摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. ii. 137 Acapnia and Shock. IV. Fatal Apncea after Excessive Respiration. YANDELL HENDERSON (Amer. J. Physiol. 1910 25 310-333. Compare Abstr. 1909 ii 421).-0ne of the most marked symptoms of pain is hyperpnoea and the drugs which relieve pain quiet breathing. The forced breathing leads to apncea owing to the carbon dioxide being swept out of the body; the apncea in the end leads to the phenomena of shock; and in fact the symptoms of shock can be induced in normal men and animals by excessive ventilation of the lungs. This in animals can be carried so far as to be fatal. This is due to lack of oxygen primarily produced by the inactivity of the respiratory centre which is not excited owing to the absence 8 of carbon dioxide. The administration of that gas during apnoea causes breathing to recommence. Failure of respiration after intense pain is produced in the same way.W. D. H. Union of Oxygen in Blood. WILHELM MANCHOT [and in part w. BRANDT] (ArtnaZen 1909 370 241-285).-An investigation on the relationship existing between the absorption of certain gases by blood and (1) the temperature (2) the partial pressure OF the gas and (3) the concentration of the blood carried out with the object of obtaining information on the absorption of oxygen by blood. A complete analogy is found to exi& between the metallic salts which combine with gases and blood-pigment in their behaviour towards certain gases ; thus not only does blood-pigment combine with acetylene carbon monoxide ethylene nitric oxide and oxygen but the dissociation is conditioned by the same factors as those which determineii.138 ABSTRACTS OF CHEMICAL PAPERS. the dissociation of the compounds of cuprous chloride with these gases (compare Manchot and Friend Abstr. '1908 ii 375 Manchot and Brandt this vol. i 85). The compounds of haemoglobin with acetylene and ethylene are dissociated to the greatest extent whilst the degree of dissociation of the oxygen compound is slightly greater thau that of the compound with carbon monoxide or nitric oxide. Changes of temperature and pressure produce a greater effect on the ethylene compound than on the carbon monoxide compound; in the case of the former substance the effect produced by altering the temperature is due rather to an alteration in the state of equilibrium than to the change in the concentration of the gas.Blood which has been reduced by means of hydrogen likewise natural blood when diluted with water serum or isotonic solutions of sodium chloride or sucrose combines with a greater proportion of oxygen carbon monoxide ethylene or nitric oxide than undiluted blood. The same observation was made with the blood of horses oxen and pigs. The absorption reaches a maximum at a dilution of about eight to ten times at which point each atomic proportion of iron is found to combine with practically two molecular proportions of the gas. The effect of further dilution likewise the addition of alkali is to decrease the absorption of gas owing t o the hydrolysis of the additive compound. Since the gases oxygen carbon monoxide nitric oxide ethylene and probably also acetylene are absorbed in equimolecular proportions it follows that the absorption of these gases by hsmoglobin is not brought about through the agency of individual valencies but through the mutual attraction of the molecules as a whole with the formation of a molecular complex as in the case of the union of cuprous chloride and carbon monoxide (Zoc.cit.). Blood which has been acted on by hydrogen €or some time after the complete reduction of the oxyhsmoglobin is found to absorb more oxygen than that which has not been thus treated; this is shown to be due to the presence of carbon dioxide which is slowly removed by the hydrogen. Carbon dioxide in this respect behaves like hydrogen chloride with carbon monoxide and cuprous chloride (Zoc.cit.). The latter part of the paper is devoted to a discussion of the absorption of oxygen by the blood in respiration and the effect of carbon dioxide on the tension of the oxygen in blood. It is shown that the presence of uncombined hsmoglobin in the blood (natural blood contains roughly one molecular proportion of oxygen per atomic proportion of iron) tends to keep the velocity of absorption of oxygen under different pressures constant. W. H. G. Physiology of Water and Sodium Chloride. OTTO COHNHEIM KREGLINGER and KREGLINCER (Zeitsch. physwl. CAem. 1909 63 413-431).-An increase in the concentration of hsmoglobin in the blood was not observed with certainty at an elevation of 3000 to 4560 metres. I n severe muscular work a noteworthy dilution of the blood occurs.Profuse sweating leads to a decrease of chlorides in the body which on the days following it is succeeded by retention of chlorides.PHYSIOLOCIICAL CHEMISTRY. ii. 139 The loss of ohlorides may lead to a cessation of hydrochloric acid slecretiou in the stomach. W. D. H. Neutrality Equilibrium fin Blood and Protoplasm. LAWRENCE J. HENDERSON (J. &l. Chem. 1909 7 29-36).-The power of proteins to preserve neutrality in solution which is regarded as of great importance by Brailsford Robertson is great but under conditions obtaining in the organiam is not comparable with that of the inorganic constituents of blood and protoplasm. There is no proof that more than a small portion of the carbon dioxide liberated from the blood in the lungs comes from sodium hydrogen carbonate which has given up its sodium to proteins according to a simple reaction which is reversed in the tissues.It is improbable that this is the chief reaction involved unless indirectly through the heterogeneous equilibrium between red corpuscles and plasma including the move- ment of chlorine ionised or otherwise across the red corpuscle wall and the consequent liberation and fixation of carbon dioxide in the plasma. W. D. H. Influence of Stereochemical Conflguration on Certain Physico-chemical Properties of Organic Colloids. GIUSEPPE BUGLIA and L. KARCZAG (Adti R. Accad. Lincei 1909 [v] 18 ii 474-481).-Investigation of the influences exerted by the various tartaric acids on the coagulation by heat of dialysed blood-serum (compare this vol.ii 52) shows that the action of these acids is due mainly to the hydrogen ions when the acids are present in very small concentrations ; when however the concentrations are relatively high the actions are determined principally by the stereochemical configur- ations. So that only when the concentrations are high are differences observable between the actions of the different acids. The actions of the various tartaric acids on muscular proteins (gastrocnemius muscle of the frog) are in general analogous t o those exerted on the neutral protein of dialysed blood-serum. Both in accelerating the coagulation of the blood-serum and rendering it non-coagulable and also in deter- mining the velocity of coagulation (contraction) of muscle by heat the Eacid is more effective than the d-acid. T.H. P. Reversed Activity of Tissue Extract made at Bigh Temper- atures. BERTRAM J. COLLINGWOOD (Proc. physiol. Xoc. 1909 xiv-xv ; J Physid. 39).-ht 115O a tissue extract loses its power to accelerate blood-coagulation. If the undissolved residue is extracted a t this temperature an anti-coagulant is formed. W. D. I€. Glycolysis. I. The Susceptibility to Alkali of Dextrose. LEONOR MICHAELIS and PETER RONA (Biochem. Zeitsch. 1910 23 364-369).-The difficulties of measuring glycolysis in the blood are mainly two ; one the difficulty of estimating sugar in a protein-rich fluid can be overcome by the authors’ method; the other is the sup- posed loss of sugar due merely to the action on it of the alkali of the blood and tissues.It has been known for a long time that sodium hydroxide and sodium hydrogen carbonate cause dextrose to disap-ii. 140 ABSTItACTS OE’ CHEMICAL PAPERS. pear from solution; this is confirmed-the optical activity gets less and less it being largely due to conversion into l;evulos6 or mannose. But the alkalinity of blood is not that which can be estimated by titration but depends on the concentration of hydroxyl ions and can be imitated by mixtures of primary and secondary sodium or potassium phosphates; such solutions cause no charige in the optical activity or concentration of sugar in solution ; the disappearance of sugar due t o mere alkalinity of the blood is therefore a negligible factor. W. D. 13. Physico-chemical Behaviour of Uric Acid and its Salts in the Blood.F. GUDZENT (Zeituch. physiol. Chem. 1909 63 455-477).- Uric acid can only exist in the blood as monosodium urate. I n pure water this salt exists in two isomeric forms; the first (a-salt) is more soluble but more unstable than the other form (b-salt) ; the same is true for artificial and probably also for natural serum. Under certain conditions for instance in gout the blood can be oversaturated with the urate and this may lead t o its deposition in the tissues but no specific affinity between cartilage and uric acid exists. W. D. H. The Behaviour of the Anti-Substances of the Blood-Serum Towards Solvents and Other Reagents. I(. KAWASHIMA (Biochem. Zeitsch. 1909 23 186-1 92).-The anti-trypsin and anti-rennet action of the blood-serum was investigated.The serum was dried in a vacuum to a powder. The anti-properties were not appreciably altered by extraction with ether or ethyl alcohol. The anti-rennet action was however appreciably diminished by treatment with methyl alcohol the anti-tryptic action being diminished by the same treatment only to a slight extent. The anti-renuet cannot be detected in the methyl alcohol. A small amount of the anti-trypsin dissolves in a mixture of equal parts of methyl alcohol and water. Acetone appears to render the anti-substances insoluble in water. Hydrogen peroxide and salicylaldehyde injure both anti-substances. Treatment with acids alkalis and ferments appears to exert no action on them. S. B. S. The Proportionality of Proteolytic and Rennetic Action of the Gastric Juice of Man and Dog in Normal and Patho- logical Cases.TH. J. MIGAY and W. W. SAWITSCH (Zeitsch.physioZ. Chem. 1909 63 405-41 2).-The experiments recorded show that the two properties of gastric juice referred t o vary directly the one to the other both in normal and pathological conditions and therefore support Pawloff’s view that both are due to one and the same enzyme. W. D. H. Partial Transformation of Alimentary Fatty Matter into Vannitols by Peptic and Pancreatic Digestion in vitro. EMILE GAUTRELET (Compt. rend. 1909 149 1150-1 151).-The author cites the results of experiments from which he draws the conclusion that the artificial acid-peptic digestion of fatty materials such as olive oil butter vr tallow converts these into I-mannitol,PHYSIOLOGICAL CHEMISTRY.ii. 141 whilst when the digestion is pancreatic in an alkaline medium the marinitol produced is dextrorotatory. The amount of mannitol produced depends largely on the state of division of the fat and in the case of peptic digestion on the acidity of the solution. w. 0. w. Action of Heat on Dry Pancreatic Extract. EUG~NE CHOAY (J. Pharm. Chim. 1910 [vii] 1 10-16).-Various observers have recorded that the proteolytic activity of dry pancreatic extract is but little affected by exposure to a temperature of 100'. The author finds that exposure to a temperature of 80' or 100' during one or two hours scarcely affects the activity of the amylase lipase or trypsin present in pancreatic ferment but that at 120' the activities of all three enzymes are rapidly paralysed. Of the three the amylase seems to be affected least by heat.I n solution on the contrary all three enzymes are rapidly affected by heat t h s mere desiccation of pancreatic ferment at 40' to 50' reduces the activity of the amylase by three-quarters and that of the lipase by me-half. Fat Cleavage by Pancreatic Juice. I. &MILE F. TEBROINE (Biochem. Zeitsch. 1910 23 404-427. Compare Abstr. 1909 ii 497).-Addition of mono- or di-glycerides does not influence the cleavage of triglycerides by pancreatic lipase. The addition of oleic acid to an emulsion of olive oil hinders the process of saponification but the addition of glycerol increases the rate of cleavage. This is specially the case for emulsions and solid fats ; the action of glycerol is slight or absent in the case of fats soluble in water (mono-butyrin triacetin).Any viscous substance (gum egg-albumin) has a similar favourable action. The optimum temperature for pancreatic lipase is 40' but cleavage QCCUW even at 0'. Warming the lipase to 45' lessens its power and to 65' destroys it. I n presence of bile salts it is more easily affected by rise of temperature. The enzyme acts in a neutral but better in a faintly alkaline medium (optimum N/150) ; it is lessened in acid or strongly alkaline media. T. A. H. W. D. H. Concentration of Anti-substances in the Body-fluids of Normal and Immune Animals. J. R. GREER and F. C. BECHT (Amer. J. Physiol. 1910 25 292-309).-A research on similar lines to that carried out by Hughes and Carlson (Abstr. 1908 ii 304) determining the amount of hamolysins agglutinins precipitins etc.in the various fluids of the body. W. D. EC. The Purine Bases of the Bone-marrow. H. THAR (Biochem. Zeitsch. 1909 23 43-44).-The following yields of purine bases were obtained from 1000 grams of bonermarrow guanine 0.3125 adenine 0.1 7 10 hypoxanthine 0.07 24 xan thine 0.02875 gram. S. B. S. The Sugar Destructions in Animal Organisms which are Measurable by the Polarimeter. ALBERT J. J. VANDEVELDE (Biochem. Zeitsch. 1909 23 324-338. Compare Abstr. 1908 ii 714).-Extracts of liver and pancreas do not cause changes in theii. 142 ABSTRACTS OF CHEMICAL PAPERS. rotation of lactose solution such as the author has already shown occurs when this sugar is kept with milk. H e hag also followed the changes in the rotation of solutions of other sugar solutions when kept with animal fluids or extracts of organs. Dextrose solutions were not changed by extracts of organs.Urine caused a slight diminution of the rotation of lactose solution and also of dextrose solution. The reducing powers in these cases were only slightly if at all altered. s. 6. s. Lactic Acid in the Autolysed Dog’s Liver. TADASU SAIKI (J. Biol. Chem. 1909 7 17-2O).-The lactic acid in autolysed dog’s liver is largely sarco-lactic [d-lactic] acid as in other organs. A small amount of fermentation-lactic acid is also observed even in the sterile condition. W. D. H. The Action of Mercury Salts on Autolysis. MARCO TRUFFI (Biochem. Zeitsch. 1909 23 270-274).-1t has been shown that mercury salts promote the autolytic process and the author has determined the optimal quantities for various salts.s. B. s. Cholesterol Esters in the Human Epidermis and their Reactions. ERNST SALKOWSKI (Biochem. Zeitsch. 1910 23 361 -363).-The cholesterol ester of palmitic acid was separated from human epidermis which was identified by its melting point colour reactions and elementary composition. W. D. H. The So-called Fat of Tissues and Organs. HUGH MACLEAN and OWEN T. WILLIAMS (Bio-Chem. J. 1909 4 455-461).-The presence of ‘‘ masked fat ” in cell protoplasm is now recognised as a fact of physiological and pathological importance. The yield of ‘‘ fat ” differs with the extracting agent employed according t o its dis- integrating action on protoplasm or the fat-products. The main material in the so-called f a t is phosphatide which may be free or combined.The organ chiefly investigated in the present research was the liver but some details are also given of other tissues. The methods of extraction are also described. W. D. H. The Importance of Phosphatides for the Living Cell. 11. WALDEMAR KOCH (Zeitsch. physiol. Chem. 1909 63 432-442. Compare Abstr. 1903 i 301)-In colloidal solutions of phosphatides reactions are observed similar to those which occur in physiological material Carbon dioxide and ammonia in small concentration affect lecithin emulsions leading to alteration in its hydrogen-ion and hydroxyl-ion concentration. Phosphatides play their part in the morphological and chemical diff~rentiation of cells especially in regard to the formation of membranes W.D. H. The Relationship of Diastatic Efflciency to Average Glycogen Content in Tissues and Organs. HUGH MACLEAN (Bio-Chem. J. 1909 4 467-179).-Great variations occur in animals even of the Sitme species in the diastatic efficiency of their tissues. Veryoften anPHYSIOLOGICAL CHEMISTRY. ii. 143 organ containing mere traces of glycogen (for instance the lung) has a higher amylolytic power than the liver. Wohlgemnth has recently published similar results. There is in fact no definite correlation between glycogen content and diastatic efficiency in the case of adult tissues. W. D. H. Chemico-physical Investigations on the Crystalline Lenrj. FILIPPO BOTTAZZI and Noh SCALINCI (Atti R. Accad. Lincei 1909 [v] 18 ii 423-430. Compare this vol.ii 56).-The authors have examined the influence exerted by sodium chloride on the imbibition of the crystalline lens of the dog in solutions of acids and of sodium hydroxide (compare Abstr. 1909 ii 502). The imbibition in 0-2N- sodium chloride solution is increased slightly by acids and very considerably by sodium hydroxide. I n the latter case the velocity and magnitude of the imbibition are proportional to the concentration of hydroxyl-ions whilst with acids the amount of imbibition is directly proportional to the concentration of hydrogen-ions hydro- chloric and acetic acids favouring imbibition rather more than sulphuric acid of the same concentration. From these and previous results it is evident that alkalis are the most potent agents influencing the imbibition of the tissues and that the extent of the physiological imbibition of every living cell and fibre corresponds with a certain relation between the concentration of the neutral salts and that of the salts which in aqueous solutions have alkaline reactions owing to hydrolytic dissociation.For a given con- centration oi hydroxyl-ions the imbibition of the crystalline lens or of the tissues is greatest in absence of neutral salts. The absorption of the lens muscles etc. should be less in a solution of barium or calcium hydroxide than in one of sodium or potassium hydroxide of the same concentration. T. H. P. The Iodine Complex in Sponges. HENRY L. WHEELER and LAFAYETTE B. MENDEL (J. Biol. Chem. 1909 7 1-lo).-Drechsel’s iodo-gorgonic acid from Gorgonian corals was shown to be 3 5-di- iodotyrosirie by Wheeler and Jamieson (Abstr.1905 i 350). In sponges also it is now shown that the iodine is present in the same form. The common bath sponge served as the source of the material. The ease with which iodine enters into combination with the aromatic group suggests certain considerations respecting the function of iodine in proteins some of which are commented on. 3 5-Di-iodotyrosine and the similar compound with bromine are precipitated by phosphotungstic acid whilst tyrosine itself is not. It does not give the tyrosine reaction with Millon’s reagent until after reduction. W. D. H. The Theory of Urea Formation. ALBERT A. EPSTEIN (Biochem. Zeitsch. 1909 23 250-261).-According to Schmiedeberg’s theory urea is formed in the organism from ammonium carbonate; according to the theories of Salkowski and Hoppe-Seyler urea is formed by the addition of ammonia to a substance in which a nitrogen atom is alrady bound to a carbon atom (for example cyanates).I f theii. 144 ABSTK ACTS OF CHEMICAL PAPERS. Schmiedeberg conception is correct then there is no limit (except the toxicity) to the amount of ammonia which can be converted in the organism into urea. If the other theories are correct then there is a limit as the amount of cyanate or other groups available for synthesis depends on the protein degradation. In the latter case if the amount of nitrogen in the ammonium salt ingested exceeds that derived from protein the excess of ammonia should be excreted in this form and not as urea.Experiments carried out on rabbits by the author in which the nitrogen of the ammonium salt (lactate) administered exceeded that of the normal nitrogen output on a fixed diet lead to the conclusion that there is no limit to the amount of ammonium salt which can be converted into urea. The results therefore support Schmiedeberg’s theory. S. B. S. The Origin of Lactose. CH. PORCHER (Biochem. Zeitsch. 1910 23 370-401).-1f the mammary glands are removed in cows and goats immediately after parturition glycosuria of variable intensity sets in rapidly and lasts about twenty-four hours. A similar result follows amputation of the breasts in lactating animals This is associated with hyperglycaemia ; lactose is not present. Phloridzin injection in suckling animals produces glycosuria as well as in lactating and male animals.In the operation cases just referred to the sugar is dextrose which in the absence of the mammary glands is not converted into lactose. W. D. H. Influence of Lactic Acid Ferments on Intestinal Putre- faction in a Healthy Individual. HELEN BALDWIN (J. Biol. Chem. 1909 7 37-48).-A full account of a prolonged series of observa- tions an a man which showed that sour milk exerted no specially favourable influence on the subject’s condition. The excretion of ethereal sulphates and phenol in the urine and of indole and scatole in the faxes was usually increased when the fermented milk mas taken. W. D. H. Experimental Glycosuria. V. The Distribution of Glyco- genolytic Ferment in the Animal Body especially of the Dog.JOHN J. R. MACLEOD and R. G. PEARCE (Amer. J. Physiol. 1910 25 255-291. Compare Abstr. 1909 ii 168).-Prolonged perfusion of the liver with isotonic salt solution does not lessen the power of the extracts of the organ to destroy glycogen ; this is against the view that the action is due to lymph. The full amount of glycogenolysis is not obtained until the tissue cells are crushed in Buchner’s press ; the ferment responsible is therefore an endo-enzyme. This is termed glycogenase ; i t is most abundant in the pancreas the liver and blood-serum (or plasma) come next and then the kidneys intestines and muscles. The nutritive condition of the dogs used is not a factor in the activity and the blood-serum from the pancreatic vein does not contain more of the enzyme than that from the carotid artery. The organs of pig rabbit and especially the lamb are less active than those of the dog.W. D. H.ii. 145 PHYSIOLOGICAL CHEMISTRY. The Urorosein Reaction. HENRY D. DAEIN (J. Biol. Chem. 1909 7 57-58).-Herter bas shown that indoleacetic acid is the chromogen of urorosein and that the reaction is obtained when nitrites are also present in the urine. Ciusa and Terni (Abstr. 1908 i 763) state that one of the derivatives of cinnamylideneacetophenone the a-oxime when given to animals causes the appearance of the urorosein reaction in their urine. This was repeated in the present experiments with negative reqults. It is suggested that the previous animals had a trace of indoleacetic acid in their urine and that the administration of the oxime was followed by the occu~rence of nitrites for it is known that hydroxylamine is converted into nitrous acid in the organism.W. D. H. The Action of Saline Purgatives. ARTHUR F. HERTZ F. COOK and E. G. SCHLESINGER (Guy’s EospitaZ Reports 1909 63 297-307). -Two views are held in regard to the action of saline purgatives ; one the more prevalent supposes that the salt attracts water into the intestine and so produces fluid stools ; the other supposes t h a t the salt is absorbed and the effect is due to a specific irritation by the absorbed salt of the intestinal neuro-muscular and secretory mechanism leading to increased peristalsis and increased secretion. The present paper i s an argument in favour of the latter theory. It is pointed out that the purgation often occurs within half an hour and that Rontgeu-ray pictures of the intestine show that what is taken by the mouth does not reach the caecum until four hours later.This time is only very slightly shortened after a saline purge. Further the watery contents which are increased consist of succus entericus not simply of water; of the sulphate administered the faeces show little if any increase whilst into the urine the excess of sulphate passes very rapidly showing that it has been absorbed. The Estimation of Ferments in the Faxes. HANS URP (Biochem. Zeitsch. 1909 23 153-178).-The following data were determined amount of fsces total solids weight of solids in aqueous extract and the nitrogen in the total and the extract. The following ferments were quantitatively estimated in the aqueous extract pepsin (by Volhardt’s method) amylolytic ferment (by Wohlgemuth’s method) the pancreatic ferment (by Volhardt’s method) the lipase the nuclease (by determination of the adenine yielded by thymus nucleoprotein) the maltase and the invertin (by the usual polarimetric methods).The results were calculated in terms of 1 gram of dry substance or of 1 gram of nitrogen except in the case of the pancreatic enzyme which mas calculated in terms of 0 01 gram of nitrogen. Pepsin was found to be always absent from fsces and also lipase. Nuclease and maltaqe were present in the fseces after administration both of senna and magnesium sulphate but absent in the normal faxes. After administration of the former drug the ferments normally present in faeces (amylase pancreatic Ferment and invertin) were in considerably increased quantities ; this was not the case after magnesium sulphate administration.The author gives W. D. H. full details of his experimental methods. s. B. 8.ii. 146 ABSTRACTS OF CBEMICAL PAPERS Chemistry of Cancer. 11. Purine Bases Creatine and Creatinine TADASU SAIKI (J. Biol. Chem. 1909 7 23-26).-After removal of fat and lipoids from a number of cancerous turnours the residue was hydrolysed with sulphuric acid and purine bases determined by the Kriiger-Schmid method. The following figures are given uric acid 0.024% ; adenine as picrate 0.032% ; hypoxanthine as nitrate 0.0034%; guanine and xanthine are only present in traces ; this suggests the presence of guanase and oxydase and the absence of adenase as in other human tissues.Creatine and creatinine were determined by Folin’s method ; the creatinine present amounted to 0.016% of t h e fresh tissue ; creatine was practicilly not present. W. D. H. The Influence of Certain Alcohols Hydroxy- and Amino- acids of the Aliphatic Series on the Sugar and Nitrogen Excretion in Phloridain Diabetes of the Dog. I. PAUL H~CKENDORF (Biochem. Zeitsch. 1909 23 281-303).-To starving dogs receiving phloridzin injections various alcohols amino-acids and other substances were administered and the alterations caused in the nitrogen and sugar excretions were noted. It was found that the administration of those alcohols which contain an uneven number of carbon atoms causes almost always an increased sugar excretion.I n the case of propyl alcohol this increase is not regular. The alcohols with three and five carbon atoms caused a diminution of the nitrogen output. The alcohols with an even number of carbon atoms did not cause an increased sugar excretion; neither did n-valeric acid. I n this case both the sugar and nitrogen excretion were somewhat diminished. Fermentation-lactic acid caused a slight increase of sugar excretion and diminution of nitrogen excretion ; d-Z-alanine caused a slight increase in the sugar and also an increase in tho nitrogen. Olive oil caused an increase in the nitrogen output. s. 13. s. Phloridzin Diabetes. I. A. EELANDSEN (Biochem. Zeitsch. 1910 23 329-360).-Phloridzin glycosuria is not regarded as a primary hepatogenous or renal production of sugar and so Minkowski’s theory is held to be untenable.It originates owing to the passage of phloridzin through the kidney calling forth there an abnormal elimination of sugar by that organ which is probably a true secretion. The sugar in the blood is removed in this way but as the amount of sugar in the carotid blood does not diminish it is necessary to suppose that a secondary compensatory sugar production occurs in the liver as Bang has proved to be the case. The maximal amount of sugar in the urine occurs simultaneously with the maximum of phloridzin excretion and it ceases at the same time as or shortly after the excretion of phloridzin ceases. W. D. H. Gout. F. GUDZENT (Biochem. Zeitsch. 1909 23 275-277).- Polemical. The author contends that the conclusions of Bechhold and Ziegler (Abetr.1909 ii 916) are unjustified as it is theo- retically impossible for uric acid to exist as such in serum. Itii. 147 PHYSIOLOGICAL CHEMISTRY. must exist in the form of B sodium salt which will form super-. saturated solutions the degree of supersaturation of which will depend on rate of formation and other circumstances. He holds also that the conclusions of these authors are unjustified because the analyses are incomplete no account having been taken of the carbon dioxide tension of the solutions and that it is impossible to entirely free the deposits analysed from serum and other substances. The author also states that other physico-chemical laws have not been taken into account in the investigations criticised.The Influence of Alcohol on the Quantity of Phosphatides in Animal Organs. NADINE SIEBER (Biochem. Zeitsch. 1909 23 304-323).-'Che phosphatides were estimated in the organs of animals which had received alcohol and in those of control animals which had received no alcohol and had been kept under otherwise similar conditions. The organs of the former showed a smaller lecithin content than those of the latter the diminution varying from 0.57% in the stomach wall to 11% in the brain these numbers being the mean of several experiments. The Chemical Constitution and Physiological Action of Alcohols and Acids. 11. JACQUES LOEB (Biochem. Zeitsch. 1909,23 93-96. Compare Abstr. 1909 ii 168).-The minimum quantities of alcohols necessary to convert negatively heliotropic copepoda into positively heliotropic organisms were determined. The higher the atomic weight of the alcohol the greater was the activity. The same result was also obtained with daphnia. The narcotic effect was similar to the heliotropic effect The heliotropic action of the acids is much stronger than that of alcohols. Hydrochloric nitric and sulphuric acids have about the same action as formic acid. The increased action of the fatty acids with higher molecular weights is not so marked as in the case of the alcohols. S. B. S. EATEIARINA KOWALEWSKY (Biochem. Zeitsch. 1909 23 l-d).-The ingestion of histidine hydrochloride caused an increase in the acidity in the urine (even when sodium carbonate was administered) and a large increase in the total nitrogen and ammonia output in the urine the ratio of ammonia to total nitrogen being also increased. The results indicated degradation of the body proteins. Methyliminazole acted toxically when administered to a dog. S. B. S. S. B. S. The Pate of Histidine in the Body of the Dog. S. B. S.

ISSN:0368-1769    

DOI:10.1039/CA9109805137

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. ii. 147 Chemistry of Vegetable Physiology and Agriculture. Action of Sodium Benzoate on the Multiplication and Production of Gas by Various Bacteria. CHRISTIAN A. HERTER (S. Bid. Chem. 1909 7 59-67).-Food preparations containing 0.1% of sodium benzoate nearly always contain small numbers of bacteria,ii. 148 ABSTRACTS OF CHEMICAL PAPERS. chiefly of the spore-bearing kind. I n dextrose bouillon the same percentage only slightly inhibits Bacillus coli and other intestinal bacteria. Gas production may however be considerably hindered. When mixed faecal bacteria are introduced into dextrose bouillon containing 0.1 t o 0.2% of sodium benzoate the bacteria are unequally inhibited. I n general the organisms of the Bacillus coli hype are more inhibited than cocci.W. D. H Decomposition of Nitrates by Bacteria. S. A. SEWERIN (Cantr. Rakt. Par. 1909 ii 25 479-492. Compare Abstr. 1909 ii 479)- Denitrification experiments with Bacillus pyocynnyus and Vibrio denitrisficans showed that both microbes can frequently utilise dung straw and urine as a means of increasing denitrification in a marl whilst in a black soil these substances were not utilised although the microbes grow readiJy in the soil without manure. I n one experi- ment the addition of a very large amount of dung (8%) resulted in a reduction of the amount of nitrate by 17% when the soil was inoculated with Bacillus pyocyaneus but no effect vas produced with Vibrio denitrijcans. N. H. J . M. Alcoholic Fermentation in the Presence of Sulphurous Acid. M.EMMANUEL POZZI-ESCOT (Bull. Assoc. Chim. sucr. Dist. 1909 27 561-562).-The author does not agree with the statement made by Martinand (Abstr. 1909 ii 823) that yeasts do not ferment sugar solutions in the presence of sulphurous acid. Pure yeasts which the author employed in his experiments became acclimatised to the presence of this acid. It is also pointed out that the beer yeast used by Martinand does not under ordinary conditions readily ferment sucrose in acid solution. w. P. s. The Influence of Fermented Sugar Solutions on the Respiration of Wheat Seedlings. S. KOSTYTSCHEFF (Biochem. Zeitsch. 1909 23 13’7-142).-Dextrose solutions were fermented by zymin until they no longer exerted a reducing action on Fehling’s solution ; the alcohol was then distilled off.Seedlings soaked in such solutions showed an increased output of carbon dioxide equivalent to 142% in twelve hours as compared with seedlings which had been soaked in water. No increased alcohol production could however be detected and the author assumes that the action is due t o increased normal respiration and not to alcoholic fermentation ; the amount of oxygen used up furthermore does not increase in the same ratio as the carbon dioxide production. S. B. S. The Influence of Mineral Salts on the Respiration of Germin- ating Seeds. W. ZALESKI and A. REINHARD (Biochem. Zeitsch. 1909 23 193-21 4).-The authors give the results of some] preliminary investigations of the action of various salts on the seeds of Lupinus angustgolius Zea mais and Pisum sativum. The solutions investigated include Knop’s solution arid magnesium sulphate potassium dihydrogen phosphate potassium nitrate magnesium sulphnte and other salt solu- tions and also of solutions containing mixtures of salts.I n each case theVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 149 output of carbon dioxide was measured and campared with the output of the same seeds grown in pure water. The results are expressed as the number of mg. of carbon dioxide expired per hour by one hundred seeds. The action of the salts was not the same on all the varieties of seed tested and depends perhaps on the mineral content of them. Attention is called to the possible antagonistic action o€ various ions such as has already been observed in other biological processes. S. B. S.The Part Played by Oxygen in the Formation of Protein in Plants. W. ZALESKI (Biochenz. Zeilsch. 1909 23 150-152).- The author has already shown that there is a considerably greater formation of proteins in the bulbs of AZlircm cepa which have been punctured as compared with intact bulbs (Abstr. 1901 ii 619 ; 1902 ii 348). A control was dried at 60-70° and two other similar portions mere kept one in dry air and the other in a dry oxygen-free atmosphere. The two latter portions contained more protein than the former the portion which was kept in presence of oxygen containing the largest quantity of the three. There was no change i n the amount of total nitrogen. The analyses were carried out by Stutzer's method. The author attributes the increased protein formation in oxygen to the increased energy supply t o the seeds and he assumes therefore that the action is only indirect. H e now extends this observation to pea seeds.S. B. S. Selective Absorption of Ions by Roots. ENRICO PANTANELLI and M. SELLA ( A t l i R. Accad. Lincei 1909 [v] 18 ii 481-488).- By means of plantlets of dwarf Cucurbitu pepo the authors have investigated the selective action of the absorptive epithelium of the roots on the anions and cations of various salts. The results confirm the capacit,y of this membrane of functioning as a septum unequally permeabfe for different ions the amounts of the latter absorbed for various salts being given in mg.-ions in the following table KCl. CaCl Ii,SO,. CaS04 KH,P04. CaHPO,. Cation 23'38 0 11'6 0 1 *15 1-10 Anion 30'68 51.39 18.07 1-98 49'04 78.93 In the case of the four soluble salt? potassium chloride calcium chloride potassium sulphate and potassium dihydrogen phosphate the amounts of carbon dioxide emitted by the young roots were determined but on comparing these amounts wlth those of the cations remaining in excess no general rule is observable.With calcium sulphate and tho phosphate CaHPO however it appears that the more rapid the absorption of the anion compared with that of the cation the more carbon dioxide is emitted by the roots. This phenomenon is based on a t least the two following causes (1) increase of the respiring surface and mass by the accelerated development of t,he roots produced by the alimentary and catalytic influences of the rapidly absorbed anions ; (2) the direct influences of these anions on the respiratory activity.T. H. P. VOL. XCVIII. ii. 11ii. 150 ABSTRACTS OF CHEMICAL PAPERS. Nitrogenous and Mineral Composition of Ornamental Plants. ALEXANDRE HBBERT and GEORGES TRUFFAUT (Bull. SOC. clkm. 1910 [iv] 7 31-37).-With a view t o the preparation of appropriate compound and complete manures for garden plants the authors have determined the amounts of nitrogen and mineral con- stituents present per kilogram of fresh plant in a large number of species grown f o r horticultural purposes. These are tabulated in the original. T. A. H. Chlorophyll. VII. Comparative Investigation of the Chloro- phyll of Different Plants RICHARD WILLSTATTER FERDINAND HOCHEDER and ERNST HUG (Aiznnlen 1910 371 1-32. Compare Willstatter and Benz Abstr.1908 i 199).-The existence of two distinct chlorophylls has been definitely established by Willstiitter and Benz (loc. cit.). Crystalline chlorophyll is now shown to contain two methoxyl groups whilst amorphous chlorophyll from determina- tions with phaeophytin contains one phytol residue and one methoxyl group for each atom of magnesium; phaeophorbin derived from crystalline chlorophyll is likewise a dimethyl ester. The primary object of this investigation mas to ascertain the extent of the distribution of these chlorophylls in the vegetable world the method employed being as follows the chlorophyll is extracted from the dry mat'erial by means of alcohol and converted as completely as possible by oxalic acid into the magnesium-free decomposition product ; the latter is then hydrolysed quantitatively the weight of phytol obtained being a measure of the phaeophytin and consequently of the amorphous chlorophyll present in the plant.Determinations made with grass plantain and stinging nettle collected from various localities and a t different times of the year in- dicate that the nature of the chlorophyll is not influenced by these factors a result not in accord apparently with the conclusion drawn by Borodin from his investigations (Bot. Zeit. 1882 40 608). The results of the analyses of the chlorophyll of seventy plants taken from thirty-six families are recorded. These show that phytol is distributed widely in nature; with the exception of one family ( Verbenacae) of which only one variety was examined representatives of all the families investigated have been obtained in which phytolsster- chlorophyll preponderates.I n six cases the proportion of phytol was small namely i n Stachys silvcctica Galeopsis versicolor Guleopsis tetralhit Datum stramonium Verbena oficinalis and Scrophularia nodosa ; crystalline chlorophyll was isolated from the first four also from Lamiurn nzaculutum which with Atropa belladonna and Salix occupies an intermediate position. The distribution of crystalline chlorophyll indicated by these results does not appear t o be as great as was deduced by Borodin (loc. cit.) and Monteverde (Acta f f o r t i Petyopolitarhi 1893 13 123). The basic decomposition product obtained from the various prepar- ations of phaeophytin from seventy plants is in the majority of cases principally a mixture of phytochlorin-e and phytorhodin-g ; the latter compound is the principal decomposition product OF phaeophytin from Piwus silvestris aid Gctouiccc oficinolis whilsjt it is not piwent in theVEGETABLE PHYSlOLOGY AND AGRICULTURE.ii. 151 decomposition product of phaeophytin from Urtica dioica and Xuliz. Analyses of the basic compounds just mentioned point to a larger proportion of carbon to nitrogen than that represented by the formulae given by Willstatter and Hocheder (Abstr. 1907 i 780). The proportion of chlorophyll in the leaves of various plants has been estimated colorimetrically by comparison of the alcoholic extract with a standard solution of crystalline chlorophyll; it is found to vary from 0.5% to slightly over 1% of the dry material a value smaller than that given by Tschirch.W. H. G. Adenium Hongkel the Ordeal Poison of the French Soudan. EM. PZRROT and M. LEPRINCE (Compt. rend. 1909 149 1393-1395). -An aqueous-alcoholic extract of the flowers of Adeniuna Hongkd from Upper Senegal showed intense toxic properties. By extraction with chloroform a neutral yellow amorphous substccnce was obtained agreeing approximately with the formula C,oH,,O,. The substance had m. p. 84-85O and is characterised by the reddish-violet coloration developed with sulphuric acid and by its marked sternutative action. Physiological experiments suggest that it belongs t o the group of Presence of a Glucoaide which is Decomposed by Emulsin in the Leaves and Twigs of Eremostachys laciniata.JOSEPH KHOUBI (J. Pharrn. China. 1910 [vii] 1 17-19).-The leaves and young shoots were extracted with alcohol the solvent distilled off and the residue dissolved in an aqueous solution of thymol. Of this solution half was treated with invertase when its optical rotation rose from - 14’ to 36’. It was then boiled to destroy the invertase and on cooling emulsin was added Under the influence of this ferment the rotation changed t o + 6’ indicating the presence of a glucoside. This deduction was confirmed by the similar action of emulsin on an aqueous solution of that portion of the alcoholic extract soluble in a mixture of alcohol and ethyl acetate. Determinations of the amount of reducing sugar formed indicated that the glucoside present has not been described previously.A New Cupric Salt and its Application as a Fungicide f o r Diseases of the Vine and other Plants. PHILIPPE MALYEZIN (Bull. Xoc. chim. [iv] 5 1096-1098).-See this vol. i 91. PHILIPPE MALYEZIN (Ann. Chim. anal. 1910 15 15-19).-1n order t o ascertain the action of various oxidising substances on wine the author has made a number of experiments in which wine was treated with copper oxide nitric acid etc. Whilst simple aeration for a period of five minutes was without effect on the different constituents of the wine employed in the experiments the addition of 125 grams of cupric oxide to 1 litre of wine caused after a lapse of five and a-half hours a decrease in the quantity of non-volatile acids and of glycerol present whilst the amount of volatile acids showed a slight increase.I n the case of another wine which was treated with 0.2% of 40% nitric acid and the action allowed cardiac poisons resembling stropanthine. w. 0. w. T. A. H. Oxidation Taking Place in Wines. VOL. xcvm. ii. 12ii. 152 ABSTRACTS OF CHEMICAL PAPERB to continlie for four days the quantity of eaters originally present was trebled; the glycerol however was diminished to the extent of about 30%. This action of the nitric acid was still more marked after twelve days’ contact. The author agrees with the opinion of other observers t h a t the presence of small quantities of iron and manganese has an effect on the formation of aldehydes and esters ; he is also of opinion that it is not necessary that these metals should be derived from the soil by the grapes and pass into the wine as organic salts.It is possible that accidental contact with a metal will result in sufficient of the latter being dissolved t o play an important part in the oxida- tion processes taking place snbsequently in the wine. As cupric salts have such strong oxidising properties it is advisable not to use copper vessels for containing wine as even traces of the metal when dissolved HUBERT (Ann. Chim. anal. 1909 14 453-454).-The author attributes the rapid disappearance of sulphur dioxide from wines not to oxidation but to the formation of a stable combination with substances of an aldehydic nature. Thig may be shown experimentally by adding to sulphited wines a little urotropine (hexnmothylenetetramine) ; the amount of total sulphur may lead to alterations in the character of the wine. w. P. s. Disappearance of Sulphur Dioxide dioxide is at once reduced. L. DE K. Difference of Races and Individual Beets with Regard to their Composition. KARL ANDRLfK v. BARTO& and 3. URBAN (Zeitsch. Zuckerind. Bohm. 1910 34 %?1-237).-D~fferent races of sugar-beet grown under the same conditions show differences i n composition especially i n the pure ash. The ash of roots with high percentage of sugar contains more calcium magnesium and phosphoric acid and less sodium than roots with low percentage of sugar; and they contain less alkalis to 100 parts of sugar. Individual roots of different races grown under the same conditions may show essential variations in composition. The amount of mineral constituents taken up per 100 parts of sugar varies both in individual roots of different races and of the same race. Roots with high percentages of sugar now take up less inorganic bases than was found to be the case by Walkhoff in 1874. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9109805147

