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VEGETABLE PHYSIOLOGY AND AURICULTURE. i. 1039 Chemistry of Vegetable Physiology and Agriculture. Azotobacter and Nitrogen Fixation in Indian Soils. J. H. WALTON (Nertz. Dept. Agric. I d i a Bact. Ser. 1915 1 97'-112).- The nitrogen-fixing power of Aeotobacter in cultures inoculated with Pusa soil compares favourably with that observed elsewhere. The pure cultures obtained from different' soils were found to vary bot,h in nitrogen-fixing powers and in their morphological and cultural characters. Black pigment was only produced in impure cultures. The results of inoculation experiments made nearly every week for a year showed that fixation of nitrogen is lowest from October to January and highest from June to September the low results being coincident with the drying of the soil and lowering of the temperature and the high results with a fairly high temperature and the rainy season.N. H. J. M. Process of Denitriflcation in Arable Soil. C. LUMIA (Aizn. Chiin. npplic. 1915 4 1-55).-Experinients on the eflect of limited aeration the action of some manurial substances thIe effect of the amount of nitrate present the action of fresh and mature farm- yard manure cereal straw and green leguminous plants and the influence of soil moisture and temperature on denitrification. Under the conditions of the experiments the effect of confined air as compared with no air was t o reduce the period of incuba- tion; in a given time however the amount of nitrate decomposed was less with air than under absolutely anaerobic conditions.i. 1040 ABSTRACTS OF CHEMICAL PAPERS.Basic slag quickened the process of denitrification but afber about a week the amount of nitrogen was somewhat less than in the control experiment. Ammonium sulpliate had no effect whilst calcium cyanamide (0.25-0.157b) retarded denitrification. When the amount of potassium nitrate varied from 0.5 t o 25 per thousand denitrification was more active with the lower than with the higher amounts and the maximum period of incubation was with the highest amount of nitrate. A number of other experiments ar.e described in which the rate of denitrification in presence of various substances was ascertained. I n presencle of citric acid addition of straw was without effect. Addition of citric acid t o the nutritive solution nearly doubled the amount of nitrogen produced in fifteen days as compared with the same solution without citric acid.Fresh and mature dung gave about the same results; straw was more favourable to denitrifica- tion wliilst still higher results were obtained with green bean- stalks. N. H. J. M. The Action of the Ferments of Carbamide in the Destruction of Organic Matter. F. BORDAS arid S. BHuBim (Co?yit. rend. 1915 161 285-287).-A comparison of the rate of destruction of foetal organic matter immersed in culture liquids containing re- spectively the ferments of carbamide intestinal bacilli inicro- organisms of cellulose fermentation and a mixture of all three shows that the dissolving action of the carbamide ferments was much more energetic than that of the others. If however the foetus of a pig was submitted t o the action of these carbamide ferments under perfectly aseptic conditions no decomposition was noticeable even after twenty days.The general experimental results show that given moisture and a suitable temperature the ferments which decompose' carbamide are the most satisfactory in producing a rapid destruction of organic matter. W. G. The Final Hydrogen Ion Concentrations of Cultures of Bacillus coli. W. MANSFIELD CLARK (J. Bid. CTzena. 1915 22 87-98).-Several cultures of the organism were used to ferment dextrose and lactose and the final H-ion concentration was determined electrometrically. I n any given medium the values agree well but with different media they vary the greater thie buffer effect of the medium the higher being the concentration.This suggests the accumulation of other toxic substances each of which produces a small effect. The final concentrations differ so little t h a t the claim of Michaelis and Marcora that we have t o deal with a physiological constant is supported. W. D. H. The Reducing Enzyme of Bacillus coli communis. AJWHU~~ HARDEN and SYLVESTER SOLOMON ZILVA (Riochem. J. 1915 9 379-384).-B. coli when washed does not reduce methylene-blue bu-t does so on the addition of certain reagents which vary widely in chemical nature. The effect of adding broth and glycerol respectively show there are two factors one which activates theVEGETABLE PHYSIOLOGY AND AGRlCULTUKE. i. 1041 other which retards the reduction. The time of reduction decreases with increase of emulsiii and increases with the amount of methylene-blue if the emulsin is the constant.The Inhibition of Indole Formation by B. coli id Culture Media to which Sugars have been Added. ALBERT FISCHER (Biochem Zeitsclz. 1915 70 105 - 118).-The sugars investigated were lactose maltose galactose lzvulose and dextrose and of the,se only the last-named completely inhibited th8e formation of indole. The inhibition was complete after forty-three hours with concentrations between 1.80 and 2'25°/,0. The acid which is formed plays no part in this inhibition so that neither the hydrion con- centration nor the concentration of the undissociated acid plays any part in the action. The dextrose appears t o have the property of inactivating the proteolytic ferment of the bacterium.The differences in the concentration of the peptone used in the culture media had no influence on the indole formation. W. D. H. S. B. 8. The Stimulating Action of Magnesium Salts on Lactic Fermentation. CHARLES RICIIET (Covzpt. 7md. 1915 161 264-265. Compare A. 1893 ii 179).-The optimum amount of magnesium chloride MgCl GH,O in increasing th'e production of lactic acid during fermentation is about 12.5 grams per litre this being also about the optimum amount found for this salt in phagocytosis by Delbet (compare Cotnpt. rend. 1915 161 268). \V. G . The Action of Certain Lactic Acid Bacteria on Proteins and Other Nitrogenous Compounds. A. SmTzm (Biochenz. Zeitsch. 1915 70 299-305).-Experiments were made with B. llelbruckis (warm lactic acid bacillus) and B. czrc~cnze~is fermentuti (cold lactic acid bacillus) which are used in the preparation cf ensilage- t o ascertain their action on proteins and other nitrogenous substances.It was found that both kinds rapidly produced acid but did not break down proteins into amino-acids. When allowed t o grow on media containing other nitrogenous substances the 13. cucumeris fermentati converted only 1.8% of ammonium acetate 17.4% of asparagine and 6.5% of carbamide into proteins under the condi- tions of experiment employed. There is no evidence therefore that the proteins of fodder can be increased by the addition of simpler nitrogenous compounds to the materials employed for ensilage. S. B. S. The Fermentation of Pyruvic Acid by Bacteria. 11. L. KAKCZAG and L. M6czh (Riochewz.Zeitsch. 1915 70 317-319. Compare A. 1913 i 1280).-The experiments confirm the specific biological relationship between pyruvic acid and dextrose dis- covered by Neuberg and Karczag according to which only those bacteria which produce fermentation of the sugar act on the acid. The following bacteria which act on sugar were found t o decom- pose the acid B. t y y k i wturium B. p t t ~ i i m o t ~ i c r p Frietlliinder and B. oedematis mnligwi. S. B. S.i. 1042 ABSTRACTS OF CHEMICAL PAPERS. The Fermentation of Pyruvic Acid by Bacteria. 111. L. KARCZAG and ELSE BREUER (Biochem Zeitsch. 1915 70 320- ). -In contrast to yeast and various saprophytic bacteria of putre- faction which decompose a-keto-acids as well as acids of most varied description with evolution of gas certain pathogenic bacteria which ferment pyruvic acid are almost without action on the higher members of the class of a-keto-acids. The Fermentation of Pyruvic Acid by Bacteria.IV. L. KARCZAG and E. SCIIIFF (Riochenz. Zeitsc7zi. 1915 70 325-332).- Pyruvic acid is decomposed almost quantitatively into gaseous products by B. coli with the formation of a number of inter- mediate products. The gases formed consist of about 90% hydrogen and 19% carbon dioxide. Formic and acetic acids could not be detected as intermediate products and the increase of butyric and propionic acids is attributed t o secondary processes. Formic and glycollic acids are acted on with evolution of hydrogen by a number of bacteria which f erm(ent pyruvic wid including B. coli B. paratyphi B.enteritidis Gaertner B. typhi m.zcriwm and B. pneumoniae. These results justify the assumption of a specific biological relationship between pyruvic acid on the one hand and formic and glycollic acids on the other. The latter may be regarded as intermediary products in the pyruvic acid fermentation. S. B. S. F. ~ ~ U C I I A ~ E K (Bioclienz. Zeitsch. 1915 70 269-293).-Investigations have been carried out to explain the differences in the action of the milk-souring bacillus as described by Effront on the one hand and by Bertrand the author and others on the other. According t'o the former the bacillus exerts a strong proteoclastic activity on caseinogen a reaction which was found to be wanting by other investigators. A com- parison was therefore made of the action of strains of bacilli obtained from Effront (from a commercial medicinal source) and from Metschnikov which was recognieed as a true strain of B.bulgaricus. The investigations revealed many marked differences. The latter strain is much more sensitive is readily killed by acids and will only develop in certain culture media which must contain sugars. The bacillus obtained from Effront was much less sensi- tive and in contrast to the true B. bulgaricus readily digested proteins. Other marked differences were found and reasons are given for supposing that Effront's bacillus was not' a mere bio- logical modification of the true Yoghurt bacillus. Attention is directed to the difficulty of completely sterilising milk t o the ease with which the true B. bulgaricus is destroyed and to the great possibilities of this taking place in commercial preparations and the predominance in these of other strains of bacteria which re- main owing to incomplete sterilisation.The Comparative Rate at which Fluorescent and Non- fluorescent Bacteria are Killed by Exposure to Ultra-violet Light. W. E. BURGE and A. J. NEILL (Amer. J. Physiol. 1915 88 401-405).-Fluorescent bacteria are relatively highly resistant S. B. S. The Yoghurt Bacillus. S. B. S.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1043 to the deleterious action of ultra-violet rays. Like the lens protein they are able to protect themselves from the coagulative effect of these rays by being able to convert rays of short wave-length into longer waves and thus dispose of the energy of the absorbed short waves.This power is absent in non-fluorescent bacteria. W. D. H. The Influence of the Alternating Current on the Fermenta- tion of Living Yeast ERIK HAGGLUND (Biochem. Zeitsch. 1915 70 164-170).-There is an increase in the zymase activity in living yeast when the culture is submitted to the action of an alternating current. This is most marked at. the commencement of the fermentation and may reach as much as 100%. After a tim‘e however the increase of the fermentation produced by the current diminishes and when 20% of the sugar has been fermented the rate is not larger than in the control experiments. The current does not lead to an increase in the hydrion concentration as compared with the increase in the control experiments. It is suggested that acids inhibit the acceleratory action of the altern- ating current.S. B. S. CARL NEUBERG (Biochem. Zeitsch. 1915 71 1-103).-Experiments are quoted to illustrate the stability of the carboxylase in permanent prepara- tions. The carboxylase is not destroyed when made from yeast- juice which has been heated for ten minutes a t 54-55O; such a preparation was without fermentative action on sugar. The carboxylase also act?s on pyruvic acid after the yeast-juice has been submitted t o dialysis. Yeast in which the sugar-f ermenting properties have been exhausted by fermentation retains the carboxylase which still exists in juices which have been kept for prolonged periods and in which putrefaction even has started. The carboxylase action can takel place between loo and 20°.A t such temperatures the action can be demonstrated not only on pyruvic acid but on other a-keto-acids such as oxalacetic acid and methylethylpyruvic acid. The highest temperature of action is 70° f o r the carboxylase of fresh yeast; for maceration juices or permanent preparations the critical temperature is 65-68O. The corresponding temperatures for the zymase action are 70° and 5 1 O . The carboxylase reaction takes place best in the presence of a “ buffer.” That generally employed was dipotassium hydrogen phosphate and boratm are equally effectiv+e. The action of the “buffers” is illustrated by a large number of curves showing the relative fates of reaction for the decomposition of pyruvic acid in the presence and absence of buffers when both fresh yeasts and dried preparations were employed.The carboxylase action is readily destroyed by previous treatment of the yeast with acids or alkalis and subsequent neutralisation. The carboxylase is very insensitive to the action of various organic substances such as the alcohols glycols glycerol acetone pyridine and the aldehydes. Tbe majority of the experimente dealing with this subject were carried out with maceration juice to avoid osmotic effects. Garboxylase and Other Ferments of Yeast.i. 1044 ABSTRACTS OF CHEMICAL PAPERS The influence of buffers on the carboxylase actioii 011 tho higher keto-acids (oxalacetic and a-ketobutyric acids) was investi- gated. I n these cases the buffers (potassium phosphate and arsenate) did not exert the favourable influence that was noticed in the case of pyruvic acid.Carboxylase exists in plasmolysed yeast. The presence of pyruvate (and the exertion of a carboxylase action) does n o t inhibit the invertase action of yeast; rather i t causes generally a slight stiniulation of this action. The general conclusion is drawn that the invertase action is independent of that of the carboxylase. Experiments to determine whether carboxylase and zymase actions taking place simultaneously inhibit one another (that is to determine whether the carboxylase is a part of the zymase corn- plex) did not lead to results which warrant any definite conclusion. By treatment of a yeast with 2% of pyruvic acid a t 3 7 O f o r forty- eight hours it loses both its carboxylase and zymase functions; similar treatment with 2% of dextrose leaves the fermentative func- tions intact.This action of pyruvic acid does not take place in the presence of a “buffer.” Potassium pyruvate stimulates the ferinenLative activity of yeast-juice on various sugars including dextrose laevulose mannose and the disaccharides sucrose and maltose. A similar activating action was observed with the salts of other keto-acids including a-ketobutyric a-ketohexoic hydroxypyruvic oxalacetic a-keto- glutaric phenylglyoxylic phenylpyruvic and hydroxyphenyl- pyruvic acids. These are all derivatives of various amino-acids derived from proteins and it is suggested that there is some natural relationship between the processes of alcoholic fermentation fermentation in the absence of sugars and protein metabolism.Experiments were carried out to determine the minimal amounts of material necessary t o produce a carboxylase action and these were found to; be very small. The autofermentation of sixty-seven maceration juices was determined. I n nearly all these cases when the juices were pre- pared by the method described by the author there was no auto- fermentation. Attention is directed to the great stability of invertase solutions one of which was kept by the author for 800 days without uiider- going in jury. S. B. S. The Fermentation of Dihydroxymaleic Acid. CARL NEUBERG and ERWIN SCHWENK (Bioche.na. Zeitsch. 1915 71 104-1 13).- Under the influence of living yeasts as well as o i dried prepara- tions and macerat8ion juices dihydroxymaleic acid undergoes de- composition a t 16-18O to yield carbon dioxide and glycoll- aldehyde.The rate of decomposition is considerably greater than that of the spontaneous change which takes place under similar conditions in the absence of yeasts. The aldehyde was isolated in the form of the hydrazone which was mixed with some of the osazone of hydroxypyruvic acid The latter can heVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1045 separated froin the former by extraction with a dilute solutioii of sodium carbonate. An improvement of Feiiton's method for the preparation of dihydroxymaleic acid is described. Phytochemical Reductions. X. Reduction of Glycoll- aldehyde to Ethylene Glycol. CARL NEUBERG and ERWIN SCIWENK (Biochem. Zeitsch. 19 15 7 1 11 4 - 11 'I).-The glycol was obtained by adding the aldehyde t o sugar-yeast fermentation mixture in a yield of about 30% of the theoretical quantity.It was isolated and identified by oxidation to glycollaldehyde which was obtained in the form of its p-nitrophenylosazone. The Behaviour of a-Keto-acids towards Micro-organisms. 111. The Putrefaction of dl-Methylethylpyruvic Acid [ a-Keto- P-methylvaleric Acid 1. CARL NEUBERG and BRUNO REWALD (Biochem. Zeitsch. 1915 71 122-l25).-1t has been shown by Neuberg and Peterson (this vol. i 356) that this acid under- goes asymmetric change in the presence of yeasksugar f ermenta- tions yielding as chief product a d-amyl alcohol. It' was therefore of interest to ascertain whether i t also undergoes asymmetric change as the result of putrefaction. The chief product formed by micro-organisms from the acid was found t o be a-methylbutyric acid the d-variety being obtained mixed with about 70% of the racemic acid.A small amount of another acid which is probably a hexoic acid was also obtained. Changes in the Alcohol and Aldehyde Content of Yeast on Keeping and on Autolysis. CARL XEUBERG and ERWIN SCHWENK (Biochem. Zeitsch. 1915 71 126-13S).-Perfectly fresh yeast does not contain acetaldehyde but if kept acetaldehyde is formed which can be separated by washing the yeast with tap- water and centrifuging. If living yeast is kept in air-tight boxes a t 5210° a marked increase in both the acetaldehyde and ethyl alcohol content can be detected. By the autolysis of both fresh and dried yeast in water saturated with carbon dioxide an increase of both acetaldehyde and alcohol could be detected.There was no quantitative relationship between the increased acetald,ehyde or alcohol formed the increase in the amount of the former being always considerably larger than that of the latter. S. B. S. CARL NEUBERG (Biochem. Zeitsch. 1915 71 133-134).-The three species of Pseudosaccharonayces (geymanicus javanicus indicus) which were found by Klocker t o have no fermentative action on sugars were also found t o be without action on pyruvic acid. This is not due t o the action of some inhibitory substance but t o the absence of a carboxylase as the addition of an ordinary yeast to the mixtures containing these organisms and the substrates raspidly produced evolution of gas. The Go-ferment Action of the Salts of a-Keto-acids.CARL NEUBERG and ERWIN SCHWENK (Biochem. Zeitsch. 1915 71 135-143).-1t was found that a mixture of salts of a-keto-acids in S. B. S. S. B. S. S. B. S. The Relationsbip of the Carboxylase to the Zymase. S . B. S.i. 1046 ABSTRACTS OF CHEMICAL PAPERS. presence of dipotassium hydrogen phosphate could activate yeasts or yeast preparations which had been freed from the co-enzyme. No single salt was found to bring about this result. A mixture of potassium or calcium salts of the following acids was employed pyruvic a-ket obut yric a-ketoisovaleric a-ke t ohexoic p henyl- glyoxalic phenylpyruvic p-hydroxyplienylpyruvic hydroxy- pyruvic oxalacetic and a-ketoglutaric acids. These may be con- sidered as derivatives of amino-acids and attention is directed t o the possible connexion indicated by the experiments between the protein and carbohydrate metabolism of yeast.The properties of the co-enzyme of yeast and of the keto-acids indicate furthermore t4hat there is nothing improbable in the assumption that the co-enzyme is a mixture of such acids. The amount of activation produced however by such an artificial co-enzyme is less than that produced by a natural one prepared (by dialysis by heat etc.) from yeast. S. B. S. The Mechanism of the Natural Formation of Succinic Acid. I. Formation by the Fermentation of a-Ketoglutaric Acid. CARL NEUBERG and M. RINGER (Bioclzenz. Zeitsch. 