercury ; but the atomic heat, on the other hand, places it between beryllium and zinc. The author furriishes a table of atomic volumes based on the most recent or best authenticated values f o r atomic weights and specific gravities. Furthermore, he shows, from tabulated data relating to atomic volumes, specific heats, heats of combustion, boiling points a'nd specific gravities, that the relationship which exists between these properties in the allotropic forms of elcments is similar to whtit108 ABSTRACTS OF CHEMICAL PAPERS. it is in isomeric inorganic and organic compounds, which may in- dicate a similarity in constitution as regards elements and those compounds. D. A. L. The Chemometer. By W. OSWALD (Zeit. physiknl. Chem., 1894, 15, 399--408).-To any instrument that would be capable of measur- ing the chemical intensity of a system, o r that would show whether auy two systeins were in chemical equilibrium, the name " chemo- meter " may be given. The author discusses gmerslly the conditions which such an instrument would have to fulfil, and points out that for ele~t~rolytes the electrometer may be considered as a chemometer, as chemical intensity and E.M.F. are proportional to one another. Preservation of Chemically Pure Alkaline Solutions. By A. I-. KALECSINSZKY (Zeit. anorg. Chern., 1894, 7, 384-35) .-The author employs a glass bottle having a removable metallic bottom, and thiii beakers of platinum or silver, of such a size that they just fit into the glass bottle. Thc alkaline solution comes into contact only with the metallic benkei-. The flask is closed with a rubber cork and fitted with tubes as in the case of an ordinary wash bottle, the longer tube is, however, made of platinum or silver. H. C. E. C. R.

ISSN:0368-1769    

DOI:10.1039/CA8956805097

出版商:RSC    

年代:1895

数据来源: RSC