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

149 Organic Chemistry. Oxidation of U n s a t u r a t e d Compounds by means of Organic Peroxides. EDUARD LIPPMANN (Ber. 19 10 43 464. Compare PrileschaBeff this vol. i 86)-The addition of benzoyl peroxide to amylene and the subsequent hydrolysis to isodiamylene oxide was studied by the author in 1884 (Abstr. 1885 366). J. J. 5. Condensation of sec.-Butyl Alcohol with its Sodium Derivative. MARCEL GUERBET (Compt. rend. 19 10 150 183-1 85. Compare Abstr. 1902 i 130 583 657; 1908 i 162 635).-When see.-butyl alcohol is heated with its sodium derivative a t 200-220" there is formed a mixture of two alcohols (1) y-Methylheptun-E-ol CHMeEt*CH,*CHEt*OH a liquid with a mint-like odour has b. p. 167-169O (corr,) DO 0,8493; its acetate has b. p. 283-185" (corr.). On oxidation the alcohol yields y-methylheptccn-€-one C,H,,O b.p. 161' (corr.) ; the semicarbaxone crystallises in needles m. p. 96'. The constitution of the foregoing alcohol and ketone was deduced from a study of their oxidation products. (2) The dodecyl alcohol '' trisec.-butylic alcohol," C,,H,,O b. p. 250-255' (corr.) an agreeably smelliug liquid is converted 011 oxidation into t h e corresponding ketone C,,H,,O b. p. 247-24s' (corr.). This forms a semicarbaaone m. p. 161-162'. W. 0. W. Methylacetenylcarbinol [Butinene-7-011. ROBERT LESPIEAU (Compt. rend. 1910 150 113-114. Compare Abstr. 1908 i 496). -A description of a method for preparing alcohols of the type OH CHR* Ci CH. P-Bromo-Aa-butevbe-y-ol OH* CB Me- CBr CH o b- tained by the action of magnesium methyl iodide on bromo- acraldehyde is a colourless liquid b.p. 59.5-60'/14 mm. or 1 5 1 O j 732 mm. (decornp.); it forms a pheizyllurethane m. p. 63*5-63.5'. Alcoholic potassium hydroxide converts the alcohol almost quanti- tatively into acetylene whilst the aqueous alkali brings about a more complex change. Amongst the products recognised were acetylene yropionic acid and butinene-y-ol OH* CHMe* CiCH. This was isolated not quite free from water as a liquid b. p. 107-109'/760 mm. By treating with an ammoniacal cuprous chloride solution a precipitate is formed which on treatment with iodine and potassium iodide is converted into aap-tri-iodo-La-butene-y-oZ OH*CHMe*CI:CI m. p. 96". w. 0. w. Unsaponifiable C o n s t i t u e n t s of Japan Tallow. HERMANN MATTHES and W. HEINTZ (Arch.Pharm. 1909 247 650-657)- Japan tallow m. p. 53-53-5 D 1.0038 is saponified by alcoholic potassium hydroxide and t h e clear soap solution is diluted with water and extracted with ether. The residue obtained by the distillation of VOL. XCVILI. i . mi. 150 ABSTRACTS OP CHEMICAL PAPERS. the ethereal extract is submitted to a repetition of these operations. The final residue thus obtained in 0.68% yield is a yellowish-brown mass (iodine number 36*25) which is separated by petroleum into an insoluble portion from which myricyl alcohol is isolated and a soluble portion from which phytosterol m. p. 139O and ceryl alcohol m. p. 79O,are obtained together with a saturated ulcol~ol m. p. 65' (ucetate m. p. 41°) which is probably nonadecyl alcohol C,,H4,0. c. s Dimethyldiethyldicarbinol [yS - Dimethylhexane - y8 - diol].Mlle CECILE FRUMINA (Bull. Acud. roy. Belg. 1909 1151-1 157).- Lawrinowitsch's pinacone obtained by reducing methyl ethyl ketone with sodium (Abetz. 1877 ii 427) lists been prepared by the action of magnesium ethyl iodide on methyl oxalate and proved to consist of a single liquid substarice y&dirnethylhexane-y8-diol OH*CMeEt*CMeEt.OH b. p. 195'/760 nim. or 10°/l10 mm. The solid modification obtained by Zelinsky and ICrapiwin (Abstr. 1893 i 390) in repeating Lawrinowitsch's experiment was not produced in the synthesis now described. The diethyl ether has b. p. 142-143'/760 mm. or 110-111'/20 mm. and is liquid. The dichloride boils at 165-166"/ 760 mm. or at 114-115°/18 mm. Drying of Moist Ether. E. VON SIEBENROCK (Monatsh.1909 30 759-'766).-A comparative study of calcium chloride potassium carbonate sodium sulphate magnesium sulphate sylvite potassium chloride calcium sulphate and carnallite having regard to their use in the anhydrous state for the removal of water from moist ether. The first two substances mentioned are shown to be most efficacious; sodium sulphate a substance frequently recommended and used for drying ether is not very effective and may be replaced with great advantage by carnallite and magnesium sulphate. Action of Sulphur and Ammonia on Organic Sulphides and Disulphides. BROR HOLMBERG. (Bey. 1910 43 220-226. Compare Abstr. 1908 i 308).-0rganic sulphides and disulphides form reddish-brown additive products of the general formula R,S,,yNH with sulphur and ammonia.The reaction is reversible the equilibrium depending on the sulphide used. I n some cases as with ethyl and p-tolyl disulphides the additive product undergoes further change into the tetrasulphide according t o the equation so that the ammonia can be considered to act catalytically on the formation of tetrasulphides from disulphides and sulphur. The organic sulphide or disnlphide is dissolved in absolute alcohol an excess of flowers of sulphur added and the solution then saturated with ammonia whereby the colour gradually changes to a dark brown. After some weeks the undissolved sulphur is collected and weighed the filtrate allowed to evaporate spontaneously and the residue then investigated. With ethyl sulphide the residue consisted of a minute trace of sulphur but the additive product must have been formed in solution T.A. H W. H. G. R,fLyNH t R p t ss-4 + yNH,,ORGANIC CHEMISTRY. i. 151 since the presence of ethyl sulphide is necessary for the formation of the brown colour. Ethyl disulphide gave a residue of a yellow uncrystallisable oil; when this was distilled under diminished pressure (1 2 mm.) a colour- less liquid distilled over a t 77-78' and the residue in the flask consisted of ethyl tetrasulphide. p-Tolyl disulphide (prepared from p-tolyl mercaptan and sulphuryl chloride in ethereal solution or by the spontaneous oxidation of an alkaline solution of the mercaptan) gave a solid residue contaminated with oil which after recrystallisation from alcohol is found t o be a mixture of the di- and tetra-sulphide the latter having rn. p.75". Diethyl dithiodiglycollate gave a dark-coloured solution from which the original substances were always regenerated no matter what the treatment ; large quantities of sulphur dissolved. If the filtrate after collecting the excess of sulphur was again saturated with ammonia and kept for six weeks the amide m. p. 156-157" derived from the original ester was formed. I n an appendix on the inorganic polysulphides the author states his opinion that compounds with simple sulphur chains are colourless or only pale yellow ; a brown colour is due to the presence of larger atomic complexes S,. Whether the compound should be formulated as M,S,S or R!I2S2,SZ is left undecided. Crystalline Form and Optical Characters of Lead Formate.B. KARANDEEFF (Centr. Min. 1910 17-24).-Crystals of lend formate Pb(CHO,) are orthorhombic with cc b c = 0.T4538 1 0.84656. Detailed determinations of the optical T. S. P. constants are given. 1,. J. 8. [Electrolysis of Carboxy-acids.] FELIX KAUFLER (Bey. 191 0 43 266).-The statement made by the author and C. Herzog (Abstr. 1909 i 870) in connexion with the attitude of Forster and Piguet (Abstr. 1904 i 965) towards the superoxide theory was incorrect. An error was also made in the reference to the work of Xiller and Hofer. R. V. S. Formation of Dichloroacetic Acid from Trichloroacet- aldehyde by Wallach's Method. ARTHUR KOTZ (Festsciwift Otto WaEZach 1909,496-501. Compare Wallach abstr. 1578 283 2SS).- The conversion of chloral into dichloroacetic acid which may be brought about through the agency of water alone is greatly facilitated by the presence of potassium cyanide probably owing to the inter- mediate formation of chloralcyanohydrin CCI,*CH(OH)*CN and aa-dichloro-~-cyano-/3-hydroxyethylene CCI,:C(OH).CN or the tautomeride dichloropyruvonitrile CHCI,*CO*CN.The following observations are quoted in support of this explanation (1) Dichloro- acetic acid is formed by the action of water on chloralcyanohydrin. (2) Nitriles of dihalogenated pyruvic acids under the conditions of Wallach's method yield dihalogenated acetic acids and hydrogen cyanide. (3) Trichlorolactic acid may be converted in aqueous solu- tion into dichloroacetaldehyde hydrogen chloride and carbon dioxide j m 2i. 152 ABSTRACTS OF CHEMICAL PAPERS.this reaction undoubtedly takes place through the intermediate formation of aa-dichloro-P-hydroxyethylenecarboxylic acid or the tautomeric dichloropyruvic acid since dihalogenated pyruvic acids decompose in aqueous solution yielding dihalogenated aldehydes and carbon dioxide. Chloroacetaldehyde and dicliloroacetaldehyde behave similarly to chloral with the difference that the first-named substance cannot be converted into formic acid and chloromethane. /3-Halogenated aldehydes such as P-chloropropaldehyde cannot be converted into the corresponding acids even under the influence of hydrogen cyanide ; it would appear therefore that reactions of the nature under discussion only take place when halogen and oxygen are united t o adjacent carbon atoms. W.H. G. Catalytic Phenomena. JACOB BOESEKEN (Proc. K. Akud. Vetensch. Amsterdam 1909 12 417-421).-By the researches of Perrier (Abstr. 1900 i 331) and the author (Abstr. 1900 i 349 ; 1901 i 474) it has been shown that in Friedel and Crafts' reaction it is not the aromatic hydrocarbon but the chloride or anhydride which is first attacked by the aluminium chloride as in many cases additive products can be isolated. The author regards this initial action a s consisting of a loosening of the chloride and possibly also of the double linkings of the benzene derivative it being known that many reactions indicate the action of aluminium chloride t o be purely a dissociating one. I n order to test this view the author has examined several additional cases and with the idea that the reaction might proceed more readily if stable chlorine compounds such as hydrogen chloride could be formed during the decomposition the substances chosen were trimethylacetyl chloride dichloroacetyl chloride chloral and trichloroacetyl chloride; these all contain a more or less over- loaded carbonyl group so that the reaction could be followed by the evolution of carbon monoxide. The results obtained are as follows Trimethylacetyl chloride is resolved a t 0' according to the equation CMe,*COCl= HC1+ CO + C,H8 the isobutylene being almost entirely poly merised When gently heated chloral undergoes decomposition i n two directions ( a ) CCl,*CHO = HC1+ CO + CCI (or C,Cl,) to the extent of 70-75% ; and (6) CCl,*CHO = CO + CHCl,.With dichloro- acetyl chloride decomposition takes place in the two directions CHCI,*COCl = CO + CHCl to 60% and CHCl,*COCl= CO + HC1+ CCI the CCl presumably being polymerised t o C a o lrichloroacetyl chloride when repeatedly distilled with aluminium chloride is decomposed in one direction CCl,*COCl= CC1 + CO.It is remarkable that i n spite of its excess of chlorine atoms trichloroacetyl chloride is the most difficult of attack. The reaction seems t o proceed particularly smoothly in the case where hydrogen and chlorine atoms are united with two adjacent carbon atoms. The course of the reaction with chloral and dichloroacetyl chloride indicates that it is the movable chlorine atom which is initially rendered active. The action of aluminium chloride on trimethyl- acetyl chloride is too violent t o admit of the first stage of the reaction being ascertained.But with sulphuric acid which in many casesORGANIC CHEMISTRY. i. 153 behaves analogously to aluminium chloride and forms the same kind of additive products the reaction appears to pass through the phaves CMe,*COCl + H,SO = CMe,*CO*SO,H + HC1 and CMe,*CO-SO,H = H,SO,+CO+C,H the chlorine atom being first detached by the sulphuric acid. T. H. P. Detergent Action of Soap Solutions. 111. WALTH~RE SPRTNG (Bull. Acad. my. Belg. 1909 1059-1065 ; Arch. Sci. phys. nat. 1910 [iv] 29 42-43 and BUZZ. SOC. china. Belg. 1910 24 17-54.* Com- pare Abstr. 1909 i 625 and this vol. i 6).-The results obtained with '' red ochre " (loc. cit.) have led to the extension of t h i s investiga- tion to the action of hydrated alumina on soap solutions The results are analogous to those obtained with red ochre. To each member of a series of fourteen solutions containing quantities of soap ranging from 1/2.5% to 1/16% 2 C.C.of a mixture of water and aluminium hydroxide (equivalent to 0.0061% A1,0,) were added. The mixtures containing 1/8% and 1/16% of soap flocculated in twenty-four hours and that containing 1/4% of soap flocculated in thirty-nine hows ; the remaining mixtures except that containing l/2.5% soap having in this time flocculated partially. Changes in the relative proportions of aluminium hydroxide and soap displace these points of flocculation and also mask the periodicity. The coagulated product is pulverulent like that obtained with ferric hydroxide (Zoc.cit.) and on ignition gives a mixture of about 3 mols. of alumina to 1 mol. of sodium carbonate indicating an original adsorption product of 3 mols. of alumina with 2 of soap. Detergent Action of Soap Solutions. IV. WALTH~RE SPRING (Bull. Acad. roy. Belg. 1909 1128-1139 and BUZZ. Soc. chim. Belg. 1910 24 17-54 *).-Silicic acid clay and cellulose react with soap solutions in the same may as lampblack (Abstr. 1909 i 628) red ochre (this vol. i 6) and alumina (preceding abstract) forming with a part of the soap insoluble adsorption compounds which are less adhesive than the original colloidal substances. A soap solution in which silicic acid has been suspended and which has been clarified by deposition does not redden with phenolphthalein solution and yields less alkaline ash on evaporation and ignition than the original solution due to combination OF the silicic acid with a basic portion of the soap.Such a suspeiision on filtration yields a filtrate containing silica and the amount of the latter in the filtrate augments with the diminution in concentration of the soap solution (compare Zoc. cit.). Solutions of soap of strengths varying from 1/512% to 2% show periodicity in suspending power for silicic acid the maxima being at about 1/16% and 1/2% and the minimum a t about Its suspension in soap solution of any strength clears with difficulty but a maximum suspending power is shown by a soap solution of 1/8% strength. After ignition the clay decomposes soap less readily and deposits much more easily from suspensions the maximum suspending power for baked clay being shown by a soap solution of 1/32% strength.* The last reference contains the complete paper Parts 1-11'. T. A. H. 1/8%. Pottery clay behaves in a similar manner.i. 154 ABSTRACTS OF CHEMICAL PAPERS Cellulose has no effect on soap in solutions containing less than 1% but for concentrations above this the soap is decomposed a basic portion combining with the cellulose. T. A. H. Xanthic Acid and Dixanthogen [Ethyl Di-oxythiocarbonate]. 11. MANFRED RAGG (Chem. Zeit. 1910,34 82-84. Compare Alostr. 1908 i 604).-A pure xanthate can only be prepared when water is excluded from the reaction mixture in order t o prevent hydrolysis. To prepare sodium xanthate sodium is dissolved in excess of ethyl alcohol and then the calculated quantity of carbon disulphide added the reaction mixture being stirred and cooled meanwhile.The solutioa so obtained is fairly stable and gives a yellow precipitate with copper salts which is free from the dark brown impurities which are formed when hydrolytic products are present. The yellow precipitate consists of cuprous xanthate and ethyl di-oxythiocarbonate the reaction taking place quantitatively according to the equation 4NaS*CS*OEt + 2CuS0 = Cu,(S-CS-OEt) + S,(CS*OEt) + 2Na,SO,. The dixanthogen can be extracted from the precipitate by means of carbon tetrachloride. It is noteworthy that if sodium is added to a mixture of ethyl alcohol and carbon disulphide sodium xanthate is not formed but a compound which gives a dark red precipitate with copper salts and only changes into yellow cuprous xanthnte on warming. The following dixanthogens [di-oxythiocarbonates] and xanthates have been prepared in a similar manner from the correspouding alcohols Methyl di-oxythiocarbomate S,(CS*OMe) is a brownish-yellow viscid oil with an odour different from that of the ethyl compound and somewhat similar to that of acetone ; D = 1.180 ; b.p. 128' (decomp.). Cuprous methyl xantlLate is a pale yellow powder. n-PropyZ di-oxytl~iocarbonate S,(CS*OPr),.-Brown liquid with no characteristic odour ; D = 1.087 ; b. p. 117" (with decomposition). Cuprous n-popyl xanthate forms a pale yellow powder. isoButyl di-oxpthiocarbonate S,( CS*O*C,H,) is a yellow oil ; D=1.080; b. p. 165". In the preparation of sodium isobutyl xanthate it is necessary to use a large excess of the alcohol and to warm the reaction mixture.After the addition of the copper salt the excess of isobutyl alcohol must be extracted with 40% ethyl alcohol in which both the cuprous xanthate and the dioxythiocarbonate are insoluble. Cuprows isobutyl xanthate is a light yellow powder. AmyZ di-oxythiocarbonate S2(CS*0*C5H1& was prepared from ordinary commercial amyl alcohol. Dark yellow oil ; D = 1.007; b. p. 158'. Benzyl di-oxythiocarbonate S,(CS*O*C7H,,),.-Yellow oil with a characteristic but not unpleasant odour ; D = 1.218. Cuprous benxyl xanthate is coloured pale yellow and is stable up t o 60'. Sodium bemzyl xanthate can be recrystallised from alcohol but the aqueous solution gradually decomposes. Attempts to prepare glycerol derivatives were unsuccessful although the results obtained point to the existence of a cuprous glyceryl monoxanthate.T. S. P. Cuprouus amyl xantlLate is pale yellow in colour.ORGANIC CHEMISTRY. i. 155 Addition of Acid Anhydrides to Aldehydes and Retonee. RUDOLF WEGSCHETDER and ERNST SPATH (Monatsh. 1909 30 825-869).-Acid anhydrides for example the anhydrides of acetic acid propionic acid chloroacetic acid and benzoic acid react with aldehydes in the presence of sulphuric acid yielding di-esters of the aldehyde hydrates ; of all the aldehydes investigated citronella1 alone did not behave in this manner owing to the extreme readiness with which it is decomposed by acids. I n the absence of sulphuric acid and at high temperatures esters of the enolic form of the aldehyde are chiefly formed (compare Semmler Abstr.1909 i 364). The mode of action of the sulphuric acid is not clear; that the mixed anhydride which is possibly formed is directly concerned in the esterification of the aldehyde is not probable for the sulphuric acid may be replaced by hydrochloric acid in which case the mixed anhydride is acetyl chloride but acetyl chloride reacts with aldehydes yjelding acetates ol chlorinated alcoholp and only very small quantities of aldehyde diacetates. The sulphuric acid may likewise be replaced by nitric acid phosphoric acid or oxalic acid but not by 3-nitrophthalic acid although this is a stronger acid than oxalic acid; possibly the acid in this case is converted into the anhydride and is thus replaced by acetic acid Attempts to acetylate acetone acetophenone and benzophenone have proved unsuccessful. The aldehyde diacetates are hydrolysed quite readily by hot water and are decomposed by phenylhydrazine with the formation of aldehyde phenylhydrazones and up-acetylphenylhydrazine.The di- benzoates are hydrolysed by hot but not by cold aqueous potassium hydroxide. Certain of the compounds mentioned later are extremely poisonous The following compounds all of which have been prepared by various investigators in different ways are readily obtained by the interaction of the aldehyde and acid anhydride under the influence of sulphuric acid methylene diacetate ethylidene diacetate heptylidene diacetate chloral diacetate crotonaldehyde diacetate cinnamylidene diacetate ethylidene dipropionate chloral bischloroacetate b.p. 168O/10 mm (compare Gabutti Abstr. 1900 i 370) and methylene dibenzoate. The interaction of salicylaldehyde and acetic anhydride in the presence of sulphuric acid leads to the formation of o-acetyloxy- benzaldehyde diacetnte ; salicylaldehyde diacetate is not formed as stated by Perkin (Annalen 1868 146 371) neither could it be obtained in the manner described by Barbier (Abstr. 1880 465). Propylidem diacetate CfH1204 is a colourless liquid b. p. 184-1859 (corr.) ; isobutylidene diacetate C,H,,041 is a liquid with a not unpleasant odour b. p. 189' (corr. ) ; benxylzdens dipropionate C,,Rl6O4 is an oil b. p. 158-159O/lO mm. ; chlorcd dibenxoate C,,H,,O,C] forms large well-defined glistening crystals m. p. 63-45' ; benaylidene di6enxoate C,1H1,04 crystallises in long silky needles m.p. 6 1-62O; o-nitrobenxylidene dibenxoate C,,H1,06N is dimorphous m. p. 123-124' and 147-148O; it decomposes when distilled in a vacuum yielding o-nitrobenzaldehy de and benzoic acid ; m-nitro benxyliclene dibenxopte farms rosgttes of silky white crystals m. p.i. 156 ABSTRACTS OF CHEMICAL PAPERS. 97-99" ; the para-isomeride has m. p. 118" ; cinnamylidene dibenzoate C,,H,,O crystallises in needles m. p. 133-1 35". Ethyladene dibenzoute C,,H,,O could not be prepared by the sulphuric acid method; i t is obtained by the action of benzoic anhydride on ethylidene diacetate in the presence of a small quantity of sulphuric acid a t looo and forms small glistening crystals m. p. 70-71". W. H. G.GABRIEL BERTRAND and GUSTAVE WEISWEILLER (Compt. end. 1910 150 180-182. Compare Abstr. 1906 i 6s; 1908 i 817).-The cyano- genetic glucoside observed by Bruyning (Abstr. 1900 ii 160) in the seeds of Vicia angustifilia undergoes hydrolysis when treated with a diastase occurring in the seeds. A new sugar uicianose C,,H,,O, has been isolated from the products of hydrolysis. This is the first biose isolated from a glucoside. The compound crystallises in spherular aggregates of small needles; it is very soluble in water but only sparingly so in alcohol. A 10% aqueous solution after fifteen minutes shows a$'-%+ 1 5 . 8 O (300 mm. tube) but after twenty-two hours the rotation remains constant a t Vicianose has In. p. about 210°; i t has a somewhat higher cupric reducing power w.0. w. Theory of the Nitration of Cellulose. ALEXIS V. SAPOSCEINIKOFF (J. Russ. Phys. Chem. SOC. 1909 41 1712-1741. Compare Abstr. 190'7 i 390).-The author first discusses the work of previous investigators on the action of nitric acids cf various concentrations either alone or mixed with sulphuric acid on cellulose. The non-homogeneity of nitro-cellulose is due largely to the dilution of the nitrating mixture by the water developed in the reaction the external parts of the mass being more highly nitrated than the inner parts. The final degree of nitration is influenced by the reversibility of the process. If the uitric acid employed is sufficiently concentrated to form nitric ethers of cellulose and if it is in sufficiently great excess chemical action proceeds very rapidly.Thus with a mixture contain- ing 23.8% HNO 71.5% H,SO and 4.7% water a t ZOO it was found that after two minutes only 1*S% of the cellulose (cotton) remained unattacked the nitrated part containing 12.7% of nitrogen correspond- ing with the introduction of 10N0,; after five minutes 11N0 were introduced. These results together with those obtained with a nitrating mixture composed of 30% HNO 65%H2S0 and 5% H20 are in accord with those obtained by Lunge and Bebie (Abstr. 1901 i 508). Ternary mixtures of sulphuric and nitric acids and water were investigated by determining the densities electrical conductivities and partial pressures of the vapours of nitric acid in the mixtures (compare Abstr. 1904 ii 251,558 614 ; 1905 ii 583). The results obtained indicate that in such mixtures there occurs a reversible process of the type HNO,,nH,O + H,SO t; HNO,,(rz - x)H,O I- H2S0,,eH,0. This dehydration of nitric acid reaches a limit with a mixture of the composition corresponding with the equntion BNO + x€€,SO + xH,O = HNO + x(H,SO,,H,O) Viciaoose a New Reducing Sugar Containing Cll.+ 9*32O= [.ID + 39.72'. than maltose and is not fermented by yeast.ORGANIC CHEMISTRY. i. 157 further addition of sulphuric acid resulting in the formation of nitric anhydride. The results of the investigation of these ternary mixtures are given in the form of a triangular diagram (compare Abstr. 1907 i 390). The relation between the composition of the nitrating mixture and the degree of nitration of cellulose is discussed with the help of a large number of numerical results.T. H. P. Synthesis of the Phospho-organic Acid of the Seeds of Plants (Posternak's Anhydroxymethylene-diphosphoric Acid). ANGELO CONTARDI ( A t t i R. Accad Lincei 1910 [v] 19 i 23-27).-By the interaction of inosite and phosphoric acid in a current of carbon dioxide the author has prepared an acid CGH1sO24PG which exhibits all the physical and chemical characters of the phospho- organic acid obtained from the seeds of plants (compare Abstr. 1909 i 203). By treating its barium or calcium salt with cupric and sodium acetates the salt CGH,0,,Cu,Ba2 or C,HG0,4Cu,lCn is obtained whilst the calcio-magnesium salt agrees in chemical and physical properties with the corresponding derivative of the phytin extracted from rice bran (Zoc.cit.). On hydrolysis the acid yields com- pounds poorer in phosphorus one of which inosite-d~~~osphol.ic acid C,H,,O,,P was fisolated as a white deliquescent vitreous mass and its barzum salt C,H,,O,,P,Ba prepared and analysed. T. H. P. Phosphoric Acid Esters 'of Carbohydrates. I. On Sucrose- phosphoric Acid. CARL NEUBERG and H. POLLAIC (Biochem. Zeitsch 1910 23 515-517).-Sucrose in water freshly prepared calcium oxide phosphoryl chloride and dry chloroform were kept together a t the temperature of melting ice and the following reaction took place 2C,,H,,O + 2POC1 + 5Ca0 = 3CaC1 + H20 + 2C,2H1,0,,*0*P0,Ca. The sucrose-phosphate of calcium was separated out and analysed ; it is a fine white powder readily soluble in water. The entrance of phosphoric acid into the sucrose molecule completely abolishes i t s fermentability. W.D. N. Lipoproteins and the meaning of Fatty Degeneration in Cells. V. Further Syntheses of Lipopeptides. VI. Further Researches on the Cleavage of Lipopeptides. S. EONDI and FRANZ EISSLER (Bioclwrt. ZeitscJL 1910 23 499-509 510-513. Compare Abstr. 1909 i 458,459).-1n continuation of former work and by t h e use of the same methods the following were prepared Butyryiglycine m. p. 70'. Butyrylalanine thin prisms m. p. 88-93' ; its ethyl ester has b. p. 135-145'/14 mm. Butyrylalanylglycine thin prisms m. p. 171O. Palmitylalanylglycine needles m. p. 128-138' not sharp. Lsurylalanylglycine groups of needles m. p. 141'. isoValerylglycine thin prisms m. p. 87-90. Laurylpeptoce crystal- line. Palmitylpeptone a brownish-yellow powder.Witte's peptone was used in the preparation of the two last-named substances. Unlike proteins and nearly all non-aromatic amino-acids they are all readily soluble in alcohol. They are insoluble in light petroleum and almost so in ether,i. 158 ABSTRACTS OF CHEMICAL PAPERS. Butyrylglycine is not resolved by pepsin or trypsin but is by an extract of autolysed kidney ; butyrylalanine is only slightly decom- posed by a similar extract of liver. Trypsin has also no action on butyrylalanylglycine or laurylalanylglycine. The latter substance however is decomposed by autolysed kidney extract. No evidence of reversible action mas found. W. D. H. A New Method of Forming isoCyanates [Carbimides] and Hofmann’s Thiocarbimide Reaction. 11.RICHARD ANSCHUTZ (Anncden 1910 371 201-226. Compare Abstr. 1908 i 326)- The behaviour of the mercuric and chloromercuric salts of eth ylthiol- carbnmic acid and isobutylthiolcarbamic acid when heated alone likewise the decomposition of mercuric and chloromercuric ethylditbio- csrbamates by boiling water and by heat alone has been investigated quantitatively with the result that the conclusions published previously (Zoc. c i t . ) have to be modified slightly. Chloromercuric ethylthiolcarbamate when heated decomposes thus 3NEIEt*CO*SHgCl -+ Hg,S,Cl + COS + 2EtNCO + NH,EtCl ; in this way it is possible to prepare alkylcarbimides without difficulty. The corresponding ethyldithiocarbamate is decomposed by heat analogously. Mercuric ethylthiolcarbamate when heated alone decomposes into red mercuric snlphide carbonyl sulphide and s-diethylcnrbsmide ; the formation of hydrogen sulphide could not be detected owing to the readiness with which it interacts with ethylcarbimide yielding csarbonyl sulphide and s-diethylcarbamide.Mercuric ethyidithio- carbamate when similarly treated decomposes in two ways represented by the equations [NHEt*CS*S],Hg -+ (1) HgS + CS + CS(NHEt) or (2) HgS + H,S + 2EtNCS ; the mercuric sulphide obtained in these reactions is black. The extent to which the reaction represented by (2) takes place depends on the rate of heating for hydrogen sulphide and ethylthiocarbimide interact yielding carbon disulphicle and s-diethylcarbamide. The salt undergoes the same change when boiled with water but to a greater extent (about 50%) in the manner indicated by (2).I n the preparation of alkyl- carbimides by. Hofmann’s method however an excess of mercuric chloride is employed ; this results in the formation of chloromercuric ethyldithiocarbamate which is decomposed by boiling water thus NHF,t*CS*SHgCl= HgS + SCNEt + HC1. The isobutyl salts undergo the same changes as the analogous ethyl compounds. Chloromercuric ethyldiihiocarbamatee is prepared by adding an aqueous solution of ethylammonium ethyldithiocarbamat e to a cold solution of mercuric chloride in acetone; it crystallises in white leaflets. W. H. G. Ethyl Oxalosuccinonitrile and Diethyl Dioxalosuccinonitrile. WILHELH WISLICENUS and HEINRICH ELVERT (Beg-. 1910,43 228-234. Compare Abstr. 1908 i 965).-Ethyl oxalosuccinonitrile has m.p. 112-113° not 102-103° as previously stated. A better yield i s obtained if the method of preparation formerly given is modifiedORGANIC CHEMISTRY. i. 159 so as to ensure the presence of an excess of succinonitrile throughout the reaction. According to observations made by A. Hantzsch and H. Ley alcoholic solutions of the @-form fluoresce. H. Ley and von Engelhardt find that 0-005N-alcoholic solutions of the a-form also fluoresce but the fluorescence disappears when an excess of sodium ethoxide is added so that i t is due t o the presence of a small proportion of the p-form. By doubling the quantities of ethyl oxalate and potassium ethoxide taken and reversing the order of addition in the method formerly des- cribed for the preparation of ethyl oxalosuccinonitrile the dipotassium salt of diethyl d~oxalosucc~noni~ri~e may be obtained (compare Nichael Abstr.1903 i 736). The substance gives a deep reddish-brown coloration with ferric chloride and ammonia is evolved when it is boiled with ammonium chloride. On acidifying its aqueous solution the monopotassium salt is precipitated. It forms small lustrous needles m.p. above 140' (decomp.) and gives a red coloration with ferric chloride. Copper acetate yields with both potassium salts and with the free nitrile the same nzonocopper salt in the form of small green needles which become brown at 170° and melt at 220-225". By acidifying an aqueous solution of the potassium salt the enolic form of diethyl dioxalosuccinonitrile may be obtained as a viscous brown oil which on shaking with water yields a hydrate which forms colourless needles m.p. 52-533 gives a weak red coloration with ferric chloride and is probably the dihyldmte. It readily loses water forming the monohydrate m. p. 102-104'. This hydrate also gives a weak red coloration with ferric chloride. The enolic form and its hydrates change spontaneously into the ketonic form which crystal- lises in yellow prisms m. p. 123-124O (Michael Zoc. cit.). The alcoholic solutions of this substance do not fluoresce. It is probably a ketonic enol of the constitution C02Et*Co*CH(CN)*C(CN):C(OH)*C02Et. R. V. S. Carbon Subnitride C,N,. CHARLES MOGREU and J. CH. BONGRAND (Compt. rend. 1910,150 225-227).-This substance has been obtained by the elimination of 2H,O from acetylenedicarboxylamide NH,*CO*C i C* CO*NH ; it may therefore be regarded as dicynnoacetylene NC*CiG.CN.The analysis of the compound presented difficulties but it has been shown t o contain less than 0.6% of hydrogen. Carbon subnitride occurs as slender colourless needles m. p. 20*5-31° b. p. 76'/753 mm. Dt50*9703. The vapour is powerfully irritant and has an odour resembling that of cyanogen ; at 1 30' i t is spontaneously inflammable in air burning with a fiame like that of cyanogen. The molecular refractions for the D-sodium line and for the a- p- and y-hydrogen lines have been determined M 21.641 ; M,-Ma 1.023. Refraction and dispersion are considerably higher than the values calculated on the assumption that the compound has the foregoing constitution (compare Abstr.1906 ii l) probably through the contiguity of the three triple linkings. The vapour density between 5 6 O and 184' is in agreement with the formula C,N,. w. 0. w.i. 160 ABSTRACTS OF CHEMICAL PAPERS. Naphthene Formation. IV. Formation of Naphthene from Olefines and from Artiflcial Lubricating Oil and the Synthesis of the Latter. CARL EKGLER and 0. ROUTALA (Bw. 1910 43 388-397).-The conversion of olefines into naphthenes does not as a rule take place directly. Probably in the first place polymerisation to polyolefines takes place and these on account of their content of labile hydrogen atoms yield firstly paraffins and subsequently decom- pose into naphthenee on the one hand and lubricating oils on the other. When the decomposition is carried out at lorn temperatures for example with aluminium chloride at the ordinary temperature or at the boiling point of amylene relatively little naphtheiie is formed along with paraffins and lubricating oil ; at higher temperatures relatively more naphthene is formed and the lubricating oils in part decompose forming naphthene.When amylene is heated in tubes under pressure methane and hydrogen are formed. By the action of aluminium chloride on amylene in the cold an oil is formed containing more than 87% of carbon having the composition CZnHglt-6 and agreeing in composition and properties with natural lubricating oil. When heated for some time at 350° the lubricating oil gives rise to a mixture of unsaturated and saturated hydrocarbons ; the lower boiling fractions are in the main honiologues of methane the higher boiling fractions contain increasing proportions of naphthenes.E. F. A. Naphthene Formation. V. The Products of Heating Cylinder Oil Under Pressure. CARL ENGLER and B. HALMAI (Ber. 1910 43 397-405).-Large quantities of a Baku cylinder oil were heated from four to six hours under pressure a t 400-430'. The product (b. p. 25-250°) was carefully fractionated and the constituents of the successive fractions identified. The earlier fractions contained almost entirely paraffin hydrocarbons ; as the boiling point rose the proportion of naphthenes present increased. The highest boiling fractions consisted of lubricating oils which behaved in a similar manner to the nctturd oils and those synthesised from amylene. E.F. A. Naphthene Formation. VI. Possible Formation of Hydro- carbons in Nature and the Origin of the Optical Activity of Petroleum. CARL ENGLER (Bey. 1910 43 405-411. Compare pre- ceding abstracts).-In nature bituniinated animal and plant residues break down into solid paraftins olefines and liquid paraffins. The effect of heat and pressure in conjunction with long periods of time causes the solid paraffins to break down into liquid paraEns and olefines. The olefines condense to polyolefines ; this gives rise t o liquid paraffins naph- thenes and lubricating oils; the last a t a still higher temperature undergo further decomposition into liquid paraffins naphthenes and lubricating oils with 1e.s hydrogen. None of these changes is reversible. They take place simultaneously and no great heat is required if the period of time be long enough. The petroleumORGANIC CHEMISTRY.i. 161 which have been exposed to the highest temperature contain most naphthenes and lubricating oils although they may be younger in the geological sense than oils which contain mostly paraffins and have been exposed to lower temperatures. The explanation given is in agreement with the fact that oils rich in naphthenes are usually rich in lubricating oils and vice versa. The higher boiling fractions of the heated natural cylinder oil (see previous abstract) still preserve some optical activity and it would appear that the optically active constituents of petroleum oppose great resistance t o racemisation by heat. Inasmuch as the heat in the natural process is probably less than that used experimentally the fact that the natural petroleums are optically active is not in opposition to the combiiied heat and pressure theory of their formation.E. F. A. Relation between Colour and Constitution. IWAN OSTROMIS- SLENSKY (Bey. 1910 43 197-198).-A claim for priority. Werner's observations on nitro-compounds and his deductions therefrom (this VOI. i 80) had been made by the author in a paper sent to but not published by the German Chemical Society. c. s. Hydrocarbons from Cinnamyl Chloride CHPh:CH*CH,Cl. HANS RUPE and J. BURGIN (Bey. 1910 43 172-178).-Cinnamyl chloride prepared by the action of hydrogen chloride gas on cinnamyl alcohol (compare Emde Abstr. 1909 i 708) is a mobile liquid b. p. 11 6-1 1 7 O p min. solidifying to large colourless needles m.p. 8-9'. Cinnamyl bromide is obtained on heating cinnamyl alcohol with phosphorus tribromide in benzene solution in colourless needles m. p. 30° b. p. 130°/10 mm. Cinnamyl chloride reacts with magnesium in ethereal solution ; the product when decomposed with water yields a mixture of two hydro- carbons. u[- Uiphen yl- Aaa- hexadiene CHPh CH*CH CH,*CH CHPh forms thin irregular colourless lustrous plates m. p. 82" b. p. 211'/11 mm. which in solution show a reddish-blue fluorescence. It yields a tetra- bromide separating in colourless feathery needles m. p. 194'. as-DiphenyZ-Aa-hexene CHEtPh-CH,*CH:CHPh is a colourless mobile fluid b. p. 190°/11 mm. D20 0.9915 12:' 1.588; the hydro- bromide is a dark viscid oil. The constitution is indicated by the fact that on oxidstion with potassium permanganate benzoic acid and phenylsuccinic acid are formed.y-Brornou-phenyt- propune is obtained by the action of phosphorus tribromide on hydro- cinnamyl alcohol; the colourless liquid has b. p. 109'/11 mm. The bromide interacts with magnesium forming propylbenzene and diphenylhexane. E. F. A. y-Chloro-a-phenylpropane could not be prepared. Mobility of the Hydrogen Atoms of the Methylene Group in Compounds of the General Formulae R-SO,. CH 2* CN R= SO,*CH,= CO-NH R-SO,*CH,=CO,Et. JULIUS TROGER and E. Lux (Arch. Pharrn. 1909,247,618-649).-Thei. 162 ABSTRACTS OF CHEMICAL PAPERS. close analogy between P-sulphonecarboxylic acids and P-ketonic acids studied by Rossing (Abstr. 1890 781) and Engelhardt (J.p r . Chew. 1889 [ii] 40,540) and further illustrated by Michael and Comey by the preparation of the sodium arid alkyl derivatives of the former (Abstr. 1884 319 ; 1885,906 ; 1890 781) suggests that the groups RSO and C0,Et exert the same influence as the groups RCO and C0,Et on the neighbouring methylene group. The mobility of the rnethylene hydrogen atoms in arylsulphoneacetonitriles has already been shown t o some extent by Troger and Hill0 (Abstr. 1905 i 336) whilst the similar behaviour of such nitriles and phenylacetonitrile with amyl nitrite and sodium ethoxide and with aldehydes and sodium hydroxide has been manifested by Tiiiger and Prochnow (Abstr. 1908 i 798). The present paper deals with the influence on the rnethylene hydrogen atoms of compounds RSO,*CH,X exerted by different groups X (where X = CO,R CO*NM or CN) the case of arylsulphonated ncetnniides being of special interest since Troger and Lindner (Abstr.190S i 633) have shown that the methylene hydrogen atoms of the corre- sponding arylsulphonated thioacetamides are not replaceable by alkali metals or alkyl groups. The results of experiments on arylsulphoriated acetonitriles amides and esters with alkalis alkyl halides aldehydes and amyl nitrite and sodium ethoxide show that in these compounds the group CO*NH does not act like CN and exerts an influence similar to but weaker than that of the group C0,Et. For example with alkalis arylsulphonated acetic acids yield carbon dioxide and sulphones ; their esters yield disodinm deriratives ; arylsulphonated ace tarnidee are insoluble in sodium hydroxide and arplsulphonated acetonitriles although soluble in dilute sodium hydroxide are not hydrolysed even by boiling this only being effected by concentrated hydrochloric acid under pressure.RSO,*CH,*CO,Et leads as is known to the formation of mono- and di-alkyl derivatives on RS0,*CH2*CX only to the production of dialkyl derivatives and on RSO,*CH,-CO*NEI results in simple hydrolysis by the alkali. Amy1 nitrite and sodium ethoxide simply hydrolyse arylsulphonated acetic esters but react smoothly with the amides and nitriles t o form isoni troso-compounds by replacement of the methylene hydrogen atoms. The compounds obtained from the nitriles have the formula RSO,*C( :NOH)*CN and the following oximes and their derivatives are described; the aodium and silver salts are yellow powders and the lead salts yellomish- white powders.The action of alkali and alkyl halides on Hethyl Benzyl Benzoyl Acetyl R. In. p. ni. p m. p. in. p; ni. p. P 11 ............... - 57" 7:" 153 91" y-C,H4Me - p-C,H,Cl ...... 147" 115 SO 162 126 p-C H4Br ...... - 125 98 171 149 p-C,H,I ......... 171 125 129 175 166 OMe'C,H ,...... 152 94 102 - - OEt'C,H ...... 147 87 97 ether ether derivatives derivatives - - ...... 99 90 - - The following compounds RS0,*C(:NOH)*CO*NH2 are obtained inORGANIC CHEMISTRY i. 163 a similar way but less readily from arylsulphonated acetamides ; the figures are m. p.,s R=Ph 153' (decomp.) ; R=p-C,H,Cl 155O (decomp.) ; R=p-C,H:,Br 152' (decomp.) ; R =p-CGH,I 178' (decomp.); the sodium silver and lead salts have been prepared. Troger and Prochnow (Zoc.cit.) have shown that arylsulphonated acetonitriles like phenylacetonitrile readily condense with certain aromatic aldehydes in the presence of a little sodium hydroxide. Arylsulphonated acetamides or acetic esters do not condense with aldehydes as a rule but from salicylaldehyde the same compounds Rs02a~-co>0 are obtained by loss of water and ammonia and water and ethyl alcohol respectively. Of such CompoundP the following are mentioned H = Ph 219'; R =p-C,H,Cl 243' ; R =p-CGH4Br 244' ; R =p-CGH41 248'. The bromination of arylsulphonated acetic acids esters and amides doe3 not proceed smoothly but the nitriles yield compounds RSO,*C Br,-CN which are also obtained by the action of bromine on the sodium salts of the corresponding oximes R = Ph 1233 ; R =p-U6H4Cl 126' ; PAUL YVON (Contpt.rend. 19 1 0 150 283-285).-Clarke's salt C4~50,(SbO)*C,H,N (Abstr. 1882 1051) separates with 1 mol. H,O when allowed to crystallise from an aqueous solution at 15" ; the crystals deposited at 35' are anhydrous. The hydrated salt forms stellate clusters of long prisms which become opaque on exposure losing water of crys tallisation. I n 2-5% aqueous solution the anhydrous salt has {a]; 121.28O D1* 2.112 ; one gram of the substance is soluble in 6-36 grams of water at 15'. The solubilities in water and alcohol at different temperatures are CH-C H R =pC,H,Br 129' ; R =p-C,H,I 132'. c. s. Aniline Antimony1 Tartrate. The hydrate has [a] 115.61' DZ0 1.569.given and also crystallographic details of the anhydrous-salt. w. 0. w. Complex Compounds of Aluminium Bromide with Organic Compounds. IWAN A. KABLUKOFF and AL. SACHANOFF (J. 12uss. Phys. Chem. Soc. 1909 41 1755-1'762. Compare Menschutkin Abstr. 1909 i 897 900).-Investigation of the melting-point curves of mixtures of aluminium bromide with benzene toluene xylene naphthalene dibromomethane bromobenzene and p-dibromobenzene iidicates either a slight tendency of these organic compounds to give double compounds with aluminium bromide or the extreme instability of such complex compounds. It seems indeed that for stable compounds to be formed with aluminium bromide the presence of oxygen or nitrogen in the organic component is a necessary condition. With aniline four compounds are formed by aluminium bromide A12BrG,2NH,Ph m.p. 90' ; A1,BrG,3NH,Yh a. p. 114' ; A12Br,,4NH,Ph m p. 105'; Al,Br,,8NH2Ph m. p. 122'. These compounds dissolve in benzene or ether and are decomposed by water giving aluminium. hydroxide and aniline hydrobromide.i. 164 ABSTRACTS OF CHEMICAL PAPERS. p-Bromoaniline gives two compounds A12Br6,2C,H,Br*NH m. p. 140" and A12Br,,5C,H,Br*NH2 m. p. 125'. Diphenylamine gives the compound Aj2Br6,2NHPh m. p. somewhat above 200' ; dimethyl- aniline A12Br,,2NMe,€'h m. p. 95' ; methylaniline Al2Br6,2NHMePh m. p. 7s"; nitrobenzene A1,Br6,2Ph-NO m. p. 8 4 O ; pyridine A12Br6,4C5NH m. p. about 170" (decomp.) ; benzonitrile the three compounds A12Br,,2Ph*CN m. p. 140-150' ; A1,Br6,3Ph*CN II;. p. about 140° and A12Br6,4Ph*CN m.p. about 150". Of the oxygenated compounds acids alcohols aldehydes and ketones form double compounds with aluminium bromide (compare Walker and Spencer Trans. 1904 85 1106). Further esters of benzoic acid give compounds of the formula A12Br6,2Ph*C02R that formed by methyl benzoate having m. p. 100". Esters of fatty acids react energeticslly with aluminium bromide hydrogen bromide being evolved. The double compounds formed by aluminium bromide with organic nitrogen compounds are more stable than those containing organic oxygen compounds. The existence of complex compounds containing an odd number of molecules of an organic compound leads to the conclusion that the aluminium bromide present exists in the form of a doubled molecule A12Br,. T. H P.Preparation of Sodium Arylimides. DEUTSCHE GOLD- & SILBER-SCHEIDE-ANSTALT (D.R.-P. 2 15339).-The replacement of an aminic hydrogen atom by sodium in aniline has been shown to occur only after prolonged heating at a high temperature. It is now found that the reaction takes place much more readily in the presence of a catalytic agent such as copper nickel cobalt or any other heavy metal its oxide or salt. Under these conditions sodium reacts with aniline a t 140"; the reaction also takes place with o-toluidine or methylaniline ; the products are hygroscopic fairly-stable substances but are decomposed by water into sodium hydroxide and original base. F. M. G. &I. Preparation of Cerium Phenoxides. CBEXISCHE FABRIK AUF AKTIEN VORM. B. SCHERING (D.R.-P. 2147S2).-The compounds formed by the interaction of cerium salts with phenolic compounds have similar disinfectant properties to the bismuth phenoxides but are less toxic and irritating than the phenols themselves.Cerium phenoxide prepnred from cerium nitrate phenol and sodium hydroxide is pale brown odourless and insoluble in water ; it contains 317; cerium. Cerium o-methoxyphenoxide analogoiisly prepared is pink insoluble in water but soluble in alcohol chloroform or ether. Cerium /3-nuphthoxide has similar properties and contains 30% of cerium. F. 11. G. 1T. Behaviour of Pheuyl Sulphide towards Hydrogen Peroxide. OSCAR HINSBERG (Bev.,l9 10,43,2S9-290).-When a solution of phenyl sulphide in glacial acetic acid is treated with the equivalent qnantit,yORGANIC CHEMISTRY.i. 165 of hydrogen peroxide at the ordinary temperature phenyl sulphoxide is formed (compare Abstr. 1908 i 875). If however an excess (more than '2 gram-molecules) of hydrogen peroxide is used and the mixture kept at the room temperature crystals of phenyleulphone begin to form after a few days. The quantity of sulphone is increased by precipita- tion with water. Phenylsulphoxide could not be detected in t h e reaction mixture. If acetone is used as the solvent (compare Smiles and Gazdar Trans. 1908 93 1833) there is no action between phenyl sulphide and hydrogen peroxide at the ordinary temperature. Reaction only takes place after heating for an hour in a sealed tube a t 80-100" and even in the presence of excess of hydrogen peroxide only phenyl sulphoxide is formed.It is assumed that when glacial acetic acid is used as the solvent it takes part in the reaction owing to the formation of peracetic acid CH,* CO *O OH. BROR HOLMBERG (Be?. 1910 43 226-227). -The author has shown previously (Abstr. 1908 i 308) that the mercaptans and thionyl chloride interact with the formation OF disulphide trisulphide water and hydrogen chloride. H e now finds that thionylaniline also reacts with mercaptans ; with ethyl mercaptan thioglycollic acid and ethyl thioglycollate the reaction is so violent that the reagents must be diluted with ether or carbon tetrachloride. It is however very difficult to isolate pure products from the reaction mixture. When p-tolyl mercaptsn is used the trisulphide is readily isolated. The mixture of the mercaptan and thionylaniline was heated on the water-bath.After cooling and remaining for a few days a solid separated which had m. p. 81-82O and proved to bep-tolgl trisulphide. It forms small plates thin prisms or needles and is pale yellow. The crude solid was contaminated with a yellow oil which was a mixture of aniline p-tolyl disulphide and aniline sulphate the latter compouud resulting from the hydrolysis of some of the thionylaniline by water formed in the reaction with the mercaptan T. S. P. p-Tolyl Trisulphide. 4RSH + C,H,N:SO = R,S + R,S + H20 + C,H,*NH2. The following summary shows that the melting points of the thio-di- acetic acids and of the p-tolyl sulphides show a regularity similar to that observed in many homologous series of carbon compounds.However the member with an uneven number of sulphur atoms has a higher melting point than the next member with an even number. S(CH2*C0,H) ................. 129" p-(C,H,Me),S ..................... 57" S,(CH2T!0,H) .................. 124 p-(C,H,Rle)2S ..................... 82 S,(CH;CO,H) .................. 113 p-(C,H,Me),S4 ..................... 75 S,(CH2*C0,H)2 ................. 109 p-(C,H,Me),S .................... 46 T. S. P. Phenanthrene Series XXVI. Conversion of 9-Chloro-10- hydroxyphenanthrene into other Phenanthrene Derivatives. JULIUS SCHMIDT and HERNANN LUMPP (Ber. 1910 43. 423-438).- 9-Chloro-10-hydroxyphenauthrene (Abstr. 1909 i 35 j can be used for VOL. XCVIIX. i. ni. 166 ABSTRACTS OF CHEMICAL PAPERS. the preparation of 3-nitrophe~anthraquinone (Zoc.cit.) of 9 1 O-chloro- 3-bromohydroxyphenanthrene and other phenanthrene derivatives. 9 (1 O)-ChZoro-3-bromo-l O( 9)-hydrox?llp~~en~nlhrene C,,H80Cl13r pre- pared by the action of a carbon disulphide solution of bromine on 9-chloro-lO-hydroxyphenanthrene forms colourless prisms m. p. 142' and dissolves in aqueous solutions of alkalis. I t s acetyl derivative C',,H,,O,ClBr has m. p. 158-159' and the bmxoyl derivative which crystallises in yellow prisms m. p. 179-1 80'. When reduced with zinc dust and glacial acetic acid the bromo- derivative yields 3-bromo-9( lO)-hydroxyphenanthrene C,,K,OEr which could not be crystallised on account of the readiness with which i t dissolves in most solvents. I t s acetyl derivative ClGH1102Br crystal- lises in pale yellow prisms m.p. 135'. The position of the bromine atom in the chlorobromohydroxyphenanthrene follows from the readi- ness with which it can be oxidised by chromic acid to S-bromophen- anthraquinone (Schmidt and Ladner Ber. 1905 37 3571) which appears to exist in yellow and reddish-brown chromo-isomeriiles. The dioxime C1,H902N2Br prepared by Schmidt. and Soll's method (Abstr. 1907 i 630) forms green crystallifie aggregates m. p. 212' (decomp.). The monosemicarbaxone Cl,Hl,02N,Br forms yellow crystals m. p. 242' (decomp.) and the mono;D?LenyllL~draxone has ni. p. 17'7'. The quinone can be reduced to the quinol by means of phenylhydr- azine but i t is difficult to isolate tho free dihydroxy-compound. Its acetyl derivative 3-bromo-9 1 0-diacetoxyphenantlwene ClSHl3O4Br1 crystallises in colourless needles m.p. 177-1 78'. 3 9( lO)-Dihydroxyphenanlhrene C,,H,(OH) formed when the 3-bromo-9( 10)-hydroxy-compound is fused at 340' with potassium hydroxide crystallises in colourless prisms m. p. 175". The yield is small Fuming nitric acid converts the bromophenanthraquinone into a dinitro-derivative C,,H,O,N?Br which crystallises in pale yellow slender needles m. p. 298'. The monoxime C,,H,O,N,Br forms green prisms m. p. 196' (decomp.) ; the semicn~baxone C15H,06N,Br forms yellowish-brown prisms m. p. 272'. The dinitro-quinone condenses with an alcoholic solution of o-phenyl- enediamine hydrochloride yielding 3-broinodiszitropl~enantl~rapJ~enccxine C,,H,O,N,Br as a reddish-white powder and when heated on the water-bath with concentrated aqueous ammonia the quinone yields 3-brmonitroaminophenant?~rccpuinone NO,*C1,H,BrO2*NH2 as a dark brown substance m.p. 280-282' (decomp.). The diacetyl derivative C18H110,~,Br forms a n ochre-yellow powder m. p. 260' (decornp.). Reduction of the 3-bromodinitrophenanthraquinone with tin and concentrated hydrochloric acid leads to the formation of 3-chloro- diamilzophenanthraquino~ which can be readily oxidised by atmospheric oxygen to 3-~hlorodiarninop~ei~~~n~~ra~uinoize Cl4H,ClO2(NH2),. The base can be diazotised readily and the diazo-solution forms azo-dyes with phenols. The dioxime C14H,102N4CI forms a deep bluish-black powder m p. 264O (decomp.). When the diamino compound is diazo- c2p&Cl Br C&,,ON,Br,,ORGANIC CIIEMISTRY. i. 167 t ised and tho solution boiled 3-ch Z o r o d i ~ y d r o ~ y ~ T L e a ~ ~ t ~ r a ~ ~ C,,H,ClO,(OH) is obtained as a dark red powder which is not a substantive dye. The acetyl derivative C,,H,,O,Cl forms brownish-red crystals m.p. 245'. J. J. S. Preparation of Carbonateguaiacol-5-sulphonic Acid and its Salts. F. HOFFMANN LA ROCHE & Co. (D.R.-P. 215050. Compare Abstr. 1909 i 780).-The preparation of carbonatoguaiacol-5- sulphonic acid and its salts by the action of concentrated sulphuric acid on guaiacol carbonate has been described previously. The free acid forms colourless to dark red hygroscopic crystals ; its cold aqueous solution gives no colour with ferric chloride but on heating carbon dioxide is evolved. Potitssiutn carbonatoguaiacoZ-5-s~~p~onnte crgstallises in needles has a neutral reaction gives no colour ,with ferric chloride but by pro- longed boiling of its aqueous solution is decomposed into potassium guaiacol-5-sulphonate with evolution of carbon dioxide.F. M. G. RE. Hydroxyphenylalkylamines and Dihydroxyphenyldkyl- amineS. CARL MANNICH and w. JAcossoHN (Be?.. 1910 43 1 89-197. Compare Rosenmund this vol. i 106 ; Barger Trans. 1909 95 11 23 21 93).-Homologues of p-hydroxyphenylamine have been obtained by reducing aldoximes or ketoximes to bases of the type OMe*C,H;CH,-CHR*NH or C,H,(OMe),*CH,=CHR-NH and converting these by heating with hydriodic acid into the corresponding phenolic amines. The ketones selected were pmethoxybenzyl methyl ketone 3 4methylenedioxybenzyl methyl ketone and 3 4-dimethoxy- benzyl methyl ketone ; the aldehydes were p-methoxyphenylacet- aldehyde and 3 4-dimethoxyphenylacetaldehyde. To obtain p-methoxybenzyl methyl ketone b.p. 136-140°/12 mm. anethole was converted into the dibromide and this into the bromo- hydrin OMe*C,H4;CE-I(OH)*CHMeBr which on heating with alcoholic potassium hydroxide gave anetholoxide ; this on heating at 220" undergoes rearrangement to the ketone OMe*C,H,*CH,*COMe. The oxime on reduction with sodium amalgam in acetic acid solution forms p-methoxyphenyZisopropyZamine OMe*C,H,*CW,*CHMe=NH,,. a colourless strongly alkaline oil b. p. 15S0/25 mm. j the hydroclJorzde forms large colourless crystals m. p. 210'. p-HydroxyphenylisopropyZamine crystallises in colourless rosettes m. p. 125-126'; the ltydriodide has m. p.155'. isoEugenoZ inethyl ether bromohydrin C6H,( OMe),*CH( 0 H) * CH MeBr has ru. p. 75". It yields the oxide already described by Fourneau and Tiffenenu (Abstr. 1905 i 591) which readily undergoes rearrange- ment to 3 4-dimethoxybenzyl methyl ketone b. p. 198O/20 mm. 3 4-Dimetl~oxyphenyZisopropyZarnine is an almost colourless oil b. p. 166-11;S0/20 mm. ; the hydrochloride has m. p. 144". 3 4-Di- hydro~~pheny Zisoprop~Za~~ne C,H,( OH),* CH,* CHMw NH yields a hydyochlmide m. p. 190-192'. TL2i. 168 ABSTRACTS OF CHEMICAL PAPERS. 3 4-MethyZenedioxyphenylisop~*opyZamins is a colourless oil m. p. 157"/22 mm. ; the hydrochloride has m. p. 18O-18lo. Homoanisaldehyde OMe* C,H,*CH,*CHO is conveniently pre- pared by oxidation of p-methoxyetyrene with mercury oxide and iodine ; the oxime forms prisms m.p 120' (compare Rosenmund this vol. i 106). The oxime of homoveratraldehyde crystallises in prisms m. p. $0-9lo; the oxime of veratraldehyde has m. p. 83". On reduc- tion the oxime yields 3 4-dirnethoxyphenylethyZamine a faintly yellow-coloured oil b. p. 18t3'/15 mm.; the hydrochloride has m. p. 15 4-1 55". C,H,(OH),* CH,=CH,*NH forms a crystalline hydrochloride decomp. 220' ; it shows a green coloration with ferric chloride. 3 4-Dih ydrox,yphen ylethyhmina E. F. A. Quinocarbonium Perchlorates (11) and the Solvent Action of Chlorinated Ethanes. KARL A. HOFMANN HEINZ KIRMREUTHER and A. THAL (Ber. 1910 43 183-188. Compare this vol. i 3).- The triphenylcarbinyl perchlorates crystallise so well that pure preparations are readily obtained from impure carbinols. I n accord- ance with their intense colour they are easily ionised so t h a t in solvents such as tetrachloroethane which is unable t o dissociate triphenylmethyl chloride they still conduct the electric current.Aurin perchlomte forms doubly refractive four-sided prisms which in direct light are orange-red with a light blue reflex. p-Trianisyl- carbinol perchlorate (compare Gomberg and Cone this vol. i 55) crystallises in cinnabar-red fiat needles. It is relatively stable towards water. Triphenylcarbinyl perchlorate dissolves with a reddish-yellow coloration in tetrachloroethane and tri-p-anisylcarbinol perchlorate with an intense orange coloration. Both solutions conduct electricity likewise those of the perchlorates in ethylene chloride.The solubility of the perchlorates in a number of solvents has been compared by the intensity of the colour produced in the saturated solution. The solvents take the following order the more highly coloured coming first ethylene chloride tetrachloroethane chloro- form dichloroethylene pentachloroethane trichloroethylene per- chloroethylene carbon tetrachloride. The last two or three solvents only become coloured when boiled with the perchlorate. Mercuric chloride dissolves in these solvents in precisely the same order the solubility being greatest in ethylene chloride and almost nothing in carbon tetrachloride. This confirms the view t h a t the perchlorates are of the nature of metallic salts. The solvents dissolve sulphur in a n altogether different order ethylene chloride being the least perchloroethylene the most effective solvent.E. F. A. Action of a-Bromonaphthalene and Magnesium on Certain Carbonyl Compounds. E. SCHURAKOVSKY (J. Rwse. Phys. Chem. Soc. 1909 41 1687-1694).-The interaction of a-bromonaphthalene magnesium and acetone yields the compound MgBr*O*CMe,*C,,H7,ORGANIC CHEMISTRY. i. 169 which is decomposed by water giving a-naphthyldimethylcarbinol (compare Grignard Abstr. 1901 i 393). When heated with anhydrous oxalic acid this alcohol yields P-naphthylpropylene (Crignard Zoc. cit.) b. p. 251-251.5'/744 mm. DF 1.0078 d5 1.60684 ; the molecular refraction calculated according to the Lorenz and Lorpntz formula is 57.554 which as is often the case with naphthalene derivatives diff ers considerably from the calculated value 55.38'7.OH prepared from a-bromonaphthalene magnesium and tolyl methyl ketone was obtained as a dark viscous impure mass. When heated with anhydrous oxalic acid this alcohol loses water giving as-a-naphthyl-p- tolylethylene C6H,Me*C(C,o~7):CH which is a viscous faintly yellow liquid b. p. 224-226O/20 mm. DZl5 1.0693 and combines with ZBr per mol. Anis y Z-a-naphth ylcarbinol OMe*C,H,*CH( CloH7)*OH prepared from a-bromonapht halene magnesium and anisaldehyde crystallises in small needles or rhombic prisms m. p. S7". a-.NaphthylpropenyZcar6inoZ CHMe:CH*CH(C,,K,)*OH prepared by the interaction of a-bromonaphthalene magnesium and croton- aldehyde is a faintly yellow viscous liquid b. p. 204-210°/22 mm. T. H. P. p- ToZyZ-a-nap~tlyZ?n~t~~~Zcar~~~Z C,H,Me* CMe( C Preparation of Nitriles.E. EMMET REID (Anzer. Chem. J. 1910 43 162-1Sl).-It was shown by Letts (Abstr. 1572 1020) that nitriles can be prepared by the action of potassium thiocyanate on organic acids. Kriiss (Abstr. 1884 1314) found in the case of benzonitrile that a better yield could be obtained with lead thio- cyanate than with the potassium salt the reaction being represented by the equation 2C,H,*C@,H + Pb(CNS) = ZC,H,.CN + PbS + H2S + 2C0,. I n attempting to prepare benzonitrile by Kruss' method the yield obtained amounted to only 36% of the calculated and it was observed that only a very small quantity of hydrogen sulphide was evolved. It was therefore considered likely that the hydrogen sulphide might have entered into the reaction and led to the formation of complex products In order to avoid the formation of hydrogen sulphide R mix- ture of lead benzoate and lead thiocyanate mas heated and it was found that in these circumstances a much better yield of benzonitrile was obtained.Experiments have been made to ascertain the effect of heating lead sodium zinc and barium benzoates with potassium cyanate lead cyanate potassium t hiocyanate lead thiocyanate barium thiocyanate lead ferrocyanide lead cyanide and sulphur lead ferrocyanide and sulphur zinc ferrocyanide and sulphur potassium ferrocyanide and sulphur and silver cyanide and sulphur. I n each case a considerable quantity of benzonitrile was obtained. The results of these experi- ments are tabulated. The best method of preparing benzonitrile in the laboratory is to distil a mixture of dry zinc benzoate and dry lead thiocyanate a yield of 79-9 1% being thus obtained.A mixture of equivalent quantities of lead ferrocyanide and sulphur may be used instead of the thiocyanatei. 170 ABSTRACTS OF CHEMICAL PAPERS. and in this case a yield of about 74% is produced. the benzonitrile takes place as follows The formation of Zn(C02*C6H,) + Pb(CNS) = PbS + ZnS + 2C0 + 2C,H,*CN. On applying this method to other acids it was found that the nitriles of the three aminobenzoic acids p nitrobenzoic acid salicylic acid and phthalic acid could not be obtained in this way but that when lead rn- or p-bromobenzoate was distilled with lead thiocyanate a satisfactory yield of the bromobenzoni trile was produced in each case.E. G. Action of Alcoholic Hydrogen Chloride on m-Methylnitroso- aminobenzoic Acid. JOSEF HOUBEN and WALTER BRASSERT (Ber. 1910,43,206-212. Compare Abstr. 1909 i 92I).-m-Aminobenzoic acid in glacial acetic acid is treated with methyl sulphate. After one hour's heating and keeping for twelve hours the crystals of m-aminobenzoic acid sulphate are removed and the filtrate is treated with sodium nitrite a t 0' whereby m-methyl.lzitrosoaminobenxo~c acid NO*NMe*C,H,*CO,H m. p. 179-180' (bath previously at 16c1°) is obtained which separates slightly impure from water in blood-red leaflets and is converted after two weeks by alcoholic hydrogen chloride into ethyl m-metlzylaminobennxoate Iydrochloride m. p. 137' (corr.) which is converted into ethyl m-?nsth?llnitrosoamin~b~n~o~te m.p.3 2 O by nitrous acid a t 0". After twenty-four hours m-methylnitroso- aminobenzoic acid and alcoholic hydrogen chloride yield m-methylanzino- benxoic acid hydrocMoride CO,H*C,H,*NHMe,HCl m. p. 244' which is converted by N-sodium hydroxide into m-methylaminobenzoic New Drugs. V. ALFRED EINHORN (Annulen 1910,371 125-131. Compare Abstr. 1900 i 439 493; 1903 i 257 ; 1908 i 312).- Mainly a resume of the work which led to the preparation of novocaine (o-diethylaminoethyl p-aminobenzonte hydrochloride corn pare Farbwerke vorm. Meister Lucius and Briining Abstr. 1907 i 923). As far as can be ascertained all soluble aromatic esters with the apparent exception of a-cocaine (compare Willstatter Abstr. 1896 i 707) are capable of producing local anaesthesia to a greater or lecs degree.Generally speaking the anaesthetic action is destroyed by the introduction of a carboxyl OF sulphoxyl group into the molecule ; other substituents such as halogen hydroxyl alkoxyl nitro amino etc. either increase or diminish but never destroy completely the Diethylaminoethyl and Piperidinoethyl p-Aminobenzoates. ALFRED EINHORN and EMIL UHLFELDER (Annulen 1910 371 131-1 42).-An account of the preparation of diethylaruiuocttiyl p-aminobenzoate (novocaine) piperidinoethyl p-aminobeu zoa te and some derivatives of these esters much of which has appeared already (compare Farbwerke vorm. Meistcr Lucius and Briining Abstr. 1507 i 923 ; 1908 i 638). Diethylaminoethyl p-aminobenzoate cbrystallises with 2H,O in small needles m.p. 51' ; the anhydrous substance ciysiailises in plates m. p. 61" ; the following derivatives have been prepared mercuri- acid m. p. 127' (corr.). c. s. activity of an aromatic ester. w. €I. Q.ORff ANIC CHEMISTRY. i. 171 chloride needles m. p. 139'; hydriodide small needles m. p. 121-122' ; merczcei-iodide C,,H,,O,N,,HI,HgI small white needles m. p. 127' ; nitrate needles m. p. 100-101' ; argentonitrate needles m. p. 107'; sulphate prisms m. p. 170'; chlorate needles m. p. 89O ; borate C H,,O2N2,4B(OH) small needles m. p. 159-1 60' ; trichloroacetate prisms m. p. 89O ; thiocyanate prisms m. p. 83'; phthnlate prisms m. p. 119'; ethochloride NH,*C6H4*C02*CH2*CH2*NEt,Cl,H,0 prisms sinters a t 135O and is completely molten a t 180'; the anhydrous ethochloride has m.p. 198' (decomp.) ; cccetyl derivative a viscid oil the hydriodide of which C,,H,,O,N,,HI crystallises in small rosettes m. p. 146-147 ; the hydrochlorade of the benxoyl derivative forms small needles m. p. 189' ; the p-nitrobenxoyl derivative crystal- lises in small needles m. p. 129-130' and when reduced yields the corresponding p-aminobenxoyl derivative small needles m. p. 124" the hydrochloride of which C,,H2,0,N,,HCl crystallises in needles Piperidin.oethyE p-ucetylaminobenzoate Cl6H22O3N2 crystallises in needles m. p. 86-87' ; tho hydrochloride has m. p. 228'; the ester is converted by a hot alcoholic solution of hydrogen chloride into the dihpdrochloride of piperidinoethyl p-aminobenzoate m. p. 225O. C,,J32,O,N,,HClO C,0H240,N,,HC1 m. p. 221O. W.H. G. Alkylaminoalkyl p-Aminobeneoates. ALFRED ELNHORN KARL FIEDLER CARL LADISCH and EMIL UHLFELDER (Annulen 191 0 371 142-1 6 l).-The compounds described in this paper were prepared subsequently to novocaine but not one of them is more suitable than this substance for the purpose of producing local anaesthesia. They are all obtained by the reduction of the corresponding p-nitrobenzoates which are prepared by the action of p-nitrobenzoyl chloride on the requisite alkamine. Dimethylaminoethyl p-nitrobenxoate NO,*C6H,*CO2*CH,*CH2=NMe2 prepared by heating dimethylaminoethyl alcohol with p-nitrobenzoyl chloride a t 130° crystallises in slender matted needles m. p. 58-59' ; when reduced with tin and hydrochloric acid it yields the correspond- ing amino-compound C,,H,,O,N crystallising in large prisms m.p. 12 lo the hydrochloride of which C,H,,O,N,,HCl forms small slender needles m. p. 185-186'. Diisop~.op?llaminoetT~yl p-nitrobenxoate is an oil ; the hydrochloride C1,H,20,N,,HCl crystallises in small needles m. p. 136.5' ; the corresponding amino-compound C15H2402N2 crystallises in slender needles m. p. 4S0 and forms a hydrochloride crystallising in prisms m. p. 195'. Diisobutylumi~zoetr~l p -witrobenzoute is an oil ; the hydrochloride C,7H,,04N,,HC'l forms slender felted needles m. p. 160-161' ; the amino-compound C17H2,0,N2 siuall slender needles m. p. 84-85' forms a hydrochloride which crystallises in prisms m. p. 195 -196'. Diisoamyluminoethyl p-nitrobenxoate is an oil j the hgdrochloride,i. 172 ABSTRACTS OF CHEMICAL PAPERS.Cl,H,o04N2,HCl crystallises in small needles m. p. 123-124' ; the ammo-compound C,,H,,O,N leaflets m. p. 44-45O forms a hydro- chloride crystallising in needles m. p. 154'. Diethylaminornethylmethylethylcarbinol NEt,*CH,*CMeEt*OH pre- pared by the action of diethylamine on the corresponding chloro-com- pound is an oil b. p. 71-73"/15.5 mm. ; the p-nitrobenzoate is a n oil the hydriodide of which Cl,H~404N~,HI forms pale yellow crystals m. p. 167'; the p-aminobenxoate is a pale yellow oil the picrute of which C,,H,,O,N is a pale yellow crystalline powder m. p. 121'. Piperidznometl~ylmet?~yl~t~~ylcarbinol NC5Hlo*CH;CMeEt*OH is a colourless oil b. p. 101-104°/18 mm. ; t h e p-nitrobenzoate is a viscid yellowish-brown oil the hydriodide of which C17H,,04N,,HI crystal- lises in yellow leaflets m.p. 190'; the p-aminobenxoate is an oil crystalline salts of which could not be obtained. Diethylaminomethylethylcarbinol has b. p. 197-200' (compare Paal and Weidenkaff Abstr. 1906 i 236) ; t h e p-nitrobenxoate is an oil the hydriodide of which C17H2,04N,,HT crystallises i n yellow prisms m. p. 154'; the hydrochloride of the oily p-aminobenxoate C17H2,0,N,,HCI forms rhomboidal crystals m. p. 166-1 6 7". Tetraethyldiaminoisopropyl p-nitrobenxoate N0,*C,H4*C0,*CH(CH,-NEt,) forms yellow crystals m. p. 41' ; the dihydrochloride crystallises in slender felted needles m. p. 198' ; the p-aminobenxoate Cl8.H3,O2N3 crystallises in colourless leaflets m. p. 50' ; the dihydrochlorsde forms faintly yellow slender needles m. p. 222'.Dipiperidinoisopropyl p-nitrobenzoate N02*C,H,~C02*CH(CH2*NC,H,o).2r is an oil ; the dihydriodide crystallises in lemon-yellow slender needles m. p. 232' ; the corresponding amino-compound C20H,,0,N3 forms colmrless prisms m. p. 137*5' the dihydrochloride of which crystallises in slender needles m. p. 261'. NEt,*CH,~CH(OH)*CH,*CO,-C,H,*NO or NEt 2* CH,*CH(CO,*C,H,*KO,)*CH,*OH is an oil ; t h e hydrochloride is a microscopic crystalline powder m. p. 152" ; the corresponding amino-ester is a n oil ; the di-p-nitrobenzoate C,,H,,O,N forms small yellow needles m. p. 90-92'; the da-p-aminobenzoate has m. p. 132' ; the hydrochloride C,,Hq70,N,,HCI is a crystalline powder m. p. 185'. The p-nitrobenzoate ot the corre- sponding piperidino-compound C15H2,0,N2 forms leaflets m.p. 60- 63'; the ILydrochZoride crystallises in white needles m. p. 212'; the p-aminobenxoate C,,H,,O,N crystallises in prisms m. p. 91" ; the hydrochloride forms white needles m. p. 206O ; the di-p-nitrobenxoate C5NH,o*CH,*CH(C0,~C,H4*NOz)*CH2*C02~C6H4*NOz crystallises in pale yellow prisms m. p. 108' ; the di-p aminobenxoate crystallises in prisms m. p. 127" ; the hg'drochloride C2,H2'704N3 HCI forms small needles m. p. 210.5'. The p-nitro benzoate of a-dieth ylaminopropane - P y - diol W. €1. G. Esters and Alkylamino-esters of 3 4-Diaminobenzoic Bad. ALFRED EINHORN and EWIL UHLFELDER ( Annalen 19 10 371 162-179. Compare Eiuhorn Abstr. 1908 i 639).-The compoundsORGANIC CHEMISTRY. i. 173 described in this paper were prepared with the object of obtaining derivatives of alkyl 3 4-diaminobenzoates yielding salts with a neutral reaction which could consequently be employed as anesthetics.The esters of 3 4-diaminobenzoic acid when boiled with organic acids yield esters of 2-alkylbenziminazole-5-carboxylic acid and when treated with acetyl chloride yield the corresponding dichloroacetyl derivatives ; the latter substances interact with secondary bases for example piperidine yielding the dipiperidinoacetyl compounds. Methyl 2-meth yl benxirninaxole-5-curbox ylate s(CO,Me)*CH $!-N CH- CH:C*NH >CMe crystallises in needles m. p. 172'; the hydrochloride forms small needles m. p. 25'7'; the ethyl ester crystallises in needles m. p. 180'. MetluJ 2-ethylbenziminazole-5-carboxylate C,,H,202N2 crystallises in needles m.p. 141'; the hydrochloride has m. p. 252'. The dibsnzoyl derivative of methyl 3 4-diaminobenzoate C2,H1804N? crystallises in small white needles m. p. 231' ; the dichloroacetyl derivative CO,Me*C,H,( NH*CO*CH,CI) forms needles m. p. 177" ; the dipiperidinoacetyl derivative CO,Me*C,H,(NH*CO*CH,*NC,Hlo) has m. p. 108'. Ethyl 3-nitro-4-chloroacetylarninobenzoute CllHliO,N,CI crystallises in small yellow needles m. p. 102'. Ethyl 3-nitro-4-piperidicfoacetyL arninobenzoate crystallises in yellow needles m. p. 70-71' and when reduced with tin and hydrochloric acid below 35" yields the corre- sponding ccmino-compound C,,H,,O,N small needles m. p. 103' the hydrochloride of which crystallises in leaflets m. p. 204O whilst at a higher temperature it is converted into ethyl 2-pipericlinonzethylbenz- irnina~ole-5-cnrboxylate C1,H2,O,N an oil the dihydrochloride of which crystallises in needles m.p 221'. The following compounds are similarly prepared ethyl 3~atro-4-diethylglycylaminobenzoate NEt,*CH2*CO*NH*C,H3( NO,)-CO,Et yellow needles m. p. 71" ; ethyl 3-amano-4-diethy?gZycyla~ni~zobenaoate small needles m. p. 64' ; hydrochloi*ide needles m. p. 194' ; etlql 2- d ieth ylaniinomet h yl! benziminazole- 5 -car box ylate C ,H2,0,N3 pointed needles m. p. 67' ; hydrochloride bmall needles m. p. 173' ; dihydro- cldoride m. p. 199'. Chloroethpl 3 4-diaminobenzoate C,H,(NH2),*C0,*CH2*CH2Cl is obtained by acting on a mixture of 3 4-diaminobenzoic acid and ethylene cblorohydrin with hydrogen chloride in the presence of a small quantity of concentrated sulphuric acid ; it crystallises in needles m.p. 80° and when heated with diethylamine under pressure at 100- 1 ZOO yields the corresponding diethylaminoethyl ester a n oil the hydrochloride of which C1,H,,O,N,,HC1 forms needles m. p. 163' ; the picrate crystallises in yellow needles m. p. 189-190'. The diethylaminoethyl ester undergoes the following changes (1) with glyoxal it yields diethylaminoethyl quinoxaline-6-carbox~late an oil the hydrochloride of which Cl,H2,02N,,HC1 cry stallises in needles m. p. 1 8 7 O ; (2) when treated with sodium nitrite and hydrochloric acid it yields diethylaminoethyl 3 4-aziminobenxoate hydrochloride Ci,H1,O2N,,HCl small needles m. p. 150-151' j (3) i t condensesi. 174 ABSTRACTS OF CREMICAL PAPERS. with p-dimethylaminobenzaldehyde yielding a substccnce which crystal- lises in yellow needles m.p. 161' and with benealdehyde yielding a n oily substance the hydrochloride of which crystallises in prisms m. p. 190'. Piperidinoethyl3 4-diarninobenxoccte crystallises in needles m. p. 103' ; when heated with glacial acetic acid it yields pipericlinoethyl 2-methpl- be~zximin~~oZe-5~cc~rboxyZ~te C1SK2202N3 needles m. p. 159-160° the hydrochloride and dihydrochloride of which crystallise in needles m. p. 162-163" and 262' respectively. Bietl~yZc~minoeth~~Z 3-nitro-4-dinacthylaminobenxoc~te prepared from 3-nitro-4-dimethylaminobenzoic acid and diethylaminoethanol is an oil; the corresponding amino-compound also an oil forms a hgdro- chloyide C,,H,,O,N,,HCl which crystallises in needles m.p. 164'. Methyl 3 4-tet~~amethyldiarnirtobenzoate dihydriodide prepared by heating me thy 1 3 -amino-4-dime t h y laminoben zoa t e with met hy 1 iodide and methyl alcohol under pressure at loo' crystallises in needles m. p. 109-1 10' ; the dihydrobromide C,,H1,0,N,,2HBr crystallises in needles m. p. 205O ; the correspondiug diethyhninoethyl ester is a n oil ; the hydrochloride 'J'17H2,0,N crystallises in small white needles m. p. 140-141°. W. H. G. Isomerism of Anils (Schiff's Bases). OTTO ANSELMINO (Bey. 1910 43 462-463. Compare Manchot and Furlong Abstr. 1909 i 805 ; this vol. i 33 ; Anselmino Abstr. 1906 i 13 ; 1907 i 913 ; Knoevenagel and Schrotter Abstr. 1905 i 64).-Polemical. J. J. S. Differences between Cinnamic Acid from Storax and Synthetical Cinnamic Acid.C. E. RIIBER and V. MORITZ GOLDSCHMIDT (Ber. 19 10 43 453-462. Compare E. Erlenmeyer jun. Abstr. 1907 i 318 ; 1909 i 156 647 648).-Although cinnamic acid from storax differs so materially in habit from the Synthetical acid it is shown that the characteristic crystnllographic constants are the same for the two acids. The chief differences are ( a ) the extremely thin plates in which the synthetical acid crystallises ; ( b ) the absence of definite faces in the crystals of the synthetical acid ; the plates as a rule have a crinkled edge. As the synthetical acid when repeatedly crystallised approaches the habit of the storax acid tho conclusion is drawn that the former acid is identical with the stoyax acid but contains a small amount of an impurity which is gradually removed by repeated crystallisation. The presence of this impurity retards to an enormous extent the develop- ment of the crystals in the direction normal t o the face bf010).By careful fractionation of the ethyl ester of the synthetical acid it has been found possible to isolate a fraction b. p. about 120°/ 0.2 mm. which when hydrolysed gives a n acid containing about 9% Cl. This acid is probably an impure chlorocinnamic acid and it is shown that when this impure .acid or when small amounts of either 0- or p-chlorocinnamic acids are added t o the acid from storax they alter its crystalline habit and transform it into the characteristic crystals of the synthetical acid. The synthetical acid is thus the sameORGANIC CHEMISTRY. i. 175 acid as that from storax but contains a small amount of a chloro-acid which completely alters its crystalline appearance.Erlenmeyer's hetero-acid contains a larger proportion of the chloro- acid than does the synthetical acid. Erlenmeyer states that specimens of benzaldehyde which are free from chlorine yield the synthetical acid. It is shown that sinall amounts (0.3%) of o-nitrocinnamic acid have the same effect on the crystalline habit of the storax acid as larger amounts of the chloro-acids. Erlenmeyer's a- and p-cinnamic acids are regarded as dimorphous forms (compare Lehmann Zeitsch. Kryst. Min. ltiS5 10 339). J. J. S. Transformations of allo-Cinnamic and isoCinnamic Acids. CARL LIEBERMANN and H. TRUCKS&S (Ber. 1910 43 411-414. Compare this vol. i 36)-It is shown that when allocinnamic or isocinnamic acid of m.p. 58' is crystallised from carefully rectified light petroleum (b. p. 30-40°) crystals of the iso-acid m. p. 42O can usually be obtained if proper precautions are taken. The method consists in introducing a comparatively dilute solution of the acid into a glass tube by means of a suitable funnel and then boiling the solution for some little time so that the walls of the tube are thoroughly purified and also that the solution may he con- centrated. The tube is then sealed and when placed in ice-cold water or in a freezing mixture crystals of the acid m. p. 42" separate. These occasionally become transformed into the less fusible acids during transference from the tube. J. J. S. Mechanism of the Transformation of a-Hydroxy-py-un- saturated Acids into the Isomeric y-Keto-acids. ENIL ERLEN- NEYER (Festschrift Otto Vcdlach 1909 404-413).-A discussion on the course of the intramolecular rearrangement of a-hydroxy-,By-un- saturated acids into y-ketones (compare Frttig Abstr.1897 i 14 ; 1898 i 196) based on the author's investigations (compare Abstr. 1898 i 66s; 1903 i 32 414; 1904 i 500 892 1025). W. H. G. [Preparation of Triphenylmethane Colouring Matters from Diortho-substituted Benzaldehydes.] ANILINFARBEN- & EXTRAKT- FABRIKEN VORM. J . R. GEIGY (D.R.-Y. 213502. Compare Abstr. 19OS i 9S6).-1t has been shown previously t h a t the diortho-sub- stituted benzaldehydes when employed in the production of triphenyl- methane dyes yield colours of remarkable depth and fastness; it is now found that these properties are enhanced when the two ortho- substituents consist of different halogen atoms.The following new aldehydes are described 2-Cidoro - 6 - brombenxaldehyde prepared from 2-chloro-6-bromo- toluene forms colourless spear-shaped crystals m. p. 68". 2-Chloro-4 6-dibromo-5-ciminobenzddehyde m. p. 1 2 4 O a colourless crpst,alline powder is obtained by the bromination in aqueous suspension of 2-chloro-5-aminobenzaldehyde. 3 4 6-T~-ibrowm 5-nminobennxalde- hyde m. p. 136-1 37". 2-Chloro-4 Ij-dibrom,o-5-l~?/clro~~ybenznldel~~cle crystallises in dark yellow needles and has m. p. 116O. F. Me G. M.i. 176 ABSTRACTS OF CHEMICAL PAPERS. p-Methoxysalicylaldehyde. PAUL FRIEDLANDER (Mornatsh. 1909 30 879 - 881).-Since p-methoxysalicylaldehyde (o-hydroxyanis- aldehyde) prepared by the action of sodium hydroxide on 4-methoxy-2- keto-1-indoxylbenzene (compare Friedlander and Schuloff Abstr.1908 i 674) did not have the properties of the o-hydroxyanisaldehyde described by Tiemann and Parrisius (compare Abstr. 1881 270) the compound has been prepared by the method employed by these investigators also by the action of methyl sulphate on 2 4-dihydroxy- benzaldehyde and found t o be identical with that derived from 4-methoxy-2-keto-1-indoxylbenzene. It is shown further that the substance obtained by Goulding and Pelly from Chlorocodon Whiteii (Proc. 1908 24 62) is o-hydroxyanisaldehyde. o-Hydroxyanisaldehyde has m. p. 41'; the oxime has m. p. 138'; the phenylhydrazone has m. p. 138' ; the aldaxine [OMe*C,H,(OH)*CH:N-I forins small greenish-yellow crystals m.p. 220°. W. H. G. Orthovanillin L2-Hydroxy-3-methoxybenzaldehydeJ and its Derivatives. FRANCIS A. &I. NOELTING (Bull. SOC. Ind. Xulhouse 1909 79 401-430).-The compound described by Tiemann and Koppe as P-m-methoxysalicylaldehyde (compare Abstr. 1882 54) is definitely shown to be 2-hydroxy-3-methoxybenzaldehyde for when treated with acetic anhydride i t yields 8-methoxycoumarin. A large number of hydroxy- and methoxy-derivatives of benzald- azine and benzylideneaniline have been prepared with the object of ascertaining the effect of these groups on the colour of the substance It is found that the para-derivatives of benzaldazine are the most highly-coloured whilst the ortho-substitution products of benzylidene- aniline are more intensely coloured than the corresponding para- isomerides ; for example vanillaldazine is golden-yellow whilst 2-hydr- oxy - 3 - methoxybenzyaldazine is lemon-yellow ; 2-hydroxy-3-methoxy benzylideneaniline is orange whilst the 4-hydroxy-isomeride is pale yellow.The ortho- meta- and para-hydroxy-derivatives of benzylidene- aniline are lemon-yellow white and pale yellow respectively ; the methyl ethers are all colourless although the hydrochlorides are lemon-yellow ; the methoxy-derivatives of the methyl ethers are not coloured although the introduction of a methoxy-group into the hydroxy-derivatives increases the colour. Derivatives of benzyl- ideneaniline containing a hydroxy- or methoxy-group are rendered more intensely coloured by the introduction of a hydroxy-group.2-Hydroxy - 3 - methoxybenzaldshyde crystallises in pale yellow needles m. p. 45*5" b. p. 265-266'; it dyes wool an intense yellow and silk a pale yellow; the m. p.'s of various mixtures of this con- pound with vanillin are recorded ; the sodium salt C,H70,Na,H,0 crys tallises in lemon-yellow plates ; the benzoate crystallises in small white needles m. p. 74-75'; the oxime crystallises in white needles; the phenylhydrazone OMe*C,H,( O€€)-CH:N*NHPh forms colourless needles m. p. 130-1 31° ; the phenyZmethy?hydraxone forms colourless crystals m. p. 62'. The methyl ether C,H,(OMe);CHO crystallises in wbite needles m. p. 52-53O and dissolves in concentrated sulphuric acid to a blood-red solution j the finely-divided substance producesORGANIC CHEMISTRY. i.177 violent sneezing ; the oxime has m. p. 98-99' ; the phenyZhydrazoae m. p. 1 3 8 O . is white. The parent substance couples with diazo- C( CHO) CH -C *N,R C(OH):C(OMe)'8H ' compounds forming compounds of the type I and forms condensation products with the following bas'es the colours of which only are given a-naphthylamine scarlet ; P-naphthylamine crimson ; p- toluidine orange ; p-anisidine yellowish-orange ; p-pv-ne- tidine yellowish-orange ; o-chloroaniline bright red ; dichloroaniline bright red ; p-nitroaniline orange-red ; m-nitrotoluidine orange-yellow ; p-phenylenediamine scarlet ; benzidine brick-red. 0-Jf etlLo~ybercxylidenean~Zine m. p. 44" is white ; the meta-isomeride is also white ; 3 4-dihydroxybenxylide~ea~~tine m.p. 172' is bright yellow whilst the dimethyl ether m. p. Sl" is white; 2-hydroxy-3- methoxybeia~ytideneaniline m. p. 84-85' is orange whilst the methyl ether m. p. 82.5" is white ; 4-hydroxy-3-methoxybenxylidenenniline m. p. 152-153" is pale yellow. M- flydroxybenxaldaxine m. p. 204-205O is pale yellow ; 2-l~ydroxy- 3-metl~ox,ybenxaZdczine m. p. 198-1 99O is lemon-yellow whilst the methyl ether m. p. 151' is pale yellow. Dimethylaniline condenses with 2-hydroxg-3-methoxybenzaldehyde and 2 3-dimethoxybenzaldehyde yieldiug 4' .4"-tetrarr~eti~ytdiamino- 2"'-h~droxy-3'''-methoxytri~hen~Zmethane m. p. 144O and 4' 4"-tetra- rnetl~ylcliamino-2'" 3"'dimethoxyt~~phenylmethcne m. p. 130-1 31" respectively j the hydrochlorides are green and bluish-green respectively.8-l%?ethoxycoumarin forms inodorous white crystals m. p. 89". W. H. G. Carbonyl Group in the Nascent State. PAVEL Iw. PETRENKO- KRITSCHENKO (J Buss. Phys. Chem. h'oc. 1909 41 1698-1703).-A reply to Stewart and Baly (compare Abstr. 1907 i 220). T. H. P. Tetrabromocyclopentenedione. C. LORING JACKSON and H. A. FLINT (Amer. Chem. J. 1910 43 135).-Jackson and Russe (Abstr. 1906 i 290) found that by the action of fuming nitric acid and bromine on tetrabromo-o-benzoquinone two substances were produced one yellow m. p. 142q and the other white m. p. 144-146'. The present investigation was undertaken with a view to the further study of these compounds. The white substance could not again be obtained but oxalic acid was invariably produced. The yellow compound has been found to be identical with Henle's tetrabromocyclopentene-1 3-dione (Abstr.1907 i 223) and is shown to have the constitution CO< CBr2* yo It is readily decorn- posed by boiling water or alcohol but is remarkably stable towards acids or oxidising agents and can be boiled for several hours with fuming nitric acid without undergoing visible change. When the compound is treated with solution of sodium carbonate for several days at the ordinary temperature it is converted into dibromomaleic CBrZCBr'i 178 ABSTRACTS OF CHEMICAL PAPERS. acid and methplene dibrornide. The action of sodium methoxide on the compound also results in the formation of dibromomaleic acid. By the action of aniline on tetrabromocyclopentene-1 3-dione there are produced tribromoanili~zocyclopentenedione NHPh* C502Br3 m.p. 1 7 8 O which crystallises in yellow needles and h,ydroxyanilinoccnal- cyclopentenedione NPh:C,O,(OH)*NHPh which forms a dark red amorphous powder and does not melt below 300'. When tetrabromocyclopentenedione is reduced with sulphurons acid dibromodiketocyclopentene C,H202Br m. p. 151' is obtained which crystallises in pale yellow plates and on treatment with bromine is reconverted into tetrabromocyclopentenedione. Phenyl- hydrazine reacts with dibromocyclopentenedione with formation of a brown amorphous substance which does not melt below 300'. When dihromocyclopentenedione is treated with aniline bromoanilinocyclo- pentenedione NHPh*C5H202Br m. p. 121' (decornp.) is produced which forms slender yellow needles and is converted by sodium carbonate solution into 1-anilino-A1-cyclopropen-3-one NHPh*C< I m.p. 2.21' (decomp.) which crystallises in yellow needles. By the action of methyl alcohol on tetrabromodiketocyclopentene tribromodiketomethoxycyclop~~e~e,~OMe~C50~Br~ m. p. 67O is obtained which forms white slender needles. The corresponding ethoxy- compound m. p. l l O o crystallises in small white needles aid is converted by aniline into ?~yd~*oxydikls.toanilinocyclopentene NHPh* C,H,O,* OH m. p. 140' (decomp.) a red amorphous substance which yields an cxcetyl derivative m. p. 150' (decornp.) as a pale brown amorphous powder. E. G. GO CH' Nitrosation of the Simplest Cyclic Ketones. WALTIIER BOSSCHE (Festschrift Otto Vallach 1909 301-312).-cycZoHexanone is converted by amyl nitrite in the presence of a small quantity of acetyl chloride into 1 3-dioximilzo-2-cycloAexano~ CH *C(N-OH) which crystallises in glistening yellow needles m.p. above 200' (decomp.) and is decomposed by water alcohol and dilute acids ; the corresponding triketone could not be isolated. The dioxime when treated with an alcoholic solution of sodium ethoxide and benzoyl chloride yields a substance C2,H2,0,Ns (?) crystallising in colourless needles m. p. 92-93'; benzoylation in the presence of pyridine leads to the formation of a di6eraoate CH2<CH:.C(C)Bz):N CH gC(oBZ):N>CO (?) which crystallises in slender yellow needles m. p. 170-172' (decomp.) and when boiled with an aqueous solution ofi sodium hydroxide is probably decomposed thus C,,H,,O,N + 4NaOH = CN*CH2*CH2*CH2*CN + Na,CO + 2Ph*C02Na + 2H20.A n alcoholic solution of phenylhydr- azine converts the dioxime into 1 2 3-triketocyclohexanet?.iphenyZ- hydmxoize C24H24NG which crystallises in slender needles m. p. 182-IS3'. The dioxime interacts with o-phenylenediamine yielding CH:2<(JH",C(N.0~)>co~ORGAHIC CHEMISTRY. i. 179 small glistening brown crystals m. p. 216-218". 3 * 5-Dioximino-l-met?~yZ-4-cyclohexanone C7Hlo0,N2 prepared f roni 4-methylcycZohexanone crystallises in pale yellow leaflets turns brown at 180' and decomposes suddenly a t 208'. The following derivatives are prepared by the methods just described dibenxoate small pale yellow needles decomposing at 172' ; 3 4 5-triketo-1-nzethylcyclo- ILexanetriphenyl?bydraxone C,,jH,,N small slender yellow needles m.p. 184' ; 1-oximino-3-rnetl~~2-l 2 ; 3 4-teti*ahydrophenazine small glistening yellow needles m. p. 210-211*. The parent substance is converted (1) by a cold solution of phenylhydrazine in glacial acetic acid into 3 ; 5-dioximi~ao-l-nzet?~~Zcyclohexa~z-4-one~hen,~l- hyclruzone C13HlG02N4 a crystalline orange powder m. p. 220' (decomp.) ; (%) an alcoholic solution of semicarbazide hydrochloride and sodium acetate into the sernicarbnxone C8H1303N5 which crystal- lises in spherical aggregates of small colourless needles and decom- poses at 200'; (3) by an alcoholic solution of hydroxplamine hydrochloride and sodium acetate into the corresponding Crioxime a colourless syrup the dibenzoccte (1) of which C21H1005N3 crystallises in small colourless needles m.p. 175'. 1 3-Dioxinzino-2-cyclopentanone C5HA03N2 prepared from cyclo- pentanone crystallises in flat ysllow needles and decomposes suddenly at 215'. W. H. G. '1 qH1 ,ON Catalytic Preparation of Aromatic Ketones. JEAN B. SENDEREMS (Compt. rend. 19 10 150 11 1-1 12. Compare Abstr. 1909 i 286 627 ; this vol. i 11).-The following aromatic ketones are readily obtained by the method already described namely aceto- yhenone propiophenone phen yl propyl ketone phenyl isopropyl ketone phenyl isobutyl ketone. To obtain a good yield it is neces- sary to employ 3 mols. of the fatty acid to 1 mol. of benzoic acid and t o maintain the temperature of the catalyst at 380-460'. The pro- duct is always accompanied by smaller quantities of the symmetrical aliphatic ketone.Benzoic acid may be replaced by its anhydride. Benzophenone could not be obtained by this method. Additive Compounds of Ketones and Quinones with Acids and Phenols. KURT H. MEYER (Ber. 1910 43 157-164. Corn- pare Abstr. 1908 i $31 ; 1909 i 395)-Whereas acetophenone only forms colourless double salts with metallic chlorides benzo- phenone in many cases yields light yellow compounds. A yellow nitmte C1,l-I,,O*HN 0 has been isolated whilst the faintly yellow-coloured solution of benzophenono in sulphuric acid undoubtedly contains a coloured sulphate. Benzophenone has although to a much less extent the same properties of halochrornism as distyryl ketone. The coloured compounds of benzophenone could not be isolated but those of fluorenone ale more characteristic.Two series of double salts are formed the one a deep violet represented by the compound with aluminium bromide and the other mange in colour. The solution in W. 0. W.i. 180 ABSTRACTS OF CHEMICAL PAPERS. sulphuric acid apparently cont,ains both forms as the deep violet solu- tion becomes orange-red on the gradual addition of water and finally colourless when the flmorenone separates. Fluorenone also combines with phenols forming deeply-coloured products. With a-naphthol two compounds are formed an orange- yellow derivative from two molecules of fluorenone and one molecule of a-naphthol and a red substance from one molecule of each component. Similar compounds could not be obtained from distyryl ketone. Disnisylideneacetone however disfolves in phenol with a n in tense yellow coloration and forms with a-naphthol a crystalline orange- yellow compound containing three molecules of a-naphthol t o two molecules of the ketone.These compounds of ketones and quinones with phenols are regarded as belonging to the same class of additive compounds as those with acids metallic chlorides and sulphur dioxide. Both classes possess a deep colour pronounced crystallising power and are easily resolved into their components by water or when heated i n solvents ; their formation is exothermic. They are regarded as loose additive products t o the quinonoid or ketone oxygen atom. Fluorenone nitwcte forms orange-red needles ; the trichloroacetate gives orange needles m. p. 58' ; the mercurichloride C13H80,(HgC12)2 separates in lustrous orange needles.The stannichloride (C,,H,O),,SnCl forms brownish-yellow crystals. With sulphur dioxide a substance crystal- lising in orange needles is obtained containing between 1 and 14 mols. of sulphur dioxide. Fluorenone aluminium b~ornide separates in dark red almost black crystals. The compound 2Cl,H,0,CloH,0 produced on heating with a-naphthol crystallises in long orange needles m. p. 66-67". I n presence of an excess of a-naphthol this is converted into C,,H,O,CloH,O separating in stout red crystals m. p. 89'. The compound of 2 mols. of disnisylylideneacetone and 3 mols. of a-naphthol separates in long orange needles m p. 69". Dirtnisylyl- ideneacetone and sulphur dioxide form an orange-yellow solution giving rise to orange-yellow needles when concentrated.Phenanthrapuinone trichloroacetate C,,H,O,,C,HO,Cl crystallises in sealing-wax red needles m. p. 138'. E. F. A. Occurrence of P-Pinene and LPinocamphone in Hyssop Oil and Some Observations on Isomerides in the Pinene Series. EDUARD GILDERIEISTER and HUGO KOHLER (Festgchrgt Otto Vallach 1909 41 4-43S).-An account of part of this investigation has appeared previously (compare Schimmel & Co. Abstr. 1908 i 666). I-Pinocamphone obtained directly from hyssop oil has b. p. 212-213'/752 mm. DZ 0.9662 nEo 1.47421 uD -13*7' whilst a sample prepared by reducing the dibromide had b. p. 212.5-213*5'/ 749 mm. D; 0.9679 n1,5 1.47509 ng 1.47343 aD - 19.33'; the dibromide has [u] -49.26' in ether; the semicurbaxone has m. p. 228-229'; a small quantity of a second semicurbaxone m.p. about 182-183' was also obtained ; the oxime is a colourless oil b. p. 105-1 10°/4 mm. which deposits well-defined crystals m. p. aboutORGANIC CHEMISTRY. i. 181 37-38' when kept for some time. The ketone is reduced by alcohol and sodium yielding I-pinocccmpheot long matted needles m. p. 67-68' b. p. 217-215" uD - 44-63' [u] -55.33" in alcohol Dt 0.9678 ng 1.48420 nz 1.48335 ; the corresponding phenylurethane crystallises in silky needles m. p. 76-77'. I-Phonic acid obtained by the oxidation of the ketone is identical with that described by Barbicr and Grignard (compare Abstr. 1908 i 852) ; when acted on by concentrated sulphuric acid i t yields 1-menthoethylheptanonolide crystallising in rectangular plates m. p. 46-47". An attempt t o prepare a pure active pinene by way of the crystal- line xanthate m.p. 36 -37' derived from I-pinocampheol (compare Tschugaeff Abstr. lYOS i 93) led to the production of a mixture OF pinene and a dicyclic terpene ; the latter when oxidised gave a crystalline dicarboxylic acid CI0Hl6O4 m. p. 192-193". W. H. G. Constituents of Ethereal Oils. Tetrahydrosan talene Cl,H28. FRIEDBICH W. SEMMLER (Ber. 1910 43 445-448. Compare Abstr. 190'1 i 431 433 1062 ; 1908 i 433).-SantaZene dihydrochloride Cl,H,,,2HC1 obtained by the addition of hydrogen chloride to santalene in methyl-alcoholic solution has b. p. 1 40-142'/0.55 mm. D20 1.076 and nD 1.4976. When distilled under 10 mm. pressure it decomposes to a certain extent yielding hydrogen chloride and when boiled with alcoholic potassium hydroxide yields /3-santalene.When the dihydrochloride is reduced with sodium and boiling ethyl alcohol it yields a mixture of hydrocarbons boiling a t 119-123'/9 mm. The unsaturated hydrocarbons may be removed from this mixture by treatment with ozone when pure tetrahydrosantalene Cl,H28. is obtained. It has b. p. 116-115°/9 mm. D20 0.564 n 1.4676 atid a +7'30' (100 mm. tube). The hydrocarbon must be dicyclic as i t has all the properties of a saturated compound ; it is thus analogous to 'dihydro- eksan talol and dihydroeksantalic acid. J. J. S. Action of Magnesium and Ally1 Bromide on Menthone. P. RYSCHENKO (J. Rum. Php. Chem. Xoc. 1909 41 1695-1698 Com pare Javor s k y A bstr . 1 9 0 9 i 1 6 8). - 1 - rMe thy Z-4-iso~ropy Z-3 -ally Z- cycloi~exan-3-oZ G H < ~ ~ ~ ~ ~ ~ ~ > C ( C H * C H C H ) * O H obtained on decomposing by means of water the Grignard compound yielded by magnesium ally1 bromide and menthone is a mobile colourless liquid b.p. 130-131°/22 mm. Di7 0.9028 n 1.470035 with an odour like that of mint. On oxidation with permanganate it yields (1) menthol- acetic acid C H ~ < ~ ~ ~ . ~ ~ ~ ~ ~ CHMe-CH2>C(CH,*C0,H)*OH which when heated with potassium hydrogen sulphate loses water and gives an acid C12H,,02 ; both of these acids were obtained by Wallach (Abstr. 1902 i 799) ; (2) the trihydric alcohol CH,<~~~~~~;>C(OH)-CH,=CH(OH)-CH,-OH which is a pale yellow syrupy odourless liquid. T. B. P. VOL. XCVILI. i. 0i. 182 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Alicyclic Hydroxylamines and Hydroxyl- amineoximes towards Nitrous Acid.I. GUIDO CUSMANO (Gazxetta 1909,33 ii 453-467. Compare Francesconi and Cusmano Abstr. 1909 i 723 724).-isoNitroamines form two classes of ethers (1) NO-NR-OEt' which readily give up nitrous acid and or \/ which under similar conditions are either stable or else yield nitrous oxide. Analogous behaviour is shown by the two classes of ether formed by the nitroamines namely (1) NO,-NRR which decompose giving nitrous acid and R*fl:N*OR RON-N*OR 0 (2) 0 R*N:R*OR R*N-N*OR' (2) 0 or \/ > 0 which yield nitrous oxide. It seems then that in these ethers the complex -N,O,- can be completely eliminated from the forms and \/ but not from the forms -N(NO,)- and -N(NO)*O-. Hence the nitroamines and isonitroamines which in the free state probably possess the forms R*NH*NO and R*N(OH)*NO respectively retain these forms when they decompose with elimination of nitrous acid but assume the forms R*N:NO*OH and R*NO:N-OH when decomposition is accompanied by separation of hyponitrous acid or nitrous oxide and water.As a rule the known isonitroamines exhibit one or other of the above two methods oE decomposition but the author finds that by varying the conditions pulegonenitroso- hydroxylamine (menthoisonitroamine) can be decomposed in both ways and can hence react in the two forms -N:N*O- N:R*O* *N-N*O* 8 0 CHMe<~~~<~>CH*CMe2*N(NO)*OH and CHMe<~~~~~>CH*CMe,*NO:N*OH. By the action of hydroxylamine onA pulggone three compounds have been obtained pulegonehydroxylamine m.p. 154' (compare Beckmann and Pleissner Abstr. 1891 936) an oxime m. p. 120' (compare Wallach Abstr. 1896 i 309) and [a] pulegonehydroxyl- amiheoxime m. p. 118' (compare Semmler Abstr. 1905 i 222). The author has obtained two new derivatives of pulegone namely an oxime m. p. 98' and a [/3] hydroxylemineoxime m. p. 143'. Wal!ach (Terpene und Campher Leipzig 1909) regards the oxime m. p. 120' as an oxime of isopulegone and the oxime m. p. 98' is either stereoiso- meric with this C H M e < ~ ~ ~ ~ ~ > C CMe cHMe<CH~-C CH -CH >C:CMe and #*OH 0H-H Y or structurally isomeric I The new hydroxylamineoxime m. p. 143' is stereoisomeric with thatORGANIC CHEMISTRY. i. 183 described by Semmler (Zoc. cit.) such isomerism being due either to the oximic nitrogen thus or to the method of rupture of t h e double linking of pulegone and the subsequent addition of hydroxylamine thus Pulegoneoxime C,,H,,:NOH m.p. 98" prepared by the action of hydrochloric acid on isopulegoneoxime m. p. 120° forms groups of lamias with triangular sections reduces Fehling's solution and is rapidly decomposed by heating with dilute sulphuric acid but is not affected by boiling with alcoholic potassium hydroxide. p-Pulegonehydroxylamineoxime GlpHzoO2Nz which is obtained together with the a-isomeride and zsopulegoneoxime when pulegone and hydroxylamine react under certain conditions forms shining needles m. p. l43' reduces Fehling's solution instantaneouFly in the cold and when dissolved in organic solvents is oxidised by the air to nitroso-compounds of a blue colour. Pzlle~onenitrosoldroxylarnine prepired by the action Lf niirous acid on pulegonehydroxylamine forms irregular hexagonal crystals m.p. 35" (decomp.) gives Liebermann's and the diphenylamine reactions and in ethereal or alcoholic solution gives a garnet-red coloration with ferric chloride ; it does not reduce Fehling's solution but forms a semicarbaaone NH,~CO~NH~N:Cl,H17*N(~O)*OH m. p. 165" (decomp.) which gives Liebermann's and the diphenylamine reactions and a red coloration with ferric chloride. With hydroxylamine in alcoholic solution pule- gonenitrosohydroxylamine gives a white hygroscopic substance decomp. at 200° which reduces Fehling's solution in the cold and gives Liebermann's reaction but gives no coloration with ferric chloride.When suspended in water or dissolved in organic solvents pulegone- nitrosohydroxylamine is moderately stable but in the dry state in the air or in a vacuum it undergoes rapid decomposition yielding (1) pule- gone and (2) 8-nitromenthone (compare Harries and Roeder Abstr. 1900 i 182) which results from the oxidation of the &nitrosomen- thone formed initially by the action of the air and of the nitric acid eliminated. With nitrous acid pulegonenitrosohy droxylamine gives 0 2i. 184 ABSTRACTS OF CHEMICAL PAPERS. pulegone and nitro- and nitroso-menthones. are formed according to the equation CioE€’,~O*NH*OJ3 + CloH,~O*N(NO)*OH + HNO = C10H170*N02 + CioHl~O*N,O + N + 2H,O. The formation of pulegone by the action of nitrous acid is due to the diazotisation of the pulegonenitrosohydroxylamine thus Ci,H,70*N(NO)*OH + HNO = ClpHJ70*N2*N0 + H20 ; the resulting aliphatic diazo-derivative is immediately decomposed by water into nitrogen nitric acid and 8-hydroxymenthone the last com- pound then losing water and giving pulegone. When however decomposition of pulegonenitrosohydroxylamine occurs in presence of an alkali it proceeds entirely in the one direction the resultant The last two compounds products boinipulegone and niirous oxide C,,H,,O*NO:N*OH + H,O = C,,Hi70*OH + H20 + N,O and C,,H,,O*OH = Cl,Hi,O + H20.T. H. P. New Occurrence of I-Camphor. THEODOR WHITTELSEY (B’estschr@ Otto WaEIach 1909 668-670).-The oil obtained from a variety of ‘‘ sage-brush ” common to western North America probably Artemisia cana was found to have the following constants DE O*94Ot5 ; a - 19.09’; rig's 1.4702 ; acid number 4.2 4.2 ; est,er number 18.5 19.8 ; saponiEcation number 22-7 23.9 ; saponification number after acetylation 111.8 110.3.It contains kcamphor to the extent of at least 44.5% an observation not without interest for with the exception observed by Wallach in the case of the broad- leafed Sulvia I-camphor has been found only in plants of the family Conzposit ae. W. H. G . Coriander Oil. HEINRICH WALBAUM and WILHELM M~LLER (FestschriJt Otto Wu,IZach 1909 654-667).-The sample of coriander oil examined had the following constants Di! 0.8735; aD +10*4O; nz 1.46387; acid number 0 ; ester number 20.22; ester number after acetylation 159 corresponding with 49.65% of linalool; it is possible to obtain however 70% of the latter substance by fractional distillation on a large scale.Roughly 20% of the oil consists of almost equal quantities of a-d-pinene p-cymene and terpinenes (a- and y-terpinene) together with very small quantities of /3-pinene dipen tene and possibly also qhellandrene and terpinolene. The presence of decylaldehyde geraniol I-borneol and esters of these alcohols was also established. I n addition to the compounds mentioned coriander oil contains small quantities of unknown substances which are of importance in imparting aroma t o the oil. ROURE-BERTRAND FILS (Sci. Ind. Bull. Roure- Bertrand FiIs 1909 [ii] 10 19-43).-This contains the following new work [JUSTIN DUPONT and LOUIS L A B A u N E . ] - ~ ~ ~ o ~ of Hydrochloric Acid on LincsZooI and Geraniol (compare Grosser Abstr.1882 525 ; Barbier ibid. 1892 1236 ; 1895 i 7S).-When dissolved in tduene and treated with gaseous hydrogen chloride at loo’ both alcohols yield Iinalyl chloride CIoHi7CI D20 0.9341 [a] 1-50’ fi 1.4813 and b. p. 95--96’/6 mm. This on treatment with silver nitrate in alcohol W. H. G. [Essential Oils.]ORGANIC CHEMISTRY. i 185 regenerates linalool. The chloride obtained from geraniol could not be obtained quite pure. At -4' to + 3 O the action of hydrogen chloride on linalool or geraniol in toluene is more complicated. No water is formed until the mixture regains atmospheric temperature. The product formed is a mixture of linalyl chloride with a dichloro- derivative. Cinnamyl alcohol a t 100' yields a chloride C,H,Cl D22 1.0857 ng 1.583 b.p. 115-116'/6 mm. which absorbs bromine forming a dibromide m. p. 104' and on treatmentwith silver nitrate i u alcohol yields a mixture of two alcohols one of which may be phenylallyl alcohol (Klages and Klenk Abstr. 1906 i 638). [J. JJ~~o~~~.]-Prepa~c6tion o f penc?bone free fyom Camphor.-The best results were obtained by warming crude fenchone with aluminium chloride and then distilling under reduced pressure. For the detection of camphor the semicarbaxide test was employed which is sufficient to show the presence of 0.1% of camphor. By this means camphor wacj proved to occur naturallyin fennel oil. Thujone cannot be eliminated from mixtures of this ketone with camphor and fenchone by treatment with aluminium chloride and bromine and in such cases oxidation with nitric acid must be resorted to the camphor being subsequently removed by treatment with aluminium chloride and bromiue. Four oils from the Comores Islands were examined and gave the following results Bigarade oil had D15 0.8812 a + 42'13' and was insoluble in 80% alcohol. Petitgrain oil had D15 0 8650 a + 42'18' and saponification value 33.6.Basil oil had DI5 0,9588 U 0'35' and saponification value 4.2. Citronella oil had D15 0.8922 a -Oo52' aldehydes 80% (by bisul phite process) and was insoluble even in absolute alcohol. Ylang-ylang oil from Nossi-BQ had D15 0.9673 a - 42'12' acid value 1.4 saponificatiori value 129.5 esters 45.3% and total alcohols 4 2 . i.%. Linaloe oil from Cayenne had D20 0.8721 aD - 12'56' nz 1.4635 and contained methylheptenone d-terpineol geraniol I-linalool and nerol (?).T. A. H Constituents of Oil of Lemon. EDUARD GILDEMEISTER and WILHELX MULLER (FestsdWt~t Otto Wallach 1909 439-451).-0il of lemon contains in addition to E-limonene a moderate quantity of I-P-pinene and very small quantities of a-pinene i-a-pinene I-camphene /3-phellandrene and y-terpinene. The sesquiterpene obtained from the oil in small quantity (compare Burgess and Page Trans. 1904 85 414) is shown to be identical with bisabolene (compare Tucholka Abstr. 1897 ii 584); the same hydrocarbon is present in opoponax oil oil of Piper Yolkensii (compare Schmidt and Weilinger Abstr. 1906 i 299) and camphor oil. The erythritol from y-terpinene (compare Wallach Abstr. 1908 i 814) undergoes the following changes (1) when boiled with acids it yields a mixture of thymol and carvacrol ; (2) it yields a brominated substance crystallising in large leaflets m.p. 93-94O when treated with an alkaline solution of hypobromite ; (3) when oxidised with ani. 186 ABSTRACTS OF CHEMICAL PAPERS. alkaline solution of potassium permanganate it yields oxalic acid and an acid m. p. 147-149' which is probably isopropyltartronic acid. W. H. G. Essential Oil from the Seeds of Monodora grandiflora. ROBERT LEIMBACH (Festschrift Otto FFaZZach 1909 502-512) .-The oil obtained by the steam distillation of the seeds of Monodorcl grandayora is a limpid pale yellow oil with an odour resembling cymene D: 0.85'74 a - 46.25' in ZL l-dcm. tube acid number 3.9 saponification number 7-12.Nearly 900/ of the oil consists of hydrocarbons chiefly Z-phellandrene camphene and p-cymene. The remainder a heavy oil with an aromatic odour contains palmitic acid carvacrol a substance C,,H,,O which reacts neither as an alcohol nor a ketone a sesquiterpene C15H24 b. p. 260-270° I):; 0.9138 aD + 24O n1,6 1.50513 a crystalline substance m. p. 160-1663' and small quantitias of other unknown substances. W. H. G. A Condensation Product of Coumaranone and its Con- version into Oxindirubin. KARL FRIES and W. PFAFFENDORFF (Bey. 1910 43 212-219).-The constitutions have been ascertained of the compound C,,H,,O obtained from 4-methyl-2-coumaranone or from w-chloro-2-hydroxy-5-methylacetophenone (Abstr. 1909 i 44) and also of those obtained by a similar process from 5-methyl-2-coumaran- one or w-chloro-2-hydroxy-4-methylacetophenone and from 2-coumaran- one or o-chloro-2-hydroxyacetophenone. An ethereal solution of 2-coumaranone is treated with sodium and then with acetvl chloride whereby the acetute m.p- 106" of 2-hydroxy-1 2'-dicoumarone C6H4<30H)>c*c<C6B4 is formed ; the parent substance has CH*O ' not been obtained pure. By warming an alcoholic solution of the acetate with sodium ethoxide and subsequently acidifying by boiling an acetic acid solution of the acetate with hydrogen peroxide or by the prolonged heating of 2-coumnranone or o-chloro-Z-hydroxyaceto- Dhenone with alcoholic sodium ethoxide 2 1'-dihvdroxu-1 2'-dicounaar- is obtained which forms orange-yellow needles gives a deep red non- fluorescent solution in concentrated sulphuric acid and by the prolonged heating of its solution in glacial acetic acid or more readily by treating the solution with hydrogen peroxide or bromine is con- verted into '' 1 2-biscoumaran-indigo " (oxindirubin) m.p. 215" which is also obtained by treating an acetic acid solution of 2-coumaranone and o-hy droxybenzoyl formic acid with concentrated sulphuric acid. By a similar series of reactions 5-methyl-2-coumaranone yields the acetate m. p. 133O of 2-hydroxy-5 5'-dimethyl-1 2'-dicoumarone 2 l'-dihydroxy-5 5'-dimethyl-l 2'-dicoumarone (5 5'-dirnethyl-leuco- oxindirwhin) m. p. 204O and '' 1 ; 2'-bis(5-methylcoumaran)-indigo "ORGANIC CHEMISTRY. i. 187 (5 5'-dimethyZoxindirubin). The compound CI8Hl4O4 (loc. cit.) is 4 4'-dimethyl-lenco-oxindirubin.c. s. Oxonium Perchlorates. KARL A. HOFMANN A. METZLEB and H. LECHER (Ber. 1910 43 178-183. Compare Abstr. 1909 ii 568).-Seventy per cent. perchloric acid yields crystalline compounds with ketones and similar substances with basic properties ; these are sparingly soluble and admirably adapted for characterising and isolating ketones. Even substances such as carbazole in which the basic properties of the nitrogen are very feeble form crystalline salts. The perchlorates afford a better test of basic properties than picrates. These salts are regarded as oxonium derivatives. A solution of xanthone in tetrachloroethane gives a bright yellow precipitate of xanthone perchlorate C13H802,HC104 which can be recrystallised from tetrachloroethane without decomposition but is very rapidly decomposed by traces of moisture.Carbaxole perchlorate crystallises in lustrous colourless plates ; it is decomposed by water. Prolonged action with an excess of perchloric acid leads to the formation of a greenish-blue compound. This explodes on heating. When moistened with water it becomes a brilliant bluish-green then violet and then brown. Benzophenone forms a yellow solution and a bright brownish-yellow crystalline mass. This rapidly decomposes in moist air leaving 4 colourless oily drops which do not crgstallise until inoculated with a crystal of benzophenone. The perchlorate is apparently derived from the allotropic low melting variety of benzophenone. Anthraquinone and alizarin do not react with perchloric acid Phenanthraquinone perchlorate forms a mass of blood-red crystals in solution which dry t o red needles but rapidly become bright orange when exposed to moist air.The hemiperchlorate (C,4H,0,)2,HC104 is obtained in flat obliquely-cut yellow or brownish-red prisms. From retenequinone only the hemiperch2orate has been isolated. Naphthazarin perchlovate forms large rectangular stout plates with a bronze lustre. E. F. A. A colourless perchlorate is also formed by quinone di-imide. New Selenium Compound. IDA FOA (Gaxxetta 1909 39 ii 527-534).-XeZenophen S.'H:CH>Se obtained by heating sodium CH:CH succinate with phosphorus triselenide is a yellow mobile irritant liquid b. p. 147-149'/250 mm.; i t dissolves in concentrated sulphuric acid giving a reddish-brown coloration whilst with a solution of isatin in concentrated sulphuric acid a dark carmine coloration is obtained.I n presence of acetic acid it forms with bromine an unstable liquid bromide. T. H. I?. Production of a Volatile Aromatic Substance from Solutions of Morphine Salts. C . REICEARD (Pharnz. 2entr.-h. 1910 51 128-130).-Then a solution of morphine hydrochloride or sulphate in water is heated a slight odour of musk is developed aud thei. 188 ABSTRACTS OF CHEMICAL PAPERS. strength of this odour increases with the concentration of the alkaloidal solution and with the quantity of water vapour produced from the solution. T. A. H. Partial Racemism. H. DUTILH (I'roc. K. Akad. Tetensch. Amster- dam 1909 12 393-400).-The author has studied the partial racemism which occurs with strychnine racemate more especially by observing the behaviour of this compound in presence of its aqueous solution.The investigation was carried out on the lines indicated by Roozeboom (Abstr. 1899 ii 401) who pointed out the probable inaccuracy of the results obtained by Ladenburg and Doctor (Abstr. 1899 i 310). By means of the solubility curves of the d- I- Z + r - and d + r-compounds at 40° 25' 16' and 7*5' i t mas found that the transition interval which Ladenburg and Doctor assumed to be non- existent extended over about 20'. Saturated solutions of the partial racemate are stable only below 75" although the solubility at higher tsmperstures can be determined by retarding the decomposition. The author has avoided determining by means of the polmimeter the content of the I- and d-compounds in liquids saturated with the r+d- r + Z - or d+I-compounds and suggests that such method of analysis gives a wrong idea concerning the inner composition of a solution saturated with two salts.This view is supported by the results obtained by Findlay and Hickmnns (Trans. 1909 95 1386) who using the polarimetric method of estimation found that the addition of I-menthyl Emandelate diminishes the solubility of I-menthyl d-mandelate at lo' whilst it increas'es i t a t 25' or 35' ; such behaviour the author regards as improlmble. T. H. P. Hmmopyrrole. LEON MARCHLEWSKI (Ber. 1910,43 259-260).- Polemical A reply to Piloty (chis vol. i 133). R. V. S. Pyridine Hydrate. WILLIAM OECHSNER DE CONINCK (BUZZ. SOC. chim.Belg. 1910 24 55).-From basic t a r oils the author has isolated a product which has the composition of a pyridine hydrate SC,H,N,7H20. This has b. D. 91-93' but it is not regarded as a definite chemical compound (dompare Goldschmidt and Coistam Abstr. 1884 61 1). T. A. H. Condensation of Esters of Acetonedicarboxylic Acid with Aldehydes by means of Ammonia and Amines. VI. Tautomerism of Ethyl 2 6-Diphenyl-4-pyridone-3 5-dicarb- oxylate. PAVEI; Iw. PETRENKO-KRITSCHENKO and JOH. SCIIOTTLE (Bey. 1910,43 203-206).-The methylation of ethyl 2 6-diphenyl-4- pyridone-3 5-dicarboxylate in alkaline solution leads to t'he formation of 2 6-diphenyl-1-methyl-4-pyridone-3 5-dicarboxylic acid m. p. 270° and a mixture m. p. 125-130O (Abstr. 1909 i 605). By hydro- lysing the latter by 7% aqueous alkali and mbsequent acidification an acid C,,H,,O,N is obtained which separates from dilute acetic acid in crystals m.p. 240' (decomp.) containing 14C,H,02,. and forms a n ethyl ester m. p. 229-230° which is insoluble in ammoniumORGANIC CHEMISTRY i. 189 hydroxide. The acid is probably 4-methoxy-2 6-diphenylpyridine Anthranil. XVI. Relation of Anthroxanic Acid (2Anthr- anilcarboxylic Acid) to Anthranil. EUGEN BAMBERGER and SVEN LINDBERG (Bey. 1910 43 122-127. Compare Abstr. 1909 i 509 510 5 1 I).-o-Amino- and o-nitro-aromatic aldehydes and ketones are converted by mild oxidising and reducing agents respectively into anthranil derivatives. To establish the constitution of anthroxanic acid as anthranil-2-carbouylic acid C H <;y >O the * C(C0,H) behaviour of isatinic acid and o-nitrophenylglyoxylic acid has been studied.By the oxidation of isatinic :acid with Caro's reagent anthroxanic acid 2 2'-azoxybenzoic acid and o-nitrosobenzoic acid are formed. The last product affords strong support to the view that o-hydroxyl- aminophenylglyoxylic acid OH*NH*C,H,*CO*CO,H is the first intermediate oxidation product. o-Nitrophenylglyoxylic acid when reduced by tin and acetic acid forms anthroxanic acid and a compound m. p. 127O probably 1-acetyl- dioxi ndole C H 4 < ~ ~ ~ ~ ~ & ~ c 0. 3 5-dicarboxylic acid. c. s. -- E. F. A. Cinchonic Acid Syntheses. WALTHER BORSCHE (Ber. 1910,43 267).-A reply to Schiff (this POI. i 134). R. V. S. Elimination of Alkyl Radicles and Fission of Organic Bases by means of Cyanogen Bromide and Phosphorus Halides.JULIUS VON BRAUN (Festschrgt Otto Wullach 1909 313-386).-A rdsum6 of the author's investigations on this subject (compare Abstr. 1904 i 688 731 841 918; 1905 i 596 634 636 826; 1906 i 576; 1907 i 28 79 105 110 127 151 524 728 899 960 ; 1908 i 625 627 675 and 685). The following observations have not been recorded previously. Quinoline is converted by cyanogen bromide and water into a crystalline substance m. p. 1 13" which probably has the formula C,H4< Benzoylhexahydrocarbazole and the 4-methyl compound (compare Borsche Abstr. 1908 i 365) when acted on by phosphorus chloridep yield 2-benxoyZnminodiphenyl m. p. 102O and 2'-benxoylamino-4-methyl- diphenyl m. p. 12l0 respectively. Indigoid Dyes. V. Indigoid Dyes of the Anthracene Series.A. BEZDZIK and PAUL FRIEDLANDER (Monatsh. 1909 30 871-878. Compare Abstr. 1909 i 415 417)-Isatin chloride and isatinanilide condense with hydroxy-derivatives of anthracene forming indigoid dyes which are far more stable towards acids and alkalis than the analogous naphthalene compounds (compare Abstr. 1908 i 673) ; for example 1 -keto-2-indoxylanthracene is not decomposed by sodium hydroxide although the isomeride 2-keto-l-indoxylanthracene when similarly treated yields anthranilic acid and 2-hydroxy- CH=$!H . N (CN);-,CH*OH' W. H. G.i. 190 ABSTRACTS OF CHEMICAL PAPERS. 1-anthracenealdehyde. dyeing animal fibres and the skin an intense yellow The latter substance has the property of 1-Keto-2-indoxykanthrucene (I) prepared b;jl the condensation of a-anthrol and isatinanilide in acetic anhydride crystallises in small dark blue needles with a bronzy reflex melts and sublimes with decomposition at a high temperature and when reduced with an alkaline solution of hyposulphite yields an orange-red solution which dyes textile fibres a pure blue.2-Keto-1 -indoxylunthracene (11) similarly prepared from /3-anthrol forms small dark blue needles with a coppery reflex and sublimes with decomposition at a high temperature. 2-Hydroxy-l-unthracenealdehyde C15HloOz crystallises in long pale yellow needles m. p. 16-1' ; the oxime crystallises in four-sided pale green plates m. p. 197' (decomp.) ; the phenylhydrazone forms flat yellow prisms m. p. 224-225'; the cddazine forms slender brick-red needles m.p. above 3 0 0 O . 5-Bydroxy-l-keto-2-indoxylanthrucene C,,H,,O,N prepared from 1 5-dihydroxyanthracene and isatin chloride crystallises in long slender dark blue needles ; tbe isomeric 8-hydrozy-compound is very similar in properties but is slightly more green. Synthesis of Oxazoles and Thiazoles. I. SIEGMUND GABRIEL (Ber. 1910 43 134-138).-By the action of phosphorus penta- cbloride on benzoylaminoacetophenone 4-chloro-2 5-diphenyloxaxole is formed and not a chlorinated isoquinoline derivative as might be expected from analogy t o the synthesis of dihydroisoquinolines from acyl derivatives of phenylethylamine. w-Benzoylaminoacetophenone is best prepared from w-aminoaceto- phenone hydrochloride by the action of benzoyl chloride in acetic acid solution; it has m.p. 124' [Robinson Trans. 1909 95 2169 gives 123'1. When heated with two mols. of phosphorus pentachloride first at the temperature of the water-bath and later to 1709 4-chloro- W. H. G. 2 5-dipherzyloxacxoZe O < c P h ~ ~ 'l is formed crystallising in slender CPh.N needles m. p. 67-68'. When heated with sodium amalgam in CPh:vH is obtained (com- C P h X alcoholic solution 2 5-diphenyloxazole O< pare E. Fischer Abstr. 1896 i 262). The same compound may be obtained in one operation from benzoylaminoacetophenone when only one molecule of phosphorus pentachloride is used. Similarly when benzoylaminoacetophenone and phosphorus pentasulphide are heated a t 170° 2 5-diphenyZthiaxoZe S<CPhi(?K is formed cry stallising in CPh.N large rhombic plates m. p.103-104'. E. F. A. Action of Hydrazines on Thiocyanoacetic Acid and its Ethyl Ester. GUSTAV PRERICHS and PAUL FORSTER (AnnaZerz 1910 371 227-257).-The nature of the interaction of thiocyanoacetic acid and phenglhydrazine as described by Harries and Klamt (Abstr.,i. 191 ORGANIC CHEMISTRY. 1900 i 413) not being strictly analogous to that of thiocyanoacetic acid and aniline (compare Rizzo Abstr. 1898 i 659; Beckurts and Frerichs Abstr. 1902 i 763) it was deemed advisable t o repeat the work of the first-named investigators the outcome of which has been the direct negation of many of the statements of these authors. When phenylhydrazine is added to a cold ethereal solution of tbio- cyanoacetic acid a white crystalline precipitate of phenylhydrazine thiocorbimidoacetate SCN*CH,*CO,H,NH,*NHPh m.p. 92-looo is obtained which when kept for some time or when boiled with alcohol passes into corbaminethiogZycoZZpheny2hydraaide colourless leaflets m. p. 149O. The latter substance is more readily obtained by the interaction of phenylhydrazine chloroacetic acid and potassium thiocyanate in alcoholic solution ; when heated at about 155’ for an hour it passes into dithiodigZycoZZph~n~Z~~ydra~~~e S,( CH,. CO*NH*NHPh) which crystallises in colourless glistening leaflets m. p. 174” and is also formed by heating carbaminethioglycollphenylhydrazide with 10% aqueous ammonia and treating the solution subsequently with hydrogen peroxide. When ethyl thiocganoacetate is boiled with an alcoholic solution of phenylbydrazine it yields ammonium cyanate a viscid oily substance and 3-aniZinothiohydantoin ZGiZ>N*NHPh colourless crystals m.p. 176O which dissolve in concentrated sulphuric acid and aqueous potassium hydroxide forming blue and violet solutions respectively ; the substance just described is also formed by the action of phenyl- thiosemicarbazide on chloroacetic acid. The interaction of chloro- acetylphenyleemicarbazide and potassium thiocyanate in alcoholic solution leads to the formation of thiocarbimidoacetylphenylsemicavb- axide SCN*CH2*CO*NPh*NH*CO*NH2 small glistening crystals m. p. 172-173’ which when boiled with water yields 2-hnino-5-kelo- 4-phenyltetrahydro-1 3 4-thiodiaxinc S< C(NH)* NH>WPh crystal- lising in pale yellow needles m. p. 161-162O; the crystalline salts with the halogen acids C,H,ON,S,HX were prepared.Hydrazine hydrate and thiocyanoacetic acid combine yielding hydvazine thiocarbimidoacetate SCN*CH,*CO,H N,H glistening leaf - lets m. p. 87-90’ which undergoes intermolecular rearrangement when kept passing probably into carbaminethioglycoZZhydyaxide NH,*CO*S*CH,*CO*NH*NH m. p. about 125” and when boiled with water yields a substance which decomDoses at 280-2909 and could not be obtained Dure. The - NH,*CO*S*CH,*CO*NH*NHPh CH,-CO action of hidrazine hydrate 0; ethyl tbiocyanoacetate l&ds to the yH,-CO CO-YH,. S*C(NH) >N”<C(NHPS ’ formation of 3 3-bisthiohydantoin the same substance is formed by the intekctibn of bisthiocarbamide (hydrazodicarboxythioamide) and chloroacetic acid ; it decomposes without melting a t a high temperature. Carbaftninethioglycollphenylhydrazide undergoes the followingi. 192 ABSTRACTS OF CHEMICAL PAPERS.changes (1) when boiled with 10% aqueous ammonia and subse- quently treated with hydrochloric acid it yields thioglycollphenyl- hydraxide NHPh*NH*CO*CH,*SH leaflets m. p. 112-113' ; (2) it is converted by alcoholic potassium hydroxide and methyl iodide under pressure at 100' into rnethyZthiogZycoZZphenylhydraxide CgH,,ON,S glistening leaflets m. p. 104-105° ; the corresponding ethyl compound C,,H,,ON,S forms colourless leaflets m. p. S4-85'; (3) when heated with alcoholic potassium hydroxide and chloroacetamide it yields thiodig Zyco Zlamidephen y lh ydrazide NH,*CO*CH,*S-CH,*CO*N€€*NHPh colourless leaflets m. p. 135-136" ; (4) with alcoholic potassium hydroxide and ethyl chlorocarbonate it yields cccrboxytlbioglycollphenyl- hydr~xicle,CO2H*SoCH,*CO*NH*NHPh m.p. 156-157'; thepotassium salt has m. p. 212-213'. The following substances are prepared by methods similar t o those just described ; pJ~enyZmethylJiydraxinethiocyanoacetat~ m. p. 65-68' ; carbaminetJ~ioglycotZpJienylmethyZh?/draxide C,oH1,O,N,S m. p. 145-146' ; nzethyZthiogZ?/coZZphen~Z~~thylhydraxide C1,H,,ON,S needles m. p. 74-75O ; carbethoxytJiiogZycoZ2pJLenylme2hylhgdraxide7 Cl,Hl,O,N,S colourless leaflets m. p. S2 -S3O ; carbanzinethioglycoll-p- tolylhydrazide Cl0Hl3O2N3S m. p. 164-1 65' ; thioglycoll-p-tolyl- hyJraxide CgH,,ON,S m. p. 125-1 26' ; dithiodigZycoZZ-p-toZyl~~~r- cmide ClsH,t202N,S glistening leaflets m. p 182-183'; rnethyltiiio- gZycoZGptoZylhydraxicEa C,,H1,ON,S glistening leaflets m.p 108-1 09'; thiodigZycoZZumide-p-toZyZh?/draxide C,,H,,O,N,S glistening pale yellow needles m. p. 148-149". W. H. G. Case of Isomerism. [Acylazoaryl Compounds.] GIAcoicro PONZIO (Gaxzettu 1909 39 ii 535-546).-The author has carried out further investigations on the yellow white and red isomerides Cl,H,004N obtained by the action of benzenediazonium acetate on the potassium derivative of o-dinitrotoluene (Abstr. 1908 i 482 582; 1909 i 443 681). The results obtained settle definitely the structure of the red isomeride and render probable the accuracy of that already assigned to the white compound but do not admit of the structure of the yellow derivative being determined. For the yellow compound the author has suggested the formula NO,*CPh(NO) 0O-N NPh which would explain its isomeric change into a-nitro-/3-nitroso-a-benzoyl-~-phenylhydrazine (Abstr.1908 I 482). On the basis of this formula Dimroth and Hartmann (Abstr. 1909 i 66) indicate an amalogy between this yellow compound and benzene-0-azotribenzoylmethane obtained by the interaction of the potassium derivative of tribenzoylmethane with benzenediazonium acetate and suggest that the yellow compound is a true 0-azo- derivative and not a diazo-derivative. But apart from the fact that the properties oE Dimroth and Hartmann's compound are explained equally well by regarding it as a true diazonium salt (compare Auwers Abstr. 1909 i 67) its analogy to the author's yellow compound is not borne out by its behaviour with ethereal hydro- chloric acid.Thus benzene-0-azotribenzoyImethane gives benzene- diazonium chloride and tribenzoylmethane whilst the diazobenzeneORGANIC CHEMLSTRY. i. 193 derivative of o-dinitrotoluene gives the isomeric compounds a-nitro- P-nitroso-a-benzoyl-/I-phenylhydrazine and o-nitrobenzaldehyde-p- nitrophenylhydrazone NO2*CPh:N*NH*C,H,*N0 treatment with water converting the former of these isomerides into p-nitroso-a- benzoyl-P-phenylhydrazine and leaving the latter unchanged. The formula NO,*CPh(NO)*N:NPh for the yellow compound (uide supra) does not however explain its reaction with alcohol with formation of w-dinitrotoluene nitrogen acetaldehyde and benzene. The reactions of the red isomeride are not in accord with the struc- ture NPh:N*CPh(N0,)2 originally assigned to it (Abstr. 1908 i 482).Thus on reduction by means of tin and hydrochloric acid it yields ammonia benzoic acid and p-phenylenediamine. By sodium methoxide it is converted in to a-dinitro t etraphen ylte trazoline (com- pare Bamberger and Grob Abstr. 1901 i 296). These results indi- cate that the red compound is r o t o-benzeneazo-w-dinitrotoluene but w-nitrobenzaldehyde-p-nitrophenylhydrazone (compare Bamberger and Grob Abstr. 1901 i 567) and direct comparison confirms this indi- cation. The isomeric change of the yellow compound into o-nitro- benzaldehyde-p-nitrophenylhydrazone consists in the passage of a nitro-group from an aliphatic carbon atom into the para-position of the benzene nucleus and such a transformation is best explained by regarding the yellow compound as w-benzeneazo-w-dinitrotoluenp NPh N*CPh(NO,),.It follows from these results that the compound m. p. 130-135' previously described as w-dinitro-w-benzeneazo-p-xylene must be regarded as w-nitro-ptolualdehyde-p-nitrophenylhydrazone N 02*C6H,*NH*N C(N0,) C,H,Me and that described as o-dinitro-w-benzeneazo-p-methoxytoluene m. p. 141-1 48O as o-nitroanisaldehyde-p-nitrophenylhydrazone N02*C6H;NH*N:C( N0,)-C,H4*UMe. But in addition to the diazobenzene derivatives of the primary dinitrohydrocarbons the ortho-substituted diazo-salts are also trans- formed into red isomerides when dissolved in moist ether and in this case too there takes place transference of a nitro-group from the aliphatic carbon atom to the para-position of the benzene nucleus.So that the compound m. p. 137' (decomp.) previously described (Abstr. 1909 i 443) as w-o-tolueneazo-w-dinitrotoluene must be re- garded as w-nitrobenzaldehyde-p-nitro-o-tolylhydrazone NO,* C,H,Me*NH*N CPh*NO a structure which is confirmed by the fact that it yields benzoic acid ammonia and 2 5-diaminotoluene on reduction with tin and hydro- chloric acid ; this compound may also be obtained by the interaction of the sodium derivative of o-nitrotoluene and m-nitro-o-toluenediazonium sulphate CHPh:NO,Na + NO,-C,H,Me*N,*HSO = NaHSO + NO,*C,H,Me*NH-N:UPh*NO,. Further the compounds described as o-o-chlorobenzeneazo-o-dinitrotoluene m. p. 140' (decomp.) and o-o- bromobenzeneazo-w-dinitrotoluene m. p. 140' (decomp.) (hbstr. 1909 i 443) must be regarded as the o-chloro-p-nitrophenylhydrazone and o-bromo-p-nitrophenylhydrazone respectively of o-nitrobenz- aldehyde NO,*C,H,Cl-NH*N:CPh*NO and N0,*C6H,Br*NH*N :CPh*NO,.i.194 ABSTRACTS OF CHEMICAL PAPERS. These results explain the observation that whilst the ortho- substituted diazonium salts give with moist ether their red isomerides that is the corresponding ortho-substituted p-nitro- hydrazones para-substituted diazonium salts under the same con- ditions lose two atoms of nitrogen and three of oxygen in the form of nitrous compounds giving acylazoaryl derivatives the isomeric acylarylnitronitrosohydrazines being formed as intermediate products R*C(N,O,)*N,Ar -+ R*C0*N(NO2)*NAr*NO -+ R*CO*N:NAr ; the para-position which the nitro-group tends to assume is in these cases occupied.It isafound indeed that these compounds by the action of absolute alcohol in the cold give small yields of red isomerides the nitro-group entering the benzene nucleus in the ortho-position. The red isomeride m. p. 153-154" (decomp.) of the p-diazotoluene deriv- ative of o-dinitrotoluene (Abstr. 1909 i 443) is found to be no6 w-p-tolueneazo-w-dinitrotoluene but o-nitrobenzaldehyde-o-nitro-p- tolylhydrazoue NO,-C,H,Me*NH*N :CPh-NO ; reduction of this compound (which may also be obtained by the interaction of the sodium derivative of w-nitrotoluene and m-nitro-p-toluenediazonium sulphate CHPh:N02Na + N0,*C,H,Me*N2*HS0 = NaHSO + NO,*C,H,Me-NH*N :CPh-NO,) with tin and hydrochloric acid gives benzoic acid ammonia and 3 4-diaminctoluene. Similarly the compound described as o-p-chlorobenzeneazow-dinitrotoluene (Abstr. 1909 i 443) m.p. 161" (decomp.) must be regarded as o-nitro- benzaldehyde-p-chloro-o-nitrophenylh ydrazone NO C,H,Cl*NH*N CPh*NO and that described as o-p-bromobenzeneazo-o-dinitrotoluene as w-ni tro benzaldeh y de-p-bromo-o-nitrophen y 1 hydrazone N0,*C,H3Br*NH *N:CPh*NO,. That the white isomeride best obtained by dissolving the diazo- benzene derivative of o-dinitrotoluene in anhydrous benzene is a-nitro-/3-nitroso-a-benzoyl-~-phenylhydrazine N02*NBz*NPh*N0 is confirmed by its transformation into benzoylazobenzene NBzzNPh (Abstr. 1909 i 681). T. H. P. Passage of the Nitro-group from an Aliphatic Carbon Atom to the Benzene Nucleus. GIACOMO PONZIO and R. GIOVETTI (Gazxettcc 1909 30 ii 546-556).-The action of the sodium deriv- ative of o-isonitrophenylacetonitrile on benzenediazonium acetate yields benzeneazo-w -nitrophen y lace toni trile NO,*CPh( CN) N NPh which by the passage of the nitro-group to the para-position of the benzene nucleus undergoes spontaneous transformation into o-cyanobenz- aldehyde-p-nitrophenylhydrazone ,CN*CPh:N,N*C,H,*NO and a small proportion of the corresponding o-nitrophenylhydrazone.This trans- formation which is similar to that observed with the diazobenzene derivative of o-dinitrotoluene (compare preceding abstract) also takes place with substituted diazo-derivatives the nitro-group entering the benzene nucleus in the ortho-position in cases where the para- position is occupied. The initial compounds formed from o-nitro- phenylacetonitrile are however less stable than those yielded by w-dinitrotoluene and undergo isomeric change so rapidly that theyORGANIC CHEMISTRY.i. 195 cannot be obtained in the dry state. Still more unstable are the compounds formed by o-nitrotoluene with diazonium-salts this reaction always giving w-nifrobenzaldehydephenylhydrazones. In the latter case it is a hydrogen atom from the aliphatic carbon atom which converts the group *N:N* into :N*NH- whilst in the previous cases i t is the hydrogen atom from the para- (or ortho-) position of the benzene nucleus. Be?txsneaxo-o-nitrophenykccetonitrile NO,*C Ph(CN)=N NPh forms a pale yellow flocculent precipitate. w-Cyanobenxaldeh yde- p-nitrophenp Zh ydrazone CN*CPh:N*NH*C6H,*N0 crystallises in yellow plates m.p. 208-209O dissolves in alkali hydroxides forming intensely violet solutions and on reduction by means of tin and hydrochloric acid yields benzoic and hydrocyanic acids and p-phenylenediamine. o-Cyanobenzaldehyde-o-nitrophenylhydraxone C10H1402N4 crystal- lises in orange-red flattened needles m. p. 1 8 7 O gives a reddish-brown coloration when dissolved in alkali hydroxide solution and yields benzoic and hydrocyanic acids and o-phenylenediamine when reduced with tin and hydrochloric acid. o-Cyanobenxaldeh yde- p-nitro-o-tolylh ydraxone CN*CPh:N*NH*CGH,Me*NO obtained by the isomeric change of o-tolueneazo-o-nitrophenylaceto- nitrile (prepared by the interaction of the sodium derivative of isonitro- phen y lace t oni trile and 0- toluenediazonium ace tat e) cry s tallises from benzene in brownish-yellow needles m.p. 188' forms intensely violet solutions with alkali hydroxide and yields benzoic and hydro- cyanic acids and 2 5-tolylenediamine on reduction. o-Cyanobenxaldehyde-o-nitro- p-tolylhydraxone CN*CPh:N*NH*C,H,Me*NO formed by the isomeric transformation of p-tolueneazonitrophenyl- acetonitrile crystallises in orange-red needles m. p. 160° gives a wine- red coloration with alkali hydroxides and yields benzoic and hydro- cyanic acids and 3 4-tolylenediamine on reduction. o-Cyanobenxaldehyde-o chloro-p-nitrophe?iyZhydraxone CN*CPh N*NH* C6H,C1*N02 prepared from o-chlorobenzenediazonium acetate and the sodium derivative of o-isonitrophenylacetonitrile forms orange-coloured needles m. p. 1 8 2 O and gives violet-red solutions with alkali hydroxides.o-Cy~nobenxaldehyde-p-chloro-o-nitrophenyl~ydraxone formed from p-chlorobenzeneazonitrophenylacetonitrile by isomeric change crystal- lises in brownish-yellow laminx? m. p. 240° and gives intensely violet solutions with alkali hydroxides in presence of a small quantity of alcohol. o.Cyanobenxaldehyde-o ; p-dinitpophenylhydraxone CN*CPh N*NH*C,H,( NO,) formed by isomeric change of either 0- or p-nitrobenzeneazonitrophenyl- acetonitrile crystallises in reddish-brown prisms m. p. 246' (decomp.) and gives intensely violet solutions with alkali hydroxide in presence of a drop oE alcohol. T. H. P.i. 196 ABSTRACTS OF CEEMICAL PAPERS. Limiting Cases between Polymorphism and Isomerism. ROBERTO CIUSA and MAURICE PADOA (Atti R.Accad. Lincei 1909 [v] 18 ii 621-626).-m-Nitrobenzaldehydephenylmethylhydrazone forms two modifications one red and the other yellow both having m. p. 120-125' (Labhardt and Zembruski Abstr. 1900 i 125 found 112" and Bamberger and Pemsel Abstr. 1903 i 286,112-113') at which temperature mixtures of the two also melt. The yellow form has the normal molecular weight in freezing benzene the solution depositing the red modification on evaporation. Certain solvents such as chloroform and benzene convert the yellow into the red form which may also be obtained by strongly cooling solutions of the yellow modification or by seeding an alcoholic solution of either form with the red crystals. The red modification passes into the yellow on boiling with alcohol or ethyl acetate on seeding its alcoholic solu- tion with a yellow crystal or on prolonged immersion in water or alcohol.There is no apparent or spectroscopic difference between solutions of the two products even when these are freshly dissolved. Both forms give with picryl chloride one and the same additive compound which undergoes a considerable amount of dissociation even in concentrated alcoholic solution giving the red h'ydrazone. p-Nitrobenzaldehydephenylmethylhydrazone also occurs in two forms one red and the other yellow both having m. p. 130' (Labhardt and Zembruski Zoc. cit. found 132'). I n this case too each form can be transformed into the other but the change in colour is less distinct than with the meta-isomeride and the red modification is very unstable unless stored under special conditions.o-Nitrobenz- aldehydephenylmethylhydrazone occurs only in a red form m. p. 90' (Labhardt and Zembruski Zoc. cit. found 77") but m-nitroanisaldehyde- p-nitropheny lhydraxone which is yellow when perfectly dry becomes red immediately in moist air (Abstr. 1907 i 137). The criteria given by Wegscheider (Abstr. 1902 ii 126) are insufficient to indicate whether this phenomenon is a case of isomerism or one of polymorphism. In this and i n other cases the phenomena of polymorphism and of isomerism approach so closely that the exist- ence of a line of demarcation is not evident (compare Fock this vol. ii 23). T. H. P. Pantachromism of Dimethyl- and Diphenyl-violurates. ARTHUR HANTZSCH and ROBERT ROBISON (Ber. 1910 43 45-68. Compare Abstr.1909 i 331 333 335).-In addition to the yellow lithium dimethylviolurate (Zoc. cit. i 335) a red salt C6H60,N,Li has been prepared. It yields carmine-red compounds with lEtOH and 1H,O. The yellow salt becomes red in the presence of traces of water. The solutions of the two lithium salts in pyridine are red and in phenol orange-coloured . A yellow compound with phenol C,H,O,N,Li,PhOH is described ; i t loses phenol when exposed to the air and forms the red hydrated salt. When the violet sodium salt is exposed to the air it absorbs moisture (I mol.) and becomes red. A red anhydrous sodium salt can be prepared by heating the compound containing ethyl alcohol TheORGANIC CHEMISTRY. i. 197 compound with phenol (1PhOH) is yellow and when heated at looo with methyl alcohol yields the anhydrous red salt.The blue potassium salt when exposed to the atmosphere yields the violet hydrate ($H,O) ; the corresponding phenol compound has a rose-red colour. The bluish-violet rubidium salt (loc. cit. 334) contains 0*5H20 and when boiled with methyl alcohol yields a pure b l w anhydrous salt ; the phenol compound has a rose-red colour. The caesium salt crystallises from alcohol in deep indigo-blue needles and yields a rose-red phenoxide. Dimethylvioluric acid and phenol yield a yellow additive compound. Two coloured silver pyridine salts C,H,O,N,Ag,C,NH have been prepared a labile green salt by the addition of ether to the pyridine solution of brown silver dimethylviolurate and a stable 6ZuislmioZet salt obtained when the green salt is left in contact with ether and pyridine.The methylamine salt C,H70,N3,NH,Me has a rose-red colour and when exposed to the air yields the yellow acid salt ; the dimethylamine salt is violet the normal trimethylamine salt is blue the acid salt orange-yello w and the tetramethykaminoszium salt is blue. The sthyl- amine salts are very similar The normal tripropylamine salt could not be isolated; the acid salt 2C6H7O4N3,NPr3 is orange-yellow. The dibenxylamine salt exists in a labile red and a stable bluish-violet modification. Piperidine yields a stable blue and a labile red salt C,H70,N,,C,H,,N. Diphenylvioluric acid was prepared by a modification of Whiteley’s method (Trans. 1907 91 1330); the pure neutral salts are best prepared in alcoholic solution as they readily decompose in the presence of aqueous alkalis.They crystallise with alcohol which can be completely removed by heating the very finely divided salt. The lithium and sodium salts exist in labile red and stable yellow modifica- tions and yield red compounds with 1EtOH. The ammonium salt forms a violet compound with EtOH. The normal potassium rubidium and caesium salts are blue and the acid ru6idium and caesium salts green ; the magnesium and xirzc salts are yellow ; the thallous silver saits exist in stable green and labile colourless forms. The acid silver salt C3,H2,0,N,Ag,3H,0 has an orange colour. The salts of dimethyl- and diphenyl-violuric acids exhibit both panta- chromism and chromotropism. The labile forms of the salts are usually stable when perfectly dry but pass readily into the more stable forms in the presence of a little water or alcohol.An increase in the depth of colour of the salts is observed as the metallic radicle becomes more positive and in the case of substituted ammoFium salts an increase in depth of colour is observed with an increase in the number of alkyl groups The addition of phenol to the molecule of the alkali salts results in a diminution of colour whereas the addition of pyridine produces an increase in colour except in the case of the compound of silver violurate and pyridine which is colourless and to which the formula Pyridiizs yields a stable yellow acid salt. is ascribed. An increase in the depth of colour with an increase in the positive VOL. XCVIII. i. Pi. 198 ABSTRACTS OF CHEMICAL PAPERS.nature of the metallic radicle is noticed in the case of concentrated aqueous or alcoholic solutions and also of solutions in non-ionising solvents such as chloroform or phenol. A negative solvent tends t o lessen the depth of colour of the solution of any given salt. Molecular-weight determinations in phenol and ethyl acetate indicate that the .different coloured isomeric salts are unimolecular. The absorption spectra solutions of the acids and of their alkali salts have been measured. A comparison of the absorption curves for diphenylvioluric acid its lithium and cmium salts and nitrosoisopropylacetone (Baly and Desch) points to the conclusion that the blue violurates should be represented as nitroso-enolic salts CO\NR.(COMe) "R*CO ->C.N*.The violuric acids as true oximino-keiones are the more completely transformed into the structurally isomeric nitroso-enols the more positive the nature of the metallic radicle present and the solvent. J. J. S. Pantachromic Salts of Oximino - oxaeolones. ARTHUR HANTZSCH and J. HEILBRON (Bey. 1910 43 68-82. Compare Hantzsch and Eemmerich Abstr. 1909 i 336).-pBromo- and p-methoxy-derivatives of oximinophenyloxazolone yield pantachromic salts with colourless bases. The esters and acyl derivatives on the other hand are only pale yellow. The salts of the bromo-derivative are comparatively stable and dissolve in various neutral solvents. Molecular-weight estimations in acetone pyridine and chloroform indicate that the salts botlh ammonium and metallic are unimolecular in solution.The colours of the salt solutions in non-ionising media increase in depth with the positive nature of the metallic radicle present. The abeorption spectra both visible and ultra-violet of the oxazolones and their salts in different solvents have been tabulated. The free acids are true oximino-compounds and their absorption spectra resemble those of their ethers and acyl derivatives. The phenolic solution of the oximino-compound is distinctly yellow. The ultra-violet spectra of the salts do not differ materially from those of the free acids but the visible spectra of the salts show characteristic absorption bands which are not present in the spectra of the free acids. The blue solutions of the potassium rubidium caesium and tetra- alkylammonium salts give practically identical spectra.The conclusion is drawn that the yellow salts derived from feeble bases possess the true oximino-ketone structure whereas the blue salts derived- from strong bases have a nitroso-enolic structure. p-BromophenyZoxazoZone prepared from ethyl p-bromobenzoylacetate and hydroxylamine crystallises in glistening plates m. p. 1 1 8 O (decomp.) and reacts with nitrous acid yielding oxirnino-p-bvomo- N- 0 phenyloxazolone C,H,Br*C<c(:N.OH). bo which crystallises as a pale yellow monohydrate. The anhydrous compound has a pureORGANIC CHEMISTRY. i. 199 yellow colour and decomposes at 166'. The salts readilydecompose in aqueous alkaline solutions but are stable in alcoholic solution. The lithium salt C9H40,N2BrLi exists in a stable yellow form only; the sodium salt forms orange-red needles which form a pale rose-coloured monohydrate.The potassium salt exists in a rose-red and a reddish-violet form and forms a pale red phenol compound CgH403N2BrK,C,H,*OH. The acidpotassiunz salt is yellow. Rose blue and violet rubidium salts have been prepared ; the mid salt is golden-yetlow and the phenol compound pale red. Rose-coloured and bluish-violet caesium salts together with pale red phenol compound are described. The barium salt (C,H403N2Br)2Ba,4H20 is red but when dehydrated is orange- coloured. Similar calcium and mapesium salts have heen obtained. The zinc salt (C9H,O3N2Br),Zn is pale yellow the lead salt pale rose and the thallium salt flesh-coloured. A blue an orange and - a Jlesh- coloured silver salt have been prepared and a carmine-red monohydrate ; the orange and the blue salts yield the same methyl ether. The silver salts are insoluble in neutral media but dissolve in pyridine yielding dichromatic solutions.The following additive compounds are described C9H40,N2BrAg,2C,H,N violet ; C,H,03N,BrAg 2NH deep blue j C6H,0,N2BrAg,NH3 rose ; CgH403N,BrAg CH,CN carmine-red. The anmonium salt is orange-coloured ; the methylamine ethylamine pi-opylamine and benzylamine salts are rose-coloured ; the dimethyl- amine and diethylamine salts are salmon-red ; the dipropylamine salt orange-coloured ; the dibenxylamine salt red ; the trimethylamine salt violet ; the triethylamine salt bluish-violet ; the tripropylamine salt is red and the quaternary ammonium salts crystallise in deep blue plates and their solutions resemble those of the alkali salts.The normal pyridine and picoline salts are pale yellow. The ntethyl ether C( :No OMe) *YO N- 0 ' C6H4B K" c< forms pale yellow crystals m. p. 129" (decomp.). The acetyl derivative also forms yellow crystals m. p. 161' (decomp.) and the benzoyl derivative decomposes at 167'. CH *CO Anisyloxmolone OMe-C,H,*C<.Ll forms crystals with a satiny lustre and m. p. 140 -141" (decomp.). The oximino-derivative O M C Y C H ~ < ~ ( ~ ~ ~ ) ~ ~ ~ forms a yellow monohydrate ; the anhydrous compound has a deeper yellow colour,and decomposes at 149'. The salts are not so polychromatic as those of the corresponding bromine derivatives The following salts are described Sodium C1,?3704N2Na orange- red ; potassium reddish-purple needles ; caeszum bluish-violet ; ammonium red ; silve~ labile rose-coloured and stable blue ; Cl,,Hv04N2Ag 2NH3 red.The methyl ether C,,Hl,0,N2 crystal- lises in pale yellow needles m. p. 126O and when hydrolysed C (C0,H) N N--- yields anisylficraxancarbozylic acid OMe*C,H,-C< A m- P. 99-100'. This acid is undoubtedly formed by the addition of water P 2i. 200 ABSTRACTS OF CHEMICAL PAPERS. and the opening of the oxazolone ring and the subsequent elimination of methyl alcohol. Pantachromism of Violurates and Salts of Analogous Oximino-ketones. ARTHUR HANTZSCH (Ber. 1910,43 82-91).- The following general conclusions are given (1) all polychromatic salts are unimolecular in solution pointing t o the isomerism and not polymerism of different coloured salts derived from the same metal ; (2) the solutions pass from yellow or orange through red and violet to blue as the positive nature of the metallic radicle increases ; (3) the absorption curves of yellow solutions are somewhat analogous t o the curves for solutions of the free oximino-ketones in indifferent solvents and to solutions of their acyl and methyl derivatives.Deep blue solutions on the other hand show distinct selective absorption and are optically closely related t o blue aliphatic nitroso-compounds. The change in colour is attributed to a chemical change namely to the passage from the oximino-ketone form to the nitroso-enolic form O:Q*$XN*OH -+ OH*Y:Q.NO. ~ l l solutions of the salts consist of an equilibrated mixture of the two forms the proportions of each depending on the positive character of the metallic or substituted ammonium radicle present and also on the nature of the solvent.It is shown that a mixture of the yellow acetone solution of zinc diphenyl- 0 0 violurate with the blue acetone solu- -@..,&f tion of potassium diphenylviolurate I Leuco-salts yield yellow solutions indicating a partial conversion into N (1.1 N the nitroso-enolic form. The solid salts of orange red or purple colour 0 0 are also regarded as mixed crystals of the two isomeric salts. When a salt exists in a yellow 1 11 and 1 I I and a blue form these are regarded as isomeric in the sense of Werner's Similarly the yellow and red salts J. J. 8. I I is red and not green.-'\do -c\/O /\/\BI \/\yo /\/'.-.,M \/\/* NO valency-isomerism (for example I). NO (11.) of nitrophenol are represented as (11) The red aci-ethers are regarded as analogous to the red salts. J. *J. S. Purpuric Acid. ARTHUE HANTZSCH and ROBERT H,OBISON (Be?*. 1910 43 92-95).-The formula of Piloty and Slimmer and Stieglitz (Abstr. 1904 i 634) for purpuric alid is analogous t o that of the blue violuratee and *<NH NHpCo>C*NO C (OH) It has not been found possible to prepare coloured ethers or to isolate the pure violuric acid. A method is recommended for the preparation of pure murexide (ammonium purpurate) (compareORGANIC CHEMISTRY. i. 201 Hartley Trans. 1905 87 1981). The values for the electrical conductivity of the pure salt are p25s = 51 -2 pb12 = 5 1.5 p,024 = 5 1-8 and pOc = 52.9.The conductivity of the system rnurexide + HC1= purpuric acid+NH,Cl has been determined a t 0'. The purpuric acid is only slowly transformed into uranil and alloxan and becomes colourless after three days. The initial value for p512 is 225 but this gradually falls to 167 after twenty-five minutes and to 21 after three days. The value ps for purpuric acid at OOhas been found to be 248.8 from the equation pOc HCl- paC NH4Cl -I- paC murexide = pZ purpuric acid. The degree of dissociation at 0" and vSJ2 is thus 0.9 and K= 0.0158. Alloxan is not regarded as a quinonoid substance since it shows only general absorption. 278.8 82.9 52.9 248-8 J. J. S. Synthesis of 5 7 5' 7'-Tetrachloroindigotin. ERWIN OBERREIT (Compt. rend. 1910 150 282-283.Compare Danaila this vol. i 137).-The constitution of this substance follows from the fact that it may be prepared from dichloroglgcine-o-carboxylic acid which has been obtained from 3 5-dichloroanthranilic acid. w. 0. w. Quinoline-Red. EDUARD VONGERICHTEN and L. KRANTZ (Ber. 1910 43 128-130).-&uinoline-red is obtained by the interaction of molecular proportions of benzotrichloride quinaldine and ! isoquinoline in presence of zinc chloride (Hofmann Abstr. 1887 380). When oxidised with potassium dichromate a base is formed m. p. 125O which is regarded as quinolyl isoquinolyl ketone C,H,N*CO*C,H,N since on heating it with concentrated potassium hydroxide isoquinoline and an acid probably quinaidinic acid are formed. The base dissolves with a yellow coloration in concentrated acids and yields an intensely yellow-coloured crystalline precipitate with phosphorus pentachloride in chloroform solution.The oxime forms somewhat grey-coloured glistening plates m. p. 245'. A second product of the oxidation is benzaldehyde. E. I?. A. Acenaph them Series. FRITZ ULLYANN and ERWIN CASSIRER (Bey. 19 10 43 439-445).-As acenaphthene is now a commercial product the authors have attempted to convert it into dyes or into products from which dyes may be obtained. A 407; yield of nayhthalic acid can be obtained by oxidising acenaphthene with sodium dichromate and sulphuric acid (compare Graebe and Gfeller Abstr. 1892 863). Naphthastyril (Ekstrand Abstr. 1886 715; 1889 52) is formed when naphthalimide is treated with sodium hydroxide solution and then with sodium hypo chlorite at 15-25'.It reacts with 10% sodium hydroxide solution and p-toluenesulphonic chloride yielding 8-p-toluenesulphonykamino- naphthoic acid C7H7*S0,*NH*CI,H,*C0,H as colourless needles m. p. 158-159O (decomp.). With acetic anhydride the acid yields p-toluenesulphonylnaphthastyril Cl,H1,O,NS as straw-yello w glistening needles m. p. 174'.i. 202 ABSTRACTS OF CHEMICAL PAPERS. Phenylacenaphthaphenazonium nitrate (annexed formula) obtained from acenaphthenequinone a-aminodiphenylamine and acetic and nitric acids crystallises in glistening yellow needles. It dyes cotton mordanted with /-\-c.N- tannin"a pale lemon-yellow The xincochloride '-' 11 I )C,H 2C2,HI,N,ZnC13 forms yellow plates with a / \ C*NPh brassy lustre ; the dichromate NO3 forms a yellowish-brown crystalline powder and the free base C2,H,5N2*OH a yellowish- green precipitate. The nzethyl ether C,,H,,ON forms glistening yellow crystals m.p. 180-185°. ('2 4H15N2)2Cr207 \-/- I 3-Chlorophenylnaphthaphenaxonium nitrate \ a/ obtained from acenaphthenequinone and 5-chloro-2-aminodiphenyl- amine forms yellow needles and dyes cotton mordanted with tannin a yellowish-green. The methyl ether C,,H170N2CL forms pale green glistening plates arid has rn. p. 200-220°. 2-A minopheny I -acenupht haphenaxonium chloride crystallises in deep violet-coloured needles and dyes mordanted cotton Bordeaux-red. The nitrate C,4H,,0,N crystallises in violet plates. The acetyl derivative crystallises in long red needles. C26H1,0N3C1 N Acenaphthaphenaximaxim (annexed formula) obtained by condensing acenapht henequinone and 2 3-diaminophenazine in acetic acid solution crystallises in red needles which are not molten at 320'.J. J. S. Methylene-Blue. PAUL LANDAUER and HUGO WEIL (Ber. 19 10 43 198-203).-Durr~chnabel has shown (Digs. Giessen 1907) that indamines oxazines thiazines and other para-quinonoid substances are converted by sulphurous acid or hydrogen sulphite into sulphonated leuco-compounds whilst ortho-quinonoid substances such as the indulines and safranines are not reduced and usually form sparingly soluble sulphites. The authors find that phenylhydrazine acts in a similar way. Methylene-blue suspended in alcohol is treated with phenylhydrazine a t the ordinary temperature ; after half an hour's warming on the water-bath the system is allowed to cool in carbon dioxide or coal gas.Nitrogen is evolved and leuco- methylene-blue m. p. 185' is obtained in yellow needles. The leuco- compound is stable in dry oxygen and in the presence of alkaline oxidising agents can be directly acetylated by acetic anhydride and yields a yellow sodium salt with alcoholic sodium ethoxide. Methg lene- green by similar treatment yields brown needles of nitroleucomethylene- blW C16Hla02N4S m. p. 146-14'7'. c. s.ORGANIC CHEMISTRY. i. 203 Synthesis of Hetero-condensed Heterocyclic Compounds with Two Nuclei. Derivatives of 2-Methyl-1 3.triaeo-'7 0'- pyrimidine [%Methyl-1 3 7 9-benztetrazole] from 5-Amino- 2-methyl-1 3 4-triazole. CARL BULOW and KARL HAAS (Ber.1910 43 375-381. Compare Abstr. 1909 i 614 615 (and Errata) 1470; this vol. i 80 81).-5-Amino-2-methyl-l 3 4-triazole contains a labile hydrogen atom attached to the nitrogen next the basic group. Accordingly it interacts with 1 3-diketones forming di- and tri- alphyl or aryl derivatives of 2-methyl-1 3 7 9-benztetrazole or with keto-esters forming methyl benztetrazolehydroxylic acid derivatives. >CMe yXe=N*Q :N CH C3le.N *N 2 ; 4 6 - Trimethyl - 1 3 7 9 - benxtetraxole prepared by interaction of the aminotriazole with acetylacetone forms colourless needles m. p. 141-142'. . - QMe==N*T :N CMe CMe'lU *N 2 ; 4 5 6-Tetramethyl-1 3 7 9-benxtetraxole >CMe obtained in a similar manner from methylacetylacetone has m. p. 4-Phenyl-2 6-dimethyl-1 3 7 9-benxtetq*azole forms colourless radi- 4-&drox.~-2 6-dimethql-1 3 7 9-benztetrccxole 11 6-1 17".ally grouped long thin prisms m. p. 110-1 1 lo. obtained by boiling aminornethyitriazole with ethyl acetoacetate in glacial acetic acid solution separates in glistening crystals m. p. above 880'. This and the following compounds are acidic forming salts with alkalis. These react neutral in aqueous solution and give amorphous or crystalline precipitates with salts of the heavy or alkaline-earth metals. Thus the lead salt forms short plates; the copper salt bright preen needles ; the zinc salt stellar aggregates of needles ; the calcium salt glistening needles. 4- Hydroxy-2 6-dimethyl-5-ethyl-1 3 7 9-benxtetraxole prepared from ethyl ethylacetoacetate has m.p. 262O and forms soluble neutral salts which are not decomposed by carbon dioxide 4-Hydroxy-6phenyZ-2-methyl-1 3 7 9-benztetvazole obtained from ethyl benzoylacetate forms long colourless needles which do not melt a t 293O. E. F. A. Yellow and Red Forms of Salts and Hydrates of Hydroxy- azo-derivatives. ARTHUR HANTZSCH and PHILIP W. ROBERTSON (Ber. 1910 43 106-122. Compare Tuck Trans. 1907 91 460; Gorke Koppe and Staiger Abstr. 1908 i 477).-The salts of hydroxy-azo- compounds appear to exist in' yellow and red modifications similar to the yellow and red salts of nitrophenols. It is only in the case of silver salts t h a t yellow and red isomeric salts have been obtained from the same compound. Salts of the type R*N,*C,H,*OM+ 0.5MeOH (EtOH CH,*CO,Et COMe or C,H,N) are common ; they are orange-coloured and are regarded as compounds of 1 mol. of red salt 1 mol.of yellow salt and 1 mol. of the crystallising medium. When the last is removed they yield red or yellow salts or sometimes orange- coloured salts.i. 204 ABSTRACTS OF CHEMICAL PAPERS. The following table gives the colours of the salts of four hydroxyazo- compounds Benzene- Benzene- p-Chlorobenzene- p-Bromobenzene- azo-o-di- azophenol. azophenol. azophenol. bromophenol. . H ......... Yellow Yellow Yellow Orange Li ...... Pale yellow Pale yellow Pale yellow Pale yellow Na ...... Orange Orange Orange Yellow K ......... Red Pale red Red Orange Rb ...... Dark red Orange Red Orange Cs ...... Pale red Red Red Orange Ag { Red (labile) Red (labile) Red (labile) Red Yellow (stable) Yellow (stable) Yellow (stable) ......It is noticeable that the lithium salts are paler in colour than the original hydroxy-derivatives and that as a rule the caesium salts are paler than the rubidium. The hydrates of hydroxyazo-compounds also appear as represent- atives of two chromo-isomeric series. The following are the colours of the hydroxyazo-compounds and of their hydrates (0.5 or 1 mol. H,O) o-Chlorobenzeneazophenol red yelIow ; meta-compound yellow red ; para-compound yellow yellowish-red ; o-bromobenzeneazophenol red yellow ; meta-compound yellow red ; para-compound yellow red ; o-tolueneazophenol yellow yellow ; meta- compound yellow yellow ; benzeneazo-m-cresol yellow yellow ; m-chlorobenzeneazo-m-cresol yellow red ; o-tolueneazo-m-cresol yellow- ish-red yellowish-red ; benzeneazo-o-chlorophenol yellowish-red (labile) yellow (stable) yellowish-red.The last-mentioned colour in each case refers to that of the hydrate. The determinations of the absorption spectra and of the molecular extinctions of solutions of the salts and hydrates show that the yellow and red forms are not polymorphous or polymeric. The solutions in indifferent solvents have much the same colours as the solid salts. The nature of the solvent also affects the colour of the solutions the more positive the nature of the solvent (namely pyridine) the deeper the colours. These solutions of salts of hydroxyazo-compounds are regarded as equilibrium mixtures of yellow and red salts just as in the case of the violurates. From such solutions the ornnge-coloured additive compounds (1 mol.yellow 1 mol. red 1 mol. solvent) separate as they are sparingly soluble. All these solid additive compounds have practically the same colour so that the effect of different solvents on the solids is practically nil ; since however the solutions have different colours it is probable that the relative amounts of red and yellow salts in the different solutions vary considerably. The increase in colour of the salts as compared with the free hydroxy-compounds indicates that salt formation as a rule favours the formation of the red form. It is shown that mere salt formation (Gorke) has not necessarily an auxo- chromic effect since lithium salts are paler than the free hydroxy- compounds and dipropylamine salts in some cases give absorption curves exactly analogous to those of the free hydroxy-compounds.The following structural valency formulae are suggested for the yellow and red forms :ORGANlC CHEMISTRY. i. 205 where the dotted lines represent subsidiary valencies. The following values for the molecular extinctions (A=546) of hydroxyazobenzene and its salts in different media at 15' and V=200 are given Rubidium salt in pyridine 510 in ethyl acetate Sl,-in:alcohol;44 ; caesium salt in alcohol 24 in benzene + 4% alcohol 18 in hexane + 4% alcohol 14 ; lithium salt in ether 12 ; dipropylamine salt + 100 mols. dipropylamine in benzene 9 ; hydroxyazobenzene in carbon tetra- chloride 8 in chloroform 7 in pyridine 7 in benzene 7 in alcohol 4. The values for the molecular extinctions (A = 546) for salts of dibromo- hydroxyazober,zene a t 15' and P= 400 are Solvent .Li. Na. li. Rb. cs. Ether 15 17 18 18 ........ 35 35 36 Alcohol 39 Pyridine.. 140 179 ............ - ....... 37 180 21 0 220 J. J . S. Formation and Decomposition of Symmetrical Bisazo- compounds of Ethyl Arylhydrazonemesoxalylbishydrazone- acetoacetates and of Ethyl Malonylbiahydraeoneaceto- acetate. CARL BULOW and C. BOZENHARDT (Ber. 1910 43 234-242).-Ethyl malonylbishydrazonebenzeneazoacetoacetate reacts with one molecule of benzenediazonium chloride yielding ethyl phenyl- hydrazonemesoxalylbishydrazonebenzeneazoacetoacetate with 72% yield (compare Abstr. 1908 i 253). I n addition small quantities of ethyl benzeneazoacetoacetate cyclomalonylhydrazide and 4-benzeneazo-3- met hy 1-5-p yrazolone are formed.E t h y 1 p heny lhy drazonemesoxaly 1- bishydrazonebenzeneazoacetoacetate when warmed with phenyl- hydrazine decomposes i n t o 4-benze neazo-1-phenyl- 3-met hylpyrazolone (orange needles m. p. 154-155' ; yield 85%) 4-bemxenenxopy~axolidone (m. p. 266") and hydrazine. When boiled with dilute potassium hydroxide it yields 4-benzeneazo-3-methyl-5-pyrazolone and mesoxalic acid-phenylhydrazone ; whilst by the action of boiling acetic acid 4-benzenenzo-3-methyl-5-pyrazolone ethyl benzeneazoacetoacetate and 4-benzeneazo-3 6-pyrazolidone are produced. Dimethyl mesoxalate- phenylhydrazone (compare Abstr. 1905 i go) when treated with hydrazine hydrate yields rnesoxalylphenylhydraxonedihy~rc~z~d~ m. p. 164O. The diacetyl derivative has m.p. 246-247'. The dihydrazide condenses with ethyl benzeneaxoacetoacetate giving ethyl phenyl- hydrazooemesoxalyLbishydrazonebenzeneazoacetoacetate the constitu- tion of which is coDfirmed by this mode of preparation. The above dihydrazide when boiled with acetic acid also yields 4-benzeneazo-3 5- pyrazolidone of m. p. 2 6 6 O already mentioned. Ethyl phenylhydr- azonemesoxalylbishydrazonebenzeneazoacetoacetate is also produced by condensing equimolecular quantities of benzenediazonium chloride and ethyl ~nalonylbishydraxonebenxeneaxoacetoacetate. The latter isi. 206 ABSTRACTS OF CHEMICAL PAPERS. formed in 80% yield by the condensation of 2 molecules of ethyl ben- zeneazoacetoacetate with malonyldihydrazide. It is decomposed by boiling alcohol into ethyl malonate and 4-benzeneazo-3-methyl-5 - pyrazolone. On heating it melts at 128' then gas is evolved and the mass solidifies melting again at 217-218'.I n this process the theoretical quantity of alcohol is evolved and the residue consists of 4- benzeneazo-3-methyl-5-pyrazolone and 1 1 -maZonylbis-4 -6enzeneazo- 3methyZ-5-pyraxolone (compare Abstr. 1907 i 986) m. p. 225.5O. On boiling with potassium hydroxide or pyridine the latter yields 4-benzeneazo-3-methyl-5-pyrazolone and malonic acid. Ethyl malonylbishydrazoneacetoacetate yields with 3 molecules of p-diazotoluene chloride ethyl-p-tolylhydrazonemesoxaZytlbishydrazone- to2uene-p-axoacetuacetate orange needles m. p. 209-2 10'. By the condensation of rnalonyldihydrazide with ethyl toluene-p-azoaceto- acetate ethyl matlo~ylbishydraxonetohenep-axoacetoacetate orange needles m.p. 114-115' is produced. Aeo-dyes derived from 2 4Dimethylpyrrole and Hmmo- 260-266 *).-For the purpose of comparison with the azo-dyes obtained from hsmopyrrole and chlorophyllpyrrole the authors have investigated the diazotisation of dimethylpyrrole. In addition to the monoazo-derivative of Plancher and Soncini (Abstr. 1901 i 432) they have obtained small quantities of a substance C,,H,,N6Cl which they suppose to have the formula (N,Ph*C6H7NoC,H~NoN,Yh)HC1. It crystallises in well-developed red needles having a metallic lustre and it is only slightly soluble in most solvents. I n physical characteristics (including the absorption spectrum) the substance shows similarity to the azo-derivative of hamopyrrole.Reduction of Nitroso-derivatives of Acetyl- and Benzoyl- hydrazobenzene. Lours NOMBLOT (Compt. rend. 1910 150 338-339).-~~&rosoacety~hydrazobenxene XAcPh-NPh-NO obtained by adding ethyl nitrite to acetylhydrazobenzene suspended in alcohol occurs in yellow prisms m. p. 65". The corresponding 6enxoyZ derivative crystallises in pale yellow leaflets m. p. 116.5". The action of reducing agents on these two substances has been studied. An alcoholic solution of hydrazine hydrate converts them into the corresponding acidylhydrazobenzene with liberation of ammonia. Aluminium amalgam gives aniline together with acetanilide or benzanilide. Zinc dust in presence of acetic acid at 0-5" gives no reduction products. Under no conditions were triazan derivatives obtained.R. V. S. pyrrole. LEON ~~ARCHLEWSKI and J. ROBEL (Ber. 1910 43 R. V. S. W. 0. W. [Preparation of p - Aminophenyl-2-azimino-5naphthol-7- sulphonic Acid.] GESELLSCHAFT FUR UHEMISCHE INDUSTRIE IN BASEL (D.R.-P. 2 14658).-p- Aminophenyl-2-azimino-5-naphthoL7-sulphonic acid a grey crystalline powder sparingly soluble in water and employed in the production of Bordeaux-red dyes is prepared by the following series of operations l-Chloro-2 4-dinitrobenzene is condensed with p-naphthylamine- * and Bull. Acad. Sci. Cracow 1910 A 1-8.ORGANIC CHEMISTRY. i. 207 5 7-disulphonic acid yielding 2 4-dinitrophenyl-P-naphthylamine- 5 7-disulphonic acid ; this is reduced with sodium sulphide and ammonium chloride to p-nitro-o-aminophenyEP-naphthylamim-5 7- disulphnic acid the disodium salt of which forms red crystalline leaflets.This substance is treated with sodium nitrite in the presence of sulphuric acid and the resulting nitroaximino-compound reduced with iron rilings to p-aminophenyl-2-axirninonaphthalene-5 7-disul- phonic acid grey needles which on heating with sodium hydroxide solution a t 180- 1 90° yields the foregoing naphtholsulphonic acid. F. M. G. M. Azoarylhydrazinesulphonic Acids. JULIUS TROGER and A. WESTERKAMP (Arch. Pharm. 1909 247 657-698).-The hydrazine- sulphonic acid obtained by the action of sulphur dioxide on aqueous benzenediazonium sulphate (Abstr. 1904 i 118 ; 1906 i 120 993 994) has been synthesised by Troeger and Puttkammer (Abstr. 1907 i 263) by converting diazotised aminoazobenzene into azo- benzenediazosulphonate and reducing the latter by ammonium sulphide NzE'h*C,H4*NHz -+ N2Ph*C6H4*N2C1 -+ N2Ph*C6H,*N,*O*S02K (Labile salt.) -+ N2Ph*C6H4*N2*S03K -+ N2Ph*C6H4*NHoNH*S03H.(Stable salt.) This synthetic process has now been applied t o numerous aminoazo- compounds whereby hydrazinesulphonic acids are obtained which are red blue violet or brown; they are best purified by means of their salts with aromatic amines and are reduced by stannous chloride and hydrochloric acid in the sense of the equation N2Ph*C,H4.NH*NH*S03H + 6H + H,O = NH2Ph -t NH2*C6H,*NH + NH + H,S04,. a monoamine and a diamine always being formed. When heated with alcoholic hydrogen chloride and an aldehyde or ketone the hydrazinesulphonic acids lose the sulphonic acid group and are con- verted into hydrazones which form coloured salts with the hydrochloric acid.4-Amino-o'm-azotoluene thus yields a reddish-brown o'm-azotoluerne- 4-hydraxinesulphonic acid C,H4Me*N2*C,H3Me- NH*NH*SO,H (the potassium and ba~ium salts are described ; the p-toluidine salt Cl,Hl,N4*S03~NH,'C,H7 m. p. 158q forms yellow needles) which yields o-toluidine and 1 2 5-tolylenediamine by reductive fission and in the presence of alcoholic hydrogen chloride reacts with salicylaldehyde t o form o-hydroxy benxylidene-o'm-axotoluene-khydraxone C,H4Me*N2*C,H,Me*NH*N :CH* C6H4* OH m. p. 130-131O (the hydrochloride C21H210N,C1 forms violet needles and the sulphute blue ueedles with :t green reflex) with p-nitrobenz- aldehyde to form a similar hydrazone C,H,Me*N,*C,H,Me*NH*N CH*C,H,*NO m.p. 158O with p-methoxybenzaldehyde to form the reddish-yellowi. 208 ABSTRACTS OF CHEMICAL PAPERS. hydraxone C22H220N4 m. p. 147' and with benzaldehyde to form an orange-red hydrazone C,,H,,N m. p. 160'. 4-Amino-mp'-azotoluene yields reddish-brown amorphous mp'-azo- toluene-4-hydrazinesuZphonic acid$ C1,Hl6O3N,S the p-toluidine salt of which m. p. 183O forms yellow needles; the hydrazone C2,Ha20N4 m. p. 1 48' from p-methoxybenzaldehyde forms golden-yellow leaflets ; the hydrazone C,1H200N m. p. 120-121' from salicylaldehyde forms red prisms and the hydrazone C21H,902N5 m. p. 176-177' from m-nitrobenzaldehyde is a reddish-brown crystalline powder. op'- Axotoluene-4-hydraxinesuZphonic acid C14H ,o3N,S obtained from 4-amino-op'-azotoluene is a dark reddish-brown amorphous powder ; the p-tohidine salt m.p. 171' forms reddish-yellow needles. mp'-AzotoZuene-6-hydraxinesuZphonic acid C,,H1,0,N4S is an indigo-blue amorphous powder obtained from 6-amino-op'-azo- toluene ; the p-toluidine salt has m. p. 154' and the aniline salt has m. p. 1 39'. Benxeneazo-p-toluene-4-hydrazinesuZphonic acid is a dark red amorphous powder which forms a yellow crystalline p-toluidine salt m. p. 170' (decomp.) arid a p-xylidine salt m. p. 175' (decomp.). Benxeneaxo-p-xylidine N,Ph*C,H,Mo,'NH m. p. 104-105° obtained by the slow addition of diazotised aniline hydro- chloride to an alcoholic solution of p-xylidine and treatment of the resulting hydrochloride with ammonium hydroxide separates from dilute alcohol in golden leaflets and from petroleum and benzene as a deep orange crystalline powder and forms a nitrate crystallising in long blue needles a violet hydrogen sulphate and a golden-yellow oxalate.It is converted by the usual processes into 6enxeneaxo-2 5-xyZene-4- ?..ydra&esuZ'honic acid C,,H,,O,N,S a dark red mioro-crystalline powder the reddish-yellow p-toluzdzne salt of which has m. p. 158'. N,Ph* C,,H,*NH*NH SO,H obtained from benzeneazo-a-naphthylamine is an amorphous violet powder which is best purified by means of its potassium salt which crystnllises in reddish-yellow needles. The acid is reduced by zinc dust and hot acetic acid y!elding aniline and 1 4-naphthylene- diamine and reacts with alcoholic hydrogen chloride and aldehydes in the manner mentioned hydrazones being produced in the form of hydrochlorides ; the hydrazone N,Ph*C,oH6*NH*N:CH*C,H4*OMe m.p. 258-160' from p-methoxybenzaldehyde forms orange needles (hydrochloride deep blue needles) ; the hydrazone from salicylaldehyde has m. p. 205' (hydrochloride bluish-violet needles) ; the hydrcmone- from p-nitrobenzaldehyde has m. p. 172-1 73" (hydrochlokle dark green powder). I n a similar manner benzeneazo-P-naphthylamine yields benzene axo-P-nuphtAyZhydraxinesuZphonic acid a coffee-coloured amorphous powder which is purified through the p-toluidine salt m. p. 1 6 5 O (decomp.). 2 4 3' 5'-Tetrurnethylaxobenzene-2-hydrazinesulphonic acid C,,H,*O,N,S9 Benxeneaxo-a- naphth y lh ydrazinesu Zphonic acid C16H1303N4SK C 6 H M e ~ N * C ~ M e 2 ~ ~ H * ~ ~ * S ~ H ,ORGANIC CHEMISTRY.i. 209 obtained from aminoazo-m-xylene is a red amorphous powder which forms a p-tohidine salt m. p. 170’ (decomp.) aniline salt m. p. 153’ (decomp.) and a p-xylidime salt m. p. 176O (decomp.). a- Napht h ylazo-a-naphthy 2h ydrazinesulphonic acid C,,H7*N C,,H,*N H *NH SO,H obtained from aminoazo-a-naphthalene is a dark blue substance. c. s. The Adsorption of Proteins WILHELM BILTZ and XANS STEINER (Biochem. Zeitsch. 1909 23 27-42) -The adsorption of egg-white by cellulose iron hydroxide and kaolin mas estimated in varying con- centrations of the protein. The amount adsorbed was determined by estimating the nitrogen in the clear solution after filtration of the adsorbent by a modification of Kjeldahl’s method the amount of ammonia being determined colorimetrically with the use of Nessler’s reagent.The adsorption process is not entirely reversible and the results do not entirely agree with the ordinary adsorption equation. The application of the adsorption formula to the combination of toxin and antitoxin was also investigated (1 - T/VA = log L + l/p log T where T’ is theconcentration of the free toxin and 1 - 27 that of the combined). The results of the neutralisation of tetanolysin and streptolysin by the antilysins and of the streptolysin by cholesterol of diphtherotoxin by its antitoxin of saponin by ox-blood of cobralysin by antivenin and other similar reactions were investigated. The results obtained were compared with those calculated from the adsorption equation and Arrhenius’ mass reaction equation.Neither of these equations agreed in a satisfactory manner with the results obtained experimentally. S. B. S. Composition of the Products of the Alkaline Hydrolysis of Cryatalline Egg-albumin. NOGENDRAMOHON GUPTA (Monatsh. 1909 30 767-771).-The products resulting from the hydrolysis of egg- albumin by sodium hydroxide (compare Skraup and Hummel burger Abstr. 1909 i 340) have been submitted to careful analysis with the following results Carbon. Hydrogen. Nitiogeii. Sulphur. Protalbic acid ....” ... 55.4 7.2 14.3 2‘4 Lysalbic . . . . . . . . . 52 -9 7.0 14 -9 1 - 2 Lysalbinpeptone ... ... 46-2 6.6 10’3 1.2 W. H. G. The Preparation and Properties of Iodo-Mucoids. GUSTAVE M. MEYER (J. Biol. Chem. 1909 7 11-lG).-Iodo-mucoids were prepared by the action of iodine on tendo-mucoid in a dilute solution of sodium carbonate ; they contain approximately 14% of iodine.W. D. H. The Relation of Proteins to Crystalloids. I. The Osmotic Pressure of Hmmoglobin and the Laking of Red Blood- corpuscles. HERBERT E. ROAF (Quart. J. exp. Physiol. 1910 3 75-96).-A simple method is described for the direct measurement of the osmotic pressure of a solution when the solute does not passi. 210 ABSTRACT@ OF CHEMICAL PAPERS. through parchment paper or other suitable membranes. Ia this way the osmotic pressure of laked corpuscles and crystallised haemoglobin was measured and pressures corresponding with the molecular weight of haemoglobin calculated from other data were obtained if conditions obtain which limit ionisation ; but otherwise much higher pressures are reached and it is suggested that this is due t o the ionising of hsmoglobin salts; both acid and alkali increase the pressure and as with serum proteins a minimal pressure is found near the neutral point.Many substances lower the osmotic pressure and thus might help to prevent laking of red corpuscles. Pressures were obtained with corpuscles laked by freezing and thawing up to 282 and 256 If ionisation occurred the calculated pressure might be as high as 960 mm. of mercury. With such a range of pressure the osmotic pressure of haemoglobin should be considered in discussing the laking of corpuscles but until further experiment has determined the pressures in mixed solutions containing the various crystalloids of the corpuscle it cannot be decided what part is played by haemoglobin and how much is due t o other factors. W.D. H. Blood Colouring Matter. WILLIAM KUSTER (Ber. 1910 43 370-375).-The compound C36H3603N4 obtained by Kuster and Fuchs (Abstr. 1907 i 572) as a bye-product of the action of aniline on haemin is also formed in small quantity when acetglhaemin is con- verted into dehydrochloridehaemin. By the action of concentrated hydrochloric acid under pressure on haematin the organic material partly loses its acid properties and partly undergoes oxidation. Haemin and haematin are regarded as ferric compounds and the ferric chloride formed oxidises part of the iron-free haematin. The oxidation product does not undergo rearrangement to haematoporphyrin. When hydrogen bromide is used the oxidising action of the ferric bromide is neutralised and haematoporphyrin formation takes place. Ten % hydrochloric acid only eliminates 5% of.the iron from hsmin a t 130° whereas under similar conditions over 90% of the iron is separated from hzematin. Haematin is slowly changed by solution in alkali whereas the fresh solution is completely precipitated by the theoretical quantity of barium chloride. After keeping a large excess of this is required. Poly- merisation to a p-haematin takes place on keeping. The conversion of haematin by reducing agents into haemochromogen is regarded as corresponding with a reduction from the ferric to the ferrous state. Haemoglobin contains ferrous iron ; oxyhsemoglobin however contains iron peroxide. Haemin forms salts with 3 mols.of alkali hydroxide; dehydro- chloridehaemin salts with 2 mols. These can be dialysed in 1% solution without the dye passing through. Hsmin only takes up 2 mols. of sodium carbonate and sodi um hydrogen carbonate appears in the outer water on dialysis. Precipitates obtained with other metallic salts showed zt very varying metal content. The iron salts dissolve in sodium hydroxide and are acids ; seemingly the second iron atom is attached to the free nitrogen atom. E. F. A.ORGANIC CHEMISTRY. i. 211 Bshaviour of Gelatinous Substances or Collains towards Carbon Disulphide. WL. S. SADIKOFF (J. Russ. Phys. Chern. XOC. 1909 41 1597-1686 ; Kolloid. Chem. Beihefte 1910 1 119-220).-When anialkali acts on glutin i n presence of carbon disulphide “thio- hydration ” occurs this consisting of two distinct processes namely hydration by the alkali and subsequent addition of carbon disulphide or ‘‘ thionylation ” (compare A bstr.1907 i 740). The most charac- teristic part of the thionplglutin thus obtained is the complex to which the carbon disulphide is added and which is termed the “ receptor.” This receptor is extremely indifferent neither being destroyed by water reacting with tannin bromine aldehydes or the majority of organic acids nor being replaced by benzoyl chloride or methyl iodide. I t takes up carbon. disulphide in neutral alkaline or acid media combines with strong mineral acids and with acetic and oxalic acids is substituted by trinitrophenol and ‘‘ immobilised,” or rendered incapable of taking up carbon disulphide by solutions of sulphates probably owing to the sulphuric acid formed by adsorptive decomposition of the salts. In the case of tendo-collagen the receptor is not homogeneous.The predominating part of it is readily reactive being replaced by carbonic acid and by organic and mineral acids acetic anhydride benzoyl chloride bromine methyl iodide or aldehydes ; it is stable towards the action of heat or water and is not replaced by picric acid. The lesser part of the receptor is highly inert is replaceable only by mineral acids and tannin and is stable towards the action of water but thermo-labile; this part is not altered by the action of alkali hydroxide. The reactive portion of this receptor would seem to be a primary or secondary amine. The Scission Products Resulting from the Partial Hydrolysis of Proteins.EMIL ABDERHALDEN (Zeitsch. physiol. Chem. 1909 63 40 1 -404).-From the partial hydrolysis of silk .glycyl-2-tyrosine was obtained previously. The present research gives details of the preparation and identification of another dipeptide from the same source namely d-alanyl-glycine. Trypsin and Antitrypsin. KURT MEYER (Biochem. Zeitsch. 1909 23 68-92).-Samples of dried pancreatic juice and juice from the small intestine were used in the experiment and dissolved t o give the necessary concentrations as required. The tryptic action was estimated by the Gross-Fuld casebogen method. The influence of the quantity of kinase on the activation of the trypsinogen was first investigated. The results indicate that the kinase action is of ferment- like character.The grade of activation is not proportional to the amount of kinase and very small quantities of the latter can activate large quantities of the trypsinogen provided that sufficient time is allowed for the action. The rate of activation is approximately proportional to the amount of kinase. The greater activity of mixtures containing large amounts of kinase is apparently due to a shortening of the activating process owing to which the concurrent destruction of the trypsin and kinase becomes less marked. An excess of kinase does not inhibit the activation. The inhibitory T. H. P. W. D. H.i. 212 ABS'I'RACTS OF CHEMICAL PAPERS. substance of the serum is neither an antikiriase nor an anti- trypsinogen. The former possibility is excluded by the fact that the anti-action is not overcome by the addition of excess of kinase and is also exerted on trypain which has been obtained from trypsinogen by calcium salts. Antitrypsinogen and antikinase are also excluded by the fact that the inhibitory action of the serum is not increased by allowing it to act on the kinase or trypsinogen alone before mixture and that the quantity necessary for inhibiting a mixture which is being gradually activated depends on the amount of trypsin actually present at the time of addition. No an titrypsinogen or antikinase could be obtained by immunisation experiments. The saturation of trypsin by the anti-substance follows the lam of multiple proportions. I n the fractional saturation of trypsin by the anti-substance the Danysz phenomenon was observed namely the inhibitory action is weaker than if the whole quantity of anti-substance had been added at one time. Previous treatment of trypsin by antitrypsin did not increase the inhibitory effect. The formation of a non-digesting but anti- substance binding trypinoid could not be effected The effect of heating trypsin and the anti-substance was also investigated. The results indicate that antitrypsin is not a negative catalyst but actually enters into combination with trypsin. No kind of specificity was noted in the case of antitrypsin. Influence of the Reaction of the Medium on the Filtration of Diastases. MAURICE HOLDERER (Compt. rend. 1909 149 1153-1 156).-Details of experiments on extracts of A8pergillus nigei. are given from which it appears that a porcelain fiker is permeable to sucrase when the solution in which this is present is neutral to phenolphthalein ; when the solution is neutral to methyl-orange however the ferment no longer passes the filter. I n order therefore to render the extraction of sucrase more complete it is desirable to have the solution alkaline whilst maceration is in process. Influence of the Reaction of the Medium on the Filtration of Malt Enzymes. MAURICE HOLDERER (Compt. rend. 1910 150 285-288. Compare preceding abstract).-The enzymes of malt amylase dextrinase and peroxydiastase resemble the diastases already studied in their behaviour when the solutions are filtered through porcelain. Filtration occurs readilyFwhen the solutions are neutral to phenolphthalein but the passage of the enzymes through the filter is inhibited if the medium is neutral to methyl-orange. Cellase and the Diastatic Decomposition of Cellose. GABRIEL BERTRAND and MAURICE HOLDERER (Compt. rend. 1909 149 1385-1387).-9n attempt to ascertain whether a specific ferment exists capable of hydrolysing cellose. Maltase and sucrase are without action on this substance whilst a maceration of Aspergillus niger converts it completely into dextrose. Preparations of emulsin from almonds and of emulsin with trehalase from barley or malt have the same action. S. B. S.' w. 0. w. W. 0. W. w. 0. w.