191.5 71 226-236). -By the action of fresh yeast or yeast-juice a-ketoglutaric acid can be converted into succinic acid and a nearly theoretical yield has been obtained.This formation is in marked contrast t o the formation of succinic acid from glutaric acid which only takes place in the presence' of living and fermenting yeast. S. B. S. The Mechanism of the Natural Formation of Succinic Acid. 11. The Formation of Succinic Acid by the Putrefaction of a-Ketoglutaric Acid. CARL NEUBERG and M. RINGER (Biochenz. Zeztsch. 1915 71 237-244).-Succinic acid has been obtained by the putrefaction of a-ketoglutaric acid in yields varying between 14 and 19%. I n addition formic acetic and propionic acids are formed. S. B. 8. Phgtochemical Reductioas. XI. The Conversion of Ethyl Disulphide into Ethyl Mercaptan. CARL NEUBERG and ERWIN SCEIWENK (Biochenz. Zeitsch. 1915 71 118-121).-This reduction takes place according to the equation Et*S*S*Et + H 2EtSH when the inercaptan is added t o a sugar-yeast fermentation mix- ture.The mercaptan was isolated in thIe form of a pure lead salt. S. B. S. Phytachemical Reductions. XII. The Conversion of Citronella1 into Citronellol. PAUL MAYER and Cmr NEUBERG (Biochenz. Zeitsch. 1915 71 174- 1'79).-The above reduction takes place when citronella1 is added t o a yeast-fermentation mix- ture the process being the same as many other reductions of aldehydes t o alcohols as described by Neuberg and his collabor- ators. The citronellol was isolated and identified by the prepara- tion of the silver salt of the phthalyl ester rn. p. 123O after recrystallisation from methyl alcohol. S. B. S.The Reducing Elnzymes of Dried Yeast (Lebedev) and of Rabbit Muscle. An.rizt;rr.I ~ K D E N and ROLAND VICTOR NORRJS (Biocfic112. J. 1 91 5 9 330 - :336).-The powc~ of iwlucing niethylenc- blue is restored t o washed dried yeast by a number of oxidisable substances but not by others. Lactic acid is in the former list and is osidised tci acetaldehyde but the yield is less than the lactic acid lost. Probably pyruvic acid is an intermediate product; this is decomposed by the yeast-carboxylase into acetaldehyde and carbon dioxide. Washed rabbit‘s muscle also loses its power to reduce methylene-blue aiid this is restored by various substances ; but the enzyme concerned is different’ from that in yeast since acetaldehyde r.estores the power to washed muscle but not to washed dried yeast. W. D. H.An Oxalic Acid Producing Penicillium. .JAMES N. CUHRIE a i d (IIIAI~LES T n o ~ (J. Eiol. Chciii. 1915 22 2Si-293). -P. oznlicwn forms oxalic acid as tlie chief product of its metabolism but less mpidly than ;2 spergi/1us nigcr. The biological significance of this is still obscure. W. D. H. Normal and Abnormal Permeability. I\-. J . V . OSTERHOUT i .3 mcr. J. not. 19 1 pj 2 93-94).-Tlw permeability in sea-watei- regarded as the normal permeability of Lmniizarirr whilst less than that in sodium chloride is not the minimum permeability and the resistance in sea-water is not the maximum so. that it is not correct to speak of the normal permeability” of protoplasm to salts unless by “permeability” merely a rate of penetration considerably lower than that found in dead cells is meant.K. IT. J. M. Extreme Alterations of Permeability without Injury. W. J . V. OSTEICIIOUT (Uot. Gux. 1915 59 246-353).--By the employ- rtiellt of quantitative met’hods it is shown that tlie permeability of protoplasm may be increased t o 2076 above normal and decreased t o 3976 below normal without causing injury. In the course of metabolism a great iiuiriber of substaiices ;LI’C prodnced which affect the permeability of protoplasm so t h a t wider normal conditions considerable fluctuations in permeability iuay occur. The whole course of met’abolism may be controlled in this manner since it depends on tlie exchange of substances between the cell and its environment. N. 13. J. M. Decrease of Permeability Due to Certain Bivalent Cations. W. J. V.OSTERIIOUT (Bot. Gm. 1915 59 317-330).-Jt is shown trhat whilst 110 univalent catioii (escept H) is able tlo decrease limmeability all the bivalent cations investigated (Mg C‘a Ba Sr R h Co Fe Ni Zn Cd a.nd Sii) produce marked depressions. N. R. J. ni. Assimilation of Carbon Dioxide by Plants. P. N. RAIKOW (Clrenr. Zeit. 1915 39 657-659). -,I new theory of the :~,~irnilat~ioi~i. 1048 ABSTRACTS OF CBEMICAL PAPERS. of carbon dioxide based chiefly on the properties of c2ilorophyll and the presence in water of the oxonium compound H,O:OH or H,O:H(OH). The initial process is the production from chloro- phyll (Ch) carbon dioxide and water of a compound Ch:O:C:OH which in presence of light at once changes t o Ch:OII*CH:O:O. This under the influence of light parts with oxygen yielding Ch:OH*CH which again forms an oxoniuwi compound with chloro- phyll and the group H-0-C-H.Simultaneously with the liberation of oxygen the reiiiaiuiiig complex may decomposei into chlorophyll and isoformaldehyde. It is however considered more probable that chlorophyll is in part liberated and that the rest polymerises. The production of isoformaldehyde as the first product of assimilation instead of formaldehyde renders the explanation of the formation of carbohydrates more easy than is the case with Baeyer's theory. The production of fructose f o r example is t o he expected as a consequence of the power of isoformaldehyde to form aldopentoses. It also makies possible the formation of pentoses as primary products instead of secondary products from hexoses.According t o the oxonium theory half of the oxygen which is liberated is derived from carbon dioxide niid half from water. I I N. 1%. 3. $1. The Properties of a Chromogen UniverPally Diqtributed in Plants. J. WOLFF and (MLLE.) NADIA ROUCHELMAXN (Compt. rend. 1915 161 399-401).-A continuation of the study of the chromogen already described (this vol. i 632). A large number of families of plants have been examined and the chromogen found t o be present. It turns brown under the influence of laccase or of carbonates of the alkalis or alkaline earths. When it is heated with sulphuric acid and resorcinol and the product diluted with water and made alkaline tbe resulting liquid is strongly fluorescent. The reaction with laccase and hydriodic acid (Zoc. c i t . ) is pre- vented by the presence of quercitannin. The presence of the chromogen prevents the oxidation of guaiacol by laccase. 'The authors do not agree with Palladin's views that' the chromogens exist in the' plants in the form of prochromogens or glucosides (com- pare A. 1910 i 760) since the glucosides populin solanin arbutin amygdalin and salicin do not give the reactions for this chromogen whilst extracts of the plants from which these gluco- sides come do give the reactions. Guaiacol is the only well-defined aromatic compound which approaches the chromogen in its sensitiveness to the combined action of laccase and hydriodic acid. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9150801039

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i. 1049 Organic Chemistry. The Preparation of Ethyl Bromide. FRANK EDWIN WESTON (T. 1915 107 1489-1490).-The author has worked out the best conditions for the preparation of ethyl bromide; these are to avoid any excess of alcohol or a high temperature and to use sodium bromide in place of the more expensive potassium salt. Absolute alcohol (1 mol.) mixed with 5-100/ of its weight of water is treated in the cold with sulphuric acid (I mol. + 5%) and to the cold mixture very coarsely powdered sodium bromide ( I ruol.) is added. A 2-litre flask is sufficient t o take 6 gram-molecular weights of the reagents. The mixture is heated very gently first on a water-bath and then on a sand-bath the rise in temperature being carefully regulated so as just to maintain a steady distillation of ethyl bromide and to prevent frothing.The only loss is of hydrogen bromide a t the commencement of the heating the yield of purified ethyl bromide lo. p. 38*5-39*5' being SO-SO% of the theoretical. Preparation of Acetic Anhydride. BOSNISCIIE ELECTRIC'IT~TS- A.-G. (E'ng. Pat. 23190 Nov. 1914; from J. SOC. Clbem. lnd. 1915 34 982).-Acetic anhydride is formed when ethylidene diacetate is heated sufficiently above its boiling point especially in the presence of a catalyst. Thw when 100 grams of vaporised ethyiidene diacetate b. p. 169q are conducted through a tuba filled with pieces of pumice at 250-300° at the rate of 70 grams per hour for each litre of tube capacity the product contains acetaldehyde (25*30/,) acetic acid (17*10/0) acetic anhydride (49%) and unchanged material (7%).The yield of pure acetic anhydride obtained after a fractionation is 43 grams J. C. W. I>. F. T. Catalytic Hydrogenation of Fatty Acids. H. DUBOVITZ (Cham. Zentr. 1915 i 1301-1302; from Seifinrrieder &it. 1915 42 301-306).-A laboratory method for the hydrogenation of oleic acid is described. The hydrogen employed is prepared from arsenic-free zinc and is purified by passing it successively through a mixture of ferric oxide and sawdust potassium dichromate and sulphuric acid sodium hydroxide solution a tube containing palladium and con- centrated sulphuric acid. The catalyst is obtained by dissolving 50 grams of nickel nitrate in hot water adding pumice-stone washed previously with hydrochloric acid and ignited evaporating the mixture and igniting the residue in a nickel basin until all nitric acid has been expelled; the ignited residue is then packed into a tube 163 cm.in length. The oleic acid dried previously at 110" is contained in a flask connected with one end of the tube the air is exhausted from the whole apparatus and the hydrogen then passed through the oleic acid beated at 270'; the tube containing the catalyst is heated a t 300-350° the nickel oxide having been reduced in a current of bydrogen under reduced pressure a t 100'. The hydrogen bubbling through the oleic acid carries with it a quantity of oleic acid vapour (a low pressure YOL. CVIII. i. 3 si. 1050 ABSTRACTS OF CHEMICAL PAPERS. being maintained in the apparatus) and the gaseous mixture p w e s into the tube containing the catalyst where hydrogenation of the acid ERWIN OTT (Ber.1915 48 1350-1353).-1n extension of the earlier work (Ott A. 1913 i 1302) on the fission of certain p-lactonic esters the behaviour of the methyl ester of the p-lactone of as-dimethylmalic acid has been examined. The p-lactone CO<;g->CH-CO2H was converted through i t s ammonium and silver salts into the methyl ester b. p. '70-72°/0*01 nim. When distilled under a pressure of 18 mm. decomposition occurred to a n appreciable extent with formation of carbon dioxide and methyl PP-dimethylacrylate the most marked effect being produced by dis- tillation in a vacuum over a feebly glowing platinum spiral. No indication was observable of the formation of dimethylketen which would be expected if the decomposition even in part followed a course analogous to t h a t observed with the isomeric series (Zoc. cit.).The relative position of the carbonyl group in the structures tahes place. w. P. M. The ,&Lactone of as-Dimethylmalic Acid. QO-? O-?O and I CMe,*CH*CO,Me C1srze2* CR*CO,Me thus appears t o decide the course of the fission. HANS PRINGSHEIM (Bey. 1915 48 1324-132?).-Sy oxidation of cholic acid in warm potassium hydroxide solution with bromine the author has obtained biliobanic acid C22H3007 needles m. p. near 2S5' a;; + 22.4' in N- sodium hydroxide solution; the molecular weight i n urothane is in accord with the formula given. The new acid could not be made to react with the usual reagents for ketonic substances and in this resembles cilianic acid (Schenck A 1913 i 1042) which is an oxidation product obt'ained from cholic acid with hot alkaline potassium permanganate solution.D. F. T. Preparation of Salts of Formaldehyde-sulph urous Acid with Aluminium Oxide. C H m . FABR VON HEYDEN (u.8. pat. 1149712 ; from J. SOC. Chem. Ind. 19 15 34 962).-Equimolecular proportions of aluminium oxide formaldehyde and sulphurous acid form a soluble salt from which sodium carbonate precipitates aluminium hydroxide and strong acids expel sulphur dioxide. Preparation of Acetaldehyde from Acetylene. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (17.8. Pats. 1151928 and 1151929; from J. Soc. Clzern. Ind. 1915 34 1031).-Acetylene is oxidised by a mercury compound in the presence of a substance capable of impeding the separation of mercury such as a ferric salt (sulphate) or a sexavalent chromium compound (chromic acid).J. C. W. ELI I,ILLY & Co. (U. S. Pat. 1150251; from J. SOC. Chem. Ind. 1915 34 982).-Alkamines of the general formula NXX'*CH,*CY(OH)-[CH,],*CH D. F. T. A New Oxidation Product of Cholic Acid. J. C. W. Alkamines and a Process for Producing Same,ORGANIC CHEMISTRY. i. 1052 in which X and X are alkyl radicles or hydrogen and Y is a univalent group which can be introduced by means of its organornagnesium haloids are prepared by treating chloromethyl o-bromopropyl ketone with magnesium alkyl haloids and condensing the tertiary carbinois so formed with substituted amines. Special claim is made for dimethyl- aminomethylethyl-n-amylcarbinol N Me,* CH,* CE t( OH) [CH,]** CH,.J. C. W. Alkamine and a Process for Producing Same. ELI LILLY & Co. (U.S. Pat. 1150253; from J. SOC. Chem. Ind. 1915 34 982).- Epichlorohydrin is treated with organomagnesium haloids the resulting secondary alcohols are oxidised to ketones these are again treated with Grignard compounds and the tertiary carbinols are then condensed with substituted amines. Por example epichlorobydrin is treated with magnesium isobutyl bromide the chloromethylisoamyl carbinol is oxidised to the ketone this is converted into chloromethyl- ethylisoamylcarbinol by the agency of magnesium ethyl bromide and finally the tertiary alcohol is condensed with dimethylamine to form dimethglaminomethylethylisosmglcarbinol CHMe,*CH,-CH2*CEt( OH)-CH,-NMe2. J. C. W. Alkamine Esters and Process for Producing Same.ELI LILLY & Go. (U.S. Put. 1150253 from J. SOC. Chena. Id. 1915 34 982)- ~imethylaminometliylethylisoamy lcarbinol (preceding abstract) is acyl- ated. The benzoate is specially claimed. The alkamine esters are local anmthetics. J. C. W. E a t e r s of Alkamines and Process for Producing Same. ELI LILLY & Co. (U.S. Pat. 1150580; from J. SOC. Chem. Ind. 1915 34 983).-Esters of the formula. NXX1*CH,*CZ(OY)*[CH,],*CH in which X and X1 are alkyl groups or hydrogen Y is an acid radicle and Z is a univalent group which can be introduced by the Grignard reaction are claimed. Particular mention is made of ihe benzoate of dimethylaminomethyleth~l-n-am ylcarbinol NMe2* CH,* CEt( OSz)*[ CH,],*CH,. J. C. W. Reactions in Liquid Ammonia.11. 1. Action of Acid Amides on the Amides Imides and Nitrides of Certain Heavy Metals. 2. Metallic Salts of Acid Ammono-esters. EDWARD C. FRANKLIN (J. Amer. Chem. Xoc. 1915 37 2279-2295).- Franklin and Stafford (A 1902 i 748) have shown that certain acid amides and potassamide interact in liquid ammonia solutions in a manner analogous t o the interaction of acids and bases in aqueous solutions and Franklin (A. 1905 ii 581) has formulated a system of acids bases and salts on the basis of ammonia as the typical substance. It has now been found that the amide OP silver the imides of lead and copper and the nitride of thallium dissolve in liquid ammonia solutions of acetamide benzenesulphonamide and p-toluenesulphonamide t o form 3 s 2i. 1052 ABSTRACTS OF CREMICAL PAPERS.well-crystallised metallic derivatives of the acid amides. 8z'Zve.r- acetanzide CH3*C0.NHAg is formed by the action of acetamide on silver amide thus it crystallises from cold liqiiid ammonia as the diamnionate CH,*CO*NHAg,3NH3. ~/~~6~~0us-aceta?1~idf CH,*CO*NHTl,obt ained from acetamide and thsllous nitride also furnishes a cliarnmonccte. The follocviog compounds a m also described. Lead -acetumicle ; silver- benxenesu Zphonamide CoH,*S0;NH Ag and its mono- and di-rrmnzonates ; thallous-benxenesu~honzmicle C H,*SO,*NHTI and its mono- and di-ammonates ; thallous-p-toEuenesuZpho.lzamicle C,HET,Me*S02*NHT1 and its ammonate ; cuprous-p-toluenesu~honanaide diacmmonate C,H,Jle*S02-NHCu 2 NH czcpric-p-tolueiiesulp?~o~z~mide (C,H,nle*f302-NH),C'u ; cu~rous-benzenesulhon~~}?zide C!,H,*SO,-NHG'u and I(;S diusnmonate ; cu~~ric-be.nxerLesulhonurrLide tetrammonate (C,L~,*S0,.NH),Cu,4NH3 and the Aeptammonate. It is shown that such compounds as acetanilide and benzylacetamide are t o be regarded as acid ammono-esters which in liquid ammonia solutions react with ammono-baseg just as acid amides do to form ammono-salts.By the action of silver amide on acetanilide in liquid ammonia solution silver-acetunilide CH,*CO-NPhAg is produced ; its ammonate was also prepared. ~'hccllous-acctanilide CH,*CO*NPhTl potassium-acetobenxy Eamide ammonute CH,* CO*N( CH,Ph) K,NH3 and yotmsium-aceto-p-p?iertetidide CH,.C'O*N(U,H,*OEt)I~ are also de- scribed. E. G. AgNH + CH3*CO*NH2 = CH,'CO*NHAg + NH ; Preparation of Carbarnide. BADISCHE ANILIN- 9r; SODA-FABRIK.(Eng. Put. 24117 Dec. 1914; from J. SOC. Chem. Ind. 1915 34 924).-Th~1 mixture of the compounds of carbon dioxide with ammonia is heated in a n autoclave and the product is then transferred to a vacuum shill and heated at about 75'. The unchanged ammonium compounds distil as carbon dioxide and ammonia and reunite in t h e cooled receiver leaving carbamide and water in the still. The water is then-removed by continuing the vacuum distillation after changing the receiver. J. C. 'TN. Ring Formation. I. The Kaufler Formula for Derivatives of Diphenyl. EUSTACE EBEKEZER TURNER (T. 1915,107,1495-1500). -The author has obtained results which although not necessarily disproving Kaufler's formula for diphenyl (A. 1907 i 307 794 ; also Cairn T. 1914 105 1437) are ditlicult t o reconcile with that view of the structure of diphenyl.Although 2 2'-dibromodiphenyl reacts with sodium producing o-diphenylene (Dobbie Fox and Gauge T. 1911 99 963) 4 4'- dibromodiphenyl fails to give any y-diphenylene under similar con- ditions a result which does not seem to accord well with the idea that the 4 $-positions in diphenyl approach more closely than the 2 2'- positions. Also the 4 4'-dinitrodiphenyl derivatives on treatment with sodium amalgam show no tendency to form a closed ring con-ORGANIC CHEMISTRY. i. 1053 taining a n azo- or azoxy-group whereas 2 2’-dinitrodiphenyl does so (Tiiuber A. 1891 570). The evidence produced by Gain (Zoc. cit.) in the ready condensation of a-diketones such ats benzil with benzidine whilst phenaothraquinone fails t o give such a reaction is weakened by the fact that acetylncetone refuses to form a cyclic compound with benzidine.When benzidine is warmed with an excess of acetylacetone a vigorous reaction sets in with formation of diacct?/lisopropylidenebe?zzidine C,,H,(N:Cil\le*CH,*COMe) pale yellow or brown crystals m. p. 198’ ; tetrctbronzide colourless needles. When the condensation product is warmed with sulphnric acid 2 4 2’ 4’- Me/\/\ ,/\/\Me tetramethyl-6 6’ - diquinolpl (annexed t i 1 I I formula) is produced. If the interaction \/\)-\\/’\/ of benzidine and acetylacetone is so Me Me effected in boiling xylene solution that the former reagent is always present in considerable excess only one amino-group is attacked the product being ~ ~ o n o a c e t y E i s o ~ r o p ? / ~ i ~ ~ ~ ~ ~ bcnxidiazs NH,*CGH,*C,H,*N :C Me.CH,*COMe pale yellow crystals m. p. 137’ ; hydrochloride colourless ; pEatini- chloride prepared only with cold solutions yellow crystalline solid ; picrate yellow needles of no definite m. p. This condensation product resembles the diacetylisopropylidene derivative in stability towards alkali and in ready hydrolysis by acids. N N D. F. T. Some Crystallographic Properties of Aniline Nitrate. F R ~ D . WALLERANT (Compt. rend. 1915 161 479-480).