ISSN:0368-1769    

DOI:10.1039/CA9109800149

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 152 ABSTRACTS OF CHEMICAL PAPERB An alg t ic a1 Chemistry . Manipulation of Small Precipitates. Qualitative and Quantitative Micro-chemical Analysis. FRIEDRICH EMICH and JULIUS DONAU (Jlortutsh. 1909 30 745-757). -Micro-fil ters of paper are cut about 6-8 min. in diameter and placed on the thickened end of a capillary tube which is cut square and polished The tube acts as a funnel and is placed in a suitable apparatus so that suction can beANALYTICAL CHEMISTRY. ii. 153 applied. The application of a little vaselin t o the rim of the filter and i t s depression in the centre over the capillary by means of a glass rod enables large drops to be filtered without danger of any loss owing to the liquid flowing off the paper. The precipitate is collected on the filter washed and placed in a sheet of platinum foil which c ~ n be wrapped round it and so prevent loss during drying ignition and weighing.A Nernst micro-balance was used for the weighings. A number of simple qualitative and quantitative estimations have been performed accurately and quickly in the manner described. Apparatus f& Filtering at a Constant Temperature. ALFRED EISENSTEIN and FRIEDRICH ZIFFER (Chem. Zeit. 1909 33 1330).- The apparatus consists essentially of a filtering tube surrounded by a constant-temperature jacket the constant temperature being main- tained either by a freezing mixture or by circulation of a liquid of known temperature. The filtering tube is made of three lengths of glass tubing of different widths the two upper sections being con- tained in the constant-temperature jacket.A piece of platinum or copper wire gauze is placed at the lower joint and on this can be placed the filter paper. The upper joint is ground t o fit the elonga- tion of the bulb of a thermometer so that the top tube can be cut off from the middle one. If a substance is to be extracted a t a constant temperature i t is placed in the middle section of the filtering tube above the wire gauze; the upper joint it then closed by the thermo- meter and the solvent poured into the top tube. When everything has attained a constant temperature the thermometer is raised and the solvent allowed to percolate through the contents of the middle section. The estimation of paraffin in paraffin shale by Holde’s method is described to illustrate the working of the apparatus.The Influence of Neutral Salts on Indicators. LEONOR MICHAELIS and PETER RONA (Biochem. Zeitsch. 1909 23 61-67).- The influence of various neutral salts on the shade of the indicator colour mas investigated the hydrogen-ion concentrations being chosen for each particular indicator in which the latter is most sensitive according to the determinations of Friedenthal. I n some cases the addition of salt alters the nuance so a s to indicate increased acidity in others increased alkalinity. In the case of Congo-red the authors think the change is due to the action of the salt in precipitating the dye; in other cases they assume the change to be due t o a different dissociation constant of the indicator in the new medium. The correc- tion due to the presence of salts is negligible when the concentration reaches 1/8 normal (a concentration met with physiologically) except in the case of methyl-violet Congo-red and neutral-red.When necessary a correction can be made in the Friedenthal method by adding salt to the control solution. The dinturbing influence of proteins is much greater than that due to salts. A New Sensitive Indicator. Dimethyl-Brown. M. EMMANUEL ’ The indicator is prepared by treating anthranilic acid in hydrochloric E. F. A. T. S. P. S. B. S. POZZI-ESCOT (Bull. Assoc. Chi%% SUW. B&. 1909 27 560-461).- 12-2ii. 154 ABSTRACTS OF CHEMICAL PAPERS. acid solution with an excess of nitrous acid at the ordinary tsmper- ature ; the diazo-substance obtained is combined with p-dimethylaniline and the product is boiled with a large excess of hydrochloric acid and p-dimethylaniline hydrochloride.The solution is filtered while hot and the filtrate is saturated with sodium chloride. The precipitate formed adheres to the sides of the vessel containing the mixture and is washed rapidly with cold water. On dissolving the precipitate in alcohol a solution is obtained which shows a brown coloration in neutral or acid aqueous solutions ; alkalis change the colour to yellow. w. P. s. Systematic Detection of the More Important Acids THADDEUS MILOBENDSKI (J. 12uss. P?tys. Cltem. Xoc. 1909 41 1301-1306).-The method devised 5p Abegg and Herz (Abstr. 1900 ii 436) for the separation and identification of acids besides omitting several important radicles possesses several disadvantages. Thus the barium (group 111) and calcium salts (group 11) are very similar in their solubilities and if excess of the reagent is used the calcium precipitate always contains radicles belonging to group I11 ; further the detection of thiocyanates in the form (FeCNS) masks the presence of iodides The author has modified the system so as t o avoid these dis- advantages.After giving a number of preliminary tests he proceeds to the systematic scheme the various groups being as follows (1) Strontium group including phosphite phosphate arsenite arsenate sulphite carbonate tartrate oxalate fluoride sulphate and part of the borate. (2) Lead group used if an iodide is present and containing iodide and sulphide ; thiocyanate detected in the filtrate.(3) Zinc group precipitated from the filtrate from group (1) and con- taining cyanide ferro- and ferri-cyanide and sulphide. (4) Silver group comprising thiosulphate iodide bromide chloride and thio- cyanate; chlorate and acetate detected in the filtrate. Details are gven for the examination of the various group precipitates. T. H. P. The Detection of Hydrofluoric Acid in Presence of Fluorides. WALTER CRONHEIM (Giocl&eni. Zeitsch. 1909 23 143-146).-As hgdrofluoric acid is used as an antiseptic in food- stuffs from which it is afterwards precipitated in the form of an insoluble salt it is of importance to know whether traces of the acid remain in products which have been treated in this manner. As hydrofluoric acid is insoluble in alcohol and ether whereas the salts are soluble the two solvents are added to the sample under investiga- tion.The fluorides are slowly precipitated from the supernatant liquid ; the free acid remaining in solution is precipitated by calcium or barium hydroxide. In these two precipitates fluorine can be detected by Hefelmann’s (glass-etching) method which can detect 1 part in SO0,OOO. Action of Iodine on Sodium Dithionate or Trithionate in Solution. JOSEPH A. MULLER (Bull. Xoc. chirn. 1909 [iv] 5 11 19-1 12 I).-The object of this work was to ascertain whether 8. B. S.ANALYTICAL CHEMISTRY. ii. 155 sodium thiosulphate could be estimated in presence of sodium dithionate or trithionate by titration with standard iodine solution. It was found that both the dithionate and the trithionate decolorise iodine solution when their solutions are warmed but that in cold solutions either neutral or acidified with acetic acid the action is so slow that sodium thiosulphate can be safely titrated with iodine in their presence.Volumetric Estimation of Selenious Acid in Alkaline Solution by Permanganate. LUIGI MARINO (Zeitsch. anorg. Chem. 1909 65 32-3’7).-None of the usual methods of titrating selenious acid are trustworthy under all conditions. Titratios with permanganate in acid solution gives an uncertain end-point but good results are obtained in alkaline solution according to the equation 2KMnO,+ 3Se0 = K,O + 3Mn0 + 3Se0,. The N/Ei-permanganate solution is prepared by dissolving 6 grams of potassium permangnnate in 800 C.C. water and adding 40 grams of potassium carbonate and 0.4 gram of potassium hydroxide ; N/Ei-oxalic acid is used to standardise the solution The selenious acid solution is made just alkaline with sodium hydroxide titrated with permnnganate heating and stirring well until the supernatant liquid is violet.It is then acidified with sulphuricnacid and titrated with oxalic acid until all the manganese dioxide has dissolved. After cooling to 80-90° the excess is titrated with permanganate. Low results are obtained in the presence of chlorides owing to the volatility of selenium chloride Nitrates should be removed by evaporating with zinc sulphate and dilute sulphuric acid. The method is applicable to insoluble selenites. C. H. D. HUGUET (Ann. Chim anal. 1909 14 453).-Five C.C. of pure sulphuric acid are introduced into a 500 C.C.flask which is then placed in an inclined position on a wire gauze and heated until sulphuric fumes appear. A mixture of 10 C.C. of urine and 25 C.C. of sodium persulphate solution (20 grams in 100 c.c.) is now added drop by drop and the whole is then heated again until quite colourless. When cold 10 C.C. of water and 2 drops of phenolphthalein are added and the liquid is neutralised carefully with pure aqueous sodium hydroxide; D 1.26. After diluting to 100 c.c. an aliquot part is taken for the gasometric estimation of the I~IENNE BARRAL (Bull. SOC. chim. 1910 [iv] 7 8-9).-It was found that in using Schloesing’s method for the estimation of nitrogen as ammonia new block-tin worm condensers absorbed considerable quantities OF ammonia and accurate results were only obtained after the condensers had been used some time.Granulated tin absorbed only traces of ammonia so that probably the loss was due to the presence of grease or tin oxides in the new condensers Estimation of Nitrogen in Nitrates by Reduction with the System Aluminium-Mercury. M. EMMANUEL POZZI-ESCOT (Compt. red. 1909 149 1380-1381).-Not more than 0.6 gram of the T. A. H. Estimation of Total Nitrogen in Urine. nitrogen by the hypobromite method. L. DE K. Source of Error in Estimating Ammonia. T. A. H.ii. 156 ABSTRACTS OF CHEMICAL PAPERS. nitrate is treated in a Schloesing flask with 4 t o 5 grams of aluminium turnings and a few drops of mercuric chloride solution ; a little water is then added and after some minutes when the action has ceased a little alkali.After distilling off the ammonia some sodium hypophosphite is added to decompose rnercurammonium compounds. The process has given excellent results with soils and manures. w. 0. w. Detection of Arsenic Acid in Presence of Arsenious Acid by means of Magnesia Mixture. OSCAR LUTZ and R. SVINNE (J. Buss. Phys. Chem. Xoc. 1909 41 1488-1491).-Magnesia mixture being recommended by many authors as a means of detecting arsenic acid and its salts in presence of arsenious acid (only the ion of the arsenic acid being precipitated in the form of the salt MgNH4As04,6 H,O) the authors have tested the reaction in presence of various proportions of ammonia and ammonium salts. The results shorn that in presence of a sufficiently large amount of arsenious acid the separation of arsenic acid by means of ordinary magnesia mixture is impossible.Further aqueous or ammoniscal solutions of arsenious acid are less sensitive t o the action of magnesia mixture than solutions of sodium and potassium arsenite. Qualitative separation may be attained under certain conditions of dilution that is for concentrations of the arsenious ion less than X/200 if ordinary magnesia mixtuie is employed or less than M/50 if a large proportion of ammonium salts is present ; but a t such dilution the lower limit of sensitiveness for arsenic acid may be passed. But as the proportions of the two anions are usually unknown and as the operation of dilution is too complicated for qualitative purposes this method of separating the arsenic from the arsenious ion is not practicable.T. H. P. Detection of Boric Acid in Butter and Milk. E. GAUVRY (Ann. Chinz. and. 1910 15 14-15).-8 portion of the butter is melted with a small quantity of hot water the aqueous layer is separated filtered and the filtrate is treated with a few drops of barium hydroxide solution. After the addition of a little alcohol the mixture is subjected t o centrifugal action the clear solution is decanted and the precipitate is treated with about 1 C.C. of hot concentrated oxalic acid solution. The barium oxalate which dissolves in the excess of ox,jlic acid is reprecipitated by the addition of alcohol and separated. The clear alcoholic solution is then evaporated after the addition of a few drops of a n alcoholic solution of turmeric As the evaporation proceeds the edges of the liquid show a red coloration should boric acid be present and eventually a red residue is obtained.The coloration is given by as little as 0.0001 gram of boiic acid. I n the case of milk the test is applied to the ash. w. P. s. Ultimate Analysis of Coals Containing [Hydrated] Clays A. LISSNER (C'heni. Zeit. 1910 34 37-3S).-II coals containing clay are submitted to the usual ultmnate analysis a large proportion of theANALYTICAL CHEMISTRY. ii. 157 water collected is due t o combined water contained in the clay which a previousdrying a t 120° has failed t o remove. The author therefore recommends the removal of the hydrated clay before proceeding t o combustion. The weighed portion of the sample is heated on the water-bath with a mixture of 2 vols.of fuming hydrofluoric acid and 1 vol. of hydro- chloric acid ; D 1.18. A twice or thrice repeated evaporation suffices to decompose the silicate. The residue is then treated with hot water and collected on a dried and weighed filter. After drying at looo the filter and contents are submitted to the usual organic com- bustion. Allowance is made for the carbon and hydrogen yielded by the filter-paper which may be taken as consisting of pure cellulose. When dealing with samples chiefly consisting of clay the process is as follows The carbon is estimated in about 1 gram of the sample as usual. A similar quantity of the sample which need not be weighed accurately is then treated with acid as described and collected on a filter.After drying for two hours at loo" thecarbonaceous matter is detached from the filter andalso submitted to analysis. I n this way the proportion of hydrogen to the carbon is found and the amorint of carbon in the sample being accurately known the hydrogen is foiind E. GOUTAL (Ann. Chim. anal. 1910 15 1-7).-A portable apparatus is described €or the estimation of carbon dioxide the process employed depending on the oxidation of the monoxide t o dioxide by means of iodic anhydride according to the equation 5CO + I,O = I + 5C0,. The iodic anhydride is contained in a tube and is heated for some hours in a current of oxygen at a temperature of 200O before being used. During tho ehtimation the tube and its contents are heated to a tempetatiire of 70" by nieans of a water-jacket and the air under examination is drawn through the tube after having passed succes- sively through mash-bottles containing acidified copper sulphate solu- tion potassium hydroxide solution and concentrated sulphuric acid respectively.A filter consisting of a tube filled with cotton-wool may be placed before the wash-bottles. The volume of air drawn through the tube is ascertained by measuring the volume of water leaving the aspirator and the rate of flow is regulated at about 1 litre per hour. The iodine liberated by the action of the carbon monoxide on the iodic anhydride is collected in a vessel containing either chloro- form and water or potassium iodide solution; this vessel is placed between the exit end of the tube and the aspirator.The iodine collected is estimated by comparison with standard iodine solutions or by titration with standard thiosulphate solution. The process may also be employed for the estimation of the occluded carbon monoxide in steel; for this purpose the steel i s dissolved in potassium cupric chloride solution and the gases evolved are passed together with a current of pure air through the tube containing the iodic anhydride. by a simple calculation. L. DE K. Estimation of Carbon Monoxide in Air. w. P. s. (Compt. rend. 1909 149 1129-1131).-Comparo this vol. ii 129. [Estimation of] Carbon Monoxide in Steels. E. GOCJTALii. 158 ABSTRACTS OF CHEMICAL PAPERS. Titration by means of Borax in Presence of Glycerol. N. TANANAEFF and D. TSUKERMAN (J. Russ. Phys. Chem.Soc. 1909,41 1469-1481).-Borax in presence of glycerol may be employed to titrate not only pure alkali hydroxide but also on boiling alkali hydroxide containing carbonate (compare Rupp Abstr. 1907 ii 194). The titration may be effected by adding alkali hydroxide to a solution containing borax and glycerol and also by adding a solution of borax to one containing alkali hydroxide and glycerol. Titration with borax in presence of glycerol affords an excellent method of estimating alkali hydroxide in presence of carbonate. Estimation of Zinc in the Presence of Iron. JAMES M. TAYLOR (J. SOC. Chem. Ind. 1909 28 1294-1295).-The process is based on the fact that a dilute neutral solution of zinc is precipitated by hydrogen sulphide with liberation of the acid whilst ferrous salts are not affected.Five to ten C.C. of the solution containing 0.1-0.3 gram of zinc are put into a flask 20 C.C. of saturated solution of ammonium chloride are added and any free acid is carefully neutralised with N/Z-sodium hydrogen carbonate with a drop of methyl-orange as indicatrr ; 100 C.C. of saturated solution of hydrogen sulphide are now added and the solution is titrated with N/2-sodium hydrogen carbonate which should be added at first at the rate of 2 or 3 drops per second and afterwards when the precipitate turns greyish more slowly The end- point is reached when the colour changes to a decided chocolate (formation of iron sulphide). One C.C. of N/Z-sodium hydrogen carbonate = 0.016 gram of zinc. In this process it is necessary that the iron should be in the ferrous state and no other metals precipitable T.11. P. by hydrogen sulphide should be present. L. DE K. New Volumetric Method for the Estimation of Copper. JEAN A. SANCHEZ (Bull. SOC. chirn. 1910 [iv] 7,9-17).-The process depends on the precipitation of the copper as cupric ferrocyanide and the solution of this in a solution of potassium cyanide previously standardised against a copper solution of known strength. The change in colour from the reddish-brown of copper ferrocyanide to the faint greenish-yellow of potassium cuprocyanide is used as indicating the end-point. The precautions to be observed are as follows the solution titrated should contain the equivalent of not more than 0.1 gram of metallic copper and must be exactly neutralised ; it must be free from iron lead zinc nickel cobalt or manganese and should contain no ammonia or ammonium salts.The results are not influenced by the presence of tin antimony or arsenic or by most organic acids provided the latter are exactly neutralised. Exact details for using the method are given in the original which also contains two tables of results obtained by its use. T. A. H. Volumetric Estimation of Lead with Alkaline Per- manganate. JULIUS F. SACHER (Chern. Zeit. 1909 33 13’2 1 4 3 2 2 ) . -A criticism of Bollenbach’s method (Abstr. 1908 ii 68) for theANALYTICAL CHEMISTRY. ii. 159 volumetric estimation of lead by means of alkaline permanganate. I n Bollenbach’s earlier experiments he found that one molecule of permanganate oxidised 3 atoms of lead but later experiments (Abstr.1909 ii 1054) gave the number 3.34. The author shows that the latter figure is probably due to the sodium hydroxide used containing carbonate. He also finds that with increasing concentration of sodium hydroxide the amount of lend niti-ate necessary for the reduction of a given quantity of permanganate decreases t h e temperature of experiment being 75-80°. Only when a series of estimations is carried out under exactly the same conditions do the results agree and even then the average error is 0.4% Pb and is probably caused by varying temperature in different experiments ; the lower the tempera- ture the more lead nitrate is necessary for complete reduction of the permanganate. The action o€ varying concentrations of sodium hydroxide is probably due to its solvent effect on the lead sesquioxide resulting in the re-formation of sodium plumbite.The method is quite untrustworthy for estimating the lead in materials containing lead sul phate. T. S. P. Substitution of Bromine and of Iodine for Chlorine in the Separation of Cerium from the other Cerium Earths. PHILIP E. BROWNING and EDWIN J. ROBERTS (Amer. J. Sci. 1910 [iv] 29 45 -46).-The authors state that Mosander’s process (passing chlorine through a solution of an alkali hydroxide containing in suspension the hydroxides of the cerium group) may be improved by substituting bromine for chlorine. At the first treatment some 50% of the admixed earths are removed and after two more treatments a depbsit of pure ceric hydroxide is obtained. It is important to remove the excess of bromine each time by heating on a water-bath.Iodine also oxidises the cerium and causes the other earths to pass into solution but the reaction is too incomplete to be of any analytical value. L. DE K. Estimation of Chromium in Chrome Iron Ore. JOSEPH A . MULLER (Bull. SOC. chim. 1909 [iv] 5,1133-11 36)-Three methods were investigated using pure chromium sesquioxide as the analytical material. In the first process the oxide was fused with a mixture of sodium hydroxide and potassium nitrate and the chromate formed after cooling was dissolved in water the solution acidified with sulphuric acid and boiled t o decompose nitrites. It was then reduced by sodium sul phi te and the chromium precipitated with just sufficient ammonia. This precipitate mas heated with sodium hydroxide and hydrogen peroxide solution the excess of the latter being finally removed by prolonged boiling.The solution was then diluted to n known volume and an aliquot portion titrated with potassium iodide and sodium thiosulphate (Abstr. 1909 ii 96). This gave a result equivalent t o 99.6% of the theoretical. In the second process the sesquioxide was fused with a mixture of sodium peroxide and potassium hydroxide. The aqueous extract from this was filtered to remove a trace of silver derived frdq the crucibleii. 160 ABSTRACTS OF CHEMICAL PAPERS. used boiled during forty minutes diluted to a known volume and the chromium in an aliquot portion determined as lead chromate or by titration with sodium thiosulphate (Zoc.cit.). By this latter method the process gave a result equal t o 99.2% of the theoretical. The Blodget-Britton process depending on heating the sesquioxide with potassium chlorate and soda-lime did not give good results owing to the difficulty of extracting all the chromate from the insoluble residue. Chromite even after grinding in a porphyry mortar requires fusing four or five times in succession before it can be completely dissolved by either of the first two processes. For each part of the mineral four of sodium hydroxide and eight of potassium nitrate or five of sodium peroxide and eight of potassium hydroxide are needed for each fusion. The aqueous extract of the fused product should be treated with a few drops of alcohol to remove any manganese present.Both processes give equally good results with chromite and the second is much more rapid although it entails greater wear on the silver crucibles used. T. A. H. Estimation of Tungsten in Tungsten-Steel. LUDWIG WOLTER (Chem. Zeit. 1910 34 2).-0-2-0-5 Gram of the sample which need not be finely powdered is fused in a covered platinum crucible with 0.5-1 *5 grams of potassium pjrosulphate aKd when sulphuric fumes escape the flame is removed for half a minute and another 4.5-13-5 grams of pyrosulphate are added in two portions. The mass is now heated gradually to redness and kept so for fifteen minutes. The lid is removed and when cold the fusion is treated with 60-75 C.C. of water and boiled with 30 C.C. of hydrochloric acid. The tungstic acid is collected washed with 10% ammonium nitrate solution then dis solved in hot dilute ammonia and evaporated in a weighed platinum crucible.On igniting the residue pure tungstic acid is left. Traces of tungstic acid retained in the acid liquid may be recovered by evaporating to dryness heating the residue for one t o two hours at 120-1 30° and then boiling with dilute hydrochloric acid which leaves the tungstic acid undissolved. I f the presence of silica is suspected this may be expelled by evaporating a few times with n few drops of hydrofluoric acid. L. DE K. Separation of Vanadium Molybdenum Chromium and Nickel in Special Steels. M. ENMANUEL POZZI-ESCOT (Compt. rend. 1909 149 1131-1132; Ann. Chim. anal. 1910 15 7-lo).-The hydrochloric acid or nitric acid solution of the steel is heated to boiling and treated with alarge excess of strongly alkaline sodium hypobromite.After boiling for some minutes bhe insoluble iron and nickel hydroxides (also those of manganese and cobalt if these metals are present) are filtered from the solution containing the chromate molybdate and vanadate of sodium. The precipitate is dissolved in dilute hydrochloric acid and the solution again treated with alkaline hypobromite in order to get into solution all traces of chromium molybdenum and vanadium.ANALYTICAL CHEMISTRY. ii. 161 The iron and nickel are then readily separated as also the chromium molybdenum and vanadium by the usual methods. T. S. P. Estimation of Antimony by Gutzeit’s Method. CHARLES R. SANGER and EMIL RAYMOND RIEGEL (Zeitach. anorg. Chem.1909 65 16-24. Compare Sanger and Black Abstr. 1908 ii 64).-A special form of reduction apparatus is used in which the gas evolved passes through a small chamber containing a disk of filter-paper saturated with lead acetate solution which removes hydrogen sulphide and supplies the moisture required for the production of a regular antimony deposit. The mercuric chloride paper is cut into strips 6-7 cm. long and 4 mm. wide and stored in the dark over calcium chloride. The reduction with zinc and hydrochloric acid is continued for thirty minutes and the mercuric chloride paper which is not coloured unless the antimony exceeds C.07 mg. is developed by means of N/1 ammonia for five minutes. The length of the dark band thus produced is com- pared with a standard series of strips prepared with known quantities of antimony.Organic matter except tartaric acid must be absent and the conditions of experiment must be exactly observed. The practical limit of sensitiveness of the method is abont 0.001 mg. Sb,O which is a smaller quantity than can be recognised with certainty by Marsh’s test. C. H. D. Analysis of Columbites and Tantalites. GABRIEL CHESNEAU (Conzpt. rend. 1909 149 1132-1135).-The mineral is dissolved by heating with a mixture of potassium hydrogen sulphate and sulphuric acid. The solid maws which is obtained on cooling is dissolved in water the solution filtered and the filtrate after neutralisation with ammonium hydroxide heated to boiling in order to precipitate the columbium and tantalum as pentoxides. The washed precipitate is digested for twenty-four hours with a tepid solution of ammonium sulphide and then washed with cold 5% hydrochloric acid.While moist it is treated with potassium fluoride and hydrogen fluoride in order to obtain the tantalofluoride and columboxyfluoride of potassium which are then separated by the less solubility of the former in water. The filtrates from the pentoxides of columbium and tantalum contain iron manganese etc. which are estimated in the ordinary way. The pentoxides also contain the silica and titanium dioxide present in the mineral; the silica is estimated by treatment of a known weight of the pentoxides with hydrofluoric acid. The titanium is estimated colorimetrically by means of hydrogen peroxide the colour not being affected by the presence of columbium and tantalum ; the pentoxides containing the titanium dioxide are dissolved by treatment with a mixture of potassium hydrogen sulphate and sulphuric acid.T. S. P. Process for the Rapid Estimation of Alcohol. D. SIDEESKY (Bull. dssoc. Chim. Sucr. Dist. 1909 2’7 562-563).-The method proposed depends on the complete miscibility of ether with coacen-ii. 162 ABSTRACTS OF CHEMICAL PAPERS. trated alcohol. Twenty C.C. of the alcoholic liquid wine for instance under examination are placed in a stoppered tube 10 C.C. of ether D 0.724 are added and 98% alcohol is run in from a burette in successive small quantities the mixture being shaken after each addition. A t first the ether separates out as a layer b u t when sufficient alcohol has been added the ether mixes completely with the alcoholic solution.‘The quantity of alcohol added is then noted and is a measure of the amount of alcohol present originally in the sample. The burette employed is graduated so as to give directly the quantity of alcohol in tbe sample; it is a patented piece of apparatus and it IS quite possible that an ordinary burette graduated empirically may he New Method for Detecting Traces of Alcohols. E. DE STGCKLIN (Compt. rend. 1910 150 43-45. Compare Abstr. 1910 i 196 198)-A description of a method for the detection of alcohols based on their conversion into aldehydes by a peroxydase system. A few drops of the liquid to be examined are rendered veiy slightly acid with acetic acid. The mixture is then treated with two drops of a solution made by adding a ferric salt to a hot freshly prepared solution of quinhydrone and containing 0.1% of iron.A few drops of a 5% solution of hydrogen peroxide are added and the mixture shaken. Schiff’s reagent is employed to recognise the aldehydes formed; if present ferric tannate is substituted for the iron-quinhydrone and the operations repeated ; under these conditions glycerol gives no result. Deniges’ reaction (Abstr. 1909 ii 2‘72-273) is recommended in conjunction with the foregoing as a Detection of Resorcinol by means of the Cyano-cupric Reaction. VOLCY-BOUCHER and J. GIRARU (Ann. Chirn. anal. 1910 15 13-14).-When a neutral or slightly acid resorcinol solution is mixed successively with copper sulphate solution and a small excess of potassium cyanide solution a bright green fluorescence is observed.The reaction takes place in the cold and the reagents must be added iu the order mentioned. The reaction is given by a solution containing The Methods of Lecithin Estimation. JOSEPH EEI~KING (Biochem. Zeilech. 1909 23 262-269).-Brain was submitted to fractional extraction with acetone light petroleum benzene absolute alcohol 85% alcohol and ether and the phosphorus determined in the extracts. These experiments led to no method for quantitatively separating the lecithin. Attempts were then made to quantitatively precipitate the lecithin from various solutions in organic solvents by means of pure acetone and acetone to which various acids or salts had been added. It was found that egg-lecithin could be quantitatively precipitated from ethereal solution by acetone if to the latter a few drops of (cold) saturated alcoholic solution of magnesium chloride had been added.From other solvents and by the other methods tried (acetone solutiops of tartaric acid etc.) the precipitation was incom- plete. S B. S. used in its place. w. P. s. sensitive test for glycerol. w. 0. w. as little as 0.1 gram of resorcinol per litre. w. P. s.ANALYTICAL CHEMISTRY ii. 163 Volumetric 33stimation of Sugars by I(. Lehrnann’s Process. ERWIN RUPP and F. LEHMANN (Arch. Pharm. 1909 247,516-526).- Fehling’s solution and a solution of the sugar are boiled for a suitable time cooled and poured into a mixture of potassium iodide dilute sulphuric acid and water the liberated iodine being then titrated with N/lO-sodium thiosulphate.Dextrose lavulose invert sugar maltose lactose starch dextrin invert sugar in wine maltose in beer and lactose in milk have been estimated by this process or by slight modifications of it. c. s. Separation of Sucrose and Lactose by the Bulgarian Ferment. L. MAaoArLLAN (Compt. rend. 1910 150 45-47).- Bertrand has shown (Abstr. 1909 i 623) that the lactic organism from curdled Bulgarian milk is capable of converting lactose almost quantitatively into lactic acid but is without action on sucrose. It is possible therefore to estimate the latter in mixtures containing lactose or dextrose by treatment with the Bulgarian ferment followed by inversion and determination of the reducing power. w. 0. w. The Method of Estimating Sugar in Urine.IVAR BANG and G~STA BOHMANNSSON (Zeitsch. physiol. Chem. 1909 63 443-454).- A defence of Bang’s method (Abstr. 1907 ii 136) against certain criticisms which have been made in reference to it. W. D. H. Cammidge’s Reaction. LEON GRIMBERT and R. BERNIEB (J. Pharm. Chim. 1909 [vi] 30 529-536).-The authors state that Cammidge’s reaction (Lancet 1904) is obtained with all urines and that the active principle formed by the hydrolysis with hydrochloric acid is glycuronic acid which yields an osazone m. p. 130-132’. L. DE K. Detection of Reducing Substances in Urine. C. J. REICHARD (Phcc~nz. Zeit. 1909 54 1007).-The author applies the gold-iodine reaction (Abstr. 1909 ii 262) for the detection of reducing substances in urine and also for their identification. The presence of reducing matters may be shown by placing in a test-tube 8 C.C.of water 0.5 C.C. of neutral 1% sodium aurichloride solution and 0.1 C.C. 1% potassium iodide solution 1 C.C. of normal urine is next added and the whole left for twelve to fifteen hours. The mixture first turns violet and then gradually deposits a blue precipitate which is examined microscopically. The precipitate may be purified by shaking the liquid first with ether and then after evaporation of the ether with chloroform. I f sodium thiosulphate is cautiously added the chloroform turns a violet- blue. For the identification of urine one drop of the gold solution one drop of the potassium iodide solution and two drops of the supposed urine are placed on an object glass and dried for twelve hours over sulphuric acid.The slide is then examined microscopically and willii. 164 ABSTRACTS OF CBEMICAL PAPERS. show the characteristic crystalline blue iodine compounds of urea uric acid and creatinine. L DE K. The Quantitative Estimation of Amino-acids in Urine by means of Formaldehyde Titration. WALTHER FREY and ALFRED GIGON (Biochem. Zeitsch. 1909 22 309-315).-The ammonia was first driven off from the urine and estimated by Spiro's modification of the Folin method (by means of a current of air after addition of barium hydroxide solution and alcohol the ammonia being received in standard acid). The residue was diluted to a definite volume in an aliquot part of which the amount of acid necessary for neutralisation with N/5-hydrochloric acid using rosolic acid as indioator was determined.Another aliquot portion was then neutralised with the experimentally-determined necessary amount of acid and in this solution the amino-acids were estimated by titration with alkali after addition by neutral formaldehyde in the usual manner phenol- phthalein being employed as indicator. s. B. s. The QU antitative Estimation of Amino-acids Polypeptides and Hippuric Acid in Urine by m e a n s of Formaldehyde Titration. VALDEMAR HENRIQUES and SOREN P. L. SORENSEN (Zeitsch. physiol. Chem. 1909 63 27-40).-The hippuric acid can be estimated by extracting the urine with ethyl acetate hydrolysing the residue after evaporation of the solvent with hydrochloric acid and then after driving off the excess of mineral acid estimating the glycine formed during the hydrolysis by the usual formaldehyde titration method. The polypeptides can be estimated by hydrolysing the urine after separation of the hippuric acid by hydrochloric acid and then after getting rid of excess of the mineral acid estimating the amino- acids in the usual way.The difference between the number thus obtained and the amino-acid number obtained before hydrolysis gives a measure of the quantity of polypeptides present in the urine. The authors also give details as to the use of indicators in the ordinary formaldehyde titration method. S. B. 8. The Formaldehyde Titration of Amino-acids in D rine. TANZO YOSHIDA (Biochem. Zeitsch. 1909 23 239-244).-The author shows that the formaldehyde titration method of Sorensen and Henriques for estimating amino-acid nitrogen gives generally satis- factory results.Only in the presence of large quantities of ammonium salts are the numbers obtained appreciably too low. He gives the results of a number of analyses of both normal and pathological urineg. S. B. 8. Detection of Biliary Acids Laevulose Glycuronic Acid and Pentoses in Urine. ADOLF JOLLES (Chern. ,Zed. 1909 33 1238-1239).-Polemical. A reply to the criticisms of Wittels and Welwart (Abstr. 1909 ii 1057) in which the author recapitulates his methods and upholds their accuracy. L. DE K.ANALYTICAL CHEMISTRY. ii. 165 Detection of Biliary Acids [and Acetone]. RODOLFO FRITSCH (Zeitsch. a d . Chem. 19 10 49 94-96).-Jolles’s process boiling with rhamnose and strong hydrochloric acid is recommended instead of the Pettenkofer sugar-sulphuric acid test.The rose coloration changing to a green fluorescence is characteristic for biliary acids. These acids may be separated from amines by precipitating with a 3% solution of casein and sulphuric acid and then extracting from the precipitate with absolute alcohol. If to dilute solutions of acetone are added a few drops of a 5% solution of rhamnose and then an equal volume of strong hydrochloric acid the liquid when heated turns a magenta colour which is very permanent. 0.01 Gram of acetone in 1 C.C. of liquid may thus be detected. L. DE K. Thiocyanates in Tobacco Smoke. JULIUS TGTH (Chern. Zeit. 1909 33 1301).-The presence of thiocyanates in tobacco smoke may be proved by passing the fumes of a dozen cigars through two wash- bottles each containing 100 C.C.of water and adding to the mixed filtered liquids copper sulphate and sulphurous acid. The precipitate is then collected and treated‘ with aqueous sodium hydroxide ; after acidifying with hydrochloric acid the liquid will give the red colour with ferric chloride disappearing on addition of mercuric chloride or the aqueous solution may be mixed with zinc sulphate which causes an abundant precipitate. The filtrate is then acidified with nitric acid and after adding copper sulphate solution heated to 86’; the precipitate obtained is washed and treated with ferric chloride when it will give a red coloration. The amount of thiocyanate present may be estimated by passing the fumes of a dozen cigars through washbottles each containing 100 C.C.of milk of lime. The united filtrates are evaporated and mixed with copper sulphate and excess of sulphurous acid. The copper thio- cyanate is then converted by ignition into oxide and weighed as such or Alt and Volhard’s process-conversion of the thiocyanate into sulphate (Zeitsch. anal. Chern. 1896 35 315)-may be used. IJ. DE K. New Test for Strychnine PAUL MALAQUIN (J. Phas-m. Cl~inz. 1909 [vi] 30 546-549).-One C.C. of a solution of a strychnine salt (about 1 1000) and 1 C.C. of pure hydrochloric acid are placed in a test-tube and 1 gram of pure and clean zinc cuttings is added. After four minutes the liquid is rapidly heated to boiling and then cooled. The solution is carefully poured down the sides of a test- tube containing 2 C.C. of pure aulphuric acid.Either at once or within a few minutes a rose-coloured ring will be noticed; after a time the colour gradually spreads through the acid The contents may also be shaken so as to accelerate the reaction. The colour is not altered on boiling and in this may there is no danger of mistaking veratrine which also turns red for strychnine. The colour is debtroyed by potassium thiocyanate but not by sulphur dioxide. Ammonia discharges the colour but acids again restore it. None of the other alkaloids or glucosides (of which a list is given) show the reaction. Hydnogenation of strychnine may alsoii. 166 ABSTRACTS OF CHEMICAL PAPERS. be effected in alkaline solution by means of sodium amalgam but this operation is less convenient. Strychnine may be extracted by agitating its salts with ether in the presence of an alkali The ether is then shaken with dilute hydrochloric acid and after warming to expel the ether the liquid is treated with zinc as just directed.Estimation of the Xanthine Bases in Cocoa and Chocolate. A. PROCHNOW (Arch. Pharm. 1909 247 698-71 I).-The author has tested the processes of Hilger and Eminger of Dekker and Welmans of Beckurts and Fromme and Katz’s modification of the last for the estimation of theobromine and caffeine in cocoa and chocolate. Katz’s process is the best if carried out as follows Six grams of powdered cocoa or 12 grams of powdered chocolate 197 grams of water. and 3 grams of dilute sulphuric acid are boiled under a reflux condenser for thirty minutes in a tared litre flask.After the addition of 400 grams of water and 8 grams of magnesium oxide the boiling is continued for one hour. Water 30 to 50 grams is added to com- pensate for that evaporated the mixture is well shaken and its weight excluding that of the cocoa or chocolate is determined. A portion of the liquid five-sixths of the weight (corresponding with 5 grams of cocoa or 10 grams of chocolate) is filtered and evaporated almost to dryness. The residue is dissolved in water the solution is made up t o about 25 c.c. treated with 25 drops of liquefied phenol and extracted with chloroform in a Katz percolator for six hours. The chloroform in the extraction flask is evaporated the phenol is carefully removed from the warm flask by the aid of the bellows and Estimation of Purine Nitrogen in Urine.STANLEY R. BENEDICT and TADASU SAIKI (J. Eiol. Cheni. 1909 7 27).-The Kruger-Schmid method of estimating purine nitrogen gives low and irregular results. Satisfactory results can however be obtained by first rendering the urine acid by adding 20 C.C. of glacial acetic acid to each 300 C.C. of urine. New Reactions of Thiocarbamide. T. SATO (Biochem. Zeitsch. 1909 23 44-45).-The following reactions are described coloration with acetic acid and potassium ferrocyanide (green changing to blue) with hydrochloric acid and potassium ferrocyanide and with the ferrocyanide alone. The rate of development and disappearance of the colour varies in the three methods of carrying out the reaction. With sodium carbonate and ferrocynnide a pink to violet colour gradually develops.This reaclion is sensitive in dilutions of I in 10,000 to 1 in 20,000 of the urea derivative. A New and Sensitive Reaction of Scatole. TAKAOKI SASAKI (Biocliem. Zeitsch. 1910 23 402-403).-1f 3 C.C. of scatole solution are mixed with 3 drops of methyl alcohol and an equal volume of concentrated sulphuric acid added a violet ring is formed at the place of contact ; on shaking the fluids together the whole mixture becomes violet-red. Dilutions up to one in five millions give the test. I t is riot given by tryptophan iudole or by 2-methylindole. L. DE K the flask is dried until the weight is constant. . c. s. W. D. H. 8. B. S. W. D. H,ANALYTICAL CHEMISTRY. ii. 167 Estimation of ‘‘ Saccharin ” [o-Beneoicsulphinide] in Various Foods. GUISEPPE TESTONI (Zeitsch.iVahr. Genu8snz. 1909 18 577-587).-The estimation of “ sbccharin ” in foods and beverages is rendered somewhat complex by the presence of other substances which are extracted together with the ‘( saccharin ” by the usual solvents. The following methods of separating the ‘ L saccharin ” from such substances are shown from the results of actual experiments to be trustworthy. Should the ether-extract contain benzoic acid in addition to the ‘( saccharin,” the extract may be heated at 110-1 1 5 O until the whole of the benzoic acid has sublimed ; the ‘‘ saccharin ” remains unchanged and may then be weighed. The benzoic acid may also be removed by steam distillation. Another alternative is to precipitate the ‘‘ saccharin ” from an alcoholic solution of the ether- residue by means of silver nitrate ; the silver compound formed has the formula AgC7H,S0,N and may be dried at 100’ before weighing. I n the case of mines beer aerated beverages syrups etc.the ether- extract will contain tartaric acid citric acid tannin and other substances ; these may be destroyed by oxidation with permanganate and the “ saccharin ” then extracted from the evaporated solution. I n the presence of salicylic acid the ether residue may be weighed and the salicylic acid then estimated in the usual way the amount of 6‘ saccharin ” present being found by difference or the salicylic acid may be precipitated by means of bromine and the “saccharin ” then extracted with ether after removing the bromine compound by filtra- tion I n cases where the ether-residue contains fatty substances essential oils etc.the oxidation process may be applied for the removal of any tsrtaric or citric acids present and the sulphur then estimated in the purified residue of ‘‘ saccharin ” ; or the ‘( saccharin ” may be hydrolysed by boiling with hydrochloric acid and the ammonia formed then estimated. Pure ‘‘ saccharin ” yields 7*65% of ammonia. The author finds that a mixture of equal parts of ether and light petroleum is the best solvent to uke for the extraction of ‘‘ saccharin ” from its solution. w. B. s. Estimation of Tannin [in Catechu]. G. C. A. VAN DORP and J. RODENBURG (Chem. Weekblud 1909 6 993-998).-The authors state that the only process which gives fairly satisfactory results in the assay of catechu is the process known as the Hunt-Loewenthal (titration with permanganate in presence of indigotinsulphonic acid before and after treatment with solution of gelatin). The separation of non-tannin matters from tannins by means of hide powder gives quite erroneous results.In one instance a sample of catechu gave 61.7% of tannin but when another specimen of hide powder was used only 34.3% was obtained. L. DE K. The Detection of Blood-pigment by its Absorption of t h e Violet End of the Spectrum. OTTO SCHUMM (Zeitsch. physiol. Chem. 1909 63 47S-483).-Details are given of the methods for studying the details of the absorption bands in the violet and ultraviolet legion of t h c spectrum which haemoglobin and itsii. 168 ABSTRACTS OF CHEMICAL PAPERS. derivatives exhibit and which Gamgee among others called attention to.By suitable means an aqueouq solution of blood examined in a thickness of 1 ceutimetre exhibits this absorption in dilutions of 1 in 4000 t o 5000. -W. 1). H. The Estimation of Pepsin by the Clarification of a Turbid Solution of Egg-white. X. HATA (Biochenz. Zeitsch. 1909 23 179-185).-The egg-white solution is prepared by diluting egg-white in a mortar to five times the original bulk with water filtering heating a t 60° for twenty minutes and filtering again through mnslin. A turbid solution is thereby obtained which can be kept unchanged for several months. For the purposes of tho test this solution is again diluted with water t o ten times its bulk. Into a series of test-tubes varying quantities of the pepsin-containing liquid are introduced and diluted to 1 C.C.0.5 C.C. of #/lO-hydrochloric acid and 2 C.C. of the diluted suspendon are then introduced and the tiiiio of clarification is noted. The procedure is then similar to that employed in the ricin and edsstin methods. The time of clarification is approximately inversely proportional t o the dilution. S. B. S. Employment of the Guaiacol Method for the Quantitative Estimation of Peroxydase. JULIUS ERUNN (Ber. Deut. bot. Ges. 1909 27 505-507).-ln employing Ostwald’s method (Abstr. 1907 ii 976) quite fresh solutions OF the resin must be used as distinct amounts of peroxydase are formed in a few hours. A special defect is the use of drops of a strong resin solution instead of C.C. of a more dilute solution. The rate of the reaction should be determined and not the final amount of colour. The following method is recommended A scale of colours of differ- ent intensity is prepared by diluting a blue water colour emulsion (Priissian blue with a little cadmium yellow and white) The back of the test-tube stand which is placed in a window is covered with tissue paper to avoid reflexions. The extracts in test-tubes are treated with hydrogen peroxide and a little concentrated (golden- yellow) solution of guaiaconic acid (1 C.C. to 10-15 C.C. extract t o which 0.2 C.C. H20,/20 had been added) poured on. The tubes to be compared are shaken simultaneously to mix the contents and the increase in intensity of the colour observed a t definite intervals and compared with the tube scale; the more rapid the coloration the greater the amount of peroxydase (compare Euler and Bolin Abstr. 1909 i 863). N. H. J. M. A Test for Mushrooms. IT. LOWY (Chern. Zeit. 1909 33 1251). -An aqueous infusion of Agaricus cunzpestris gives with sulphuric acid D 1-86 a deep violet coloration. The reaction is best carried out as a ring test. The author has not as yet succeeded in isolating the active principle. Infusions of other fungi do not give the reaction. The colour disappears on warming. L. 1 ) ~ K.

ISSN:0368-1769    

DOI:10.1039/CA9109805152

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

169 General and Physical Chemistry. Pulfrich’s Ratio between Volume Contraction and Refractive Power of Liquid Mixtures. EDMOND VAN AUBEL (Compt. rend. 1910 150 210-213).-Pulfrich has established the relationship (R - R,)/R = q.(B - D,)/D = qc for binary mixtures where R denotes the refraction and U the density of the mixture R and D the refraction and density respectively which the mixture would have shown had there been no volume change on mixing whilst q is a positive constant. The author shows by calculation from results obtained by Wintgen (Thesis Bonn 1908) that in the case of a mixture of aqueous solutions of tartaric acid and ammonium hepta- molybdate q is negative. w. 0. w. Molecular Refraction of Ieomerisable Unsaturated Acids and their Salts. ARTHUR HANTZSCH and KURT MEISENBURG (Ber.1910 43 95-105. Compare Briihl Abstr. 1904 i 969; 1905 i 17O).-The molecular refraction of nitroethane and nitropentane in ethyl alcohol and in potassium ethoride solutions shows that the relationship between the two nitro-compounds in ethyl-alcoholic solution is perfectly normal. The difference is 13.83 and the value for 3CH is 13-80 The results also show that the effect of the solvent on the refraction is not marked. Similarly p-chloro- or p-bromo-phenol has practically the same molecular refraction in alcohol and in sodium ethoxide solutions A comparison of p-nitrophenol and p-nitroanisole provds that the phenol in isobutyl butyrate acetone and methyl-alcoholic solutions is a true phenol the diflerence between the two compounds being practically the value due t o CH,.On the other hand the p-nitro- phenol in methyl alcohol and potassium methoxide solution shows a difference of 9.67 units; this undoubtedly indicates that the salts are derived from the &-phenol. The following numbers give the increments in the mol. refractions of the three nitrophenols when transformed into their salts P. 0. m. Mol. ref. D ......... 9 -68 4.26 1 -80 Mol. ref. Q ...... .,. 7 ‘87 3-63 1-71 The molecular refraction and also the colour of solutions of 0-nitrophenol indicate that it is partly converted into the aci- derivative. With 0- and p-benzaldehydes the following increments due to salt formation were obtained ortho 3.20 para 4.88 results which point to the conclusion that the salts cannot be simple phenolic salts.It is pointed out that the relationships between colour and molecular refraction are not so simple as stated by Kauffmann (Die Aecxochrome p. 6 5 ) . VOL. XCVIII. ii 13ii. 170 ABSTRACTS OF CHEMICAL PAPERS. The refraction of the azo-group calculated from the value for azobenzene is 13.95 whereas in ethyl diazoacetate i t has the value 8.41. The values for p-hydroxyazobedzene its ethyl ether and its acetyl and propionyl derivatives agree with the normal hydroxylic structure for the free hydroxy-compound. The value for the hydroxy- compound is somewhat increased when ethyl alcohol is used as solvent probably owing to the formation of an additive compound. The values for the salts show an increment of some 12 units. This is attributed not to structural molecular rearrangement but as due to the play of subsidiary ralencies for example p 2 3 3 - N P / W h *\OH *\& - or C H and C H C H Similarly the large increments noticed by Briihl in the salt formation of ethyl acetoacetate are not necessarily due to a structural alteration (enolisation) but may be due to the calling into play of subsidiary valencies.It is pointed out that the molecular refraction of the salts is greater than that of the true enolic alkyl and acyl derivatives and therefore this high exaltation can only be due to a further constitutive change due to subsidiary valencies -C*CO*OEt C C( OM) OEt or possibly I I I *c*o I I U*OM J. J. S. Theory of Dispersion in Gaeeous Substances. LADISLAS NATANSON (Bull. Acad. Sci. Cracow 1909 907-9 15).-Recent measurements of the dispersive power of nitrogen oxygen hydrogen carbon monoxide carbon dioxide methane hydrogen sulphide sulphur dioxide helium and argon have been made use of to test a deduction made by the author from Lorentz's electronic theory of absorption. The calculations based on these data indicate with some degree of probability that the product u.A in which u is the number OF dispersion electrons contained in n molecule of a gas and A the constant in the equation (122 + 2)/(n2 - 1) = A( l/Xi - 1/X2) has the same value for all gases.The average value of u.A is 16-3 x l O - ' ~ r n . ~ and although in certain cases the experimental data of different observers differ widely the author considers that sufficient evidence has been obtained to justify the conclusion that there is a close connexiou between dispersion and valency.The Long-waved Portion of the Spectrum of Titanium. PAUL EIEBIG (Zeitsch. wiss. Photochem. 1910 8 73-101).-The author has made a detailed photographic investigation of the line and band spectra of titanium between X 4200 and X 7360. For the pro- duction of the spectrum metallic titanium was introduced into a cavity made in the positive electrode of a carbon arc and the requisite large dispersion was obtained by a Rowland grating having a radius of curvature of 6-6 metres and 20,000 lines to the inch. The measured wave-lengths together with the estimated intensities are H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 171 recorded in tabular form and the results compared with those previously obtained by ThalQn Hasselberg and Rowland.H. RI. D. Investigation of the Sodium Spectra. HANS ZICKENDRAHT (Ann. P h y d 1910 [iv] 31 233-374).-The author has examined in detail the emission spectra obtained from the arc discharge between electrodes of different materials in an atmosphere of sodium vapour and from the glow discharge under different conditions with and without an interposed spark gap. The consequent variations in the emission spectrum are described in detail. In the second part of the paper a summary is given of spectral observations relating to sodium and these are discussed in reference to the author’s measurements. H. M. D. Spectra of the Erbium Compounds and Stark’s Valency Hypothesis. KARL A. HOFMANN and HEINZ KIBMREUTHER (Zeitsch.physikcd. Chern. 1910 71 312-324).-Stark (compare Abstr. 1908 ii 574) has suggested a theory of valency based on the assumption that a t the surface of a chemical atom there are positively charged spheres and minute negative electrons. When the atom enters into chemical coalbinathion the lines of force from certain of the electrons become attached to the positive spheres on the other atom (saturated valency electrons) ; other electrons are not affected their lines of force remaining attached to the positive spheres of their own atom (unsatur- ated valency electrons) while a third kind of electrons are affected in such a way that their lines of force are partly separated from the positive spheres of their own atoms (loosened electrons). According to Stark the band spectra of the unsaturated valency electrons have their lower limit at least in some cases in the unattainable ultra- violet X = 0*06p the band spectra o€ the saturated valency electrons lie in the ultra-red above X = 0 .5 ~ . Hence in the visible region only the absorption due to the loosened valency electrons is of importance. The work of the authors on the spectra of erbium compounds supports Stark’s theory The spectra of a number of solid anhydrous erbium salts were first measured at different temperatures by concentrating on them the light fiom the positive carbon of an arc lamp by means of a quartz lens and examining the reflected light by means of a double prism instrument. The spectra of erbium sulphide and chloride are very similar and the change from chloride to oxide and from oxide to sulphzte only brings about displacements of 1-3 X in the absorption bands so that the electrons concerned in the absorption are not the saturated ones effecting the combination between erbium and the other elements or groups.Similarly the effect of temperature in displacing the absorp- tion bands is very slight wherea.s the chemical linkings produced by saturated electrons are very greatly affected by change of temperature On the other hand the addition of water to the salts produces a great alteration in the spectxa and it is suggested that this is due t o hydrate formatim with participation of the ‘‘ loosened ” electrohs. 13-2ii. 172 ABSTRACTS OF CHEMICAL PAPERS. The saturated valencies may therefore correspond with Werner’s “Hauptvalenzen” (principal valencies) the valencies due to the loosened electrons with Werner’s ‘‘ Nebenvnlenzen ” (subsidiary valencies). From an examination of the groups of absorption bands of the binary anhydrous erbium compounds the conclusion is drawn that the effects are produced by three “ loosened ” electrons which with the three ‘( saturated ” valencies make a total of six correspond- ing with Werner’s co-ordination number.G. s. GUSTAVE A. HEMSALECH and CHARLES DE WATTEVILLE (Compt. rend. 1910 150 329-332. Compare Abstr. 1908 ii 445 547).-When sparks are passed through an oxygen-acetylene flame between iron electrodes the spectrum shows fewer lines than the simple flame spectrum. The lines are more intense than those obtained with the oxy-hydrogen flame.Some of the lines are identical with those seen in the blue cone of the Bunsen burner. A comparison is made in tabular form showing the relative intensities of lines in the two flames. Lockyer’s enhanced line X 3935.92 has been observed but apart from this the lines are those characteristic of low temperatures and are only visible Measurements in the Long-waved Spectrum. HEINRICH RUBENS and H. HOLLNAGEL (Sitxzcngsber. K. Akad. Wiss. Berlin 1910 26-52).-The authors have examined the ultra-red rays of very great wave-length which are obtained as the result of selective reflexion at the surfaces of polished plates of crystals of sodium chloride potassium chloride bromide and iodide. The wave-length measurements were effected by means of a quartz interferometer the ready absorbability of the long-wave rays necessitating however special arrangements in connexion with the details of the apparatus.The residual rays which were examined by a micro-radiometer after reflexion at four surfaces of the substance under investigation form two bands of different intensity in the case of sodium chloride potassium chloride and potassium bromide. Although not definitely indicated by the data for potassium iodide i t seems probable that this grouping is also characteristic of potassium iodide. The mean wave- lengths of the bands are recorded for the first three salts and it is found that these wave-lengths increase with the molecular weight of the salt. As a result of the experiments with potassium bromide and iodide the known spectrum has been extended by half an octave in the remote ultra-red region.The known part of the ultra-red region is thus approximately seven times as long as that of the visible spectrum. Absorption Spectra of Various Salts in Solution and the Effect of Temperature on Such Spectra. HARRY C. JONES and W. W. S T R O N G ( A ~ ~ ~ . Chem. J. 1910 43 97-135).-A continuation of the work described previously (this vol. ii 87). A review is given of recent spectroscopic investigations. Attempts have been made to obtain the Zeeman effect for the absorption bands of uranyl chloride Flame Spectrum of Iron at a High Temperature. in traces in the spectrum of the electric furnace. w. 0. w. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 173 and neodymium salt solutions but without success.It is hoped however that the Zeeman effect may be obtained with solutions of erbium salts I n studying the effect of change of temperature on the absorption spectra of salts spectrograms have been made of the spectra of aqueous solutions a t various concentrations of cobalt chloride (alone and in presence of aluminium chloride' and of calcium chloride) cobalt thio- cyanate nickel acetate and sulphate copper bromide copper chloride (alone and in presence of aluminium chloride and of calcium chIoride) uranyl chloride nitrate acetate and sulphate uranous chloride and sulphate praseodymium chloride neodymium nitrate and bromide neodymium chloride (alone and in presence of calcium chloride) and erbium chloride. The results are discussed in the light of the electron hypothesis. It has been found that the effect of a rise of temperature of an aqueous salt solution is to increase the general absorption and also to broaden and intensify the bands and that as a rule the increase of the general absorption is much greater in concentrated than in dilute solutions.The presence of calcium and aluminium chlorides causes the chromium chloride bands to widen very unsymmetrically on the long wave-length edge as the temperature rises. The uranyl chloride bands are shifted towards the red with rise of temperature. The uranyl acetate and sulphate bands are also slight15 shifted but those of the nitrate are not affected in this way. I n the case of the neodymium and erbium salts the bands do not appear to be shifted as the temperature increases.I n presence of calcium chloride however the neodymium chloride bands are shifted and the bands become fainter with rise of temperature. Restoration of Phosphorescence to Sulphides of the Alkaline Earths. D ~ S I R ~ GERNEZ (Compt. rend. 1910 150 295-300).-Specimens of the phosphorescent sulphides of calcium barium and strontium were found to have lost their phosphorescence after an exposure of six years to moist air. This appeared to be due to oxidation to the sulphates since the phosphorescence was restored by heating the substances in a current of hydrogen. The action of heat alone had very little effect on the phosphorescence. w. 0. w. E. G. Photochemical Equilibria. 111. Photochemical Equilibrium of Carbonyl Ghloride. ALFRED COEHN and HANS BECKER (Ber.1910 43 130-133. Compare Abstr. 1909 ii 846).-Weigert (Abstr. 1907 ii 835) has found that the dissociation equilibrium of carbonyl chloride at 500° is not affected by light ; the action of the latter is simply to accelerate catalytically t h e attainment of equilibrium. His experiments are not conclusive however since glass vessels were used. The authors now find that when carbonyl chloride is passed through a quartz tube at the ordinary temperature and at the same time submitted to the actionof light from a mercury- quartz lamp it is partly decomposed into carbon monoxide and chlorine. When 1 C.C. of carbonyl chloride passed through the quartzii. 174 ABSTRACTS OF CHEMICAL PAPERS. tube (20 cm. long and 0.5 cm. in diameter) per minute the amount of decomposition was 3*3-4%.The effect is chiefly due to the short ultra-violet rays since when tubes of Uviql glass were used which are only transparent to waves of greater wave-length than 265pp the decomposition was only 0-46-0.5%. I n ordinary glass tubes there was no decomposition. I n all thecases hitherto examined namely the photochemical equilibria of sulphur trioxide hydrogen chloride and carbonyl chloride the actual equilibrium is affected only by ultra-violet rays. Rays of greater wave-length simply act catalytica\ly on the attainment of equilibrium. Experiments which are a t present in progress show that water vapour is decomposed to a considerable extent by ultra-violet light. T. S. P. Chemical Action of Light. V. Photochemical Phenomena Compare Abstr.1908 ii 5 748 914; 1909 i 219 ii 532).-1n liquids exposed to the action of light condensation nuclei are formed ; these bring about local increases in concentration and accelerate chemical reactions which do not take place in the dark. Proof of the formation of condensation nuclei is afforded by the fact that solutions of dyes exposed to light show an increased solvent action towards gases. The dyes studied were uranin erythrosin-G and -J phloxin methyl-violet and malachite-green. These were enclosed in tubes with nitrogen maintained at 1 5 O and exposed to the light from a mercury lamp. A manometer was arranged to indicate the gas pressure in the tubes which were constantly shaken. The solubility of nitrogen in water is not affected by exposure to light. I n the dye solutions a decrease in pressure took place at first with constant velocity but subsequently becoming slower.After keeping the tubes in the dark again an increase in pressure was found but the original value was never ti ttained. A special diff erential-adsorptiometer was designed to remove the absorbed nitrogen by boiling the dye solution but it was found only possible to recover a portion of the gas absorbed. The amount of dye present in solution is far too small to explain the increased solubility of the gas as due to the influence of the dye. Undoubtedly condensation nuclei form and the nitrogen condenses a t their surface. E. F. A. Radioactivity of some Waste Springs in the Vosges. ANDRB BROCHET (Compt. rend. 1910 150 291-293).-Near the thermal springs of PlorubiBres Luxeuil and Brtins there exist in the region of the Vosges some springs running to waste.The radio- activity both of the gases and water of these springs has been found to be high. Particulars are given of springs of the Chaudeau Radioactivity of Halogen and Oxyhalogen Compounds of Thorium. J. CRAUDIER and BDOUARD CHAUVENET (Compt. rend. 1910 150 219-22 1)-The radioactivity (a-radiation) of a number in Dye SOlUtiOnS. FRITZ WEIGERT (Be?*. 1920 43 164-172. Pontaines-Chaudes and Chaudea- Fontaines or Reherrey. F. s.GENERAL AND PHYSICAL CHEMISTRY. ii. I75 of freshly prepared halogen and oxyhalogen compounds of thorium has been compared with that of thorium dioxide and thorium in a Curie electroscope. The powdered substances were sifted over plates 4 cm.in diameter the weight of substance employed being varied up to 0.35 gram for which the a-radiation is a maximum. I n the latter case the intensity of the radiation diminished RS the atomic weight of the elements combined with the thorium increased. The substances arranged in descending order of activity were as follows Th Tho ThOF ThF ThOCl ThCl ThOI,. ThBr,. As the weight of the substance employed is reduced the differences in the relative activities of the compounds disappear. Below 0.01 gram all are of similar activity indicating that the radioactivity is an atomic property of thorium F. S. The Action of the a-Rayg on Glass. ERNEST RUTHERFORD (Mein. Nanchester Phil. Soc. 1909 54 v l).-Fine capillary tubes of soda-glass that had contained radium emanation show in transverse section a coloured region extending about 0.04 mm. from the inner wall of the capillary corresponding with the range of the most penetrating a-rays of radium in glass.This confirms the correctness of Joly's explanation of pleochroic halos (Phil. Mag. 1907 [vi) 13 The Absorption Law of P-Rays. W. WILSON (Physikal. Zeitsch. 1910 11 101. CompareProc. Roy. floe. 1909 A 82 612).- The former conclusion that the exponential law of the absorption of P-rays is indicative of non-homogeneity of the rays which have a certain distribution of velocities is reaffirmed and the criticisms of Hahn and Meitner (this vol. ii 8) are replied to in detail. The con- clusion is drawn that the &rays suffer diminution of velocity in ERNEST RUTHERFORD and BERTRAM B.BOLTWOOD (Mem. Manchester Phil. SOC. 1909 54 vi 1-2).-The gases generated in eighty-three days from a solution of a barium-radium salt containing 0.2 gram of radium which had been freed chemically from polonium and radium-D were subjected to repeated absorptions with charcoal cooled in liquid air and the un- absorbed part was found to consist of heliuh essentially pure in amount corresponding with a rate of production of 163 cu. mm. per gram of radium per year. This is in very close agreement with the calcu- lated rate (158 cu. mm.). Other experiments not described showed that helium is produced from polonium. F. S. The Accumulation of Helium in Geological Time. 111. ROBERT J. STRUTT (Proc. Rag. Xoc. 1910 A 83 298-301. Compare this vol. ii 9).-The ratioof helium to uranium and thorium has been determined for zircons extracted from fourteen rocks ranging from Tertiary to Archean.Minerals like zircon and sphene contain hun- dreds of times as much helium as the average of the rock of which they are constituents and accordingly the whole of the contairred helium may be regarded as having been generated since the consolida- 381; 1910 19 327). I?. s. passage through matter. P. s. Production of Helium by Radium.ii. 176 ABSTRACTS OF CHEMICAL PAPERS. tion of the rock and the separation of the mineral. The zircons were decomposed by fusion with borax in a platinum boat in a quartz tube filled with oxygen. The oxygen was removed from the extracted gas by phosphorus leaving the helium. Each unit in the helium ratio (c.c.per gram of “ total equivalent uranium oxide,” 1 gram of thoria being reckoned equivalent in helium producing power t o 0.203 gram of uranium oxide) is provisionally taken to indicate a period of eleven million years. The helium ratio of zircon stands in very close relation to the geolcgical age of t h e specimen. For four specimens of the tertiary rocks the ratio is below unity whilst for four specimens of paleozoic rocks the ratio is between 13 and 29. The oldest specimen from the archzean rocks of Canada has a helium ratio 56.6. These ratios fix the minimum values of the geological age but in spite of the enormous lengths of time indicated i t may be that the whole of the helium generated is not retained. The fraction retained depend- ing on the structure of the zircon must be supposed however to be fairly definite and similar for all.I?. s. Rate of Evolution of Heat by Pitchblende. HORACE H. POOLE (Phil. Mag. 1910 [vi] 19 314-326).-About half a kilogram of carefully dried powdered Joachimsthal pitchblende containing 64% of uranium was placed in a spherical Dewar vessel surrounded with ice and when a steady thermal state had been attained the constant difference of temperature between the under-surface layer of the pitchblende at the bottom of the vessel and the ice outside was determined. by means of thermocouples. The heat evolved per hour by the pitchblende was reckoned as the product of this constant difference and the tbermal conductance of the calorimeter. The last which was separately determined with water in the calorimeter is the number of calories escaping from the calorimeter per hour when the inside is 1’ hotter than the outside.To avoid chemical action of which indications were obtained in the preliminary experiments in air the calorimeter was filled with carefully dried nitrogen. The conclusion is drawn t h a t 1 gram of the pitchblende evolved 6.1 x 10-5 calories per hour as a mean value of three experiments the separate results being 7.1 5.45 and 5.85 ( x The value is surprisingly high the value calculated presumably from the kinetic energy of the various a-particles expelled being only about 4.4 x for the sample of pitchblende employed. F. S. The Emission of Positive Rays from Heated Phosphorus Compounds. FRANK HORTON (Proc. Camb. Phil. Soc. 1909 15 329).-The object of the experiments was to test whether the large positive ionisation produced by heated phosphates notably aluminium phosphate observed by Sir J.J. Thomson had any connexion with the $‘ anode rays ” of Gehrcke and Reichenheim (Abstr. 1908 ii 343). The latter found most suitable the halide salts of the alkali and alkaline-earth metals whereas the positive ionisation produced from these when heated is not nearly as great as from the phosphates. The salt mixed with graphite to make it conduct and sometimes with silver chloride to fuse the mass together was rammed into a quartz tube andGENERAL AND PHYSICAL CHEMISTRY. ii. 177 strongly heated. The prepared tube was then mounted as anode with another electrode as cathode in an exhausted flask and a discharge from a large coil passed.No “anode-rays” of the kind obtained from the halides of the alkali metals were obtained from the phos- phates but calcium phosphide and silver chloride did give such rays the spectrum of their light rjhowing the calcium and silver lines respectively. There is probably no connexion between the two phenomena in question. The experiments support Gehrcke and Reichenheim’s conclusions that the “anode rays ” owe their origin to the electrolytic decomposition of the salt and expulsion of the metal from the anode into the vacuum. F. S. Electrical Conductivity and Constitution of Dissolved Sub- stances. s. W. SERKOFF (J. Buss. Phys. Chern. SOC. 1910 42 1-1 4 [Physical Part]. Compare Abstr. 1909 ii 372).-According to the solvate theory (compare Jones Abstr.1909 ii 221) a compound like lithium nitrate containing the ion Li which undergoes intense hydration should exhibit a well-marked maximum conductivity in mixtures of acetone with an alcohol whilst potassium iodide should show no trace of a maximum conductivity. The author’s conductivity curves are not in agreement with these conclusions. It is found indeed that potassium sodium and lithium iodides which differ considerably in the extent of hydration which they undergo show no maximum conductivity whilst lithium bromide exhibits a maximum which is not very clearly marked and lithium chloride a distinct maximum. Neither is there any parallelism observable between the sharpness of this maximum and the magnitude of pa calculated by the ordinary method of extrapolation.Thus for lithium chloride pa = 63 for lithium iodide ,urn = 181.0 and for lithium bromide pa = 144. The influence of the formation of complex compounds on the molecular conductivity is discussed and it is found that all the abnormal conductivity curves corrected for the formation of complex compounds exhibit characters determined by the corresponding fluidity curves. T. H. P. Electrical Conductivity of Soap Solutions. JAMES W. MCBAIN and MILLICENT TAYLOR (Ber. 1910 43 321-322).-A preliminary account of measurements of the conductivity of solutions of sodium palmitate. The measurements were made in silver vessels with the following results Dilution in litres ............... 1 18 2 5 10 20 100 Mol. conductivity in mhos ... 64.82 71.13 77’42 77-47 78.77 86.04 135.3 The results are compared with the conductivities o€ solutions of sodium hydroxide and sodium acetate and show that the normal soaps do not exist as colloids in concentrated solution.T. S. P. Diminution of Conductivity by Colloids and Observations relating to the Conductivity of Serum. WALTER FREI (Zeitsch. Chem. Id. KoZEoide 1910 6 94-103).-The influence of serum- albumin serum-globulin gelatin and saponin on the electricalii. 178 ABSTRACTS OF CHEMICAL PAPERS. conductivity of a O$N-solution of sodium hydroxide at 37" has been examined. For 1% solutions of the four colloids the conductivity is diminished to the extent of 7 5 6.6 5.5 and 5.6% respectively. The specific influence of a given colloid varies somewhat with the concen- tration.When the conductivity is plotted as a function of the con- centration of the colloid curves are obtained which are slightly convex towards the origin. It is shown that the observed effects are in part due to phenomena of swelling and adsorption which cause alterations in the concentration of the dissolved ions. I n addition the conductivity is diminished in consequence of a reduction of the cross-sectional area of the electro- lytic solution by the colloidal particles and also of the increase in the viscosity. The simultaneous changes observed in the conductivity freezing- point depression viscosity and clensity on dilution of solutions of serum are interpreted on the basis of the above coneiderations. H. M. D. Dielectric Cohesion of Neon. EDMOND BOUTY (Compt. rend.1910 150 149-150. Compare Abstr. 1904 ii 309 604).-The author has shown previously tbat the dielectric cohesions of the monatomic gases helium argon and mercury vapour are considerably less than those OE polyatomic gases of comparable molecular weight. The dielectric cohesion of neon obtained by fractionation of a gaseous mixture of neon helium and traces of air is found to be 7.6 that of air being 435. It is considerably less than that of helium (18.31 although its value would be expected to lie between those of helium and argon. This is in agreement with the fact that Mendeleeff in his last periodic table places neon in a separate group from the other rare gases. Attention is called to luminous effects obeerved when the pressure on neon is diminished by means of a mercury pump.T. S. P. Thermodynamics of Standard Cells. ERNST COHEN and HUGO R. ERUYT (Chem. Weekblad 1910 7 69-78).-h criticism of Hulett's cnlculation of the chemical energy of the Weston standard cell (Trans. Amer. Electrochem. Xoc. 1909 15 435). A. J. W. Electrochemical Equivalent of Silver. F. LAPORTE and P. DE LA GOBCE (Compt. rend. 1910 150 27t3-280).-Improvements introduced into the purification of silver nitrate have brought the authors' earlier results into better agreement with those obtained at the National Physical Laboratory and elsewhere. Crystallisation of the salt between 30' and 40° under reduced pressure and in the absence of air gave as a mean of eight experiments 1.11827 mg. per Coulomb as the electrochemical equivalent of silver.A s a mean between this and other results the authors adopt 1.11829 mg. as correct. It is important that the air to which the solutions of silver nitrate are exposed should be free from impurities. I n one experi- ment in which tobacco smoke was present a high result was obtained. w. 0. w.GENERAL AND PHYSICAL CHEMISTRY. ii. 179 Correction for the Method of Determining Galvanic En- nobling qf Metals. CHARLES M. VAN DEVENTER and H. J. VAN LUMMEL (geitsch. physikal. Chern. 1910 71 11 7-1 27).-1n connexion with the experiments on the galvanic ennobling of metals already described (compare Abstr. 1908 ii 12 558; 1909 ii 958) i t has been found necessary to apply a correction for the alteration of the surfaces of the metals during the experiment. This has been done by comparing the potentials of the two metals in acid before and after the “en- nobling ) ) experiment. The application of this correction does not greatly alter the results already given Thus as regards cadmium lead tin nickel and amalgamated zinc one electrode can be ennobled with regard to another of the same metal and for the following pairs of metals zinc-cadmium tin-lead zinc-tin cadmium-tin and lead- nickel the first metal can readily be ennobled with reference to the other. G.S. Electrolysis of Molten Salts. RICHARD LORENZ (Festschrift Otto Wulkuch 1909 513-539).-An account is given of the chief results obtained in recent investigations on the electrolysis of molten salts. The possibility of explaining the observed facts in terms of the theory of electrolytic dissociation is discussed. H.M. D. Magnetisable Alloys of Manganese. FRIEDRICH HEUSLER (Festschyt Otto VaZZach 1909 467-477. Compare Abstr. 1909 ii 54l).-Polemical against Wedekind. A summary is given of the chief results of work already published irl connexion with the magnetic pi operties of manganese-copper-aluminium alloys. H. M. D. Magnetic Measurements of Platinum Metals a n d of Mono- clinic Crystals in Particular of Iron Cobalt and Nickel Salts. WILHELM FINHE (Ann. Physik 19 10 [iv] 31 149-1 68)- Measurements have been made of the magnetic susceptibility of platinum palladium iridium and rhodium and also of ferrous sulphate nickel sulphate cobalt sulphate ferrous ammonium sulphate nickel ammonium sulphate cobalt ammonium sulphate cobalt potass- ium sulphate cobalt copper sulphate epidote augite hornblende adularia and sucrose.For the isotropic metals the susceptibilities are platinum + 22.6 x 1W6 ; palladium + 66.26 x ; iridium + 4.89 Y 10-o ; rhodium + 12-58 x 10-6. In the case of the monoclinic crystals no connexion could be traced between the position of the magnetic axes on the one hand and t h a t of the optic and di-electric axes on the other. H. M. D. Use of the Magnetic Field as a means of Determining Constitution in Organic Chemistry. IV. PAUL PASCAL ( B d d . SOC. chim. 1910 [iv] 7 45-51. Compare Abstr. 1909 ii 487 788 859 and this vol. ii loo).-In this paper the anomalous magnetic susceptibilities shown by halogenated and cyano-compounds are con- sidered and it is shown that the apparent departure from the simpleii.180 ABSTRACTS OF CHEMICAL PAPERS. additive character of this constant is due in the case of haloid deriv- atives to (1) mutual action of a hydrogen and a halogen atom and (2) mutual action of halogen atoms and in the case of cyano-deriv- atives to the acid character conferred by the cyano-group. I n the case of simple alkyl haloids the diamagnetic deficit for the whole molecule amounts to about 32 x 10-7 for monochloro-derivatives and to 42.5 x 10-7 €or monobromo- and monoiodo-compounds. For symmetrical dichlorides it is about 45 x 10-7 arid for dibromides about 60 x Where the two chlorine atoms are attached to the same carbon atom the deficit is about 67 x 10-7 in open-chain compounds but it is less where the carbon is attached t o a benzene nucleus thus for CHPhCl it is 425 x 10-7.for benzonitrile phenylacetonitrile or ethyl cyanoacetate and is of about the same order as in the mineral acids. In cyano-compounds the diamagnetic excess is about 45 x T. A. H. Conduction of Heat through Rarded Gases. FREDERICK SODDP and ARTHUR J. BERRY (Proc. Roy. Soc. 1910 A 83,254-264). -The beat dissipated from a bright platinum strip maintained by a current at 61O in various gases has been measured by an electric method at various pressiires down to a thermally perfect vacuum. The process of producing high vacua by means of the vapour of calcium was employed. At pressures such that the actual path of the gas molecule is comparable with its mean free path the heat dissipated is proportional to the pressure of the gas.The conductivity under these conditions bears no relation to the ordinary conductivity at higher pressures where the conductivity is independent of pressure. The conductivity of acetylene methane and cyanogen slightly exceeds that of hydrogen whilst helium conducts but slightly better than carbon dioxide. In the table the second column represents the ordinary con- ductivity of the gases as expressed by the watts dissipated by a definite portion of the strip at pressures above which the conductivity does not further increase with pressure. The third column (R) indicates the found values of the conductivity at low pressure expressed as the calories ( x 10-5) dissipated per cm. of surface per 0.01 mm. pressure per 1' difference of temperature. The fourth column (0) is the value for this conductivity calculated from the kinetic theory on the assumption that the heat interchange at impact is perfect.The last column shows the ratio of K to &. Argon.. ................... Neon .................... Carbon dioxide.. ....... Oxygen .................. Helium .................. Carbon monoxide.. .... Nitrous oxide ......... Nitrogen ............... Hydrogen ............. Cyanogen ............... Methane ............... Acetylene ............... Watts. 1 ' O i 2.35 0 9 5 1'55 7 '30 1.37 0.97 1'44 8.75 0.97 2.81 1 '24 K. 1 '30 1 -76 1 9 9 1 *91 1 '94 1-96 2-11 2.21 2'29 2-35 2.70 2-75 &. 1 *20 1 *70 2-64 2 '23 3'80 2.38 2-75 2-35 8 -95 3 -95 3 -82 - Kl&. 1.09 1.04 0 '72 0 -86 0.51 0 '82 0 -77 0 '94 0.25 0.68 0 '72 -GENERAL AND PHYSICAL CHEMISTRY.ii. 181 The results indicate a method of obtaining information concerning the nature of ihe single impact of a molecule on a surface. The inter- change of energy appears perfect for the denser monatomic gases but for the more rapidly moving molecules of helium and hydrogen this is far from the case. In such cases a t low temperatures or for hydrogen if a palladium instead of a platinum surface were used the con- ductivity ought to be increased owing to more perfect interchange of energy on impact. F. S . Heat Capacity of Certain Metals and Compounds of Metals. HERMANN SCHIMPFF (Zeitsch. physikal. Chem. 1910 '71 257-299).-The specific heats of fifteen metals and twenty-nine binary compounds of metals have been determined by the method of mixtures for the three temperature intervals 17 to loo' 17 to - 79' and 17 to - 190'.As the metallic compounds were mainly prepared in the course of the investigations on alloys by Tammann and his pupils they may be regarded as of well-defined composition. From the results the mean specific heats at + 50° O' - 50° - looo and - 150' are calculated and are given in tabular form. The limit of experimental error is about 1%. The mean specific heats of the metals for the three temperature intervals 17 to loo' 17 to - 79' and 17 to - 190" are as follows Magnesium 0.2475 0.2384 0.2046 ; aluminium 0.21 73 0.1976 0.1696 ; silicon 0.1'753 0.1470 0.1166 ; chromium 0.1102 0 0980 0.0805 ; iron 0,1098 (17 to 100' only) ; nickel 0.1088 0.0974 0.0830 ; cobalt 0.1030 0.0942 0.0818 ; copper 0.0925 0.0880 0 0786 ; zinc 0.0934 0.0886 0.0819 ; silver 0.0560 0.0544 0.0506 ; tin 0.0556 0.0521 0*0488 ; antimony 0.0503 0.0482 0.0450 ; gold 0.0310 0-0297 0.0283 ; platinum 0.0310 0.0292 0-0286 ; bismuth 0.0303 0.0285 0.0275.The results are compared in detail with those of previous observers and in the majority of cases the agreement is satisfactory . For about half the compounds the specific heats are equal to the sum of the specific heats of the component metals with a maximum deviation of 2%; in the other cases the deviations from Kopp's rule are in general within 4%. It is remarkable that in all cases the observed specific heats of the magnesium compounds are smaller and in most cases those of the antimony compounds greater than the values calculated according to Kopp's rule.A formula with three constants is suggested to represent the variation of the specific heats with the temperature between +50° and - 150' and the respective constants for each metal and compound are calculated from the above observations. In all cases the specific heat increases with the temperature but except for bismuth and lead the magnitude of the temperature-coefficient diminishes as the temperature rises. The observations afford no definite information as to the variation of the specific heats above +50° and below - 150'. As regards the atomic heats of the free metals the average values excluding silicon are 4 56,5*13 5-60 5.93 and 6.13 at - 150° - looo - 60° O' and 50° and the mean values for the metals in combination are 4.24 4.89 5.40 5.75 5.95 at the same temperatures.I G . S.ii. 182 ABSTRACTS OF CHEMICAL PAPERS. Speciflc Heat of Metallic Alloys. ALEXIS V. SAPOSHNIKOFF (J. Buss. Phys. Chern. Soc. 1909 41 1708-1711).-In order to test Regnault's law according to which the specific heat of an alloy is equal to the mean arithmetic specific heat of its components (Awn. Chim. Yhys. 1841 [iiij 1 l a g ) the author has determined the specific heats at 15-100' of alloys of various compositions of (1) bismuth and cadmium which form neither compounds nor solid solutions ; (2) lead and tin which do not give compounds and only form solid solutions of low concentrations ; (3) bismuth and antimony which form an uninterrupted series of solid solutions ; and (4) zinc and aotimony which form the two compounds SbZn and Sb2Zn,.I n all cases Regnault's law is contirmed within the limits of experimental error so that the specific heat of an alloy is an additive property. T. H. P. Melting-Point Determinations at Low Temperatures. H. STOLTZENBERG (Chem. Zeit. 1910 34 66-67).-The author describes a modification of his melting-point a-pparatus for low temperatures (this vol. ii 17). The tube into which the thermometer dips is double walled the space between the walls being evacuated. T. S. P. Measurement of the Heats of Liquefaction of Acetic Acid Benzene and Nitrobenzene. JULIUS MEYER (B'estschrift Otto Wallach 1909,540-568).-The author bas measured the thermal and volume changes which accompany the liquefaction of benzene nitrobenzene and acetic acid.Both series of measurements were made with apparatus resembling the Bunsen ice calorimeter. The mean values obtained for the heats of liquefaction are benzene 30.39 nitrobenzene 22.53 acetic acid 45-96 cal. From these data and the observed melting points (5.44' 5-82' and 16-54') the respective mole- cular freezing-point lowerings are found to be 5.059 6.849 and 3.631. The increments of volume on liquefaction of one gram of substance amount to 0.1333 0.0808 and 0.1578 C.C. respectively. Prom these data the influence of pressure on the melting point is calculated. The rise of temperature per atmosphere pressure amounts to 0.0295' 0*0243O and 0 0241' for benzene nitrobenzene and acetic acid respec- tively and in all cases these values are found to be in satisfactory agreement with the experimental determinations H.M. D. Cbloroacetic Acid as a Cryoscopic Solvent. EFISIO MAMELI (Gaxxetta 1909 39 ii 579-586).-0f the various modifications of chloroacetic acid only the most stable or a-form gives good results as B cryoscopic solvent (compare Tanatar Abstr. 1893 i 624 ; Hulett Abstr. 1899 ii 468). The mean of the results obtained with xylene m-cresol safrole and acetic acid in concentrations not greater than 3% gives the value 53 for the cryoscopic constant of chloroacetic acid the number calculated by means of van't HOE'S formula being 54.19. Neither the a- nor P-modification of chloroacetic acid forms solid solutions with acetic acid both giving normal molecular weights in this solvent.GENERAL AND PHYSICAL CHEMISTRY.ii. lt33 The molecular weight of water in freezing chloroacetic acid is slightly above the normal value at low concentrations and about 1.5 times the calculated value for a 12% solution. With phosphoryl chloride the molecular weight is less than the normal at low concen- trations and increases with the concentration the calculated value being passed a t about 1.3%. With aniline! pyridine and quinoline chloroacetic acid behaves as a slightly dissociating solvent the molecular weights being somewhat lower than the normal values even for very dilute solutions and decreasing gradully as the concentration increases. T. H. P. A New Fractionating Column. ALFRED HAHN (Ber. 191 0 43 41 9- 423).-The princi- ple of the column is that the vapour from the boiling liquid passes through a space which is kept at a constant temperature but never- theless can absorb heat readily.The details of the apparatus will be readily understood from the diagram. The constant tempera- ture in the narrow space a through which the vapour of the boiling liquid passes is main- tained by the boiling liquid in b. This latter liquid must be chosen to give a suitable temperature and its boiling point may be altered by connecting k with a water pump; g is a condenser for the liquid boiling in b. With this apparatus the distillate from a 45% alcohol consisted of 96% alcohol the liquid in b being a t 76'; other fraction- ating columns gave a 92-93% distillate. Mixtures of ether and alcohol methyl and ethyl alcohols and of methyl ethyl ketone (b.p. 81') and diacetyl (b. p. 87') were satisfactorily separated. The apparatus possesses the great advantage that it does not require continual watching. T. S. P. An Apparatus for the Measurement of the Vapour Pres- sures of Dilute Aqueous Solutions. RUDOLF MAIER (Ann. Physik 1910 [iv] 31 423-435).-An apparatus has been devised by means of which the small differences between the vapour pressures of water and dilute aqueous solutions can be measured with considerable accuracy. The arrangement is such that absolute measurements of small vapour pressures can also be made. The mercury manometer consists of a U-shaped tube supported firmly on a stand provided with levelling screws. A fine platinum- iridium point is supported in each arm of the tube and contact of these with the mercury is indicated electrically.Each of the supports to which the platinium-iridium needles are attached is capable of vertical movement the amount of which is measured by means of a micrometer screw.ii. 184 ABSTRACTS OF CHEMICAL PAPERS. Another essential feature of the apparatus is the special arrange- ment adopted for ensuring that the two liquids shall have the same temperature. This consists of a double vessel the inner and outer parts of which are connected with tubes lending to the manometer by carefully ground glass joints. The inner vessel in which the water is placed is of platinum which facilitates the attainment of thermal equilibrium between its contents and the solution which surrounds it. The data obtained in experiments with solutions of sucrose in water at 0' are recorded.The vapour-pressure differences thus found are in good agreement with those calculated from Raoult's vapour-pressure equation. H. M. D. Partial Pressures of Liquid Mixtures. WILLIAV E. STORY (Zeitsch. physikal. Chem. 1909,71,129-151).-A mathematical paper. The Duhem-Margules equation which refers to the vapour pressures of the components of a binary mixture has been extended to mixtures with any number of components and a general solution of the equation is given. It is shown that Raoult's law can be deduced directly from the Duhem-Margules formula and that the latter formula is based on no other assumptions than those comprised in Raoult's law. The series containing the solution of the equation are more convergent than those hitherto used.The methods of deducing the coefficients of the formulae from the experimental data are discussed in detail. G. 8. Binary Mixtures and Concentrated Solutions. 11. FRIEDRICH DOLEZALEK (Zeitsch. physikal. Chem. 1910 71 191-213. Compare Abstr. 1909 ii 23 ; Bein ibid. 471 ; Moller ibid. 981).-The theory of the vapour-pressure of binary mixtures described in the previous paper is illustrated by further examples and is extended to other properties of these mixtures. From the total vapour-pressure curve of mixtures of ethyl ether and chloroform as determined by Guthrie (Abstr. 1885 339) the partial vapour-pressure curves of the components are deduced and it is shown that the components enter into combination in molecular propor- tions. A t 1 9 O when the components are present in equimolar propor- tions the mixture contains 24 mol.% of the compound. The view that a compound containing one molecule of each of the components is formed is further supported by the fact that the heat of admixture and the contraction on miging both attain a maximum value when the components are present in equivalent proportions. Similarly from the determination by Inglis (Abstr. 1906 ii 332) of the partial pressures of nitrogen and oxygen above mixtures of the liquefied gases it is shown that liquid nitrogen is non-associated and liquid oxygen associated. At 74.7' abs. i n a mixture of liquefied oxygen and nitrogen in molar proportions there is about 1 mol. 0 for every 7 mols. O and in pure oxygen 1 mol. 0 for 3.03 mols.0,. At 79.07O there is 1 mol. 0 for 4.53 mols. O and above 8 6 O abs. oxygen exists only as simple molecules. The application of the theory to the solubility of a gas in a liquid on the assumption that the system is a highly concentrated solution ofGENERAL AND PHYSICAL CHEMISTRY. ii. 185 the liquid in the liquefied gas leads to the expression p/po = q where p is the partial pressure of the gas and po is the vapour pressure of the liquefied gas (in the unimolecular form) at the same temperature. Hence if the sahae gas is dissolved at the same pressure and temper- ature in different liquids p and po and therefore Q have the same values throughout; khe solubility of a gas expressed as a true molar fraction should be the same for all chemically indifferent liquids.This deduction is shown t o be approximately valid for the solubility of carbon dioxide in benzene chlorobenzene bromobenzene and chloro- form when for po the corrected pressure po + a;/v2 in the sense of van der Waals is used. The applicability of the method is limited by the fact that at the temperatures a t which solubilities are usually measured the permanent gases are far above their respective critical temperatures. Further the theory leads t o the result that the ratio of the solu- bilities of two indifferent gases should be the same for different solvents provided that the molecular weights of the solvents are not greatly affected by dissolving the gases in them. This law has already been discovered experimentally by Just (Abstr. 1901 ii 439). The expansion of a liquid produced by dissolving a gas in it has also been calculated and the observed and calculated values are in good agreement.Finally the thermal phenomena observed on admixture of liquids are also satisfactorily represented by the theory. G. 8. Experimental Determination and Thermodynamic Calcula- tion of the Vapour Pressures of Toluene Naphthalene and Benzene. JONATHAN T. BARKER (Zeitsch. physikcd. Chem. 19 10 71 235-253).-The vapour pressures of toluene through a wide range of temperature of liquid and solid naphthalene and of solid benzene have been determined by the dynamical method a current of oxygen being saturated with the organic vapour and the amount of the latter carried over determined by combustion. Various arrangements for securing saturation of the oxygen are described. The method proved satisfactory down to vapour pressures equal to 0.005 mm. of mercury.The vapour pressures of toluene in mm. of mercury at O' are as follows 0.0054 at - 78" 1.61 at - 2l0 16.8 at 14-8' 28-75 at 25.8"; of naphthalene 0.064 at ZOO 0.164 at 30° and 0.378 at 40'; and of benzene 0.0180 at -77.5". Data for these substances at other temperatures are already available. The object of the determinations was to test the vapour-pressure formula of Nernst log p = - x,/4.57117+ 3*5/R.logT- ~T/4*571+ c where A L and C are constants related in a definite way to the properties of the substance. The formula represents the experimental resnlts satisfactorily. The calculated molecular heat of vaporisation of toluene at 111' is 7775 cal.as compared with the experimental values 7687 cal. (Schiff) and 8044 cal. (Campbell Brown). The latent heat of fusion of naphthalene (calculated) is 4435 cal. per mol. in good agreement with the experimental value. The calculated heat of vaporisation of solid benzene is 10,220 cal. per mol.; i t has not been determined directly. The calculated heat of fusion of benzene VOL. XCVIII ii. * 14ii 186 ABSTRACTS OF CHEMICAL PAPERS. 1900 cal. per mol. does not agree very satisfactorily with the mean of the experimental values 2326 cal. KIRSTINE BIEYEB ne'e BJERRUM (Zeitsch. physihl. Chem. 1910 71 325-336).-1n a pievious paper (Abstr. 1900 ii 263) it was pointed out that van der Waals' theory of corresponding states is not strictly applicable but that a good agree- ment between theory and experiment is observed when for each substance a special minimum temperature and minimum volume is calculated and different units of pressure volume and temperature are used.In this way a common vapour-pressure curve for twenty-five substances has been obtained with the ordinate y = (Pc - P)/Pc and abscissa x= (Tc- T)/K where K is a temperature constant and the other symbols have the usual significance. It is now shown mainly by means of data due to Young t h a t octane diisopropyl diisobutyl and hexamethylene as well as chlorine and carbon dioxide follow the law fairly accurately. I n the former paper 5"mi.n was taken as zero for fluorbenzene and other substances were referred to this arbitrary value. I n order to give K a more definite meaning hydrogen is now chosen as reference substance so that K represents the difference between the critical temperature of the substance 2') and the lowest temperature Tmin at which the substance can exist in the gaseous condition the assumption being made that this is true for hydrogen in the neighbour- hood of the absolute zero.On this basis i t is shown from the data of Ramsay Travers Olszewski and others that nitrogen and the gases of the argon series follow the law and the values of Ymin= Tc - K are calculated for a large number of substances. When helium is chosen as the reference substance for which Tmin is zero Tmin for hydrogen becomes 7.9 but the values for Tmin calculated on this basis for other substances are too high a result due to the uncertainty as to the critical temperature and other data for helium.G. S. Corresponding States. G. S. Laws of Evaporation. PIERRE VAILLANT (Compt. rend. 1910 150 213-216. Compare Abstr. 1908 ii 460 ; 1909 ii 544).-The supposition has been advanced that the rate of evaporation of an aqueous solution depends solely on the rate of diffusion of aqueous vapour out of a layer of saturated air in the immediate neighbourhood of the surface. This is supported by the observation that when the solution is contained in a vessel with an opening of known area the quantity of liquid evaporated per second ( Q ) is not proportional to X the area of the opening but is a function of S independent of the nature of the liquid. It has also been shown that in the cake of an incompletely filled straight-walled vessel the speed of evaporation is governed by the formula &=aMP4/' where M denotes the molecular weight of the liquid and P its vapour tension whilst a is a constant almost independent of the nature of the liquid.Eighteen liquids have been studied including water carbon disulphide hydrocarbons alcohols ethers and organic halogen derivatives; the results are given in tabular form w. 0. TY.GENERAL AND PHYSICAL CHEMISTRY. ii. 187 Thermochemical Investigations of Organic Compounds. IV-VII. Sulphur Halogen and Unsaturated Compounds. w. 6WIgTOsLAWSKI [SVENTOSLAVSKY] (Budl. Acad. Sci Cracow 1909 941-972. Compare Abstr. 1909 ii 23 213 547).-The analysis of thermochemical data is extended to compounds containing sulphur and the halogens and to unsaturated compounds.From the data for mercaptans and sulphides the conclusion is drawn that the heat of formation of the linking C-S is greater in the sulphides than in the corresponding mercaptans. This result is the same as that found in the case of ethers and the corresponding alcohols. Although the data for halogen compounds have not been accurately determined the numbers obtained by different observers exhibiting considerable divergence the heats of formation of the linkings C-Cl C-Br and C-I appear t o be regulated by the same lams as those which govern the heat quantities associated with the linkings between carbon and other univalent groups. From the data for unsaturated compounds the conclusion is drawn thnt the minimum value of the heat of formation of the linking C-C is about 18.0 Gal.By means of the equations which express the thermochemical values of the linkings between carbon and other elements and between hydrogen and other elements the heat changes corresponding with the equation (C-X) + (H-Y) = (C-Y) + (H-X) are calculated X and Y representing any of the elements carbon hydrogen oxygen nitrogen sulphur chlorine bromine and iodine. H. M. D. Andrews’ Measurements of the Compression of Carbon Dioxide and of Mixtures of Carbon Dioxide and Nitrogen. C. G. KNOTT (Proc. Roy. SOC. Edin. 1909 30 1-22).-The data obtained by Andrews in his classical experiments on the com- pressibility of carbon dioxide are tabulated in compact form. Similar d a b are also recorded for mixtures containing nitrogen and carbon dioxide in the volume ratios 1 3.43 and 1 6.3.These data have been collected partly from the memoirs published in 1869 1876 and 1886 and partly from note-books left by Rndrews. H M. D. Dependence of the Cubic Compressibility of Potassium and Sodium on the Temperature. LUDWIG PROTZ (Ann. Physik 1910 [iv] 31 127-148).-By means of thermodynamic reasoning i t can be shown that the difFerence between the specific heats of a substance a t cohstant pressure and a t constant volume is dependent on the com- pressibility of the substance. With the object of obtaining information in regard to the variation of this difference with the temperature the author has measured the compressibility of potassium and sodium at different temperatures. The piezometric arrangement used in the experiments was similar to that described by Rontgen and Schneider.Measurements of the com- pressibility of water and petroleum were made in the first instance the data for water being utilised in the calibration of the apparatus 14-2ii. 188 ABSTRACTS OF CHEMICAL PAPERS. and those for petroleum in connoxion with the compressibility of the solid metals. The experimental results show t h a t the compressibility of potassium sodium and petroleum increases with the temperature according to a linear equation. From this i t follows that the difference between the two specific heats increases with the temperature in the case of the two alkali metals. I n the case of water a minimum compressibility is found a t about 60'. H. X. D. Condensation of Water by Electrolytes. FRANK I(.CAMERON and WILLIAM 0. ROBINSON ( J . Physical Chem. 1910 14 1-1 I).-The densities of solutions of certain acids bases and s:flts in cou- centrations varying from N/10 to N/200 have been carefully determined at 2 5 O by a pyknometer method and from the results the amount of water '' condensed " by a mol. of each electrolyte has been calculated on the assumption that the latter retains its volume in the anhydrous form unchanged in solution. The results do not show any very definite regularities. Substances which show large heats of solution or have a tendency to crystnllise with water of crystallisation have relatively high condensing power. The specific condensing power usually diminishes with increased concentration but for hydrochloric and nitric acids the condensation increases at first with the concen- Lration attains a maximum io approximately 1% solution and beyond that point diminishes.The results of previous observers on this subject are summarised. G. S. A Method of Determining the Viscosity of Gases especially those available only in Small Quantities. A. 0. RANKINE (PYOC. Roy. Soc. 1910 A 83 265-276).-The apparatus which has been designed for measurements of viscosity with small quantities of gases consists of two parallel tubes connected at both ends. One of the tubes consists of a very fine capillary the other being of much greater cross-sectional area yet sufficiently narrow for a pellet of mercury to remain intact inside it. Taps are provided above and below for the purpose of cleaning the tubes and fillingthe apparatus with gas.The rate of fall of the mercury pellet in the wider tube is determined by the viscosity of the gas which is forced through the capillary tube as the mercury descends. The formula from which the viscosity is calculated is q=,rITR4pt/81v in which R is the radius of the capillary tube I its length p the difference of pressure on the two sides of the mercury v the volume of gas forced through the capillary and t the time of fall. On account of capillary attraction the value of p is not proportional to the length of the pellet of mercury but it is shown t h a t the capillary effect can be eliminated by using different lengths of mercury. The apparatus was used for determining the viscosity of dry air at different temperatures.The absolute values at 11.2' 1 5 * 5 O and 1 9 0 2 ~ are respectively 1.770 1.803 and 1.838 x 1 0 - 4 . It is proposed to use the apparatus for the examination of neon xenon and krypton. For observations a t high pressures the methodGENERAL AND PHYSICAL CHEMISTRY. ii. 189 described is much simpler than those which have been previously used. On the other hand it is not suitable for work at low pressures. H. M. D. Torsional Elasticity and its Connection with Viscosity. 0. FAUST and GUSTAV TAMMANN (Zeitsc?b. physikaZ. Chem. 1910 71 51-58. Compare Lauer and Tammann Abstr. 1908 ii 667).-The elasticity measurements were made by the method already described (Zoc. cit.) ; the viscosity measurements were taken from available data and in a few cases were made by the usual time of flow method.Data for twenty-five liquids are given. For liquids of high viscosity there was only one back movement after the impulse and then a slow move- ment to the null position ; for those of smaller viscosity unsymmetrical swinging about the null position ; both phenomena indicate the exist ence of torsional elasticity. For those with still less viscosity the swinging was symmetrical about the null position indicating absence of torsional elasticity. For all substances with a viscosity less than 4.3 x 10-2 no torsional elasticity was observed under the experimental conditions but all substances with a viscosity greater than 8.6 x showed the above property. The ratio of the single backward movement to the movement produced by the impulse increases with the viscosity and even exceeds unity for liquids of the highest viscosity.The magnitude of the viscosity a t which torsional elasticity becomes marked depends on the sensitiveness of the measuring apparatus. The proportionality between viscosity and elasticity has also been shown by allowing certain liquids to cool slowly and determining the viscosity at which torsional elasticity can just be detected by a very sensitive method. I n all cases it appears at approximately the same value of the viscosity. Certain viscous liquids become doubly refracting under stress and i t is shown from the data of previous observers that for castor oil the magnitude of the forced double refraction alters with the temperature proportionally to the viscosity.Viscosity and torsional elasticity are directly proportional. G. S. Absorption of Liquids by Porous Substances. J. H. RUSSEN- BERGER (Compt. rend. 1910 150 275-278).-The L L absorptive power” of a substance may be determined by suspending a thread of the material at one end of a wire passing over a pulley. The thread dips in water which rises to a height h and a weight p is attached to the other end of the wire to secure equilibrium. The author develops the following expression to represent the absorptive power x=- - dh- . * where S is the area of the cross section of the QS’dt Q d t thread Q the weight of absorbent material in unit-volume and dh/dt denotes the speed a t which the water rises. It is found by experiment that for the same kind of material Xis approximately constant.It is therefore orzly necessary to By integretion h2=2QXt+C.ii. 190 ABSTR SCTS OF CHEMICAL PAPERS. measure the height t o which water rises in a thread of cotton held between two glass plates to have a measure of its absorptive power. w. 0. w. Three-phase Equilibrium (with a Pressure Minimum) of a Dissociating Compound of Two Components. 111. GERARD H. LEOPOLD (Zeitsch. physikal. Chem. 1910 71 59-89. Compare Abstr. 1908 ii 218 472)-The complete equilibrium between aniline hydrochloride and its components has been investigated. The m. p. of aniline hydrochloride is 199*2-199*3" and at this temperature i t is only very slightly dissociated. The freezing-point curve of the system aniline-hydrogen chloride has been determined and no evidence of the existence of a compound other than the above has been obtained.Within certain narrow limits aniline hydrochloride and hydrogen chloride are not completely miscible ; the lowest temperature at which this occurs is 10.5' the mixture containing 5.3 mol.% of aniline and the highest temperature 51.1° which is the critical temperature of the upper liquid layer and the vapour. This critical temperature is very slightly lower (0*15-Oo2O0) than that of pure hydrogen chloride. The mixture of maximum boiling point a t atmospheric pressure contains about 51 mol.% aniline. The b. p. of aniline hydrochloride itself cannot be determined in the ordinary way as part of the hydrogen chloride at once escapes and the constant boiling mixture is obtained ; the boiling point of the latter is 244.4'.The boiling-point curve of mixtures of the constant-boiling liquid and aniline has also been determined. The boiling-point curve for a lower pressure has also been deduced by construction from the three-phase curve and the melting-point curve; in this case the maximum occurs in a mixture containing 50.8 mol.% of aniline. The vapour-pressure curve of aniline hydrochloride has been determined. In this case the melting point occurs as already mentioned a t 199*2O and a vapour pressure of 19.4 cm. whilst the maximum sublimation point occurs at 198O and a pressure of 16-2 cm. Finally the three-phase curves have been determined for mixtures containing excess of aniline and of hydrogen chloride respectively i n the liquid phase. In the curve of the former system there is a maximum at 175' and 29.2 cm.pressure anda minimum a t 197 5 and 16.0 cm. pressure. The maximum for mixtures containing excess of hydrogen chloride could not be measured directly owing to the high pressure but other parts of the curve have been determined. G. S. Relation between Density and Degree of Dissociation of Aqueous Salt Solutions. S. TERESCHIN (Ber. Deut. physikal. Ges. 1910 12 50-53).-Th~ author has shown previously (Abstr. 1909 ii 552) that the constant A of Hegdmeiller's formula (Ber. Deut. physikal. Ges. 1909,11 37) may be regarded as the sum of two moduli each belonging to one of the ions and independent of the nature of theGENERAL AND PHYSICAL CHEMISTRY. ii. 191 other ion. By means of Heydweiller’a further results (this vol.ii 106) the author shows that these density moduli are subject to certain laws. Thus the moduli of the elementary ions increase proportionally to the atomic weight in the separate groups of the periodic system. The magnitude of the water envelope surrounding the ion is doubtless related closely to the density modulus (compare Kohlrausch Abstr. 1902 ii 489). Possibly the irregular position occupied by fluorine as regards its mobility and the temperature- coefficient of the latter in comparison with the other members of the halogen group (Eohlrausch Zoc. cit.) is to be attributed to the abnormal magnitude of its density modulus which is considerably higher than it should be according to the straight line curve between the moduli and atomic weights.T. H. P. Behaviour of Aqueous Solutions in Capillary Actions. ZDENKO H. SKRAUP (Nonatsh. 1909 30 773-824).-The present communication contains the results of a large number of observations made with acids b;zses and salts of the most varied character; it is not yet possible to make strictly accurate generalisations although the statements made previously (Abstr. 1909 ii 868) receive further support from the results of the extended inquiry. The following are the most striking results not published hitherto (1) I n equivalent and extremely dilute solutions strong bases ascend higher than strong acids. (2) Phosphoric acid although a relatively weak acid does not ascend to the same height as the strongest acids. (3) I n general salts ascend much higher than the acids or bases in equivalent solutions of which they are formed ; in many cases the salt rises to practically the same height as the water.(4) Sucrose and antipyrine in all degrees of dilution ascend to the same height as the water. ( 5 ) Colloidal ferric hydroxide i n strong solutions appears to retard the ascent of water. Observations similar to those made with filter paper have been made with silk wool and plates of unglazed porcelain and plaster of Paris. W. H. G. Diffusion a n d the Kinetic Theory of Solutions. J. THOVERT (Compt. rend. 1910 150 270-212. Compare Abstr. 1903 ii 13). -The relation between the molecular weight M and the diffusion coefficient D of a substance in solution has been represented by the formula D,J@=C where C is a constant. For a large number of substances it has been shown that C = 12 x 10-5; it is now found however that in many cases G may have a much larger value.Com- pounds of similar structure usually show the same value for C. An explanation based on the kinetic theory is put forward to account for these observations. w. 0. w. Action of Membranes. HEINRICH BECHHOLD and J. ZIEGLER (Zeitsch. Chem. I n d . XoZZoide 1910 6 122-123).-The authors object t o the view put forward by Liesegang respecting the nature of precipitation membranes. I n the case of the membrane which is formed when equimolecular solutions of sodium chloride and silverii. 192 ABSTltACTS OF CHEMICAL PAPERS. nitrate in gelatin are allowed to diffuse towards one another a con- dition of statical equilibrium is set up.After the formation of the membrane no further reaction between the two substances can be observed. H. &I. D. Properties of Solutions at their Critical Solution-Tempera- tures. A. N. SCHUKAREFF (Zeitsch. physikal. Chem. 1910 '71 90-108. Compare ibid. 1897 23 308).-It is shown that at the critical solution-temperature of two liquids many properties of the solutions follow very simple rules. It has already been shown (Zoc. cit.) that the internal energy E of mixtures of phenol and water at their critical solution-temperature can be represented as the sum of two factors thus E=E,+nEph where Ew represents the internal energy of 1 mol. of water EPh that of 1 mol. of dissolved phenol and n the number of mols. of phenol for 1 mol. of water. It is now shown that the same rule holds for mixtures of acetylacetone and water propionitrile and water and resorcinol and benzene but not for propionitrile and an aqueous solution of sodium chloride Further the respective capillary coefficients ( = rsH where the symbols have the usual significance) of mixtures of phenol and water and of acetylacetone and water are constants independent of the com- position of the solutions at the respective critical solution-temperatures. Similarly the vapour pressure of certain pairs of liquids with an upper critical solution-temperature is independent of the composition within the limits of 20-80% at the temperature in question and the vapour pressure of mixtures of nicotine and water is constant between 17 and 82% nicotine a t the lower critical solution-temperature.At the upper critical solution-temperature the vapour pressure of the solutions is generally greater than that of the more yolatile component. Finally the expansion-coefficient of mixtures of acetylacetone and water is approximately constant between 15 and 79% of the former component in the neighbourhood of the critical solution-temperature. The influence of a number of compounds (acids salts and sugars) on the critical solution-temperature of a mixture of propionitrile and water has been determined but there is no apparent connexion between the magnitude of the elevation and the nature of the third substance. G. S. An Example of Solubility Influence. WALTER HERZ (Zeitsch. anorg. Chern. 1910 65 341-344).-The solubility of succinic acid in water at 25" is 6.72 millimols.in 10 C.C. This value is much lowered by the addition of alkali salts the lowering being approximately proportional to the concentration of the salt in the case of potassium chloride bromide and iodide but being greatest in small concentrations for sodium and lithium chlorides. The reciprocal lowering of the solubility of sodium chloride by succinic acid has also been measured. The formula given by Rothmund and Wilsmore (Abstr. 1902 ii 447) is not exactly confirmed owing to the high concentration of the solution. In the aalts examined the influence increases with diminishingGENERAL AND PHYSICAL CHEMISTRY ii. 193 electro-affinity of the metal and also although to a less extent with increasing electro-affinity of the anion C. H.D. Difference in the Speed of Dissolution of Sucrose Crystals at their Different Faces. GASTON GAILLARD (Compt. rend. 19 10 150 217-219).-0bservations have been made on sucrose by immersing diffbrent faces of a crystal in water for a definite time. The area of the crystal face was measured and the amount of dissolved solid determined polarimetrically. Results are given in tabular form from which it appears that the speed of dissolution varies somewhat according to the face of the crystal undergoiug attack by the solvent. w. 0. w. Crystallisation in Fused Masses owing to the Liberation of Gas. FRITZ RINNE (Jahrb. Min. 1909 ii 129-139).-By the evolution of a gaseous product the composition of a fused mass may be so altered that crystallisation takes place without any fall in temperature.The conditions of equilibrium in such systems are illustrated by diagrams and the example most fully worked out is the conversion of white cast-iron into wrought-iron by the puddling process. Samples of iron were taken at different stages of the process the percentage of carbon determined and sections of the metal examined under the microscope. As the carbon is burnt off there is a crystallisation of martensite from the fluid metal. In the same way crystallisation of silver or gold may take place during the cupellation of silver-lead or gold-lead alloys owing t o the distillation or oxidation of the lead. In aqueous solutions of salts a similar change in composition is effected by the evaporation of the solvent ; and in igneous magmas it is possible that crystallisation may also be induced by an alteration in composition accompanying the liberation of volcanic gases.L. J. S. Spontaneous Crystallisation of Sugar. G. FOUQUET (Compt. rend. 1910 150 280-282).-0bservations have been made on the temperature at which spontaneous crystallisation begins in super- saturated sugar solutions submitted to mechanical stirring. As a result the author confirms the observations of Miers in the case of other substances that the curve of supersaturation obtained by plotting concentration against the temperature at which crystallisation commences is approximately parallel t o the curve of solubility. The addition of impurities does not appear to affect this parallelism. w. 0. w. Liquid Crystals and Avogadro’s Hypothesis.OTTO LEHMANN (Zeitsch. physikd. Chem. 1910 71 356-381).-The paper consists largely of references to the author’s earlier work on liquid crystals. The generally accepted view as t g the nature of liquid crystals is incompatible with Avogadro’s hypothesis a d the author therefore considers that the hypothesis in question is not valid. The conse- quences drawn from it as to the identity of molecular weight in different states of aggregation (including van der Waals’ theory ofii. 194 ABSTRACTS OF CHEMICAL PAPERS. continuity) cannot be upheld. The existence of a transition ternper- ature for enantiotropic modifications and of mixed crystals of non- isomorpbous modifications are also regarded as incompatible with Avogadro’s hypothesis. The assumption made in deducing Avogadro’s hypothesis from the principles of the kinetic theory that the mass of a molecule is constant is not applicable to gases and liquids where the molecules can readily combine and decompose.The views as to the nature of liquid crystals advocated in different editions of Nernst’s Theoretische Chernie are adversely criticised and the author contends that his priority in reference to a number of discoveries referring more particularly to crystals has been disregarded by Nernst. G. S. Self-purification of Liquid Crystals. OTTO LEHMANN (PhysikaZ. Zeitsch. 1910 11,44-49).-Experiments are described which indicate that the formation of liquid crystals from isotropic liquids is accompanied by a purification process analogous to that which attends the separation of solid crystalline aggregates from isotropic liquids.This can be observed for instance when very finely divided and specifically light substances (such as spores of Lycoperdon) are added to p-azoxyanisole in the isotropic condition and the temperature is then allowed to fall SO that the anisotropic form of the substance makes its appearance. The observations indicate that in general colloidal solutions in crystalline liquids are not obtainable This is regarded as another argument in favour of the author’s theory of the nature of liquid crystals as against the emulsion theory. H. M. D. Emulsions. WA. OSTWALD (Zeitsch. Clem. Ind. Kolloide 1910 6 103-109).-1n connexion with the technical impregnation of wood with coal-tar oils the author has investigated the nature of the emulsions which are formed by oils with water.Since both the oil and the water can take the part of the disperse colloid or of the dispersive medium it is evident that there are two critical points which determine the limiting concentrations for disperse systems in which the respective substances play the part of dispersive medium. For mixtures of the two substances which fall between these limits two kinds of emulsions can be obtained which have quite different properties. The character of the emulsion which is formed in any given case is shown to depend on the previous history of the substances. If the carefully cleaned interior surface of the vessel in which the emulsion is prepared has been previously covered with oil the emul- sion obtained is of the one type ; if cpreviously covered with water the second type of emulsion is obtained.The effect of a surface layer of oil is apparently to destroy the colloidal disperse oil particles which may be formed on agitation and similarly the effect of a water surface is to nullify the tendency of the water to distribute itself in the form of a disperse colloidally suspended phase. H. M. D. Independent Components and Compounds. RUDOLF RUER (Zeitsch. physikcd. Chem. 1910 71 337-354).-8 theoretical paper. The conditions are investigated under which in a two-phase system,GENERAL AND PHYSICAL CIIEMIYTRY. ii. 195 a system made up of n elements behaves as a system of n - 1 substances. For a system made up of two elements these conditions can only be fulfilled in one way and the simple relation 7*,/s1 =r2/s2 holds (rl and r2 being the amounts of heat taken up by the system arid s1 resp.s2 the changes of volume which occur when unit mass of the first of the second component respectively is traneferred a t constant temperature and pressure from the first to the second phase) which is equivalent to the law of constant proportions for a binary compound which boils fuses or undergoes transition without decompo3ition. When n exceeds 2 the conditions may be fulfilled in different ways but the preferable solution leads to an equation of the same form as the above which therefore applies to a binary system on addition of other elements provided that the compound behaves to these as a whole. Allotropy and Internal Equilibrium.ANDREAS SMITS (Chem. Weekblad 1910 7 79-83).-A theoretical paper. The Equilibrium Solid-Liquid-Gas in Binary Systems which Present Mixed Crystals. HUGO R. KRUYT (PTOC. K. Akad. Wetensch. Amsteydam 1909 12 537-545).-A theoretical paper in which the author discusses the various possible forms of the three-phase equili- brium curves for binary systems in which the two components are completely miscible in the solid state. The System Lithum Sulphate-Ammonium Sulphate-Ferrous Sulphate and Water. FRANS A. H. SCHREINEMAKERS (Zeitsch. physikul. Chem. 1 9 10 71 109-1 16).-The three ternary systems and the quaternary system have been investigated by solubility measurements a t 30" in the usual way and the results are represented in two ways on projected space diagrams. The solid phases in the quaternary system are (NH,)2S0 Li,SO,,H,O FeS0,,7H20 Li2S0,,(NH,)2S04 = DLi and FeSO,,(NH4),SO4,6H,O= D,.,.The results show that FeS04,7H,0 can co-exist with Li2S04,H20 and BPe but not with (NHJ2S0 and DLi ; that Li2S04,H20 can co-exist with FeS0,,7H20 DPe and DLi but not with (NH&SO,; thac (NH,),SO can co-exist with D and ULi but not with the other two salts; that DLi can co-exist with all the other salts except FeS0,,7H20 and finally that D can co-exist with all the other solid salts. G. S. A. J. W. H. M. D. Equilibria in Quaternary Systems. G. S. Criteria for the Determination of the Sensitiveness of Pre- cipitation Reactions. WILHELM BOTTGER (Festschrift Otto Wallach 1909 282-300).-Experiments have been made to determine the smallest concentration a t which potassium chloride bromide and iodate can be detected by the formation of a visible precipitate on the addition of silver nitrate. For this purpose a definite volume of a solution containing a relatively large excess of silver nitrate was added to measured volumes of solutions of the halogen salts of gradually decreasing concentration.The observations indicate that the limiting concentrations for the chloride bromide and iodate are respectively 0-16 x 10-5 0.04 x 10-5 and 1 x 10-5 mol. per litre. In the case of theii. 196 ABSTRACTS OF CHEMICAL PAPERS. precipitation of silver chloride the limiting concentration falls to 0.04 x This increaw in sensitiveness is attributed to the formation of particles of larger size when nitric acid is present in the solution. On the other hand there appears to be a limit to the increase in sensitiveness on this account for the silver iodate is precipitated in the form of well-defined crystal- line particles of relatively large size and it is to this circumstance that the relative insensitiveness of the visible reaction between iodate and silver nitrate appears to be due. It is shown that observations of the above nature can be utilised to determine approximately the solubility of slightly soluble substances provided that these are not especially characterised by the ready formation of supersaturated solutions. Relationship between the Structure of the Aliphatic Alcohols and their Rate of Esteriflcation. ARTHUR MICHAEL (Bey. 1910 43 464-465. Compare Michael and Wolgast Abstr. 1909 ii 8’73).-Polemical in reply to B. N. Menschutkin (ibid. 988). It is pointed out that the methods used by N. Menschutkin and by Michael and Wolgast are essentially different and the results are not comparable. J. J. S. Modiflcation of Dunstan and Short’s Extraction Apparatus. P. E. F. PERRODBS (Phurm. J. 1910 [iv] 30 106).-In using this apparatus in its original form the contents of the inner tube are liable to be carried into the outer tube of the extractor if the solvent is boiled vigorously. To avoid this the author inserts a spiral spring of brass wire provided with a suitable disk of wire gauze a t the lower end and a ring at the other. The lower end rests on the contents of the inner tube and the other end against the cork with which the mol. per litre in presence of nitric acid. H. M. D. extractor is closed. The modified apparatus is figured in the original. T. A. H. [Lecture] Experiments in Physical Chemistry. Uao GRASSI (~Yzcovo Cim. 1909 [v] 18 ii 408-412).-The ztuthorndescribes suitable apparatus for (1) measuring the catalytic action of hydrochloric acid on the reaction between menthone (or acetophenone) and phenyl- hydrazine; (2) studying the law of mass action in the dissociation of nitrogen peroxide and (3) measuring the lowering of solubility in water effected by a substance dissolved in ether T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805169