-Aniline nitrate orthorhombic a t the ordinary temperature crystallises from water in very flat plates parallel to the faces g‘ the plane of easy cleavage and the plane of the optical axes. The faces m and bl/ are on the contrary very reduced.Crystallised from alcohol the crystals are octahedra showing only the faces bl/ without traces of faces 9’. It is a further exnruple showing that the frequency and development of a face depend essentially on the conditions of crystnllisation. Further aniline nitrate is dimorphous being transformed at 97.6’ into. mono- clinic crystals showinm striations parallel to one plane under the influence of pressure. ?!he transformation is reversible and indirect. A plate having orthorhombic cleavage on heating a t 97.6’ is con- verted into monoclinic fibres not having any orientation which on cooling are transformed assuming the first orientation. This change takes place without superheating or crystalline superfusion with quite a noticeable development of heat W.G. The Constitution of the Salts of Benzylideneanilines A . HAwrzscR ( B e y . 1915 48 1340-1344).-.In reply to Franzen and Benglein (this vol. i 230) who favour the structure C€IRCl*NHR for the hydrochlorides of the benzylideneanilines the author insists on the character of these as true ammonium salts of the formula CHR:NRHCI. and suggests explanations for the abnormal behaviour of the salts and uibromides of these bases. 1). F. T.i. 1059 ABSTRACTS OF CHEMICAL PAYERS. Stereochewistry of Quinquevalent Nitrogen. 111. Auto- racemisation of Optically Active Ammonium Compounds. SHIGERU KOMATSU (Mem. CoZZ. Sci. Iiyoto Imp. Urziv. 1915 1 231-248. Compare At. 1913 i 39).-With a view of discovering the cause and the mechanism of autoracemisation in optically active ammonium compounds the author has determined polarimetrically the velocity of inversion of cert.ain iodides.I n chloroform which had been kept in the dark in a cold place for a year the results were the following :-( 1) y-d-phenylbenzylmethylallylammonium iodide a t 25' bad k= 0.0017 (2) a t 3.09 k = 0.0038 ; (3) y-6-phenylbenzylmethylallyl- ammonium iodide at 25" had k = 0*0014 ; (4) a-d-phenylbenzylmethyl- allylammonium iodide a t 25' had k = 0.0019 and ( 5 ) at 30° k = 0.0023 ; 2 I-phenyibenzylmethyl- m-propylammonium iodide a t 2 P had k=0*0016. I n chloroform which had been treated with water with sulphuric acid and distilled (6) a-d-phenylbenzylmethylallylammonium iodide at 25' had k=0*0014 whilet in this same chloroform after it had been made N / 2 0 0 0 with hydrogen chloride (7) at 25' L-0.0012. The inversion of a-d-phenylbenzy lmethylallylnmmonium iodide was also examined (9) in allyl alcohol at 25'; and that of Z-phenylbenzyl- methyl-m-propylammonium iodide a t 25' in (10) acetonitrile and in alcohol containing 20 per cent. of the following substances (11) amylene (12) a-crotonic acid (13) butyric acid (14) carbon tetrachloride (15) acetylene dichloride (16) chlorobenzene.The fact that the inversion constants of a- and y-d-phenylbenzylmethylallyl- ammonium iodide in chloroform are the same whilst their specific rotations are different is considered to support Halban's decomposition theory rather than Pope's dissociation theory. The ultraviolet absorption spectra OF (1) a freshly-prepared chloroform solution of d-phen y 1 ben zylm e thy I a1 1 y lam moniu m iodide [ 21 the same solution after keeping for a day and (3) a n equivalent solution of methylallyl- aniline were photographed.The results are regarded as substantiating the above view that when a- and y-d-phenylbenzylmethylallylammonium iodides are dissolved in chloroform they decompose into methylallyl- aniline and benzyl iodide the decomposition products then recombining t o form y-r-phenylbc nzylmethylallylammonium iodide. Some other decomposition experiments are also held to support this conclusion. Since the value OF the constant in experiments (l) (a) (4),and (?),above is practically the same i t is considered that the primary cause of the reaction is to be awribed to the solvent itself and not to any catalytic action of halogen acid derived from the chloroform or from other impurities present in it The effect of different solvents on the velocity of the change is indicated by the time (in hours) required for balf change chloroform 3 ; arnylene 3 ; chlorobenzene 48 ; carbon tetrachloride 49 ; acetylene dichloride 52 ; acetonitrile 53 ; crotonic acid 58 ; allyl alcohol 119.From this it is concluded that the decomposition of the optically active substance is caused by the residual affinity of the solvents due to the presence of a multivalent element or unsaturated linking. Cooling curves are also given for d- and r-a-phenylbenzylrriethylallylammonium iodide. T. s. PA.ORGANIC CHEMISTRY i. 1055 Metaquinonoids. EUG. BAMBERGER (Ber. 1915 48 1354-1357). -In a n endeavour t o decide the structure of the o-diazoxides produced by diazotising o-aminophenols the author has attempted to prepare similar compounds from m-aminophenols.The entire lack of success is possibly connected with the impossibility of producing a hexacyclic metaquinonoid and so may be regarded as evidence in favour of the structure O:C,H,:N for the o-diazoxider. 2 4 6-Tribromo-m-nitrophenol when reduced with tin and hydro- chloric acid yields only nz-aminophenol no tribromo-m-aminophenol being obtained although a little of the latter is produced if reduction is effected with iron and acetic acid 2 4 6-Tribromo-m-aminophenol i s best prepared by bromination of m-aminophenol in acetic acid the m. p. being 119' instead of t h a t accepted hitherto ; diazotisation under various conditions gave no indication of the formation of a diazoxide.Treatment of 4 ; 6-dinitro-maminophenol in alcoholic suspension with nitrous gases gave rise t o the formation of 2 4-dinit~oresorciszoZ monoethyl ethcv OH*C,H,(NO,),*OEt yellow prisms m. p. 122 -1 22.5' t h e constitution of which was determined by conversion into 2 ; 4-dinitroresorcinol by heating with hydrochloric *acid a t 180 -200°. D. .F. T. Some Homologues of Menthol. EYVIND B~DTKER (Bull. Soc. chirn. 1915 [iv] 17 360-367).-The author has prepared a number of homologues of menthol by reducing the corresponding derivat'ives of menthone by means of sodium in ether saturated with water. The following are described Methylmenthol C,,€I,,*OH a viscid liquid b. p. 129-130'/32 mm.; D:* 0.9124 ; ( Y L ~ 1,4692 ; [a] - 3'26' giving with acetic anhydride a n acetate b. p. 125'117 mm. ; Di8 0.9313 ; nz 1.4578 ; [a] - 18T'. Ethylmenthol CI2H2,*OH b. p. 124'/13 mm. ; D:' 0.9246 ; rhz 1.4769 ; [a] + 4"55' giving an acetate h. p. 131-132'/14 mu]. ; Di8 0.9366 ; Propylnzenthol C,,HI,*OH b. p. 141-145'/27 mm. ; Dfi' 0.9075 ; 'YL; 1.4675 ; [u]g +29'7' giving an cccetate b. p. 152O/30 mm. ; Ui8 0.9515 ; nl,Y 1.4741 ; [u] +8'58'. isoArnyZmenthoZ C,,H,,*OH a clear liquid b. p. 150'/83 mm. ; D 0.8985 ; Benzylidenementhone C8Hl,< C:CHPh I when reduced in the same co way gave benzylmenthol C17H,,-OH b. p. 203-205'/24 mm. ; Di0 0.9819; n$ 1.5267; [a] - 43'19' (cornpare Sernmler A. 1904 i 260). Benzylmenthoiie b. p. 17'i0/S mm.; Di8 0.9979 ; rt; 1.5332 ; [a] +28'4' was prepared from benzyl chloride and menthone by Haller's method (compare A.1904 i SOO) a small ywtotity of the dibenzyl derivative m. p. 52' being obtained at tho Farno time. All the above rotations mere obtained in benzene solution. 71 1.4636; [a] - 6'6'. 1.4661 ; [a] + 33'44'. w. G.i. 1056 ABSTNACTS OF CHEMICAL PAPERS. Preparation of Derivatives of 8-Amino-@-naphthol. BADISCHE ANILIN- & SODA-FABRIR (Eng. Pat. SO58 of 1915 ; from J. SOC. Chen2. Ind. 19 1 5 3 4 828).-Halogenated 8-benzoylamino-/3-napbthols containing halogcii in the benzene nucleus only are prepared by the action of a halogenated benzoyl chloride in the presence or absence of substances like sodium acetate which can fix hydrogen chloride. 8-0-C hloro ben zoylamino-P- naph tho1 is mentioned.J. c. w. Action of Magnesium Phenyl Bromide on Tellurium Di- haloids. KARL LEDERER (BeT. 1915 48 1345-1350).-Tellurium dibromide reacts vigorously with a n ethereal solution of magnesium phenyl bromide ; by distillation of the product diphenyl and diphenyl telluride can be obtained whilst the residue contains tellurium and diphenyl ditelluride. Tellurium chloride and iodide gave similar results the yield reaching 70% of diphenyl telluride in tho interaction of tellurium iodide and magnesium phenyl iodide. Diphen$ ditellurid'e the first organic ditelluride t o be isolated forms lon,p red fibres m. p. 53-54' When treated in alcoholic solution with sodium i t decomposes partly into tellurium and diphenyl telluride but also gives rise t o some phe.iayl telluromsrcaptctn which was separated as thenzevcuTyc1doride derivative C,H,*Te*HgCI a yellow amorphous solid decornp.near 90". Oxidation with nitric acid converted the ditelluride in to the mixed nnhydride of nitric and phenyltellurinic acids NO;TePhO needles rn. p. 232-233' from which hg careful successive treatment with sodium hydroxide and hydrochloric acid phenyZteZZurinic acid TePhO*OH mas obtained as a white powder m. p. 210-211"; the seleniixm analogues of these compounds have already been described (Krafft and Lyons A 1896 i 304). A solution of diphenyl telluride in benzyl bromide gradually deposits a crystalline mass of d~pphan?/lhenzylteEluroniurn bi*omidc TeP h,Ur CH,Ph m. p. 90-9!" which is converted by silver hydroxide and water into the corresponding hydyozide a yellow oil very soluble i n water ; this gives a sparingly soluble picrcite.D. F. T. Reaction between A l k a l i s and Metol and Quinol in Photo- graphic Developers. FRANCIS C. FRARY and ADOLPH H. NIETZ (J. Amev. Chem. Xoc. 1915 37 2273-2279).-ITn the work on the single potential of developers (this vol. ii 815) it was observed that the addition of quinol caused a change of 30 millivolts in the hydrogen potential of a solution containing sodium carbonate and sulphite. As this indicated a combination between the alkali and the reducing agent it was considered t h a t the hydrogen potentials might be applied to a study of the reactions which take place when the developer is mixed Determinations of the hydrogen potentials of sodium hydroxide solutions and the hydrolysis constant of sodium carbonate (this vol.ii 816) have supplied the data necessary for the purpose. The inveat'jgations now described have indicated that in the reaction between sodium hydroxide and quinol either a mono- or a di-quinoxide may be formed according to the conditions I n the case of sodiumORGANIC CHEMISTRY. i. 1057 carbonate and quinol in the concentrations usually used for developers most of the quinol wonld be converted into the monoquinoxide if sodium sulphite was not present. When sulphite and carbonate are both present the quinol seems t o be shared between them Complete Oxidation of a quinol developer can be effected without changing its alkalinity. I n lhe absence of a. sulphite metol (1 mol.) seems able to combine with 3 mols.of sodiutn hydroxide. E. G. Dialkylcyclohexadienes and their Carboxylic Acids. K. YON AUWERS and R. HINTERSEKER (Rer. 1915 48 1357-1376).-A re-examination of the earlier results (von Auwers and Hessenland A . 1908 i 550 551) as to the structure of the dialkylcyclohexadiene and the diolefinic cyclohexadienecarboxylic acid obtainable from 1 4-dimethyl-4-dichlorornethyl-A6-cycZohexen-5-one (dichloropulenen- one) by warming with alcoholic potassium hydroxide. The previous decisions as to structure are confirmed. 1 4-Dimethyl-Al ' 3-cycZohexadiene-3-carboxylic acid (A1 '3-dibydro-p- xylic acid) obtained by the action of alcoholic potassium hydroxide on dichloropulenenone has m. p. 41-42O b. p. 139-l4O0j14mm. I):' 1.043 rn$ 1.4927. When reduced in boiling amyl-alcoholic solution by sodium this acid yielded 1 4 - d i m e t ~ ~ ~ Z - A ~ - - c ~ c ~ o ~ ~ e ~ e ~ ~ - 3 - c c acid prisms or rhombohedra m.p. 71" b. p. 136-138"/14-16 mrn. 244'/ord. pressure (methyl ester a colourless oil b. p. 77.5-79*5°/12 mm. 300°/ord. pressure Df" 0.968 n$' 1 *4577) the constitution of which is demonstrated by its oxidation with cold alkaline perrnmganate to 8-acet y Z-p - me tlb ylvaleric acid C,H,,O (p-niti*ophenplh y draxone orange coloured crystals m. p. 294-195"). This result together with the spectrochemical and other evidence suggests t h a t the cyclohexadiene CMGCH acid has the structure CH,<cI-I ,CMe>C*C02H in accordance with i t s description above. This acid can be converted into 1 4-dimethyl- ~l~:~-cycZohexadiene by heating at 130-125° in a current of hydrogen or by treating its dibromide with sodium the product having b.p. 135-136' Di0 0.833 nf:' 1.4804. Confirmatory evidence of the structure of this hydrocarbon is supplied by successive bromination and treatment with diethylaniline when p-xylene is produced and by oxidation with ozone t o acetonylacetone. Under similar treatment with alcoholic potassium hydroxide l-metbyl-l-dichloromethyl-4-ethyl-A3-c~cZo~~exen-2-one was converted into l-methyl-4-ethyl-A1~3-cyclohexadiene-3-carboxylic acid b. p. 152*5-153°/13 mm. D:' 1.024 n 1,4965 ; l-rnethyl-4-isopropyl- A~:3-cycZohexadiene-3-carboxylic acid m. p. S3-N0 b. p. 170"/12 mm. (sodium salt pearly leaflets ; silver salt' colourless ; ethyl ester b. p.128O/11 mm. I):' 0.975 ~i 1.4987) was obtained in like manner. Final proof of the structure of the latter acid is still lacking. The substance described as l-methyl-4-isopropyl-A1 3-cgcZohexadiene (von Auwers A. 1909 i 596) on oxidation with ozone gives rise to aa-dimethylacetonylacetone so that if not identical with a-terpinene it 2 must at least consist largely of this hydrocarbon. n. F. r r . 3 s*i. 1058 ABSTRACTS OF CHEMICAL PAPERS. Unsaturated Hydroaromatic AcidB. K. VON AUWXRS aid W. TREPPlCrANN (Bey. 1915 48 1377-1388).-Dehydration of ethyl 1 3-dimetbyl-a"-cycZohexen-5-01-5-acetic acid gives rise to ethyl 1 3-dimethyl-A3-cycZohexenylidene-5-acetate (von Auwers and Peters A. 1910 i 841) ; the corresponding free acid when reduced in sodium carbonate solution by sodium amalgam is converted into 1 3-dimethyl-A4-cyclohexenyl-5-acetic acid an oily substance b.p. 159-160'/20 mm. DS' 0.993 mnf," 1.4767 ; the et?tyZ ester an oil b. p. 114-115*4°/13*5 mm. D:' 0.938 n 1.4577 gives a n oily &bromide; the anaids leaflets m p. 152-154O was obtained by the action of aqueous ammonia-on the chloride the latter being prepared by treating the acid with thionyl chloride. The above decision as to the structure of the new acid was confirmed by oxidation when an oily ketomonocarboxylic acid was obtained which gave a silvei- salt approximating to the composition C,H1,O,Ag. An endeavour was made to prepare the above acid in an independent manner by treating 1 3-dimethylcyclohexan-5-one with zinc and ethyl bromoacetate in the presence of benzene the product being etJ& 1 3-dimeth&yclohexan- 5-01- 5-acetate CH2<CHMe.cH:>C( OH)*CH,* CO,Et a viscous oil of pleasant aromatic odour b. p. 137*5-139°/'18 mm. DiO 0.985 ~~$1.4543 which when heated with potassium hydrogen sulphate at 160' gave ethyl 1 3-dimethyl-A4-cycTohexenyl-5-acetate as a colourless oil b. p. 1 1 6 O f 1 4 mm. D;O 0-936 n 1.4580; this on hydrolysis gave the corresponding acid as a crystalline mass leaflets m. p. 56-57' b. p. 150-151°/15 mm. DY 0.993 ng 1.4766 both in the supercooled condition. I n spite of the agreement in the physical data it was not found possible to cause the oily acid to crystallise by inoculating with a little of this solid product but the identity of the two products appears t o be demonstrated conclusively by the identity of the amide prepared from the two; the refusal of the former acid to crystallise is probably to be attributed to slight impurity. I n order to exclude the possibility of one of the above products being one of the likely ieomerides 1 3-dirnethy2cyclohexan-5-ol-5-acetic acid prisms m.p. 97-98' was obtained by hydrolysis of its ethyl ester described above and boiled with acetic anhydride by which means 1 3 -dirneth~lc~clol~ex~Z~dene-5 -acetic acid CHMe*C H prisms m. p. 1264 was prepared ; rnk%J ester a pleasant aromatic oil b. p. 113-114°/14 mm. U&O 0.953 n 1.470; ethyl ester b. p. 126-128'/15 mm. UiO 0.941 n 1.4723. If 1 3-dimethyl-A'-cyclohexen-3-one is treated with zinc and ethyl a-bromopropionate condensation occurs with formation of an ester theORGANIC CHEMISTRY.i. 1059 dehydration of which with potassium hydrogen sulphnto yielded ethyl a- 1 3 -dimet h yl- A"-cyclohexen y 1 idene- 5 -p?*opion at e CH,<C Me==CH>C c1 iie*CO,Et an oil b. p. 136-138°/12 mm. D:' 0.969 n2,0 1.5069 whilst in a similar manner from zinc ethyl a-bromoisobutyrate and dimethylcyclo- hexenone there mas obtained ethyl a-1 3-dinzethyl-A" "-cyclohexadienyZ- >C*CMe2*C0,Et an oil b. p. 5-isobutyrccte CH2<&&-CH C'k -CH 141-14Z0/20 mm. DY 0.963 nz 1.4865. The corresponding free acid obtained by saponification formed hexagonal tablets m. p. 114-115"; si2ver salt sparingly soluble in water very soluble in ether. I). F. T. CHMe*CH Hydroaromatic Cyanohydrine and a-Hydroxycarboxylic Acids.K. ON AUWERS and F. KROLLPFEIFFER (Bey-. 1915 48 1389-1397).-The preparation of unsaturated cyclic hydrocarbons by elimination of carbon dioxide from the corresponding carboxylic acids is rendered of little practical value from the difficulties encountered in the production of these unsaturated carboxylic acids. The cyanohydrin synthesis can be effected with such compounds as 1 3-dimethyl- cycbohexan-&one but the hydrolysis of the resulting hydroxy-nitrile in certain cases for example that,uderived from 1 -methylcycZohexan-2-one instead of yielding the corresponding carboxylic acid merely eliminates hydrogen cyanide regenerating the ketone and its condensation products. Another difficulty encountered in this method of preparing unsaturated cyclic hydrocarbons is in the unexpected resistance of the hydroxy-acids and their esters towards dehydrating agents even under widely varied conditions; in such cases as permitted dehydration to proceed the action was often so slow as to cause the resulting unsaturated acid or ester to undergo partial polymerjsatioa.The most satisfactory dehydrating agent was sulphuric acid which could however only be applied to the esters because under its influence the free acids decomposed into ketone and formic acid. Still less encouraging was an attempt to convert the final cyanohydrins into Unsaturated nitriles to be subsequently hydrolysed as the final yields of acids were very small. From the cyanohydrin of cyclohexanone cyclohexan-l-ol-l-carboxglic acid and its ethyl ebter were obtained; the latter forms nredles or prisms M.p. 20-22O b. p. 99-101"/15 mm. I3;O 1.044 taz 1.4554 (compare Tarbouriech A 1'309 i 796); the corresponding amide was also obtained m. p. 128-129". The cyanohydrin derived from l-methylcyclohexan-2-one was B pale yellow oil which decomposed when distilled in a vacuum and resisted all attempts at hydrolysis. 1 3-Dimethylcyclohexan-5-one yielded a cycmohydrin the hydrolysis of which produced 1 3-dimethyZcyclohexan-5-ol-5-ca~boxylic acid leaflets m. p. 124-125'. cycloPentan-1 -01-l-carboxylic acid when heated with phosphoric oxide in benzene solution gave cyclapentene-l-carboxplic acid the yield being only 10% of the theoretical. Ethyl cyclope?Lticn-1-02-l-cctrboxylccte is A. 3 s* 2i. 1060 ABSTRACTS OF CHEMICAL PAPERS.colourless pleasant smelling liquid b. p 99'/20 mm 1.057 n:' 1.4498 ; the corresponding methyl ester b. p. 85'/16 mm. gave 11;' 1.102 93% 1.4554. D. F. T. Preparation of Magnesium Acetylsalicylate [o- Acetoxy- benzoate]. CHENISCHE FABRIK GEDEON RICHTER (E~ig. Pat. 10946 May 19 14 ; from J. Xoc. Chenz. Ind. 19 15,34 982).-Magnesium oxide (40 grams) or hydroxide or carbonate is stirred with o-acetoxybenzoic acid (360 grams) and water (180 grams) and after some time the mass is digested with methyl or ethyl alcohol. Magnesium o- ncetoxybenzoate is then precipitated from the filtrate by means of ether as a white micrccrystalline powder which is almost tasteless and readily soluble in water. J. C. W. The Action of Nitrosylsulphuric Acid on p - Hydroxybenzoic Acid.J. BIEHRINGER and W. BORSUM (Uer. 1915,48,1314-1319).