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 196 ABSTRACTS OF CHEMICAL PAPERS Xnorganic Chemistry. Formulation and Nomenclature of Ilsorganic Compounds. MAX K. HOFFMANN (Chem. Zeit. 1910 34 73-7.6).-A scheme is put forward for the systematic formulation and nomenclature of inorganic compoundp. The following points are considered (1) The sequenceINORGANIC CHEMISTRY. ii. 197 of the elements and radicles in the various compounds. (2) The order in which the various oxidation stages of the same eIement should be placed in a formula. (3) The naming of numbers for example mono- di- tri- etc. (4) The nomenclature of (a) individual elements ( b ) anions ( c ) alloys (d) metalammines (e) double salts. (5) Method of denoting the number of components in compound (double triple etc.) salts. (6) Nomenclature of (a) salts of condensed ac+ids (b) special groups of elements.(8) Use of old names. (9) Method of denoting water of crystallisation. T. S. P. Chemical and Biological Effects of Ultra-violet Light. MAURICE LOMBARD (Compt. rend. 1910 150 227-229. Compare Courmont Abstr. 1909 ii 753 ; Aubel this vol. ii 28).-Owing to the contradictory results obtained by previous observers the author has re-examined the chemical effects of quartz-mercury lamps on water. The sterilising action of the Kromayer lamp has been ascribed to the formation of hydrogen peroxide ; it has been found however that the production of iodine from potassium iodide is more marked with a feebly alkaline natural water than when the water is slightly acidified. Distilled water gave comparable results only after addition of a nitrate.The liberation of iodine therefore appears to be due to the formation of nitrites and this has been confirmed by the production of a coloration with sulphaniiic acid and a-naphthylamine. Hydrogen peroxide is probably formed first in accordance with the equation 2 H 2 0 = H,02 + H2 and this is followed by reduction of the nitrate. The sterilising action of the lamps is considered to depend Utilisation of Electrolytic Chlorine for the Simultaneous Production of Hydrochloric and Sulphuric Acids. ANGELO COPPADORO (Gaazetta 1909 39 ii 616-642).-The author discusses the various processes devised for utilising the chlorine yielded by the electrolytic soda industry and describes his own investigations on the reaction expressed by the equation C1 + SO + 2H20 = 2HC1+ H,SO,.Study of the equilibrium between the three components water and sulphuric and hydrochloric acids in the liquid phase at 17" 40° and 70' shows that with increasing proporBions of sulphuric acid the solubility of the hydrochloric acid undergoes considerable diminution. The amount of such diminution cannot however be calculated by means of the formulse given by Nernst (Abstr. 1890 3) and Noyes (Abstr. 1891 l42) such formula giving accurate results only for dilute solutions. With Bodlander's formula ( Abstr. 1891 794 795) W/lg=const. where W a.nd X indicate grams of water and hydrochloric acid respectively the value of the expression is constant only for solutions containing small proportions of sulphuric acid and increases with the amount of the latter.If however allowance is made for the formation of the hydrate H,S0,,H20 in solutions containing much sulphuric acid the value of Wbeing diminished by the amount of water in this hydrate approximately constaot results are obtained for the expression W'/ 7x7 (7) Method of writing long names. on the direct action of the rays on bacteria. w. 0. w.ii. 198 ABSTRACTS OF CHEMICAL PAPERS. The industrial application of this process and i t s economics are discussed. T. H. P. Solubility of Gases in Concentrated Sulphuric Acid and in M i x t u r e s of Sulphuric Acid and Water. CHRISTIAN BOHR (Zeitsch. physikal Cherub. 191 0 71 47-50).-The solubility of nitrogen oxygen and carbon dioxide in 96% sulphuric acid and of the first two gases in mixtures of sulphuric acid and water in varying proportions has been measured in the neighbourhood of 21'.The results for the 96% acid in terms of Bunsen's absorption- coefficient x 100 are as follows carbon dioxide 92.6 ; oxygen 2.748 ; nitrogen 1.292 from which I t will be seen that the solubilities are not very different from those in water. The solubilities are however much less in mixtixres of sulphuric acid and water and for oxygen and nitrogen reach a minimum in 25Nsolution at which the solubility is less than. one-third of that in water. A t the same point the contraction on mixing sulphuric acid and water attains its maximum value. G. S. Amides of Sulphuric Acid. FRITZ EPHRAIM and &I. GUREWITSCH (Ber. 1910 43 138-148. Compare Abstr. 1909 ii 994).-The methods for preparing sulphamide are f a r from satisfactory and the authors have consequently investigated new methods. Theoretically dirnethyl sulphate and ammonia should give rise to sulphaiide and methyl alcohol but instead of these compounds methylamine and ammonium methyl sulphate are formed.The difficulties met with in the preparation of methyl amidosulphonate NH2*S02=OMe were too great to use t h a t compound as the starting point. Attempts were then made to prepare the chloroamide of suiphuric acid C1-S02*NH2. Amidosulphonic acid NH,*SO,H and phosphorus pentachloride in the proportion of 1 5 by weight readily interacted at 70-90'. After filtering the olive-green liquid so obtained through glass wool i t mas distilled on the water-bath under diminished pres- sure.Phosphoryl chloride and phosphorus trichloride passed over leaving a viscous dark brown liquid which deposited white crystals (m. p. 33-34') aftera long time a t 0'. The analytical results were only in approximate agreement with the formula NH2.S02*C1 + PCl,. The compound is very sensitive t o water and water vapour hydrogen chloride phosphorom acid and amidosulphonic acid being formed. Boiling sodium hydroxide does not liberate ammonia which is only produced on prolonged heating with fuming hydrochloric acid in a sealed tube. All attempts to decompose it into its components were unsuccessful. When thionyl chloride and amidosulphonic acid are heated together in a sealed tube a t 105-1 1 O' ammonium chlorosulphonate CI*SO,*NH is formed and is purified by washing with carbon disulphide or light petroleum and after drying it forms a white mass with a yellowish tinge (m.p. about 152' in sealed tubes). It fumes in the air and gradually deliquesces. On treatment with liquid ammonia there is a violent reaction the product of which dissolves in the excess of ammonia. After evaporation of the solvent the residue isINORG A N IC CHEMISTRY. ii. 199 dissolved in water the solution acidified with nitric acid and silver nitrate added in large excess. After collecting the silver chloride the filtrate is fractionally precipitated with ammonia the first and smallest fraction being rejected. From a hot solution the precipitate consists of silver sulphamide SO,(NHAg) whereas from a cold solution i t is silver imidosulphamide NAg(S0,-NHAg) with varying amounts of water of cry stallisation. Trisulphimide was not found in the reaction products.When sulphuryl chloride is added drop by drop to liquid ammonia cooled by an ether-solid carbon dioxide freezing mixture there is a violent reaction according to the equation 2S02C1 + 7NH = NH(S02*NH2) + 4NH4C1. No trisulphimide is formed aqd after evaporating oft the excess of ammonia silver imidosulphamide may be obtained from the residue in a manner similar to that already described. It is always coutaminnted with silver sulphnmide the sulphamide being formed from the imidosulphamide according to the equation NH(SO,*NH,) + H20 = NH,*SO,H + SO,(NH,) In fact silver imidosulphamide may be readily transformed into silver sulphamide by solution in dilute acid and precipitation from the warm solution by ammonia. Pure sulphamide is best prepared by dissolving the product of the reaction between sulphuryl chloride and liquid ammonia in a small quantity of waher and making the solution just acid.After two t o three days the hydrolysis is complete the mixture is evaporated to dryness in a vacuum and the residue extracted with ethyl acetate which dissolves out the sulphamide,' amidosulphonic acid and ammonium chloride being insoluble. After evaporating off the ethyl acetate pure sulphamide m. p. 93" is left. Pure silver imidosulphamide was prepared by extracting the product of the reaction between sulphuryl chloride and liquid ammonia with ethyl acetate in order t o remove the sulphamide and then working up the residue at the ordinary temperature to silver imidosulphamide in the manner already indicated.When a solution of amidosulphonic acid is neutralised with ammonia and the calculated quantity of silver nitrate added to form the silver salt no precipitate forms until the liquid has been evaporated to a syrupy consistence. It then solidifies suddenly to a radiating crystal- line mass which after crystallisation from water gives rhombohedra1 crystals of silver ammonium amidosulphonate It contained 46H,O. NH2*S0,Ag,NH,-S0,NH,. T. S. P. Allotropy of Tellurium. ERNST COHEN and J. F. ERONER (Chem. Weekblud 1910 '7 57-61).-A summary of the literature on the allotropy of tellurium. A. J. W. Behaviour of Nitric Oxide at Low Temperatures. KAROL ADWENTOWSKI (Bull. Acad. Sci. Crucow 1909 742-767).-The gas investigated by the author was prepwed by the action of nitric acid on ferrous sulphate or of sulphuric acid on a solution containing potassium iodide and potassium nitrite and was purified by condensation and fractional distillation.ii.200 ABSTRACTS OF CHEMICAL PAPERS. The relative density of nitric oxide remains unchanged when the temperature is lowered to about - 150'. The mean coefficient of expansion a t 760 mm. between - 140' and 0' is 0.0037074. Liquid nitric oxide is colourless in thin layers and light blue when examined in thick layers. It is however,. probable that the blue colour is due to traces of nitrogen trioxide which cannot be removed by fractionation. The critical temperature is - 92.9' the critical pressure 64.6 atmo- spheres.It boils at - 150*2O and solidifies a t - 160.6'. The vapour pressure at this temperature being 168 mm. of mercury. The vapour-pressure curve of liquid nitric oxide is somewhat anomalous and this is attributed to polymerisation of the molecules at low temperatures. The fact that the vapour density at atmospheric pressure is quite normal at these temperatures indicates however that the dissociation of the polymerised molecules is practically complete a t this pressure. The high density of the liquid at its boiling point D 1.269 is cited as evidence in support of the view that the liquid molecules are associated H. M. D. Molecular Weight of Nitrous Acid in Aqueous Solution. ALEXIS v. SAPOSHNIKOFF (J RUM. Phys. Chem. soc. 1909 41 1704-1 708).-That the molecule of nitrous acid in aqueous solution is represented by the formula HNO is partly confirmed by Schiimann's measurements of the electrical conductivity and affinity constant of the acid (Abstr.1900 ii 264). Simple shaking of solutions of nitrous acid with chloroform results in the expulsion of the anhydride N,O the appearance of which is explainable as due either to the occurrence of the anhydride in the solution or to the slight stability of the acid and its consequent decomposition into water and nitrogen trioxide under the influence of the chloroform. Cryoscopic measure- ments of aqueous solutions of nitrous acid give the molecular weights 46 0 46.6 and 46.6 which are very nearly identical with the value 47 required by the formula HNO,. T. H. P. Compounds of Sulphur and Phosphorus.V. Tetra- phosphorus Trisulphide P4S3. ALFRED STOCK [ with MAX RUDOLPH] (Ber. 1910 43 150-157).-The author has shown previously that the only three compounds of phosphorus and sulphur are P,S P,S7 and P,S (P4S,,) (compare Abstr. 1909 ii 569). The present communication descrr bes the preparation and properties of the first compound tetraphosphorus trisulphide. An excess of red phosphorus is mixed with finely-powdered sulphur and the mixture heated in a wide tube sealed at one end in an atmosphere of carbon dioxide. The temperature is first gradually raised to I O O O and then the reaction started by stronger local heating near the surface of the mixture. When the reaction has spread through the whole mass the tube is strongly heated until the contents begin to distil otherwise higher sulphides of phosphorus are formed ; the reaction product which consists of red phosphorus and tetra- phosphorus trisulphide is allowed t o cool in the atmosphere of carbon dioxide The trisulphide may be separated from r;he red phosphorus by extraction with carbon bisulphide or by distillation in anINORGANIC CHEMISTRY.ii. 201 atmosphere of carbon dioxide but in both cases it is somewhat impure. After purification and recrystallisation from benzene a pure light- yellow product is obtained which siirters at 171.5" m. p. 172.5'. The b. p. is 407-40S0/760 mm. but at the same time there is slight decomposition as indicated by a variation in the melting point. D17 = 2.03. The molecular weight both in carbon disulphide solution and as vapour corresponds with the formula P,S,.A t 17" 1 part by weight of P,S is dissolved by 1 40 and 32 parts by weight respectively of carbon disulphide benzene and toluene. The concentrated solutions are intensely yellow. Tetraphosphorus trisulphide is decomposed by both concentrated and dilute potassium hydroxide solution hydrogen and phosphine (1 1 to 2 1) being evolved. The evolution of gas lasts for days at the ordinary temperature. If the brownish-red solution is acidified immediately after being prepared a yellow precipitate resembling solid phosphorus hydride P1,H6 is obtained which decomposes and becomes brown after a time. This precipitate is not obtained from solutions which have been preserved for some time. T. S. P. Compounds of Sulphur and Phosphorus.VI. Tetra- phosphorus Heptasulphide P,S7. ALFRED STOCK [ with BERLA HERSCOVICI] (Ber. 19 10 43 4 14-41 7). -An intimate mixture of purified red phosphorus and sulphur in such proportions that the reaction product would consist of P,S + 5% P4Sss is heated in a hard glass tube in the way described in the preparation of tetraphosphorus trisulphide (preceding abstract) until distillation begins. The cooled product is then recrystallised from carbon disulphide in which the heptasulphide is sparingly soluble (1 part in 3500 parts solvent at 17O and 1 part in 20,000 parts at OO) whilst the trisulphide is readily soluble. Tetraphosphorus heptasulphide crystallises in small slightly yellow prisms D17= 2.19 ainters a t 305-30S0 m. p. 310O. The b.p. is 523O/760 mm. and the vapour density at 700" corre- sponds with the formula P,S7 ; above 750° the vapour density rapidly diminishes to one-half its normal value. At the ordinary temperature it is stable but on melting and at higher temperatures it decomposes to some extent. It is more sensitive to moisture than the trisulphide. When exposed to the air for some time it smells strongly of hydrogen sulphide. T. 8. P. Crystalline Boron. 11. HEINRICR BILTZ (Ber. 1910 43 297-306).-Bo-called crystalline boron has hitherto been obtained in two different crystalline forms the one being black and having the formula AlB, whilst the other consisted of colourless to yellow quad- ratic crystals having the composition C,Al,B (Hampe this Journ. 1877 i 273). The preparation of the colourless crystals has hitherto been a very troublesome matter but the author obtains them readily as follows A mixture of 50 grams of boron trioxide 75 grams of sulphur 100 grams of aluminium and 2 grams of soot is fired by an VOL.XCVIXI. ii. 15ii. 202 ABSTRACTS OF CHEMICAL PAPERS. appropriate fuse. The fused mass is treated with water and concen- trated hydrochloric acid and the residue finally left under dilute hydrochloric acid for some days. When all action has ceased it is well washed by decantation with hot water. The resulting prepara- tion consists mostly of the transparent yellow quadratic crystals but it is also mixed with the black crystals. The black crystals have Di8 = 2.554 k 0.005 and the yellow Di:= 2.590 +_ 0-006 and are separated by the flotation method in a mixture of methylene iodide and benzene.The quadratic crystals are not attacked by hot concentrated hydro- chloric acid or sulphuric acid or by a solution of chromium trioxide in concentrated sulphuric acid. They are dissolved by hot concen- trated nitric acid especially when heated in a sealed tube at 150-180'. In transmitted light they are yellow to brownish-yellow in colour whereas in reflected light they are dark brown to grey. Analysis gave 4.07% C 13.38% Al and 82.1% B (=total of 99*6%) which corre- sponds with the formula C,Al,B, which is slightly different from that obtained by Hampe (Zoc. cit.). It is not possible to say whether these crystals are a definite chemical compound or a saturated mixed crystal. T. S. P. Action of Carbon Tetrachloride Vapour 'on Anhydrides and Oxides PIERRE CAMBOULIVES (Compt.Tend. 19 10 150 175-1 77). -The author gives in tabular form a list of those oxides which undergo conversion into chlorides or oxychlorides when heated in a stream of carbon tetrachloride vapour ; the nature of the products is indicated as well as the temperature at which the reaction com- mences. No action occurs with the oxides of boron and silicon. In other cases chlorination occurs between 215' and 580'. The oxides of niobium and thorium give a mixture of oxychloride and chloride whilst tungstic oxide gives the oxychloride only. All the other metallic oxides examined yielded the corresponding chloride. w. 0. w. Action of Carbon Tetrachloride Vapour on Minerals. PIERRE CAMBOULIVES (Compt.rend. 1910 150 221-223. Compare preceding abstract).-The ease with which natural or artificial metallic oxides undergo chlorination when heated in carbon tetrachloride vapour renders possible the application of this substance to the analysis of complex minerals. A separation of free and combined silica in bauxite for example can be effected in this way since aluminium silicate is transformed into the chlorides of aluminium and silicon whilst uncombined silica is not attacked. I n the same manner molybdenite The Explosibility of Gaseous Mixtures. FRIEDRICH EPSTEIN and P. KRASSA (Zeitsch. physikaZ. Chem. 1910 71 28-46).-The authors describe the experimental work on which the conclusions of Haber (this vol. ii 122) as to the connexion between luminosity and electrical conductivity in the Bnnsen flame are partly based.A steady flame was secured by thorough mixing of the coal-gas and has been shown to contain free molybdenum oxide. w. 0. w. Conductivity of the Inner Gone of Divided Flames.INORGANIC CHEMISTRY ii. 203 air before reaching the burner. As electrodes for the conductivity measurements two platinum-iridium wires 0.05 mm. in diameter were stretched horizontally across the flame; they were fixed 1-2 mm. apart and the position of the cone of the flame with reference to them could be altered by means of a screw arrangement. In order to minimise the effect of the ends of the electrodes and thus obtain more regular results 3 cm. in the middle of each wire was covered with magnesium oxide. Measurements of temperature were made simultaneously by means of a thermo-couple.As the electrodes are gradually lowered in the flame the electrical conductivity increases regularly but there is a sudden increase when the electrodes reach the luminous cone. I n one experiment with the electrodes 1 mm. apart the conductivity was three to four times greater a t the summit of the luminous zone than at a point 1 mm. above it. As the proportion of oxygen in the mixture is gradually diminished the change of conductivity on reaching the luminous zone is less abrupt a result which is due in part to the lowering of tempera- ture. The addition of carbon dioxide to the gas mixture also renders the change of conductivity at the margin of the luminous zone less sharp but at the same time broadens out the luminous zone so that in this case also there is a close connexion between conductivity and luminosity.Further in the case of the carbon monoxide flame which is only slightly luminous there is no great increase of conductivity on reaching the inner cone. Contrary to the general opinion as to the action of an inert gas on the luminosity of a flame it was found that when the supply of gas and air was kept constant and carbon dioxide was added to a flame it became more explosive and it is even possible in this way to bring about the separation of an undivided flame. This conclusion is borne out by the results of Eitner (Bubilitationsschrift Miinchen 1902j which are discussed at length I n this connexion it is shown that Le Chatelier’s rule according to which the lower limit of explosibility of a gaseous mixture is an additive function of its composition is approximately valid but this rule does not hold for the higher limit of explosibility.G. 8. Existence of Real Percarbonates and t h e i r Differentiation from Carbonates with Hydrogen Peroxide of Crystallisation. SEBASTIAN TANATAR Ber. 1910 43 127-128).-Riesenfeld and Reinhold (this vol. ii 33) class the potassium percarbonate of Constam and Hansen as a real percarbonate because it liberates iodine immediately from neutral potassium iodide whereas Tanatar’s sodium percarbonate does not react in this may and is therefore considered to be a carbonate with hydrogen peroxide of crystallisation. The author points out that these reactions prove nothing and could be foreseen.Potassium percarbonate (K2C208) forms potassium hydrogen carbonate in aqueous solution and this would have no action on iodine whereas not hydrogen carbonate but carbonate is contained in aqueous solutions of Tanatar’s sodium percarbonate. The carbonate would prevent the liberation of iodine owing to the formation of hypoiodite; the latter compound would then react with hydrogen 15-2ii. 204 ABSTRACTS OF CHEMICAL PAPERS. peroxide with evolution. of oxygen as observed by Riesenfeld and Reinhold. The author states that he does not bind himself to any particular conception of the constitution of his percarbonatex. T. s. P. So-called Amorphous Silicon. ERNST WILKE-D~RFURT (Pest- ~ c h r i f t Otto CPaZZach 1909 671-684).-The form of silicon which is obtained in the reduction of silicon fluoride by sodium at a dull red heat reacts readily with sulphuric acid and with hot water.I n the former case sulphur is formed as one of the reduction products. The great readiness with which the silicon reacts on these substances explains the poor yields which have been obtained by previous workers who have prepared amorphous silicon by this process. It also prevents this process from being economically used for the preparation of large quantities of the reactive amorphous form. A similar amorphous product is obtained with a comparatively high yield when sodium silicofluoride is melted together with sodium and aluminium and the metallic regulus obtained is treated with acids. This first product of a grey colour is not very reactive and on that account it can be separated more or less completely from admixed silica.When heated with hydrofluoric acid the greyish-coloured variety of silicon is however converted into a brown variety which is very much more ,reactive. The product thus obtained is violently attacked by concentrated nitric acid with the formation of a white substance which appears to be a nitride since it evolves ammonia when acted on by sodium hydroxide. When heated the brown amorphous silicon is transformed into a much less active form. Many apparently conflicting statements in the literature can be explained on the basis of the author's observations. H. M. D. Alloys of the Chlorides of the Alkali Metals. S. F. SCHEMTSCHUSCHNY and F. RAMBACH ( J . Russ. Phys. Chem.Soc. 1909 41 1785-1814. Compare Kurnakoff and Schemtschuschny Abstr. 1906 ii 443).-The authors have traced the melting-point and solidification curves of binary mixtures of the chlorides of the alkali metals. For lithium and potassium chlorides the m. p. diagram consists of two branches meeting a t the eutectic point 3 5 2 O which corresponds with 40.5 mol. % KCl and 59.5 mol. % LiC1. Solid solutions are not formed the two components separating from the molten mixtures in the pure state. The molecular depression of the m. p. of lithium chloride (100 mols.) by potassium chloride is 45-4*3O whilst with potassium chloride as solvent the molecular depression is 4.9-4.8O. Theeutectic alloy m. p. 352O furnishes a good protecting layer for metals which oxidise on heating to 400-500'.The m. p. of lithium chloride is 614' (Carnelley this Journ. 1876 i 489 found 602 & 5" and Guntz Zeilsch. angew. Chem. 1898 11 158-159 600'). With lithium and rubidium chlorides the curve is composed of two branches which meet at the eutectic point 312O corresponding with 44.75 mol. % RbCl and 55.25 mol. % LiC1; no solid solutions are formed. The molecular depression for lithium chloride is 4-3-4.1",INORGANIC CHEMISTRY. i i 205 and for rubidium chloride 4.6-4.3'. Rubidium chloride has m p. 726' (Carnelley Trans. 1878 33 273 found 710'). For lithium and sodium chlorides the cooling curves exhibit no eutectic halt solidification proceeding over a certain interval of temperature and solid solutions of various concentrations being formed. The m.p. diagram is a continuous curve of Roozeboom's type 111 exhibiting a minimum at 552' corresponding with 27 mol. % NaCl. The molecular depression of the m. p. of sodium chloride is 3.8-3*7° and of the lithium salt 2.5'. With rubidium and potassium chlorides the m. p. curve is con- tinuous and proceeds at first almost horizontally and then gradually rises to the m. p. of potassium chloride. Solid solutions are formed in all proportions of the components the m. p. curve being of Room- boom's type I. These observations are confirmed by the structures of the alloys. The molecular depression of rubidium chloride is in this case negative and equal to 0.15-0-1 lo whilst for the potassium salt it amounts t o 1*4-1*3'. The m. p. diagram of rubidium and sodium chlorides consists of two branches meeting a t the eutectic point 541° which corresponds with 54.96 mol.% RbC1. The molecular depression is 4.4-4-0'for rubidium chloride and 4-3-4.1' for sodium chloride. Caesium chloride has m. p. 646' (Carnelley and Williams Trans. 1880 3'7 125 gave 631'j. The cooling curves for mixtures of rubidium and caesium chlorides exhibit two halts the second at 451* being conditioned by the existence of a polymorphoue modification of caesium chloride. The ratio of the heat of transformation into this second modification to the latent heat of fusion of caesium chloride is found to be 0.35. The m. p. diagram is a continuous curve of Roozeboom's type 111 and exhibits a minimum at 440° corresponding with 11.5 mol. % of rubidium chloride. The mole- cular depression for casium chloride is 1.6-1*5O and for rubidium chloride 1 -6- 1 -5'.With csesium and potassium chlorides the m. p. diagram is a con- tinuous curve (Roozeboom's type 111) with a minimum at 616' corresponding with 34 mols. % KCl. None of the cooling curves shorn a eutectic halt solid solutions of various concentrations being formed. The presence of potassium chloride lowers the temperature of polymorphous transformation of caesium chloride ; with 11 a 5 mol. % of KC1 the change becomes very indistinct and with higher pro- portions disappears completely. The molecular depression is 1 *lo for caesium chloride and 2.8-2.9O for potassium chloride. For sodium and caesium chlorides the m. p. diagram is formed of two branches meeting at 493O which corresponds with 34.5 mol.% NaCl; no solid solutions are formed. Similar results are obtained with the system CsCl + LiCl. These chlorides may be divided into two groups ( 1 ) those of potassium rubidium and caesium which mix in all proportions and (2) those of lithium and sodium which at high tempeiatures form uninterrupted series of solid solutioiis these decomposing at lower temperatures. By means of van't HOE'S formula the latent heats of 'fusion areii 206 ABSTRACTS OF CHEMICAL PAPERS. found t o be for NaC1 97 ; LiCI 86 ; KCI 63 ; RbC1 38 and CsCl 24 Cals. these valuee diminishing with increase of the molecular weight. The heats of formation of a number of the solid solutions formed by the above salts have been measured and it is found that in all cases considerable absorption of heat occurs the solid solutions being consequently unstable and undergoing gradual decomposition.T. H. P. Some Thiophosphates. FRITZ EPHRAIM and ETTA MAJLER (Ber. 1910 43 285-288).-When solid sodium tetrathiophosphate Na3PS (compare Abstr. 1905 ii 318) is treated with the solutions of sulphides of other metals reaction takes place either according to the equation 2Na3P8 + 3M2S + 2H20 = 2M,PS,O + 3Na2S + 2H2S or according t o the equation 2Na,PS4 + 3M2S + 4H20 = SR13PS202 + 3Na2S+4H2S. I n no case is the tetrathiophosphate of the second metal formed owing to hydrolysis by the water. Barium ozytrithiophosphate Ba,(PS,0)2,20H20 was obtained from sodium tetratbiophosphate and a solution of barium sulphide. It is stable when dry but is decomposed by water or dilute acids with evolution of hydrogen sulphide.Concentrated nitric acid dis- solves it the sulphur being completely oxidised to sulphuric acid. When barium hydrosulphide is used instead of the sulphide barium dioxpdithiophosphate Ba3(PS202)2,1 8H20 is obtained (compare Stock Abstr. 1906 ii 535). Attempts to prepare strontium and calcium thiophosphates were unsuccessful. Magnesium oxytrithiophosphate Mg,(PS,0)2?20H,0 was obtained from magnesium hydrosulphide. It was precipitated from solution by alcohol in the form of white needles. It is decomposed by water or dilute acids. Selenophosphates. FRITZ EPHRAIM and ETTA MA JLER (Ber. 19 10 43 277-285).-Selenophosphates of the a1 kali and alkaline-earth metals and of magnesium can be prepared by the action of phosphorus pentaselenide on aqueous solutions of the selenides of the respective metals the reaction proceeding according to the equation 3M2Se + P2Se5 = 2M3PSe,.I n no case however could n solid tetraseleno- phocphate be obtained water decomposing i t thus M,PSe + H20 = M,PSe,O+H,Se. In some cases the decomposition may go further still with the formation of the compound iU3PSe202 or even M,PSeO,. I n many cases intermediate compounds for example K,PSe,.,O,. are formed which the authors consider may be isomorphous mixtures of the different oxyselenophosphates. I f the compounds crystallise from a mother liquor rich in hydrogen selenide they are also rich in selenium but if precipitated by alcohol they are poorer in selenium. The oxyselenophosphates may also be prepared from the hydroxide of the metal and phokphorus pentaselenide.Even in the presence of excess of alkali the normal salts sometimes hydroiyse with the forma- tion of the monohydrogen salts the process being conditioned by the relative solubilities of the two salts in the mother liquor. 01; solution in water especially in hot water all the compounds decompose according to the equation M,PSe + 4H,O = &&PO + T. S. P.INORGANIC CHEMISTRY. ii. 207 4H,Se. becoming red and depositing selenium. stable in dry air. alkaline-earth metals give monohydrogen salts. The mother liquors oxidise quickly on exposure t o the air The solid salts are fairly Normal salts were only obtained with the alkali metals ; the An ammonium tellurophosphate could not be obtained.SodizLrn trioxyselenophosphate Na,PSeO3,20H,0 was prepared by digesting a strong solution of sodium hydroxide with phosphorus pentaselenide. The same substance was obtained when sodium hydro- selenide was used in the place of sodium hydroxide. It crystallises in needles. Ammonium ox ytriselenophosph ate was obtained from phosphorus pen taseleriide and a saturated solution of hydrogen selenide in strong ammonia. From the warm mother liquor leaflets crystallised having the composition (NH,)3PSe30,10H,0 and later the cold mother liquor deposited octahedra and four-sided leaflets of the composition (NH,),H(PSe30)2,18H,0. Potassium oxyselenophosphute K,PSe,.,O,.,,H,O was obtained in the form of greenish-yellow octabedra by using potassium hydroselenide.It reacts violently with nitric acid. Barium dioxydiselenophosphate BaHPSe,O 1 4H,O is formed when phosphorus pentaselenide is treated either with a solution of barium hydroxide or with a saturated solution of hydrogen selenide in barium hydroxide. When 2 grams of strontium hydroxide dissolved in a little water were treated with 3 grams of phosphorus pentaselenide and the filtrate from the deposited selenium treated with alcohol a light yellow precipitate of a strontium oxyselenophosphccte having the composition SrHPSe2/301013,7H20 was obtained. When a larger excess of the pentaselenide was used the crystals were colourless and had the composition SrHPSe,,308,,,8H,0 which may possibly be 2SrH PSeO XrHPSe,O 2 4H,O. With calcium hydroxide a calcium oxyselenophosphate was formed.With the smaller proportion of phosphorus pentaselenide the yellow crystals obtained had the composition CaHPSel/301,/,,5H,0 whilst with the larger proportion their composition was CaHPSe0,,8H20. A magnesium dioxydiselenophosphate was also obtained but not in a pure condition. T. S. P. FRITZ EPHRAIM and MAX BBAND (Zeitsch. anorg. Chem. 1910 65 233-236).-Five lithium phospho- molybdates two of which are of rather complicated composition have been prepared. The sult 3Li2O,P,0,,5MoO3 with both 16H20 and l?'H,O is obtained from the mother liquor of its additive compound described below in white prisms. The salt 5Li20,2P,0,,8M00,,28H20 is obtained when lithium carbonate phosphoric acid and molybdenum trioxide are mixed in the proportions of the first salt and the solution is evaporated.It forms long slender needles readily soluble in water. The salt SLi,O,P,O,,l 2Mo0,,1 8H,O is obtained on adding dilute nitric acid to the hrst salt in concentrated solution and forms a yellow It forms a white micro-crystalline powder. . Lithium Phosphomolybdates.ii. 208 ABSTRACTS OF CHEMICAL PAPERS. micro-crystalline precipitate. When the mother liquor is evaporated orange crystals of the salt 3Li,0,P205 1 8M00,,2'TH20 are obtained. The doubb salt 3Li20,P,0,,5Mo0 + 6Li3P0,,18H,O is obtained when 52 grams of lithium molybdate are dissolved and 29 grams of molybdenum trioxide and 15 grams of phosphoric oxide added. It crystallises in short rods and has an alkaline reaction whilst the other lithium phosphomolybdates are acid.Water decomposes it leaving a residue of lithium phosphate. C . H. D. Rubidium and Caesium Phospho- and Arseni-molybdates. FRITZ EPHRAIM and HEINRICR HERSCHFINKEL (Zeitsch. anorg. Chem. 1910,65,237-247).-The salt 7Rb,0,P20,,22Mo0,,~12H20 is obtained by mixing the components in the molecular proportions 3 1 2 when a yellow salt usually slightly green owing to partial reduction is precipitated. By the addition of nitric acid D 1.2 to a solution of rubidium phosphomolybdate a yellow precipitate of the salt 3Rb20,P20,,20M00 1 2H20 is obtained. If this salt is suspended in water and rubidium'carbonato is added until the yellow colour of the solid disappears a white salt 6Rb20,P205 1 8Mo03 1 OH,O is obtained. I f 0.5 mol. phosphoric acid is added to 1 mol. rubidium carbonate and then boiled with 1 mol.molybdenum trioxide a solution is formed which deposits very large crystals of the salt 5Rb20,2P,0,,9M00,,13H,0. The last portions of the mother liquor deposit crystals of 7Rb20,3P,0 10M00,,15H20. A yellow caesiwm salt has the composition 2cS20,P,05 1 4Mo0,,3H20. A white salt ~ C P O P ~ ~ ~ M ~ ~ ~ H ~ O is obtained similarly to the white rubidium salt. A simple w.hidium arsenomolybdate Rb,O As2O,,6MoO is obtained as a white micro-crystalline precipitate by adding rubidium nitrate to a concentrated solution of arsenomolybdic acid (Pufahl Abstr. 1884 715). A salt 4Rb20,As,0,,18M00,,40H20 is obtained as a yellow precipitate by mixing molecular proportions of rubidium hydroxide and molybdenum trioxide and then adding nitric acid and arsenic acid.If an excess of arsenic acid is used colourless crystals of the salt 3Rb,0,3As,0,,5M00,,9H20 are obtained readily soluble in water It contains more arsenic than any previously known arsenomolybdate. A yellow caesium arsenomolybdate 4Cs2O,As,0,,26Mo0 1 5H20 is obtained ib similar manner. It was not found possible to prepare a white caesium salt the product isolated being caesium amenate Cs,0,2As,0,,5H20 which forms well-developed crystals. C. H. D. Dimorphism of Ammonium Haloids. ROBERT C. WALLACE (Centr. Min. 1910 33-36).-When ammonium chloride is sublimed there is a marked change in the heat effect at 159' ; under the micro- scope the crystals exhibit a change a t this temperature although they still remain optically isotropic ; and on cooling in a dilatometer filled with oil the crystals show an appreciable contraction in volume at this point.Ammonium bromide exhibits the same reversible phenomena a t logo but ammonium iodide shows no change. The molecular volumes of ammonium chloride and ammoniumINORGANIC CHEMISTRY. ii. 209 bromide in their modifications stable at the ordinary temperature indicate that these (more highly polymerised) salts are not iso- morphous with the potassium haloids and ammonium iodide ; but it is probable that the modifications stable a t the higher temperatures do belong to this isomorphous series. L. J. S. Properties of Precipitated Silver. TARAK NATH DAS (Chem. News 1910 101 51).- When the solution of hypophosphite obtained in the preparation of phosphine from phosphorus and sodium hydr- oxide is acidified and treated with silver nitrate a yellow precipitate of silver separates after a time and gradually changes in colour becomidg successively brown red grey and finally black.The pre- cipitate dissolves very readily in solutions of potassium cyanide and potassium chlorate less readily in sodium thiosulphate and is nearly insoluble in ammonia and sodium hydroxide. H. M. D. Atomic Weight of Strontium. Sir EDWARD THORPE and ARTHUR G. FRANCIS (Proc. Roy. Soc. 1910 A 83 277-289).-The atomic weight of strontium has been determined by measurement of the ratios (1) .SrBr2 2Ag (6 determinations) (2) SrBrz 2AgBr (5 determinations) (3) SrC12 2Ag (6 determinations) (4) SrC1 2AgC1 (5 determinations). The strontium salts were purified by very exten- sive processes of fractional crystallisation and all reagents used in connexion with the measurements were freed from possible impurities by suitableemethods. From the four ratios the atomic weight of the metal is found to be 87.646 +_ 0.0016.In order to obtain an independent check on these determinations two further series were made depending on the ratio of SrSO to SrCl and SrBr (4 and 3 determinations) respectively. In consequence of the more complicated character of the manipulative processes involved in these estimations the accuracy obtainable by this method is not so high as in the methods of the first four series. The mean value obtained for the atomic weight is 87.645 & 0.0107. As a final result the authors adopt the number 87.65 which is only 0.03 in excess of that obtained by Richards.H. M. D. Action of some Salts of Ammonium on the Alkaline Earth Carbonates. ETTORE SELVATICI (Bull. Assoc. Chirn. Sum*. Dist. 1910 27,669-670).-1t is proposed to prepare barium chloride and nitrate and the corresponding strontium compounds by heating the carbonates with equal mol. weights of ammonium chloride and nitrate respect- ively. The barium nitrate may be used for preparing the oxide by heating to redness in a current of oxygen and the peroxide by merely heating to redness. N. H. J. M. Electrolysis of Cupric Solutions. OCTAVE DONY-H~NAULT (Butt!. SOC. chim. Belg. 1910 24 56-83).-A reply to Foerster (Abstr. 1909 ji 314) on behalf of Meyer (Abstr. 1908 ii 803 ; 1909 ii 314). As the result of new experiments the author con- cludes that the explanation given by Meyer holds for temperatures below 509 whilst that due'to Foerster Abel and others is true forii.210 ABSTRACTS OF CHEMICAL PAPERS. temperatures near the boiling point. Luther’s method of estimating cuprous salts by means of permanganate (Abstr. 1901 ii 301) gives results concordant with those obtained by weighing the copper which separates when a solution of copper sulphate in dilute sul- phuric acid which has been heated at 200’ in presence of copper is cooled. Tor neutral solutions the results obtained by the two methods do not agree. Luther’s value for the equilibrium constant Cu/Cu is confirmed. T. A. H. Coloration of Salts. ANDRB RASSENFOSSE (Bull. Acnd. roy. Belg. 1909 1289-132 l).-The various theories which have been advanced to account for the colour changes of solutions of cupric and cobaltous salts do not give a full explanation of the subject (compare Donnan and Bassett Trans.1902 81 939 and Werner Abstr. 1909 ii 49). I n the case OF copper sulphate the colour of a solution is shown to depend (a) on the dissociation of the salt and ( b ) on its hydration. Evidence is brought forward to show that in the case of cupric chloride solutions colour changes induced by the addition of hydro- chloric acid by heating by the action of alcohol and in other ways are probably due to the formation of compounds of cupric chloride either with the reagent used or with a product of its own decom- position. In this connexion reference is made to the additive products of hydrochloric acid with cupric cobalt,ous mercuric and other chlorides isolated by Engel (Abstr.1888,555 918 1042 1248 ; 1890 109 and 1892 569). The addition of hydrochloric acid to a cold saturated solution of cupric chloride causes the precipitation of either the mono- or di-hydrate of cupric chloride so that the colour change caused by the addition of the acid cannot be due to dehydration of the salt. Further addition of a dehydrating agent such as phosphoric oxide induces no colour change in cupric chloride solution. Zinc chloride added to a green solution of cupric chloride containing hydrochloric acid restores the blue colour probably because the zinc chloride destroys the cupric chloride hydrochloride existing in the green solution. Sodium potassium or barium chloride does not react in the same way as zinc chloride but calcium or magnesium chloride changes the blue colour of an aqueous solution of cupric chloride to green probably by the formation of a molecular compound of the two salts.A mixture of saturated solutions of cupric and calcium chlorides deposits after a time a mass of greenish-brown deliquescent needles of the double salt 2CuC12,CaC12,6 H20. When a solution of cupric chloride in water is boiled the colour changes to green the water vapour evolved contains hydrogen chloride and the boiled solution on cooling shows less absorption for light and an increased electrolytic resistance. Such a solution contains cupric oxide. The blue colour is restored to the hot solution if zinc OF mercuric chloride is added.A solution of anhydrous cupric chloride in ethyl alcohol deposits on evaporation under reduced pressure greenish-y ellow crystals of an additive product CuC1,,2C2H,*OH and a similar product is formed with isobutyl alcohol. It is probably to the existence of the former substance thatINORGANIC CHEMISTRY. ii. 211 the green colour of an aqueous solution of cupric chloride to which alcohol has been added is due. Cupric chloride is decomposed by paper and to this cause is due the brown stain produced on drying paper which has been soaked in cupric chloride solution. Similar evidence in favour of the view that colour changes in cupric chloride solution are due to the formation or decomposition of compounds of the type indicated is afforded by comparison of the absorption spectra and electrolytic resistances of such solutions. T.A. H. Reactions in Non-Aqueous Solutions. V. In Ethyl Acetate. ALEXANDER NAUMANN [with MAX HAMERS and EMIL HENNINGER] (Ber. 1910 43 313-321. Compare Abstr. 1909 ii lOl8).-The anhydrous ethyl acetate used distilled at 74*5O/750 mm. and had Di8 7 0.8995. For the experiments half-saturated solutions were used. A list is given of salts which are soluble or insoluble in ethyl acetate. When hydrogen sulphide is passed into strongly ammoniacal ethyl acetate a precipitate of ammonium hydrosulphide in the form of white leaflets is obtained. The colourless liquid gradually becomes yellow owing to the formation of polysulphide. The same compound is formed when ammonia is passed into a solution of hydrogen sulphide but it then crystlallises in needles.With hydrogen chloride the ammoniacal solution of ethyl acetate gives a precipitate of ammonium chloride. At 18O a saturated solution of mercuric chloride in ethyl acetate contains one part of solute to 2.05 parts of solvent. With hydrogen sulphide a white compound HgC12,2HgS is produced and with ammonia the compound HgCl,,SNH,. Hydrogen sulphide and am- monia together give a greyish-black precipitate of merciiric sulphide. Molecular-weight determinations by the boiling-point method gave 254.9-269-2 as the molecular weight of mercuric chloride when dissolved in ethyl acetate. Mercuric bromide dissolves in ethyl acetate to the extent of one part in 7.66 at 18'. Hydrogen sulphide gives a yellow precipitate of the composition HgBr 2HgS and ammonia a white precipitate with the composition HgBr2,2NH,.Ammonia and hydrogen sulphide together give a precipitate of mercuric sulphide. The molecular weight of the dissolved mercuric bromide was found t o be 330.0-351.4 by the boiling-point method. Mercuric iodide dissolves in ethyl acetate to the extent of 1 part in 68-03 a t lSo and has the molecular weight 413.7-442.3. Hydrogen sulphide gives a yellowish-red precipitate which probably has the composition HgI,,ZHgS. No precipitate is produced with ammonia. Ammonia and hydrogen sulphide together give a precipitate of mercuric sulphide ; at first the precipitate is black but on continued passage of ammonia it turns red. Saturated solutions of potassium mercuri-iodide in ethyl acetate do not give a precipitate with either ammonia or hydrogen sulphide.With both these gases together a black precipitate is produced which contains mercury and sulphur. At 1 8 O the saturated solution of cadmium iodide in ethyl acetate has Di8= 009145 and contains 1 part of solute in 54.3 parts o€ solvent.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. With hydrogen sulphide i t gives a yellow precipitate of the com- position Cd12,2CdS. With ammonia the compound Cd12,2NH is precipitated. Ammonia and hydrogen sulphide together produce a precipitate of cadmium sulphide mixed with ammonium hydro- sulphide. Hydrogen chloride produced no precipitate but a slight liberation of iodine. Chlorine gave a white flocculent precipitate of cadmium chloride as also did mercuric chloride and bismuth tri- chloride.Bromine gave a dark-coloured liquid but there was 'no evidence of reaction. A t 18' a saturated solution of stannous chloride in ethyl acetate contains 1 part of stannous chloride to 22.40 parts of ethyl acetate and has Di8= 0.9215. With hydrogen sulphide a brown precipitate of stannous sulphide is produced and with ammonia the compound SnC12,2NH3. Ammonia and hydrogen sulphide together give a precipitate of stannous sulphide mixed with ammonium hydro- sulphide. Hydrogen chloride produces no precipitate. Chlorine and bromine both give stannic salts. Mercuric chloride gives a white precipitate of mercurous chloride even in the presence of excess of stannous chloride. At 18' a saturated solution of antimonytrichloride in ethyl acetate has Dig = 1.7968 and contains 1 part of solutle to 16.97 parts of solvent.No precipitate is produced with hydrogen sulphide but with ammonia the compound SbC1,,3NH3 is produced. Ammonia and hydrogen sulphide together give a precipitate of antimony trisulphide mixed with ammonium hydrosulphide. There is no reaction with either hydrogen chloride chlorine bromine iodine mercuric chloride or bismuth trichlori de. A t 1 8 O 1 part of bismuth trichloride dissolves in 60.36 parts of ethyl acetate and the solution has Di8=0*9106. When kept the solutions become cloudy owing to the formation of bismuth 0x7- chloride. Hydrogen sulphide gives a precipitate of bismuth sulphide and ammonia a precipitate of the composition RiC1,,2NH3. Ammonia and hydrogen sulphide together give bismuth sulphide.Neither hydrogen chloride chlorine bromine iodine mercuric chloride nor antimony trichloride have any action. T. S. P. Action of Heat on Aluminium in a Vacuum. &MILE KOHN- ABREST (Compt. rend. 1910 150 169-173).-When aluminium is heated in a porcelain boat at l l O O o in a vacuum the metal is rapidly volatilised at first but after some hours the loss in weight from this cause becomes negligible. After prolonged heating the residue is found to be coated with a yellow film consisting of an alloy of aluminium and silicon. The same results are obtained when boats of pure graphite are employed but only when these are contained in a porcelain tube. The conclusion drawn is that aluminium vapour attacks the porcelain liberating silicon which is absorbed by the molten aluminium. The porcelain tubes employed are found to be coated internally with a black crystalline deposit from which the AUGUSTE VERNEUIL (Compt.rend. 1910 150 185-187).-Hitherto artificial compound A1,Si has been isolated. w. 0. w. Synthetical Production of Sapphires by Fusion.INORGANIC CHEMISTRY. ii. 213 sapphires have been obtained which owed their colour either to chromium oxide or the iron oxide in a lower state of oxidation than ferric. Those coloured by chromium oxide were obtained by Sainte- Claire Deville and Caron in 1858-1865 but no one has been able t o repeat their experiments. The sapphires coloured by iron oxide are of inferior quality. The author finds that when alumina containing 1.5% of magnetic oxide of iron and 0.5% of titanic acid is fused in the oxyhydrogen flame which has reducing properties sapphires are produced which are identical in properties with the natural stones ; the colour in this case is due to the presence of the oxides of iron and titanium.T. S. P. Do Clays a n d Cements Adsorb CO," Ions? JOH. D'ANs (Zeitsch. Chem. Ind. Kolloide 1910 6 38-40. Compare Rohland Abstr. 1909 ii 662).-In reference to the statement of Rohland that carbonates are adsorbed from solutions by cements experiments were made in which weighed quantities of powdered cements and clays were agitated for several hours with a measured volume of a sodium carbonate solution. After filtration the hydroxide and carbonate in the solution were determined. The experimental data show that the dissolved carbonate is partly converted into hydroxide by the free calcium oxide of the cements.In a similar manner ammonia is set free when the cements are agitated with a solution of ammonium chloride. On the other hand the clays examined were found to have feebly acid properties and as a con- sequence small quantities of sodium hydrogen carbonate were found in the solutions after agitation. The author's observations are considered to be incompatible with,Rohland's view of carbonate adsorption. H. M. D. Formation and Properties of Colloidal Manganese Dioxide. EUGEN DEISS (Zeitech. Chem. Ind. Kolloide 1910 6 69-77).-Stable colloidal solutions of manganese dioxide can be readily obtained by the reduction of permanganate solutions by means of dilute sodium arsenite.They can also be prepared by the oxidation of manganous salts if pro- tective colloids are present in the solution. Various organic colloids can be used for the purpose and it is also shown that colloidal ferric and aluminium hydroxides act as protective colloids if the amount of manganese in solution is relatively small. If larger quantities of manganese are present ferric hydroxide behaves quite differently in that it favours the precipitation of the dioxide. It is probable that the precipitation of manganese dioxide is always preceded by the temporary formation of a colloidal solution of the substance coagulation resulting as a consequence of the presence of electrolytes. The formation of the iridescent flakes of manganese dioxide which can be frequently observed in the oxidation or reduction of manganese compounds is also attributable to the transient formation of a colloidal solution.The so-called manganites must in many cases be regarded as adsorption compounds of manganese dioxide and bases. H. M. D.ii. 214 ABSTRACTS OF CEEMICAL PAPERS The Thermal Formation of Manganates. I. OTTO SACKUR (Bey. 1910 43 381-388).-A mixture of manganese dioxide with an excess of potassium carbonate was fused in a platinum crucible and maintained at a temperature slightly higher than the melting point of potassium carbonate. At the same time air or oxygen or carbon dioxide or a mixture of these gases was passed through the fusion by means of a platinum tube. From time to time portions of the fused mass were withdrawn by means of a tube of hard glass and after cooling the percentages of available oxygen and of manganese were determined.The portions withdrawn were taken after the passage of gas had been stopped and the manganese dioxide still unacted on had been allowed to sink to the bottom of the crucible. Is one case the oxide Mn304 was used in place of the dioxide The results show that the absorption of oxygen by the fusion ceases as soon as the atomic proportion of available oxygen to manganese becomes 1.6. This value is independent of the con centration of the manganese in the fusion and of the partial pressure of the oxygen in the gas above the fusion so that there does not exist an equilibrium between the different oxidation stages of manganese in the fusion and the oxygen in the gaseous phase but a definite compound is formed which contains manganese and oxygen in the proportion of 1 2.6 and would therefore have the formula Mn,Ol3 = 2Mn0,,3Mn03.The fusion is dark green in colour. With a little water or with an alkaline solution it gives a dark green solution (manganate) and a dark brown precipitate (MnO,). With much water or dilute acids a violet solution (permanganate) and manganese dioxide result. A similar result was obtained when the potassium carbonate was replaced by potassium hydroxide but with sodium carbonate the atomic propo[tion of available oxygen to manganese was 1.5 instead of 1.6. A mixture of potassium and sodium carbonates in equal proportions gave the same proportions as with sodium carbonate alone. The fusions containing sodium salts were grass-green in colour as opposed to the dark green of the potassium compound.Calcium oxide gave similar resuits to sodium carbonate. When oxygen is absorbed by the fusion carbon dioxide is simul- taneously evolved as shown by the equation 5Mn0 + go2 + zK,C03 7 Mn,O,,,zK,O + zC0,. By estimating the carbon dioxide evolved it was found that the potassium compound formed in the fusion had the composition Mn,0,,,5K20 whereas the sodium compound was Mn20,,2Na,0. The results obtained also showed that unless the oxygen was passed for a considerable time after the evolution of carbon dioxide had ceased the compound formed in the fusion was Mn,01,,5M,0 where M is either K or Na. All the above results are only valid when an excess of alkali carbonate sufficient to hold the manganese compound formed in solution and so permit of full oxidation is used.The complex compounds formed may be considered to be manganio manganates. T. S. P.INORGANIC CHEMISTRY. ii. 215 The Thermal Formation of Manganates. 11. Molecular- Weight Determinations in Fused Alkali Carbonates. OTTO SACKUR (Ber. 1910 43 445-453).-The influence of dissolved salts on the melting points of potassium and sodium carbonates was deter- mined by the method of cooling curves using a platinum-platinum- rhodium thermocouple. The solutes used with potassium carbonate were potassium chloride sodium chloride and sodium carbonate and with sodium carbonate potassium chloride sodium chloride and potassium carbonate. I n each case with concentrations of the solute up to 1.2 gram-molecules per kilogram of the fusion the lowering of the freezing point was proportional to the concentration of the solute.The molecular lowering for a binary salt which contains no ion in common with the solvent is approximately twice that for a salt contain- ing a common ion. Ternary salts containing an anion common to the solvent have melting-point constants which are intermediate between those of the two classes of binary salts. These results are in accord- ance with the views of Goodwin and Kalmus (Physical Rewiew 1909 The molecular lowering of the freezing point is 41' in potassium carbonate as solvent and 31' in sodium carbonate. Sodium chloride dissolved in potassium carbonate is dissociated to the extent of 73% and potassium chloride in sodium'carbonate to 77%.The latent heats of fusion of potassium and sodium carbonates are calculated t o be 66 and 82 cals. per gram respectively. The molecular weights of the complex alkali manganic manganates dissolved in the a1 kali carbonates (see preceding abstract) were then determined. Pure manganese dioxide was melted with excess of the alkali carbonate and a current of gas consisting of 4/5 oxygen 1/5 carbon dioxide passed through the fusion for some hours after which time a portion was removed for analysis and the melting point of the remainder determined. It was found when oxidation was com- plete that the ratio lowering of the melting point concentration of the manganese in gram-atoms per 1000 grams of the fusion was constant and equal t o 43 in potassium carbonate and 35 in sodium carbonate.These results show that the solute in each case contains only 1 atom of manganese to the molecule so t h a t their formulae must be written K,Mn03.6 and Na,MnO,. respectively that is with a fractional number of atoms to the molecule. The full theoretical bearing of this result can only be properly discussed after further experimental results have been obtained. 28 1). T. 5. P. Cementation of Iron by Solid Carbon. GEORGES CHARPY and S. BONNEROT (Compt. Fend. 1910 150 173-175).-The experiments which have hitherto been made on the cementation of iron by solid carbon have been inconclusive either because carbonising gases were not eliminated with certainty or else because it was not proved that the iron and the carbon had been in intimate contact. The authors proceed as follows soft Martin steel containing only traces of elements other than carbon and manganese and carbon (pure sugar carbon purified graphite or clear white diamonds) were heatedii.216 ABSTRACTS OF CHEMICAL PAPERS. in separate tubes in a vacuum to 1000° until practically no further gas (less than 0.1 C.C. per hour) was evolved the pump working con- tinuously. The iron and carbon were then brought into contact with sa little exposure to the air as possible and again heated in a vacuum at 700° which is below the temperature of rapid cementation until the evolution of gas ceased. The temperature was then raised to 1000° and maintained a t that temperature for several hours the pump working continuously.I n every case the results were negative ; microscopic examination of the surface of the metal did not show the least trace of cementation. If however small quantities of gas were let into the apparatus or if the pump was not continually worked cementation took place no matter what kind of carbon was used. The adherence of carbon to iron under high pressures (3,000 atmos.) is very slight; hitherto it has mot been possible to carry out such experiments in a vacuum a t high temperatures in order to ascertain if cementation is affected by the pressure. If it be granted that carbon cannot penetrate into steel from the outside except by means of some gaseous medium (carbon monoxide) it does not follow that the same thing holds for the diffusion of carbon to the interior of a casting or of steel.Fresh experiments in this direction are necessary. T. S. P. Metallic Tungsten. LUDWIG WEISS (Zeitsch. anorg. Chem. 1910 65 279-340).-[With A. MARTIN.] -The aluminothermic reduction of wolframite is very violent and an alloy is obtained but by employ- ing an insufficient quantity of aluminium the reaction is modernfed and the product contains up to 90.66% W. A part of the iron and manganese can be removed by treatment with hydrochloric acid. It is not possible to reduce wolframite with zinc or magnesium but heating with carbon in an arc furnace followed by fusion with tungstic acid and calcium fluoride to remove carbon gives a product containing only 0.24% C and 8.34% Fe. Tungstic acid is best prepared by fusing wolframite with calcium carbonate and calcium chloride and decomposing the product with acid.If magnesium carbonate is employed the product contains large red crystals of magnesium tungstate which is not decomposed by acids. Tungstic acid may be readily electrolysed if mixed with cryolite 250 amperes being employed at 13-14 volts. The metal is only obtained in globules and contains 96% of tungsten. In order to raise the temperature alumina may be added to the bath the aluminium liberated reacting with the tungstic acid but the product is still in a fine state of division. Experiments have also been made on the electrolysis of barium tungstate and the reduction of calcium tungstate with aluminium. The best metal containing 98.96% W is obtained by fusing tungsten trisulphide with lime by means of an arc in a crucible of Acheson graphite.[With A. STIuMELMAYR.]-TUngSten fused in a hydrogen vacuum is white and metallic; H 6-5-7.5 D20 18.72. The malleability varies according to the heat treatment it has received. Small fragments may be hammered out. It is non-magnetic. The specific heat is 0.0358 and the heat of combustion of 1 gram is 1047 cal.INORGANIC CHEMISTRY. ii. 217 Tungsten forms coloured films like steel when heated in the air. Heating in oxygen converts i t completely into the trioxide. Hydro- chloric acid is without action ; concentrated siilphuric and nitric acids and aqua regia only act slowly on the surface. Chlorine acts slowly ; sulphur is without action. A mixture of nitric and hydrofluoric acids is the only reagent capable of dissolving the fused metal.C. H. D. Corrosion of Bronzes in Solutions of Electrolytes. FEDERICO GIOLITTI and 0. CECCARELLI (Gaxzetta 1909 39 ii 555-575).-The authors have studied the corrosion of bronzes containing various pro- portions of tin and subjected to different methods of cooling by means of SO C.C. of N/lO-hydrochloric acid containing 2% of ferric chloride. The losses in weight were determined after 169 and 366 hours the results being compared with the aid of micrographs. It is found that two bronzes of identical composition after subjec- tion t o different thermal treatment may exhibit quite different powers of resistance to corroding agents ; such differences correspond with structural differences (compare Curry Abstr. 1906 ii 756 ; Giolitti and Tavanti Abstr.1908 ii 946). Under similar conditions the simultaneous presence in a bronze of the two a and p solid solutions and especially of the products of segregation of these accelerates the corrosive action. With bronzes containing not much more than 7% of tin the velocity of corrosion increases with the proportion of the p-solution present no matter whether such increased proportion is due to a different composition of the alloy or to different thermal treatment such as altered velocities of solidification and of subsequent cooling. When the proportions of a and /3 solutions and of their segregation products remain constant the velocity of corroaion is greater when the differences of concentration of the nuclei and margins of the separate mixed crystals of the two series are greater.As such differences of concentration are observable under the microscope the degree of resistance of a bronze to corrosion may be determined beforehand by the same means. T. H. P. Metallic Zirconium. LUDWIG WEISS and EUGEN NEUMANN (Zeitsch. anorg. Chem. 1910 65 248-278. Compare this vol. ii 133).-Crystallised potassium zirconium fluoride is mixed with purified sodium covered with potassium chloride and compressed into an iron vessel. After starting the reaction with a flame it proceeds without further heating. The finely powdered metal thus obtained is washed with alcohol and boiled with hydrochloric acid. If washed with water first instead of alcohol some oxide is always formed by the action of the sodium hydroxide produced on the metal.The zirconium may be compressed t o form rods which conduct electricity well by high pressure without the use of binding material but only globules of metal c m be obtained in this way as the rods break when acurrent is passed. A better product is obtained by reducing the double fluoride with aluminium forming the powdered regulus into rods and heating in a specially constructed furnace in an atmosphere of nitrogen preferably VOL. XCVIII. ii. 16ii. 218 ABSTRACTS OF CHEMICAL PAPERS. under reduced pressure The metallic zirconium containing 99-82 Zr is white resembling cust-iron ; i t has H 7-S D18 6.40 and specific heat 0.0804. Combustion in air only takes place a t a very high temperature and the formation of the dioxide is not complete unless oxygen is used.The heat of combustion of 1 gram is 1958.7 cal. It reacts with chlorine forming the tetrachloride. Hydrogen a t a red heat forms a grey hydride ZrH (compare Winkler Abstr. 1890 1372). When heated in oxygen the hydride burns to zirconium sesquioxide Zr203 which is stable and only burns slowly to the dioxide. C. H. D. Natural Zirconium Earths. EDGAR WEDEKIND (Ber. 1910 43 290-297. Compare Abstr. 1908 ii 1046. [Compare Weiss arid Lehmann this vol. ii 133]).-The author has investigated three varieties of a natural zirconium earth from S ~ O Paolo in Brazil. I. consisted of black. kidney-shaped masses of glassy appearance. 11. consisted of broken stones varying in colour from dark brown to a light matt-grey; very often crystals of zirconium silicate were contained in it.111. consisted of more or less rounded pebbles. Analyses gave the following results SiO ZiO,. TiO,. Fe,O,. SiO,(free) (combined). Total. I. 94.12 0 '98 3'22 0'43 1 -98 100.73 11. 88-29 3 *09 4.07 2-38 3 -38 101'22 111. 74'48 1.35 30.26 14-08 100.17 v The admixed ferric oxide could be removed mechanically from I. ; it then contained 9S% Zr02 and had D 5.41. To obtain zirconium oxide free from iron the filtered acid aqueous extract of the finely-powdered mineral was mixed with ammonia until a cloudiness resulted. Powdered ammonium carbonate was added until the precipitate first formed no longer dissolved. A further equal quantity of ammonium carbonate was then added and the solution warmed to precipitate the iron. The warming mas continued until a filtered portion of the liquid gave no coloration with sulphuric acid and hydrogen peroxide.The whole was then cooled filtered the filtrate acidified with sulphuric acid and warmed to expel carbon dioxide and the zirconium hydroxide precipitated with ammonia. The hydroxide was washed by decantation and then converted into the oxide by heating. To prepare the zirconium tetrahalogenides directly the finely- powdered mineral was intimately mixed with excess of magnesium powder and the mixture heated in a current of dry hydrogen. After treatment of the resulting mass with ammonium chloride dilute hydrochloric acid and warm dilute potassium hydroxide respectively in order to remove the magnesium magnesia iron and silicon the residue was dried in a current of hydrogen and then heated in a stream of either chlorine or bromine. The corresponding tetrahalogenide sublimes. The broken stones and pebbles were found t o contain carbonMlNERALOGICAL CHEMISTRY. ii. 219 dioxide nitrogen hydrogen oxygen helium and traces of argon the broken stones containing the most gas. The mineral has been found by Gockel to be radioactive (Abstr. 1909 ii 956) and he concluded that thorium was present This element has however not yet been detected in any of the author's specimens. T. S. P. Physical and Chemical Properties of some Varietiee of Antimony Trisulphide. VITO ZANI (Bull. Acad. roy. Belg. 1909 1 169-1 182. Compare Guinchant and Chdtien Abstr. 1904 ii 538 568 644).-The varieties examined were (1) the orange-red form produced by precipitation ; (2) the greyish-black form obtained by heating the orange-red modification and (3) natural stibnite. The conclusions arrived at are (a) that all three forms have the formula Sb,S and (b) that their specific gravities are 4.1205 4.2906 and 4.6353 respectively. The first form gradually changes into the second on heating and determinations made in various ways agreed in indicating 2 17" as the temperature at which transformation to the second form occurs with the development of heat. The changes of weight observed on heating the orange-red sulphide at about 100' are not due as generally supposed to loss of water but to secondary reactions involving first the absorption of oxygen then the loss of sulphur dioxide and the eventual production of some metallic antimony. Stibnite seems to differ from the second form only in specific gravity. T. A. I€.