- The authors have submitted p-hydroxybenzoic acid to the action of nitrosylsulphuric (nitrosulphonic) acid and have in this way extended the observations of Deninger (A. 1891 307) on this reaction. A solution of sodium nitrite in sulphuric acid was added to a solution of p-bydroxybenzoic acid in the same liquid and the mixture was kept well stirred for 7 hours at 35-40° after which it was left overnight. The chief product was 3-sulpho-4-hydroxybenzoic acid accompanied by smaller quantities of 3-nitro-4-hydroxybenzoic acid and 2 ; 4-dinitro- phenol and possibly of 3 5-dinitro-phydroxybenzoic acid. Further nitration of the 3-sulpho-4-hydroxgbenzoic acid by treating a solution of the sodium salt in a mixture of acetic and sulphuric acids with fuming nitric acid gave 3 5-dinitro-4-hydroxybenzoic acid and dinitrophenol.D. F. T. Tyrosine. ARTHUR GEAI~E and MAXIMILIAN NIERENSTEIN (Bioclmz. J. 1915 9 309-312).-Tyrosine is not affected by diazomethane which indicates that not only are the amino-acid groups arranged in a betaine ring (compare A. 1914 i 1057) but the hydroxyl group is rendered dormant by the nitrogen atom Glycyl-l-tyrosine in which the betaine ring is opened yields the metlql ester OH*C,H 4*CH2* CH(CO,&le)~NH*CO*CH:,.NH m. p. 123-124' but here again the phenolic group is protected from methylation. In 3 4-dihydroxyphenylalanine the meta-hydroxyl group should be open to methylation. The compound does react with diazomethane but more material is required before a definite product can be described.J. C. W. Nitrated Proteins. 11. Synthesis of 3 5-Dinitrotyrosine. TREAT B. JOHESON and EDWARD F. KOHMANN (J. Awes. Chem. Soc. 1915 37 2164-2170).-1n connexion with the authors' work on nitrated proteins (this vol. i 899) an attempt was made to prepare dinitrotgrosine by Stiideler's method (Anncdeyt 1860 116 82) but without success and i t is considered that the product obtained by Stideler probably consisted of impure nitrotyrosine. DinitrotyrosineORGANIC CHEMISTRY. i. 1061 can however be easily obtained by nitrating tyrosine with a mixture of nitric and sulphuric acids and it is shown that the compound thus prepared has the nitro-groups in the 3- and 5-positions. OH C,H,( N02),*C H,* C H( NH,) CO,H H20 forms golden yellow plates ; it does not lose its water of crystallisation at l l O o but when heated a t 140-150' the water is expelled and the substance assumes a brick-red colour.It does not give a red coloration with Millon's reagent but yields a yellow insoluble mercury salt which begins to decompose a t 170' and effervesces at 185'. The hydrochloride forms yellow plates and decomposes at 220-230' ; the ammonium salt crystallises in red prisms and decomposes above 230'. When 3 5-dinitrotyrosine is warmed with ammonium thiocyanate 3 5 -Dirtit rot yrosi ne and acetic anhydride it is converted into 4-(3 5-dinitl.o-4-~~y;ll.ozl/- benx?lZ)-Z-tliio?~ydccntoin OH*C,H2(N0,),*CH2*CH<N H bx m. p. CO-NH 225-230' (decomp.) which crystallises i n short prisms and when heated with chloroacetic acid is desulphurised with formation of which forms golden-yellow blocks and decomposes a t 235'.On re- ducing ttce latter compound with tin and hydrochloric acid diazotising the resulting diaminohydantoin and digesting the product with cuprous chloride solution 4-(3 5-dichloro-4-hydroxybenxyl)-hydantoin (Wheeler Hoffman and Johnson A. 1911 i 923) is produced. E. G. Studies in the Phenylsuccinic Acid Series. IT. Some Derivatives of the Optically Active Diphenylsuccinic Acids. HENRY WREN and CHARLES JAMES STILL (T. 1915 107 1449-1459 ; compare Zoc. cit. 444)-An account of some of the derivatives of the d- and Z-diphenylsuccinic acids described in the earlier communication. Btc~izcm d-diphenylsuccinate forms well defined prisms with 5H,O and resembles the corresponding salt of the racemic acid in its sparing solubility in water. Methyl r-diphsn~~lsuccinctte forms rhombic platelets m.p. 173*5-174° ; mdthpl meso-diphenylsuccinccte forms needles m. p. 21 S.5-2 19.5' ; methyl d-diphenpleuccinccte forms platelets m. p. 165-166' [ U ] E ' ~ + 341.9' in acetone [UJE'~ + 376.8' in chloroform whilst its lzevo-isomeride possessed the same m. p. and has -342.1' in acetone [a]g'' -365.3' in ethyl acetate and [a]l,6'3 - 43 1 *So in carbon tetrachloride. Ethyl d-di~lzenylsuccinale rectangular plates m. p. 104-105' gives [u] + 'L79.4' in acetone solutioa +281*3O in methyl alcohol [a]g +294-9' in ethyl acetate and + 305.5' in chloroform whilst the l-isomeride gives [a]:" - 2'79T' and [a]:;' - 2S3.6O in acetone and ethyl alcohol respectively.I n esterificntion of the Z-acid by the Fischer-Speier method ethyll hydrogen l-diphenylsuccinate a bulky powder m. p. 113-5-1 14*5" - 328.7' in acetone [a]:'* - 315.6" in ethyl alcohol [a] - 3864' in carbon tetrachloride was obtained as a by-product being first isolated as the aodium salt ; ethyl sodium d-diphenylsuecinate farms pearly leaflets with 4'L-f20.i. 1062 ABSTHACTS OF CHEMICAL PAPEltS. d-Diphenylsuccinic acid is not appreciably racemised a t 100' by aqueous potassium hydroxide but considerable racemisation occurs during the hydrolysis of the optically active esters with aqueous- alcoholic potassium bydroxide the first inactive product being the meso-acid. Treatment with acetyl chloride or thionyl chloride corrverts the active diphenylsuccinic acids into the corresponding an?bydrides oblique prisms m.p. 105*5-106.5° ; the following figures were obtained with the I-anhydride - 287.7" in benzene [a]:.' - 285.4' in toluene [~,];4" - 263-1O in ethyl acetate [a];'' - 247.6' in carbon tetrachloride solution whilst the d-anhydride gave [a]:,"5 + 286.2" in benzene and [a]:'' + 246.0" in chloroform. These anhydrides react with hot water giving active di phenplsuccinic acids of the same sign but containing about 8% of an inactive acid consisting a t least partly of the meso-acid whilst with alcohol the product is in each case an ethyl hydrogen ester containing approximately 80% of the active form. D. F. T. The Chromoisomerism of Salts of the Phenolaldehydes. A. HANTZSCH (Bey. 1915 48 1332-1338).-PolemicaI in reply to the views of Pauly (this vol.i 689) which do not accord with those of the author (this vol. i 549). D. F. T. The Action of Diazomethane on Some Aromatic Acyl Chlorides. DOUGLAS ARTHUR CLIBBENS and MAXIMILIAN NIERENSTEIN (T 1915 107 1491-1494).-An extension t o acpl chlorides of the observations of Schlotterbeck (A. 1907 i 185 478 ; 1909 i 553) and Meyer (A. 1907 i 323) that aldehydes react with diazomethane giving methyl ketones. The same reigent with acyl chlorides yields chloro- methyl ketones the reaction being effected in ethereal solution. w-Chloroacetophenone and w-bromoacetophenone were obtained in this manner from the corresponding acyl haloids. Phenylacetyl chloride gave rise to bermyl chlorornethyl ketone CH,Ph*CO.CH,CI stellar aggregates of needles m.p. 72-73'. Phenylpropionyl chloride yielded P-phenylethyl cltloronzethy? ketone CH,Ph*CH,*CO*C€€,Cl needles m. p. 84- 85O. Anisyl chloride gave misyl chlorornethyl ketone OMe*C,H,*CO*CIT,Cl. I n the case of two o-acetoxyacyl chlorides which were examined the primary product could not be isolated on account of the elimination of wetyl chloride with formation of a coumaranone. Thus o-acetoxy- benzoyl chloride yielded coumaranone itself c6H,<O->CH whilst 2 -acetoxy - 4-methoxyben xoy I chloride OMe C6H3( 0 Ac)* COCI prismatic needles m. p. 81- S2O gave 3-methoxycoumaranone c H2 0 Me C H 3<gi> CH . The necessary 2-acetoxy 4-methoxybenzoyl chloride was obtained from resorcinol by treating in sodium hydrogen carbonate solution with carbon dioxide the process being a modification of that of Bistrycki and Kosbnecki (A 1885 1037) ; the resulting P-resorcylic acid was then converted into 2-acetoxy-4-methoxybenzoic acid (m. p.145-147 O ; Nagai A 1892 58 gives 140') by way of p-methoxgsalicylic acidORGANIC CHEMISTHY. i. 1063 I n experiments on t h e action of diazomethane on triphenylcarbinol benzhydrol benzyl alcohol and benzoylcarbinol these substances were recovered unaltered ; benzilic acid and mandelic acid were converted into their respective methyl esters. D. F. T. The Behaviour of Nitriles towards Organometallic Deriv- atives of Magnesium. E U s T A c E EBENEZER TURNER (r. 1915 107 1459-1464).-8 marked case of steric hindraoca appears to exist in the behaviour of 2 6-diethoxybenzoni trile towards organomagnesiurn haloids variation of the reagent the temperature and the solvent all failing to effect any reaction whilst benzonitrile reacts readily with this class of compounds. p-Tolyl benzyl ketone can be obtained only in very poor yield by the action of magnesium p-tolyl iodide on phenyiacetonitrile the acidic character of the methylene group of the latter compound possibly interfering with the normal course of the reaction.By using msgnesium benzyl chloride and p-toluonitrile in ethereal solution p-tolyl benzyl ketone can be obtained in good yield but in xylene solution the reaction takes a n abnormal course giving dibenzyl and p-tolyl a@-diphenykthyl ketone C,H,Rle*CO*CHPh*CH,Ph colourless needles m. p. go" the identity of which was confirmed by synthesis from p-tolyl benzyl ketone benzyl chloride and sodium ethoxide in alcoholic solution.p-Tolyl up-diphenylethyl ketone is not affected by the usual reagents for a ketone; when prepared by the Grignard reaction in xylene solution as described above it is accompanied by a sdstance m. p. near 230° and a magnesium salt of uncertain nature. When p-tolyl benzyl ketone is heated with semicarbazide hydro- chloride in alcoholic solution a t 180" for three hours a sparingly soluble substance C29H2sN2 yellow nieedles m. p. 1 81° molecular weight i n benzene and naphlhalene batween 400 and 450 was obtained which on hydrolysis with hydrochloric or sulphuric acid regenerated the original ketone. D. F. T. Indones. I. Synthesis of 3-Phenyl-2-ethylindone. R.DE FAZI (Atti R. Accnd. Lincei 1915 [v] 24 ii 150-156 and Gnzxetta 1915 45 ii 143-150).-The formation of 2 3-diphenylindons by the action of phosphoric oxide on P-hydroxg-ap/3-triplienylpropionic acid (this vol. i 542) indicates the possibility of obtaining derivatives of indone from cinnamic acid. The interaction of ethyl a-bromobutyra te and benzophenone in presence of granulated zinc yields ethyl P-hydroxy-PP-diphenyl-a- ethylpropionate (compare Schroeter A. 1901 i 415 ; 2907 i 530; Rupe and Busolt A. 1908 i 23 ; Rupe Sbeiger and Piedler A. 1924 i 281) Ph*COPh + CHEtBr*CO,Et + Zn = ZnBr*Q.CPh,*CHEt.CO,Et and the latter + H,Q = ZnO + HBr + QE*CPh,*CHEt*CO,Et. With cold concentrated sulphuric acid this estier gives a transitory yellow coloration which changes rapidly to emerald green.Such 3. green coloration is indeed,. given by p- hydroxy-a/@-triphenylpropionic acid and by 2 3-diphenylindone ; by ethyl /I-hydroxy-PP-diphenyl-a-ethyl- propionate and by 3-phenyl-2-ethylindone ; by ethyl P-hydroxy-P/3-i. 1064 ABSTRACTS OF CHEMICAL PAPERS. diphenyl-a-methylpropionate and by 3-phenyl-2-methylindone. That the coloration given by these acids with sulphuric acid is a sign of the formation of indones is confirmed by the results of Stoermer and Voht (this vol. i 684) who found that a-methylcinnamic acid which cannot be converted into 2-methylindone gives no coloration with sulphuric acid in the cold whereas allo-a-methylcinnamic acid which gives a violet-blue coloration is readily transformed into 2-methyl- indone ; similar behaviour is shown by a-ethyl- and allo-a-ethyl- cinnsmic acids. It should therefore be possible t o synthesise indone by transforming cinnamic acid into ah-cinnamic acid and dehydrating the latter.Graebe and dubin (A. 1887 589) used sulphuric acid t o effect dehydration between D phenyl and a carboxyl group obtaining diphenylene ketone from diphenyl-o-carboxylic acid. By similar means Roser and Haseloff (A. 18SS 1304) prepared 2 3-dibromoindone from up-dibromocinnamic acid whilst Lieberrnann (A. 1898 i 662) from allocinnamic acid obtained not indone but i t s dimeride truxone. By cold Concentrated sulphuric acid ethyl P-hydroxy-PP-diphenyl- a-ethylpropionate is first hydrolysed to the free acid this then losing 1 H,O giving P-phenyl-a-ethylcinnamic acid which undergoes dehydra- tion t o 3-phenyl-%ethylindone OH*CPh,.CHEt*CO,Et -+- OH*CPh,*CHEt*CO,H + This method of synthesising indones is simple to carry out and gives good yields.Ethyl P..~yclroxy-PP-d2Tpl~enyZ-a-et~~~Zp~o~~onate C,,H,,O forms large white needles m. p. 107-10B0. With Concentrated sulphuric acid it gives in the cold a n emerald green coloration becoming deep yellow on dilution and in the hot a red coloration. 3-P/ienyZ-2-etJiyZindone C17H140 forms shining orange-yellow prisms m. p. 92-93O and gives a green coloration with cold and a red one with hot sulphuric acid and a red coloration with cold concentrated nitric acid. Its oxime CI7Hl50N forms long golden-yellow needles m. p. 1S8-183° and gives a blood-red coloration with concentrated sulphuric acid in the cold ; the phenyllqdraxone C23H20N2 forms yellow prisms m.p. 136-13So and gives a reddish-brown coloration with eulphuric acid in the cold. WILHELM WISLICENUS and ALFRED FEHRLE (Beg.. 1915 48 1320-1323).--The authors have T. 11. P. Preparation of 9-Benzoylfluorene. investigated the best conditions for the preparation of 9-benzoyl- fiuorene ~'H4>>CIIGz by the interaction of fluorene and an alkyl C,H* benzoate (compare Werner A. 1906 i 436) and have by the following method been able to obtain a yield of 80% of that theoretically expected from the fluorene. A mixture of 1 4 grams of smyl benzoate 2-4 grams of potassium shavings and 5 grams ol fluorene is kept for one or two days and theORGANIC CHEMISTRY. i. 1065 reaction is then completed by warming on a water-bath.The gelatinous reaction mixture is treated with alcohol t o remove any excess of potassium and the benzoylfluorene can then be liberated by the addition of water and acetic acid. The product is accompanied by a small quantity of a yellowish-red Rubstance probably 1 4-bidiphenyl- enebutadiene (this vol. i 519). 9-Benzoylfluorene could not be made to give a phenylhydrazone; the product of interaction with phenylhydrazine in acetic acid solution was a substance C,,HI7N yellow rectangular plater m. p. 217-218' possibly of the structure *>C< >N which under certain conditions was accompanied by a substance almost black crystalline grains m. p. 150-155' soluble in sulphuric acid giving a violet-red coloration. D. F. T. Preparation of 4-Halogeno- 1 -hydroxyanthraquinone and Substitution Products Thereof.F. ULLMANN (Eng. Pat. 14954 June 1914; from J. Soc. Chem. Ind. 1915 34 952).-Phthalic anhydride or a substitution product is condensed with a p-halogeno- phenol or a substitution product by means of aluminium chloride and the 5-halogeno-2-hydroxybenzoylbenzoic acid or derivative so obtained is converted into the anthraquinone compound by an agent such as sulphuric acid monohydrate. Preparation of Arylsulphonylaminoanthraquinone-sul- phonic and -carboxylic Acids. AKTIEN GESELLSCHAFT:F~~R ANILIN- FABRIKATION (Ens. Pat. 8109 June 1915; from J. SOC. Chem. I d 19 15 34 95 2)-Halogenoanthraquinone-sulphonic and -carboxylic acids are condensed readily with arylsulphonplamides in aqueous alkaline solution at 100'.The products are useful for the preparation of dyes. J. C. W. Preparation of 2-Arylant hraquinonylthiocarbamides. $'ARB- WERKE VORM. MEISTER LUCLUS & BBUNING (D.R.-P.,! 254744 ; addition to 229111. Compare A. 1911 i 469).-The formation of by- products in the condensation of 2-aminoanthrayuinone with an aryl thiocarbimide is prevented by the use of a condensing agent such as aluminium chloride. J. C. W. Process for Hydrogenising Olefinic Terpene Alcohols Aldehydes and Terpenic Acids. C. PAAL (Eng. Pat. 16180 July 1914; from J. Xoc. Chem. Ind. 1915 34 982).-A claim is made for reduction with hydrogen under ordinary or increased pressures in the presence of finely divided or colloidal metals of the platinum group or of their protohydroxides in the non-colloidal state deposited on finely divided inert substances which are not anti-catalytic such as magnesium nickel cobalt magnesium oxide magnesium or calcium carbonate barium sulphate kieselguhr carbon sawdust cellulose powder etc.The Volatile Oil of Cymbopogon Senaarensis Ghiov. OSWALD DIGBY ROBERTS (T. 1915 107 1465-1470).-The above grass on distillation with steam was found to yield 1.2% of an oil ID:! 0.9422 YH CPh C t P 6 4 J. C. 'IV. A number of examples is given. J. c. w.i. 1066 ABSTRACTS OF CliEMICAL PAPERS. u g +29*6" acid number 4.2 ester number before acetylation 14.5 ester number after acetylation 62.1. I n this oil were detected the followiog constituents :-acetic decoic and octoic acids in the free condition also octoic decoic aud palmitic acids as esters (total approx.2 % of the oil) ; ketones (45 %) perhaps entirely Al-menthenone (bimitroso- compound C20.H3004N2 colourless crystals m. p. 96- 97' with decornp.) which on oxidation with neutral potassium permanganate solution gave a-hydroxy-a-methyl-a1-isopropyladipic acid together with diosphenol and an acid needles m. p. 126-127O; phenolic substances (0.2%) yielding n benxoyl derivative needles m. p. 70-72" ; a sesquiterpene aZcoho2 (25%) C,,H,,O;I b. p. 170-175"/21 mm. 280-285 a t atmos. pressure Dii 0.9544 U; + 10-8' having a faint resinous odour which could be dehydrated by phosphoric oxide to a sesquiteipene b. p. 150-155O/37 mu. Dii 0.9114 + 24.4' of no appreciable odour ; an alcohol (3%) with a faint odour resembling that of geraniol; a terpene mixture (13%) in which d-limonene was detected; i t also probably contained pinene ; the residue (1 1.8%) probably contained squiterpenes.D. F. T. Power of Colophony of Combining with its Solvents especially with Petroleum Hydrocarbons. LUDWIG PAUL (Chem. Zentr. 1915 ii 189-190 ; from Seifensieder Zeit. 1315 42,393-395 412-413 431-435. Compare this vol. i 828 829)-When y-pinic acid (KS acid) is ground with 90% alcohol and the mixture warmed the so-called '' plastic colophony '' is obtained m. p. 105-1 10' ; after some time the mass which contains absorbed alcohol loses its plasticity and after heating a t 50-60' for a long time the m. p. rises to 115-1204 The aqueous solution of the sodium salt of y-pinic acid absorbs a comparatively large quantity of ether.Colophony readily dissolves in petroleum and when the solution is distilled the greater part of the solvent is removed; a small portion however remains with the colophony even when the latter is heated a t 340'. This residue m. p. 2 5 O (approx.) frequently yields crystals of y-abietic acid; i t (the residue) amounts to about 40% of the weight of the colophony employed is bright yellow in colour and consists apparently of a compound of colophony with the higher hydrocarbons of petroleum The light balsam mentioned previously by the author (A. 1924 i 976) is a compound of colophony with hydrocarbons of high boiling point and deposits crystals of abietic acid ; the heavy balsam has more the properties of a resin oil and is free from hydrocarbons. If the calcium salt of y-pinic acid is dissolved in petroleum and distilled the residue remaining at 345O consists of a red-brown mass which when dissolved in twenty times its volume of petroleum b.p. 275-300' yields a brown solution; the latter forms a caoutchouc-like mass when cooled. Substances similar to vaseline are obtained when the mass is treated with benzene or nitrobenzene. The sodium salt of y-pinic acid when heated at 120' with 10 parts of petroleum yields a colourless mass ; this '' solid petroleum " gradually gives off its petroleum. If petroleum b. p. 170-250° is employed the mixture begins t o thicken a t 115O and "solid petroleum " separates. The latter burns with a smoky flame and loses its petroleum when heated a t a high temperature,ORGANIC CHEMISTRY.i. 1067 yielding a grey viscous residue. The ammonium salt of the acid also yields a solid product when hezted with petroleum and the mixture cooled. w. P. s. Constitution of Anemonin. YASUHITO ASAHINA ( J . I’hajsnz. Chirn. 1915 [vii] 12 293-294 ; from Y(hkugakuzasslbi 1915 Feb. 1). -The author considers anenionin t o be a dilactone of cycloocta- dieneonedicarboxylic acid of the annexed constitu- CH,-CR,-C tion sinae i t is shown to contain two ethylenic / I linkings and on oxidation gives anemonic acid which I 0-CO is identified as acetonediacetic acid. Further c<O-CO anemonin gives a phenylhydrazone and reduces I \I 1 amnioniacal silver nitrate and Pelding’s solutions CH,-CH,-C although the oxime and semicarbazone could not be obtained. The question as to whether anemonin is a dilactone or an anhydride was investigated by warming a solution to which half an equivalent of alkali hydroxide had been added.A neutral solution was obtained which became alkaline on further addition of alkali in the cold but the alkalinity disappeared on warming. This behsviour is regarded as favouring the idea OF a lactonic rather than an anhydride constitution and is in accord with the above-suggested formula. G F. M. Loss of Weight of Musk in a Current of Dry Air. CHARLES €3. BAZZONI (1. Franklin Inst. 1915 80 463-469).-Dry musk loses weight when exposed to a current of dried air and when after a period of about seven months the loss of weight ceases the musk is no longer odorous. The odour moreover was not restored by exposure to moist air.1.32245 mg. of dried musk lost 0.18941 mg. during the course of seven months the average daily loss in milligrams during the consecutive months being 0*00318,0*00135,0*00087 0*00035,0*00035 0*00017 and 0*00002. This gradual decrezse in weight is regarded as being due solely to the evaporation of odorous volatile constituents. The weighings were made with a micro-balance consisting essentially of a quartz fibre rigidly supported in a horizontal position to $he free end of which a light pan containing the musk was attached the whole being enclosed in a glass case; changes in flexure of the fibre due to changes in weight were measured by means of a microscope and micrometer screw. A sensibility of 0.00007 mg. was thus attained. G. P. M. Condensation of Aromatic Hydroxyaldehydes with Diketo- hydrindene.SOSALE GARALAPURY SASTRY and BROJENDRA NATH GHOSH (T. 1915 107 1442-1449).-The condensation of aromatic hydroxyaldehydes with 1-ketohydrindene in the presence of alkali (Perkin and Robinson T. 1907 91 1073) or of hydrochloric acid (Perkin Robinson and Turner T. 1908 93 lOS5) can be extended to diketohydrindene ; this substance reacts wtth an o-hydroxy-aldehyde in the presence of an alkali hydroxide giving an unsaturated ketonic co derivative of tho type C H,<CO>C:CH.C~~~,*OIr whilst underi. 1068 ABSTRACTS OF CHEMICAI PAPERS. the influence of hydrogen chloride the product is ZL ketoindenopyranol anhydrohydrochloride derivative of the type I I >C,H which C H *C:OCI CO-C CH can be obtained from and converted into the iormer product by treatment with hydrogen chloride and aqueous alkali hydroxide respectively. The constitution of these products is confirmed by the results of Wislicenus and Kotzle (A.1889 1067) who have caused di- ketohpdrindene to condense with other aldehydes. The high colour of these products obtained by the condensation of aromatic o-hydroxy- aldehydes with diketobydrindene is referred to the orthoquinonoid structure represented above which however differs slightly from the formulation l 6 I I erkin Robinson and Turner loc. 2'-Hydroxy-1 3-diketo-2-benzylidenehydrindene (dib?.omide pale yellow needlep m p. 122O) when treated with phenylhydrazine does not give a corresponding pheoylhydrazone but appears to undergo fission of the molecule.Salicylaldehyde and diketohydrindene condense together in methyl- alcoholic solution containing hydrogen chloride and there slowly Eeparates at the ordinary temperature 4'-keto-2 3-indeno-1 4-benxo- >C,H prisms orange-red pyrcunol anhydrohydrochloride when moist brown when dry decornp. above 320O. This substance is also obtained when a methyl-alcoholic solution of 2'-bydroxy-1 3- diketo-2-benzylidenehydrindene is saturated with hydrogen chloride. When the above anhydrohydrochloride is treated in alcoholic solution with an aqueous solution of sodium acetate a precipitate of 4'-keto- 2 3-indeno-l 4 - benxopyranol 8 t 1 x 0 g 2 > C 6 H 4 brown needles of no defioite m. p. is obtained. I n hot aqueous-alcoholic solution the anhydrohydrochloride is decomposed by sodium bydroxide with formation of 2-hydroxy-1 3-diketo-2- benzylidenehydrindene.I n alcoholic solution containing potassium hydroxide the con- densation of resorcylaldehyde and diketohydrindene yielded 2' 4'- dihydroxy-l 3-cliketo-2-ben2yZideneh?/dri?de.lze C H *C*OCl>c (p CO--C *CH cit.). Q6H4*y oc1 CO--C C H C,H,<Eg>C :CH* C,H,( OH) brown prisms decomp. at high temps. ; the acetyl derivative brown prisms m. p. 235O (decomp.) gives a dibromide brown needles unfused at 320O. When a solution of this dihydroxyhydrindene compmnd in methyl alcohol is treated with hydrogen chloride further condensation occurs with formation of 7-hydroxy-4'-keto-2 3-indeno- >C,H,*OH bright 1 4 - bensopyranol anhyhohgdroch loride red prisms decornp. a t high temperatures which is also obtainable directly by the condensation of reborcylaldehyde and diketohydrindene in methyl-alcoholic hydrogen chloride solution.On treatment with sodium acetate the anhydrohydroohloride is converted into 7-hydroxy- F6H4=Y OC1 CO--C=CNORGANIC CHEMISTRY. i. 1069 Q,;H,*$XO( OH) 4'-keto-2 ; 3-indeno-1 ; 4- benxopyrunol >C,H,*OH a dark CO--C==CH brown amorphous powder with a metallic lustre whilst decomposition by sodium hydroxide in aqueous-alcoholic solution gives rise to 2' ; 4'- dihydroxy-1 3-diketo-2-benzylidenehydrindene. Condensation of 2-naphthol-1-aldehyde with diketobydrindene in alcoholic solution in the presence of potassium hydroxide yields the potassium salt of 2'-hydroxy-l 3-dikato-2-nu,phthylidenehydridene C,H,<Fd>C :CH* CloH6* OH as a dark red crystalline mass ; the free hydrozy-compound liberated by acetic acid forms dark red plates m.p. 298' (decornp.) and gives a red coloration with ferric chloride; sodium salt brown. I n the presence OF hydrogen 'chloride condensation of the above naphthol- aldehyde and diketohydrindene yields 4'-keto-2 3-indeno-1 4-maphthc~- pyranol an~ydro?~ydrochloride >CloHG dark brown prisms decomp. at 130-150° from which can be obtained in the usual manner ?,H,*$XOCI CO--C :CH y,H,yO( OK) 4'-keto-2 3-indeno-1 ; 4-nciiul~th~py,.aiaol CO--C==CH >C,,H6 brown prisms m. p. 125' (decornp.). Conversion of the Natural Flavone Colouring Matters into Pyranol Dyes. EDWIN ROY WATSON K u m D BEHARI SEN and VISHNU RAM MEUHI (T. 1915 107 1477-1489.Compare Watson and Sen T. 1914 105 389).-It has been shown (Zoc. cit.) that 3 5 7-trihydroxy-2-mp-dihydroxyphonyl-4-ethyl-1 4-benzopyranol an- hydrobydriodide wrongly termed 3 5 ; 7-trihydroxy-Z-?np-dihydroxy- phenyl-4-ethyl-1 4-benzopyran anhydrohydriodide i n the previous communication can be obtained by de-ethylation of the reaction product of quercetin pentaethyl ether and magnesium ethyl iodide. As dyes this substance and the correspocding a?zh?ldro,'rydroclilaride lack fastness. D. F. T. 3 5 ; 7- Triet?~oxy-2-mp-diet~ox~p~~nyl-4-et?~ylbenxo~~ru~aol C,,H ,O(OEt),Et-OH the free base corresponding with the above anhy drohydriodide and obtained by the action of aqueous ammonia on this salt is a colourless viscous oil which gives a platiaichloride (C,7~!+0$1)2PtC1,,~ H,O red needles m.p. 197'. When the anhydrohydriodide is heated with aluminium chloride for an hour at 160" partial de-ethylation occurs with formation of 3 ; 5 ; 7 - t r i l ~ y d r o x y - 2 - m p - d i h ~ d r ~ x y ~ h e ~ ~ y l - 4 - e t 1 4-benxopyranol aiz?~ydrohydrochloride triethyl ether C15H50( 0 Et),(OH)2EtC1 H20 an almost black powder which can also be produced from the anhydro- hydriodide by the action of 33% sulphuric acid at 140'; this substance has tinctorial power equal to t h a t of the analogous substances mentioned above giving blue greenish-blue crimson and navy blue shades respectively with alum chrome tin and iron mordanted wool the colours being fast to all agents. I n the preparation of t h e triethyl ether as described a small quantity of 3 5 7-tyihydroxy-1.1070 ABSTRACTS OF CHEMICAL PAPERS. 2 -m p-di/qdroxyphen yl- 4-ethyl- I 4 -benzopymnol ai~bytli.oh~/d?.ochloi,ide tetraethyl ether mas also obtained and mas isolated as the platini- chloride (C,,H,,0,)2PtCI,,H,0 short scarlet prisms m. p. 170-176" (d ecom p. ). The action of magnesium ethyl iodide on quercetin trimethyl ether gave 3 5 7-trihydroxy-2-mp-d~l~ydrox~phenyl-4-~thyl-l ; 4-benxopy~anol anhydroh ydriodide trimelliyl ether C1,H,O( OMe),( OH),EtI,#,O red needleP m. p. 163-165" but the tinctorial power of this compound is small compared with that of the above triethgl ether thus suggesting t h a t the alkyloxy-groups occupy different positions in the two compounds. With magnesium phenyl bromide and quercetin pentaethyl ether the product after treatment with hydrochloric acid was 3 5 7-t~iethoxy- 4-phenyl- 2-mp-diethoxyphenyl-1 4- benxopyranol anhydrohydrochloride C,,H,O(OEt),PhCl red needles which by boiling with hydriodic acid (D 1.7) was converted into 3 5 7-trihydroxy-4-phenyI-2-mp-diT~ydroxy phenyl- 1 4-benxopyranol anh ydrohydriodide C,,H,O(OH),PhI deep red prisms the corresponding free base being a n unstable amorphous violet-coloured solid ; as a dye the salt was exceedingly fugitive.3 5 7-Triet~~oxy-4-o-methox~phenyl-2-mp-~~ie~hoxyph~nyI-l 4-benao- pgranol anhydrohydrocldorid e C,,H,O( OEt),( C,H;OMe)CI HCI H,O obtained by the intemction of magnesium o-methoxyphenyl bromide and quercetin pentaethyl ether was a crimson crystalline solid which gave dyeings of greater fastness and deeper shades than the preceding compounds ; it forms a ferrichloride C,,€€,707C1,€lFeCl red needles m.p. 190". The constitution of this compound is represented by either formula I or 11. When this substance is heated with hydro- 01 or chloric acid a t 150-180° de-ethylation occurs with production of a substance C,1H1,06Cl dark red needles with a blue reflex which gives a green coloration with potassium hydroxide and greenish-blue green dark blue and olive-green shades respectively with alum chrome tin and iron mordante. By t h e interaction of magnesium methyl iodide and naorin pentaethyl elher (the latter substance m. p. 112-114O being obtained by exhaustive ethylation in the manner of Perkin P. 1912 28 328) in the presence of only a little ether there was obtained 3 5 7-tri- melhoxy-2 -0p-di~~TitetiLoxyp~en~ I- 4 -nzethy?- 1 4- benzopyrano I anh ydrohydr- iodide C,,H,O(OMe),MeI yellow needles which on demethylation by boiling with hydriodic acid (D 1.7) was converted into 3 5 7-tri- hydroxy-2-op-dihy/dro~~phen yl-4-methyl-1 4-benxop9ranol anTLydrohydr- iodide CI5H,O(OH),MeI ; this gives a crimson colour with potassium hydroxide and maroon pink and salmon-coloured shades respectively with wool mordmted with chrome tin and iroa.Luteolin tetraethyl ether reacted readily with magnesium ethylORGANIC CHEMISTRY. i. 1071 iodide yieldi~g 5 a-d7'etJ~oxy-2-mp-diet~~o~~pJ~e~~~l-/il-~ 4-6enxo- pyrccnol an~Lydroh~driodicle C,,H60( OEt),'Et I orange-coloured needles m. p. 169-172" from which the corresponding free base C,,€€,O(OEt),EtOH was obtained as colourless needles m.p. 116-1 17". When the tetraethyl ether anhydrohydriodide is de- ethylated by hydriodic acid the product is 5 7-dihydroxy-2-mp-di- hydroxyphenyl-4-etlgl-I 4-benxopyyanol anhydrohydriodide which gives a violet coloration with potassium hydroxide and fast mauve blue-black maroon and blue-black shades respectively with alum chrome t i n and iron mordants. The interaction of apigenin trimethyl ether and magnesium ethyl iodide gave 5 ; 7-diethoxy-2-p-ethoxyphenyl-4-ethyl-1 ; 4-benxopyranol anhydrohydriodide C,,H,O(OEt),EtI orange-coloured rhombs m p. I 78-1 80' (platirzichloride 2C,,H,70,CI,PtC1,,2H~0 a bright red solid) which on de-ethylation by hydriodic acid was converted into 5 ; 7 -d ih y dvox y-2- p-12 y drox ypheny E- 4- et hy l - 1 I-benxopy r ano 2 a nh y dro- ?hydriodide C,,H70(OH),EtI,H,0 needles ; this gave a crimson coloration with potassium hydroxide and brownish-orange to orange shades with various mordants.Curves are given representing the absorption spectra of the above dyes only one band being present throughout the whole class i n the visible portion of the spectrum although there are indications of a second band beginning near the ultra-violet end of the spectrum. C,,H,O( OH),E tI H,O D. F. T. T b e Diflavone Group. 11. Derivatives of Diflavanone. HuaH RYAN and PAULINE O'NEILL (Proc. Roy. Irish Acud. 1915 32 By 167-184. Compare this vol. i '707),-For the synthesis of diflavanone and diflavonol considerable quantities of dihydroxydichalkone or dibenzylidenediacetoresorcinol [4 6-dihydroxyphenylene distyrgl di- ketone] were required. Whilst exa.mining possible methods for pre- paring this compound four isomerides were brought to light.The first of these " a-dibenzylidenedires~rcinol,~' was prepared by adding 50% sodium hydroxide to a solution of diacetylresorcinol and benzaldehyde in boiling alcohol (Eykman Bergema and Henrard A 1905 i 359) and crystallises in long orange-yellow rhombic prkms m. p. 204". The next the P-modification was obtained by shaking a dilute aqueous-alkaline solution of diacetylresorcinol with benzaldehyde for about a month (Zoc. cit.) and crystallises in almost cubical monoclinic yellow prisms m. p. 198-301*. If the latter process is prolonged to three months the I' 7-" form is formed in pale yellow equilateral triangular plates m.p. 218'. A fourth isomeride '' S-," is obtained by gently boiling the a-modification in solution in acetic acid saturated from time to time with hydrogen chloride. It forms yellow diamond-shaped crystals m. p. 205". The /I-modification gives a deep red coloration with alcoholic ferric chloride the a-compound a fainter colour the 6- a still paler colour and the y-isomeride practically no colour. The a- p- and &isomerides yield oily acetates which form the same tetrabromide of 4 6-dihydroxy-rn-phenylene distyryl diketone diacetate (ibid.) on treatment with bromine and then the same diflavonei. 107'2 ABSTRACTS OF CHEMICAL PAPERS. with alcoholic potassium hydroxide. Since by another synthesis it has been shown that the P-compound is a true dihydroxyphenylone distyryl diketone (did.) the conclusion is drawn that the a- p- and 6- compounds are the three possible stereoisomerides of this.This is supported by the fact that the a-form changes into the /3- when left with a trace of bromine in chloroform solution in the light The y- isomeride does not behave in the same may on acetylation and bromioation and is therefore a structural isomeride. An attempt was made to prepare the dihydroxgphenylene distyryl d i ketone by heating resorcinol dicimzamu te C6H4( GO,- CH CHPh) with zinc or aluminium chloride but without success. This ester was obtained by boiling together resorcinol cinnamog 1 chloride axid pyridine and crystallised in prisms m.p. 122-124'. Derivatives of diflavanone can be prepared most readily by the condensation of diacetylresorcinol with aldehydes under the influence of alcoholic hydrogen chloride. Thus with benzaldehyde the product i q dibenzylidenediflavnnone m. p. 268' (Ey kman Bergemn and Henrard loc. cit.) whilst pi peronalde byde yields dipiperonyliderbe- 3' ; 4' 3" ; 4"-dimethylencdiox~d~~av~none CH, 0, CiH3*FII*0 . 6-yH*C,H,:O2:C H CH,:o2:C6H3* CH :c- CO>CGH2<CO* c CH *C,H,:O,:CH,' yellow prisms m. p. 289" almost insoluble in alcohol mixed with the more soluble inteimediat e compound 7-lqdroxy- 6 -mp-meth ylenedioxy- which crystallises in yellow prisms m. p. 240-242'. This condensation of hydroxy-ketones with aldehydes in the presence of alcoholic hydrogen chloride is also applicable to the monoflavone group and is probably better than the usual process in alkaline media.Thus gallacetophenone dimethyl ether [2-hydroxy-3 - 4-dimethoxy- acetophenone] yields with benzaldehyde 7 S-diiizetl~ox~-3-benx?/lidene- fluvanone C,H,(oMe~,<~~.~:~HPh' colourless needles m. p. 125-126' and with anisaldehyde 4' 7 8-trin~ethoxy-3-ani~$idene- fluvuno~~e C26H240G nearly colourless prisms m. p. 148-143'. With piperonaldehyde the chief product is 7 8-dimethoxy-3' 4'-niethylene- dioxy-3-piperonylidenefEavunone C,,H,,O colourless r eedles m. p. 184-186' but some of the intermediate chalkone namely piperonyl- ideizegallucetophenone dimethyl ether [2 3-dimethoxy-6-mp-methylene- dioxycinnanzoyl~henol] OH*C,H,( 011 e) CO CH CH* C H 10, CH may also be isolated as it is soluble in dilute alkali hydroxide and more soluble in alcohol and chloroform than the main product.The chalkone is also formed by the alkaline condensation and crystallises in yellow prisms m. p. 174-176'. Eykman Bergema and Henrard (loc. cit.) prepared di benzylidenedi- flavanone by the condensation of their a-dihydroxyphenylene distyryl diketone resorcinol with benzsldehyde in the presence of alcoholic hydrogen chloride. This method differs from the present one in that the intermediate chalkone is first isolated but it may be applied to 0- CHPhORGANIC CHEMISTRY. i. 1073 other aldehydes with advantage. In this way d~anisyZideizsdifEccvanone yHPh.0 0-YHPh pale yellow 0 Me*C,f-I;C K C--C?O>c6H2<C0 C CH*C,H,*OMe' rhombi& crystals m.p. 278-279' and d ~ ~ ~ e ; o n y l i d e n e d i ~ v ~ n o n e C,,H,,O pale yellow prisms m. p. 296O have been prepared. J. C. W. Preparation of 2-Phenylquinoline-4-carboxylic Acid. KALLE & Co. (Eng. Pat. 17725 July 1914; from J. SOC. Chem. Ind. 1915 34 9 24).-2-Phenylquinoline-4-carboxylic acid is prepared by the condensation OF isatin with acetophenone in aqueous-alkaline solution. Thus isatin (16 kilos.) acetophenone (12 kilos.) and 33% potassium hydroxide (60 kilos.) are heated and stirred for eight hours on the water-bath then diluted and filtered. Acetic acid is added as long as brownish-red flakes separate and then the filtrate is treated with the calculated quantity of acetic acid in order to precipitate the 2-phenyl- quinoline-4-carboxylic acid.J. C. W. The Chromoisomerism of Acridoniurn Salts. A. HANTZSCH (Bw. 1915 48 1338-1 340).-The author maintains his view of the chromoisomerism of acridonirrm salts and advances arguments against the suggestion of Kehrmaon Havas and Grandmougin (A 1913 i 1341) that the variation in colour may be due to the formation of meriquinonoid salts. D. F. T. Diazonium Psrhaloids. A. HANTZSCH (Bey. 1915,48,1344-1345). -The author opposes the formula N LIX-NX suggested by Chattaway (I?. 1915 107 105) for the diazonium perhaloids and insists on their nature as ammonium perhaloids this view being confirmed by the resemblance of the d iazonium per bromide t o phen?/ZfriniethyZaminonium tdwomide golden-yellow scales which is sparingly soluble in water with loss of bromine and can be preserved almost unaltered over lime for two months.D. F. T. The Mechanism of the Coupling of Diazonium Salts with Amines Phenols and Phenolic Ethers. P. KARRER (Bey. 1915 48 1398-1406).-Tn an endeavour to prepare certain dialkylphenyl- enediamines by way of Euitable aminoazo-compounds the author ha.s obtained results which suggest that in the coupling of a diazonium salt with an amine a primaryaddition of the salt occurs at the amino-group with formation of an ammonium derivative. This intermediate product then undergoes rearrangement into the azo-compound. An analogous intermediate formation of an oxonium compound is believed to occur in tbe Condensation of a diazonium salt with a phenol or phenolic ether. If the nitrogen or oxygen atom is heavily laden with radicles the affinity of the atom may be too nearly saturated for the formation of an additive compound so that such substances as dibutylaniline and its isoamyl analogue cannot undergo condensation with diazo- sulphanilic acid without loss of an alkyl group the final product being a monoalkylamirioazohenzenesixlphonic acid N €1 R C 1-1 N C H .S 0 H.i. 1074 ABSTRACTS OF CHEMICAL PAPERS. This view of the reactiou is beliewed to accord satisfactorily with the results of Auwers and Michaelis (A. 1914,'i 744) Meyer Irschick and Schloaser (A. 1914 i S82) and also with the observation t h a t whereas m-chlorodimethylaniline reacts in the normal manner with a diazonium salt and with nitrous acid o-chlorodimethylaniline fails to react a t all with either reagent.According t o the author's view of the action the first effect with each reagent is a n addition a t the amino- group and the process of addition is checked by steric hindrance i n the case of the o-chloro-derivative. In the light of this explanation of the condensation of diazonium salts with amines or phenols t h e intermediate compounds obtained with t h e latter by Dirnroth and Hartmann (A. 1909 i 66) should be of oxonium structure. p - P ? i e n ~ Z e n e d i ~ r o p ~ Z d ~ a ~ ~ i n ~ obtained by reduction of nitrosodipro- pyIaniline with hyposulphite fnrms in addition to the normal sulphate a sulphate 2NH,*06H,*NPr2,H,S04 colourless leaflets which become red i n the air. Condensation of diazosulphsnilic acid and dibutylaniline in aqueous acetic acid solution gives rise to red butylaminoaxobenxcinemdphonic m i d C,HooNH*C,H,*N,*C6R,*SO~H which was separated as the sodium salt.When treated i n nqueoi1.s solution with sodium hyposulphite the sodium salt is reduced to p-butylaminoaniline. I n a similar manner iso- am~Zaminonxobenzenesulphonic (ccZd C,H N H C €3,. N,*G,H,*SO,H and its sodium salt (orange-yellow leaflets) were obtained the latter llndergoi hg reduction with formation of p-isoa?nyEaminocc?Eiline NH,*CY,H,*NH*C,H, leaflets m. p. 3 1-39' ; hydrochloride leaflets. D. F. T. Polymorphic Phthalyl-halogen-subs tituted-phenyl- and- tolyl- hydrazides. FREDERICK DANIEL CHATTAWAY and ERNEST VONDERWAHL (l'. 