ISSN:0368-1769    

DOI:10.1039/CA9109805196

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

213 Organic Chemistry. Action of Magneeium on the Vapours of Organic Com- pounds. EDWARD H. KEISER and LEROY MCMASTER (J. Amer. Chem. Xoc. 1910 32 3S8-391).-Keiser and Breed (Abstr. 1895 i 405) have shown that when the vapour of an aliphatic alcohol was passed over heated magnesium a black residue was obtained which was decomposed by water with evolution of hydrogen and allylene. I n a later paper (Keiser Abstr. 1896 i 457) an account was given of the action of magnesium on the vapours of other compounds. It was found that if the metal was heated in an atmosphere of carbon monoxide or dioxide a hard mass was obtained which gave only small quantities of allylene when treated with water and the conclusion was therefore drawn that a magnesium compound of allylene was probably present in the black residue.Attempts have now been made to prove definitely whether the substance which yields the allylene is a magnesium allylide or merely a carbide. Experiments have been made with various classes of organic compounds including paraffin and benzene hydrocarbons aliphatic acids and esters aromatic alcohols halogen derivatives acetylene and cyanogen. In each case the residue obtained was treated with water containing a little ammonihm chloride and the gases evolved were led into an ammoniacal solution of silver nitrate. The silver precipitates were analysed and the results are tabulated In all cases in which the magnesium was heated with the vapour of a compound containing hydrogen the unsaturated hydrocarbon formed was mostly allylene. When the compound did not contain hydrogen as in the cases of cyanogen and carbon monoxide only very small quantities of the unsaturated hydrocarbon were produced but even then the gas evolved contained some allylene as well as acetylene.This fact seemed to indicate that a carbide is produced which yields allylene on treatment with water. Since however it was found that the magnesium powder contained hydrogen and that only R very small quantity of allylene is obtainable from carbon compounds which do not contain hydrogen the conclusion is drawn that it is not a carbide but an allylide which yields the allylene. This is supported by the fact that when magnesium is heated in acetylene the black residue on treatment with water gives both allylene and acetylene. E. G.The Electrochemical Preparation of Chloroform. B. WASER (Chm. Zeit. 1910 34 141-142).-Chloroform is not obtained in satisfactory yield by the electrolysis of potassium or calcium chloride in presence of alcohol. Barium chloride gives better results owing t o the greater solubility of barium than of calcium hydroxide. A special apparatus is described in which a porous cylinder surrounds the platinum cathode. The anode is a platinum plate. The cathode VOL. XCVIII. i. 2i. 214 ABSTRACTS OF CHEMlCAL PAPERS. solution is 30 C.C. of hydrochloric acid D 1.19; the anode solution contains 80 grams of barium hydroxide 1 gram of barium chloride and 300 C.C. of water ; 30 C.C. of alcohol are then added slowly the tempera- ture being 50’. Chloroform and alcohol distil off together the temperature being gradually raised to 70°.The cathode solution is renewed from time to time. The anode current density is about 4 amperes per sq. dm. and the current efficiency is about 35%. Barium carbonate must be absent. Acetone gives a lower yield than alcohol. C. H. D. Physiod and Physiological Properties of Tetrachloroethane and Trichloroethylene. VICTOR H. VELEY (Proc. Roy. Xoc. 1910 B 82 2 1 ?-225).-TetruchZoroethane. -The commercial product was fractionally distilled with a Young’s still-head with three bulbs and the portion of b. p. 147.2O was taken as pure. The densities found were Di= 1,6208 and D$ = 196013,. Determinations of the refractive index pD made at temperatures 15.2’ to 17*3O and corrected to a standard temperature 17O gave as final value 1.495587 + 0 ~ 0 ~ 6 calculated by Bessel’s function.Gladstone’s factor p - l/d = 0.3095 and Lorenz’s factor pz - l(p2 + 2)d = 0.1824 which multiplied by the molecular weight give 53.0 and 30.7 respectively. Tp-ichZoroethyZene.-One sample after purification boiled a t 87.4 & O - 1 (corr.) and another a t 87*55+,0*1 (corr,). Practically no hydrogen chloride is given off during distillation. Densities at different temperatures Dt = 1*4904 D:; = 1*4702 DE = 1*4598 the relative volumes ‘being V4 = 1 V17.5 = 1.0128 V25.5 = 1.0209. Refractive index pD determinations at the same temperatures and above give as final value reduced to 17” 1.479141 k 0*0,3 ; Glad- stone’s factor = 0.326 and Lorenz’s factor = 0.193 ; multiplied by the molecular weight the results are 42.7 and 25% respectively. Tetrachloroethane is four times more toxic than chloroform mole- cule for molecule but recovery from anaesthesia or paralysis is more regular in the case of the former than in that of the latter.Trichloroethylene is 1 *5 times more toxic than chloroform molecule for molecule or 1.36 times weight for weight. Not only the course of abolition but also of recovery is much more regular than in the case of chloroform. E. J. R. Grignard’s Reagent and the Barbier-Grignard Reaction. EWIND B~DTKER (Chem. Zeit 1910 3.2 150).-Attention is called to the fact that the reaction between alkyl iodides and other com- pounds in presence of magnesium was first employed by Barbier (Abstr. 1899 i 323) at whose suggestion Grignard studied the reaction and then devised the reagent in its present form.C. H. D. The Oxidation Products of Erythritol (d-Z-Erythronic Acid and &-Z-Hydroxyerythronic Acid). CARL NEUBERG (Biochem. Zeitsch. 1910 24 166-170).-The erythritol was oxidised by nitric acid. The calcium salts were formed and the concentrated solution of the latter dropped into alcohol. The calcium salt of the hydroxy- acid remains partly in solution whereas the calcium salt of theORGANIC CHEMISTRY. i. 215 erythronic acid is precipitated. The calcium salt is then dissolved in water concentrated barium hydroxide added and the mixture warmed. The remainder of the hydroxy-acid is precipitated. The mother liquor contains the erythronic acid which is purified by conversion into.the copper salt and finally into the calcium salt again which latter when pure crystallises.The hydroxy-acid is purified by fbst obtaining it in the form of the basic barium salt (by means of barium hydroxide) and then in the form of the normal barium salt (by means of barium carbonate). The latter is purified by repeated resolution in water and precipitation from aqueous solution by alcohol. s. 8. s. Carnaubon a Glycerol-free Phosphatide Containing Galactose. EDWARD K. DUNHAM and C. A. JACOBSON (Zeitsch. physiol. Chem. 1910,64,302-315).-This new phosphatide C74H150013N3P pre- pared from ox-kidney is soluble in alcohol and almost insoluble in ether. It is a triazomonophosphatide is free from glycerol and yields on cleavage galactose (or amino-galactose) carnaubic stesric palmitic and phosphoric acids and choline.I t s constitution appears to be like that of lecithin the sugar taking the place of glycerol ; this allows of more acid groups being united with the molecule. There are probably other similar phosphatides differing in the nature of the sugar and acid groups. W. D. H. The Simplest Fat Glyceryl Triformate. PIETER VAN ROMBURGH (Zeitsch. physikat. Chew. 1910 70 459-461).-Glyceryl triformate has been obtained pure for the first time by the following method. Glycerol was heated repeatedly with 100% formic acid the excess of acid being distilled off uutil a mixture rich in the triformin was obtained. The mixture was then cooled in liquid ammonia until a small crystal of the triformin was obtained ; on then warming slowly up t o Oo with stirring the triformin was obtained in colourless crystals m.p. 1 8 O ; Dl8= 1.330 (fused ester) ; nF = 1.4412.. When rapidly heated the pure ester distils almost. uochanged at 2 6 6 O (762 mm.). When heated very slowly slight decomposition occurs a t 210'. When traces of the lower esters are present triformin decomposes on heating. It is practically insoluble in and only slowly hydrolysed by cold water; it is soluble and fairly rapidly hydrolysed in hot water. It is acted on normally by ammonia and aliphatic amines. G. S. Preparation of Salts of Dibromobehenic Acid. FARBEN- FABBIKEN VORM. FRIED&. BAYER & Co. (D.R.-P. 215007,215008 and 215009. Compare Abstr. 1908 i 122).-The lead and barium salts of dibromobehenic acid have been previously described. Calcium dibromobehenate can be prepared (1) by saturating an alcoholic solution of calcium chloride with dry ammonia filtering from precipitated ammonium chloride and treating with a solution of dibromobehenic acid in the same solvent; (2) decomposing a very dilute aqueous solution of potassium behenate with calcium chloride ; (3) shaking dibrorriobehenic acid during several days with a saturated solution of calcium hydroxide.It is a colourless tasteless odourless powder 4 2i 216 ABSTRACTS OF CHEMICAL PAPERS. insoluble in water or alcohol and -8s a therapeutic agent compares favourably with potassium bromide Strontium dibromobehenate and mag?zesium dibromobehenfite are analogously prepared as colourless tasteless powders insoluble in water or alcohol. F. M. G. &I.Structure of the Acids of Drying Oils. G. L. GOLDSOBEL (J. Rust?. Phys. Chern. Soc. 1910 42 55-57).-The structure CH3*[CH2I4* CH :CH*CH,*CH :CH*[CH2I7*CO2H previously given by the author (ibid. 1906 38 182) for linoleic acid is confirmed by the optical properties of the acid the second formula discussed CH,*[CH 2],*CH :CH*CH CH*[CH,],* C02H requiring higher molecular refraction and dispersion than those actually found. Oxidation of the initial products of oxidation of linolenic and iso- linolenic acids namely linusic and isolinusic acids by means of permanganate yields in both cases (1) azelaic acid in almost quanti- tative amounts and (2) propionic acid which forms the principal product of the reaction. Consequently linusic and isolinusic acids have the formula OH*CHEt CH(OH)( C,H80,)*CH( OH) *CH(OH)- [ CH,I7*CO,H and linolenic and isolinolenic acids the formula CHEt :CH( C4HJ CH CH*[CH,],*CO,H.As the presence of an allenic linking is excluded the formula for linolenic and isolinolenic acids must be one of the three following (1) CHEt:CH*CH,*CH,*CH:CH-CH:CH,I,.CO,H ; (2) CHEt CH* CH,*CH:CH*CH,*CH CH*[ CH,]7*C0,H ; (3) CHEt:CH-CH:CH*CH,*CH,*CH:CH*[CH,J,*CO,H. The optical data show that (2) is the correct formula; this result is confirmed by the observations of Erdmann Bedford and Raspe (Abstr. 1909 i 358). T. H. P. Oxidation of Methyl Ricinoleate by Ozone. ALBIN HALLER and ANDR$ BROCHET (Conzpt. rend. 1910 150 496-503).-When methyl ricinoleate containing one-tenth of its weight of water is treated with ozone it forms an ozonide m.p. 80-S5' having the constitution CH,*[CH2],*CH(OH)*CH,*CH*CH*[CH2]7*CO*OISle. 6 \ / 0 3 An examination of the decomposition products of this substance has established the constitution usually assigned to ricinoleic acid. When added to aqueous sodium carbonate solution the mixture separates into two layers. When acidified the aqueous layer yields a mixture in which azelaic acid with its monomethyl ester and P-hydroxynonoic acid CH,.[CH,] * CH( OH). CH,*CO,H have been ident Xed. The latter has been isolated as brilliant lamella? m. p. 47-4So showing [a]? 2'26' in alkaline solution. The silver salt is crystalline. The optically inactive acid m. p. 61' has been prepared by the action of heptaldehyde on the magnesium derivative of ethyl bromoacetate.In an attempt to separate the above mixture of acids by distillation at 15 mm. Aa-nonenoic acid was obtained but not in the pure state. Those portions of the decomposition products which remained insoluble iu alkali were found to contain (1) the methyl ester of azelaicORGANIC CHEMISTRY. i. 217 semi-aldehyde CHO*[CH,17*C0,Me which was isolated by means of its bisdphite compound andlobtained as a liquid b. p. 140-145'/ 15 mm. (compare Harries Abstr. 1906 i 11 ; Molinari ibid. 792). (2) A brown liquid possibly having the composition CH,*[CH,]5*CH(OH)*CH2*CH0 since on oxidation it furnished heptoic acid. palmitate together with oily substances of unknown composition. (3) Methyl stearate and w. 0. w. Preparation of Calcium Antimony Lactate. CHEMISCHE WERKE SCHUSTER & WILREMY (D.R.-P.216 158).-Calcium antimony lactate was previously prepared by treating freshly precipitated antimony oxide with a solution of calcium hydrogen lactate or a mixture of free lactic acid and calcium lactate. The double salt 8b( C,H,0,),,Ca(C3H50s) can be readily prepared by treating an aqueous solution of antimony fluoride with the requisite amount of normal calcium lactate dissolved in a saturated solution of calcium sulphate the presence of which is necessary to induce the reaction t o take place. F. M. G. M. Conductivity Measurements with Dibasic Unsaturated Structure-isomeric Acids. FRITZ FJCHTER and HANS PROBST (Annalen 1910 372 69-79 Compare Fichter and Muller Abstr. 1906 i 622).-The dissociation constants of four isomeric un- saturated dicarboxylic acids having the formula C7H,,04 have been measured with the object of ascertaining the effect of the position of the ethenoid linking on the strength of the acid. The acids measured and the dissociation constants at 25' are allylsuccinic acid CH,:CH*CR,*CH(C0,H)*CH,°C02H R= 0.0109 ; propenylsuccinic acid CHMe:CH*CH(CO,H)*CH,*CO,H K = 0.00596 ; ethylitaconic * acid CHEt:C(CO,H)*CH,*CO,H K = 0.00356 and ethylrnesaconic acid CH,Et*C(CO,H):CH*CO,H R= 0.093.As usual the highest value is obtained when the ethenoid linking is situated betweeh the carboxyl groups; in the remaining cases the strength of the acid increases as the ethylene linking becomes further removed from the carboxyl groups. This relationship does not always exist however for Stobbe has shown (Abstr.1902 i 461) that y-ethylidene-y- methylpyruvic acid CHMe:CNe*CH( CO,H)*CH,*CO,H is a weaker acid than methylethylitaconic acid CMeEt:C(CO,H)*CH,*CO,H. Propenylsuccinic acid was prepared by boiling the isomeric ethyl- itaconic acid with aqueous sodium hydroxide ; it crystallises in large colonrless transparent crystals m. p. 135' ; the calcium salt C7H804Ca is crystalline. An attempt to prepare it by distilling y-pzethylparaconic-a-acetic acid led to the production of methylethyl- maleic anhydride. y-Methylparaconic-a-acetic acid CHMe<~H(co2~~>CH*OH2* CO,H prepared by reducing ethyl a-acetotricarballylate in alcoholic solntion with sodium amalgam is a crystalline powder m. p. 1 7 5 O ; the ethgl ester C1,H1806 is a viscid oil b. p. 198'/13 mm.W. H. G.i. 218 ABSTRACTS OF CHEMICAL PAPERS. Molybdo-tartrates. P. QUINET (Bull. SOC. chim. 19 10 [iv] 7 105).-The author points but in connexion with Grossmann's claim for priority on this subject (ibid. December 5th 1909) that his own work (Abstr. 1908 i 713) does not cover the same ground as that of Grossmann and Patter (Abstr. 1904 ii 153 ; 1906 ii 211 ; 1906 i 799). The erroneous composition assigned to the compound of tartaric acid with sodium molybdate given in the author's paper (Zoc. cit.) and noted by Grossmann (Zoc. cit.) had already been corrected (J. phys. April 1909). The Electrolytic Degradation of the Saccharic Acids from Mono- and Di-saccharides and also of Certain Hydroxy- amino-acids. CARL NEUBERG L. SCOTT and SIEGIBERT LACHNANN (Biochem.Zeitsch. 1910 24 152-165).-The general scheme of degradation may be represented by the formulae OH=CH,*[CH*OH],-CH(OH)*CO,H -+ OH*CH,*[CH*OH],*CHO. In this way the successive degradation of glucoheptonic acid to formaldehyde may be carried out. The electrolysis of the following acids is described d-galactonic acid d-Z-erythronic acid d-Z-glyceric acid and glycollic acid. The products obtained were d-lyxose d-1-glycernldehyde glycolaldehyde and formaldehyde. isoSerine was also electrolysed. Aminoacetaldehyde was not directly isolated in this case but the products of electrolysis on oxidation with mercuric chIoride and sodium hydroxide yielded its oxidation product pyrazine. Melibionic acid which was obtained in the form of the calcium salt was also submitted to electrolysis.A sugar was obtained only in small quantity and isolated in the form of its p-nitrophenylo sazone . I n most cases the salts of the alkaline earths of the above acids were employed in the electrolysis experiments. LUDWIG RAMBERG (Ber. 1910 43 580-584).-Cryoscopic measurements show that platinous ethylthiolacetate (Abstr. 1,906 i 791) is slightly polymerised in aqueous solution. On exposure to sunlight or to the rays from a Uviol lamp the aqueous solution which is slightly yellowish-green gradually deepens in colour and after a few days deposits canary-yellow anhydrous needles or prisms having the formula Pt(CO,*CH,*SEt),. They have m. p. 204-205O and possess the normal molecular weight in glacial acetic acid solution so that they are isomeric with the original compound of m.p. 189-190". Werner's theory would give two isomerides having the configurations O*CO-C H,*S*Et O*CO*CH,*S*Et \ \ /' T. A. H. S. B. S. Photo-transformation of an Internal Complex Salt. and >Pt( ," \ Et*S*CH,*CO;O T. S. P. Bimolecular Polymeride of Crotonaldehyde and the Corresponding Acid. MARCEL DELI~PINE (Compt. rend. 1910 150 394-396. Compare Abstr. 1909 i 84).-The compound C,H,,02 formed in small quantity during the preparation of crotonaldehyde by the method already described may be prepasred in larger quantities byORQANIC CHEMISTRY. i 219 heating in a refliix apparatus for half an hour a mixture of croton- aldehyde with the same weight of hydrochloric acid (D 1-18) and five times its weight of water. The new aldehyde forms an axine C,6H2402N2 crystallising in sulphur-yellow prisms m.p. 168O. On treatment with silver oxide (Abstr. 1909 i 632) it yields the corresponding acid C,HI20,,H20 m. p. 68-71O. The anhydrous acid obtained by heating at 60° has m. p. 85-87O b. p. 262-5464'. The ethyl ester has b. p. 107-109°/18 mm. DT 1,014 12 1.46102. Addition of bromine t o an aqueous solution of the acid results in the formation of a bromohydroxyacid C8HI3O4Br which crystallises in monoclinic prisms and does not lose water at 1 OOO. w. 0. w. The liquid is then distilled. Constitution of the Bimolecular Polymeride of Crotoa- aldehyde. MARCEL DEL~PINE (Cmpt. rend. 1910 150 535-537. Compare preceding abstract).-The polymeride obtained during the preparation of crotonaldehyde probably has the constitution $!H,-CH Q m CHO CHMe-0-CHMe ' since on oxidation with chromic acid it forms acetic acid and carbon dioxide and on treatment with magnesium ethyl bromide yields an alcohol C7H,,0*CHEt*OH having a mint-like odour and forming a monoacetyl derivative.The compound C7H,,0 *CH:CHRTe bas also been obtained as an agreeably-smelling liquid with a sweet taste b. p. 82-84"/18 mm.; D!j 0.92061; ng 1.48567. The ethyl ester of the acid corresponding with the above aldehyde furnishes on treatment with magnesium ethyl iodide a compound C12H2202 ; this is probably a tertiary alcohol; it has an odour resembling that of pinacone and does not form an acetyl derivative; b. p. 260°/760 mm. 151-154'/ 19 mm. ; Dt 0.9731 ; lzz 1.46291. Refractometric determinations are in agreement with the constitu- tion suggested for the aldehyde.Crotonaldehyde has n'," 1.44361. w. 0. w. Alkylation of Aliphatic Ketones by the Use of Sodamide. ALBIN HALLER and EDMOND BAUER (Compt. rend. 1910 150 582-589. Compare Abstr. 1904 i 600; 1905 i 276; 1909 i 987).-Pinacolin is readily attacked in ethereal solution by sodamide forming a soluble sodium derivative which on treatment with alkyl iodides gives rise to a mixture of mono- and di-alkylpinacolins ; these can be separated by fractional distillation. Trialkylpinacolins are not produced unless the reaction is carried out in presence of benzene or toluene when the yield is practically quantitative. The ketones prepared in this way have been reduced to the corresponding secondary alcohols by means of sodium and absolute alcohol.Whilst the mono- and di-alkylpinacolins form oximes and semicarbazones the trialkyl derivatives do not react with hydroxylamine or semicarbazide. The following compounds are described the oxime of P/3-dimethylpentan- y-one crystallises in lozenges m. p. 78-80" (compare Wischnegradsky AnmaZen 1875 178 104). Nef's isopropyl butyl ketone (Abstr. 1900 i 349) has DS 0.80536 nD 1.40513 and on reduction yieldsi. 220 ABSTRACTS OF CHEMICAL PAPERS. @8-trimethylpentan2-y-ol CMe,*CH(OH)* CHMe a liquid having an odour like borneol b. p. 145-148' ; the phenylurethane has m. p. 79'. PP68-Ilet.ramethyZpentan-y-one CMe,*CO*CMe obtained by the action of sodamide on the foregoing ketone has a camphoraceous odour b. p. 149-151° D!5 0081992 n 1*41702.PP66-Tetramethyl- pentan-y-ol CH(OH)(CMe,) m. p. 50° b. p. 165-166' forms a phenylurethane m. p. 118-119° ; the fornzyl derivative has b. p. 185". PP66-Tetramethylhexan-y-one CMe,* CO.CMe,Et b. p. 172-1 74' ; PP66-tetramethyMea~y-ol b. p. 187-1 88'; its phenylurethane has m. p. 94-95'. P/?-Dimethylhexan-y-one CMe,*CO*Pra b p. 146-1 45' DF 0.81055 n 1.40952 ; the oxime has m. p. 76-77' P/3-Dimethyl- hexnn-y-ol b. p. 155-157' forms a phenylurethune m. p. $0-71'. ~P-DimethyZ-8-etliylhexun-y-one CMe,*CO*CHEt has b. p. 174-1 76' DF 0.82521 nD 1.12227 and on reduction yields PP-dimethy1-8-etILyl- hexan-y-ol CMe,*CH(OH)*CHEt b. p. 187" ; the phenylurethane has m. p. 107'. PP-Dimethyl-86-diethylhex~n-y-one; CMe,*CO*CEt b. p. 214-21 6' ; PP-dz:methyl-66diethylhex~n-y-ol b.p. 226-22S0 gives a phenylurethrae m. p. 1 10'. CMe,*CO*CHMeEt b. p. 155-156' ; pp8-trimethylhexan-y-ol CMe,*CH(OH)*CHMeEt b. p. 169'; the phenylwethune has m. p. 78". PP~-Trimethylhexan- y-one CMe,*CO*CH,PrS b. p. 157.5-158.5" forms an oxime m. p. 77-78' (compare Nef Abstr. 1902 i 6). P/?-Dimethyl-AS-hepten- y-one CMe,*CO*[CH,],*CH:CH b. p. 61-643/14 mm. &!3-Dimethyl- 8-allyl-Ac-hepten-y-oqe CMe,*CO*CH(C,H,) b. p. 83-86'/14 mm. w. 0. w. Relation between the Chemical Constitution and the Optical Rotatory Power of the Sugar Lactones. C. S. HUDSON (J. Amer. Chenz. Xoc. 1910,32,338-346).-Data are quoted which show that the aldose sugars and their glucosidic and lactonic derivatives exhibit strong optical rotatory power whilst the corresponding alcohols and acids have but slight optical activity.It is therefore evident that the lactonic structure causes considerable rotatory power. There are two possible stereochemical configurations for the lactonic -c*c*c.co and -c,:J,o. If the rotation is due ring namely to this ring the sign of the rotation must be determined by the position of the ring. This position is determined by the position of the hydroxyl group attached to the y-carbon atom before the ring was produced. The hypothesis is advanced that dextro- rotatory lactones have the lactonic ring on one side of the structure laevorotatory lactones have it on the other side and the position of the ring shows the position in which the hydroxyl group was attached t o the y-carbon atom. A list is given of all the sugar lactones of which the structure and specific rotation have been determined and it is shown that in all cases the theory is confirmed.Suggestions are made with reference to the application of this theory to the determination of the constitution of the sugars. PP8- Trimethylhexan-y-one I I I I " I -0- E. G,ORGANIC CHEMISTRY. i. 221 Behaviour of the Ordinary Hexoses towards Hydrogen Peroxide in Presence of Alkali Hydroxides as well as of Various Iron Salts. H. A. SPOEHR (Amer. Chem. J. 1910 43 227-254).-1t has been shown by Nef (Abstr. 1908 i 5) that when the hexoses are oxidised by air or mercuric oxide i n presence of alkali hydroxide or by Fehliifg's solution the same oxidation products are formed in each case and in the same proportions. A study has now been made of the oxidation of dextrose lawulose and galactose by hydrogen peroxide in presence oE alkali hydroxide.It has been found that instead of the various products being obtained which are formed when the oxidation is effected in alkaline solution by means of air Fehling's solution or mercuric oxide the only oxidation products obtained with dextrose and lavulose are formic acid carbon dioxide glycollic acid and a-hydroxymethyl-d-arabonic acid whilst with galactose formic acid carbon dioxide glycol lic acid and a-hydroxy- methyl-d-lyxonic acid are produced. The amount of formic acid obtained varied from 48.3 to 6503% of the calculated amount possible in the case of dextrose and lsvulose and was over 80% in the case of galactose. From these results it follows that the only sugars present in the alkaline solutions which are actually selectively oxidised are (1) formaldehyde ; (2) glycollaldehyde which is converted partly into glycollic acid and partly through glyoxylic acid into carbon dioxide and formic acid ; (3) a- and P-d-glutose (from dextrose and laevulose) OH*CH,* C -CO-q -f! *CH,*OH and ?H ?H VH J!T H H H QH QH OH*CH,* 7- CO-7 -$!*CH,'OH OH H H which give the same glutosone OH*CH,*CO*CO* C-C *CH,.OH this yielding only a-hydroxymethyl-d-arabonic acid CO,H*C--C-C*CH,*OH ; or a- and P-galtose (from galactose) which similarly yield a-hydroxy- methyl-d-lyxonic acid C0,H.C) C- y*CH,*OH.OH VH h l r r YH,*OH OH ?H i)H h H I QH,*OH 7 ?H OH AH H a-Hydroxymethyl-d-arabonic Zactone [a] + 72*5O is a viscous sub- stance.The phenylhydraxide C,Hl10,*NH*NHPh m. p. 21 2-215O forms lustrous needles. The bruczne salt m. p. 186-lSSo [a] about - 25.7" and the culcium salt [alD about - 3*0° are described. Bmcine a-hydroxynzethyZ-d-Zyxonate m. p. 171-1 75" the corre- sponding quinine salt m. p. 21 3O and the phenyZhydraxide m. p.:144O are described. Experiments have shown that ethylene glycol and glycollic acid,i. 22'2 ABSTRACTS OF CBEMICAC PAPERS. when oxidised by an alkaline solution of hydrogen peroxide yield small quantities of formic and carbonic acids but no oxalic acid. Morrell and Crofts (Trans. 1899 75 786 ; 1902 81 666; 1903 83 1290) have studied the oxidation of dextrose lawulose and galactose with hydrogen peroxide in presence of ferrous snlphate and have obtained the hexosone and glycollic glgoxylic and oxalic acids as the oxidation products.These anthors have also stated that erytbronic (trihydroxybutyric) acid is formed from dextrose and laevulose. On repeating these experiments erythronic acid could not be obtained but it is regarded as probable that a ketonic acid or a mixture of ketonic acids containing four carbon atoms irJ produced. Formic carbonic and oxalic acids were isolated. It is considered that the large quantity of oxaiic acid (18-27%) produced is due to a direct OH ?H hydrolysis of polyhexosones such as CHO*CO*CO*C-C*CH,OH h l i eH li and CHO*CO*CO*CO*C*CH,OH formed as the first products of the oxidation. E. G. Mechanism of the Oxidation of Dextrose by Bromine. HERBERT H. BUNZEL (J. Biol. Cliem. 1910 7 157-169.Compare Bunzel and Mathews Abstr. 1909 i 289).-Experiments have been made on the oxidation of dextrose with bromine in the presence of dilute sulphuric acid (0.1N). The equation used for calculating K was R= l / t ( a - x)log.nnt.b(a - ~ ) / a ( b - x) where a and 6 are the respec- tive concentrations of the active bromine and sugar at the start and n the amount of sugar and bromine used up during the time t . This equation gave constant values for K when sodium bromide was added so that the concentration of the Br ions was 0.3N in the final mixture ; as the bromine in these experiments was only O*OlN the slight increase in the concentration of the Br ions during the reaction was negligible. When no sodiuni bromide was added K was calculated from the equation R= t - - b(a -x) log- a(b - x) 1 0.05 (a - b ) (a - b) HBrt - HBrt 2 - Br 0.5 + Br (at start) + Titrations of the acid formed during the reaction indicate that for each molecule of bromine used up a molecule of gluconic acid is formed. Of the total acidity produced during the reaction it was shown that two-thirds are due to hydrobromic acid and one-third to organic acid (gluconic acid). The results agree with the view expressed previously that dextrose in aqueous solution can ionise in two different ways.J. J. S.ORGANIC CHEMISTRY I. 223 The Contraction Occurring when Sucrose is Dissolved in Water and the Density of Sucrose. A. D~MICHEL (Bull. h O C . chinz. Sucr. Dist. 1910 27 753-755. Compare Abstr. 1909 ii 795 ; this vol. i 96).-The author calculates the density of sucrose to be 1.581 using for this purpose the tables published by Buisson and he shows that the contraction taking place when sucrose is dissolved in water may be calculated when the densities of the sucrose of the water of the sucrose solution and the amount of sucrose in the latter are known.He shpws that thereis alwaysa contraction and never an expansion. w. P. s. Contraction Occurring during Solution and the Law of Gubritsch. A. D~MICHEL (Bull. Assoc. chim. Smr. Dist. 1910 27 755-757).-The contraction taking place when sucrose is dissolved may be measured by differences in density but the author considers that it is more rational to express the contraction as a difference in volume and gives formulz for thus calculating the contraction. The law of Guhritsch only allows a more or less imperfect approximation of the contraction to be obtained even in cases where the concentration is such that the phenomenon is most appreciable.w. P. s. Change of Rotation of Sucrose in Presence of Alkaline Uraa yl Salt Solutions. HERMANN GROSSMANN and B. ROTHGIESSER (Ber. 1910 43 676-682. Compare Abstr. 1906 ii 61).-Sucrose is slowly changed into lzvorotatory compounds by the action of uranyl nitrate and sodium hydroxide. Variations in the relative proportions and concentration of sucrose uranyl nitrate and alkali are of the greatest influence on the character of the change and on the end point of the reaction. Using 1 mol. of sucrose to 1 mol. of nitrate the initial rotation is twice that of sucrose ; it falls gradually to a negative value. With 2 mols.of nitrate and 15 mols. of sodium hydroxide to 1 mol. of sucrose the initial rotation is nil and the final reading - 126.7". The change is due to the slow hydrolysis of the many complex salts in solution in accordance with the scheme C,2H,00Q(0*Ur02*ONa)2 + 2H,O Z C,,H200Q(O* UrO,*OH) + 2NaOH C,,H2,0,,,(0*Ur0,*0N a) + H,O Z C12H210,,(0*Ur0,*OH) + NaOH. The complex salts are probably strongly dextrorotatory but their products of hydrolysis are highly laevorotatory. Hence an increase in the amount of water displaces equilibrium in favour of the right-hand equation whilst concentrated sodium hydroxide favours the reverse change. E. F. A. Configuration of Rhodeose. EMIL VOTO~EE (Ber. 1910 43 469-475).-Polemical. Rhodeose is the mirror image of fucose and the configuration is established by the behaviour of rhodeitol towards sorbose bacteria and by the oxidation of rhodeonic acid to I-trihydroxy- glutaric acid (Votokk Abstr.1906 i 378 483). The configuration of fucose was accordingly established in 1906 (compare M a p and Tollens Abstr. 1907 i 588). E. F. A.i. 224 ABSTRACTS OF CHEMICAL PAPERS. Additive Products of Hydrogen Cyanide with Rhodeose. CYRILL KRAUTZ (Ber. 1910 43 482-488. Compare Votofiek pre- ceding abstract).-By the addition of hydrogen cyanide to rhodeose and hydrolysis two isomeric rhodeohexonamides are formed the a-isomeride forms large colourless prisms m. p. 206' ; the /3-isomeride is amorphous m. p. 197-198'. On hydrolysis with barium hydroxide the barium salts of the isomeric rhodeohexonic acids are obtained; that from the a-amide has [a] + 6-88' and from the P-amide [a]E - 1.49'.a-Rhodeohexonic acid is rapidly converted into the lactone and shows [a32 - 30.25' in solution. The salts are amorphous and deliquescent with theqexception of the barium and lead compounds. P-Rhodeohexmic acid gives [u] - 44.25' in solution; the salts are similar t o those of the a-isomeride. The lactone of the a-acid separates in large well-formed prisms of sweet taste and neutral reaction m. p. 129-131' [a] - 34.8'. The lactone of the P-acid reacts faintly acid tastes sweet m. p. 115' [a] - 40.6O. The a-phenylhydrazide crystal- lises in lustrous silver plates m. p. 231' (decomp.); the /3-phenyl- hydraxi& is a glistening yellow compound m.p. 211' (decomp.). The lactones on reduction with sodium amalgam in faintly acid solution at - 5' form the corresponding rhodeohexoses. a-Rhodeo- hexose is a microcrystalline substance m. p. 125-126' [u] + 11.96' ; /3-rhodeohexose is amorphous. The following derivatives were prepared by the usual methods from a-rhodeohexose The phenylhydrazone forms yellow plates m. p. 150' ; the p-bromophenylhydraxone is a colourless powder m. p. 173' ; the phenylmethylhydrazone forms colourless plates m. p. 188' ; the phenylosazorne separates in golden-yellow needles m. p. 231' ; the p- bromophenylosazone is similar m. p. 2'1 9'. Of P-rhodeohexose the phenylhydvax'one crystallises in colourless plates m. p. 131-137' ; the p-bromophenylhydrazone is colourless m. p. 145' ; the phenylmethylhydracxolts forms silvery glistening tablets m.p. 163' ; the phenylosaxone is a citron-yellow powder m. p. 213' ; the p-6rornophenylosaxone is an orange-yellow powder m. p. 200'. a- and P-Rhodeohexone lactones are mutually interconvertible when heated in aqueous solution with pyridine at 1 5 0 O . E. F. A Acetylation of Cotton Cellulose. CARL G. SCHWALBE (Zeitsch. angew. Chem. 1910 23,433-441).-A rdsum6 of the different methods of acetylation of cellulose is given. Mork Little and Walker (Amer. Pat. '709922) use aromatic sulphonic acids instead of mineral acids as catalysts. The author's experiments point to the fact that phenol- sulphonic acid acts as a catalyst in the acetylation of cellulose owing to the fact that free sulphuric acid is formed during the reaction.The addition of sodium phenolsulphonate t o the mixture does not get rid of the free sulphuric acid as the reaction between the sodium salt and sulphuric acid is slow. In commercial specimens of phenolsulphonic acid appreciable amounts of sulphuric acid are always present but even when the pure sulphonic acid is used with pure acetic anhydride and cellulose the presence of sulphuric acid can be detected after some little time. I f barium phenolsulphonate is added to the mixture the acetylation requires a much longer time owing to the removal ofORGANIC CHEMISTRY. i. 225 most of the sulphuric acid as insoluble barium sulphate. The addition of sulphates for example ferrous sulphate dimethylamine sulphate and sulphates derived from feeble bases to acetic anhydride has also been recommended and in these cases also the catalytic action is due to the liberation of small amounts of free sulphuric acid.Various specimens of acetylcellulose have been prepared by Bayer’B method (D.R.-P. 159524) and by Lederer’s method (D.R.-P. 163316). The products have been hydrolysed by 25% aqueous potassium hydroxide solution at the ordinary temperature during forty-eight hours and the reducing powers of the products of hydrolysis deter- mined by means of boiling alkaline copper solution. After allowing for the reducing properties of the original cellulose and of the hydrated cellulose formed by the action of acids and alkalis on the cellulose (Normann Abstr. 1906 i 560) a mean copper value of four was obtained. This is due to the formation of hydrocelluloses and the conclusion is drawn that the processes of Bayer and of Lederer are identical as regards their chemical mechanism.Fixation of Bases by Soluble Starch. EUG~NE FOUARD (Bull. SOC. chim. Belg. 1910 24 105-109).-1t is pointed out that there is no actual difference between the author’s interpretation of his results (Abstr. 1909 i 13 209 699) and that given by Reychler (Abstr. 1909 ii 977). The action of bases appears to be to disintegrate the complex starch molecules with the formation of a simple group (C6Hl0O5)’ which then reacts with the base so that in the reversible reaction disintegration and re-formation of complex molecules occur. T. A. EL CARL NEUBERG and SIEGBERT LACHMANN (Biochem. Zeitsch. 1910 24 171-177).-Stachyose is only attacked very slowly by emulsin.It readily undergoes hydrolysis however when treated with yeast maltase and kephir lactase yielding laevulose and manniao- triose. The last-named trisaccharide was obtained in the form of its osazone which melts at 192-194’ and not at 122O the melting point given by Tanret for the mannotrisaccharideosazone prepared by him from stachyose. The authors also give their method of preparation of stachyose from the bulbs of Stachys tub$era. S. B. S . A. BACKE (Compt. r e d . 1910 150 540-543).-Baked bread and biscuits contain traces of a crystalline compound m. p. 953 which resembles in some respects Brandt’s maltol and shows many of the reactions of salicylic acid. It differs from the latter in its behaviour in Zipper’s and Jorrisen’s reactions and in undergoing decomposition when heated with sodium hydroxide. With traces of ferric chloride it develops a red coloration becoming violet on adding a larger quantity of the reagent.The substance is isolated by treating bread with sulphuric or phosphoric acid distilling in steam and extracting the distillate with ether. It appears to be formed together with maltol when many sugars and starchy materials are acted on by an unknown enzyme and then heated at 120-150°. The enzyme necessary to its formation occurs J. J. S. Stachyose. New Compound Contained in Foods. together with amylase in flour and malt. w. 0. w.i. 226 ABSTRACTS OF CEEMICAL PAPERS. Preparationof Choline and Some of it8 Salts. ROEMERR. RENSHAW (J. Amer. Chem. Xoc. 1910 32 128-130).-Choline hydro- chloride can be obtained in nearly quantitative yield by passing a current of dry trimethylamine into freshly distilled anhydrous ethylene chlorohydrin at - 12' to -.20° contained in a tube which is afterwards sealed and heated for two hours at 80-90'.The salt can be purified by adding ether to an alcoholic solution. Choline acetate suZphatte and dihydrogen phosphate are described. E. G. Derivatives of Amino-acids. I. Compounds with Glycerol. EMIL ABDERHALDEN and MARKUS GUGGENHEIM (Zeitsch. physiol. Chem. 1910 65 53-60).-The authors have attempted to prepare derivatives of amino-acids with various aliphatic and aromatic com- pounds including glycerol in order to examine the behaviour of such compounds under the conditions which exist in the complete hydrolysis of proteins.It has not been found possible to condense glycine or tyrosine with glycerol in the presence of dry hydrogen chloride at 185O or glycerol- sulphuric acid with glycine at 100'. Silver glycine and silver alanine do not react with the monohalohydrins of glycerol. Glycerolsulphuric acid however condenses with halogenated acyl chlorides. obtained from bromoisovaleric acid sulphuric acid and glycerol at 70-80' (compare Grun Abstr. 1905 i 562; 1907 i 462 464) is a thin colourleswoil with a bitter taste b. p. 185-200'/0*3 mm. Treatment with aqueous alcoholic or liquid ammonia leads t o decomposition of the ester and formation of a halogenated acid amide. Glycine chloride does not appear Go react with the sodium deriva- tives of glycerol or yet with dipalmitin in the presence of chloroform but bromoisovaleryl bromide reacts with dipalmitin at 1 O O O yielding glyce~yl bromoisovalerate dipalmitate C~,H,Br*CO~O~CH(CH,*O*CO*C1,H,l) which crystallises in microscopic needles ; it melts at 51' to a turbid liquid which clarifies at 60'.Tyrosine derivatives of glycerol are readily prepared but are very sparingly soluble and difficult to purify. Glycerolmonotyrosine Bis brornoisovuZer ylg Z y cerol OH CH( C H,*O*CO C,H,Br) OH*CH,*CH(OH) CH,*O* C,H,*CH,*CH(NH,)*CO,H obtained by the action of glyceryl-a-monochlorohydrin on freshly pre- pared sodium tyrosinate forms colourless needles m. p. 245' (uncorr. decomp.) and is optically inactive. It is not hjdrolysed when boiled for six hours with fuming hydrochloric acid.Derivatives of Amino-acids. 11. Compounds with Aliphatic Acids. EVIL ABDERHALUEN and CASIMIR PUNK (Zeitsch. physiol. Chem. 1910 f% 61-68. Compare Bondi Abstr. 1909 i 458 ; Bondi and Frankl ibid. 459).-The authors object to the name lipopeptide for the condensation products of acyl chlorides with amino- acids; the name should be reserved for compounds containing a free amino-group. Pdmit ylglycine CH,*[ CH,] 1,*CO*NH*CH2 CO,H obtained by the J. J. S.ORGANIC CHLMISTRk'. i. 227 action of palmityl chloride on glycine in the presence of dilute sodium hydroxide solution crystallises in slender needles m. p. 125' (cow.) after sintering at 119". The corresponding ethyl ester C,,H39O,N also crystallises in needles has m. p. 80-85' and on hydrolysis yields palmity lg ly cine.PnZmityl-d-danine CH,*[CH,],,*CO*NH-CHMe*CO,H has m. p. llOo after sintering at 105' and la12 - 5.98'. Palrnityl-1-tyrosine CH,* [ CH2]14* CO*NH*CH( CO,H)* CH,*C,H,*OH crystallises in plates m. p. 133' after sintering at 120° and [a] -+ 24-35". PalmityZ-1-tyrosinyl palmitate C,,H,,*CO-NH*CH(CO,H) *CH,*C6H,*O*CO*Cl,H3 forms colourless needles m. p. 95-96O after sintering at 87" [a] + 15.28'. Palrnityl-3 5-di-iodo-1-tyrosinyl pahitate C,,H,1~CO*NH~CH(C0,H)*CJ32*U6H2~2~O*CO* C15H31y forms microscopic needles sinters at 50° melts at 55' and forms a clear liquid at 62'. Stearyllglycine C17H3,*CO*NH*CH2*C0,H crystallises in plates 'm. p. 155" after sintering at 145'. crystallises in needles m. p. 105-108' [.I$' - 4.55'. Stearyl-d-alanine C11~35*C0.NH*CHMe*C0,H Stear y l -1-t yrosiny I stmrate C,7H3,*CO*NH*CH(C0,H).CH,.C,H,.0.C0.C,p35 forms slender needles it sinters at SSO melts at 98' to a turbid liquid and becomes quite clear at 108".Palmityl-dl -phenylalanine palmityl-dZ-leucine stear y 1-d-glutamic acid palmitylcystine and palmityl-Z-tryptophan have also been prepared. It is difficult to obtain the tyrosine compounds in a state of purity. J. J. S. Synthesis of dl-Arginine (a-Amino-8-guanino-12-valerio Acid) and of the Isomeric a-Guanino-6-amino-n-vderio Acid. SOBEN P. L. SOBENSEN (Ber. 1910 43,643-651).-The proof that d-2-arginine is a-amino- 8-guanino-n-valeric acid has been established by condensing cyanamide with a-benzoylornithine to a-benzoylamino-6- guaninw-valeric acid and subsequent hydrolysis with hydrochloric acid when a product identical with d-1-arginine is obtained.The isomeric 6-amino-a-gusnino-m-valeric acid can by obtained in a similar manner from 6-benzoylornithine. A 75% yield of 6-benzoylornithine is obtained when ornithuric acid is boiled with hydrochloric acid and a 52% yield of the isomeric u-bemxoylornithine NH2*[CH2],- CH( CO,H)*NH*COPh is obtained when ornithuric acid is boiled with barium hydroxide solution. The a-compound forms long thin crystals m. p. 264-267' ia some three to four times as soluble in water as the &compound and does not crystallise so readily. The &compound (Fischer Ber. 1901 34 463) has m. p. 286-288'. The constitution of the two benzoyl derivatives has been established by replacing the amino-groups by hydroxyl.a-Benzoylamino-6-hydroxyvalerio acid (Abstr. 1908 i 651) has m. p. 160' (not 170"). C,H,= CO*NH*[ CH,],*CH( OH) CO,H The 8-benaoylccmino-a-hydroxyualeric acid,i. 228 ABSTRACTS OF CHEMICAL PAPERS. is readily soluble in water crystallises from benzene in needles m. p. 85' yields a sparingly soluble buriurn salt and when hydrolysed yields Fischer and Zemplen's 6-amino-a-hydroxyvaleric acid (this vol. i NH,*C( NH)*NH* [ CH,!,*CH( CO,H)-NH*COPh obtained together with dicyanodiamide and barium carbonate by leaving a-benzoylornithine and cyanamide in contact with 0.4M- barium hydroxide solution for a month crystallises in well developed four- and six-sided plates and also in stout prisms m. p. 315' (decomp.). 100). a- Benzoylarnino-Gguanino-n-valeric a d 8-Benxoplamino-a-gwanino-n-uale?$c acid COPh*NH*[CH,];CH(CO,H) >NH*C( :N€€)*NH obtained in a similar manner from &benzoylornithine forms a curdy mass of minute needles containing 3H2O.When anhydrous it has m. p. 175-180". J. J. S. Synthesis of Glycylaminoacetaldehyd e. CARL D . HARRIES and IRNFRIED PETERSEN (Ber. 1910 43 634-639).-PoIypeptides obtained from amino-acids and amino-aldehydes are termed peptacls the simplest representative being glycylaminoucetalde~y~ NH,*CH,*CO*NH* CH,*CHO. This aldehyde has been synthesised by the two following methods 1. Glycylallylamine obtained by the action of ammonia on the con- densation product of allylamine and chloroacetyl chloride is readily oxidised in the form of its hydrochloride to glycylaminoacetaldehyde by means of ozoze (compare Harries and Richard Abstr.1904 i 295). 2. Glycylaminoacetal obtained by the action of ammonia on the condensation product of cbloroacetyl chloride and aminoacetal is h ydrolyaed by hydrochloric acid to glycylaminoacetaldehyde. The aldehyde has so far not been obtained pure but merely in the form of a syrup with strongly reducing properties. Chloroacetylacllyla~~ne CH,Cl*CO*NH*CH,*CH:CH is a colourless syrupy liquid b. p. 110-112'/14 mm. and solidifies in a freezing mixture ; it has Di:: 1.1683 and ng'5 1.48917. Glycylallylamine NH2*CH,*CO*NH*CH,*CH:CH is a colourless oil b. p. 85-9 lo/ 0*19 mm. D$ 1.0532 and ng 1.49585. It absorbs carbon dioxide rapidly and forms a picrate CIlHl3O8N5 m. p. 136-138O. The 6enxogZ derivative C1,H1402N2 crystallises in plates m.p. 138O. If liquid ammonia is used instead of an aqueous solution for replacing the chlorine in chloroacetylallylamine a by-product is obtained which has b. p. 187O/0.19 mm. ; it is probably iminodiucetycldiacllyl~m~ne NH( CH,*CO*NH*CH,*CH:CEI,),. Chloroacetylaminoacetal CH,Cl*CO*NH*CH,*CH(OEt) has b. p. 80-85°/0.1 4 mm. and solidifies to a colourless crystalline mass m. p. 29-30'. Glycyluminoacetal N H,*CH,*CO*NH*CH,*CH(OEt) has b. p. 107-110°/0~14 mm. and m. p. 42-45O and yields a colourless crystalline hydrochloride C8H1,03N2 HCI. The acetal is readily hydrolysed by cold dilute hydrochloric acid. J. J. S.ORGANIC CHEMISTRY. i. 229 Preparation of Nitrogen Derivatives of Formaldehydesulph- oxylic Acid. CHEMISCHE FABBIK VON FRIEDR.HEYDEN (D.R.-P. 216074).-The reduction of sodium arni~~o~ethylsulphite NH,( CH,=O*SO,Na) sodium iminodimethylsulphite NH(CH,*O*SO,Na) and of sodium nitrilotrirnethylsulphite N(CH,=O*SO,Na) with zinc at 60-70' in either acid or ammonium hydroxide solution yields respectively sodium amiqaometh y Zsu Zphoxy late N H2( CH2* 0 SONa) sodium irninodimeth y Z- sulphoxylate NH(CH2*O*SONa)2 and sodium ?ziti.ilotrimethyZsecZpr2- o q l a t e N( CH,-O SONa),. The relative proportion of indigotin reduced by these substances is stated in the patent. Preparation of Nitrogen Derivatives of Aldeb yde Bisulphites. CHEMISCHE PABRIK VON FRIEDR. HEYDEN (D.R.-P. 216072).-Sodium iminodimethyZsulpllLite NH( CH,*O*SO,Na) is prepared by treating a solution of ammonium hydroxide with two molecular proportions of formaldehyde bisulphite solution at 4 5 O and evaporating under reduced pressure when the product separates as a colourless powder or as hard crystals. The ammonium hydroxide in the foregoing reaction can be replaced by other primary amines the resulting products being powerful reducing agents.Preparation of Nitrogen Derivatives of Aldehyde Bisulphites. CHEMISCHE FABRIK VON FRIEDR. HEYDEN (D.R.-P. 21 6073. Compare preceding abstract).-Sodium nitrilotrirnethylsulphite N( CH2*O*S02Na)3 3H,O separates as prismatic crystals when a solution containing three molecular proportions of formaldehyde bisulphite and one of ammonia is concentrated under reduced pressure ; it is readily soluble in water sparingly so in alcohol is decomposed by sodium hydroxide with evolution of ammonia and by mineral acids with elimination of sulphurous acid.Preparation of Nitrogen Derivatives of Formaldehyde- sulphoxylates. CHEMISCHE FABRIK YON FRIEDR. HEYDEN (D.R.-P. 2 161 2 l).-Sodium nitl.ilotrimethyZszcZphoxylate N( CH,*O*SONa) can be prepared by reducing sodium nitrilotrimethylsulphite N(CH2*O*S0,Na) with zinc in either acid or ammonium hydroxide solution and subse- quently concentrating in a vacuum ; it is a colourless resinous mass very readily soluble in water insoluble in anhydrous solvents and reduces indigo-carmine rapidly in the cold. The zinc salt is a powerful reducing agent ; the calcium salt is somewhat sparingly soluble in sodium chloride solution. 5-Amino-ketones. 11. SIEGMUND GABRIEL (Uer. 1910 43 356-362.Compare Abstr. 1909 i 801).-Methyl I-aminohexyl ketoue the benxenesulphonyl derivative of which has m. p. 77-78" is reduced by sodium and alcohol to q-hydroxyoctylamine which forms a hydrochloride OH-CHMe*[CH,],*NH,,HCl m. p. above SO" a platini- chloride m. p. 2 0 1 O (decomp.) and is converted by concentrated hydrochloric acid at looo into q-chloro-octylamine which forms a F. M. 0. M. F. M. GF. M. F. M. G. M. F. M. 0. M. VOL. XCVIII. i. Ti. 230 ABSTRACTS OF CHEMICAL PAPERS. platilzichloride darkening at 206O and decomposing at 210'. A by- product of the reduction is a substance C,H,,N which appears t o be a saturated secondary base and is possibly 2-methylheptametbylene- imine ; i t forms a hydrochloride m. p. 148-149' platinichloride m. p. 153-155O aurichloridc m.p. 67-68" picmte m. p. 152-153' and a benzenesulphonyl derivative C,H,,N*SO,Ph m. p. 114-1 15O which is insoluble in alkalis. c. s. Partial Inversion of Optical Antipodes. CSCAR LUTZ (Zeitsch. physikat. Chem 1910 70 256- 262) -In the coiirse of his investiga- tions on t h e Walden inversion Fisvher (compare Fischer and Raske Abstr. 1907 i 381) has shown that the occurrence of inversion depends on the pature of the substance acted on as well as on that of the reagent. The author has already shown (compare Abstr. 1908 i 345) that by the action of dibenzylainine on l-bramosuccinic acid both a malnmic acid and an aspartic acid are produced ; the former action proceeds normally the latter abnormally. It is ncw shown that a similar partial inversion occurs when methylamine acts on Z-bromo- succinic acid. The reacting substances were brought together in a mixture of methyl alcohol and water; the mixture was kept for a week at the ordirary temperature and was then heated on the water-bath.The products d-P-methylmalamic acid and Z-methylaspartic acid were separated by fractional crystnllisation of the silver salts. The former acid has [a] + 13 0'. The latter acid crystallises with lff,O melts a t 183-184' and forms a salt with one molecule of hydrogen chloride. Its optical behaviour does not correspond with that of aspnrtic acid. I n aqueous solution methylaspartic acid in the presence of varying propoitions of hydrochloric acid gave values of [.ID between - 22 6' and - 30.8"; in the presence of alkali (5 C.C. of N/l-sodium hydroxide added to 0 1105 gram of the anhydrous salt and the solution made up to 20 c.c.) [a] - 29.8".As this acid has not so far been brouglit into simple relationship with the opt ically active malic acids its configura- Glutamic Acid and Pyrrolidinecarboxylic Acid. EMIL ABDERHALDEN and KARL KAUTZSCII (Zeitsch. physiol. Chem. 1 9 10 64 447-459).-As a preliminary to a study of the importance of these substances in metabolism especially i n bRmoglobin formation a number of salts were prepared and their properties investigated. Monobasic sodium glutamate C H804NNa a cry st alline hygroscopic salt containing 2% water of crystallisstion m. p. 160-170'. Mono- basic calcium glutanaccte (C,H804N),Ca amorphous. Monobahic barium glufamate hygro-copic crystallisable from dilute alcohol.Dibasic copper glutamate C H70,NCu,$H,0 amorphdus greenish- blue. Potassium glutamate C,H,O,NK. Monobasic kccd glutccnzccte (C,H,O,N),Pb hygroscopic. Attempts were also made to prepare iron salts but with indifferent results. Pyrrolidinecarboxylic acid was prepared by heating glutamic acid at 180-190'. It has m. p. 182-184' (cow.) [a]$ +7*29'. After tion is not regarded as being conclusively established. (2 s.ORGANIC CHEMISTRY i. 231 treatment with hydrochloric acid gas a crystalline substance was obtained with the m. p. of glutamic acid hydrochloride. The ~caZcium salt (C,€€,03N),Ca was prepared ; it is crystalline and hygroscopic. The monobasic cnlcizcm aspartate ( C4H405N),Ca and the dibasic copper aspartate were also prepared.W. D. H. Decomposition of Metallic Cyanates by Water. ORME MASSON and IRVINE MASSON (Zeitsch. phpsika2. Chern. 19 10 70 290-314).-The rate of decomposition of the metallic cyanates by water was followed by estimating both the carbonate and unaltered cyanate after heating for definite intervals. The carbonate if not already precipitated in the course of the reaction was thrown down by excess of barium nitrate the precipitate washed and estimated volumetrically. The cyanate remaining in solution was precipitated by a known excess of silver nitrate washed and the unprecipitated silver determined by Volhard's method. All the measurements were made at 80'. The cyanates of metals forming insoluble carbonates (for example barium and calcium) are decomposed by water in accordance with the equation M(CNO) + 2H,O = MCO + CO(NH2)2.The change consists of two consecutive reactions (1) a slow reaction representing the hydrolysis of CNO' ions which immediately yield insoluble carbonate and NH,' ions ; (2) the reaction of the NH4* ions with CNO' ions to form carbamide. As the second action is relatively rapid the NH,' ions are kept a t a very small constant concentration. No appreciable effect is produced by the reverse decomposition of carbamide even if some excess of the latter is added at the outset. The cyanates of sodium and potassium are decomposed by water according to the equation 4MCNO + 6H20 = 2M2C03 + (NH,),C03 t CO(NH2) and the ratio of the products thus indicated persists for the whole course of the reaction after a short initial stage.The products of the reaction more particularly the ammonium carbonate accelerate the reaction and if initially added in proportions other than that in which they are produced in the reaction they alter the relative proportion of the products. Excess of ammonium carbonate tends to increase the carbamide formation relatively to that of ammonium carbonate whilst excess of metallic carbonate has the converse effect so that the action is automatically regulated in the direction of the normal ratio. G. S. Fulminic Acid. LOTHAH WOHLER (Ber. 1910,43 754-756).- Polerriical against the historical accuracy of a monograph by Wieland on fulminic acid (Ahrsnsche Samirdung Vol. XIV Xos. 11 a i d 12). T. S. Y. Dicyanodiamidine Compounds. HERMANN GROSSMANN and B.SCH~CK (Uer. 1910 43 674-676. Compare Sol1 and Stutzer this vol. i 14).-Commercial dicyanodiamidine sulphate contains no other organic compound as impurity and may be used for the quantitative estimation of nickel. r 2i. 232 ABSTRACTS OF CHEMICAL PAPERS. Dicyanodiamidiniuna platinichloi-ide (C,H,ON,),PtCl is a yellow crystalline substance. Palladiunadicycod~a~~~ine Pd( C,H,0N,),,2H20 is obtained as a yollow crystalline almost insoluble precipitate on mixing dicyano- diamidine sulphate with palladium chloride and potassium hydroxide. It is soluble in ammonia. E. F. A. Molybdenum Cyanides. ARTHUR ROSENHEIM (Zeitsch. anorg. Chem. 1910 66 95-96).-The doubled formula suggested by Kosenheim Garfunkel and Kohn (this vol. i 101) for potassium molybdenum cyanide must be abandoned. Miolati points out that No2”(CN) requires just as much oxygen to convert it into molybdic acid as 2hl0~~(CN) as MO,~(OH) must first be converted into ITO,~~(OH), or ~ M O ~ ( O H ) ~ and then into 3MoV1(OH),.R. Weinland suggests the formula K4MoV(OH)(CN),aq. which is possibly correct. C. H. D. Aliphatic Diazo-salts KARL A. HOFMANN and RUDOLF ROTH (Ber. 1910 43 682-688. Compare Abstr. 1906 i 907).-Amino- guanidine dinitrate when diazotised in aqueous solution a t 0” with sodium nitrite forma ccnainoguanidine diazohydroxide C,H7N,,*OH. This is obtained as a colourless crystalline powder composed of microscopic transparent pointed prisms. It explodes when struck or when heated at 135-140O. It behaves as a diazo-compound; when boiled with water 3 atoms of nitrogen are eliminated; 15% sulphuric acid liberates 2 atoms.A fourth nitrogen atom is concerned in the formation of aminotetrazolic acid when the diazohydroxide is boiled with water. The diazohydroxide does not form a hydrazine and yields 4 molecules of ammonia when evaporated with concentrated potassium hydroxide showing that the amino- and imino-groups of the aminoguanidine molecule remain intact Tho chloride C,H,N,,*Cl is obtained in colourless silky lustrous prisms or needles and explodes a t 140’. When boiled iu water between 3 and 4 atoms of nitrogen are liberated. Water eliminates hydrogen chloride indicating that the salt is not of the basic type of the aromatic diazonium salts but belongs to the group of thediazhydroxides N:N-OH. The chloride couples slowly with aromatic amines ; a-naphthylamine shows a deep red solution ; P-naphthylamine and m-phenylenediamine give a brownish-red-yellow coloration.Both hydroxide and chloride when heated with resorcinol and sulphuric acid shorn an intense violet coloration which becomes red with a red fluorescence on the addition of excess of ammonia. 1 he perchlorate forms colourless clear prisms of very explosive nature. The nitrate crystallises in minute doubly refractive needles; it is less easily exploded. The sulphccte is a fine colourless powder. The diazohydroxide also combines with bases ; with sodium hydroxide After evaporation on the water- Excess I 1 It is completely hydrolysed by cold water. it forms an almost colourless solution. bath and the addition of acid the product can still be coupled.ORGANIC CHEMISTRY.i. 233 of silver nitrate causes a precipitate; from the ammoniacal solution the silver salt separates in lustrous centrically-arranged snow-like crystals which are very explosive. A copper salt is more stable. E. F. A. Preparation and Decomposition of the Oximino-derivative of Ethyl Malonylbishydrazoneacetoacetate. CARL BULOW and CARL BOZENHARDT (Bey. 1910 43 551-563. Compare Abstr. 1908 i 253 ; this vol. i 102).-When ethyl malonylbishydi~azone- acetoacetate reacts with nitrous acid only two of the three reactive methylene groups take part namely the two terminal groups and the product obtained is the dioximino-derivative CH2[ CO*NH*N:CMe*C( C0,Et) N-OH],. A better yield of the same compound can be obtained by the con- densation of V.Meyer's ethyl oximinoacetoacetate (Abstr. 1878 487) with malonyldihydrazide. When an excess of nitrous gases is led into a chloroform solution of ethyl malonylbishydrazoneacetoacetate a molecule of ethyl osimino- acetoacetate is eliminated and the bisoximino-derivative of malonyl- hydrazoneacetoacetic acid 0H.N :C( C0,H) CMe N*NH*CO*C( C0,H) N *OH is formed according to the equation CE-I,CCO*NH*N:C~e*CH,*CO,'Et] + 3HN02 = EtOH + N,H + COAle*C( W*OH)*CO,Et + Ethyl oxinLinomaZon?llbishydraxoneoxin~inoacetoacetate CH [ CO9NH.N :C Me*C( :N* OH) CO,Et] crystallises in needles with a nacreous lustre and has m. p. 200-201°. When boiled for some sixty hours with pure alcohol it yields malonic acid and the hydrazone of ethyl oximinoncetoacetate which is immediately transformed into 4-oximino-3-methyl-5-pyrazolone (com- pare Knorr Abstr.1903 i 6 6 0 ; Betti Abstr. 1904 i 5 3 3 ; Wolff ibid. 722; Biilow and Schaub Abstr. 1908 i 687). The same decomposition can be effected by sulphuric acid sodium hydroxide solution or ammonium hydroxide whereas phenylhydrazine reacts with it yielding hydroxylamine malonic acid and 4-anilinoazo- 1 -phenyl- 3-rnethyl-5-pyraxolone C,,H,,ON m. p. 154-1 55". Attempts have been made to synthesise ethyl oximinomalonyl- hydrazoneoximinoacetate from malonamidehydraxide NH,.CO*CH,=CO.NH*NH which can be obtained by the action of hydrazine hydrate on an alcoholic solution of ethyl malonnmate (Pinner and Oppenheiiner Ber. 1895 28 478). The hydrazide crystallises in glistening needles resembling urea and has m.p. 126-127'. Ethyl acetoacetate con- denses with the hydrazide at 40' in the presence of a few drops of water yielding ethyl malonamidehydvaxoneacetoacetate NH,*CO*CH,*CO*NH*N CMe* CH,*CO,Et which crystallises in colourless felted needles m. p. 118.5'. It decomposes at 160° solidifies again at 1 6 2 O and then melts at 190-192O to a yellow liquid. It reacts with nityous acid yielding OH*N:C( CO,H)*CMe N*NH*CO*C( CO,H):N* OH.i. 234 ABSTRACTS OF CHEMICAL PAPERS. ethyl oximinoacetoncetate according to the equation NH,*C'O*C~R,*CO*NH*lS :CMe*CH,*CO,Et + 5HN02 = COMe*C( :NOH)*CO,Et + 5N + NO + 5H,O + 2C0 + HCN J. J. S. Amphoteric Nature of Cacodylic Acid. BROR HOLMBERG (Zeitscl'. physihl. Chern. 1910 70 153-157).-Hantzsch and others regard cacodylic acid as an ordinary weak acid whilst Johnston (Abstr.1904 i 9S4) has brought forward evidence t o show that it is an amphoteric electrolyte. In order to settle the question the author has determined the KO-ion concentration by the diaeoacetic ester method in mixtures of the acid with picric acid and nitric acid respectively and also in aqueous solutions of the acid itself. The results confirm the view of Johnston that cacodylic acid is an ampho- teric electrolyte; the value of k is about 7.5 x 10-7 and that of k b about 5.6 x 10-13 at 25'. Bromination with Aqueous Hypobromous Acid. OTTO STARK (Ber. 1910 43 670-674)- The use of hypobromous acid prepared by digesting bromine and water with excess of powdered mercuric oxide in the form of a straw-yellow solution containing about 6.2% of bromine is suggested as a brominating agent.It suffices to shake this in the cold with benzene toluene or benzoic acid to obtain satisfactory yields of monobromobenzene o- and p-bromotoluene and m-bromobenzoic acid. Aniline yields tri- bromoaniline ; phenol gives tri bromophenol under similar conditions ; nitrobenzene resists bromination as also does phthalic acid. G. S. New Method of Bromination. E. F. A. Compounds of Aluminium Chloride with Nitro-compou nds of Benzene Hydrocarbons and their Derivatives. BORIS N. MENSCHUTKIN (J. Russ. Phps. Chem. SOC. 1910 42 58-94).-Tbe author has investigated the freezing-point diagrams of the systems formed by aluminium chloride with nitrobenzene and with each of the three chloronitrobenzenes bromonitrobenzenes and nitrotoluenes.The m.p.'s of tbe compounds formed the two eutectic points and the compositions corresponding with them are compared with the corre- sponding data €or the systems with aluminium chloride (Abstr. 1909 i 900). h'itrobenzene forms the two compounds (1) AlCI,,C,H,*NO ; and (2) A1CI,,2C6H,*N02 which crystallises in almost colourless hygro- scopic rhombic plates m. p. 2 5 % O (decomp.). 0- m- and p-Chloronitrobenzenes form compounds of the type A1c13,CGH,C1*NOT having m. p.'s 89O 1 0 4 O and 126' respectively. With the bromonitrobenzenes compounds of the type AlCl,,C6H,Br*N02 are formed the m. p.'s being looo 1 1 6 O and 145O respectively for the 0- m- and p-derivatives. 0- and m-Nitrotoluenes form compounds of the two types (1) AIC13,CGH,Me*N0 both of which bave m.p. 99*5O and (2) AIC13,2C6H,Me*N0 decomposing a t 5 5 - 1 O and 35' respectively. p-Nitrotoluene gives only the compound A1CI,,C,H,Me*N02 rn. p. logo.ORGANIC CHEMISTRY. i. 235 Excepting in the case of m-bromonitrobenzene the compounds with aluminium chloride melt at higher temperatures than the corresponding compounds formed by the bromide. The first eutectic points and the compositions at these points differ only slightly for the two series of compounds ; in the case of the meta-derivatives the eutectic mixture always contains a larger proportion of the organic compound than with the corresponding ortho- or para-derivatives. The temperatures of the second eutectic points are considerably higher for the aluminium chloride than for the bromide systems although the m.p.'s of the two series of compounds exhibit only small differences. The proportions of organic compound to 1 mol. of aluminium chloride (or bromide) at the second eutectic point vary only slightly the mean value being 0.653 (or 0.484) mol. The stability of the aluminium chloride systems is i n general greater than that of the corresponding aluminium bromide systems but the solubility curves exhibit similar forms in the two cases. T. H. P. The Real State of Metastyrene and the Polymerisation of S t y r e n e by Light and Heat. HANS STOBBE and GEORG POSNJAK (Annulen 1910 371 259-286).-This investigation was undertaken owing to the contradictory nature of the statements of many investigators who have worked on this subject (compare Blyth and Hofmann Annalen 1845 53 289; Berthelot Bull.SOC. chim. 1866 [ii] 6 294; Krakau Ber. 1878 11 1260; Lemoine Abstr. 1898 i 70; 1900 i 91 ; Kronstein Abstr. 1903 i &I). Metastgrene is formed by the action of light or heat on styrene and is obtained as a white odourless amorphous substance by adding alcohol to a solution of the compound in benzene ; it does not produce an elevation of the b. p. of a solvent and is consequently to be regarded as a colloid. The substances described hitherto as meta- styrene are mixtures of this substance and styrene; thus the gelatinous variety is composed of equal parts of these substances whilst the vitreous modification contains about 20% of styrene. Metastyrene is quite indifferent towards bromine and potassium permanganate and' is undoubtedly a polymerisation product of styrene since it passes almost quantitatively into this hydrocarbon at about 320".The velocity with which styrene changes into metastyrene under the influence cf light and heat has been ascertained by comparison of the viscosity of the substance under observation with t h a t of mixtures of the two substances having a known composition. It is found that (1) the velocity of polymerisation increases with the time; (2) the reaction proceeds in the dark and without the application of heat after it has been started by the action of light and (3) freshly distilled styrene under identical conditions does not polgmerise so rapidly as a sample which has been kept in the dark for several days after distillation.W. H. G Liquid and Solid Distyrene. Ham STOBBE and GEORC POSKJAK (Annalen 1910 371 287-302).-Liquid distyrene which resultsi. 236 ABSTRACTS OF CHEMICAL PAPERS. from the action of hydrobroniic acid or 50% sulphuric acid on cinnamic acid (compare Erlenmeyer Annalen 1865,135 122 ; Erdmann Abstr. 1883 474) is shown to be ay-diphenyl-ha-butene whilst the crystalline distyrene obtained by the destructive distillation of calcium cinnamate (Engler and Leist Abstr. 1873 901) and p-truxillic acid (Liebermann Abstr. 1889 11 94) is as-diphenyl-Aa-butene. Both hydrocarbons yield benzaldehyde when oxidised with chromic acid ; the absorption spectra have also been measured and are represented graphically. ay-Diphenyl-Aa-butene combines with bromine forming up-dibrorno- ay-diphenylbutane m.p. 102" (compare Erdrnann loc. cit.) and when reduced with hydriodic acid and red phosphorus yields ay dipht?npZ- butane CH,Ph*CH,*CHMePh a pale yellow oil b. p. 295'. ap-Dibrorno-a6 diphenylbntane m. p. 338' (compare Liebermnnn Zoc. c i t . ) when reduced with alcohol and sodium amalgam yields as-diphenylbutane (compare Freund and Immerwahr Abstr. 1890 1407). py-Bibronao-py-diphenylbutane CMePhBr-CMePhBr was prepared for the purpose of comparison by treating acetophenonepinacone with acetyl bromide and subsequently with phosphorus pentabromide ; i t crystdliees in small slender silky needles m. p. 140-145' (decomp.). W. H. G. Triarylmethyls. 11. Triphenylmethyl and Analogues of Triphenylmethyl in the Diphenyl Series.WILHELN SCHLENK TOBIAS WEICKEL and ANNA HERZENSTEIN (Anizalen 1910 372 1-20. Compare Abstr. 1909 i 791).-TridiphenylnzethyZ (4 4' 4 - triphennyltrip7LenyLmethyE) C(C6H,Ph) has beeri prepared by the action of copper bronze (Naturkupfer C) on a solution of 4 4' 4"-triphenyl- triphenylmethyl chloride in benzene; it is a dark green crystalline powder m. p. 186' (in a sealed tube) solutions of which in organic solvents are deep violet although thin layers are green. Unlike triphenylmethyl solutions which have been decolorised by shaking with a small quantity of oxygen do not become coloured when kept ; this is due to the fact that from mo1.-wt. determinations tridiphenyl- methyl is present in solution only in the unimolecular coloured modification. Tridiphenylrnethyl combines rehdily with oxygen yielding the peroxide C74H5402 a white crystalline powder m.p. 198'. 4-Phennyltriphenylmethyl and 4 4'-dip~enyltriphenylmethyZ have been prepared by the same method but do not crystallise readily. The solution of the former in benzene is orange-red; it is decolorised by shaking with a small quantity of oxygen the peroxide C50113802 m. p. 180° being formed ; as in the case of triphenylmethyl the colour returns when the solution is kept for a short time. The solution of 4 4'-diphenylt1 iphenylmethyl in benzene is red and likewise contains the coloured and colourless modifications in a state of equilibrium but in this case the proportion of the latter is very small. 4-Pheny ltriphenylmethyl is converted by hydrogen chloride in benzene into 4-phenyl tripheny lmethane and 4-phenyi triphenylme t h yl chloride and in this respect diff ers from triphenylmethyl which under similar treatment has been shown to yield benzhydryltetra-ORGANIC CHEMISTRY. i.237 phenylmethane ; it is found however that small qnantities of triphenylmethane and triphenylmethyl chloride are also formed from triphenylmethyl. Solutions of 4 -phenyltriphenylmethyl chloride 4 4’-diphenyl- triphenylrnethyl chloride and 4 4‘ 4-triphenyltriphenylmethyl chloride in liquid sulphur dioxide are orange-red red and violet respectively ; the unaltered substances are obtained when the sulphur dioxide is allowed to evaporate except in the last case when the additive product (C6H,Ph),CC1,4SO is obtained in magenta-like crystals having an intense metallic lustre ; a similar additive compound is obtained with tridiphenylmethyl.It follows from these observations that the liquid sulphur dioxide does not function merely as a solvent and consequently the assumption that the electrical conductivity of solutions of triphenylmethyl in sulphur dioxide is due to negative and positive triphenylmethyl ions (compare Gomberg Abstr. 1907 i 504) is very improbable. It is shown however that triphenylmethyl chloride and bromide are dissociated in liquid sulphur dioxide for it has been found possible to obtain a solution of triphenylmethyl in the cathode chamber by electrolysing these solutions. The mono- di- and tri-phenyl derivatives of triphenylmethyl chloride in analogy to the alkali halides turn yellow orange-red and violet respectively under the influence of ultraviolet light probably owing to dissociation into triarylmethyl and halogen ; the colour disappears when the substance is subsequently exposed to ordinary light for some time.The bearing of the observations recorded in the paper on the question of the constitution of triphenylmethyl is discussed ; the conclusion is drawn that the Constitution of this Substance is most suitably represented not by a quinonoid structural formula but by the simple formula CPb in which the carbon is tervalent; the unimoleculnr triarylmethyls are electrically neutral molecules and not ions for solutions of tridiphenylmethyl in benzene do not conduct. 4-PhenyZtriphenyZmetltane CHPh,*C,H,Ph prepared by reducing the correspoudjng carbinol with glacial acetic acid and zinc dust crystallises in long needles m.p. 1 12-1 13’. 4 4‘-Diphenylt~~p~erayl- methane CHPh(*C6H,Ph)2 crystallises with 1C6H6 in leaflets m. p. 161’. W. E. G. Triarylrnethyls. 111. Diphenyldiphenylenecarbinol. WILHELM SCHLENK and ANNA HERZENSTEIN ( AnnaZtm 19 10 372 2 1-3 1. Compare preceding abstract).-In the preceding paper tridiphenyl- methyl is shown to differ from other triarylmethyls in that it exists wholely in solution in the unimolecular state ; an attempt to obtain a ‘‘ triarylmethyl ” of an opposite character namely one which in solution exists only in the bimolecular state has been successful. I n the preparation of 4 4‘ 4”-triphenyltriphenylcarbinol (compare Abstr. 1909 i 791) a substacce mas obtained which examination has shown to be diphenyldiphenylenecarbinol(4-phenylphenyldiphenyl- enecarlinol) ; this substance when treated with acetyl chloride yields the corresponding chloride which differs frpm the analogous triarylmethyi chlorides examined hitherto in that the solutions ini.238 ABSTRACTS OF CHEMICAL PAPERS. phenol and liquid sulphur dioxide are colourless ; further the solution in benzene when treated with metaIs remains colourless the product formed being up-bisdiphenyl-up-bisdiphenylene-ethane. The latter substance differs from hezaphenylethane (triphenylmethyl) and other triarylrnethyls not only in existing in solutions in an undissociated state but also in not combining readily with oxygen; a peroxide is formed however by passing oxygen into the solution during the action of copper on the chloride.The fact that up-bisdiphenyl-ap- bisdiphenylene-ethane does not dissociate in solution shows that the valency acting between the two substituted methyl groups represents a much greater affinity than in the other hexa-aryletfianes which have been investigated. I n complete agreement with this diphenyldiphenyl- enemethyl chloride does not so readily form additive products as other triarylmethyl chlorides (compare Werner A bstr. 1906 i 436) ; thus tridiphenylmethyl is completely dissociated in benzene and tridiphenyl- methyl chloride forms a moderately stable additive compound with sulphur dioxide (compare preceding abstract) ; 4-phenyltriphenyl- methyl and 4 4'-diphenyltriphenylmethyl are partly dissociated in benzene whilst additive compounds of the chlorides with sulphur dioxide exist but are unstable ; diphenyldiphenylenemethyl chloride does not form an additive product with sulphur dioxide Diphenyldiphenylsnemethyl is most readily prepared by the action of 9 9-dicLlo;ofluorene on a solution of diphenyl in carbon disulphide in the presence of aluminium chloride; it crystallises in coarse granules m.p. 138-1 40° and forms intensely coloured double salts with stannic chloride and aluminium chloride ; when treated with hot glacial acetic acid and sodium acetate it yields dip~enyldip~enylenecccrb~~ol) ?6H4>C(OH)*C,H4Ph which crystallises from benzene-light petroleum in stellate groups of slender needles m. p. 137-139' and by precipitation from glacial acetic acid in four- sided leaflets m.p. 149'; the latter compound forms (1) an additive compound with fluorenone crystallising in pale yellow octahedra m. p. 123'; (2) aperchlorate crystallising in deep blue prisms with a metallic reflex ; (3) an ethyl ether m. p. 167'. up-Bisdiphenyl-ap-bisdip~en ylene- ethane '6=4 C6H,Ph*C( :Cl2HS)*C( :C12Hs) C6K4Ph forms small colourless prisms m. p. 175-176'; the peroxide C,,H,,02 forms six-sided leaflets m. p. 193". W. H. G . Formation of Colourless Ions from Triphenylmethyl Bromide. ARTHUR HANTZSCH and KURT H. MEYER (Ber. 1910 43 336-340).-Triphenylmethyl bromide forms a colourless electrically conducting solution in pyridine and in acetone ; its conducting solution in acetonitrile is yellow at the ordinary temperature colourless a t 0'.Its conductivity in pyridine diminishes rapidly with time attain- ing after about one hour a constant value about half the initial value and identical with that of triphenylmethylpyri~iniu~ bromide CPh3-C,NH,Br a colourless crystalline substance obtained by theORGANIC CHEMISTRY. i 239 addition of pyridine to a benzene solution of triphenylmethyl bromide. The change of conductivity is attributed to the conversion of the bromide which functions initially as a carbonium salt by the addition of pyridine into an ammonium salt. Triphenylmethyl chloride exhibits a converse behaviour in pyridine the conductivity slowly increasing with time. 5%-a-phenyldi-P-methytpropane CPh;CMe m. p. 185O is obtained from magnesium tert.- butyl chloride and triphenylmethyl bromide in Structure of Retene.PAUL Lux (Be?.. 1910 43 688-692. Compare Abstr. 1908 i 873).-Retene is either 2-methyl-8-isopropyl- or S-methyl-2-isopropyl-phenanthrene [compare following abstract]. The mono-oxime of retenequinone undergoes the Beckmann re- arrangement when heated with acetic acid acetic anhydride and hydrogen chloride forming one of the two possible nitrites of methyl- isopropyldiplumic acid CN*CGH,R* C,H,R*CO,H where R and R' are the alkyl residues. This acid has m. p. 112-114' and forms on hydrolysis the corresponding methyl isopropyldiphenarnic acid m. p. 202-204'. The nitrile interacts with thionyl chloride forming the chloride CN*CGH,R*C,H3.R'*COCI m. p. 96-97" decomp. 150' ; it is converted into the amidenatrile on treatment with ammonia in benzene solution.This has m. p. 141-142*5' and is hydrolysed to the diamide NK,*CO*C,H,R*C,H,B'*CO*N H or by means of concentrated alcoholic potassium hydroxide to the second methytisopropyldiphecnamic acid CO,H*C,H,R*C,H,R'*CO*NH m. p. 194-1 96O decomp. 21 0'. When heated it probably forms the diphenimide R * $!,H,*CO >NH. ether by decomposing the initial product with water. c. s. NH,*CO* C,H3R*C6H3R'* CO,H R' C,H,* CO - - E. F. A. Constitution of Retene and its Derivatives. JOHN E. BUCHER (J. Amer. Chem. SOC. 1910 32 374-382).-1n the course of a study of the condensation of acids of the phenylpropiolic series to derivatives of 1-phenyl-2 3-naphthalenedicarboxylic acid (Abstr. 1908 i 791) it was found that the constitution of most of these compounds could be ascertained by converting them into diphenyltetracarboxylic acid or by oxidising them to benzenepolycarboxylic acids.These methods have now been applied to the determination of the constitution of retene (rnethylisopropylphenanthrene). When a solution of retenequinone in pyridine is oxidised with potassium permanganate it is converted into a mixture of acids containing 3-hydroxyisopropyldiphenyl-1 1' 2'-tricarbox?jlic acid OH*CMe,*C,H,( CO,H)*C,H,(CO,H) which loses water on heating with formation of a residue soluble in sodium carbonate solution. The formation of this acid from retene- quinone shows that two of the carboxyl groups occupy the 1- and 1'-positions whilst the production of water on heating indicatss the presence of another carboxyl group in the 2'-position.As the iso- prop91 residue still remains the 2'-carboxyl group must have been derived from the methyl group which therefore occupies the 8-positioni. 240 ABSTRACTS OF CHEMICAL PAPERS. in retene. When this tricarboxylic acid is further oxidised i t yields the corresponding tetzacarboxylic acid together with cz small quantity of benzene-1 2 3-tricarboxylic acid. The last mentioned acid is also formed together with the 1 2 4-isomeride by the oxidation of diphenyleneketonedicarboxylic acid which Bamberger and Hooker (Abstr. 1885 905 1070) obtained by the oxidation of retene. The production of these two acids shows that retene has one group in the 8-position and the othe in either the 2- or 3-position and excludes the formula proposed by Bamberger and Hooker (Zoc.cit.). When the mixture of acids obtained by the oxidation of retene- quinone is heated with potassium hydroxide at 2 1 8 O and the resulting acids are reduced with hydriodic acid a mixture of hydrocarbons is obtained which when oxidised with potassium permnnganate yields diphenyl-3-carboxylic acid. The isopropyl gron p in retene must there- fore occupy the 2-position and hence retene is S-methyl-2-isopropyl- phen an threne [compare preceding abstract]. It is pointed out that now the constitution of retene has been established it will be necessary t o correct the structural formulac of its various derivatives. The constitution assigned to abietic acid by Easterfield and Bagley (Trans. 1904 85 1238) is discussed. F,. G. Quantitative Development of the Sandmeyer Reaction.GUSTAV HELLER (Zeitsch. angew. Chem. 1910 23 389-392). -The author has worked out the conditions under which the introduction of chlorine by the Sandmeyer reaction in the case of aniline and p- and o-toluidines can be effected almost quantitatively. The most important factor is the concentration of the hydrochloric acid in the solution ; if rather more acid is taken than is recommended by Erdmann (Abstr 1893 i 151) the separation of a solid intermediate product does not occur and the rise in temperature necessary to decompose it may be avoided. The reaction is therefore carried out a t a lower temperature than is possible under the conditions given by Erdmann. It is probable that the intermediate compounds formed in these circum- stances are very soluble complex salts of cuprous chloride.R. v. s. Preparation of 1-Naphthylamine-4 7- disulphonic Acid and of -2 4 7-trisulphonic Acid from 1 8-Dinitronaphthalene. FARBWERKE VORM MEISTER Lucrus & BRUNINC; (D.R.-P. 215338).- When 1 8-dinitronaphthalene is reduced in aqueous solution with sodium sulphite sodium anirnonium sulphite or ammonium sulphite at 70-90° free alkali is produced; this results fiom the entrance of sulphonic groups into the nucleus and is accompanied by the elimina- tion of a nitro-group. If the solution is kept neutral or only slightly alkaline and the heating continued until the reaction is complete there separates when cool colourless needles of sodium or ammonium 1 -naphthyZsulphamin- 4 7-disulphonate which on warming with mineral acid yields l-naphthyl- amine-4 7-disulphonic acid crystallising from hot water. The more soluble 1 -naphthyZsuZphamin-2 4 7-trisulphonates remain in solution from which after heating with mineral acid 1-naphthylamine-2 4 7- trisulphonic acid can be separated by means of salt.F. M. G. M.ORGANIC CHEMISTRY. i. 241 a-p-Hydroxyphenylethylamine and the Synthesis of Horde- nine an Alkaloid in Malt Germs. KARL W. ROSENMUND (Ber. 19 10 43 306-31 3).-/?-p-Methoxyphenylethylamine hydrochloride (this vol. i 106) is heated with alcoholic potassium hydroxide and methyl iodide at loo' the product is treated with water and a little ether the methiodide of the tertiary base is removed and the mixture of primary secondary and tertiary bases obtained by the evaporation of the filtrate is heated with acetic anhydride; after the addition of water and ether the tertiary base alone remains in the aqueous solu- tion as the acetate.It is liberated by sodium hydroxide extracted with ether and demethylated by hydriodic acid. The product is P-p-hydroxyphenylethyldimethylamine (hordenine) OH*C,H,*CH,-CH,*NMe (compare Ldger Abstr. 1906 i 204) its identity with the natural alkaloid being proved not only by its physical properties but also by the identity of the methiodides ; the lather is also produced by heating /I-p-methoxyphenyletbyltrimethylammonium iodide with hydriodic acid. a-p-Metl~o~~plenyZethylacmine OMe*C,H,* CHMe*NH b. p. 125-1 2 6 O / 16 mm. is a strongly basic oil obtained by reducing an alcoholic-acetic acid solution of the oxime of p-methoxyacetophenone by sodium amalgam; its hgdrochloride has m.p. 160'. When heated with alcoholic potassium hydroxide and methyl iodide (3 mols.) it yields a substance wbich melts at 162' suddenly solidifies again an$ then has m. p. 250O. When heated with hydriodic acid however a-p-hydroxy- plwnylethyZa*rnine is obtained in crystals rb. p. 120-121'. The hydro- c. s. chloride forms needles m. p. 185'. y-Tolylethylamine and its Optically Active Forms. G. A. STENBERG (Zeitsch. physikal. Chem. 1910 70 534-535).-a-p-l'oZgZ- ethylamine C,H,Me*CHMe*NH has been prepared by transforming p-tolyl methyl ketone into the oxime and then reducing with sodium amalgam in a solution slightly acidified with acetic acid. It is a colourless liquid b. p. 204O ; D20 = 0.937.Cy repeated fractional crystallisation of its salt with I-malic acid (the acid salt) the pui e d-form of the base was obtained ; Po = 0,9366 ; [a] = + 36-57'. Similarly the 2-form has been obtained by fractional crystallisation of the acid salt which the base forms with camphoric acid ; D20 = 0.7375 ; [a] = + 36-23'. The sulphates and oxalates of the active salts are considerably more soluble than the racemic salts. Xylylethylamine is now being investigated ; the 2-form of the salt has already been prepared G. S. Isomeric Arylimines of Unsaturated Ketones. FHITZ STRAUS and A. ACKE~LMANN (Bey. 19 10 43 596-608).-Ammonia does not react with the keto-dichloride of p-chloropheuyl p-chlorostyryl ketone (Abstr. 1909 i 489) but p-nitroaniline reacts in the normal manner yielding p-nitroanilino-~-chlorophenyl-p-chlorost3.rylmethyl chloride C,H,Cl* CH CH*CCl(C,H,Cl) *N H*C,H,*NO,. The chlorine atom of the CC1 group is not reactive; for example the compound dissolves in concentrated sulphuric acid without evolution of hydrogen chloride.It reacts however with acids in hydroxylic solvents yielding the1. 242 ABSTRACTS OF CHEMICAL PAPERS. ketone. The chloride reacts with sodium methoxide or ethoxide losing hydrogen chloride and yielding the p-nitrophenylimine C,R4CloCH:CH*C( C,H,CI) :N*G6H4*NO2. When p-toluidine is used instead of p-nitroaniline an intermediate chloride is not obtained but the tolylimine is formed immediately. The p-tolylimino-p-chlorophenyl-p-chlorostyrylmethane exists in two isomeric modifications a yellow and a colourless.They are both stable and can be crystallised or fused without undergoing transforma- tion ; they yield isomeric salts and can be recovered unaltered from these salts. The two compounds are regarded as stereoisomeric in the same sense as oximes and anils. p-Nitroanilino-p-chZorophenyZ-p-chlorostyryl~ethyZ chloride ( 3 2 3 3 1 5 0 P 2 C 4 9 crystallises in yellow plates m. p. 11s-119". trated sulphuric acid is yellowish-red and has a bluish-red dichroism. Its solution in concen- The yellow ptoZyZimino-p-chlorop?~nyl-p-chZorostyryZmethane C,H,C1*CH:CH*C(C6H,C1) N*C,H,Me crystallises in soft lustrous yellow needles m. p. 130-131° and is the only product formed when the condensation is carried out at the ordinary temperature for some forty hours.crystallises i n reddish-yellow needles m. p. 167-188' and when boiled with alcohol yields the ketone and p-toluidine picrate. The hydrochloride C22H17BC12,HCl has m. p. 170-171'. The isomeric p-tolylimind is formed when the reacting substances are left together for some weeks; it crystallises in colourless glistening plates m. p. 144-145' and is not so readily soluble in most solvents or so readily burnt as is the yellow isomeride. forms heavy yellow crystals m. p 102-103' (decomp.). These crystals contain benzene of crystallisation and after heating until constant in weight have m. p. 11 6-1 17'. It is not decomposed when boiled with alcohol. The hydyocitZoi*icle forms snow-white needles m. p. 1OO-l0lo and when heated at 110-115' decomposes yielding p-chloroacetophenone and p-chlorophenyl p-chlorostyryl ketone. The picrate C',?,H17NC'2,C6K307N The picrate C,2H,7NC12,0H*C6H2(N0~)3 J.J. S. Coloured Additive Products of Aromatic Amines. The Question of the Mechanism of Substitution in the Benzene Nucleus. VII. HEINRICH WIELAND and ERNST WECKER (Bey. 1910 43 699-712. Compare Abstr. 1907 i 1076 and following abstract).-The authors have more fully investigated the strongly coloured unstable compounds of tertiary and secondary amines with bromine and with the chlorides of the metalloids. They consider that these compounds are quinonoid additive products of the type NAr,Br:C,H,:MeBr which undergo spontaneous rearrangement forming compounds with substituted benzene nuclei. The reaction in the case of the blue bromide OF tri-p-tolylamine is expressed by the equation 2N(C,H4Me),Br = N(C,H,BrNe) + N(C6H4Me) + 3HBr.Tri-p-tolylamine when treated with bromine in benzene solution atORGANIC CEEMISTRY. i. 243 - 15' yields a ti-ibronzide N(C,H,),Br which forms dark blue crystalline scales. When a chloroform solution of the substance is kept a t the ordinary temperature tribromotri-p-toZyZamino m. p. 1 90° and tri-p-tolylamine are formed. The dibromotri-p-tolylamine m. p. 160-165' formerly described (Zoc. cit.) is a mixture of tri- bromotri-p-tolylamine and tri-p-tolylamine. Tri p-anisykanzine pre- pared by Goldberg's method (Abstr. 1908 i 17) has m. p. 94.5'. With bromine it yields a tribromide N(C6H,*OMe),Br which cryatallises in daik violet lamin% and is very stable. I n chloroform solution it slowly decomposes forming tribl.onLotri-P.I1Cnisylamine m.p. 1 7 go and tri-p-anisylamine. Tri-p anisylamine also forms a deep blue crystalline compound with antimony pentachloride. Diphenyk-p- anisidine NPh2*C1,H,*OMe prepared by Goldberg's method has m. p. 104'. The compounds of this substance with bromine and autimony pentachloride could not be isolated. Diphenylamine and di-p-tolylamine do not give coloured additive products with bromine or antimony pentachloride ; phenyl-p-anisidine gives colorations indicating the formation of such compounds and from the solution tribromo~he?zyZ-p-nnisidincz m. p. 100.5" is obtained. Phenyl-p-anisidine (compare Willstaiker and Kubli Abstr. 1909 i 976) was prepared from aceto-p-anisidide by Goldberg's method. In the case of di-p-anisylamine the colorations observed are abnormal owing to the formation of some anisazonium bromide which is red.The additive bromide can be obtained by workirkg in ethereal solution as a da1.k bluish-green flocculent precipitate which can be filtered. On dissolving it in chloroform rearrangement occurs so rapidly t h a t the solution is colourless unless strongly cooled. I n solvents other than ether di-p-anieylamine and bromine directly yield dibromodi-p- c~ni.~yZamiize m. p. 79". When this is treated with a further quantity of bromine in benzene-chloroform solution a green crystalline stable dibromida Cl,Hl,02NBr,,Br2 is formed m. p. 104" (decomp.). I n chlor ofoi-m solution it undergoes rearrangement yielding besides dibromodi-p-anisylamine a mixture of tribromodi-p-anisylamine m.p. 135*5O and tetl.ab7omodi-p-aizissylar,.Line m. p. 183". A compound of di-p-anisy lamine and antimcny pentachloride C1,H,,0,N,SbC15 is foimed on mixing chloroform solutions of the two substances. It crystallises in dark steel-blue prisms m. p. 116-118" and is stable. From it anisazonium chloi ide and di-p-anisyldihydroanisazine can be prepared (compare Abstr. 1908 i 1015). R. V. S. Oxidation of p- Anisidine and of Dimetbyl-~-anisidine. 71 2-728 Compareprecedingabstract.)-the fact that themethoxylated amines 1 ield coloured additive products with bromine whilst the amines themselves do not leads to the supposition that these additire products may be oximonium compounds of the type OMe*C,H,*NHBr:C6H,:OBrXe. The action of bromine on p-anisidine and on dimethyl-p-anisidke a t low temperatures eff ecbs the removal of the methoxyl group with remarkable ease the ultimate product of the oxidation being quinone.HEINRICH WlELAND [with ERNST WECKER] (Be?-. 1910 43,i. 244 ABSTRACTS OF CHEMICAL PAPERS. The formation of rrteri-quinonoid and quinonoid bromine compounds as intermediate products also occurs although these are less stable than the corresponding nitrogen derivatives (compme Willstatter arrd Piccard Abstr. 1908 i 475 915). p-Anisidine is oxidised by ferric chloride chromic acid hypochlorous acid bromine and other oxidising agents in acid solution with formation of a violet dye which yields a leuco-base on reduction indicating that several molecules of the amine have become united (compare Willstatter and Piccard Abstr.1909 i 517). I n acetic acid solution in the presence of sodium acetate bromine water oxidiees all the anisidine to the violet dye which soon decomposes. When the oxidation is effected by bromine water a t a low temperature however a pure blue coloration develops which gradually becomes violet. It is probable that the blue colour is due to the meri-quinonoid additive product (OBrMe:C,H,:NH2Br,0Me*C,H,*NH2}. The violet dye only appears in acid solution when insufficient bromine is present ; when the oxidstion by bromine water in faintly acid solution is rapid and complete the p-aoisidine is converted almost quantitatively (98%) into quinone. I n this rmction 2 molecules of free acid are formed showing that hydrolysis of the methoxyl group occurs ; this con- firms the theory as to the primary formation of a quinonoid oximonium salt.Aminophenol also yields quinone quantitatively when oxidised with bromine water under the above conditions (compare Willstatter and Dorogi Abstr. 1909 i 535) and in this case also the intermediate formation of quinonemonoimine (Willstiitter and Pfannenstiel Abstr. 1905 i 69) is probable. When treated with bromine in chloroform solution p-anisidine yields a dibromo-p-anisidine which crystallises in long needles m. p. 81'. The bromination is accompanied by the development of an evanescent blue colour and when it is effected in ethereal solution an unstable blue compound (perhaps the primary quinonoid product) can be isolated. Dimethyl-p-anisidine (compare Griess Abstr.1880 636) is obtained by methylating p-anisidine with methyl sulphate. It has m. p. 49" (Griess 48'). The chloride bromide and picrate crystallise well. When the base is treated gradually with bromine in chloroform solution a vivid red coloration is first produced which gradually changes to a blue colour ; eventually the quinonoid perbromide OBrMe:CGH4:NMe2Br2 is precipitated. It crystallises in small lustrous green laminz m. p. 49-50' and on reduction yields dimethyl-p-anisidine. Its aqueous solution (which is orange) rapidly decomposes into quinone dimethylamine hydrobromide hydrobromic acid and methyl alcohol. Oxidation of dimethyl-p-anisidine in aqueous solution with one molecule of bromine (in the form of bromine water) yields a quinonoid bromide of dimethylaminophenol NMe2Br:C6H,:0 in solution for on reducing the liquid dimethylami~iophenol is obtained. If a second molecule of bromine is added however the fairly stable yellow perbromide NMe,Br:C6H,:OBr m.p. 90° is precipitated. On reduction this yields almost quantitatively dimethyl- paminophenol m. p. 78" (von Pechmann Abstr. 1900 i 173 gaveORGANIC CHEMISTRY. i. 245 74-76"). When left in contact with water the perbromide decom- poses into quinone dimethylamine hydrobromide and bromine. The estimation of quinone is effected by reducing to quinol and titrating the latter with iodine in the presence of sodium hydrogen carbonate. On acidifying the quinone liberates the iodine again and as a control this may be titrated with thiosulphate.This is of value when traces of other oxidisable substances are present. The quinone in ethereal solutions may also be estimated by a modification of Nietzki's method. Bromioe is best recognised in the presence of quinonoid compounds and mineral acid by adding sodium acetate solution before testing with potassium iodide and starch paper which is then only affected by the free halogen. It. V. S. Garbodiphenylimide. KARL SCHALL (J. pr. Chem. 1910 [ii] 81 19 l-l92).-The author disputes some of the statements concern- ing 7-carbodiphenylimide made in a footnote in Busch Blume and Punge'a paper on carbodiphenylimide (Abstr. 1909 i 565). C. S. A-1 '-Dihydrophenol. [A2-cycZo-Hexenone.] LEO TSCHUGAEFF (J. pr. Chem. 1910 [ii] 81 188-l89).-Polemical. A reply t o Kotz and Grethe (this vol.i 24). The author claims priority for the method used to concert cycto-hexanon-2-01 into A1:5-dihydrophenol and dissents from these authors representing the xanthogenate as contain- ing :C(OH)-CS*SM.e in preference to the constitution :CH*O*CS*SMe usually accepted. c. 5. Phenol and m-Nitrophenol as Acids. HARALD LUND~N (Zeitsch. physikal. Chm. 1910 70 249-255).-The acid dissociation constant k of phenol has been determined by measuring the electrical con- ductivity of solutions of the ammonium salt ; the values are k x 1010 = 0.56 at lo" 0.66 at 15" 0.97 at 25' 1.51 a t 40' and 2.05 at 50°. These values have been confirmed by direct determinations of the conductivity of aqueous solutions of phenol and are also in good agree- ment with the results obtained by Buch (Abstr.19OS i 259). The dissociation constant of m-nitrophenol has also been determined by conductivity measurements with carefully purified aqueous solutions ; the values are k x lo9= 3.31 at lo' 3.91 at 1 5 O 5.33 at 25O 7-12 at 40° and 9-64 at 50'. From the data for phenol the heat of neutralisation with ammonia and the heat of dissociation have been calculated in t h e usual way; the value of the former is 7605-6.5t cal. arid of the latter - 7095 + 43.5t cal. per mol. Both values are in excellent agreement with the direct determinations of Berthelot (1873). The heat of neutralisation of nt-nitrophenol is 8520 - 2-18 cal.; the heat of dissociation - 6180 + 47*9t cal. The data for the influence of temperature on the total and free energy of the above changes are tabulated.G. S. New Method. of Formation of Ethers of Glycerol and Phenols. PETAR ZIVKOVI~ (dfowtsh. 1908,29,951-958).-A mixture VOL. XCVIII. i. si. 246 ABSTRACTS OF CHEMICAL PAPERS. of a phenol or naphthol (1 part) glycerol (2 parts) and anhydrous sodium acetate (1 part) contained in a flask in an atmosphere of coal gas is heated for twelve to twenty hours by the vapour of ethyl benzoate. In the case of the phenols the benzene extract of the product is directly precipitated with light petroleum ; when dealing with a-naphthol the mass is boiled with water and dried before being treated with benzene. In addition to glycerol phenyl ether the following mono-ethers have been obtained the o-tolyl ether C,H,*O-C,H,(OH) m. p. 66O ; the m-tolyl ether m.p. 65" ; the p-tolyl ether m. p. 73-74'; the a-naphthyl ether m. p. 91-92' ; P-naphthyl ether m. p. 109-110'. None of the ethers give a colour reaction with ferric chloride but form brown or green solutions in concen- trated sulphuric acid when treated with potassium nitrite which become green or red by dilution and the addition of alkali. Amino-alcohols. Derivatives of Glycerol and Phenyl Ethers. ERNEST FOURNEAU (J. Phann. Chim. 1910 [vii] 1 55-6 I 97-l03).-The complex ethers obtained by the condensation of epichlorohydrin with phenols have been studied and especially their reaction with amines. When phenol or sodium phenoxide is heated in a closed tube with epichlorohydrin the three chief products formed are (1) phenyl glycide ether OPh*CH,*CH<x b.p. 242*5'/755 mm. (compare Rossing Abstr. 1886 345; Lindemann Abstr. 1891 i 1198; Cohn and Plohn Abstr. 1907 i 605) ; (2) y-chloro-P-hydroxy-a-phenoxypropane OPh*CH,*CH(OH)*CH,Cl b. p. l7Oo/21 mm. (compare Lindemann loc. cit.; Fischer and Kriimer Abstr. 1908 i 858) and (3) glycerol diphenyl ether (Lindemann Zoc. eit.). In some cases a small amount of diphenoxydipropanol oxide [OPh*CH,*CH(OH)*CH,120 m. p. 81" b. p. 300-305"/16 mm. is formed; it crystallises in colourless spangles. Phenyl glycide ether reacts with water to form glycerol phenyl ether m. p. 69O and with[alcohol to form glycerol phenyl ethyl ether OPh*CH,*CH(OH)*CH2-OEt b. p. 158-1 60°/25 mm. a colourless inodorous liquid. With magnesium ethyl bromide phenoxypropylene brornohydrin b. p. 160-162'/18 mm. is formed (compare Abstr.1907 i S17) but with magnesium phenyl bromide /3-hydroxy-y- phenoxy-a-phnylpropune OPh*CH,*CH(OH)*CH,Ph m. p. 91-92" crystallising in spangles is obtained. In the action of epichlorohydrin on (a) p-cresol and ( b ) a-naphthol the corresponding glycide ethers described by Lindemann (luc. cit.) are produced and in addition glycerol di-p-tolyl ether in the one case and glycerol di-a-nuphthyl ether (m. p. 116') in the other. The product obtained by the action of catechol on epichlorohydrin is not diglycidylcatechol as Lindemann supposed (Zoc. cit.) but is identical with Moureu's substance obtained by condensing sodium catechol with up-dibromohydrin. The glycide ether prepared in an analogous manner from guaiacol has b. p. 170°/16 mm.and m. p. 79*5" whilst that from thymol boils at IS0°/20 mm. melts at SSO and crystallises in colourless needles C. S . HORGANIC CHEMISTRY. i. 247 By the action of sodium p-nitrophenoxide on dichlorohydrin glycerol di-p-nitrophenyl ether OH*CH(CR2*0*C,H,-NO,) m. p. 122-1 23O crystallising in bright yellow needles is obtained together with p-nitro- phenyl glycide ethev m. p. 69' which forms yellow tablets. Phenyl glycide ether reacts with ammonia to form diphenoxypropunol- arnine NH[CH,-CH(OH)*CH,*OPh] m. p. 97-98' ; its hydrochloride has m. p. 175'. The following amino-alcohols have been obtained in like manner by the action of appropriate amines on the glycide ethers described above. y -Dirneth y Zamino -a-phenox ypropanol OP h CH C X( OH)* CH,* NMe has b.p. 161°/13 mm. or 169'/25 mm. ; thepicrate m. p. 105O crystallises in spangles; the hydrochloride of the benzoyl derivative m. p. 166' the ethyl bromide derivative m. p. 112' and other similar compounds were prepared. The corresponding y-anilino-derivative OPh-CH,*CH( OH) * CH,*NHPh has m. p. 57' and the analogous y-phenetidino-compound m. p. 95" both crystallise in colourless needles. y-Dimethylamino-a-p-tolyloxppropanol b. p. 175-1 76"/10 mm. yields a benxoyt derivative the hydrochloride of which has m. p. 156' and crystallises in slender needles. y-L)imethylami?zo-a-gzcccicccy~ropanol m. p. 6 1 ' yields a rnethiodide m. p. 114' and a benzoyl derivative the hydrochloride of which has m. p. 142'. y-DimetiZyluminon~phthox~~opanol m. p. 81-82' b. p. 217'11 1 mm.crystallises in slender needles and yields a methiodide m. p. 204". y-Dimethylamino - a- p-nitrophenoxypropanol exists in two forms (tablets and prisms) both having m. p. 81-82' ; the picrate m. p 153' and the hydrochloride of the benzoyl derivative m. p. lSl' were prepared. y-Dimethylamino-a-thynaoxypropanol b. p. 177'/11 mm. crystallises on cooling and gives a methiodide m. p. 160'. The methods of preparing these substances are described in some detail in the original. As a rule these amino-alcohols exhibit antipyretic and analgesic properties but owing to their cardiac action they are unsuitable for therapeutic use in this way. Preparation of Tribromocatechol. CHEMISCHE FABRIK VON FRIEDR. HEYDEN (D.R.-P. 215337)-When catechol is treated with 3 mols. of bromine in acetic acid solution no tribromocatechol is formed the product consisting of a mixture of the di- and tetra- bromo-derivatives.Tribromocatechol m. p. 138-139' is obtained by the action of bromine in chloroform on a suspension of catechol in the same solvent ; it is colourless odourless and insoluble in water but readily soluble in alcohol ether or acetone and contains 1 mol. of water of crystallisation. It is employed therapeutically and also in the preparation of dyes. T. A. H. I?. M. G. M. Action of Phosphorus Trichloride on Guaiacol. PIERRE DUPUIS (Compt. rend. 1910 150 622-623).-Three compounds may be formed when guaiscol is heated with phosphorus trichloride s 2i. 248 ABSTRAcTS OF CHEMICAL PAPERS. according to the proportions in which these substances react.Gu,ct,iacyZphosphoms chloride OMe*CGH;O*PC1 prepared at 1 15-1 20° is a colourless refractive liquid b. p. 135'/13 mm. 1.568. When dissolved in dry ether and treated with chlorine a yellow tetrachloride OMe*C,H,*O*PCl is formed which is converted by sulphur dioxide into Auger's compound OMe*CBH,*O*POCI (Abstr. 1908 i 529). Diguaiacylphosphorus chlorade P( O-C,H,*OMe),Cl has b. p. 335'/13 mm. P Z ~ 1.586 and forms a trichlorade P(O*CGH,*OMe)2Cl3 from which diguaiacyl phosphoryl chloride may be obtained by the action of sulphur dioxide. Triguaiacyl phosphite P(O*C,H,=ONe) b. p. 275-280°/13 mm. solidifies on cooling forming octahedra m. p. 594 This is not identical with Ballard's compound obtained by the action of phosphorus trichloride on the sodium derivative of guaiacol The foregoing compounds are solubla in ether and benzene and undergo decomposition when treated with water. Some Derivatives of Phloroglucinol and a New Synthesicj of Benaoresorcinol [2 4 - Dihydroxybenzophenone].EMIL FISCHER (AnmaZen 1919 371 303-318)-2 4-Dihydroxybenzo- phenone may be prepared by hydrolysing the product formed by the interaction of benzene aluminium chloride and 2 4-dimethylcarbonato- benzoyl chloride (compare Abstr. 1909 i 161). Phloroglucinolcarboxylic acid reacts with only 1 mol of methyl chlorocarbonate in N-sodium hydroxide solution ; all attempts to obtain the corresponding trimethylcarbonato - derivative were un- successful ; consequently 2 4 6-trihydroxybenzophenone could not be prepared in the same way as 3 4 5-trihydroxybenzophenone (compare Abstr.1909 i 309). Attempts to prepare 3 4 6-trihydroxgbenzo- phenone by other methods mere unsuccessful but many new benzoyl derivatives of phloroglucinol have been obtained the most interesting of which are the dibenzoyl derivatives of phloroglucinol dialkyl ethers ; these probably have the constitution represented by one of the (D.R.-P. 95578). W. 0. W. YBz:C(OR)*gH CBz:C(OR)*-f?x C(OH):CB~*C-OK. or &OH):CHOOR' and the following formuh similarly to hydrocotoin (C-benzoylphloroglucinol dimethyl ether) are stablo towards warm aqueous alkali; in t h i s respect they differ from trincetylcyclohexanetrione and its tribenzoyl derivative (compare Heller Abstr. 1909 i 656). 1 3 5-l~imethylcarbonatobenxelze C,H3(O*C02Me) prepared by acting on a solution of phloroglucinol in a N-solution of sodium hydroxide with methyl chlorocarbonate crgstallises in long glistening prisms m.p. 99-100' (corr.) ; 4-~~ethyZc~rbonato-2 6-dahydromj- benxoic acid CO,Me*O*C,H2(0H~~'CO2H,- similarly prepared from phloroglucinolcarboxylic acid crystallises in tuf t a of flexible needles m. p. 162' (corr. decomp.). - I Benxo ylphlorogluciizolcnrbo~~lic acid OBZ C < g g i ~ ~ ~ ~ ~ > C * C O H prepared from phloroglucinolcarboxylic acid and binzoil chloride crystallises in small prisms m. p. 195" (corr. decornp.) ; the silver salt is a colourless crystalline powder ; the acid loses carbon dioxide whenORGANIC CHEMISTRY. i. 249 heated at 200° yielding benzo?/lphZoroglucinoZ C13H1004 which forms slender leaflets and needles m.p. 198-199" (corr.). 0-Benxoylphloroglucinol diethyl ether C,H 3( OEt),*OBz is formed by acting on phloroglucinol diethyl ether with benzoyl chloride and alkali ; i t crystallises in colourless slender pointed prisms and needles m. p. 84' (corr.) and when heated with benzoyl chloride and zinc chloride in benzene yields Iribenzoylphloroglcinol diethyZ ether CHBz2(0Et,)*OBz which crystallises in microscopic long slender plates m. p. 163-164" (corr.); the latter substance is con- verted by an alcoholic solntion of potassium hydroxide under pressure at loo3 into C-dibe~zxoylphloroglucinol diethyl ether C,HBz,(OEt),*OH which forms slightly yellow microscopic rhomboidal leaflets m. p. 156' (corr.) ; the potassium salt forms glistening pale yellow leaflets ; the sodium salt crystalliaes in slender needles.Tribenzoylphloroglucinol dimethyl ether C29H2206 may be prepared by treating either the monobenzoyl compound or hydrocotoin with benzoyl chloride and zinc chloride in benzene; it crystallises in microscopic plates m. p. 198' (corr.) ; C-dibenxoylphloroglucinol dimethyl ethr CP2HlSOB crystallises in microscopic needles and plates m. p. 170' (corr.) ; the potassium salt C,,HI7O,K forms yellow microscopic plates . W. H. G. Derivatives of Triphenylcarbinol. 11. ADOLF VON EAEYER [and in part AICKELIN CARL DIEHL HALLENSLEBEN and HERMANN HESS] (Annalen 1910 372 80-151. Compare Abstr. 1907 i 757).-The present communication contains the results of a systematic investiga- tion of the binary derivatives of triphenplcarbinol namely those con- taining two hydroxyl or amino-groups in at least one of the benzene nuclei.I. B i n a r y Dihydroxy-derivatives.-(1) Dihydroxytriphenyl- cur6inoZs.-2 5-Di~ydroxytri~henyZcarbi~ol CI9H1,O3 prepared by Grignard's reaction from ethyl 2 5-dihydroxybenzoate and bromo- benzene has m. p. 136'; it crystallises with $CsHs in colourless glistening leaflets m. p. 110' (decomp.); a green substance which probably has the formula C,H3(OH),-CPh,C1,HCl is obtained by passing hydrogen chloride into an ethereal solution of the carbinol and evaporating in a vacuum desiccator over potassium hydroxide ; it dissolves in ether forming a colourless solution of the carbinyl chloride C,H3(OH)2*CPh,CI whicb when treated with alkalis assumes a transient blue colour owing to the formation of an unstable o-fuchsone with a hydroxyl group in the quinonoid ring The compounds described immediately were prepared in an un- successful attempt to obtain a p-fuchsone with a hydroxyl group in the quinonoid nucleus.Methyl 2 4-dihyd~oxybenxoate CSHSO4 crystallises in colourless glistening rhombohedra m. p. 11 7-1 18" ; when treated with mag- nesium phenyl bromide it yields a red tar from which 2 4-dihydroxy- triphenylcarbinol could not be isolated. 2 4-Dihydroxytriphenylcarbinol C,,R,,O is prepared by Grignard's reaction from 2 4-dihydroxybenzophenone and bromobenzene ; it y( ONa):CH* $l:CPh2 CH:-CH*C:O .i. 250 ABSTRACTS OF CHEMICAL PAPERS. crystallises in colourless prisms m. p. 124O (decomp.) and is hydrolysed by aqueous sodium hydroxide yielding benzophenone resorcinol 2 4-dihydroxybenzophenone and benzene ; the perchlorate Cl,Hl,OGC1 forms large brown plates and explodes slightly when heated; all attempts to isolate the corresponding fuchsone were unsucceesf ul ; when a solution of the carbinol in nitrobenzene is heated at looo it yields a substance which crystallises in dark brown needles m.p. 264'. 2 4-~~hydroxy-~'-methoxyt~~pheny~cc6rb~no~ CzoHlSO4 prepared from 2 4-dihydroxy-4'-methoxybenzophenone and bromobenzene crystallises in colourless prisms m. p. 138-139' (decomp.). (2) DihydroxydiphenyZphthaZides.-2 4-Dihydroxydiphenylphthalide is best prepared by the action of concentrated sulphuric acid on a cold fused mixture of o-benzoylbenzoic acid and resorcinol ; contrary to von Pechmann (Abstr.1882 184) it has m. p. 198-199' and does not give a coloration when the solution in glacial acetic acid is treated with concentrated hydrochloric acid ; the solution in aqueous alkalis is orange and probably contains the f uchsone derivative 3 4-Dihydroxydip~enylpr~t~aZide C,,H;,O,,' forms colourless prisms m. p. 1 60-161'. 2 5-Dihydroxydzphen$plithaZicle crystallises in needles and prisms m. p. 246-247O (decomp.) and dissolves in aqueous sodium hydroxide in the absence of oxygen forming a blue solution which becomes colourless when kept but in the presence of air turns brown owing to oxidation ; the blue solution undoubtedly contains the salt CO,Na*CGH,*CPh:C<CH. CO-CH\ C(oH)>CH ; the corre- sponding quinone C20H1204 obtained by treating an ethereal solution of the di hydroxy-compound with silver oxide forms aggregates of dark yellow crystals m.p. 147'; the latter substance forms a quinhydrone with quinol ; the dihydroxy-compound also forms a quinhydrone with p-benzoquinone but not with its own quinone. 11. Unitary-binnr y Trihydrorcy-derivatiues. - Trihydroxytri- phenylcarbinols. - Since xan- /\ then is a saturated compound /'>\//\(''\ OH{/">/\& 5' >O the author proposes to desig- \ 1; o / \ ?I /\ I! 2' 344 / l3 11' :j'I nate this substance xanthan; \/ \/ \/ ':/'\$$;:/ the use of the annexed system of numbering the positions in co xanthoneand resorcinolbenzein is advocated [but is not adopted in this abstract] as the author dissents from that used in Beilstein [and in this Journal].o-3-Methoxgplnoxybenzok acid OMe*C,B,*O.C,H,*CO,H prepared by Ullmann's method (Abstr. 1905 i 597) from o-chlorobenzoic acid and 3-methoxyphenol crystallises in colourless silky needles m. p. 132" ; when treated in benzene with phosphorus pentachloride and subse- quently with aluminium chloride it yields 3-methoxyzanthone 0 0 O-$?:CH*E.OMe C6H4<C0 C CH- CH which forms tufts of colourless needles or leaflets m. p. 132". The latter substance is converted by magnesium phenyl bromide intoORQANIC CHEMISTRY. i. 251 3-methoxy-g -phen y2xsnthen-9-ol7 ~ 6 ~ 4 < c ~ h -'> (OR) C 6 H 3 *OMe which crystallises in colourless prisms m. p. 127O and when treated with a solution of aluminium chloride in antimony trichloride yields phenyl- fluorone m.p. 207' (compare Kehrmann and Dengler Abstr. 1908 i 1002). 2-Methoxyxanthone has m. p. 135O (compare Ullmann loc. cit.) ; 2-methoxy-9-phenylxanthen-9-oZ C2,,H1603 crystallises in short prisms and plates m. p. 136'; 2-hydroxy-9-phenylxanthen-9-01 has m. p. 170' (compare Kropp and Decker Abstr. 1909 i 248). 4-Jfethoxy-9-phenyZxa.lzthen-9-ol crystallises in colourless prisms m. p. 1'72' ; 4-hydroxy-9-phenylxantlhen-9-02 C19H1403 forms bundles of small needles m. p. 162'. 111. B i n a r y Te t r ah y d r ox y- d e r i v a t ives.-( 1) Resomino1 group i n the o p-position.-Fluorescein hydrochloride (compare Gattermann Abstr. 1899 i 513) is readily obtained in hexagonal leaflets by treating fluorescein with concentrated hydrochloric acid. The nature of the changes which take place when fluorescein is treated with alkali is discussed.The conclusion is drawn that the blue salts of the fluorescein group result from the hydrolytic fission of the oxygen-bridge of the xanthone nucleus and contain at least in the rhodamine series an ortho-quinonoid group. Since fluorescein is a carboxylic acid of resorcinolbenzein it seemed probable that the latter substance would yield a violet salt when warmed with aqueous potassium hydroxide ; under certain conditions an evanescent violet coloration is obtained which seems to point to the formation of an unstable violet salt with fission of the oxygen-bridge. (2) Resorcinal gq-oup in the o 0'-position. -Meyer's a-orcinolphthalein (Abstr. 1897 i SO) undoubtedly has the annexed constitution since it corresponds completely with &.-resorcinol- 0 benzein (I 8-dihydroxy-9-pl~mylxanthen-9-01! Me/\/ \/\Me in properties; it is proposed therefore to J 1 1 designate this compound vic.-orcinolphthalein.v \ C / > k The addition of alcoholic potassium hydroxide to an alcoholic solution of vic.-orcinolphthalein produces a violet coloration .probably owing t o the formation of a salt having the constitu- tion (I); the colour however disappears rapidly and a colourless potassium salt (11) separates in elongated rectangular prisms ; the latter substance when warmed with concentrated aqueous potassium hydroxide yields a blue potussium salt crystallising in prisms which probably has the formula (111) ; an analogous sodium salt crystallising in slender violet needles has been prepared.OH/ \ C,H4*CO*0 2 6 2' 6'-Tetr~nzethoxydiphenylca.rbinol CH[C,H,( OMe),],*OH isi. 252 ABSTRACTS OF OHEMICAL PAPERS. prepared by Grignard's reaction from 2-iodoresorcinol dimethyl ether and ethyl formate (compare Kauffmann and Franck Abstr. 1907 i 1094) ; it crystallises in colourless hexagonal prisms m. p. 179O and is oxidised by acetic acid and sodium dichromate yielding 2 6 2' 6'- tetramethmybenxophenone C17H which forms colourless elongated six-sided plates m. p. 204'. The latter substance when treated with a solution of aluminium bromide in benzene yields 1 S-dzhVdroxj/- QH:CH- E-O-;C;'-CH;QH which crystallises in tufts of CH:C(OH)*C~CO~*CCOH):CH~ xanthone \ I pale yellow leaflets m. p. 187q and interacts with magnesium phenyl bromide yielding 1 8-dihydroxy-9-pheizyZxanthen-9-ol C19H1404 which farms elongated hexagonal and rhombic plates ; the carbinyl chloride crystallises in black opaque needles.3. Quinol group-Quinolphthalein unlike aic.