1915 107 1503-1509).-The substitution of a halogen atom into the phthalyl-phenyl- and phthalyl-tolyl-hydrazides at the para-posi- t,ion only causes the crystalline habit to become somewhat moreslender all thep-halogen derivatives crystallising in a yellow modification similar to the yellow modification of the psrent compound.With the introduction of two halogen atoms into the 2- and 4-positione the crystals become more elongated and hair-like whilst a third halogen atom in the remaining ortho-position restores the original compact habit of the crystal. The meta-substituted derivatives whether one position is substituted or both crystallise in slender needlea. The nature of the halogen is of little effect. Three cases of polymorphism were observed the non- observance of other cases being probably due t o excessive instability of one form or to unsuitable conditions.co PF,tiiaZyl-o-chZoro~hennylh ydraxide C6H,<@O>N*N H* (3 H,Ul forms compact pale yellow plates m. p. 22 1'. PfLt~ccbyl-o-bromopl~en~l- hydraaide pale yellow plates m. p. 2 12'. I'litAalyl-o-iodophenyl- hydyazide crystallises in two polymorphic forms ; very pale yellow hair-like needles and bright yellow compact rhombic plates both m. p. 144-1 45" ; both forms give identical deep yellow solutions. I'/&LI~Z- m-chZorop~~e~ayZliydra~.ide pale yellow hair-like ptisrns m. p. 180'.ORGANIC CHEMISTRY. i. 10'75 PhtF,alyl-m-bro~~zophenylhydruzicle pale yellow hnir-like prisms m. p. 208'. Yhthalyl-m-iodophenylhydraxade long very slender yellow prisms m. p. 232'. Fhe solubility of these meta-derivatives diminishes with increase in the atomic weight of the halogen whilst the colour deepem.Phtha~yl-p-iodophenylhydrazide forms long bright yell0 w p riams rn. p. 193.5'; the 0- and m-isomerides have already been described (Chattaway and Wiinsch T. 1911 99 2260). Phthulyl-2 6-dibromophenylhydruzicle sepsrates from toluene in pxle yellow microscopic prisms m. p. 203' which on suspension in toluene a t the ordinary temperature are slowly replaced by large colourless hexagonal plates; when rapidly heated this form shows signs of fusion near 190° but simultaneously changes to the yellow form which re- solidifies and then melts a t 203". Phthalyl-3 5-dibromophenylhyd~axide faintly yellow hair-like prisms m. p. 268'. PhtJmZyl-3 4-dibromo- phenyl?iydraxide pale yellow needles m. p. 206'. Phthalgl-2 4-dichltoro- phsnylhydrazide pale yellow hair-like prisms m.p. 206'. Phthulyl- 3 4-dibromophertylhydi.aside pale yellow hair-like prisms m. p. 224'. Phthalyl-2-chloro-4-bromophenylhydraxide very pale yellow hair-like prisms m. p. 2 10". PhthuZyl-4-chloro-2-bromophenylhydi~azide very pale yellow hair-like prisms m. p. 211". 2 4 6-Tribromophenylhydrazine was obtained by diazotising a solution of tribromoaniline in solution in a mixture of concentrated sulphuric and glacial acetic acids with aqueous sodium nitrite and reducing the resulting solution with an acid solution of stannous chloride (compare Neufeld A 1889 251). I t readily undergoes atmospheric oxidation with formation of tzibromobenzene and nitrogen (compare Chattaway T. 1907 91 1323 ; 1908 93 270). Phthalyl-2 4 6-tribromopJ~enylhydru~ide forms pale yellow short compact prisms rn. p.205". Phthulyl-2 4 ; 6-trich20~.0pl~enylAy~lru~~~e stout almost colourless prisms m. p 191'. Phthalyl-2 6-dichlo~~o-4-bromopi~enylhyd~~c~o,ide pale yellow compact rhombic plates m. p. 188". Phthalyl-2 4-dichloro-6-liromopl~enylf~~dr~~~i~e pale yellow short stout prisms terminated by pyrilmids m. p. 1 9 3 O . Pf&thalyl-4-chloro-2 6-dibrornopl~er~?/I~y~raxide very pale yellow short; stout prisms m. p. 217". I'hthalyl-6-chloro-2 4-dibromoz~?~s,L?/l~~yclracide very pale yellow com- pact stout irregular plates m. p. l t 1 5 O . PhthalyE-3 5-dibromo-o-tolylhydrccx.lde fornis long colourlehs very slender prisms m. p. 236O. Phthalyl-3 B-dibro./no-p-tolyWycl.ruxide separates from hot toluene or glacial acetic acid in very pale yellow long needles which when left i n contact with acetic acid a t the ordinary temperature soon change into pale yellow compact crystals apparently very short stout prisms ; the m. p. of both forms is 196". The trihalogen-substituted hydrazines other than 2 4 6-tribromo- phenylhydrazine of which derivatives are clescribed above were pre- pared in a similar manner to 2 4 ; 6-tribrornophenylhydraziue and will be described later. r). F. I!.i. 1076 ABSTRACTS OF CHEMICAL PAPERS. The Activity during the Biochemical Synthesis of P-Alkyl Glucosides by P-Glucosidase of the Other Ferments Ac- companying it in Ernulsin. EM. BOURQUELOT and A. AUBRY (Compt. rend. 1915 161,463-466; J. Phccrna. Chim. 1915 [vi] 12 Of the enzymes occurring along with P-glucosidase in emulsin lactase and P-galactosidase do not exert any influence on the synthesis of alkyl glucosides from dextrose Gentiobiase and cellase exert their own synthesieiog action tending to produce gentiobiose and celloae. The formation of these sugars is found to be much greater as the proportion of dextrose t o water in the mixture increases and as t h e alcohol becomes lees concentrated. The addition of acetone t o the aqueous sugar solution does not affect the amount of these two hexobimes formed relative to the water-sugar volume. I n order to obtain tbe best yield of alkylglucoside when working with emulsion the aqueous sugar solution should not contain more than 15-20% of dextroee. W. G. 305-3 1 4).

ISSN:0368-1769    

DOI:10.1039/CA9150801049

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

i. 1076 ABSTRACTS OF CHEMICAL PAPERS. Physiologic a1 C heniis t ry. ARespiratory Chamber for Small Animals. A. C. KOLLS mid is devoted entirely to a full description with figures of the apparatus. Results will be presented later. W. D. H. ~1. s. LOEVENH-4RT (d??Zt!Y. J. PhySiOl. 1915 39 6’7-76).-%?lie paper The Mechanism Adapting the Oxygen Capacity of the Blood t o the Requirements of the Tissues. H. C. DALr,\m A. C. KOLLS and A. S. LOEVEKITART (Anm. J. Physiol. 1915 39 77-108). -Decrease in oxygen tension t o 14% of mi atmosphere stimulates the bone marrow in rabbits rats and dogs. The consequent’ iii- crease of red corpuscles arid h~moglobiii is marked in five t o seven days but the maximum occurs later. The increase is absolute and in rats it may reach 43%. The effect is more marked when the oxygen pressure is reduced t o 10% of an atmosphere and is still seen when 6% is employed.Carbon dioxide also stimulates the bone niarrow to a certain small extent. W. D. H. The Gases of the Blood During Hibernation in the Wood- chuck (Marrnota Monax). Rxr)rci<\v T. RASWSSISN (Avzer. J. Physiol. 1916 39 20-30).-7’he amount of carbon dioxide i n the blood of the woodcliuclr is always liigli ; i t increases during hibernation aiid falls OH wakiiig. There is also more oxygen iii tlic arterial blood j u s t preceding and diiriiig torpidity than a t ofher times. The difference between arterial and venous 1)lootl is greater during hibernation especially in the carbon dioxide content. W. D. 11.PHYSIOLOGICAL CHEMISTRY. i. 107’7 The Influenee of Nutrition and Exercise on the Blood-sugar Content.W. VON MOHACZEWSKI (Biochem. Zeitsch. 1915 7 1 268-288).-The effect of ingestion of carbohydrates by individuals on insufficieiit diet is t o cause a transient rise of the blood-sugar; proteins under similar conditions cause a smaller but more lastr ing rise. The effect on individuals on a diet more than sufficient for bodily needs is as follows carbohydrates are without action whereas proteins and fats cause an insigiiificant but lasting rise. The influence exerted by exercise on tlie blood-sugar depends on the diet; the rise is somewhat greater on a diet of Carbohydrates and gelatin than on a meat’ and €at diet. I n the case of diabetic individuals the rise of the blood-sugar produced by diet and exercise is smaller; o n all diets muscular exercise causes an in- crease in the blood-sugar. The tolerance t o sugars is increased by muscular exercise and eveii in the case of diabetics there is a diminution of tlie excretion of sugar after muscular work in spite of the rise of the blood-sugar.The Origin of the Proteolgtic Enzymes of the Blood. LE ROY H. SLOAN (24me~. J. Pliysiol. 1915 39 9-19).-The proteo- lytic action of the serum rises in pregnancy. Normal serum has a weak non-specific proteolytic action and tlie enzyme during pSeg- nancy is not specific for placental protein. Many pathological conditions produce the same effect as pregnancy. The Abderhalden *J. J. WELLS and J. E. Xuwox jun. (Arne?.. J. Pl~ysiol. 1915 39 31-36) -Statistical. Enormous variations occur from less than a million red corpuscles per cubic millimetre in cold-blooded animals t o more than twenty millions in goats.Details of the white corpuscles are also given but’ no differential counts were attempted. The Osmotic Equilibrium between Blood Milk and Bile. F. H. VAN DER Lnm (Biochem. Zeitsch. 1915 71 289-305. Com- pare this vol. i 622).-Milk and bile have the same osmotic con- centration as the blood from which they are secreted. The normal depression of freezing point f o r ox-blood is 0.53-0.57O. The freezing point is independent of the temporary state of nutrition of the animal and even starvation for several days leads t o n o change in the freezing point of the blood or milk. By dilution of the contents of the small intestine or by administration of sodium sulphate the depression of the freezing point of the blood can be altered ; even under these conditions the osmotic equilibrium between blood and milk can be maintained. The estimation of the freezing point of milk is the most certain method for detection of t]lel addition of water and any milk which freezes above -0-53O must be regarded as adulterated.The Influence of Acids and Alkalis. Action of Protein Precipitants. A Theory of Clot Formation. E. HXRZFELD and It. I(LIR’(:ER (Bioche??~. Zeitsch. 1915 71 391-405).-The optimal condition for the formation of S. B. 8. test is therefore quantitative not qualitative. w. D. H. Blood-counts in Frog Turtle and Twelve Mammals. W. D. H. S. B. S. The Physiology of Clot Formation.i. 1078 ABSTRACTS OF CHEMICAJ PAPERS.thrombin is the presence of a neutral medium or one slightly alkaline to sodium hydrogen carbonate ; the formation is inhibited by acids in very small concentrations. On the other hand acids accelerate the thrombin action (precipitation of fibrin) whereas alkalis exert an inhibitory action. Thrombin action is also accelerated by various protein precipitants. Attempts were made t o apply Herzfeld’s theory of the solubility and precipitation of proteins to the process of clotting and it was shown that the solu- bility of fibrinogen is affected by certain protein degradation pro- ducts especially fibrin peptoiie (compare this vol. i 1019). S. B. S. Physiology of the Stomach. XXVII. The Mechanism of the Regurgitation of Duodenal Contents into the Stomach.CLARENCE J. HICKS jun. and JOJIN W. VISIIER (Anzcr. J. Pliysiol. 1915 39 1-8).-Hydrochloric acid (150 C.C. of 0.5%) causes regurgitation when left in dogs’ stomachs for fifteen t o thirty minutes. The same is frequently noticed in man. Froin similar observations on cats i t is coiicluded that this is not due t o anti- peristalsis but t o “ segmentation movements ” of the duodenum. W. D. H. Physiology of the Stomach XXIX. The Gastric Hunger Contractions of the Normal and Decerebrate Guinea Pig. JESSIE L. RING and HELENE CONNET (3wei.. J . I1liysiol. 1915 39 123-130).-Hunger contractions appear in the guinea-pig four t o five hours after feeding while the stomach is well filled. Water 0.5% hydrochloric acid and other substances which usually inhibit these contractions give negative results.After eating the vigorous movements continue for half an hour and then merge into those of the mild peristaltic type. Hunger movemeiits appear to be vigorous peristaltic contractions. After decerebration the stomach is in a hypertonic condition owing presumably to the absence of inhibitory impulses from the cortex. W. D. H. The Utilisation of Blood for Human Diet and the Behaviour of Formaldehyde in the Organism. E. SALKOWSKI (BZocl2~1n. Zeztsch. 1915 7 1 365--390).-0~-blood contains nearly the same amount of protein as fat-free meat and has nearly the same nutritional value. Experiments are described on the methods of preserving the material by the addition of antiseptics. It was found that the coagulated proteins could be preserved in chloro- form water and in 3% formaldehyde solution. The effect of formaldehyde on the system was investigated and it was found that dogs could tolerate 0-6-1 gram daily in their food of which aboutl 0.6% was excret4ed unchanged in the urine.It is contended that the toxicity of this substance has been over-estimated. Atten- tion is directed t o the fact that there exists in urine a substance which gives with iodine and sodium hydroxide the iodoform re- action and of which the nature is unknown. s. B. s.PHYSIOLOGICAL CHEMISTRY. i. 1079 The Influence of the Depressor Nerve on Suprarenal Secre- tion. A. N. RICE-TSRDS and WILSON G. WOOD (Avw. J . Phpsiol. 1915 39 54-66).-The processes in the suprarenal gland responsible for the discharge of adrenaline are subject to reflex inhibition via the depressor nerve.W. D. H. The Stimulation of the Hypophysis in Dogs. ROBERT W. K I ~ T O N and FRANK C. B E ~ T (Amc7~. J. Plzysiol. 1915 39 109-122). -If asphyxia is avoided ether anEsthesia causes no marked rise in the reducing power of the blood; after one t o three hours it may fall. Stimulation of the hypophysis (pituitary) then increases the reducing power but this does not occur i f the splanchnic nerves are cut. W. D. H. A Labile Form of Proteins and its Relationship to Living Protoplasm. OSKAR Lomv (Biochm. Zcitsch. 1915 71 306-320). -A labile form of protein exists in many cells generally in the cell-juice but sometimes also in the protoplasm. This substance is distinguished from ordinary proteins by the fact that it is separated from solutioii by the addition of ammonia and organic bases and then rapidly undergoes a change and is converted into a more stable compound.The action of the alkali is not a mere neutralisation. The more reactive bases cause as a rule the separation of numerous small granules whereas weaker bases such as caffeine and antipyrine act in quite a different manner. I n the presence of these bases cell life can remain intact for several days and the protein can retain its labile form. Very small drops of thO substance separate a t first and these combine gradually to larger refractive drops which can reach the diameter of 30p that is about half the diameter of the cell. The changes produced on these objects (“ proteosomes”) can be readily followed by the micro- scope.They coagulate by the expulsion of water forming either a hollow sphere or a sphere containing varying numbers of cavities or an amorphous mass without definibe form. Such a change can be produced by hydrogen cyanide hydroxylamine or hydrazine. Ammonia produces a solid structure without as a rule cavities. The labile protein behaves towards dyes like the living protoplasm whilst the coagulated proteosomes ” behave like dead protoplasm. It is claimed that there is an intimate relationship between the stored labile protein and the organised labile protein or protoplasm. S. B. S. The Colloidal Nitrogen in Normal and Pathological Urine. GII. DUMITRESCU (C‘hem Zentr. 1915 ii 34-35 ; from Bul. SOC. Ftiiiztc Bzicwesti 1915 17 13-22).-The colloidal nitrogenous matter was precipitated with zinc chloride and the organic matter in the precipitate was destroyed in the usual manner.After neutralisatJon with sodium hydroxide the nitrogen was estimated by hypobromite. By this method it was found that the relation- ship of colloidal t o total nitrogen could rise to 2-57 on a meat diet whereas it was less on a mixed diet and still less on a milk andi. 1080 ABSTRACTS OF CHEMICAL PAPERS. vegetable diet. I n cancer there was a tendency for tlie iiurriber t o rise according to the severity of the disease. The same was true in diabetic cases but here the amount of dextrose in the absence of acidosis was without influence on the number. This was also influenced by diseases of the liver and kidneys but not in cases when the urine contains pus.S. B. S. Acidosis and its Regulation in the Human Body. .A. I~MXJN R. HERnBIAhrN and E. MUNzmt (Biochenh. Zeitsch. 1915 71,255-267) -From experiments and clinical observations itl is found tliat acids in the system whether introduced in experiment or result- ing from a pathological condition are eliminated as ammonium salts in the urine. No change in the tension of carbon dioxide in the venous blood is produced thereby so that this factor cannot be regarded as a measure of acidosis. Diminished carbon dioxide tension cannot by itself without taking into account other factors be regarded as a measure of acidosis. The carbon dioxide tension of the blood does however sink after prolonged acidosis but this is due t o the impoverishment of the' blood in substances capable of combining with carbon dioxide or perhaps t o an alteration in the tissnes; whether alteration in the respiration is involved a t the same1 time cannot be decided without further experiments.The tension of the carbon dioxide oE the venous blood standing in equilibrium with the alveolar air is in the first instance dependent ,on the carbon dioxide content' of the blood and is apparently a function of the capacity of the blood for binding this gas. The ,carbon dioxide tension of the blood can sink also without any .acidosis. S. B. S. The Immediate Effects of the Inhalation 6f Chlorine. SIR EDWARD A. SCHAFER (Brit. *&fed. J. 1915 ii 245-247).-In anzesthetised cats and dogs injection o€ chlorine dissolved in Ringer's solution directly into the blood-stream is not followed by serious results but' inhalation is always followed by toxic symptoms the most marked of which is cessation of breathing which follows exaggerated efforts t o respire and recovery after two successive inhalations of 1 partl of chlorine t o 100 of air is not usually obtainable; the blood pressure after a slight rise falls.There appears to be no bronchial constriction but the chief cause of the symptoms is circulatory failure through the lungs which amounts in some cases t o complete stasis. There is also rriuch aederna in the pulmonary tissue. The bodies of the animals do not sinell of chlorine. Tl10 heart beats for some time after the respiration stops. Nothing special was noted in other organs. Tracings and drawings of microscopic specimens of the l~ings are given. W. D. 13. The Influence of Oil of Chenopodium on Intestinal Con- tractility. WILLIAM SALANT and C. MITcrIer,L ( A ?mr. J. Physiol. 1915 39 37-53).-0i1 of chenopodium in dilution of 1 5000 and 1 10,000 markedly lessens the tone and contractions of intestinalVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1081 loops especially of the colon; in dogs this may be preceded by a rise of tone. Recovery occurs in pure Locke’s solution. Large doses are necessary t o inhibit peristalsis in intact rabbits if intra; venous injection is used. Nerve-endings as well as muscle fibres are attacked the latter being the more resistant. The action’ of the oil is not antagonised by caffeine pilocarpine or barium chloride. W. D. €3.

ISSN:0368-1769    

DOI:10.1039/CA9150801076

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1081 Chemistry of Vegetable Physiology and Agriculture. Schumann Rays as an Agent for the Sterilisation of Liquids. W. T. BOVIE (Bot. Gax. 1915 60 144-148).-1t is shown that a hydrogen discharge tube as described by Billon- Daguerre is not an efficient source of light for photo-sterilisation. An apparatus similar to the one referred to’ is described in which the exposure was much longer whilst the volume of liquid exposed a t any one time was much less. Although the numbers of bacteria were greatly reduced sterilisation was not complete. N. H. J. M. Fermentation of Carbohydrates by Living and Killed Yeast Cells. HANS EULER ( B i d Zentr. 1915 44 42 9-481 ; from Zeitsch. Gdhrungsphysiol. 1914 5 I).-Yeast was dried in a vacuum (3-5 mm.mercury pressure) a t a temperature of 2 5 O which was gradually raised to 60° and treated with alcohol previously distilled over lime and calcium. On adding toluene (2 c.c.) t o an emulsion of 1 gram of the dry yeast in 25 C.C. of 8% dextrose solution i t was found that the fermenting power was reduced 60% t o 125%. It was found that about 5% of the yeast cells remained uninjured and when examined microscopically with atid without dyes behaved the same as living cells. The cells termed “zymatic cells,” retain the function of fermentation catalysis whilst the power of growth is lost. N. H. J. M. Fixation of Elementary Nitrogen by Yeasts and Moulds. ALEXANDER KOSSOWICZ (Bied. Zentr. 1915 44 425-427 ; from Zeitsch. Garzmgsphysiol. 19 14,4,25-32).-The results of experiments with yeast and several moulds showed that very little nitrogen is necessary to obtain growth and that the combined nitrogen in the air was sufficient. It is therefore considered doubtful whether any yeasts and moulds have the po,wer of utilising elementary nitrogen.N. H. J. M. Effect of Some Tervalent and Quadrivalent Cations on Permeability. W. J. Y. OSTERHOUT (Bot. Gax. 1915 59 464-473).-It is shown that all the tervalent cations investigated. VOL. CVIII. i. 3 ti. 1082 ABSTRACTS OF CHEMICAL PAPERS. namely lairthanurn cerium yttrium iron a i d aluiniriiurr~ arid the quadrivalelit cation thorium can decrease permeability. N. H. J. M. Constant Changes in the Forms of Antagonism Curves. W. J. V. OSTERHOUT (Jahrb. zuiss. Botaiz. 1914 54 645-650).- Experiments are described in which sections of Laminnria were kept in solutions containing sodium chloride (100-0 mols.) and calcium chloride (0-100 mols.) for varying periods the antagon- istic action being measured by the electrical method.It is shown that the curves for the different' relations of sodium and calcium chlorides change in form as the experiment proceeds. After immersion for half an hour the resistance in pure sodium chloride fell from 100% to 85% whilst in the pure calcium chloride there was a rise from 100% to 138%. I n a solution containing 80 mols. of NaCl to 20 mols. of CaCl the resistance rose from 100% t o 126%. After one hour ,the resistance in pure sodium cliloritle fell to 60% whilst in pure calcium chloride it rose t o 140%. I n sodium chloride and calcium chloride (38 62) the resistance rose to 147%.After seventeen hours the resistance in pure sodium chloride' fell t o 10% (death point) and in pure calcium chloride t o 41% whilst the greatest resistance 119% was in sodium chloride and calcium chloride 80:20. Curves are also given for twenty- four forty-two and sixty-two hours. A t first sodium chloride increases the permeability of the tissues whilst calcium chloride has the opposite effect. Later calcium chloride increases permeability ; the process by which this is effected is however probably different from that with sodium chloride. N. H. J. M. Absorption of Ions by Living and Dead Roots. H. V. JOHNSON (Amer. J. Botmz. 1915 2 250-254).-When livo beet roots were placed in solutions of calcium chloride it was found that 41.31% of the calcium and 43.74% of the chlorine were re- moved from the solution.Dead roots of the same plant removed 44% of calcium and only 26.25% of the chlorine. Similar results were obtained with carrots. I n experiments with sweet maize the dead roots took up somewhat more calcium than chlorine. The presence of dead cells has therefore in some cases a marked effect on the results and it' is desirable t o avoid toxic solutions which may kill some of the cells while the experiment is going on. In Meurer's experiments (Jahrb. wiss. Bot. 1909 46 503) the outer layers of beet and carrots were cut away with a knife so that the solutions had t o penetrate a layer of dead cells before reaching the living tissue. p. H. J. M. The Organic Diet of Green Flowering Plants. TH.BOKORNY (Biochem. Zeitsch. 1915 71 321-364).-A large number of experi- ments are described in which comparisons are made between the growth of plants nurtured on the one hand with the ordinary in- organic media and on the other with the same media and the addition of organic substances. Beans cabbages Spirogyra,VEGETABLE PHYSIOLOGY AND AGRTCULTUI~E. i. 1083 CucuIiilJers a i d otlier plaiits were ciiiployetl a i d tlie orgaiiic sub- stances used were methyl alcohol glycerol and methylal. 111 many cases i t could be shown that the a,ltlitioiz of organic sub- stances increased the growth of the plant. s. B. s. Evidence for the General Distribution of Oxydases in Plants. G. B. REED (Bot. Gnx. 1915 59 407-409).-1t is shown that a l p as a class possess a ferment capable of activating the oxidation of a limited nuniber of compounds a i d that the ferment is specific in its action.Oxydases are of general occurrence among the aIgE and tlie resnlts together with observations on acid tissues indicate that the oxydases are universally distributed in living plants. N. H. J. M. The Localisation of Acids and Sugars in Fleshy Fruits. E. DEMOUSSY (Covzpt. nmd. 1916 161) 443-496).-Various species of fleshy fruit both fully and partly ripe have been subjected to gradually increasing pressure and t.he juices expressed fractionally collected the successive fractions being separately aiialysed for acidity and sugar content. Tliere was often marked difference in the acidity of the various fractions the last fraction in the case of plums being seven times more acid than the first.These varia- tions were also marked for apricots and grapes slight for peaches and non-existent in the case of strawberries melons and apples. With cherries and tomatoes the acidity diminished as the pressure increased. Of the sugars the reducing sugars varied in the same sense as the acidity but to a lesser extent whilst the sucrose con- tent varied in an opposite direction. Similar results were obtained by plasmolysis in a strongly liypertoiiic solution in place of pressure. The author considers that those cells which are less resistant to pressure or the walls of wliiclIt are more permeable anti in consequence empty first contain a iuice having a different chemical composition from those which em,pty last.There is local- isation but the direction of variation is not always the sairie for all fruits. These results are discussed from thL! point of view of the osmotic pressure in the cells and they afford an apparent explaim- tion of the increase in acidity of fruits on coQking tlie more acid cells not being broken in the process of eating in the raw ripe state. W. G. Influence of the Pyrrole Nucleus on the Formation of Chlorophyll. GINO POLLACCI and BERNARDO ODDO ( A t t i R. Accad. Li?zcei 1915 [v] 24 ii 37-39).-The authors have investigated the influence of magnesium pyrrole-2-ca~bozylate on the production of chlorophyll in Zea mazs (compare Oddo A. 1914 i 1176; Mameli this vol. i 631 633). The plant grows well in solutions containing 0.05% of this salt.The seeds were then germinated in two solutions containing calcium and potassium nitrates anirnoniuin sulphate and potassium dihydrogen plios- ( C4H4N*C02),Mg 2H20,. 3 t 2VEGETABLE PHYSIOLOGY AKD AGRICULTURE. i. 1089 taiiied in the body on the one hand and the amounts of phospliorus ingested the amounts of protein ingested or the body-weights of the lambs on the other. Variations in the amount of digestible protein consumed from 1.56 t o 3.19 lbs. per 1000 lbs. of live weight per day have no significant effect on the forms of phosphorus in the faeces the total phosphorus in the urine or the total phosphorus stored in the body expressed in percentage of the total phosphorus ingested. N. H. J. M. Antagonism between Anions as Affecting Barley Yields on a Clay-adobe Soil.CHARLES B. LIPMAN and W. F. GERICKE ( J . Ayieic. Research 19 15 4 201-3 18).-Pot experiments in which two crops of barley were grown with an interval of three months in soil t o which different amounts of sodium chloride sulphate and carbonate respectively were added ; also experiments on antagonism between sodium chloride and sulphate sodium chloride and carbonate sodium carbonate and sulphat'e and calcium sulphate and sodium sulphate. I n the control experiment the yield of the second crop was much greater than that of the first owing tol improvement in the soil from alternate wetting and drying and the t'horough drying during the period of rest. Small amounts (0.1%) of sodium chloride and of sodium sulphate acted as stimulants on the first crop and as poisons in the second crop whilst sodium carbonate was not toxic at all but showed stimulation in concentrations up t o 0.3% of the dry weight of the soil.Antagonism was shown between sodium chloride and sulphate and between sodium chloride and carbonate in the second crop but not in the first. I n the case of sodium carbonate and sulphate a slight antagonism was shown in the first crop. Both the first and the second crops showed a marked antagonism between sodium sulphate and calcium sulphate. The pots received insufficient water t o give drainage and practically the whole of the sodium chloride and sulphate could be recovered a t the end of the experiments. I n the case of sodium carbonate the highest amount recovered was 25%. N.I€. J. M. Assimilation of Colloidal Iron by Rice. P. L. GILE and J. 0. CARRERO (J. Agiaic. Research 1914 3 205-210).-Water culture experiments with rice in which colloidal iron and ferric chloride were compared as sourcw of iron. I n order tol prevent precipita- tion of the colloidal iron the nutrient solution was put into one flask and the iron into a second flask the plants being grown with part of their roots in each flask. The colloidal iron employed was the ordinary dialysed iron and cont'ained some chlorine. The plants supplied with colloidal iron assimilated a small amount of iron probably soluble iron which must be assumed to be present. The conclusion is drawn that colloidal iron was not assimilated and that if roots secrete acids a t all there was a t any rate no secretion in the unbalanced solution employed.I n theVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1085 extracts of Boletus edulis but more particularly those which yielded amino-acids. The dried' fungus has now been extracted with ether alcohol and then water according tot Reuter's method and the dried residue after these extractions has been examined for amino-glucosides by the method of Kotake and Sera. After hydrolysing with sulphuric acid however no glucosamine could be detected but using concentrated hydrochloric acid as the agent the same amount of the hydrochloride was isolated as Reuter obtained. The conclusion is drawn that the glucosamine in BoZetzcs c.d?ilis is pre-existent as a glucoprotein and not as a glucoside and that it is only under special conditions that glucosamine is a cleavage product.Thus a glucoprotein might be hydrolysed t o a sugar and an amide or an amino-sugar and an acid according to the scheme :CH*NH*CTO*CH + ZCH-OH + NH,*CO*CH or :CH*NH + CO,H*CH:. J. C. W. The Root Bark of Calotropis gigantea. ERNEST GEORGE HILL and ANNODA PRASAD SIRKAR (T. 1915 107 1437-1442).-By extracting large quantities of the root bark of Calotropis gigaiztect with boiling alcohol the authors have obtained an oily substance a white solid a substance somewhat resembling gutta-percha and a small quantity of a yellow bitter principle. The white solid was separated by fractional crystallisation from hot alcohol into a substance C'35H5603 nodular crystals m. p. 140° [u]:~ +128O (in ether) and a substance C43H7003 needle crystals m.p. 210° [a] +119O. The former substance on hydrolysis with potassium hydroxide yielded potassium isovalerate and an alcohol rndarol C30H4802 hexagonal plates m. p. 176O (acetate needles m. p. 195-196O) and wa3 therefore identified as nzudary2 isoualerate C,,H,70*C0,*C4HQ ; the alcohol was oxidised by a mlu- tion of chromic acid in acetic acid solution to mudarici acid C,,H4,O3H an amorphous solid m. p. 225O; the silver salt was a very pale green amorphous solid. The solid m. p. 210° on hydro- lysis gave isovaleric acid and alcundarol a monohydric primary alcohol CBH,,O*OH needles m. p. 215O (acetate needles m. p. 222O) and was thus identified as akundaryl isoualerate C,,H,,0*C0,*C4H ; when oxidised with chromic acid the alcohol was convertled into akundaric acid C,,H5Q0,H ; silver salt an amorphous pale green solid.These two alcohols and their isovalerates give colour reactions similar to those of cholesterol and p h ytosterol. The third product obtained by the extraction of the root-bark resembled gutta-percha only when warmed ; its composition approxi- mated to the formula C34H.&,N. No caoutchouc whatever could be detected in the plant. The yellow bitter principle gave the usual precipitation reactions for alkaloids but i t was not possible to isolate any alkaloid in a pure condition. These results are a t considerable variance with those obtained by Warden and Waddel (Pharm. J. 1885 165) who reported a ' I caoutchouc " as being present in the plant; the " madar-alban "i. 1086 hBSTRAC1'8 OF CHENICAL PAPERS.of these irivestigat ors is probably jdentical with the crntle iiiixture o f mudaryl and akundaryl isovalerates described above. D. F. T. Plant Chemistry. P. &. KE;E(:.zY (Chem. S c i u s 191 5 112 203-205) .-Analyses organic and inorganic of caiiary grass purple loosestrife heather and ragwort. Application of the Biochemical Method t o the Examination of %he Stoae-kernels of the Cherry Laurel. MAIN 8 R I m r A ( J . Phumz. Chinz. 1915 [vii] 12 249-252).- The stonw of the cliewy laurel fruit (Priin?is Lniimcerasrrs) yield about 55% of their weighb of kernels and the latter have a composition very similar t o t h a t of bitter almonds. The kernels contain 4.0% of amygdalin (about 19% more than is present in bitter almonds) and 3.0% of sucrose.The leaves of the cherry laurel contain a cyanogenetic glucositle a derivative of racemic phenylglycollic acid whilst that present in the kernels is a derivative of 6-phenylglycollic acid. Chrysanthemum cinerariefolium Trev. P. SIisurm ( B e r . Dczit. phamz. Ges. 1915 25 ~SS-;302).-l)il.cc.tions :tr~' given for tli(1 cultivation of this plant the dried powdered flowers of whicli are largely used as an insect powder. The insecticidal principle is shown to be present mainly in the discoid flowerets ant1 is not removed by clistillatioii with steam. The pasty mass ultirriately obtained in a yield of 0.067% by distilling the flowers with steam has a pronounced aromatic odour and gives indications of the presence of acids aldehydes ketones phenols esters and hydro- carbons b u t in almost' every instance the amount of substance isolated has been too small to admit of identification. One of the acids obtained is regarded as palmitic acid on the evidence of its m.p. 6 2 O ; a hydrocarbon C13H30 slender needles in. p. 54-5G0 has also been isolated. c . s. J ULIUS Zi<r,~,~eie (JIoolzcit.~h. 1915 36 611-632).-Analyses of different extracts (light petroleum ether alcohol and water) of Lircttrriirs sc'rohic./tlui itp< Hydn 'ZG m I'o7yp r I ( s From the alcoholic extract of Hydii urn f e r m y i i i errm there were obtained tlielephoric acid (Zopf) marinitol dextrose a i d two benzoic esters which when liydrolysed yielded resinotannols. IIydi!u- msinotniinol 7_1 enzotit o (A) C33H2Cds7 forms inicroscopic ( 1 rhombic) crystals sparingly soluble in hot alcohol ni.p. 272O (uncorr.) with decomposition. The rrcPtyl derivative m. p. 276O resembles the parent substance. If ?/dnorP8itiotniiiInT 7)eiizoafr ( B ) C,,,H,,07 or C,,H,,O dissolves readily in hot alcohol; m. p. 251-252O (decomp. uncorr.). The ncetyl derivative C30H7S07(CO*CH:3)2 or C,,B,,O,(CO*CH,) forms microscopic groups of fine needles and prisms in. p. 182* (uncorr.). A iiit/,o-compoui~d m. p. 237O (uncorr.) with decom- position was also prepared. N. H. J. &I. W. P. S. Chemistry of the Higher Fungi. f e r r N g i i i e u t i i H y d n 1 I ?ti. i?n 7) 7' i c n t 11 T I ? a 11 d ( I 11 pl a na t w s . N. H. J. M.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1087 The Carbohydrates of Fir-wood. ERIK HAGGIANLI (BzoclLem.Zeitsch. 191 5 70 416-425).-The carbohydrates yield 011 hydro- lysis chiefly xylose and mannose together with some Izevulose and galactose. Dextrose cannotl be detected. On hydrolysis of the wood with dilute acids a t higher temperatures the carbohydrates are first rendered soluble. Prolonged action brings about the solu- tion of the cellulose; in this case dextrose can be detected in the products of hydrolysis. S. B. S. The Enzymes of Cacao. HARVEY C. BRILL (PhiZiiipiize J . Sci. 19 15 10 123 -1 33) .-The pulp surrounding the cacao bean shows activity for the enzymes casease protease oxydase raffinase and invertase whilst the fresli beans gave reactions for casease raffinase and very strongly for oxydase. The fermented bean reacts for casease protease oxydase diastase raffinase and invertase and shows the presence of protease and invertase which are present in the pulp but not in fresh beans.The conclusion is drawn that the presence of these enzymes influences the character of the fermentation and that the tempera- ture must be controlled during fermlentation so that they may not be destroyed. N. H. J. M. H. KOXDO and TANAKA (J. Phurm. Chim. 1915 [vii’] 12 293-293 ; from Yaku- gnkuxcmhi 1915 J d . 