-orcinolphthalein does not yield a violet salt when treated with a small quantity of alcoholic potassium hydroxide probably because the formation of an ortho-quinonoid grouping without fission of the oxygen-bridge is impossible; a violet solution is obtained however when a large excess of alkali is employed; it probably contains the salt (annexed constitution) and when acidified yields the parent substance. /-\- c! - -/-\ Quinolbenzein (2 7 - dihydroxy - 9 - \-/ I \=o/K pbenylxanthen-9-01) may be prepared I by hydrolysing 2 5 2' 5'-tetrameth- OK oxytriphenylcarbinol with a solution of aluminium chloride in antimony trichloride or more readily by the phenylation and subsequent hydrolysis of 2 7 - dimethoxy - xanthone.The latter substance may be prepared from 5-methoxy-2- p-anisyloxybenzoic acid by treatment with hot concentrated sulphuric acid but is more readily obtained from the dihydrovyxanthone pre- pared by Graebe from p-dinitroxanthone (compare Abstr. 1890 504) thereby showing that the hydroxyl groups in this compound occupy the 2 7-positions. 2 5 2' 5'-Tetramethoxytriphenylcarbinol may be prepared by the action of benzotrichloride and aluminium chloride on quinol dimethyl ether ; it crystallises in colourless plates and prisms m. p. 125' (com- pare Kauffmann and Fritz Abstr.1909 i 99). 5-Met~oxy-p-anisylsaticylic acid (5-met?~oxy-P-p-methoxyphenoxy- benzoic acid) C1,Hl,05 prepared by the interaction of 2-chloro-5- methoxybenzoic acid and 4-methoxyphenol in the presence of copper powder crystallises with &H,O ; the anhydrous substance has m. p. 95O. 2 7-Dihydroxyxanthone is best prepared from 2 7-diaminoxanthone by warming the diazonium sulphate with 70% sulphuric acid; when treated with methyl sulphate it yields 2 7-dimethoxyxanthone C15H1204 yellow needles m. p. 180° which interacts with magnesium phenyl bromide yielding 2 7-dimethoxy-$!-phenyZxanthen-9-ol C21H1804 colourless prisms m. p. 153". The latter sub&ance when hydrolyeed by aluminium bromide in benzene yields quinolhenxein the chloroform compound of which 2CI,H140,,CHCl forms small colourless prisms OK C0H4*C02KORGANIC CHEMISTRY.i. 253 and decomposes at 100' ; the chloride C19H130,CI crystallises in brilliant red prisms or leaflets and is not readily hydrolysed by water. The black substance obtained by heating the chloroform compound at 100' is probably an anhydride of the ortho-quinonoid form of the carbinol or a mixed anhydride of the carbinol with the ortho-quinonoid form. 4. Euxanthone group.-PhemyZeuxanthenoZ dimethyl ether (2 ; 8- dimethoxy-9-phenyZzanthen-9-ol) C21HlS04 results from the interaction of magnesium phenyl bromide and euxanthone dimethyl ether; it crystallises in colourless prisms m. p. 164-165' and when treated with aluminium chloride in antimony trichloride yields 9-chloro-2 8- dihydroxy-9-phenyZxanthen C,,H,,O,Cl a vio€et-black crystalline powder ; the corresponding carbanol is obtained as a greyish-white flocculent precipitate by adding acetic acid t o a solution of the chloride in an excess of aqueous sodium hydroxide; it could not be obtained in a crystalline form ; the carbinol chloride is converted (1) by aqueous ammonia into the corresponding arnide C,,H,,O,N which crystallises with lC,H,N in colourless prisms and turns bluish-black when heated ; (2) by an alcoholic solution of sodium ethoxide into the carbinyl ethyl ether C21H which forms colourless prisms and rhombic plates m.p. 118-120" (decomp.) and when heated a t about 130-140' yields the anhydride of the carbinol C,,H1,O a bluish-black powder. W. H. G. Derivatives of Amino-acids. 111.Compounds with Choles- terol. EMIL ABDERHALDEN and KARL KAUTZSCH (Zeitsch. physiol. Chem. 1910 65 69-77. Compare t h i s vol. i 226).-Chloroacyl chlorides react with cholesterol yielding chloroacyl derivatives of the alcohol but it has not been found possible to replace the halogen in these compounds by the amino-group as ammonm simply hydrolyses the acyl derivatives to cholesterol and the acid nmide. ChoZesteryl a-bromoisovalerate CHMe2*CHBr*CO*O*C27H34 crystal- lises in rhombic plates sinters a t 130' and has m. p. 134*2-135=2" (corr.). Cholesteryl a-bronzoisohexoate crystallises in needles. Glycylcholesterol hydrochloride C,7H,,*O-CO*CH2*NH2,HCl ob- tained by the action of glycyl chloride hydrochloride on cholesterol in the presence of chloroform crystallises in slender needles which decompose at 250". The free base C27H,3-O*CO*CH2*NH2 has m.p. 140-5' (corr.) and [a]$ - 24.98' in chloroform solution. Cholesteryl isobutyrate CHMe,*CO*O*C,7H43 crystalliees in plates has m. p. 125' (corr.) after sintering at 108" and has [a] - 31.05' in chloroform solution. Cholesteryl isoualerate CHMe,*CH2-CO*O*C,7H43 has m. p. 1 ld' and [a] - 32.7". ChoZesteryZ Iaurate CllH2,*CO*O*C,7H, crystal- lises in slender needles has m. p. l l O o after sintering at 78' and [a] - 31 *3'. Cholesteryl palmitate C,,N,;CO*O*C,~H4 has m. p. 78.5-79.5' (corr.) and [a] - 24*2O and the StectrutP has m. p. 85-90" U17H,,*CO*O*C27H4,,i 254 ABSTRACTS OF QHEMICAL PAPERS. Resorcinol dichloroacatute C6H4(O*CO*CH$3)2 crystallises in four- sided colourless prisms m.p. 71 5-72'. Catechol dichloroacetate crys- tallises in brilliant long colourless prisms m. p. 57*5-58' and quinol dichloroacetate in brilliant plates m. p. 127'. The compounds are hydrolysed b r ammonia to the phenol and chloroacetamide. J. J. S. The Cholesterol Group. VI. Bombicesterol and the Presence of Cholesterol in the Chrysalis of the Silkworm. ANGELO MENOZZI and A. MORESCHI (Atti E. Accad. Lincei 1910 i 126-129. Compare Abstr. 1908 i 265).-The authors find that the chrysalis of the silkworm contains two members of the cholesterol group namely bombicesterol and ordinary cholesterol the latter constituting about 13-14% of the mixture. Various hydrocarbons are also present. The following new derivatives of bombicesterol have been prepared. Dihyclrobombicesterol obtained by passing hydrogen through an ethereal solution of bombicesterol in presence of platinum-black has m.p. 134' [u] + 19*1l0 ; i t gives an acetyl derivative m. p. 128' [a]? + 13.454 T. H. P. Action of Nascent Hypoiodous Acid on Unsaturated Acids. a-cycZoGeranic Acid. J. BOUGAULT (Compt. rend. 1910 150 397-399. Compare Abstr. 1905 i 9 ; 1906 i 848; 1908 i 179 269 537 983).-When a-cyclogeranic acid is dissolved in moist ether and treated with iodine and mercuric oxide it undergoes oxidation with loss of carbon dioxide. I n addition to substances of high boiling point the product contains Wallach's trimethylcyclohexenone C,B140 (Abstr. 1902 i tSOS) together with the corresponding alcohol 1 3 3- trirnethykA1-cyclohexene-6-ol C,H160. The latter was isolated by means of its phthalyl derivative and obtained as a viscous liquid with a camphoraceous odour b.p. 193'/760 mm. Di7 0.9310. The acetate has b. p. 206-207'. On oxidation it yields aa-dimethylglutaric acid the ketone beiug formed as an intermediate product. w. 0. w. a-cycZoGeranic Acid. J. BOUGAULT (Compt. rend. 1910 150 5 3 4-5 3 5. Compare preceding abstract) . -Merc uric a-c yclogeranate decomposes in aqueous solution liberating carbon dioxide and forming a complex liquid mixture identical with that obtained by the action of nascent hypoiodous acid on a-cyclogeranic acid. When the latter substance is added t o a boiling solution of mercuric acetate in acetic acid a good yield of trimethylcyclohexenyl acetate is obtained ; this is readily hydrolysed thus affording a convenient method for the preparation of trimethylcyclohexenol Trimethylcyclohexenone is readily prepared by heating the alcohol on the water-bath when it rapidly undergoesoxidation.[Dichlorobenzoic Acids and Substances Derived Therefrom.] FRITZ ULLMANN and CART WAGNER (AnnaEen 1910 371 388. Com- pare Gomberg and Cone this vol. i 58)-The dichlorobenzoic acid employed in a recent investigation (compare Abstr. 1907 i 846) was the 2 5- and not the 2 4-compound. The compounds obtained from W. 0. W.ORGANIC CHEMISTRY. i. 255 this acid are consequently 4-chlorodiphenylamine-2-carboxylic acid 3-chl~roacridone 5-chloro-2-phenoxybenzoic acid and 2-chloroxanthone. Melting-point and Saturation Curves of Binary Systems ; Substituted Benzoic Acids and Water.OTTO FLASCHNER and IRVINE GILES RANEIN (Monatsh. 19 1 0 31 23-50. Compare Trans. 1909 95 66S).-The solubilities of the hydroxy- nitro- amino- and chloro-benzoic acids of the toluic acids and of p-bromobenzoic acid p-iodobenzoic acid o-phthalic acid p-methoxybenzoic acid o-acetoxy- benzoic acid and of 1 3 5-dinitrobenzoic acid in water have been determined by AlexBeff’s method (Abstr. 1886 847) in order to trace the relation between constitution and solubility and the influence of the critical-solution point on the shape of the m.-p. curve. The results show that the introduction of a hydroxy- amino- nitro- acetyl or ‘carboxyl group into benzoic acid lowers the critical solution temperature whilst the presence of a methyl or methoxyl group or of a halogen atom causes a rise.The influence of position is not always the same; the hydroxy- and the amino-groups have the greatest lower- ing effect in the para- the nitro-group in the ortho- position. The elevating influence of the methyl group is the same in all three positions but that of the chlorine atom is greatest in the para-position. A comparison of the critical-solution point with any other property such as the m. p. or the dissociation constant shows that a close parallelism does not exist; the nearest agreement is shown in the case of the m. p.’s the critical solution points and the m. p.’s of substituted benzoic acids containing the same group always changing in the order Action of Concentrated Sulphuric Acid on Some Aromatic Nitroamines. FRBDPRIC REVERDIN (J. pr.Chem. 1910 [ii] 81 177-183; Bull. Xoc. chim. 1910 [iv] 7 130-136; C‘ornpt. rend. 1910 150 399).-The author gives instances of the reduction of the nitro- to the nitroso-group by concentrated sulphuric acid. Nethyl 3 5 - dinitro - 4 - nitromethylaminobenzoate digested with sulphuric acid for twenty-four hours at the ordinary temperature is converted into methyl 3 5-dinitro-4-nitrosomethylaminobenzoate and 3 5-dinitro 4-methylaminobenzoate ; if the reaction is prolonged for six weeks the first-mentioned ester and 3 5-dinitro-4-methylamino- benzoic acid are formed the same result being obtained in two and a-half hours however at 40-60°. 2 4 6-Trinitronitromethylaniline yields trinitromethylaniline by heating with concentrated sulphuric acid for many hours on the water-bath.Grimaux and Lefkvre (Abstr. 1891 1031) by the nitration of dimethyl-o-anisidine obtained amongst other products the nitrosoamine and the nitroamine of 3 5-dinitro- methylanisidine. The nitrosoarnine is converted quantitatively into the nitroamine by fuming nitric acid in the cold. The nitroamine is remarkable in that it responds to Liebermann’s test ; it is converted u. s. Partial Ester Formation of Benzoylaspartic Acid. HERMANN PAULY and JOHN WEIR (Ber. 1910,d43 661-670).-Half-esters of W. H. G. ortho mets para. c. s. into the nitrosoamine by concentrated sulphuric acid.i. 256 ABSTRACTS OF CHEMICAL PAPERS. benzoylaspartic acid may be produced either by opening the ring of the anhydride by means of methyl alcohol or by the partial hydrolysis of the normal ester with 1 mol.of alkali. The two methods yield the two isomeric half-esters practically free from admixture with their isomerides. That obtained from the anhydride is the a-methyl ester-P-acid C0,Me*CH(NHBz)*C.H2-C0,H ; it is converted by phosphorus pentachloride into the P-acid chloride and this by ammonia into the P-arnide which is identical with the compound obtained from benzoyl-Z-asparagine by the action of methyl iodide on the silver salt. The half-ester from the normal eater is accordingly the P-methyl ester-a-acid CO,H* CH( NHBz) CH,*CO,Me. Benzoylaspartic acid is about eight times as strong as succinic acid whilst the a-ester-P-acid is six times and the /I-ester-a-acid sixteen times as strong as the half-ester of succinic acid.It is the more strongly acid carboxyl which attracts the methyl group in the splitting of the anhydride and the metal when the normal ester is hydro1 ysed. The anhydride crystallises in asbestos-like needles m. p. 208-209" (corr.). a-Methyl P-hydrogen benxoybaspartate forms minute needles which sinter at 1 17-1 20° m. p. 123-124' K=0-0186. The cldoride prepared by the action of phosphorus pentachloride on the suspension of the acid in acetyl chloride in the absence of moisture by Fischer's method (Abstr. 1905 i 863) forms minute needles m. p. 143-144'. The nmide forms needles which sinter at 180° m. p. 184' [a] - 14-03' ; prepared by the esterification of benzoylasparagine it had ni. p. 184' [a] - 13.68". BenzoyZaspamginP prepared by benzoylating I-asparagine was obtained as needles m.p. 190-196' which contained about 10% of benzoylaspartic acid. Dim& yl benzoylaspartate prepared either by the action of methyl iodide on silver benzoylaspartate or by the action of methyl alcohol and dry hydrogen chloride on the acid forms needles m. p. 92.5' (corr.). P-Methyl a-lqdrogen benzoylaspartate forms prismatic plates m. p. 154' (corr.) K = @0500. It is less soluble than the isomeric acid. Benzoyl-Z-aspartic acid has K = 0.0531. E. F. A. Preparation of Organic Dithionic Acids (Carbithionic Acids). IGNAZ BLOCH and FRITZ HOHN (D.R.-P. 214888. Compare Abstr. 1906 i 847; 1907 i 382 474).-The clithio-acids of general formula R*CS,H have nsually been prepared by the action of organo-magnesium compounds on carbon disulphide which method is expensive and not of ready technical application.It is found that dithio-acids are easily prepared by treating the corresponding aldehyde with hydrogen persiilphide in the presence of condensing agents such as zinc chloride hydrogen chloride or sulphuric acid the reaction being general for both aliphatic and aromatic aldehydes. Phenylcarbithionic acid (dithiobenzoic acid) C,H,* CS,H is prepared from benzsldehyde crude h j clrogen persulphide and zinc chloride the excess of benzaldehyde being removed by steam; the bismuth salt is yellow ; the iyon salt green and soluble in et,her ; the methyl ester anORGANIC CHEMISTRY. i. 257 oil b. p. 1 5 4 - - 1 5 7 O / 2 2 mm. ; the ethyl ester a red oil b. p. 165-168O/19 mm. Thiobenzoyl disulphide S,(CSPh) forms dark lilac needles m.p. 1 1 7 O Houben (Abstr. 1906 i 847) gives 92.5'. BithiosaZicylic acid (o-hydroxyphenylcarbithio& acid) HO*C,H,* CS* SH m. p. 46-50' is more stable and separates from petroleum in orange- red needles; the lead salt crystallises from xylene in orange-red needles ; the methyl ester is an orange oil of unpleasant odour; the disdphide S,(CS*C,H,*OH) m. p. 122.5' forms brown leaflets with a blue metallic lustre. Bithioanisic acid ( p-methoxyphenylcarbithionic acid) CH,O*C,H,*CS,H forms dark rose-coloured oxidisable crystals ; the lead salt separates from xylene in orange-yellow needles ; the xinc salt forms rhombic yellow crystals ; the n~ercury salt glistening brown needles ; the bismuth salt is yellow ; the methyl ester m. p.31' forms lake-red leaflets ; the ethyl ester red crystals ; the disulphide S,(CB*C,H,OMe) dark red crystals and has m. p. 163'. These compounds are therapeutically active and are intermediate products in the colour industry. F. M. G. M. Preparation of Dibromophenylglycine-o-carboxylic Acid. AKTIENGESELLSCHAFT FOB ANILINFABRIKATION (D.R.-P. 2 1626 6).- Bromophenylglycine-o-carboxylic acid has previously been prepared by the action of bromine on phenylglygine-o-car boxylic acid in either mineral or acetic acid or organic solvents. A dibyomophenylglycine- o-carboxplic acid is produced when phenylglycine-o-carboxylic acid (19.5 parts) dissolved in 50% sulphuric acid is kept at 30' and constantly agitated whilst bromine vapour (32 parts) is introduced with a current of air.The crude product is dissolved in the calculated amount of alkali reprecipitated with hydrochloric acid and warmed when it becomes converted into a colourless crystalline powder insoluble in water but soluble in alcohol or acetic acid m. p. 227-228' (decomp.). That the bromine has entered the phenyl ring is shown by the non-formation of sodium bromide when the substance is boiled with sodium ethoxide. F. M. G. M. Syntheses Effected by Phenylacetonitrile. F. BODROUX and FELIX TABOURY (Compt. rend. 1910 150 531-533).-The sodium derivatives of nitriles of the type R=CHNa.CN prepared by treating the nitriles in ethereal solution with sodamide readily undergo condensation with alkyl halides ; thus ethyl iodide reacts with the sodium derivative of phenylacetonitrile forming a-phenylbutyronitrile (Neure Abstr.1889 597). a-PhenyZ-P-methylbutyronitrile CHPrfT?h.CN has b. p. 245-249'/765 mm.; D1j5 0,967; on hydrolysis it forms u-phenyl-P-methyl-n-butyrantide CHPrpPh*CO*NH silky needles m. p. 11 1-1 12'. a-Phenyl-y-methylvuleronitrile C,,H,,N has b. p. 263-266O/765 mm. ; D 0.942 When hydrolysed it yields a-plm~yZ- y-methylvaleric mid prisms m. p. 78-79'. w. 0 w.i 258 ABSTRACTS OF CHEMICAL PAPERS. Acids of the Phenylpropiolic Series and their Condensation to Naphthalene Derivatives. JOHN E. BUCHER (J. Amer. Chem. Soc. 1910 32 212-221).-A review of work done in connexion with phenglpropiolic acid and its derivatives with special reference to that of the author and his collaborators (compare Michael and Bucher Abstr. 1896 i 85; 1898 i 256 ; Bucher Abstr.1908 i 791 ; Bucher and Slade this vol. i 38). Preparation of Di- and Tetra-hydro-P-ketonic Acids or their Esters. ARTHUR KOTZ (D.R.-P. 215424).-When the halogen derivatives of hydroaromatic-p-ketonic-carboxylic acid esters are treated with agents for removing halogen or distilled under atmospheric pressure hydrogen halide is eliminated and un- saturated compounds many of which are of therapeutic value are produced. The preparation and properties of 2-bromocycZohexanone A2-cyclohexenone and its semicarbazone and of ethyl-2-hydroxy-A' cyclohexadienecarboxylate from ethyl bromo-1-cyclohexanone-2-carb- oxylate are described (compare Abstr. 1908 i 173). Ethyl 4-bromo-l-methyl-3-cyclohexanone-4-carboxylate on distilla- tion yields ethyl 1-methyl- A3-~yclohexen-5-one-4-carboxylate (I) a yellow oil b.p. 110°/15 mm. or its enolic form ethyl 1-methyl- A2:4-hex~idie(ne-3-ol-4-carboxylute (11) the bromination of which with E. G. * (11.) 2 atoms of bromine in carbon disulphide solution leads to the forma- tion of ethyl 4 5-dibromo-l-methyl-A2-cyclohexene-3-ol-4-carboxylate (111) ; this on distillation gives ethyl bromo-l-rnethyl-A25-cyclohexudiene- 3-oZ-4-carboxylate (IV) a pale yellow oil b. p. 161°/13 mm. UV.1 F. M. G. M. Preparation of a-Monohalogen-substitution Products of Hydroaromatic-/3-ketonic-carboxylic Esters. ARTHUR KOTZ (D.R.-P. 215423).-The a-halogen-substitution products of hydro- aromatic-P-ketonic carboxylic esters can be obtained by the direct halogenation of these substances. EthyZ l-chloro-2-cyclohexanone-l-carboxyZate C H < ~ $ ~ ~ > C C l * CO,Et b.p. 138-139'/13 mm. an oily fluid with penetrating odour isORGANIC CHEMISTRY. i. 259 Obtained when ethyl 2-cyclohexanone- 1 -carboxylate is cooled and treated with dry chlorine ; hydrogen chloride is removed by a current of dry carbon dioxide and the product distilled under reduced pressure . Ethyl 1 - bromo-2-cyclohexanom- 1 -carboxy late is similarly prepared by employing bromine instead of chlorine as in the previous experiment ; it is a pale yellow oil with unpleasant odour and has b. p. 144'/13 mm. CH,. C H < ~ ~ ~ ~ ~ ~ ~ > C C l * C 0 2 E t b. p. 138'/11 mm. is obtained from ethyl l-methyl-3-cycZohexanone-4- carboxylate but the action proceeds with less violence. Ethyl 1-bromo-1 -methyZ-3-cyclohexc~nom-4-carboxyZate b.p. 149-150°/ 12 mm. has similar properties but in this case the reaction does not proceed readily unless hydrogen bromide is expelled by shaking during the experiment. Ethyl 4-chloro- 1 -methyl-3 -c y clohexanone-4 -carboxykate F. M. G. M. Some Derivatives of Salicylic Acid. ALFRED EINHORN and ALEXANDER VON BAGH (Ber. 19 10 43 322-336).-0-4-NitrobenxoyZ- oxgbennxoic acid CO2H.C~H,.O*C0*C,H3"O m. p. ZOS' is a yellow crystalline powder obtained by adding a benzene solution of p-nitro- benzoyl chloride to a well cooled solution of salicylic acid and di- methylaniline in the same solvent. m. p. 107-108' prepared from ethyl salicylate and p-nitrobenzoyl chloride in pyridine is reduced by stannous chloride and alcoholic hydrogen chloride to ethyl 0-4-aminobenaoyloxybenxoate m.p. 109-1 loo. Ethyl 0-4-dimethykuminobenzoyZoxybenxoGcte m. p. 1 0 6 O is obtained by heating ethyl salicylate and p-dimethylaminobenzoic anhydride for ten hours at 180-200'. The chZos*ocarbonate of methyl salicylate CO,Me*C,H,*O-COCl m. p. 24O h p. 141-142O/O mm. is ultimately obtained when a cooled 20% benzene solution of carbonyl chloride is slowly added to methyl salicylate and quinoline dissolved in benzene ; its ethereal solution yields with ethereal ammonia the caybarnate CO,Me*C,H,*O*CO*NH m. p. 145O and with ethereal diethylamine the disthylcarbamate b. p. 182O/O mm. The passing of hydrogen chloride into a well-cooled suspension of the carbamate in 40% form- aldehyde leads to the formation of the cZichZorodimethyZca1.bccmctte CO,Me*C,H,*O*CO*N( CH,CI) m.p. 75-76O a cold ethereal solution of which reacts with piperidine to form methyl salic J late formaldehyde and a-pipe?*idyl-P-( 1 )-piperidyZ- methylcarbamide C,NH,,*CO*NH*CH,*C,N Hlo m. p. 142-143'. The ethyl ester C0,E t C,H,* 0 * COO C,H,*NO o-CarbomethoxyphenyZ m-carbethoxyphenylcaybamate CO,Me* C,H,*O* CO*NH* C,H,* CO,Et m. p. 123' is obtained by slowly mixing cold ethereal solutions of the chlorocarbonate of methyl salicylate and ethyl m-aminobenzoate. The corresponding para-compound m. p. 153-154' prepared in a similar manner loses methyl alcohol after some hours a t 130-140' andi. 260 ABSTRACTS OF CHEMICAL PAPERS. yields the ethyl carbonylsalicyl-p-acminobmxoate m. p. 185-187" described below.0- Eth ylcarbonatobenxo yl chloride COCl*C,H,*O*CO,E t b. p. 155-165O/20-25 mm. obtained by the action of phosphorus penta- chloride on o-ethylcarbonatobenzoic acid (Abstr. 1909 i 161) in chloroform reacts with methyl anthranilate in cold pyridine to form methyl o-ethylcarbonutobenxoyZanthrunilate C02Et*O*C,H4*C0.NH*C6H4*C02Me m. p. 113' which loses ethyl alcohol at 230° forming methyl carbonyl- salicyl-o-aminobenxoate C02Me*CsH4*N<co->C6H4 co*o m. p. 145". o-Ethylcarbonatobenzoyl chloride reacts with ethyl m-aminobenzoate in cold pyridine directly to form ethyl carbony~sc6~~cy~-m-~~~nobenzoate m. p. 185-186O and similarly with ethyl p-aminobenzoate to form ethcyl carbonylsulicyl- p-aminobenzoate M. p. 185-1 87'. Ethyl o-ethyl- ccwbonutobenzoy I-p-aminobenxoate CO,E t *C,H,-NH CO C6H4*O*C02E t m. p.90-92' is obtained however when an ethereal solution of ethyl p-aminobenzoate is treated with o-ethyl cnrbonatobenzoyl chloride at 0'; it is converted into the preceding compound at 160-200'. o-Ethylcarbonatobenxoic unhydride O(CO*C,H,*O*CO Et) m. p. 62-64' is obtained fxom salicylic acid diethyl dicarbonate (D.R.-P. 11 7267) by prolonged keeping and is converted by cold concentrated ammonium hydroxide into cccirbon?/Zsulicylumide m. p. 227'. C. S. Colourless a.nd Yellow Thiosalicylic [o-Thiolbenzoic] Acids. OSCAR HINSBERG (Ber. 1910 43 651-654).-o-Thiolbenzoic acid SH*C,H(CO,H exists in a colourless as well as in the ordinary yellow modification whereas its methyl and acetyl derivatives have been obtained in colourless modifications only.Other thiophenols also exist i l l two modifications (Abstr. 1906 i 654). a-o-Thiolbenzoic acid obtained by treating the crude acid or dithiosalicylic acid (rn. p. 289') with glacial acetic acid tin and con- centrated hydrochloric acid until all is dissolved crystallises in colour- less prisms m. p. 164-165'. It is less soluble than the yellow isomeride from which it is obtained by treatment with stannous chloride and glacial acetic acid or by heating at 200". The yellow isomericie P-o-thiolbenzoic acid has m. p. 163-164" after softening at 158'. The rnethgl ether SMe*C6H4*C02H crystallises in long colourless needles m. p. 169" and undergoes no alteration when heated to 250'. o-Acetylthiolbenxoic acid SAC* C,H,*CO,H crystallises in colourless needles m.p. 125' and when hydrolysed with hydrochloric acid yields a-o-thiolbenzoic acid. J. J. S. Derivatives of Thiosalicylic [o-Thiolbenzoic] Acid and of Thioxanthone. FBITZ MAYER (Ber. 1910,43 584-596. Compare Abstr. 1909 i 405,823).-Methyl carboxy- polynitro- and chloronitro- derivatives of thiosalicylic [o-thiolbenzoic] acid have been prepared mainly by heating substituted benzoic acids with thiosalicylic acid and copper powder under pressure. The products can be oxidised in much the same manner as the corn- pounds already described but it is found that 2 2'-thiodibensoic acid,ORGANIC CHEMISTRY. i. 261 like other ortho-compounds is completely destroyed by chromic acid ; the ester on the other hand is readily oxidised to a sulphoxide ester.Dinitro-2 2'-thiodibenzoic acid is only slowly oxidised by chromic anhydride in acetic acid solution and the s-trinitro-derivative is extremely resistant to oxidising agents (Blanksma Rec. traw. china. 1901 20 426). Most of the sulphides can be transformed into thioxauthones by means of sulphuric acid. The dinitro-derivative does not yield a thio- xanthone by this method but the corresponding amino-compound does. When the acid chloride of dinitrothiodibenzok acid is heated with aluminium chloride and nitrobenzene it yields 2 4-dinitrothio- xanthone but with benzene and aluminium chloride yields 2 4-dinitro- 2'-benzoyldiphenyl sulphide. The thioxanthonecarboxylic acids readily loses carbon dioxide yield- ing thioxanthones. 4-Methyl-2'-carboxydiphenyl sulphide [Z Z'-thio-4-methyldibenzoic acid] (compare Goldberg Abstr.1905 i 59) can be prepared by con- densing o-diazobenzoic acid with an alkaline solution of p-thiocresol. The corresponding sulphoxide C,H,Me*SO*C6H4*C02H crystallises in colourless needles and has m. p. 244O after softening at 236'. 2-MethyZthioxanthone C,H,<i\>C,H,Me crystallises in yellow needles m. p. 1 2 3 O and when oxidised with chromic anhydride yields 2-methylbenzophenonesulphone (Ullmann and Lehner Abstr. 1905 i 290). 2 2'-Dicarboxydiphenyl sul@hicle [2 2'-thiodibensoic acid] S(C6B4*C02H)2 obtained by heating thiosalicylic acid o-chlorobenzoic acid copper powder potassium carbonate and water a t 135-140° for three hours crystallises in colourless needles m. p. 229-230°. The methyl ester C,,H,,O,S has m.p. 84O and the ethyl ester C,,Hl,04S m. p. 5 7-5 8'. 2 2'- Dicarboxydiphenyl sulphoxide [sulphonyldibenxoicaoic acid] o:s( C6H,* CO,H) is best obtained by hydrolysis of its esters and crystallises in well developed colourless prisms m. p. 312'. The methyl ester C16H1405S crystallises in brilliant plates m. p. 156O and the ethyl ester in compact needles m. p. 107-108'. 2 2'-Dicar6ox~diphenyl8~zpho~ S02(C6H,*C0,H) obtained by oxidising the suiphide with perman- ganate crystallises in felted needles m. p. 138-139O. Thioxanthone- c18H1805s) 4-carboxylic acid C,H4<cO>C6H3*C02H 8- forms yellow microscopic crystals m. p. 336-33'7'. The methyl ester Cl5H1,O3S has m. p. 19l0 and the amide Cl,H,02NS forms pale yellow needles m. p. 286'. 0-2' 4'-Dinitrophenylthiolbenzoic acid C6H3(~02)20SoC6~4'C02H obtained from 1-chloro-2 4-dinitrobenzene forms yellow crystals m.p. 179-180°; the methyl ester has m. p. 117-117.5°; the sulphoxila C,,H,07N2S forms compact pale greenish-yellow crystals m. p. 239-240° and yields a meth,yl ester C,,Hl,07N2S m. p. 171-172O ; VOL. XCVIII. i. ti 262 ABSTRACTS OF CHEMICAL PAPERS. the sulphone C,,H,O,N,S forms colourleas crystals m. p. 215-217" ; 2 4-dinitro-2'-benxoyldap~~nyl sulphide C,H,(N02),*S*C6H4~COPh has m. p. 155-156O and the corresponding toluoyl derivative (N02)2C,H3*S*C,H4*CO*C,H,Me has m. p. 1220. 2 4-Dinitrothioxanthone c,H~<~~>c,H,(No~) forms greenish-yellow needles with a metallic lustre and has m. p. 0-2' 4' 6'-~r~nitrophelzylthioZbelzxoic acid (N02),C6H2~S~C,H4~C02H~ obtained from picryl chloride forms yellow crystals m.p. 240-241". The rnethyl ester forms brilliant reddish-yellow needles m. p. 181 *5O. 2 25-2 2 6". 0-4'-Chloro-2'-nitrophen ylthiol be2 uoic acid N 0,. C,H3CL*S ' C6H4* co,H has m. p. 155-156*5" and 2-chZoro-4-natrothioxantho:,~e C6H~<~O>c~H2C1'R02 forms slender yellow needles m. p. 219-220". o-5-Chloro-2-nitrophenylthiolbenxoic acid C,,H,O,NClS obtained from 1-chloro-3 .Q-dinitrobenzene has m. p. 188-189" and 1-chloro- 4-nitrothiownthor~e C,,H,O,NClS m. p. 204-205". Action of Sulphosalicylic Acid on Trisodium Phosphate. LI~ONCE BARTHE (Compt. remnd. 1910 150 401-403. Compare Abstr. 1908 i 271 ).-#odium oxyphosphodisulphosalicylate PO[O*C6H,(S03H)*C0,Na]2*ONa is obtained in the form of brilliant prisms containing 2H,O when a boiling aqueous solution of trisodium phosphate is mixed with an alcoholic solution of sulphosalicylic acid.The compound is a dibasic acid ; it gives a red coloration with Millon's reagent and a bluish- violet colour with ferric chloride. By the interaction of trisodium arsenate and sulphosalicylic acid a compound has been obtained the composition of which appears to agree with the formula AsO[O*C,H,(S~~H)*C~~N~],. J. J. S. w. 0. w. Preparation of 0- and peri-Thiophenolcarboxylic Acids. FARBWEBKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 216269).- 0- or peri-Cyanoarylsulphinic acids are obtained in the form of their zinc salts by the slow reduction at the ordinary temperature of cyano- arylsulphonyl chlorides with zinc dust and water ; the free acids are colourless powders sparingly soluble in water without characteristic melting point and readily undergo atmospheric oxidation to the corresponding sulphonic acids.The zinc salts are somewhat sparingly soluble in water. When the preceding reduction mixture is treated with sulphuric acid and a further quantity of zinc and the action allowed to proceed during several days until the evolution of nitrogen ceases the corresponding zinc thiophenolcarboxylates are precipitated the hydrolysis of the nitrile group having taken place simultaneously with the reduction OF the sulphinic group. These acids are colourless crystalline powders soluble in alkali carbonates yielding character- istic colours with concentrated sulphuric acid and are readily oxidised to the corresponding dithio-acids.ORGANIC CHEMISTRY.i. 263 5-Chloro-3-thiol-o-toluic acid SH*C,H,MeCl*CO,~ m. p. about 2359 is prepared by treating diazotised 5-chloro-o-toluidine-3-sulphinic acid with cuprous cyanide and the 2-cyanotoluene-3-sulphinic acid then formed with phosphorus pentachloride and subsequently re- ducing first with zinc dust in acetone solution and finally in the presence of sulphuric acid ; it forms colourless needles yields a blue coloration with concentrated sulphuric acid and is readily oxidised to dithiochlorotoluic acid. The following compounds are mentioned in the patent 3-Thiol-p-toluic acid SH*CtH,Me*C02H prepared from the corre- sponding cyanotoluenesulphinic acid. 6-Thiol-2 4-dimethylbenxoic acid SH*C,H,RIe,*CO,H from cyano- xylenesulphinic acid. 2-Thiolnaphthalene-1 -carboxylic acid SH* C!,H,*CO,H from 1 -cyano- naphthalene-2-sulphinic acid ; and 8-thzolnaphthalene- 1-carboxylic acid from the corresponding 1 8-cyanosulphinic acid.F. M. G. M. Methyl Anisoylacetates. ANDRE WAHL and C. SILBERZWEIG (Compt. rend. 1910 150 538-540. Compare Abstr. 1908 i 647). -The three methyl anisoylacetates have been prepared by condensing methyl acetate with 0- m- and p-methoxybenzoic acids in presence of sodium. Nethyl o-anisoykacetate OMe*C,H,*CO*CH,*CO,Me is a pale yellow liquid boiling a t 179-180"/15 mm. with formation of small quantities of o-ccnisoyldehydracetic acid occurring in yellow crystals m. p. 214-215". The green copper salt (C,,H,,O,),Cu has m. p. 170-172'; a solution in methyl alcohol deposits on boiling blue crystals of a basic salt C12H1,0,Cu (compare Wislicenus Abstr.1899 i 192). The follow- ing derivatives of the new ester are described the nitroso-derivative m. p. 145-147' ; o-arkoylphenylpyrazohne m. p. 133 - 134' ; o-anisoyl-p-nitrophenyZpyrctxolone m. p. 2 17-2 18" ; methyl benxeneatxo- o-anisoylucetate m. p. 138-139'. Methyl m-anisoylacetate is an amber-coloured liquid b. p. 180'/14 mm. forming a green coppeg. salt m. p. 172-173" and a nitroso-derivative m. p. 115-1 16O. m-Anisoyldehydracitic acid occurs in yellow crystals m. p. 185'. m-Anisoylphen~Zpyraxolone has m. p. 1.24'; methyl benxeneaxo-m-anisoyhcetate has m. p. 72 -73'. Methgl p-anisoylacetate forms pale yellow crystals m. p. 27-28' b. p. 190-192'/10 mm.The copper salt has m. p. 248-250° and the nitroso-derivative m. p. 154". p-Anisoyldehydracetic acid has m. p. 190" ; p - a n i s o y l p ~ ~ e n y ~ y r ~ z o l o ~ has m. p. 136-137O. Nethyk benxewazo-p-anzsoylacetute m. p. 121-1 22" forms an acetyl derivative m. p. 111-113'; as this yields acetanilide on reduction it would appear to be an acetylhydrazone (compare Schoonjans Abstr. 1898 i 435). w. 0. w. Action of Amines on Phthalic Acid. VI. J. BISHOP TINGLE an B. F. PARLETT BRENTON (J. Amer. Chem. Soc. 1910,32,113-117). -A study has been made of the action of phthalic anhydride on several amino-compounds. With camphylamine phthul~lcarrzyhylimi~e t 2i. 264 ABSTRACTS OF CHEMICAL PAPERS. C,H,<~~>N*CloH7 m. p. 54" is produced. I n the case of benzi- dine an insoluble compound is obtained which does not melt below 300O.m-Aminobenzoic acid yields phthalyl-rn-aminobenzoic acid C02H*C,H4*NH*CO*C,H4*COzH (compare Gabriel Abstr. 1 S79 323 and Piutti Abstr. 1883 999). Acetanilide ace t 0-p -t oluidide and formo - (I-naphthalide react with phthalic anhydride with the replacement of the acetyl or formyl group by the phthalyl group phthalyl-P-naphthylimide for example being produced from formo-P-naphthalide. Carbamide methylcarbsmide ethylcarbamide benzylcarbamide and phenylcarbamide are con- verted into phthalimide methylphthalimide ethylphthalimide benzyl- phthalimide and phenylphthalimide respectively ammonia and carbon dioxide being evolved in each case. Phenylthiocarbamide behaves in the same way as phenylcarbamide except that carbonyl sulphide is evolved instead of carbon dioxide. Action of Unsaturated Dicarboxylic Acids on p-Amino- phenols.AENALUO PIUTTI (Rend. Accad. Sci. Pis. Mcbt. Napoli 1909 [iii] 15 315-318).-8 resume is given of the work of the author and his assistants on the amic acids imides and diamides derived from the actions of maleic fumaric citraconic mesaconic itaconic pyro- cinchonic phthalic and camphoric acids on various p-aminophenols (compare this vol. i 22). The cases of chromo-isomerism and of true chemical isomerism observed with these compounds are indicated. E. G. T. H. P. New Synthesis of 4 4'-Dimethylpyranthrone. ROLAND SCHOLL KURT LIESE KARL MICHELSON and ERNST GRUNEWALD (Bey. 1910 43 512-518. Compare this vol. i 271).-The reaction in carbon disulphide between 2 4 2' 4'-tetramethyl-1 1'-diphenyl phthalic anhydride and aluminium chloride leads to the formation of a tarry product containing a t least three substances.The residue left by treating the product with a large volume of cold benzene is crys- tallised from chloroform and consists of 2 4 2' 4'-tetrumethyl- dipheiayl-5 5'-diplhthalop?ic acid CJ2H4Me,(CO* C,H,*CO2H) m. p. 242O the constitution of which is proved by Its conversion by concentrated sulphuric acid into 2 4 - 2' 4'-tetramethyl-1 1'-dianthra- quinoyl which in turn was converted into 4 4'-dimethylpyranthrone. The benzene extract of the tarry product is evaporated aEd the residue is separated by ether and by cold chloroform into two substances the one soluble the other insoluble. The latter is recrys- tallised from nitrobenzene and consists probably of 2 4 2' 4'-tetm- methyldiphenyl-3 3'-diphthaloylic acid m.p. 320° since it is con- verted by concentratdd sulphuric acid not into a n anthraquinone derivative but into a disulphonic acid C,,H,,012S2. The soluble substance has not been obtained pure. It has m. p. 92-94' and appears to have the composition C,,H2,O5 ; it is not an anthraquinone derivative and is not converted into one by concentrated sulphuric acid at 120° is soluble in dilute alkali and is provisionally regarded as 2 4 8' 4'- tetrametAy1- 5 5'-phthalo?/ldi~l~e?zyl-3-p~~t~alo~~ic acid. c. 8.ORGANIC CHEMISTRY i. 265 Constitution of Tannin. VII. MAXIMILIAN NIERENSTEIN (Be?.. 1910 43 628-634. Compare Abstr.1906 i 446; 1907 i 331 ; 1908 i 80 897 ; 1909 i 402 948).-The following facts are brought forward in favour of the view that pure tannin is a mixture of a digallic acid and leucotannin. By repeated conversion into its ethyl carbonato-derivative and hydrolysis of this with pyridine (Fischer Abstr. 1908 i 892) it has been found possible to isolate digallic acid in a crystalline optically inactive form. d-Z-Hexa-acetyl-leucotannin can be obtained by the reduction of penta-acetyldigallic acid with zinc dust and acetic acid in the presence of acetic anhydride and is readily resolved into its optically active com- ponents by means of strychnine. Both acetyl compounds can be hydrolysed by means of sodium carbonate solution saturated with carbon dioxide. The view that the activity of tannin is due to the leucotannin and not to the presence of a sugar (Abstr.1909 i 174) is still held. Digallic acid C,H:,(OH),*CO*O*C,H2(OH)2*C02H crystttllises with 2H20? which it loses at llOo and then has m. p. 268-270° after sintering a t 214'. It is inactive and when oxidised with hydrogen peroxide yields luteoic and ellagic acids (Abstr. 1908 i 897). The pentcc-acetyl derivative C24H20014 crystallises in slender needles m. p. 21 1-?14O and the pentccbenxoyl derivative C,,H,,O, has m. p. 187-1 89'. The pentaetJ&arbonato-compound C6H2( O*CO,Et ),* CO*O*C,H,( 0. CO,Et),*CO,H crystallises i n small cubes m. p. 194-195'. d-1- Hexa-acetyl-Zeucotannin C6H2(OAc),*CH(C)Ac)*O*C,H2(OAc)2*C02H also crystallises in small cubes m. p. 154-155'.Strychnine 1-hexa-acetyl-leucotannin is less soluble than the d-salt and I-hexa-acetyl-leucotannin itself crystallises in minute needles containing 1H,O and having m. p. 151' and [a] -46'. The d-compound has m. p. 153-154' and [a] + 121.5'. The digallic acid is not identical with Fischer's acid. J. J. S. Methylcarbonato-derivatives of Phenolcarboxylic Acids and their Use for Synthetic Operations. IV. EMIL FISCHER and KARL FREUDENBERG (AnnaZen 191 0 3'72 32-68. Compare Fischer Abstr. 1908 i 892 ; 1909 i 161 309).-The present communication contains a description of the syntheses of many complex substances which have been effected by coupling the sodium salts of phenolcarb- oxylic acids with the chlorides of methylcarbonato-carboxylic acids ; for example p-ethylcarbonatobenzoyl-p-oxybenzoyl chloride reacts with sodium p-hydroxybenzoyl-p-oxybenzoate yielding the ethyl- carbonato-derivative of tri-p-oxybenzoyl-p-oxybenzoic acid C02Et*O*C6H,*CO*O*C6H4*CO*O*C6H4*C~*O* C,H,*CO,H which when hydrolysed cautiously yields the corresponding phenol- carboxylic acid ; di-p-oxybenzoyl-p-oxybenzoic acid OH*[ C6H,*CO*O*],*C6H,*C02H is similarly prepared from pethylcarbonatobenzoyl chloride and p-hydroxybenzoyl-p-oxybenzoic acid.It will no doubt be possible t o prepare by similar means n large number of analogous substances fromi. 266 ABSTRACTS OF CHEMICAL PAPERS. other hydroxybenzoic acids and since many undoubtedly occur in nature as for example tannin it is .considered advisable to classify them under the collective name depside ( ~ ~ $ E L Y tan) and as in the case of the polysaccharides and polypeptides to distinguish between di- tri- tetra-depsides etc.according to the number of phenolcarboxylic acid residues contained in the molecule. The preparation and properties of vanilloylvanillin and vanilloyl- glycine are described likewise a method whereby a 45% yield of p-hydroxybenzoyloxybenzoic acid may be obtained by acting on an ethereal solution of p-hydroxybenzoic acid with phosphoryl chloride. p-EthyZcar6onatobenxoic mid C@,Et*O*C,H,*CO,H prepared from p-hydroxybenzoic acid and ethyl chlorocarbonate crystallises in long colourless needles m. p. 156-157' (corr.) ; the chloride Cl0H9O4CI has m. p. 41' b. p. 170'/12 mm. The latter substance interacts with phydroxybenzoyl-p-oxybenzoic acid in an aqueous solution of sodium hydroxide yielding ethy hadonat odi- p-oxy benxoy E-p-ox y benxoic acid which crystallises from amyl alcohol in aggregates of colourlesfs leaflets and from pyridine in small slender needles m.p. 243-244' (corr. decomp.) and when hydrolysed cautiously yields di-p-oxybensoyl-p- oxybernxoic acid C,,H1,07 which crystallises in long colourless needles commences t o decompose a t 283' (corr.) fuses at 300' (corr.) and is probably identical with the compound obtained by Klepl by strongly heating p-hydroxgbenzoic acid (compare Abstr. 1884 446). p-Ethylccwbonatobenzo?/loxybenzoic acid Cl7HI4O7 obtained by the action of p-ethylcarbonatobenzoyl chloride on p-hydroxybenzoic acid crystallises in colourless leaflets m. p 112' (corr.); the chloride Cl1HI,O6C1 crystallises in small slender needles m. p.11 3' (corr.) and couples with p-hydroxybenzoyloxybenzoic acid yielding ethyl- carbonatotvi-p-oxy6enzoyl-p-oxybenxoic acid C,,H,,0, which crys tallises from acetylene tetrachloride in stellate aggregates of microscopic slender leaflets m. p. 275' (corr. decomp.) and on partial hydrolysis yields tri-p-oxybenxoyl-p-oxybenxoic acid crystallising from ethyl oxalate in microscopic colourless silky needles m. p. 325' (corr. decomp.) ; the tetradepside is extremely insoluble in organic solvents and is not identical with Schiff's tetra-p-oxybenzoid (compare Abstr. 1883 335). C24H,8099 OH* [C,~,*C~~O*~,C,H,*CO,H 4-Methylcarbonato-3-methoxybenzoic acid CO,Me*O*C,H,( OMe)*CO,H is prepared by the interaction of vanillic acid and methyl chlorocarbon- ate in a N-sodium hydroxide solution ; it crystallises in small colourless needles m.p. 159' (corr. decomp.) and may be sublimed in a current of carbon dioxide at 145-150'; i t does not give a coloration with ferric chloride although contrary to Tiemann's statement (compare Abstr. 1875 1198) vaniilic acid gives an intense reddish-brown coloration ; the chloride CloH905Cl crystallises in small colourless needles m. p. 79' b. p. 18O'(corr.)/ll mm. and interacts (1) with p-hydroxybenzoic acid yielding 4-methylcarbortato-3-methoxybencoyl-p- oxybennoic acid C0,Me*O*C,H,(OMe)*CO*O*C6H4*C02H colourless microscopic leaflets In. p. 21 9' (corr. decomp.) which is hydrolysedORGANIC CHEMISTRY. i. 267 by a cold NIsolution of ammonium hydroxide yielding uanilloyl-p- oxybenxoic acid OH*CGH,(OMe)*CO~O*C,H4*C02H small needles prisms and leaflets rn.p. 227' (corr.); (2) with p-hydroxybenzoyl- oxybenzoic acid yielding 4-methylcarbonato- 3 -methoxybenzoyl- p- oxybenxoyl-p-oxybenzoic acid C2,H1801, glistening slender leaflets and needles m. p. 244-246' (corr.) the chloride of which C2,H170CI crystallises in microscopic leaflets m. p. 170-171 (corr.) ; the former compound when hydrolysed yields vanilloyl-p-oxybennxoyl-p-oxybenzoic acid C2,H1608 m. p. 241' (corr.) crystallising with 1Me*OH in long slender prisms ; (3) with vanillin yielding 4-methylcarbonato-3-methoxy- benzoylvanillin C,,H,,O arid is converted by a dilute aqueous methyl- alcoholic solution of sodium hydroxide into vanilloylvanillin OH* C6H3(OMe)*C0,*C,H,(OMe) *CHO crystallising in tufts of colourless,.glistening needles m. p. 140-141O (corr.) the sodium hydrogen sulphite compound of which forms slender colourless needles ; (4) with ethyl aminoacetate yielding ethyl 4methyZ- carlionato-3-methoxybennxoylaminoacetate C14H1707N which crystallises in glistening four-sided leaflets m. p. 93-94' (corr.) and on hydrolysis yields vanilloylglycip OH* C,H,(OMe)* CO* NH*CH,*CO,H short microscopic prisms m. p. 167" ; the latter substance crystallises with H,O in large colourless leaflets which sinter at about 75'; it has both an acid and bitter taste. 4-~fethylcnr6onato-3-methozybenzoyl-poxybenzoyl chloride C,,H,,O,Cl crystallises i n microscopic leaflets and needles m p. 128-129' (corr.) and reacts with p-hydroxybenzoyloxybenzoic acid yielding 4-methyl- cccrbonato-3-methoxybenzoyldi-p-oxyb~zo~l-p-oxyben~o~c acid CO,Me* 0.C6H3( OMe) C02-[C,H4*CO*O*],C,H4*C0,H which crystallises in stellate groups of small leaflets m. p. 272' (corr. decomp.) andl when hydrolysed yields vanilloyldi-p-oxybenzoyl-p- oxybenzoic acid crystallising in small needles and microscopic spear- shaped plates m. p. 254' (corr. decomp.). 4-Methylca~bonato-3-methoxybenxaldehyde Ci,Hl,O prepared from vanillin and methyl chlorocarbonate forms colourless needles m. p. 89' (corr.) ; it yields the corresponding acid when oxidised with potassium permanganate which readily passes into vanillic acid W. H. G. EUGEN BAM- BERQER and FRANZ ELQAR (Annalen 1910 371 319-365).-The formation of ethyl o-nitrosobenzoate by the action of light on an ethyl- alcoholic solution of o-nitrobenzaldehyde (compare Ciamician and Silber Abstr.1901 i 390; 1902 i 433) is shown to take place in the following stages NO,*C,H,*CHO E " o ~ NO,*C,H,*CH(OEt) -+ [NO*C6H,*C(OEt),-OH] -+ NO*C,H,*CO,Et + Et*OH ; it has been found possible to isolate the o-nitrobenzaldehydediethylacetal formed in this way. A second reaction takes place simultaneously namely the formation of 2 2'-azoxybenzoic acid by way of o-nitrosobenzoic acid. Methyl alcohol propyl alcohol isopropyl alcohol and isobutyl alcohol react in the same way as ethyl alcohol ; in the case of hopropy1 alcohol however only a very small quantity of isopropyl o-nitroso- benzoate is formed the chief product being o-nitrosobenzoic acid ; fhis is found to be due to the slow rate with which the isopropyl- Photochemistry of o-Nitrated Benzaldehydes.i. 268 ABSTRACTS OF CHEMICAL PAPERS.metal of o-nitrobenzaldehyde is formed for the latter substance decomposes into isopropyl o-nitrosobenzoate and isopropyl alcohol under the influence of light with almost the same readiness with which the other acetals undergo the analogous transformation. Quantitative experiments carried out with the alcohols mentioned show that the rate with which the acetal is formed either through the agency of sunlight or by using hydrogen chloride as a catalyst decreases as the mol. wt. of the alcohol increases except with isopropyl alcohol when the quantity of acetal formed in a given time is con- siderably less than with isobutyl alcohol.The behaviour of 2-nitro-4 5-dimethoxybenzaldehyde 3 6-dichloro- 2-nitrobenzaldehyde and 2 4 6-trinitrobenzaldehyde under similar treatment has been studied. The first named undergoes the same transformations as the parent substance. The dichloro-compound when dissolved in methyl or ethyl alcohol is converted under the influence of light into the corresponding acetal and 2 2'-azoxybenzoic acid derivatives but esters of a dichloronitrosobenzoic acid are not formed possibly because the intramolecular reaction - =cc1 >C*CH(OR) -+ -~~$XW(OR),*OH -C(*O2) is prevented by steric hindrance; a solution of the aldehyde in benzene when acted on by sunlight yields 3 6-dichloro-2-nitrosobenzoic acid. The formation of an ester of o-nitrosobenzoic acid by the decomposition of an o-nitrobenzaldehydeacetal imdoubtedly takes place through the intermediate formation of the compound NO C6.H4* C (OR) ," OH since under similar conditions o-nitrobeDzaldehyde passes into o-nitrosobenzoic acid ; consequently it is extremely probable that the esterification of an acid proceeds through the mono-alkylated ortho-acid -CO,H 5sH [-C(OH),*OR] -+ -CO,R + H,O a suggestion first advanced by Henry.The following acetals were prepared by the action of hydrogen chloride on a mixture of the aldehyde and alcohol; they were also obtained by exposing solutions of aldehyde in the necessary alcohol to the action of sunlight for a short time. o-Nitro- benxaldehydediethylacetal N0,-C6H4*CH(OEt) is an aromatic slightly yellow oil b. p.147*8-148*3°/11 mm. 154.8-155-3°/15 mm. ; the corresponding dipropylacetal C1,Hl9O4N has b. p. 168'/10 mm. ; the diisopropylacetal has b. p. l5O0/l2 mm. ; the diisobutylacetal has b. p. 179"Jll mm. ; 2-nitro-4 5-dimethoxybenxaldehydediinethylacetal crystallises in colourless flat glistening prisms m. p. 54 5-55*5O. Attempts to prepare the dimethylacetal of 2 4 6-trinitrobenz- aldehyde were unsuccessful. The following esters were prepared by acting on the requisite acetal with sunlight during a few hours; in the molten state they are green. Propy2 o-nitrosobenxoate C,,H,,O,N,~colourless glistening prisms m. p. 95' ; isopropyl o-nitrosobenxoate stout white prisms m. p. 11 7-118" ; isobutyl o-nitrosobenxoate CllH1308N colourless 11 Hl 5°6N,i. 269 ORGANIC CHEMISTRY.compact needles m. p. 99-99.5' ; methyl 2-nitroso-4 5-dimethoxy- henxoate C10H1105N faintly green granular crystals sinters a t 125" m. u. 126.5-127.5'. I 3 6 3' 6'-Tetrachloro-2 2'-a~oxybenzoic acid Cl,H,0,N2Cl is a pale yellow crystalline powder m. p. about 281-28%" (decomp.) when heated in a bath from 265'. 3 6-Dichloro-2-nitrosobenxoic acid forms small faintly yellow crystals. 2-Nitro-4 5-dimethoxybenx- aldoxime C,H,,O,N crystallises in glistening yellow needles m. p. 17S0 when heated in a bath from 168'. W. H. G. Metallic Calcium and Absolute Alcohol as Reducing Agents. CHARLES MARSCHALK (Ber. 19 10,43,641-642).-Attempts have been made to reduce coumarone and benzophenone with metallic calcium and absolute alcohol. Coumarone is not affected but benzo- phenone is reduced to benxhydral.Sodium and alcohol on the other hand reduce coumarone to coumaran and benzophenone to diphenyl- methane (Klages and Allendorf Abstr. 1898 i 433). J. J. S. Condensation of Cuminaldehyde with Methyl Propyl Ketone. THEODOR ST. WARUNIS and P. LEKOS (Ber. 1910 43 654-660. Compare Warunis Znaug. Diss. 1903).-Cuminaldehyde condenses with methyl propyl ketone yielding two isomeric cuminyl- idenemethyl propyl ketones. These when reduced with sodium amalgam in acid solution yield isomeric cuminplmethyl prop91 ketones. When treated with sodium hypochlorite according t o Stoermer and Wehln's method (Abstr. 1903 i 46) the unsaturated ketones yield cuminaldehyde. a-Cuminylidenemeth,yl propyl ketone C,H,Prp*CH:cH*COPra ob- tained by shaking the aldehyde and ketone with 10% sodium hydroxide solution is a pale yellow liquid with b.p 176-180°/14 mm. The dibromide C15H200Br2 crystallises in plates m. p. 124-1 25O. The semicarbaxone C,,H,,ON has m. p. 163'. The oxirne C15H,,0N m. p. 122-123' and the phenylhydraxone C,H,PrF*CH CH*CPra:N*NHPh m. p. 11 1'. C6H4Pr.p*CH2* CH,*COPra is a colourless oil with b. p. 155-160°/12 mm. and yields a semi- carbaxone C,,H,,0N3 m. p. 126'. y-CurrLinylideizepro~yl methyl ketone C,H,Pr~*CH.:CEt*CO~e ob- tained by saturating a mixture of the aldehyde and ketone with hydrogen chloride is a pale yellow oil .with b. p. 174-175'/15 mm. or 167'112 mm. The dibvomide is oily; the semicarbazone C,,H,,ON crystallises in needles m. p. 198' and the oxime C,,H,,ON in large crystals m.p. 107". y-Curninylpropyl methyl ketone C,H,Prp*CH,*CHEt*COMe is a colourless liquid b. p. 159-161'/14 mm. ; its semicarbaxone crystallises in plates m. p. 135". has m. p. 211'. a-Cuminylmethyl propyl ketone C16H250N3 The semicarbaxone of cuminnldehyde OGH4Prp*CH :N*NH-CO*NH J. J. S.i. 270 ABSTRACTS OF CHEMICAL PAPERS. Compounds of Quinones with Esters of Amino-acids. EMIL FISCHER and HANB SCHRADER (Ber. 1910 43 525-529).-By the addition of an alcoholic solution of benzoquinone to a cold alcoholic solution of ethyl glycine quinol is formed and also a red substance C1,H,,06N2 which from analogy to dianilinoquinone receives the constitution C,H,O,(NH*CH,-CO,Et) and the name diethyl diglycinoquinone. It separates from chloroform in red quadratic plates has m.p. 215" (corr.) develops a fine bluish-violet colour in cold alcoholic potassium hydroxide and by treatment with bromine in chloroform yields ethyl glycine hydrobromide m. p. 175-176" (decornp. corr.). Diethyl dialaninoquinone C,H,O,(NH*CHMe*~O,Et) m. p. 140° (corr.) crystallising in red prisms and diethyl diglycinotoluquinone C,HMeO,(NH-CH,-CO,Et) m. p. 162' (corr.) are similar substances obtained in a similar manner the solvent in the former case being ether. c. s. Oxidation of P-Naphthaquinone. C. H. ROBINSON (J. Amel-. Chsrn. Xoc. 1910 32 117-119).-It kiss been found by Daly (Abstr. 1907 i 407) that in the oxidation of P-naphthsquinone by an alkaline solution of potassium permanganate the reaction ceases before the amount of permanganate has been reduced which is theoretically required to oxidise the nnphthaquinone to phthalonic acid and he has suggested that the acid C,H,(CO*CO,H) may possibly be formed in the solution.Experiments have now been made which indicate that P-naphthaquinone is oxidised directly t o phthalonic acid in alkaline solution without the formation of any intermediate compounds. E. G. The Anthraquinone Series. FRITZ ULLMANN (Ber. 1910 43 536-539).-1n this preliminary paper the author summarises briefly the results of previous work on the mobility of halogen atoms in anthraquinone derivatives. His intention is to study anthraquinone derivatives in comexion wit,h the problem of colour and constitution and also to examine the affinity of their leuco-compounds for the fibre. c. s. Preparation of Chloro- and Bromo-anthraquinonesulphonic Acids BADISCHE ANILIN & SODA-FABRIK (D.R.-P. 216071).-The direct halogenation of anthraquinonesulphonic acids in aqueous solution does not proceed smoothly owing to the frequent replacement of sulphonic groups by hydroxyl.It is found that if concentrated sulphuric acid or that containing anhydride is employed as solvent and the required halogen introduced either in the presence or absence of a carrier the reaction proceeds normally. 1 4-DichZoroanthraquinone-~-su~honic acid prepared by thus treating sodium anthraquinone-P-sulphonate with chlorine at 160' until t h e necessary increase of weight has been obtained is a dark yellow powder crystallising from 90% acetic acid in glistening yellow scales. The position of the chlorine atoms was indicated by the formation of quinizarinsnlphoaic acid on replacement of halogen by hydroxyl.ORGANIC CHEMISTRY.i. 271 Sodium bromoanthraqzlinoZphonate dark yellow spear-shaped crystals together with other more highly brominated acids were pre- pared from sodium anthraquinone-P-sulphonate. F. M. G. M. Preparation of Dianthraquinone Oxide. FARBWERKE VORM. MEISTEB LUCIUS & BRUNINU (D.R.-P. 2 16268).-~/3-Bianthraquinone oxide is prepared by condensing 1 -chloroanthraquinone with 2-hydroxyanthraquinone in the presence of copper powder and fused sodium acetate in nitrobenzene solution ; on cooling the product separates in grey crystals which are almost insoluble in all the ordinary solvents except acetic acid. F. M. G. M. Preparation of Dianthraquinonyl and of Dibenzanthronyl Derivatives.BADISCHE ANILIN- & SODA-FABBIK (D. R.-P. 21 5006).-Dianthraquinonyl derivatives have previously been prepared by treating the diazonium salts of aminoanthraquinonea with copper in the presence of acetic anhydride (Abstr. 1907 i 942) ; it is now found that the reaction will take place in dilute aqueous solutions containing copper salts or such mixtures as cupric chlorido and iron ferric chloride and copper potassium bromide and zinc dust cupric chloride and hydroxylamine or cupric chloride and sulphurous acid. The patent mentions 1 l'-dianthraquinonyl (from 1-amino- anthraquinone) 2 2'-dianthraguinoiyZ (from 2-aminoanthraquinone) 2 2'-dimethyl-1 1'-dianthraquinonyl (from 1-amino-2-methylanthra- quinone) and dibemanthronyl prepared from aminobenzanthrone.F. M. G . M. Pyranthrone A Non-nitrogenous Methine Analogue of Flavanthren and Dimethylpyranthrone. ROLAND SCHOLL (Bey. 19 10 43 346-356).-[ With CHRISTIAN S~~~.]-Dinitro-2 2'-di- rnRthyl-1 1'-dianthraquinoyl C,H,,O,N a yellow crystalline substance is obtained by keeping a solution of dimethyldianthraquinoyl in nitric acid D 1.52 for three to five days at the ordinary temperature. By boil- ing foroneto two hourswith sodium hydroxide and sodium hyposulphite it is reduced to t h e /\/\/\ diamino-compound C30H2004N2 which forms I I I I dark red microcrystalline octahedra. The \/v\/\'\ conversion of dimethyldianthraquinoyl into 11 I I !I pyranthTone (annexed formula) is effected by \/\ \/\ (1) heating a t 350-380' for thirty minutes (2) heating with zinc chloride at 280' for h/\/ fifteen minutes (3) heating with alcoholic potassium hydroxide for two hours at 140-145'.In the last method a blackish-red hydrogenised compound is produced which is converted into pyranthrone by passing air through the reaction mixture diluted with boiling water. Pyranthrone is a brown powder which is insoluble in low boiling solvents but separates from nitrobenzene in reddish-brown needles with a steel-blue lustre ; it is carbonised by heating gives a blue solution in concentrated sulphuric acid is slowly oxidised by fusion with alkalis and by reduction with alkaline hyposulphite yields a purplish-red vat co f 1 1i. 272 ABSTRACTS OF CHEMICAL PAPERS. which regenerates pyranthrone in the presence of air and produces on ixnmordanted cotton lustrous purplish-red colours which change in air to orange-yellow or fiery-red shades of unrivalled fastness./\/\/\ [With JULIUS PoTsCHIWAUSCHEG.]-T~~ I I I I preceding vat probably contains the \ / \ / \ A H sodium derivative of tetrahydropyran- H?! I l 2 throne (annexed formula) because with \/\/\/\ ethereal p-bromobenzoyl chloride i t yields I I I di-p-bromobenzo~~tQtra?Lydrop~ranthroiLe OH V\/V c 4H 2404Br2 7 OH which forms yellow needles and does not melt below 360'. Pyrcmthrene C30H18 is obtained by heating pymn- throne red phosphorus and hydriodic acid D 1.7 for seven hours a t 165-175'. It has m. p. above 360° crystallises in brown needles or yellowish-green prisms develops a violet-blue coloration in sulphuric acid and forms a fluorescent solution in xylene and a non-fluorescent solution in nitrobenzene.4-Nitro-1 3-dimethylanthraquinone m. p. 234' is obtained by boiling dimethylanthraquinone with nitric acid D 1-37 for ten hours ; i t is reduced by sodium hydroxide and sodium hyposulphite to the amino- compound m. p. 235-236'. 2 4-Dinitro-1 3-dimethyZanthraquinom m. p. 2S3-285' is obtained by agitating dimethylanthraquinone with nitric acid D 1.52 for ten hours a t the ordinary temperature; the diamino-compound has m. p. 230" (decomp.). 4-Iodo-1 3-dimethyl- anthraquinone ClGHl1021 ru. p. llS-119' obtained from diazotised 4-amino-1 3-dimethylanthraquinone and potassium iodide is converted by Ullmann's copper process at 210-250' into 2 4 2' 4' tetramethyl- 1 l'-dianthraquinoyl CGH,<CO>C6HMe2* co C6HMe,<CO>C,H GO m.p. 296-298' which by treatment with alcoholic potassium hydroxide at 1 3 5 O and subsequent oxidation of the product by air yields 4 4'-di- metAyZpyrantlwone C32H1802. The latter separates from nitrobenzene in orange-red needles and yields with alkaline hyposulphite a purplish- red vat which develops on unmordanted cotton purplish-red shades changing t o a fine golden-yellow in air. 4 4'-DirnethyZpyranthrene ' C32H22 crystallises in brown needles and forms a fluorescent solution in m-xylene. c. s. Monoterpenes Limonenes and Carvones. ERNST DEUSSEN and ALFRED HAHN (Be?.. 1910,43,519-524).-The new d-P-carvoxime (Abstr. 1909 i 502) can be obtained from either d-a- or p-limonene- nitrosochloride by elimination of hydrogen chloride.I n a similar way I-limonenenitrosochloride yields in addition t o d-carvoxime a n oil which forms a benzoyl derivative m. p. 76-77' [a] - 73.58' in benzene from which Z-/I-caruoxime m. p. 56-57' is obtained by hydrolysis by alcoholic potassium hydroxide. d-Limonene-a-nitrolanilide and also d-limonene-P-nitrolanilide when heated at 1 40'/1 2 mm. yield aniline and I-a-carvoxime. I-a-Carvoxime is converted into i-carvoxime by prolonged heating in alcohol or petroleum and I-hydrochlorocarvoxirne i s also rendered inactive byORGANIC CHEMISTRY. i. 273 heating its methyl-alcoholic solution ; the benzoyl and the phthalyl esters of I-a-carvoxime however remain unaltered under these con- ditions. I- and d-a-Benzoylcarvoximes yield by bromination tetmbromo- compounds each having m.p. 135-136O; that derived from I-a- benzoylcarvoxime has [a] + 25.9’i0 and that from the d-isomeride Ethereal Oils Free from Terpenes a n d Sesquiterpenes. ERICH BOCKER (1. pr. CAem. 1910 [ii] 81 266-%1).-Frequently the odour of a natural ethereal oil is prejudicially affected and its solubility in alcohol largely diminished by the presence of terpenes and sesquiterpenes. A table is given comparing the specific gravity rotation solubility in alcohol of different strengths saponification ester acid and acetylation numbers aldehyde and phenol content and the solidifying point of sixty-three natural ethereal oils with those of the oils left after the removal of the hydrocarbons by processes which are trade secrets c.8. CARLO GRIMALDI (Chem. Zeit. 1910 34 920).-In an earlier communication (Abstr. 1909 i 943) the author recorded the occurrence of camphene in ‘‘ spirits ” prepared from American and Austrian colophony but only in small quantities. H e has now succeeded in isolating it in the pure state E. J. R. Characters Distinction and Detection in Plants of Arbutin and Methylarbutin. EMILE BOURQUELOT and MLLE. A. FICHTENHOLZ (J. Pharm. Chim. 1910 [vii] 1 62-66 104-109).-The arbutin of commerce is now known to be a mixture of true arbutin with methylarbutin (compare Bourquelot and Hdrissey Abstr. 1908 i 356) and in the present paper the constants and reactions of the two substances are detailed with a view to facilitating their identification in plants. Arbutin is hydrolysed by emulsin yielding quinol and dextrose and the cupric-reducing power of the solution resulting from the action of emulsin on a solution of the ‘glucoside is due to both these substances.Owing to the presence in eniulsin of a small amount of an oxydase the quinol formed by the hydrolysis of arbutin in this way becomes slightly oxidised and the solution assumes a yellowish- brown colour. This oxidation does not seriously affect the cupric- reducing power of the product so long as the action is not allowed to go on for more than eight days. Arbutin gives a blue coloration with ferric chloride solution and a sapphire-blue colour with Jungmann’s reagent. Methylarbutin on hydrolysis by emulsin furnishes quinol methyl ether and dextrose and the cupric-reducing power of the hydrolysed product and its rotation are due to the latter only.On hydrolysis with emulsin a solution of methylarbutin does not darken in colour even if an oxydase is added. Further it is hydrolysed much more rapidly than arbutin (compare Abstr. 1908 ii 995 ; 1909 i 862) and gives no coloration with either ferric chloride solution or Jungmann’s reagent although quinol methyl ether gives like arbutin a blue colour with each of these reagents. - [25*51°] in benzene. c. s. Occurrence of Camphene in Rosin Spirit.i. 274 ABSTRACTS OP CHEMICAL PAPERS. For the detection of either of these glucosides in presence of the other determination of the rotation before and after hydrolysis with emulsin is recommended the colour reactions mentioned being used for confirmatory evidence. T.A. H. Glucosidic Acids of Convolvulin and the Composition of Crude isoRhodeose. EMIL VOTO~EK (Bey. 1910 43 476-482).- Convolvulin is resolved by hydrolysis with alkali into a-methylbutyric acid and two glucosidic acids the crystalline convolvulinic acid and amorphous purgic acid. Couvolvulinic acid when hydrolysed with acids forms convolvulinolic acid dextrose rhodeose and a sugar which gives rise to mucic acid when its hydrogen cyanide additive product is oxidised; this is now proved to be rhamnose. Purgic acid is converted by acid hydrolysis into decenoic acid hydroxylauric acid and syrupy isorhodeose ; the last contains only methylpentoses and has [a] + 25'; it forms no mucic acid when the hydrogen cyanide additive product is oxidised.The phenylosuxone has m. p. 183-184" the p-brornophmylosnxone has m. p. 2 17" whilst dodeose-p-bromophenyl hydraxone has m. p. 202-204'. Crystalline hydrazones could not be obtained. E. F. A. Aloin. OTTO A. OESTERLE and G. RIAT (Xchweix. Voch. Chern. Pha~m. 1909 717-721. Compare Oesterle Abstr. 1899 i 538 ; 1900 i 304; Tschirch and Pedersen Abstr. 1898 i 599 ; Jowett and Potter Trans. 1905 87 878 ; Robinson and Simonsen ibid. 1909 95 1085).-Aloe-emoidin and a sugar are formed when aloin is boiled for some eighty hours with sulphuric acid and 95% alcohol or for twenty-four to thirty-six hours with alcohol and hydrochloric acid. The sugar gave an osazone m. p. 208-209'. The oxidation of aloin with sodium peroxide (Lhger Abstr. 1902 i 549) has been studied. Tbe best yields are obtained when 30 grams of aloin are warmed with 500 C.C.of water a t 70-80". Thirty grams of the peroxide are added gradually and with constant stirring. The addition of hydrochloric acid precipitates crude aloe-emoidin (compare Jowett and Potter). J. J. S. . Tetrahydrothiophen and cycZoPentamethylene Sulphide. JULIUS VON BRAUN and A. TRUMPLER (Ber. 1910 43 545-551).- Whilst substances containing four- five- six- seven- sixteen- and eighteen-membered rings of carbon and a t least two atoms of sulphur are formed easily and sometimes quantitatively from acyclic generators the production of heterocyclic systems containing only one atom of sulphur is accompanied by anomalies the comparatively easy formation of thiophen being in strong contrast to the difficulty of obtaining methylpenthiophen (Krekeler Abstr.1887 239). The authors have prepared compounds of the type (CH,),>S and FH,*CH CH,*CE encounter similar anomalies. Tetruhydrothiophen >s b. P. 119O is obtained in almost quantitative yield when an alcoholic solution of as-di-iodobutane is added to a concentrated aqueousORGANIC CHEMISTRY. i. 275 solution of potassium sulphide whilst under similar conditions the yield of pmtamethylerns szclphide [pentahydropent~iophe~~ CH,*CH b. p. 141" from ar-di-iodopentane is less than 30%. Tetrahydro- thiophen and pentamethylene sulphide which form methiodides volatilising at 185-190° and 192' respectively are very reactive substances but their thorough examination has been postponed for CH2<CH2.&S? the present on account of their insufferable odour. c.s. Action of Cyanogen Bromide on Brucine and Strychnine. GUSTAV MOSSLER (Monatsh. 19 10 31 1-22).-Since brucine and strychnine probably contain a tetrahydroquinoline or a dihydroindole skeleton in which the nitrogen atom is linked to a nuclear carbonyl group the author has applied to the two alkaloids Braun's methods of rupturing heterocyclic nitrogenous systems by means of phosphorus pentachloride (Abstr. 1904 i 918) or cyanogen bromide (Abstr. 1900 i 430). The attack of the former reagent does not lead to definite results but by the action of cyanogen bromide in chloroform additive compounds are formed which cannot be isolated in a pure state. The compound obtaiqed from strychnine is decomposed by water yielding ammonia and the hydrobromide of the alkaloid.The additive com- pound of cyanogen bromide and brucine is further attacked by the reagent in two directions according to the experimental conditions. When cyanogen bromide is added slowly to a cold solution of brucine in chloroform crystals are obtained of a substance C47135208N5Br CHCl 3H20 which by heating at 110' and crystallisation from 70% alcohol yields crystals of the composition C,7H,208N,Br,2H20 ; both have m. p. 203-205O (decomp.). The substance which does not possess basic properties and retains its halogen in the presence of cold alkali is regarded as a quaternary ammonium bromide produced by the rupture of one brucine molecule by the cyanogen bromide and the combination of the resulting brominated cyanamide with a second molecule of brucine.When a solution of brucjne in chloroform is added to an excess of cyanogen bromide in the bame solvent and the mixture is treated with 90% alcohol a precipitate is obtained which by solution in water and reprecipitation by alcohol yields needles of a hydrobromide C23H2@*N2,HBr,4H@ containing two methoxyl groups and decomposing at 250'. The free base allobrucine C23H260,N2,5H20 is isomeric with brucine into which it is converted by crystallisation from boiling water but differs from it in containing water of crystallisation in its rotation [a]? - 112*6O in chloroform m. p. and derivatives. The hydrated base melts at 69.5' resolidifies at 75-80" softens a t 120-130° and fuses again at about 182' (decomp.). The anhydrous base melts a t 126-128' to a transparent indistinctly liquid substance becomes opaque and then melts at about 182' (decomp.) aZloBrucine which is a mono- acidic base exhibits all the colour reactions of brucine.The hydro- chloride C2,H,,0,N,,HCl,4H40 crystallises in leaflets which efflorescei. 276 ABSTRACTS OF CHEMICAL PAPERS. in air; the methiodide C,,H2,0,N,,Me1,1~I€,0 has m. p. 265O (decomp.). When allobrucine is warmed with hydrogen peroxide a peroxide C,,H2,06N2 is obtained which contains 5H20 when dried in air and H20 when dried in a vacuum and at 110' is converted into the oxide C,,H,,O,N,,H,O which is also produced by heating an aqueous solution of the peroxide with platinum-black. The two hydrated peroxides and the oxide all have m. p. 182' (decomp.) ; by very rapid heating the air-dried peroxide decomposes at 115-120' and the monohydrate a t 150-152' both resolidifying and then melting again at 182'. An aqueous solution of the peroxide is neutral and optically inactive liberates iodine from potassium iodide bleaches litmus and exhibits the reactions of hydrogen peroxide when treated with potassium dichromate and sulphuric acid. alloBrzccic acid C,,H,,O5N,,7H,O obtained by the action OE sodium ethoxide on allobrucine crystallises in yellow needles has m.p. 165-1 66' (decomp.) when anhydrous forms a nitrosoamine the hydrochloride of which C,,H,,O,N,Cl carbonises at 2 lo' and is stable in boiling water but is converted by cold acids-into the corresponding brucine salts. c. s. Hofmann's Iodomethylation of Cinchotoxine. I.Con- stitution of Freund and Rosenstein's Dimethylcinchonine. EZIO COMANDUCCI (Rend. Accad. Sci. Pis. Mat. Napoli 1909 [iii] 15 240-254).-Assuming the accuracy of the fQrmula C9NH6* CO* CH2*CH2*CH<CH2. UH(CH c H,. CH,)> NH CH2 for a-cinchonicine (cinchotoxine) (compare Abstr. 1909 i 409) the dimethylcinchonine prepared by Freund and Rosenstein (Abstr. 1894 i 151) will have one of the two formulae and C,NH,*(~O*CH,*CH2*CH(CH:CH,)*CH(CH:CH2)-CH,*NMe2 (11). The author's experiments shorn that oxidation of dimethylcinchonine (1 mol.) by means of cold permanganate yields 1 mol. of formic acid together with an unsaturated acid compound which is named dimethylcinchotenine thus -CH:CH + 40 -+ H*C02H + -GOSH. [With ONOFRIO ~'ONGEIA.]-~imethy~cinc~oninep~en~~~~drazone C,,H,,,N,~,:N,HPh forms 'yellow mamillary crystals m.p. 101-103. C1,H ,ON,Br,Me 2HBr forms a dark yellow deliquescent powder m. p. 20-22'. The picrate C,,HI,ON Br,Me,,HBr C6H307N3 forms a lemon-yello w crystalline powder m. p. 143-1 4 5 O . Cl,H1,0N,Br,Me2 H,P t Cl is obtained as a dark yellow powder m. p. 230° and the aurichloride Cl9H1,0N2Br4Me2 2HAuCl in reddish-yellow granules m. p. 85" (decomp.). Dimethylcinchotenine forms a reddish-brown powder with an acid reaction and turns brown and contracts at 250O. Its dibromo- derivative C1,H,,0N,Br,Me2* C02H is obtained as a reddish-brown powder which contracts at 200° but does not melt a t 250". T. H. P. C,NH,*CO CH,*CH,*C H( CH,*C H,- NMe,) C( CH CH,) CH (I) TetrabromodimethyZcinchoniiw hydrohromide The phtinichloride,ORGANIC CHEMISTRY i 277 Synthesis of Fyrrole Derivatives Pyrroles from Ethyl Succinylosuccinate and from Azines.OSCAR PILOTY (Ber. 1910 43 489-498).-Pilotg and Quitmann (this vol. i 133) have shown that haemopyrrole and haemopyrrolecarboxylic acid are trisubstituted pyrrole derivatives and consider that the haematin or hRmin molecule C,,H,,O,N,FeCl or C,,H,,O,N,FeCl contains each of these units repeated twice. Four such units contain 52 atoms of hydrogen so that 20 or 18 atoms must be eliminated in the condensation. One method of realising this is the formation of an intermediate ring from the side-chains of two molecules. Tryptophan for example might condense to yield derivatives of the parent substance >CH CH-E- CH z*X NH CH<NH*C*CH,*C-CH which may be termed hydyoyyrrindole.The possibility of tryptophan having some relation to the colouring matter of blood has already been emphasised by Abderhalden. Knorr's pyrrole synthesis can be extended to the condensation of 2 mols. of aminoacetone with 1 mol. of ethyl succinylosuccinate This substance is inclined to polymerise and forms ied green and violet dyes when oxidised. The full investigation has been delayed by the poor yields obtained the constitution being assumed from the met hod of for mation. A more promising method of obtaining pyrrole derivatives is by the action of zinc cbloride at high temperatures on the azines of aliphatic ketones. Bisdiethylazinemethylene gives rise to 3 4-di- methyl-2 5-diethylpyrrole NH< The condensation of aminoacetone hydrochloride with ethyl succinylosuccinate takes place i n sodium hydroxide solution Dimetl~ylhydropyrrindole purified by sublimation in a vacuum forms colourless lustrous nacreous plates which sinter at 2609 m.p. 271O. It gives a cherry or violet-red coloration with ferric chloride. By the action of solid potassium hydroxide on aminobutanone hydrochloride tetramethylpyrazine is formed m. p. 86-87" together with a pyrrole derivative which was not obtained crystalline and decomposed into tetramethylpyrazine when distilled. 3 4-Dimethyl-2 5-diethylpyrrole is obtained as a faintly yellow- coloured oil b. p. 133-135'/55 mm. The ethereal solution becomes dark brown on the addition of picric acid without yielding a picrate. It forms an amorphous potassium salt.The acetate is a light yellow oil b. p. 1t30-184°/88 mm. CEt:yMe CEt:CMe' E. F. A. Anthranil. XVII. Heller's Recent Experiments in Connexion with Anthranil. EUGEN BAMBERGER (J. p r . Chem. 1910 [ii] 81 254-265).-To disprove Heller's statement that aniline not anthranil is the product obtained by heating anthroxanic acid with water a t 150' (Abstr 1909 i 832) the author has performed nine experiments in which anthroxanic acid (1 gram) is heated with 40-60 grams of water VOL XCVIII. i. 'ui. 278 ABSTRACTS OF CHEMICAL PAPERS. at temperatures between 145O and 1 5 6 O and for periods varying between three and four hours and in every case anthranil can be detected by its odour and frequently also by the formation of the mercurichloride. In reply to Heller's contention (Zoc.cit.) that 23% hydrochloric acid and sodium nitrite act as a chlorine generator the author shows that the nitrite produces less than 0.5% of chlorine from hydrochloric acid of this dilution. c. s. [Preparation of Isatin Derivatives.] KALLE & Co. (D.R.-P. 215785. Compare Abstr. 1907 i 1073).-Alkyloxyisatins having co the general formula OR*C6H4<NH>C0 R = alkyl can be readily obtained by known methods for the preparation of isatins. ~~ 7-Methoxyisatin OMe*C,H,<FH>CO bluish-red needles m. p. 240-242O is formed (1) by the oxidation of dimethoxyindigotin (2) from the cyanohydrin of di-o-methoxycarboxydiphenylimide (3) from di-o-anisyloxalimide chloride ( A bstr. 1908 i 695). 5-Methoxyisatin prepared from o-nit ro-m-me t hox ybenzaldehy de f ormg brown ish-red needles m.p. 200-202°. The condensation products from these compounds with 3-oxy-( 1)- thionaphthen and with 6-ethoxy-3-oxythionaphthen-2-carboxylic acid form valuable vat dyes. F. M. G. M. Indigoid Dyes. VI. A. FELIX and PAUL FRIEDLANDER (Morncctsh. 1910 31 55-79. Compare Abstr. 1908 673 674 ; 1909 415 417 ; this vol. i 176).-Indigoid dyes are obtained by the action of a-isatin chloride or anilide on keto- and diketo-hydrindene various coumar- anones and dihydroxyisoquinolines. The dyes are very similar to indigotin but give redder shades and are more sensitive towards alkalis ; they are sparingly soluble crystalline substances which can be sublimed and be reduced in alkaline solution to easily oxidisable leuco-compounds.The following dyes of these types have been prepared 2-lndane-2-indole-indigo [2(2')-indoxyl- 3-indanone1 C 6 H 4 < g g 2 C c<gE>c6 H* 9 prepared by heating equal molecular quantities of hydrindone and isatin chloride in benzene crystallises in red needles and is reduced by alkaline hyposulphite to a yellow vat from which cotton is dyed bluish-red. 2(2')-Indoxyl-l 3-indandione obtained in a similar manner from diketohydrindene forms brownish- violet needles and is decomposed by warming with 5% sodium hydroxide yielding ant hranilic acid and 3-h ydroxy- 1 -indernone-2-aZde- hyde C,H4<y&tH!>C*CH0 m. p. 139*5" which separates from hot water in white and from organic solvents in red needles reacts with hydrazine and phenylhydrazine develops a cherry-red colour with ferric chloride and forms yellow alkali salts which are not decomposed by acetic acid.5 6-Dimethoxy-l(2')-indoxyZcoumaranoneORGANIC CHEMISTRY. i. 279 C,H,( OMe),<~>C:C<~&>C,H ob taingd from a-isatinanilide and dimethoxycoumaranone in naphtha forms copper-red crystals which yield a reddish-violet vapour almost without decomposition. Hydroxymethoxycoumaranone and isatinanilide under similar con- ditions yield an analogous indigoid dye C,,.H,,O,N. Both of these dyes in alcoholic or acetic acid solution react with aldehydes in the presence of sodium carbonate or hydrochloric acid to form oxygen isologues of the indogenides of which the following are described C,H,(031e),<O)C:CHPh co C,H2(OMe),(o->C:CH*C,H,=OH co from salicylaldehyde orange- C,H,( OMe),(o>C co C6H2( OMe),(O->C co C,H,(OMe),<-O>C:CH*C,~2(0H)2 co from protocatechualdehyde from benzaldehyde yellow prisms m.p. 148-149". yellow needles m. p. above 240'. CH* CGH4* OH from m-h y droxybenzaldehy de CH*C,H,*OH from p-hydroxybenzaldehyde yellow needle. m. p. 202*5-203'. citron-yellow crystals. orange-yellow needles m. p. 21'7'. The dimethoxycoumuranone m. p. 1225-123' required in the pre- ceding preparation is obtained by adding an excess of methyl sulphate to a warm solution of w-chlorotrihydroxyacetophenone (obtained from pyrogallol and chloroacetic acid) in aqueous sodium carbonate. I n faintly alkaline solution and with a deficit of methyl sulphate the monomethylated derivutive m. p. 197' is also produced. A dilute alcoholic solution of equal molecular quantities of dimethoxycoumar- anone and P-naphthaquinone-4-sulphonic acid by treatment with aqueous sodium carbonate yields the sodium salt of 5' 6'-dinzethoxy- coumaranonyl- 1 - i~~drox.~-4-oxc/izaphti~alene \ I which crystallises ic orange-brown needles.3( 2')-IndoxyZ-3-isopuino- line-1 4-dione7 C 6 H < ~ ~ ~ > c < ~ ~ > c 6 H 4 prepared from a-isatin chloride or anilide and dihydroxyisoquinoline forms dark blue needles and is reduced by alkaline hyposulphite to an orange-red vat from which the dye is regenerated in the air. Indigoid dyes have also been produced by the action of isatin chloride or anilide on rhodanic acid methylpyrazolone phenyl- methylpyrazolone and barbituric acid. The increased aliphatic character of these dyes is accompanied by increased sensitiveness towards acids and especially alkalis.5-Keto-4( 2')-indoxyZ-l -phenyZ- 3-mmthylpyraxole ?Ph*Co>C:C<FG>C,H obtained from phenyl- methylpyrazolone and isatin-a-anilide in boiling xylene separates N=CMe 212i. 280 ABSTRACTS OF CHEMICAL PAPERS. from nitrobenzene in almost black plates gives a light yellow vat with alkaline hyposulphitc and is decomposed by boiling 10% sodium hydroxide yielding anthranilic acid and l-phenyZ-3-mthyZ-5-pyrazoZone- This aldehyde 4-aldehyde COH*C< is amphoteric the acid character predominating ; it form's a fairly stable silver salt a phenylhydrmone m. p. 159O an aldazine m. p. agoo and the axomethine derivative ~Ph*C(oH)>C*CH:N*C6H4*C0,H N == CMe m.p. 240° with anthranilic acid in the presence of dilute acids. 4(2')-IndoxyZ-3-methyZ-4-pyrazoZe x H i g > C C< >C,H4 obtained from equal molecular quantities of 3-methylpyrazolone and isatinanilide in nitrobenzene at 150° separates from alcohol or dilute acetic acid in dark violet needles ; it possesses pronounced basic properties and is easily decomposed by alkali hydroxides. 4-Keto-2-thio-5( 2')-ilzdoxyZ- thiazole ~ ~ ~ ( ~ > C C < ~ ( & > C H or N- 8 (SH).s 'O>C c < ~ ~ > c ~ H ~ obtained by heating rhodanic acid and a-isatinanilide in acetic an- hydride forms almost black needles. 4-Reto-Whio-5( 2')-thiomphthenyZ- thiazole TH'Co>C:C<c~>C61€ obtained from thioisatinanilide and rhodanic acid in a similar manner forms reddish-brown needles.5(2')-lmdoxy~yrintidine-2 4 6-triorze m. p. 173-174O. C(OH>*rlJPh C M e r N NH cs-s co<NH*CO NH*CO>C c<g>c;EJ prepared from barbituric acid and a-isatinanilide in acetic anhydride forms orange-red needles. The absorption spectra of those indigoid dyes which differ from indigotin by containing in the place of one of the NH groups the atoms or groups S CH:CH CO*NH CH or CO are plotted and the influence of these replacements on the colour are briefly discussed. c. s. Coloured Salts of Schiffs Bases. 111. Salts of Bases Formed by Condensing m-Aminodimethylaniline and m- Amino- diethylaniline with Aromatic Aldehydes. FORRIS J. MOORE (J. Amer. Chern. Soc. 1910 32 382-.388).-1t has been shown in earlier papers (Moore Abstr.1908 i 368 ; Moore and Woodbridge Abstr. 1908 i 686) that benzylidene compounds of the type R*CH:N-C,H,*NRR unite with hydrogen chloride in two pro- portions forming dark red hydrochlorides and yellow dihydro- chlorides. The present work was undertaken with the object of determining whether the difference in the colour of these salts is due to the dark- coloured salts having a quinonoid constitution. I n order to test this it was decided to prepare analogous compounds of such a structure that they could not readily assume the quinonoid form and to study their salts. It seems probable that the bases previously used in this work would readily formpuinonoid salts since in all cases the twoORGAKIC CHEMISTRY. i. 281 nitrogen atoms were in the para-position to each other.This behaviour however would not be expected from the analogous meta-compounds. as-Dimethyl-m-phenylenediamine and cts-diethyl-m-phenylonediamine condense readily with benzaldehyde anisaldehyde cinnamaldehyde and piperonaldehyde to form compounds which on treatment with hydrogen chloride invariably yield light-coloured salts. This be- haviour seems at first sight to indicate that the dark-coloured salts of the corresponding p-compounds have a quinonoid structure but this inference is weakened by the fact that the m-bases are polyrnerides and can only be obtained in an amorphous condition. m-Nitrodiethylaniline and as-diethyl-m-phenylenediamine picrates melt at 138' and 152' respectively. E. G. Preparation of Benzophenoneimine Derivatives. FORRIS J.MOORE (Bey. 1910 43 563-565. Compare Reddelien this vol. i 1 18).-Diphenylmethylenedimethyl-~-phenylenediamine m. p. 86O is readily obtained by heating together equivalent quantities of benzophenone and p-aminodimethylaniline with finely-powdered barium oxide in an atmosphere of hydrogen a t 180". With other amines the condensation proceeds more readily in the absence of the barium oxide. Thus benzophenonephenylimine is readily obtained by heating benzo- phenone and aniline for an hour at 210'. Benzophenoneimine hydrobromide is readily obtained by passing ammonia into a chloroform solution of diphenyldibromomethane (Friedel and Balsohn Abstr. 1880 558). I t crystallises in colourless needles and reacts with water yielding benzopheuone. The free base can be obtained by Hantzsch's (Abstr.1892 338) or Thomae's (Abstr. 1905 i 718) method. A small amount- of the hydrobromide is also formed by the action of magnesium phenyl bromide on benzobromoamide. J. J. S. Preparation of Dianthraquinonylphen ylenediamine. FARBEN- FABRIKEN VORM. FRIEDR. BAYER & Go. (D. R.-P. 215294).-Dianthra- quinonylphenylenediamine C6H4( NH*C6H,<CO>C6H4)2 co is prepared by condensing aminoanthraquinone with p-dichlorobenzene in the presence of naphthalene sodium acetate and cupric chloride at 200-215'. The product crystallises from nitrobenzene in black needles ; the solution in concentrated sulphuric acid is greenish-yellow from which water precipitates a violet-red powder. F. M. G. M. Tetramethyldiaminobenzophenone and Dianilinodiphenyl- methane.FRITZ STRAW and RICHARD BORMANN (Bey. 1910 43 728-739).-The authors cannot state with certainty that the blue compounds obtained by the action of carbonyl chloride on tetramethyl- diaminobenzophenone (Staudinger Abstr. 1909 i 905) and tetra- methyldiaminothiobenzophenone (Baither Abstr. 1887 81 6) are identical ; the bishydrochloride of the former is colourless that of the latter yellow becoming colourless i n the presence of excess of hydrogen chloride and yellow again when kept over potassium hydroxide.i. 282 ABSTRACTS OF CHEMICAL PAPERS Di-p-nitro-o-sulpitoanilinodipheny lmet ham C H,[C,H,*NH-C,H,( NO,)*SO,H] obtained in the form of the sodium salt by heating diaminodiphenyl- methane with an aqueous solution of sodium hydrogen carbonate and sodium p-nitrochlorobenzene-o-sulphonate (3 mols.) is a n orange-yellow powder.If only 2 mols. of the sulphonate are used the chief product is the sodium salt of amino-p-nitro-o-sulphoanilinodiphenyl- methane NH2*C,H,*CH,*C,H,~NH*C,H,(N0,)*S0,H a citron-yellow powder. An aqueous solution of the sodium salt of the disulphonate is reduced by zinc dugt and ammonium chloride to the corresponding amino-compound C,,H,,0,N,S2 which is converted by concentrated hydrochloric acid at 100" into the hydrochloride C2,HZ4N4,4HCl of di-p-aminophenyldiaminodiphenylmethane. The base itself m. p. 1 31" forms white needles ; its alcoholic solution when treated in a freezing mixture with concentrated sulphuric acid and amyl nitrit'e and subsequently with copper powder yields p p-dianilinodiphen ylmethane CH,(C,H,=NHPh) m.p. 11 4O which is soluble in concentrated acids. c. s. Magnesium Alkyl Haloids and Aldazines. MAX BUSCH and MARTIN FLEISCHMANN (Rer. 1910 43 740-'750).-Franzen and Deibel found that benzaldazine was reduced t o benzaldehydebenzyl- hydrazone by magnesium ethyl bromide (Abstr. 1905 i 843). The authors find that in addition t o this reaction which may proceed to the extent of forming dibenzylhydrazine the normal addition occurs the course of the reaction being most conveniently followed by the use of magnesium aryl halides. Thus the product of the interaction of benzaldazine and magnesium phenyl bromide in ether when decomposed by dilute hydrochloric acid at O" yields a mixture of the hydrochlorides of benzaldehydebenzylhydrazone and benzaldehydediphenylmethyl- hydrazone.The hydi-azone itself CHPh,*NH*N:CHPh decomposes at 85" explodes very readily and easily loses its nitrogen yielding products from which letraphenylethane and diphenylmethane have been isolated. To account for their formation the authors offer the suggestion that the hydrazone changes into the azo-compound CHPh,*N:N*CH,Ph which then decomposes like Thiele's azomethane yielding nitrogen diphenylmethyl and benzyl from the last two of which the two hydrocarbons in question are generated. The inter- action of magnesium benzyl chloride and benzaldazine and the treat- ment of the product successively with ice-water acetic acid ammonium chloride and excess of ammonium hydroxide lead t o the formation of benzaldehydediphenylelhylh ydraxone CHPh N*NH*CHPh*C H,Ph m.p. 104-105° (decomp.) which forms a f hydrochloride m. p. 124" and is converted by benzoyl chloride in pyridine into P-bemoyl-a-diphenyZ- ethylhydrazine NHBz*NH*CHPh*CE2Ph m. p. 140". The chief product of the interaction of magnesium ethyl bromide and benzaldazine is benzaldehydebenzylhydrazone (Franzen and Deibel Zoc. cit.) ; with an excess of the organo-magnesium bromide (4 mols.) however the main products are those formed by the decomposition of the initially formed benzaldehydephenylpropylhydrazone namely benzaldehyde andORGANIC CHEMISTRY. i. 283 y8-diphenylhexane. The reaction between anisaldazine and magnesium benzyl chloride leads t o the formation of two substunces one having m. p. 84' (decomp.) the other decomposing at 99' ; since both have the same properties and composition and yield anisaldehyde by treatment with mineral acids they are regarded as the stereoisomeric modifica- tions of meti~ox~benxaldehydemethoxydiphe~~let~ylhydrazone 0MeeC6H4*CH:N*NH-CH(CH,Ph)*C6H400Me. C.S. Opening of the Glyoxaline Ring. RDOLF WINDAUS (Bey. 1910 43 499-501).-Glyoxaline and its homologues alkylated in the a- and &positions on treatment with benzoyl chloride and sodium hydroxide are converted into dibenzoyl derivatives of unsaturated diamines but glyoxaline derivatives containing a free carboxyl group in the side-chain are stable towards these reagents. The stability is due to the presence of the free carboxyl group as glyoxalylpropion- anilide is very readily converted into an unsaturated diamino-acid. formed NH*RH N-C-CH; CH;CO*NHPh' Glyoxalglpropionanilide CH< by heating glyoxalylpropionic acid with anhine &at 185O forms short prismatic crystals m.p. 190-191'. The oxalate forms four-sided plates ; the picronolate long light yellow needles ; the platinichloride crystallises in bright orange fork-like needles; the sibvev salt is colourless. On heating with benzoyl chloride and potassium hydroxide the ring is broken and the dibenxoyl compound is formed crystallising in long lustrous needles m. p. 197". COPh*NH-CH:C( NH*COPh)*CH,*CH,*CO*NHPh E. F. A. Action of 1-Ghloro-2 4-dinitrobenzene on Pyridine Bases. FRITZ REITZENSTEIN and GEORG STAMM ( L p r . Chem. 1910 [ii] 81 160-1 66).-Phenanthroline or y-dipyridyl reacts with 1-chloro-3 4- dinitrobenzene in boiling acetone to form an.unstable substance probably by the addition of 1 mol. of chlorodinftrobenzene to each of the nitrogen atoms; these additive compounds are isolated as the platinichlorides [C,,H8N2,2C,H,(N0,)2C1],H,PtC16 m. p. above 300° and .[C,?H,N,. 2C,R,(N0,),Cl],H,PtC16 sintering above 270'. When aniline is also present in the solution the additive compound is not produced 2 4-dinitrodiphenylamine being obtained by the interaction of the aniline and the chlorodiditrobenzene. c. s. Quinazolines. XXIV. Oxalylanthranilic Compounds and Quinazolines Derived Therefrom. MARSTON T. BOGERT and Ross A. GORTNER (J. Amer. Chem. Xoc. 1910 32 119-128).-This paper gives an account of compounds derived from oxalylanthranilic acid which was first obtained by Kretschy (Abstr. 1883 674; 1884 750).When methoxalyl- and ethoxaly 1-snthranilic acids and oxaiyldianthrani- lic acid (Mauthner and Suidn Abstr. 1889 139) are heated with acetic anhydride they are converted into acylanthranils ?6H4>N*CO*C0 R co-i. 284 ABSTRACTS OF CHEMICAL PAPERS. '6 H4 co and &,>N*CO*CO*N<t ~ . Methoxalyl- and ethoxalyl-nnthranil condense with primary amines to form the corresponding quinazolines 6 4 N=C*CO,R '6*4<Co_kR ' Methoxalylanthranilic acid CO,H=C,H,*NH*CO.CO,Me m. p. 1'76.5' (corr.) obtained together with some oxalyldianthranilic acid by heat- ing anthranilic acid ( 1 mol.) with methyl oxalate (1 mol.) at 140-155" forms colourless crystals. Ethoxalylanthranilic acid has m. p. 184' (corr.).Oxalyldisnthranilic acid can be prepared by heating anthr- anilic acid (2 mols.) with ethyl oxalate ( 1 mol.) as stated by Mauthner and Suida (loc. cit.) or by the action of oxalyl chloride on the acid. Methoxalylanthranil 'GH4 I )N*CO*CO,Me m. p. 177.5' (corr.) forms co light brown needles and is readily hydrolysed by water. Elhoxulyl- anthranil m. p. 129-130' (corr.) crystflllises in large colourless plates and is more stable than the methyl derivative but is rapidly hydrolysed by boiling water. Oxalyldianthranil m. p. about 345" (uncorr.) forms a yellow powder and is hydrolysed slowly by boiling water and rapidly by hot concentrated hydrochloric acid. When ethoxalylanthranil is treated with alcoholic ammonia it is converted into ammonium 4-quinaxoZone-2-carboxylate m.p. 229' (decomp.). 4-Quinaxolone-2-carboxylic acid (4-hydroxyquinaxoline-2- forms white silky needles and CarbOXy& acid) C6H4< melts at 230' (corr.) with evolution of carbon dioxide and formation of 4-quinazolone (4-hydroxyq~inazoline)~ m. p. 21 4" (corr.). By heat- ing ethoxalylanthranil with carbamide a t 140-1 SO' ethyl 4-quinaxo- lone-2-carboxykcte7 m. p. 185.5' (corr.) is produced. When ethoxalyl- anthranil ( 1 mol.) is heated with an aqueous solution of methylamine (2 mols.) 3-methyl-4-quinc~xoZone-2-carboxyrnethylumide7 N=y *CO,H CO-NH N=v *CO*KHMe ' G ~ ~ < ~ o - N M ~ 9 m. p. 160" (corr.) is produced which forms pale rose-coloured prisms. Methoxalylanthranil reacts with aniline to form methyl 3-phenyl-4- - - N=C*CO,Me CO-&Ph m. p.203.5' (corr.) quinaxolone-2-carboxytate CGH,< which crystallises in small colourless plates. The corresponding ethyl ester m. p. 160" (corr) is accompanied in its formation by ethyl 4-phenylimino- 3 -phen~lquinaxoline-2-cccrboxy late N==y *CO,Et CGH4<C (NPh)*NPh ' m. p. 291O (decomp.) which forms a colourless crystalline powder. Ethyl 4-~-naphthylimi.no- 3 - P-naphthylquinaxoZine-2-carboxglate m. p. 253-254" (corr.) is similarly obtained as ft grey crystalline powder. When ethoxalylanthranil (1 mol.) is heated with phenylhydrazine (1 mol.) ethyl 3- anilino- 4-quinaxolone-2 curboxplu + e N=C*CO,Et C 6 H 4 < ( 3 - j - ~ . ~ ~ p ~ 9ORGANIC CHEMISTRY. i. 285 m. p. 148’ (corr,) is produced which forms long lemon-yellow needles. By the action of hydrazine hydrate on ethoxalyl- or methoxalyl- anthranil s-bis-3-amino-4-quinazoZone-2-curboxyZic hydraxide PI’=y*CO-NH* [ T C 6 ~ 4 < c oewm2 1 2 y rn.p. 157-158O (corr.) is obtained as a yellow nrriorphous solid. When this compound is boiled with concentrated hydrochloric acid it is converted into 3-nmino-2-car6cczino-4-qzrinaxoZone m. p. 202.5’ (corr.) which crystalliles in transparent plates; its hydrochloride has m. p. 190-191O (corr.) and its diacetyl derivative C6H4<C0*N*NHAc N=y *CO*NH*NHAc has m. p. 125’ (corr.). E. G . Indanthren and Flavanthren. XII. Products of the Action of Nitric Acid on Flavanthren. Elementary Analysis of Difficultly Combustible Substances Rich in Carbon. KARL HOLDERMANN and ROLAND SCHOLL (Ber. 1910 43 340-345. Compare Abstr. 1908 i 696)-When flavanthren (Abstr.1907 i 540) is boiled for eight hours with a mixture of nitric acid D 1.52 and concentrated sulphuric acid at least three products are obtained of which the least soluble has been examined. It is a yellow microcrystalline powder of the composition C,,H,O,,NG and appears t o be a diniti*odinitrosoclihydrox&vanthren. It is unchanged by sulphurous acid forms a black potassizlm derivative yields dinitroso- dianilinodihydroxydavanthren C,,H,,O,N when boiled with auiline and is reduced by alkaline hyposulphite t o the blue vat dye of tetra- aminodihydlroxyjavanthren ; the latter is obtained by reduction with ammonium sulphide and ammonium hydroxide and is a blue substance resembling indigo. It is again reduced by alkaline hyposulphite to t h e deep blue vat dye which produces on unmordanted cotton bluish- black shades turned green by hydrochloric acid the original shade being restored by treatment with water.The estimation of the carbon and the nitrogen in anthracene derivatives of high molecular weight which may be several units % too low by the ordinary processes may be accurately effected by the Dennstedt method or by modifications of t h e ordinary processes which ARTHUR MICHAEL (Ber. 1910 43 621-627). -The conclusion is drawn that the results obtained by Acree Johnson Brunel Shadinger and Nirdlinger with urazoles (Abstr. 1908 i 9 19) are in complete harmony with the author’s theory of addition. Acree’s investigations merely show that the laws of mass action hold good i n the reactions between urazole salts and alkyl halides.The views held by Acree on the mechanism of tautomeric changes are not baaed on experimental facts and are untenable. Phthaleins and Dibenzoylbeneenes. ALFRED GUYOT and ALBIN HALLER (Ann. Cham. Phys. 1910 [S] 19 297-353).-This paper are described by the author. c. s. Addition Theory. J. J. S.i. 286 ABSTRACTS OF CEEMICAL PAPERS. consists mainly of a rdsum6 of previous communications together with further experimental details (compare Abstr. 1898 i 670; 1900 i 170; 1901 i 146 270 350; 1903 i 348 748; 1904 83 314 659 660; 1905 188 226 270 516 540; 1906 i 761 ; 1907 i 76 565 ; 1908 i 569). The dehydration of tetramethyldiaminotriphenylmethane-o-carboxylic acid is best effected by heating the substance with acetic anhydride.The yield is 92% and the product probably has the annexed constitution of a furfuran derivative. Details are given for the preparation of tetra- met hyldiaminodibenzoyl benzen e NMe2*C,H,*C--C*C,H,-NMe from the product. When the substance is heated with sul- ph u r ic acid d epol y rn eri sation /\ /\ \/ 0 C,H 0 UGH \/ occurs and a compound U*C,H,*NMe C24H240N29 NMe,*C6H,* C-- is obtained. This crystallises in orange-red prisms m. p. 140° showing an orange-yellow phosphores- cence when heated and readily reverting to the original substance. The action of sulphuric acid leads also to the formation of a higher polymeride occurring as a pale yellow crystalline mass. W. 0. W. The Optical Inactivity of Allantoin. LAFAYETTE B. MENDEL and HENRY D. DAKIN (J. Biol. Chern.1910 7 153-156).- Ackermann draws attention to the fact that the substances derived by putrefaction from optically active protein derivatives are them- selves optically inactive. HN-C:O NH HN-c*oH y H 2 Bacteria are prone to oh I co 0 0 11 co attack the H~-C-NH I I I I C*H( NH,)* C0,H HN-C- NH group and the removal of this group abolishes H (1.) (11.1 molecular asymmetry. Allantoin however contains an asymmetric carbon atom according to the accepted formula but no examination of its actual behaviour has yet been made. Allantoin of urinary origin was found to be inactive. An attempt to effect a resolution of the inactive substance by bacterial action failed. Several possibilities are discussed to explain the inactivity the one most favoured is that allantoin exhibits tautomerism; thus it may be represented by the two annexed formulae the first is the usual one whilst the second contains no asymmetric carbon atom.W. D. H. Influence of Hydroxyl Ions on Azo-coupling. 11. GUSTAV HELLER [with WILHELM E. GALLEH] (x p. Chevi. 1910 [ii] 81 184-187. Compare Abstr. 1908 i 300).-Solutions of benzenediazo- nium chloride (1 rnol.) prepzred in the usual way are added to aqueous solutions of phenol (1/3 mol.) containing sodium hydroxide (1; mol.) together with 20 40 70 or 100 grams excess of the alkali. The amount of bisbenzeneazophenol increases slowly but continuously that of trisbenzeneazophenol decreases very largely and rapidly as the con- centration of the alkali increases The by-products are regarded asORGANIC CHEMISTRY.i. 287 Copper in ‘‘ Acid mixture ” Acid mixture Acid mixture with without I protein I 1% protein protein without cupric chloride 0-azo-compounds since by prolonged heating with alcohol they are converted into bis- and tris-benzeneazophenol. The conversion of the 0-azo-compounds into real azo-compounds appears to be retarded by an excess of alkali. c. s. Action of Heat on o- Aminoazo-compounds. G. CHARRIER ( A t t i R. Accccd. Sci. I’orino 1910 45 131-139).-0n heating a t about 3(30” o-aminoazo-compounds decompose into triazole primary amine and ortho-diamine. This decomposition supports the formula NH,*Ar*N:NAr’ for the o-aminoazo-compounds and is represented by the equation 3NH2*Ar*N:NAr’= 2Ar< I >NAr’+ NH,Ar’+ Ar(NH,)2. Thus tolueneazo-p-toluidine yields 2-p-tolyl-5-methyl-2 1 S-benztri- azole (compare Zincke Abstr.1886,236) p-toluidine and tolylene-3 4- diamine. Benzeneazo-F-naphthylamine gives phenylnaphthatriazole (compare Zincke Zoc. cit.) aniline and 1 2-naphthylened~amine. p-Tolueneazo-P-naphthyZarnGne NH,*C,,H,*N,*C,H,Me prepared by the action of p-toluenediazonium chloride on p-naphthylamine forms rod needles m. p. 113’. When heated a t 300’ it decomposes into p-toluidine 1 2-naphthylenediamine and 2-p-tolylnaphthatriaxo~e N -N .? Silver in sodium chloride N C,,H,< I >N*C6H4Me which crystallises in slender white needles Ni. 288 ABSTRACTS OF CHEMICAL PAPERS. The acid mixture was in one set of experiments varying proportions of primary and secondary phosphates and in the second set varying proportions of acetic acid and sodium acetate. The isoelectric point was found in one case when the relative amounts of primary t o secondary phosphate were as 50 1 or H = 1.4 and in the other case where the ratio of acetic acid to sodium acetate was between 1 2 and 3 7 or H= 1.08 x 10-5and 0-85 Theabove results were obtained with unheated albumin. With heated albumin it was observed that coagulation rapidly took place when the hydrogen ion concentration was near the isoelectric point.The optimum condition for coagulation could be determined with great accuracy using either of the ’‘ acid mixtures ” mentioned above. It was found to take place when [H’] = 0.82 x Theoretical reasons are deduced for believing that the optimum conditions for coagulation correspond with the isoelectric point.From these results it is calculated that the relative acidity constant for ox-serum at 18’ is 1.1 x lo-*. s. €3. s. Putrefaction of Lyaine-free Protein. D. ACKERMANN (Zeitsch. physiol. Chem. 1910 64 91-94).-Previous experiments have shown that there is reason to believe that arginine is the parent substance of tetramethylenediamine and 8-aminovaleric acid and that lysine is the parent substance of pentamethylenediamine. On the addition of lysine to a putrefying mixture the yield of pontamethylenediamine is increased. The present experiments now show that in the putrefaction of gliadin which is a protein free from lysine there is no formation of pentamethylenediamine. W. D. H. JOSEPH BARCROFT and A. V. HILL (J. Physiol. 1910 39 41 1-428).-The velocity of dissociation of oxyhzemoglobin obeys an equation derived from the laws of mass action and bas a high temperature-coefficient increasing about four times for a rise of 10’.The variations of the eauilibrium constant K The Nature of Oxyhzemoglobin. ‘li’ - q where with change of temperature 2’ follow the equation - ~ = __ K dT 2T2’ q is constant and equal to 28,000 calories. From the second law of thermodynamics p is the heat of combination of 1 gram-molecule of hzemoglobia with oxygen. The amount of heat given out when 1 gram of haemoglobin unites with oxygen is 1 *85 calories. The Ieast possible value for the molecular weight of hEmoglobin in dialysed solution is 16,669. The general conclusion is that hsmoglobin unites chemically with oxygen according to the formula Hzem.+ 0 €€aern.O and that it is not an adsorption phenomenon. W. D. H Modiflcation of Fischer’s Ester Method. B. 0. PRIBRAM (Monatsh. 1910 31 51-54).-Dry ammonia is employed to liberate the esters of amino-acids from their hydrochlorides. I n a preliminary trial 10 grams of ethyl glycine hydrochloride dissolved in the smallest necessary quantity of absolute alcohol were treated with dry ammonia and after the addition of dry ether and removal of the ammonium chloride the solution was evaporated under diminished pressure the ester was redissolved in alcohol and the hydrochloride regenerated byORGANIC CHEMISTRY. i. 289 hydrogen chloride; its weight was 6.9 grams or 69% of the original quantity . The applicability of the process to the isolation of the products of the hydrolysis of a protein is defined by the following experiment.Dry gelatin is hydrolysed by concentrated hydrochloric acid the glutamic acid hydrochloride is removed in the usual way and the filtrate is evaporated to a syrup which is esterified by the ordinary process of Fischer. After the removal of the ethyl glycine hydrochloride the filtrate is concentrated under diminished pressure mixed with dry ether and saturated with dry ammonia; after about ten minutes the ether is poured off replaced by fresh dry ether and the current of ammonia passed anew the processes being repeated until the ether remains colourless. The combined ethereal solutions can be directly fractionated whilst the other products of the hydrolysis can be extracted from the paste of ammonium chloride by means of alcohol.In this way 400 grams of gelatin yield 119.3 grams of esters whereas by Fisher’s process oE liberating the esters from the hydrochlorides 500 grams of gelatin give 117 grams of esters. c. s. Course of the Hydrolysis of Proteins by Aqueous or Alcoholic Hydrogen Chloride. M. PFANNL (Monatsh. 1910 31 81-85).-Pribram (preceding abstract) has observed that the amount of glycine obtained by the hydrolysis of gelatin by alcoholic hydrogen chloride is very much smaller than that produced when the hydrolysis is effected by hydrochloric acid and also that the quantities of the esters of amino-acids richer in carbon are about the same in the two processes of hydrolysis. The author now finds that if care is taken to prevent the hydrolyyis of the easily decomposable glycine ester gelatin yields qualitatively and quantitatively the same products whichever method of hydrolysis is employed.The same is true of the hydrolysis of silk fibroin. c. s. Comparative Investigations on the Composition and Cleavage of Different Kinds of Silk. VIII. The Mono- amino-acids from Tai - Tsao - Tsam Silk (China). EMIL ABDEBHALDEN and JULIUS SCHMID. IX. The Mono-amino-acids from Chefoo Silk. E.. ABDERHALDEN and ERNST WELDE (Zeitsch. phy8iol. Chem. 1910 69 460-461 462 -463).-The following table shows the amount of amino-acids in grams per cent. of the two varieties of silk investigated Tai - T sao - Tsam silk. Glycine ..................... 25.2 Alanine ..................... 18’2 Leucine .................... 0.9 Serine .......................1 -2 Aspartic acid ............... 2 ‘1 Glutaniic acid ............ 2.0 Pheny lalanine ............ 1-0 Tyrosine ..................... 7’8 Proline ..................... 1‘0 Chefoo silk. 12-5 18-0 1’2 1 -0 2-0 2 0 1 -0 8-5 2-5 W. D. H.i 290 ABSTRACTS OF CHEMICAL PAPERS. Gataphoresis of Ferments and Colloids. HENRI TSCOVESCO (Biochem. Zeitsch. 1910 24 53-'78).-The experiments were carried out in an apparatus which is figured in the text consisting essentially of a combination of U-tubes with a central part,:which can be shut off from the remainder by glass taps into which the substance under investigation is introduced. In investigating enzymes this substance is coagulated egg-white or gelatin the remainder of the apparatus being filled with enzyme solution.By this arrangement the distance between the electrodes by means of which the current is introduced is great and the effect of electrolysis can be practically eliminated. By determining on which side the ovalbumin or gelatin undergoes alteration conclusions can be drawn as to the behaviour of the enzymes in an electrical field. By choosing a sufficiently low potential and current strength appreciable destruction of the enzyme can be avoided. Pepsin wanders towards the negative pole passes through the ovalbumin on the positive side and digests i t ; this can happen before destruction of the enzyme takes place; the latter is ailected chiefly by the amount of energy employed (expressed in watts). Similar results with regard to ferment destruction were obtained by the catalase of pigs' liver which wanders towards the anode.Arsenious sulphide wanders through hardened gelatin towards the positive pole. Similar experiments were performed with colloidal iron silver and Magdala-red and coagulated blood-serum. The result in tho last-named case indicated the presence of electropositive and s. B. s. electronegative a1 bumins in the serum. The Kinetics of Enzyme Actions. SVEN G. HEDIN (Zeitsch. physiol. Cham. 1910 64 82-90. Compare Abstr. 1909 i 73).-The experiments recorded with trypsin and rencet show that the law of enzyme action is frequently nullified by the presence of inhibiting substances either in the preparation of the enzyme or in the substrate. W. D. H. The Question of the Identity of Pepsin and Rennet. W.VAN DAM (Zeitsch. physiol. Chem. 1910 64 316-330).-From the experiments described it is held that there is no ground for distinguish- ing a proteolytic from the milk curdling enzyme of the gastric juice. By altering various factors sometimes the one sometimes the other action becomes predominant and the bulk of the paper is concerned with variations in the conditions which lead to such results. W. D. H. The Enzymes of Gum Acacia. physiol. Chem. 1910 64 16.1-168. -Polemical. FRIEDRICH REINITZER (Zeitsch. Compare Abstr. 1909 i 751). A reply to criticisms by Grafe (this vol. i 148). W. D. H. New Observations on the Individuality of Cellase. GABRIEL BERTRAND and NAUHICE HOLDERER (Compt. Tend. 19 10 150 230-232. Compare this vol. i 212).-Evidence is adduced in support of the existence of a specific ferment cellase capable ofORGANIC CHEMISTRY.i. 291 effecting the hydrolpis of cellose. The new diastase has been recog- nised in apricot seeds in the grains of barley and in the mycelium of Aspergillus wiser. It does not appear to occur in blood-serum of horses in top fermentation yeast or in glycerol macerations of Russula queletii. Partial separation of cellase from emulsin can be effected by taking advantage of the diEerent rates at which the enzymes filter through porcelain. w. O.W. Method for the Rapid Preparatioa of Oxidising Enzymes from Plant Extracts. ALEXIS BACH (Ber. 1910 43 362-363). -The addition of 5-10% of magnesium sulphate to a plant extract has the effect of so changing the colloid substances present that they can be easily and quickly precipitated by relatively small quantities of alcohol.Thus from the extract of Russula delica 5% of magnesium sulphate followed by alcohol until the solution contained 48% caused the precipitation of the major part of the impurities. The further addition of alcohol until 70-75% was present precipitated light- coloured crystalline substances very rich in oxydases the last fraction being mainly tyrosinase. The fractions may be freed from magne- sium sulphate by dialysis against running water. The precipitates settle rapidly and the whole process only takes three to four hours. E. E. A. Theory of the Action of Oxydases. I. Oxydases free from Manganese and Iron. ALEXIS BACH (Bet-. 1910 43 364 -366).- Bertrand (Abstr. 1898 i 53 ; ii 128) has suggested that oxydases are to be regarded as organic manganese compounds. Others have prepared active oxydases containing iron instead of manganese whilst the peroxydases (Bach and Tscherniac Abstr. 1908 i 746) have been proved to contain neither metal. Active oxydase preparations have UO w been obtained from Lactarius vellereus and Russula delica by precipitation with 65-75% alcohol after the addition of magnesium sulphate (see preceding abstract) which are absolutely free from either manganese or iron. E. F. A. Theory of the Action of Oxydases. 11. Influence of Metallic Salts on the Subsequent Change of the Products of Oxydase Action. ALEXIS BACH (Bey. 1910 43 366-370).- Metallic salts do not take part in the primary oxidation of tyrosine and phenols by tyrosinase or phenolase that is the absorption and activation of the oxygen but they very greatly accelerate the further change of the primary oxidation products. Thus a tyrosine solution coloured deep red by the action of tyrosinase becomes violet and then black in a few minutes on the addition of aluminium sulphate and the characteristic black precipitate soon forms. Aluminium sulphate similarly accelerates the formation of purpurogallin from the yellow product formed by the action of oxydase on pyrogallol. Metallic salts also indirectly accelerate the actual oxydase action when they facilitate the removal of products of the action which are acting to stop the oxydase. This explanation applies to the accelerat- ing action of manganese salts on the oxidation of drying oils andi. 292 ABSTRACTS OF CHEMICAL PAPERS. quinol. Oxydase action is to be regarded as a process taking place i n two phases and brought about by the agency of two kinds of catalyst. The niolecular oxygen is activated by the oxygenase forming peroxide whilst the peroxydase brings about the transference of the labile peroxide oxygen to the sbbstrate. In the case of phenolase the peroxydase can be replaced by metallic salts but with tyrosine the metallic salts are not replaceable by peroxydase. E. F. A. Formation of Phosphates in Alcoholic Fermentation. ARTHUR HARDEN and WILLIAM J. YOUNG (Centr. BaLt. Par. 1910 ii 26 178-1184. Compare Abstr. 1908 i 590).-The formation of hexose phosphate is accompanied by an exactly equivalent amount of alcoholic fermentation and does not precede the alcoholic fermentation as required by Iwanoff’s theory (Abstr. 1909 i 752). The loss of fermenting power caused by washing zymin with water is shown t o be due to the removal of the soluble co-enzyme. There is no experimental evidence that Iwanoff’s synthease exists. N. H. J. M. Transformation of Aromatic Alcohols into Phosphinous Acids by Hypophosphorous Acid. ROBERT FOSSE (Compt. rend. 1910 150 17s-180; Bull. Xoo. chim. 1910 [iv] 7 2218-231. Compare Abstr. 1906 i 691 975 ; 1907 i 414; 1908 i 567).- Certain aromatic alcohols react with hypophosphorous acid with the elimination of water and the formation of a substituted acid; simultaneously a portion of the alcohol undergoes reduction to the corresponding hydrocarbon. Thus triphenylcarbinol forms triphenyl- methane and triphenylmethylphosphinous acid CPb,*PHO*OH. Di- naphthapyranol forms dinaphthapyran and dinaphthapyrylphosphinous acid O<CIOH6>CH*PHO*OH Michler’s carbinol forms the corre- sponding hydrocarbon and the acid CH(C6H,*MMe2),*PHO*OH. When the corresponding aldehydes or ketones are treated with hypophosphorous acid additive compounds are formed of the type C H 10 6 R*CH(OH)-PHO-OH. w. 0. w. Preparation of an Arsenic-albumin Compound. FRIEDR. AUGUST VOLKMAR KLOPFER (D.R.-P. 214717).-When the nuclein-free vegetable albumin obtained from wheat is treated with arsenious chloride in the presence of a diluting agent reaction takes place at the ordinary temperature. The ameno-albumin so obtained is readily soluble in water but insoluble in the gastric juice; it contains N = 12.95% S = 1*7S% C1= 4~72%~ and As = 4.33%. F. M. G . M.

ISSN:0368-1769    

DOI:10.1039/CA9109800213

出版商:RSC    

年代:1910

数据来源: RSC

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MlNERALOGICAL CHEMISTRY. Min e r a 1 o gi c a1 C h e mi 8 try. ii. 219 Mineralogy of Franklin Furnace New Jersey. CHARLES PALACHE (Amer. J. Xci. 1910 [iv] 29 17'7-187).-Arsenopyrite brilliant crystals from limestone,.gave anal. I (by E. C. SULLIVAN). The associated iron-pyrites contains about the same proportion of cobalt but the associated pyrrhotite contains no cobalt and only a trace of nickel Fe. co. As. S . Total. I. 32.48 1-16 48'72 18'80 101'16 E'luorite pale red and granular the matrix of franklinite grains gave I1 (by G. STEIBEK). The deficiency is probably fluorine but even then there is not quite enough for the formula CaF Ca. Mg. Fe. Mn . 81. F. Cl,CO Total. 11. 51-21 0.24 0.27 0 -09 0.18 45.85 nil 97-84 Manganosite (111 by G. Steiger) forms a granular aggregate with franklinite and zincite ; the irregular grains are dark green and have a cubic cleavage being emerald-green in thin flakes; D 5.364; formula MnO. This rare species has previously been found only in Sweden.16-2ii. 220 ABSTRACTS OF CHEMICAL PAPERS. Gahnite variety dysluite (IV by W. T. SCHALLER) large crystals from Sterling Hill; D 4.56. Franklinite (V by W. T. Schaller) small crystals of cubo-octahedral habit and adamantine lustre and showing a deep red colour on edges or where splintered ; D 5.09. Hetcerolite (VI by W. T. Schaller); under the microscope it is seen to be tetragonal with indistinct prismatic cleavages; D 4.85. This hitherto doubtful mineral may be described as a zinc hausmannite Zn0,hln203 (hausmannite being MnO,Mn2O3) Pyroxenes jeffersonite (VII by G.Steiger) and schefferite (VIII by 'CV. T. Schaller). Bementite (IX by 0. Steiger) is orthorhornbic with three pinacoidal cleavages. The water is expelled only at a red-heat and the formula H6Mn,(Si04) shows a relation to tephroite (Mn,$i4Ol6). Friedelite (X by MT. T. Schaller) scales and indistinct tabular rhombohedra1 crystals. Formula Hg( MnC1)Mn7(Si0,)6 or perhaps Vesuvianite variety cyprine (XI by G. Steiger) bluish-green fibrous ; D 3.451 ; formula H,(A~,E'e)6Ca12Si,o04,. Cuspidine (XII by C. H. WAHREN) glassy white crystal fragments ; D 2.965-2.989 ; formula Ca2Si(0,F2),. This species has hitherto been known only from Vesuvius. H,0(MnC1)Mn1,Sil~049' Total - ~ . ~ H20 H200 (less SiOz. A1203 Fe203. FeO. MnO. MnO2. ZnO. CaO. MgO. (105").(>lo5 ). F. Ofor F.) c-z 111. - - 0.26 94'59 1-30 3'41 - 0'11 0.38 0'40 - 100'45 IV. 1-47 47'27 9.90 - 0'93 - 37'10 1-01 1'09 1.21 - 100.36" + v. - - 66-58 - 9'96 - 20.77 0'43 0'34 0'71 - 99'51t w VI. 1.71 - 0.77 - 60'44 32 43 - - 2'47 1'48 - 10024 VII. 49'03 0'86 4.22 3.95 i.91 - ('14 19.85 5.81 0'60 0.70 - 100'14 VIII. 49'80 0.26 1'46 1'61 9%9 - trace 21'07 12'35 1.55 1'31 0.31 99*80$ IX. 38.36 0'96 0 71 4-94 39.22 - 2 93 0'62 3'35 0 60 801 - 99'70 X. 34'69 - - 1'45 48.00 - 1'05 0'63 0'98 1'94 9.08 - 100.48s XI. 36-41 17'35 1.86 1.75 - 1'74 33.21 118 0'24 3.51 0'36 100'0611 XII. 32'36 - - - 071 - - 61'37 - - - 905 100'43ll * Including CO2 0.38. 1 Including Na20 0'9 ; COz 0.43. 11 Including CuO 1.85 ; PbO trace ; Na20 0'44 ; KzO 0'50. w t State of oxidation of iron and manganese not known.9 Including C1 3.43. 7 Including Na20 0-48 K20 0.27. Crystallographic descriptions are also given of zincite (a c = 1 1.5870) ; nasonite (hexagonal a c = 1 1.3167) ; glaucochroite (a b c = 0,4409 1 0-5808) ; willemite (a c = 1 0.6612) ; datolite ; humite and leucophoenicite (a b c = 1,1045 1 2,3155 ; /3 = 76"44'). Ninety-three species of minerals are recorded from this locality several of them now for the fir& time. L. J. S. Bismite. WALDEMAR T. SCHALLER and FREDERICK L. EANSOME (Amer. J. Sci. 1910 Liv] 29 173-176).-Bismite occurs in the oxidised zone in several mines in the Goldfield district of Nevada. It has the form of minute! pearly scales with a brilliant almost metallic lustre and a silvery whiteness. It encrusts the cavity-walls of spongy limonite and quartz and has been derived by the alteration of bismuthinite ( Bi2S8).Under the microscope the thin colourless scales shorn a hexagonal outline with triangular markings on the base,MINERALOGICAL CHEMISTRY. ii. 221 and a negative uniaxial interference-figure ; there is a perfect basal cleavage. The crystals are therefore rhombohedral n c = 1 0.5775. (Artificial crystals of bismuth trioxide are orthorh0,mbic.) Analysis of material mixed with much gangue (mainly quartz) gave Bi,O,. H,O (loss on ignition). Fe,Oa. Insoluble in HCl Total. 17.04 3 ‘96 0 -36 78‘94 100-30 These results indicate that the crystals are either bismite (Bi,O,) or a hydrous bismuth oxide. If the latter be the case the mineral is a new species (providing of course that Bi,O is the correct formula for bismite or bismuth ochre).L. J. S. Variety of Cobaltiferous Calcite from Capo Calamita Elba. FEDERICO MILLOSEVICH ( A t t i R. Accad. Lincei 1910 [v] 19 i 9 1-92).-The author describes a sample of vivid red calcite occurring in crystalline masses on a limonitic and partly magnetitic rock. It is slightly harder than normal calcite has D 2.75 and has the following corn posi t ion CaO. COO. FeO. MgO. MnO. COP Total. 54.41 1.27 0-15 0 ‘27 trace 43 *55 99.65 which corresponds with CaCO 97.16 ; CoCO 2.03; FeCO 0.24 and MgCO 0.56. The name cobalto-calcite is given to the mineral. T. H. P. The Plumboniobite Earths. OTTO HAUSER (Ber. 1910 43 41 7-41 9).-Speckroscopic examination of the plurnboniobite described in a previous communication (Abetr. 1909 ii 676) shows that the formula therein given must be modified to R,”Cb,O,,R,”’(Cb,O,) where R” represents Pb Fe UO and Ca and R”’ represents Y Gd Yb and Al.T. s. P. A Uranium Ore from German East Africa. WILLY RIARCK- WALD (Landw. Jahrb. 1909 38 Erganx. band V. 423-425 Thiel Festschri.t).-An account of the methods employed with the tabulated results of the analysis of a mineral found in German East Africa containing 80-90% uranium oxides (UO = 45% UO = 39%) and 7-8% lead oxide (PbO). F. M. G. M. Minerals from the Pegmatites of Madagascar. LOUIS DUPARC R. SABOT and R I . WUNDER (Arch. Xci. phys. nut. 1910 [iv] 29 62-7l).-The pegmatite veins in the neighbourhood of Antsira b6 are intrusive into quartzites and cipolins ; they consist mainly of quartz and orthoclase with some mica and various accessory minerals (tour- maline beryl spodumene garnet.etc.) in large crystals of gem- quality Spessartite (anal. I) of gem-quality and honey-yellow or brown in colour occurs in pegmatite at Tsilaisina ; refractive index (Na) 1,79980. Cordierite (anal. 11) was found as irregular fragments in the Usually the pegmatite is much decomposed.ii 222 ABSTRACTS OF CHEMICAL PAPERS. micaceous quartzite of the Ibity range ; refractive indices a = 1.53958 p= 1.54516 y = 1.54853. Loss on SiO A1,0,. Fe,O,. FeO. XnO. CaO. MgO. TiO,. ignition. Total. Sp. gr. I. 35.76 21 06 1.78 - 39.40 1.23 0.46 0'10 - 99-79 4.0586 11. 49-05 33-08 0.83 4.38 - - 11.04 - 1'64 100.02 2'5933 Crystallographic descriptions are also given of large zoned (red and brown) crystals of tourmaline from several localities.These crystals are optically biaxial with a small axial angle ; refractive indices are given. L. J. S. Chemico-physical Investigations and Analysis of the Iron- and Arsenic-containing Water of Roncegno. RAPFAELO NASINI MARIO GIACONO LEVI and F. AGENO (Gaxxetta 1909 39 ii 48 1-51 a).-The results of the authors' chemico-physical measure- ments on this water are as follows DY 1.00293; freezing point - O.lOo ; osmotic pressure P = 1.205 atmos. ; specific electrical con- ductivity K25 = 0.00453 ; radioactivity intensity of saturation current I = 167.8 x 10-15 amperes. The large amount of arsenic renders the full analysis interesting. The dissolved matter in grams per litre is as follows CUO. FeO. Pep,. AI,O,. MnO. NiO . coo. CaO. MgO. Nti,O. K,O. SO,. SiO,. P A 0.01463 0*01006 1.21230 0.26670 0.01952 0.00325 0.00295 0'58919 0*11400 0.01109 0'00325 3.53850 0'13160 0-00740 Residue Residue AS,^,. As20,. NH,. C1. Li,O. l'iOz. at 100". at 180". 0.00350 0.05714 0.00027 0*00007 Trace. Trwe. 7.1610 6.5560 T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805219

出版商:RSC    

年代:1910

数据来源: RSC

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ii 222 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry Narcosis and Want of Oxygen. 11. The Effect of De- privation of Oxygen on the Resting Current of Frog’s Skin. G. MANSFIELD (PJEiger’s Arcbiv 1910 131 457-464).-Alcock has shown that narcotics of the fatty series abolish or lessen the secretion current of the frog’s skin but only if the mrcotic is applied to its outer surface. Deprivation of oxygen acts in exactly the same way and this is considered to support the theory that the narcotics in question produce their effects by lessening the supply of oxygen to the cell lipoids. Gaseous Metabolism of the Dog’s Heart during Vagus Inhibition. J. M. WOLFSOHN and L. W. KETRON (Proc. Amel.. physiol. Soc. 1909 25-26 ; Amer. J. physiol. %).-The gases of the blood mere analysed by the use of the mercury pump and Barcroft and W.D. H.PHYSIOLOGICAL CHEMISTRY. 5. 223 Dixon's results were confirmed that vagus inhibition lessens the oxygen absorbed and the carbon dioxide produced the latter being the more marked W. D. H. The Inhibition of Soap Haemolysis. WILHELM MEPEESTEIN (Arch. exp. Path. Pharm. 1910 82 145-155).-The hzemolysis pro- duced by soaps is inhibited by cholesterol and also by two other lipoids kephalin and cerebron. Sodium stearate and palmitate which possess bamoly tic properties increase the hamolysis produced by sodium oleate. Alcoholic extracts of organs inhibit hamolysis produced by soaps and by saponin. Dissolved red corpuscles protect other red cells from the solvent action probably by the fact that lipoids are liberated. W.D. H. Observations on the Inhibitory Influence Exerted by Hypertonic Saline Solutions and Calcium Chloride Solutions on the Action of Specific Haemolysins with Suggestions as to the Therapy of Blackwater Fever. W. D. SUTHERLAND and DAVID MCCAY (Bio-Chem. J. 1910 5 1-32).-In blackwater fever the corpuscles are more vulnerable than in the normal state and the liberation of haemoglobin is due to a hzmolysin. Salts which decrease the number of inorganic ions in the plasma are recommended for such salts to a large extent inhibit hsmolysis in uitcro. The intra- venous injection of a mixture of sodium chloride and calcium chloride is recommended. W. D. H. Action of Biotoxin on Blood. FRANCESCO MARINO-ZUCO and L GIUGANINO (Gaxxetta 1909,39 ii 586-61 6).-Further experiments on the toxin previously ,described (,4bstr.1904 ii 754) give the following results. The biotoxin as the authors term it has an energetic poisoning effect on the blood its action which can be followed by means of the spectroscope being as follows. The oxyhaemoglobin is resolved by the action of the enzyme into two principal substances one of which has a protein character and contains all the iron of the hsmoglobin tho other being a non-protein pigment which is apparently analogous to the colouring matter of the bile and exhibits a spectrum characterised by B band in the red X = 650-632 and another between the blue and green X = 520-490. This action on the blood pigment is so sensitive that by means of the spectroscope the presence of one five-millionth (1/5,000,000) of the biotoxin in 1 c.c of 10% defibrinated blood solution can be recognised. I n small pro- portions the biotoxin occurs in circulating blood its presence being demonstrated not only by direct extraction but also by the changes taking place in sterilised blood solutions when these are maintained for three months at 40-41' (the optimum temperature of the toxin) or for a longer period at t h e ordinary temperature.T. H. P. Influence of Alcohol on Metabolism. LAFAYETTE B. MENDEL and WARREN W. HILDITCH (Proc. Amer. physiol. Xoc. 1909 11 ; Amer. J. Physiol. %).-The most marked result of alcohol as revealed by urinary analysis is to increase the amount of purineii. 224 ABSTRACTS OF CHEMICAL PAPERS. substances. 6‘ Protein sparing ’’ so frequently observed before was also shown to occur.The paucity of the results indicates that the body can maintain its catabolic functions along normal channels despite the interference of toxic agents a factor of safety being present. I n the more marked conditions OE alcoholism conjugated glycuronates may be excreted both in men and animals these disappear with the cessation of the intake of alcohol. W. D. H. Relation of Pancreas t o Sugar Metabolism. WESLEY M. EALDWIN (Proc. Anaer. physiol. SOC. 1909 21-22 ; Amer. J. Physiol. 25).-Experiments with the muscles and pancreas of catP frozen solid by liquid air and then powdered show that when extracts are made the presence of the pancreas increases glycolysis in an alkaline medium and thus the original statements of 0.Cobnheim are confirmed. W. D. H. Digestion of Inulin. H. BIERRY (Compt. rend. 1910 150 116-1 18).-In the higher animals transformation of inulin is effected by the hydrochloric acid of the gastric juice and is not due to the presence of a soluble pancreatic ferment. The pancreatic juice of dogs is incapable of effecting hydrolysis. The gastro-intestinal secretion of Helix pomatia however slowly hydrolyses inulin with formation of laevulose. w. 0. \v. Effects of Carbohydrates on the Artiflcial Digestion of Casein. NELLIE E. GOLDTHWAITE (J. Biol. Chem. 1910 7 69-42). -Carbohydrates retard the digestion of caseinogen in uitro in proportion to the amount added. W. D. H. Chemical and Bacteriological Study of Fresh Eggs. MARY E. PE~NINQTON (J. Biol. Cherra. 191@ 7 109-132).-1n fifty-seven eggs seven only were sterile ; in the remainder bacteria of which thirty-six varieties were identified were present both in white and yolk.The chemical data relate mainly to nitrogenous compounds in both white and yolk-nitrogen coagulable by heat in filtrate in tannic acid precipitate etc. These details are given in nunieroiis tables. W. D. H. The Phosphorus-content of Growing Dogs. ALEXANDER LIPSCH~~TZ (Arch. exp. Path. Pharnt. 1910,62 210-243).-1n growing dogs restriction of the diet to rice and white of egg leads to a rela- tive I‘ phosphorus hunger,” the body containing only from one-sixth to one-fifteenth of the normal amount of phosphorus. This diet poor as it is in phosphorus leads to changes in the skeletal system similar t o those found in the bones in ‘I Earlom’s disease,” and to a slower rate of growth than normal.W. D. H. Irregularities of the Mammalian Heart under Aconitine. ARTHUR R. CUSHNY (Heart 1909 1 1-22).-From experiments on dogs in which aconitine in 0.05 mg. doses was injected intravenously it was found that sever31 forms of cardiac irregularity could be pro-PHYSIOLOGICAL CHEMISTRY. ii. 225 duced among which impaired conduction through the auriculo- ventricular bundle may be mentioned. Aconitine has a greater tendency to muse pulsus alternans than most other poisons. W. D. H. Influence of the .Pancrew on the Glycolytic Power of Muscle. G. C. E. SIMPSON (Bio-Chem. J. 1910 5 126-142).-By incubation of muscle juice or extract especially in the presencg of pancreatic juice large amounts of reducing substances are formed possibly from glycogen but more largely from autolytic or tryptic digestion of the muscle plasma.The nature of these substances has still to be investigated. The dificulty of maintaining asepsis is however almost insuperable and the difficulty of estimating sugar in the presence of large amounts of proteins leads to great experimental error. So far as observations are possible under these limitations the glycolysis obtained by the combined action of pancreatic and muscle juices is believed to be not as a rule greater than the sum of the actions of the constituents of the mixture. W. D. H. The Silicio Acid in whartonian Jelly. HUGO SCHULZ (Pfliiger’s Archiv 1910 131 447-456).-Frauenberger (Abstr. 1908 ii 969) having thrown doubt on the statements of the author regarding silicic acid in the Whartonian jelly cjf the human umbilical cord the experiments in question have been repeated and the results are practically the same as in the previous investigation (Abstr.1902 ii 275) namely that the jelly contains 4% of ash not 11.6% as stated by Frauenberger and that 1 kilogram of the dried jelly contains 0-26 gram of silica. W. D. H. The Parent Substance of Glycogen. EDUARD PFLUGER and PETER JUNKERSDORF. Postscript. EDUARD PFLUGER. Influence of Phloridzin on the Sugar in the Blood. PETER JUNKERSDORF. Estimation of Glycogen in the Tortoise’s Liver. EDUARD PFLUGER (Pfl.iiger’s Arckiv 1910 131 201-201,302-305,306-313 314-3 16)-The first paper contains protocols of over 150 experi- ments on dogs.The liver was rendered almost free from glycogen by means of phloridzin and inanition ; but twenty-four hours later if no more phloridzin is given the liver may contain as much as 3% of glycogen ; the mean percentage in thirty-eight experiments was 1.1%. If cod’s flesh is given the percentage rises enormously and the conclusion is drawn that this is not n ‘‘ sparing ” phenomenon neither is the glycogen derived from fat but from protein. I n fact this is regarded as the first absolute proof of the origin of carbo- hydrate from protein. Excessive doses of protein food do not increase the percentage of glycogen so much as moderate doses. I n the postscript a few experiments given seem to indicate that glycine may act as a parent substance of glycogpn but these are to be repeated on a larger scale.The third paper confirms the previously well-known fact that in phloridzin diabetes the amount of sugar in the blood is not higher than normal it may be lower.ii. 226 ABSTRACTS OF CHEMICAL PAPERS. Pfluger’s method of estimating glycogen has been tested already in thousands of cases ; the tortoise’s liver however does not lend itself for certain unexplained reasons to the method ; in this case therefore reliance has t o be placed on a previous method which is not so exact. W. D. H. Physiology of Lymph. X. The Comparative Electrical Conductivity of Lymph and Serum and its Bearing on Theories of Lymph Formation. A. B. LUCKHARDT (Amer. J. Physiol. 1910 25 345-353).-Several observers have stated that lymph contains more chlorides than serum ; this is confirmed by the electrical conductivity method.The serum is certainly richer in protein than lymph but the increase of protein (as shown by experiments on white of egg) is inadequate to explain the lesser conductivity of the former fluid. Fat droplets in the chyl depress the conductivity of lymph. A 10% increase in the amount of sodium chloride in physio- logical saline solution produces an effect on conductivity comparable to that seen in comparing lymph and serum. The excess of chlorides awaits explanation and is not compatible with purely mechanical theories of lymph formation. W. D. H. Physiology of Lymph. XI. The Fractional Coagulation of Lymph. HERBERT 0. LUSSKY (Amer. J. Physiol. 1910 25 354-366).-Lymph may coagulate in successive crops of fibrin ; this will depend on tbe amount of thrombin present.I n lymph the conversion of prothrombin into thrombin by calcium appears to occur very slowly. A small yield of fibrin with a small amount of ferment in a given time is no proof that thrombin is not an enzyme as Rettger (Abstr. 1909 ii 680) considers. The time factor was neglected by this observer; after the lapse of a longer time as much fibrin may be formed as in other specimens is famed by larger amounts of the enzyme in a shorter time. W. D. H. Presence in Cow’s Milk of an Anzeroxydase and a Catalase. J. SARTHOU (Compt. re92d. 19 i O l 5 0 119-121. Compare this vol. ii 57) -Polemical against Bordns and Touplain (Eoc. cit.). The author quotes the results of experiments which appear to show that the catalytic actions brought about by filtered milk ale clne not to casein but to lactic ferments.w-. 0. w. Reactions of Curdled Milk due to t h e Colloidal State. FR~D. BORDAS arid F. TOUPLAIN (Compt. rend. 1910 150 341-343. Compsre this vol. ii 57).-Thcl authors consider that the reactions of cixrd1e.d milk hithclrto ,ztt,rihiited to the presence of enzymes may be explained by the colloidal state of the casein. Colloidal solu- tions of ferrous oxalate or ferric lactatve are found to give all the catalytic reactions of curdled milk decomposing hydrogen peroxide for example and developing a blue coloration with p-phenylenediamine. Curdled milk which has been heated to 110’ and cooled gives no reaction with these substances ; if however the casein is brought to a very finely-divided state by allowing a jst of the liquid under a pressurePHYSIOLOGICAL CHEMISTRY.ii. 227 of 300 atmospheres to impinge on an agate plate it becomes endowed ALEXANDER LIPSCH~~TZ (Arch. exp. Path. Pharrn. 1910,62,244-252).-The normal faces of the growing animal (dog and man) are poorer in phosphorus than in the adult condition. W. D. H. The Degradation of Fatty Acids in Diabetes mellitus. JULIUS BAER and LEON BLUM (Arch. exp. Path. Pharm. 1910 62 129-138. Compare Abstr 1908 ii 1057).-1t has been shown previously by the authors that the administration of butyric acid hexoic acid P-methylbutyric acid P-ethylbutyric acid leucine pheny!- alanine and tyrosine t o diabetics causes an increahe of ,8-hydroxybutyric acid and members of that group in the body that coristitutes acidosis.Stress is laid on the importance of the P-position in the substances given. The present research relates mainly to leucine ; d-leucine produces no effect but the naturally occurring I-leucine is effective in the direction above indicated. Embtlen states that by perfusing the liver with d-leucine acetone formation is observed and that this does not occur with I-leucine. These experiments were repeated but no marked difference could be observed between the two isomerides. with marked catalytic properties. w. 0. w. The Phosphorus in Faeces. W. D. H. Formation of Glycogen in the Liver of Tortoises with Pancreatic Diabetes. M. NISHI (Arch. exp. Path. Pharrn. 1910 62 170-179).-The blood of normal tortoises contains no reducing substance ; total extirpation of the pancreas leads to intense glgczemia and glycosuria ; in this condition perfusion of the liver with a solution of dextrose leads to glycogen formation there as in normal animals.W. D. H. The Production of Sugar from Amino-acids. A. I. RINGER and GRAHAM LUSK (Proc. Amer. ph?~sioZ. SOC. 1909 19 ; Arner. J. Physiol. %).-Both glycine and alnnine administered to dogs suffer- ing from phloridzin glgcosurix are completely converted into sugar ; and three of the four carbon atoms in aspartic acid and three of the five in glutnmic acid are similarly convertnble into dextrose. W. D. H. Phloridzin Glycocholia. R. T. WOODYATT (J. BioZ. Chem. 1910 7 133-1 36).-The administration of phloridzin leads to presence of sugar not only in the urine but also in the bile; its action is therefore not confined to the kidneys.W. D. H. Acapnia and Shock. V. Failure of Respiration after Intense Pain. YAND~LL HENDERSON (Am,e?* J. Physiol. 1910 25 385-402. Compare this vol. ii 137).-A continuation of work along the same lines as in previous papers. The point specially insisted on is that serious and even fatal apncea may be a result of intense pain and a case in support of this view in a man is recorded. W. D. H.ii. 228 ABSTRACTS OF CHEMICAL PAPERS. Antagonistic Action of Barium and Magnesium. DON R. JOSEPH and SAMUEL J. MELTZER (Proc. Amer. physwb. Xoc. 1909 17-18 ; Amer. J. Physiol. %).-In rabbits 1.2 grams of magnesium sulphate per kilo. of body-weight are fatal. It has been previously &own that these effects are antagonised hy calcium salts.The effect on the respiration is also antagonised by barium salts although the animal remains anzesthetised and otherwise paralysed. The same dose of barium chloride alone is fatal so that the toxic effects of barium are antagonised by magnesium. W. D. H. The Increase of Susceptibility to Adrenaline Produced by Cocaine. ALFRED FROHLICH and OTTO LOEWI (Arch. exp. Path. Pharrn. 1910 62 159-169).-Small inactive doses of cocaine increase markedly the intensity and duration of the effects of adrenaline on the blood-vessels eye and bladder. The combination of the two is therefore recommended for therapeutic use. W. D. H. Fate of Sodium Benzoate in the Human Organism. HENRY D. DAKIN (J..BioZ. Chem. 1910 7 103-108).-Sodium benzoate in doses of 5 to 10 grams a day for two or three days is wholly elimin- ated in the urine as hippuric acid.The increase of glycuronic acid derivatives is trifling. These results confirm those of Lewinski (Ahstr. 1908 ii 518 ; 1909 ii 820) and are in opposition to those of Brugsch and Tsuchiya (Zeitsch. e-cpt. Path. Ther. 1909 5 937). An improved method of hippuric acid estimation is described. W. D. H. The Action of Ether on the Circulation. E. H. EMBLEY (Bio- Chenz. J. 1910 5 79-93).-Ether administered with plenty of air lowers the blood-pressure j in high concentration it paralyses the heart muscle. It stimulates the inhibitory mechanism of the heart and relaxes the arterioles. It is in every way safer than chloroform. W. D. H. The Chemistry and Bio-chemical and Physiological Pro- perties of a Sapo-glucoside obtained from the Seeds of Baasia loagifolia (Mowrah Seeds).BENJAMIN MOORE MISS 5. C. M. SOWTON F. W BAKER-YOUNG and T. ARTHUR WEBSTER (Bio-Chen7. J. 1910 5 94-125).-The sapo-glucoside in question is named rnowrin. Directions for its isolation are given; on hydrolysis i t yields mow& acid furfuraldehyde and dextrose. It is very toxic and workers with Mowrxh meal siiffer from virulent cellulitis of the hands and feet. Details are given inter alia of its haemolytic action and of its action on tho heart; in the latter relation i t resembles drugs of the digitalis group. W. D. H. Comparative Action of Stovaine and Cocaine as Measured by their Direct Effect on the Contractility of Isolated Muscle.VICTOR H. VELEY and AUG~USTUS D. WALLER (Proc. Roy. Xoc. 1910 B 82 147-151). -Stovaine methylstovaine and cocaine have approximately equal nffinity vnliies as measured by the methyl-orangeVEGETABLE PHYSlOLOGY AND AGRICULTURE. ii. 229 and borax precipitation methods. toxicities of these drugs to plain muscle are also equal. Measured by Waller's method the G. S. W. Toxicity of Thallium Salts. ROBERT E. SWAIN and W. G. BATEMAN (L Bz'ol. Chem. l910,7,137-151).-The toxicity of thallium salts has been a matter of divergence of opinion. The present experi- ments on numerous specios of animals show that it is among the most toxic of the elements. The symptoms closely resemble those of urremic poisoning but the kidneys so far examined show no very severe changes. W. D. H. Mercury and Hirudin. MLLE. GUVTAYA PRUSSAK (Arch. exp. Path. Pharrn 1910 62 201-209).-The toxic action of mercury (given as sublimate) is much increased by the administration of hirudin; the minimal lethal dose of the former is thus lessened. The same symptoms and pathological appearances occur as when the blood is not rendered incoagulable by hirudin. W. D. H. Cobra Poison and Hzemolysis. 111. IYAR BANG (Biochem. Zeitsch. 1910 23 463-498. Compare Abstr. 1909 ii 681).-Although pure lecithin has no influence on the hamolysis produced by cobra venom it is shown that commercial lecithin acts as an activator under a number of different experimental conditions. This is explained by the hypothesis that the membrane of the corpuscles is rendered more permeable to salts especially to their acid constituents the lecithin combining with the alkali. It is further supposed that there are two receptors and that the poison reacts with the second receptor in the presence of lecithin; it is this which renders the lipoid membrane permeable. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9109805222

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

VEGETABLE PHYSlOLOGY AND AGRICULTURE. ii. 229 Chemistry of Vegetable Physiology and Agriculture. Assimilation of Carbon by Bacteria which Oxidise Hydrogen. A. J. LEBEDEFF (Ber. deut. bot. Ges. 1910 27 598-602).-The development of the microbe employed in a solution containing minerals and nitrate is coincident with an absorption of carbon dioxide hydrogen and oxygen and a slight liberation of free nitrogen. The average result of about fi€ty experiments showed that for 100 C.C. of carbon dioxide used 500 to 1500 C.C. of hydrogen were oxidised. The oxidation of hydrogen takes place however when carbon dioxide is absent the hydrogen and oxygen being absorbed in the relation H O,= 2. In the autotrophic assimilation of carbon dioxide the volume of The process I n complete oxygen liberated is equal to that of the carbon dioxide.is the same as that which takes place in green plants. absence of free oxygen the process is slow. N. H. J. M.ii. 230 ABSTRACTS OF CHEMICAL PAPERS. Cellulose as Source of Energy in the Assimilation of Atmo- spheric Nitrogen. HANS PRINGSHEIM (Centr. Bakt. Par. 1910 ii 26 222-227).-Clostridiunz in conjunction with organisms which decompose cellulose gives better results with cellulose than Clostridzum alone with dextrose sucrose starch lactose or mannitol. The amount of nitrogen fixed depends on the concentration being higher per gram of substauce fermented the lower the concentration. With Clostrzdiuin + methane fermentation the amounts of nitrogen fixed were 10.4 and 5.4 mg. per gram with 0.5 and 1% whilst with Clostridium + hydrogen fermentation the amounts were 8.3 and 7.7 mg.respectively. Axoto- bacter + methane fermentation gave 4.5 mg. nitrogen per gram (05% cellulose). N. H. J. M. Agar-Agar as Source of Energy in the Assimilation of Atmospheric Nitrogen. HANS PRrNasHEIM and ERNST PRIHGSHEIM (Centr. Bakt. Par. 1910 ii 327-231).-J.n a solution containing 0.2% agar and 0.04% dextrose inoculated with Bacillus gelaticus + Clostvidium Americanum 26 6 rng. of nitrogen were assimilated per gram of agar whilst with a similar solution containing 0.005% of ammonium phos- phate instead of dextrose the amount of nitrogen fixed was 15.4 mg. per gram. Two experiments in which solutions containing (1) 0.5% agar and 0.1% mannitol and (2) the same proportion of agar and 0.04% mannitol were inoculated with B.gelaticus + Axotobacter chroococcum resulted in the fixation of 14 and 6.8 mg. nitrogen respectively. The results are of interest as they account for the origin of the nitrogen required by the vegetable and animal organisms in the sea. Benecke and Keutner (Ber. deut. bot. Ges. 1903,21 333) showed that both Axotobacter and Chtrid~um occur in sea-water and the present results indicate that the agar present in the red and brown Algae is rendered available as source of energy with the help of Bacillus gslaticus. N. H. J. M. Ammonia and Nitrates as Sourcea of Nitrogen for Mould Fungi. G. RITTER (Bey. deut. bot. Ges. 1910 27 582-588).-The assimilation of ammonia by moiild fungi is the more complete the weaker and less poisonous the acid liberated from the salt and the development of the fungi on nutritive solutions containing ammonium salts is in direct proportion to their power of resisting the action of free acids.AspergiJlus niger and Rhixopus nigricuns liberate considerably more acid than the amount which permits the germination of their spores whilst with submerged fungi such as the dfucoruceup the amount of acid produced tends to be below the limit. Aspergillus glaucw Mucor racernosus and Cladosporiurn hevbarum which are termed '' nitrate " fungi (Laurent Ann. Inst. Paateur 188S 2 593 and 1889 3 362) develop at least as well and in part better when supplied with ammonium salts as with nitrates. Rhixopus nigricans Nucor mucedo and Z'humnidium elegans do not assimilate nitrates appreciably N.H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 231 Production and UtiliRation of Nitrous Oxide by Bacteria. BRUNO TACKE (Centr. Bakt. Par. 1910 ii 26 236. Compare Beyerinck and Minkrnann ibid. 25 30).-The author refers to a previous paper (Lmdw. Jahrb. 1887 16 917) in which he showed the production of considerable amounts of nitrous oxide in denitrification experiments. An experiment in which beet was fermented in a vacuum yielded so much nitric oxide in eight or ten days that red fumes were seen on opening the vessel. Nitric oxide may also be produced in considerable quantity. N. H. J. M. Influence of Depth of Cultivation on Soil Bacteria and their Activities. WALTER E. KING and CHARLES J. T. DORYLAND (Kansas State Agric. Coll. E x ~ T . Stat.Bul. 161 1909).-Two plots each 42 feet square the one a silt loam and the other a fine sand were divided into six sub-plots the soil of which was stirred to the depth of two four six eight and ten inches respectively one sub- plot being left undisturbed. Samples were frequently taken and the number of bacteria determined. The temperature of the soil was recorded and the amount of moisture in the first twelve inches of soil determined each time. The results showed that deep ploughing (eight t o ten inches) increased the number of bacteria in both soils. It also increased the production of ammonia in the soil whilst denitrification was decreased. The maximum number of bacteria was found within the fifth and sixth inches. An excess of moisture in the soil reduces the number and diminishes the activity of the bacteria.There are however more or less regular periods of increased and diminished bacterial life and activity to some extent independent of moisture and temperature and due perhaps to the presence of bacterial by-products. N. H. J. M. New Theory of Alcoholic Fermentation. R. KUSSEROW (Centr. Bakt. Par. 1910 ii 26 184-18T).-The theory is essentially as follows The yeast requiring oxygen reduces the sugar to a hexahydric alcohol which decomposes into ethyl alcohol carbon dioxide and hydrogen. The nascent hydrogen cau3es a further reduction of sugar followed by the decomposition of the alcohol and this continues until the sugar is used up or until the fermentation is stopped by the oxidation of the hydrogen. Fermentation is therefore first brought about by the reducing action of the living yeast cell or by similarly acting organisms whilst its continuation is purely chemical depending on the production of hydrogen.N. H. J. M. Action of Ultra-violet Light on Wine During Fermentation. CHARLES MAURAIN and G. WARCOLLIEH. (Compt. rend. 19 10 150 343-344. Compare Abstr. 1909 ii 752).-The sterilisation of white wine under the action of ultra-violet light takes place with greater rapidity than in the case of cider previously studied. Thus aii. 232 ABSTRACTS OF CHEMICAL PAPERS. layer of wine 1.7 mm. in thickness is sterilised in thirty to sixty seconds when exposed at 4 cm. Erom a quartz-mercury lamp whil3t under the same conditions cider requires about fifteen minutes. w. 0. w.Causes Favouring t h e Formation of Acetaldehyde in Wine. AUQUSTE TRILL~T (BUZZ. Xm. chim. 1910 [iv]? 7 71-78).- I n previous papers (Abstr. 1909 ii 429 606 607) the author has shown that wine contains acetaldehyde and has directed atten tion to the important influence of this constituent in the “ageing,” ‘‘ yellowing,” and other changes which take place in stored wine. I n the present paper the conditions under which aldehyde is formed are considered. It is shown that mine agitated with air or merely exposed to air produces acetaldehyde more rapidly than an aqueous solution of alcohol of the same strength. ‘J’he amount formed varies with the temperature and the nature of the containing vessel. Old mines contain more aldehyde than new ones. The amount of aldehyde is increased by the presence of yeast and other micro-organisms and by the addition of oxidising agents and its formation is accelerated by iron (Abstr.1909 ii 429). T. A. H. Germicidal Action of Metals and its Relation to the Production of Peroxide of Hydrogen. ALLAN C. RANKIN (Yroc. Roy. Xoc. 1910 B 82 78-87. Compare Barnes and Shearer Abstr. 1908 ii 344 829).-The capacity of the pure metals zinc aluminium and copper to destroy Bacillus coli suspended in an alkaline tap-water is associated with the coincident presence of oxygen and the solution of minute traces of the metals. The simultaneous liberation of hydrogen peroxide in the case of the first two metals although easily recognised is not sufficient in amount to explain the germicidal action. I n the case of copper no formation of hydrogen peroxide could be detected.Disinfection by the Incomplete Combustion of Straw. AUQUSTE TRILLAT (Compt. rend. 1910 150 339-341).-The fumes produced during the limited combustion of straw in air owe their disinfectant properties to the presence of aldehydes and phenolic compounds. These appear to be produced by catalytic oxidation of alcohols acetic acid acraldehyde etc. in presence of finely-divided carbon. Formaldehyde which has been recjgniued by its action on dimethylaniline is formed to the extent of 0.002 to 2 grams per kilo. of straw. The results of experiments on bacteria are given from which it appears that the germicidal action is wsll marked with pathogenic organisms such as Bacillus coli comrrmnis but that the fumes are less efiicacious in the case of more resisting bacteria.G. S. W. w. 0. w. Action of Aqueous Solutions of Electrolytes on Germination. HENRI MICBEELS (Bull. Acad. roy. Belg. 1909 1076-11 18).-The first of two papers on the influence exerted by electrolytes on theVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 233 germination of seeds. Wheat was used for the experiments. The chief conclusions arrived at are as follows The osmotic pressure of the solutions employed (N/10 to N/lOOO) did not influence the germination ; the greater difference between the effects on germination of N/10 and N/100 solutions than between the effects of N/100 and N/lOOO solutions is due not to greater differences in osmotic pressures of the solutions but to greater differences in ionisation ; the formation of root hairs is favoured by the presence of -NO ions; the experimental evidence does not support the view that the growth of cells is due to the osmotic pressure of cell sap.Wheat grains of about equal size were soaked in water for twenty-four hours and then placed for a certain time on muslin lying in a solution of the electrolyte. A t the end of this time the seedlings were removed and the progress of germination determined by measuring (1) length of first leaf ; (2) length of radicle ; (3) average weight of seedling. The last of these factors for single electrolytes is given in the following table Concentration. NaC1. KC1. KNO,. KHO. Ca(NO,),. N/lO 0’133 0.130 0’146 - 0.126 grain N/100 0.216 0.235 0’291 - 0.152 N/1000 0’211 0.214 0’315 0.226 0’221 N/100 solutions of potassium chloride and potassium nitrate are each more favourable to germination than mixtures of such solutions whilst mixtures of sodium nitrate and potassium nitrate solutions (N/lOO) are more favourable than those of either salt alone.Previous investigations on the antagonistic action of sodium chloride to other salts (compare Coupin Abstr. 1900 ii 236 ; Micheels Abstr. 1907 ii 124; Osterhout t h i s vol. ii 62) as regards their influence on germination are extended and the same action is shown to occur with strontium chloride zinc sulphate and barium chloride. The Changes Taking Place in the Composition of Fruits which Ripen after being Gathered. RICHARD OTTO and W. D. KOOPER (Zeidsch. Nahr. Genussm. 191 0 19 10-1 3)-Results of analyses are given showing the changes which take place in the chemical composition of certain fruits (Prunus spinosa etc.) when the latter are allowed to ripen (nachreifen) after being gathered.It was found that the lzevulose increased from 14.44 to 21.00% whilst the dextrose decreased from 16.04 to 10*75% these results being calculated on the dry substance. The total acidity (as malic acid) decreased from 9.17 to 6.56% and the tannin from 9.45 to 6.82%. The decrease in the amounts of acid and tannin was therefore much larger than the increase in the quantity of total sugar. The tannin appeared to be converted into an oxidised compound. The increase in the ‘‘sweetness’’ of the sloe-fruit during ripening thus seems to be due to a decrease in the amounts of acids and tannin present and to the conversion of dextrose into levulose.LUIGI ERMANNO CAVABZA (Zeitsch. wigs. Mikroskopie 1909 26 59-64).-8 tabulated record of the microchemical reactions shown by catechol T. A. H. w. P. s. Microchemical and Physiological Studies on Tannin. VOL. XCVIII. 11. 17ii. 234 ABSTRACTS OF CHEMICAL PAPERS. caffetannic acid pyrogallol resorcinol .phloroglucinol vanillin quinol and salicylic acid with ferric chloride ammonium metavanadate potassium hydroxide potassium dichromate tellurium carbonate gold chloride and palladium chloride. The tannates of indium lanthanum iridium yttrium palladium and cerium were pi epared. A comparative study of the quantity of tannin contained in the leaves and in the branches of oak chestnut tamarisk fir and other forest trees at different periods of the year showed that the amount frequently varied inversely ; the tannin content of the leaves reaching its maximum in September that of the twigs in July and December.F. M G . RI. Choline Content of Certain Edible Fungi. KARL POLSTORFF (.Festschrift Otto Wullach 1 909 579-583).-Since choline is converted under certain conditions by micro-organisms into neurine (compare Schmidt Abstr. 1892,219) the proportion of choline in three common edible fungi namely Cantharellus cibarius Agaricus campestris and Boletws edulis has been estimated and found to be present to the extent of 0 Ol% 0 015% and 0.0056% respectively. It is evident therefore that cabes of poisoning arising from eating preserved fungi are not to be attributed t o the action of neurine derived from choline.W. H. G. Presence of Gen tiopicrin in Chlora perfoliata. EMILE BOURQUELOT and MARC BRIDEL (Conzpt. rend. 1910 150 114-1 16 ; J. Pharm. Chim. 1910 [vii] 1 109-113).-Gertiopicrin has been isolated from Chlora perjoliata i n which it occurs to the extent of 1.5%. The product was found to be iden5cal with the glucoside Occurrence of Betaines and Choline in Drugs containing Caffeine and Theobromine. KARL POLSTORFF (Festschnyt Otto Wullach 1909 569-578).-Kola beans contain from 0.25 to 0.45% of betaine in addition to caffeine and small quantities of theobromine. Coffee beans contain about 0.2% of trigonelline whilst choline is present in cocoa beans Indian tea and Pasta Guztrana. Presence of an Alkaloid in the Seeds of Lunaria biennis.EUC~NE HAIRS (Bull. Acud. roy. Belg. 1909 1042-104S).-The seeds yield about 1% by weight of an alkaloidal residue contailling a well- defined crystalline alkaloid and possibly a second similar substance. The crystalline alkaloid m. p. 220' (decomp.) isolated and purified in the usual way forms slender colourless needles possesses a bitter taste and dissolves readily in chloroform but is scarcely soluble in ether or watsr. It is distinctly alkaline in reaction dissolves readily in dilute acids and gives precipitates with the usual alkaloidal reagents Unlike the alkaloids sinapine and cheiroline already isolated from plants of the same natural order (Cruciferae) it does not contain sulphur. T. A. H. GIACOMO L. CIAMICIAN and CIRO RAVENNA (Atti R.Accad. Lincei 1909 [v] 18 ii 594-596. Compare Abstr. 1909 ii 604).-Not only living maize occurring in the yellow gentian. w. 0. w. W. H G. Formation of Glucosides by means of Plants.VEGETABLE PHYSIOLOGY AND AORTCULTURE. ii. 235 plants but also the pasty mass obtained by triturating them with water are able in presence of toluene to decompose salicin and to transform saligenin catechol and possibly quinol and mandelonitrile into glucosides which are decomposed by emulsin. T. H. P. Occurrence of Formic Acid in Raspberries. A. ROHRIG (Zeitsch. Nahr. Genussm. 1910 19 1-8).-The author has investigated the question of the occurrence of formic acid in fruits more particularly in raspberries the matter being of some importance seeing that this acid is employed to preserve fruits and fruit- juices and that the quantity thus added has to be estimated.He finds that fresh raspberries contain 0*000176% of formic acid a quantity that would scarcely come into consideration when dealing with the amounts of formic acid used for preservative purposes. The method described by Wegner (Abstr. 1903 ii 700) was employed for estimating the formic acid it having been found to be the most trustworthy. As regards the fact that lactic acid also yields carbon monoxide when heated with sulphuric acid the author shows that the volatile acids obtained from raspberries contain only a trace if Influence of Cultivation on the Alkaloid-content of Certain Solanacie. J. CHEVALIER (Compt. rend. 191 0 150 344-346)- The yield of alkaloids obtained from specially cultivated plants can be considerably increased by the employment of an appropriate manure.I n experiments carried out on a large scale it was found that Belladonna plants yielding 0.3 %-0.3 3% of a1 kaloids under ordinary conditions of cultivation gave 0*48-0*49% when manured with phosphates and 0*40-0.61% when treated with nitrates. Under certain conditions a nitrogenous manure gave 0.75% of alkaloids for the dried leaves. Similar results were obtained in experiments on Occurrence of Anisyl Alcohol and Anisaldehyde in the Fruit of Tahiti Vanilla. HEINRICH WALBAUM (Festschzyt Otto Wallach 1909 649-653).-VanilIa from Tahiti has not the same aroma and is not so valuable as that from Mexico or Rkunion; it is found to contain anisic acid anisaldehyde anisyl alcohol (p-methoxy- benzyl alcohol) and very small quantities of substances which have not been isolated and have an intense odour.The occurrence of p-methoxybenzyl alcohol in nature has not been observed previously. W. H. G . any of this acid. w. P. s. Datura strarnonium and H ~ o s c ~ a r n u s . w. 0. w. Behaviour of Plants towards Lithium Salts. CIRO RAVENNA and M. ZAMORAMI (Atti R. Accad. Lincei 1909 [v] 18 ii 626-630). -It is usually supposed that lithium has a highly toxic action on higher plants. Finding that the ash of tobacco leaves contains sufficient lithium to impart a marked coloration to a flame the authors have investigated the effect of lithium sulphate on various plants. On tobacco and the potato this salt has no toxic action but with oats and to a still greater extent with beans there is a distinct poisoning effect. T H.P. 17-2ii. 236 ABSTRACTS OF CHEMICAL PAPERS. Accumulation of Nitrogen in Soils. A . KRAINSKY (Centr. Bakt. Par. 1910 ii 26. 231-235).-Liquid cultures of Axotobactee* utilise 100-200 units of sugar for 1 of nitrogen fixed. I n sand cultures owing to better aeration the amount of carbon used is 11-30 units to 1 of nitrogen fixed. The economy of organic matter in soils is attributed to the co-operstion of autotrophic organisms which in absence of light produce organic compounds by the decomposition of carbon dioxide with liberation of oxygen. N. H. J. M. Use of Boron as a Catalytic Manure. H. AGULHON (Compt. rend 1910 150 288-291. Compare this vol. ii 241).-The addition of boric acid t o n nutrient sterile medium in which wheat was grown has been found to be distinctly beneficial to the plant^ unless added in amounts greater than 0.01 gram per 1000 grams of medium when germination is prevented and the plants become etiolated.Similar results were obtained in experiments carried out under natural conditions in earth. The incransed yield (calculated on the dried plant) amounted to 50% with maize 21% with rape-seed and 32% in the case of turnips when a dose of 0.5 gram of boric acid per sq. metre was employed. No distinct increase occurred in the case of peas or oats. Estimation of boron in the ash showed that plants grown under these conditions contained only the normal proportion of this element. w. 0. TN. Manuring with Carbon Dioxide.EILHARD A. MITSCHERLICH (Landw. Jahi*b. 1910 39 157-166).-Two series of pot experiments are described in which oats were grown in three different soils (sandy soil loam and peat soil) without manure with complete manure and with manures in which phosphoric acid nitrogen and potassium respectively were wanting. The one series was watered with tap- water the other with water saturated with carbon dioxide. The results showed that no increased yield was obtained by increasing the amount of carbon dioxide in the soil. A small amount of carbon dioxide rapidly increases the solubility of sparingly- soluble plant nutrients and it would seem that under natural conditions the soil almost always contains sufficient carbon dioxide either given off by roots or produced by the oxidation of organic matter.Application of substances for the production of carbon dioxide in the soil is therefore unnecessary. N. H. J. M. Actions of Zinc in Pot Experiments. Contribution to the Ammonia Question. 11. PAUL ERRENBERG (Landw. Versuchs-Stat. 1910 '72 15-142. Compare Abstr. 1908 ii l068).-Tt is shown that the employment of zinc may obscure the results of pot experiments by acting sometimes favourably and sometimes unfavourably. Soils having unfavourable physical properties map be improved by the presence of zinc especially when manured with sodium nitrate. As regards the effect of zinc on manures it is shown that when ammonium salts are employed the zinc may liberate a portion of the ammonia which will act injuriously on the roots of the plants. Under sterilisedANALYTICAL CHEMISTRY. ii. 231 conditions the injury will be much greater owing t o the absence of nitrification. Other possible modes of action are discussed such as the stimulating action of zinc on plants the poisonous effects of zinc dissolved by acid soils etc. and the conclusion is drsmn that the use of zinc should be avoided in vegetation experiments in drainage experiments and for collecting rain-water when the amounts and condition of the nitrogen are to be determined. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9109805229

出版商:RSC    

年代:1910

数据来源: RSC