1)-White ginseng yields 47.662% of aqueous extract which contains a substance oxidisable by nitric acid with formation of considerable quantities of mucic acid. The ethereal extract (0.683%) furnishes a volatile oil possessing the odour of ginseng and a non-volatile portion consisting of a mixture of a phytosterol having [a],+29.l0 and m.p. 1 3 3 O and an amorphous acid m. p. 150-156O. The methyl-alcoholic extract of ginseng (25.662%) contains sucrose a small quantity of a nitro- genous substance and a glucoside o f saponin character which forms a white hygroscopic powder of puiigent taste melting about 220O. It reduces Fehling’s solution only after hydrolysis when appar- ently a mixture of dextrose and pentose together with a sapogenin is produced. The latter is likewise a mixture of several substances which have not yet been separated. Chemical Composition of Korean Ginseng. G. F. M. Availability of the Nitrogen in Pacific Coast Kelps. GUY R. ~,TEWART (J. Agric. Research 1915 4 21-37).-When mixed with soil the nitrogen of Nereocystis lzcetlccatia is readily converted into ammonia whilst that of Yelagophyczis porrn is less readily changed.ilfcccrocystis pyrifera the only one of the three which is com- mercially important in California changep very slowly in the soil especially when i t has been dried. Whilst addition of moderate amounts of Nereocystis to fresli soil has not much effect on the ammonificatiori or nitrification of readily available organic matter such as dried blood the presence of Mn c ro c y R t is re t a r d s am m on i fi cation and es p e c ia 1 1 y nit r i fi c at i o n for a time after which they become normal.i. 1088 ABSTRACTS OF CHEMICAL PAPERS. I n practice i t is not probable that kelp or the salts whicli it contains would interfere with ammonification o r nitrification. N. H. J. M. Organic Constituents of Pacific Coast Kelps.11. R. HOAGLAND ( J . Agric. R C S C ~ ~ C ~ Z 191 5 4 39-58).-Of tlic h t a l nitrogen of‘ the kelps examined from one-third to one-fifth is soluble ir water and about the same proportion was found hy Stutzer’s method t o be in the form of non-protein nitrogen. As regards the iodine only a small proportion seems to be present i i i organic forms. The most important of the carbohydrate constituents of kelp is ‘(algin,” a very complex resistant compound or mixture of com- pounds of the pentosan type possibly containing cellulose in the complex. The total sulphur whicli is higher in the leaves than in the stems varied from 0.45% in the stems of Nereocystis luetkenntl; t o 8.16% in Iridaea. The relative amount of inorganic and organic sulphur varies considerably in different samples.N. H. J. M. Carbohydrates and Enzymes of the Soja Bean. J. P. Srriimx and E. M. BAILEY ( J . Iqzd. Eng. Chem. 1915 7 853-8:SS).-Tlie nitrogen-free extract of soja beans (grown in Ohio) contains the following substances galactan (includinv 0.24% from raffinose) 4.86% ; pentosan 4.94% ; organic acids (as citric acid) 1.44% ; invert-sugar 0.07% ; sucrose 3.31% ; raffinose 1.13% ; starch 0.50% ; cellulose 3.29% ; hemicelluloses 0.04% ; dextrin 3.14% ; waxes tannins etc. (by difference) 8.60%. I n addition t o urease amylase and a glucoside-splitting enzyme soja beans contain a protease of the peptoclastic type a peroxydase and a lipase. Sucrase and a peptonising protease do not appear to be present. W. P. S. Phosphorus Metabolism of LambsFed on a Ration of Lucerne Maize and Linseed Meal.E. L. Ross M. H. KEITH and H. R. GRINDLEY ( J . Agric. Besearch 191 5 4 459-473).-The percentages of the different forms of phosphorus and the relations of phos- phorus to protein in lucerne maize and linseed meal show marked differences. I n lucerne a large proportion of the phosphorus is in inorganic form soluble in acid; in maize i t is equally divided between acid-soluble which is largely organic and acid-insoluble ; and in linseed meal the phosphorus is largely insoluble in acid whilst the soluble portion is about equally divided between inorganic and organic forms With 8 ration of the three foods lambs excrete in the urine only 0*2-0.5% of the total phosphorus. The fmes contain relatively small percentages of acid-insoluble phosphorus and relatively high percentages of soluble inorganic phosphorus.Indications were obtained that the amount of phosphorus re- quired for the normal growth and fattening of lambs does not exceed 3 grams per day per 100 lbs. live weight. No evidence was obtained of correlation between the amounts of phosphorus re-VEGETABLE PHYSIOLOGY AKD AGRICULTURE. i. 1089 taiiied in the body on the one hand and the amounts of phospliorus ingested the amounts of protein ingested or the body-weights of the lambs on the other. Variations in the amount of digestible protein consumed from 1.56 t o 3.19 lbs. per 1000 lbs. of live weight per day have no significant effect on the forms of phosphorus in the faeces the total phosphorus in the urine or the total phosphorus stored in the body expressed in percentage of the total phosphorus ingested.N. H. J. M. Antagonism between Anions as Affecting Barley Yields on a Clay-adobe Soil. CHARLES B. LIPMAN and W. F. GERICKE ( J . Ayieic. Research 19 15 4 201-3 18).-Pot experiments in which two crops of barley were grown with an interval of three months in soil t o which different amounts of sodium chloride sulphate and carbonate respectively were added ; also experiments on antagonism between sodium chloride and sulphate sodium chloride and carbonate sodium carbonate and sulphat'e and calcium sulphate and sodium sulphate. I n the control experiment the yield of the second crop was much greater than that of the first owing tol improvement in the soil from alternate wetting and drying and the t'horough drying during the period of rest.Small amounts (0.1%) of sodium chloride and of sodium sulphate acted as stimulants on the first crop and as poisons in the second crop whilst sodium carbonate was not toxic at all but showed stimulation in concentrations up t o 0.3% of the dry weight of the soil. Antagonism was shown between sodium chloride and sulphate and between sodium chloride and carbonate in the second crop but not in the first. I n the case of sodium carbonate and sulphate a slight antagonism was shown in the first crop. Both the first and the second crops showed a marked antagonism between sodium sulphate and calcium sulphate. The pots received insufficient water t o give drainage and practically the whole of the sodium chloride and sulphate could be recovered a t the end of the experiments.I n the case of sodium carbonate the highest amount recovered was 25%. N. I€. J. M. Assimilation of Colloidal Iron by Rice. P. L. GILE and J. 0. CARRERO (J. Agiaic. Research 1914 3 205-210).-Water culture experiments with rice in which colloidal iron and ferric chloride were compared as sourcw of iron. I n order tol prevent precipita- tion of the colloidal iron the nutrient solution was put into one flask and the iron into a second flask the plants being grown with part of their roots in each flask. The colloidal iron employed was the ordinary dialysed iron and cont'ained some chlorine. The plants supplied with colloidal iron assimilated a small amount of iron probably soluble iron which must be assumed to be present.The conclusion is drawn that colloidal iron was not assimilated and that if roots secrete acids a t all there was a t any rate no secretion in the unbalanced solution employed. I n thei. 1090 ABSTRACTS OF CHEMICAL PAPERS. iiasks coiitainilig iron aloiie tile root develoyrr~e~~l was very ~ J O U ~ but better with colloidal iron than with ferric chloride which produced less growth than distilled water. The toxicity of dis- tilled water and of ferric chloride cannot be overcome by supplying other roots of the same plant with a balanced solution. The question is of importance because upland rice grown on more or less calcareous soils is affected with chlorosis due at least in part t o diminished assimilation of iron. N.I€. J. M. The Character of the Water-soluble Nitrogen of Some Common Feeding StuffB. E. B. HART and W. H. J~EN'I'LEY ( J . Biol. ClwZ. 1915 22 477-483).-!L'lie '' amitle " nitrogen of feediiig- stuffs is largely composed of free amino-acids arid peptide linkings. I n most cases this nitrogen constitutes 50 -70% of the waber-soluble nitrogen. The acid amide nitrogen is relatively sinall usually under 10%; corn stover is an exception the figure there being 40%. The ammonia nitrogen rarely exceeds 574 anti is sometimes absent. The substances investigated include clover peas corn barley rape grasses and cabbage. Soil Gases. J. WALTER LEATHER (J. Agric. Ski. 1915 7 240-241).-From the results of experiments with undisturbed and ordinary samples of Pusa soil which were subjectled t o the treat- ment described by Russell arid Appleyard (iliid.s) the con- clusion is drawn that the gas obt<ained on successive days by Russell and Appleyard was formed and liberated gradually pre- sumably by bacterial action. W. D. 11. N. H. J. 31. [Soil Gases.] A. APPLEYARD and E. J . ~ ' L U ~ S E L I ( J . Ay7-i~. Sci. 1915 7 242).-In reply to Leather (preceding abstract) it is pointed out that the successive extractions were not made on succlessive days and that in some cases there were practically 110 intervals between them. The conclusion previously drawn that the dissolved gas in the surface films of water consists mainly of carbon dioxide and n little nitrogen is supported by tlie results obtained with tlie l'usa soil which also yielded small amounts of gas poor in oxygen.N. 11. J. &I. Changes in the Soil brought about by Heating. (MISS) A. WILSON (Sci. Proc.Boy. Dubl. Soc. 1915 [N. S.] 14,513-520).-Soi1s which were heated at4 temperatures from GOo to 150° showed a regular depression in the freezing points of its aqueous extracts which increased from 0.06O in the case of soil heat'ed a t 60° t o 0'19O in the soil heated a t 1 5 0 O ; coincidently the electrical con- ductivities of the extracts showed an increase from 36.0 x 10-5 t o 198 x 10-5. It is therefore evident. that the amount' of soluble matter is increased by heating. Whilst extracts of the original soil were practically colourless the ext'racts of the heated soil varied from a faint brownish-yellow colour (COO) to a very deep brown (150O).Soils which were heatedVEGETABLE PHYSIOLOGY AND AGRICULTURE i. 1091 a t tlie higlier temperatures absorbed iiiore water tharl u~illeated soils. Experiments in which the soil extracts were prepared by stirring the soils with water and filtering instead of by percolation gave similar result6. The conclusion is drawn that the increased fertility of heated soils may be partly due t o the increase in soluble constituents and t o the change in soil texture resulting in an increased power of retaining water. N. H. J. M. Effect of Alkali Salts in Soils on the Germination aad Growth of Crops. FRANK S. HARRIS ( J . Agl-ic. Beseul-ch 1915 5 1-53)- The effect of alkali salts varies with different soils and different plants. I n sand only about' half as much alkali is required to inhibit growth as in loam whilst the power of plants to resist the action of alkali salts diminishes in the following order barley oats wheat lucerne beet maize and Canada field peas.The toxicity of alkali salts in soils is determined by the acid radicle chlorides being the most toxic. Of the bases sodium is the most toxic. The toxicity of soluble salts in the soil was found to be in the following order sodium chloride calcium chloride potassium chloride sodium nitrate magnesium chloride potassium nitrate magnesium nitrate sodium carbonate potassium carbonate sodium sulphate potassium sulphate and magnesium sulphate. The following approximate amounts of soluble salts will prob- ably indicate the necessity of reclamation to produce ordinary crops.I n loam chlorides 0.3 nitrates 0.4 carbonates 0.5 and sulphat,es more than 176. In coarse sand the amounts should not exceed about two-thirds of the numbers given for loam. The antagonistic effects of coinbined salts is less in soil than in wa t er-cultures N. H. J. M. Amino-acid Nitrogen of Soil and the Chemical Groups of Amino-acids in the Hydrolysed Soil and their Humic Acids. Ib. 8. POTTER and 1%. 8. ~ ~ T ) I F R (J. Anzer. Chenz. soc. 1915 37 2219-2227).-An account is given of the examination of several samples of soil. I n each case the soil was first extracted with l y i hydrochloric acid to render the humus more soluble and the amount of nitrogeii extracted by the acid estimated. The soil was hydrolysed with 22% hydrochloric acid and the mixture was filt'ered and the residue washed until free from chlorides.A portion of the combined filtrate and washings was employed for the estimat'ion of total nitrogen whilst other portions were ex- amined by van Slyke's method (A. 1910 ii 751) for the determina- tion of the chemical groups of amino-acids. The humic acids were removed from the acid-extracted soil by means of 17; sodium hydroxide ; the alkaline solution was neutralised with sulphuric acid and then acidified with amtic acid. The mixture was boiled for fifteen minutes and the precipitated humic acids were collected and hydrolysed with 22% hydrochloric acid. The product ofi 1092 ABSTRACTS OF CHEMICAL PAPERS. hydrolysis was examined by vaii Slyke's method arid the total nitrogen was also estimated. The results show that the amounts of nitrogen extracted by the strong acid were fairly constant whilst those extracted by the dilute alkali varied widely.The quantities of humic acid in the various soils were quite diffe'rent. The amount of amide nitrogen in the soils was in all cases very high in comparison with the basic and non-basic nitrogen. The quantJty of huinic nitrogen extracted from the soil by dilute alkali was very large when compared with the amounts in proteins. The relative proportions of the various groups in the extract obtained with the strong acid and in the humic acids were very similar and it is evident that dilute alkali does not extract any typical class of organic compounds from the soil. It is considered that the estimation of the amount of humus is of little value in soil analysis.The quantity of amino-acid and peptide nitrogen existing in a soil is very small in cornparison with the amounts of amino-acids produced by hydrolysis. E. G. A Nitrogenous Soil Constituent Tetracsrbonimide. EDWARD C. SHOREY and E. H. WALTERS ( J . Agric. 12eseawh 1914 3 175-178).-1n 1913 a compound having the properties of tetra- carbonimide was isolated from several soils ( J . Wash. Acad. Sci. 1913 [v] 3 260). The substance has now been obtained in a pure state and compared with tetracarbonimide from uric acid. Tetracarbo'nimide was found in soils from Florida Virginia Maryland and Washington D.C. From 18 kilos. of the latter soil 30 nig. of the pure compound were obtained and as the loss in purification is a t least SO% it8 is estimated that the upper 12 inches of the soil contains about 8 kilos. of tetracarbonimide per hectare. As uric acid has not been found in soils or plants it seems prob- able that the tetracarbonimide in soils is derived from purine bases. Xanthino hypoxanthine and adenine all occur in soils whilst guanine has been found in a heated soil. All four bases have been found in plants. N. El. J. M. Presence of Proteoses and Peptones in Soils. E. H. WALTERS (J. Ind. Eng. Chenz. 1915 7 860-863).-It is shown that soils contain a mixture of proteoses and peptones resulting from the hydrolysis of proteins and that they either exist and persist in the soil as such f o r a considerable period or the original protein is hydrolysed only very slowly in the soil. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9150801081

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

British Patents 1912. 1913. 7488 A i 33 8137 A. i 33 9969 A. i 32 12402 A. i 4 14246 A . i 2 14247 A. i 26 15049 A. i 1 15481 A. i 27 15482 A. i 28 16828 A. i 9 17003 A. i 26 17123 A. i 11 17780 A. i 22 20107 A. 1 12 20736 A . i 13 21027 A. i 30 21211 A ii 16 22694 A i 11 22854 A. i 16 22980 A. i 18 23732 A. i 17 24932 A. i 13 25971 A i 2 26825 A . i 3 26826 A. i 3 27830 A. ii 16 29224 A. i 31 29546 A. i 32 30068 A. i 9 30072 A. i 28 1247 A. i 33 1869 A. i 6 2314 A i 34 2787 A. i 10 3053 A. i 13 3312 A . i 17 5408 A. i 6 8690 A. i 19 8917 A. i 20 9472 A. i 14 10377 A. i 3 11836 A. i 27 12061 A. i 16 14954 A i 1065 17234 A. i 9 1914. German Patents(D. R. -P.). 254744 A. i 1065 267544 A . i 20 267596 A i 26 268099 A . i 13 268486 A. i 15 268982 A. i 13 268984 A i 21 269337 A.i 28 269428 A i 29 269129 A. i 26 269692 A. ii 4 269749 A . i 697 270789 A. i 21 270790 A. i 21 251271 A. i 729 271681 A . i 20 271745 A. i 697 271790 A. i 18 271821 A. i 29 271892 A. i 32 271893 A. i 33 271894 A. i 33 272289 A. i 34 272291 A i 24 272292 A. i 29 272301 A. i 18 272613 A. i 21 272614 A i 21 272690 A i 32 273073 A i 8 273220 A. i 1 273221 A. i 15 273320 A. i 8 273321 A. i 10 273323 A. i 7 273341 A. i 18 273444 A. i 28 273667 A ii 17 273809 A. i 21 273850 A. i 23 274046 A i 15 274047 A. i 17 274349 A. i 16 274350 A. i 11 274782 A. i 1 274783 A i 22 274784 A. i 22 INDEX TO PATENTS. 15058 A. i 22 17501 A. i 395 17725 A. i 1 0 i 3 23190 A. i 1049 24117 A. i 1052 8058 A. i 1056 8109 A i 1065 417803 A. i 655 451927 A. i 1 8 452537 A. i 19 458949 A. i 65 459885 A.i 11 460432 A. i 22 460553 A. i 5 460971 A. i 3 461094 A. i 22 461539 A . i 4 461540 A. i 4 462276 A. i 32 462438 A i 14 462439 A. i 14 464478 A. i 17 464645 A i 9 465965 A. i 3 466236 A. i 16 466619 A. i 7 466804 A. i 2 467085 A. i 13 467515 A. i 2 467778 A. i 2 468363 A. i 13 468920 A. i 6 468949 A. i 16 468963 A. i 3 469040 A. i 13 469497 A. i 56 469741 A i 63 471933 A. i 396 472233 A. i 657 473158 A. i 645 473518 A. i 793 473697 A. i 765 473704 A. i 855 473705 A. i 855 474056 A i 855 474246 A. i 773 1915. French Patents. 1135ii. 1136 German Patents(D. R. - P.). 275038 A. i 681 275092 A. i 7 275093 A. i 16 275200 A. i 8 275216 A. i 728 275248 A. i 10 275299 A. i 21 275378 A. ii 17 275499 A. ii 553 275442 A. i 8 275443 A. i 1 7 275517 A. i 18 275518 A. ii 540 275794 A.i 702 275795 A. i 720 275833 A. i 28 275847 A. i 8 275897 A. i 1 7 275932 A. i 34 275963 A . i 27 275974 A. i 6. 275975 A. i 28 276072 A. i 18 276273 A. i 14 276541 A. i 29 276667 A. i 26 276809 A. i 61 276810 A. i 62 277022 A i 11 277188 A. i 73 277392 A. i 367 277395 A. i 464 277438 A i 161 277439 A i 419 277466 A. i 122 277467 A i 145 277659 A. i 401 277901 A. i 368 278107 A. i 160 278111 A. i 160 278777 A. i 368 278778 A. i 682 278884 A. i 167 278885 A. i 121 279011 A. ii 552 INDEX TO PATENTS. 279193 A. i 462 279194 A. i 709 279195 A. i 173 279199 A. i 129 279313 A. i 692 279549 A. i 409 279864 A. i 707 279865 A. i 681 279866 A. i 419 279867 A. i 407 279957 A . i 732 279958 A. i 682 279999 A. i 709 280026 A. i 366 280092 A. i 407 280190 A .i 458 280225 A. i 677 280502 A . i 710 280739 A. i 658 280970 A i 720 280971 A. i 714 280972 A . i 711 280973 A. i 719 281007 A i 720 281008 A. i 722 281009 A. i 731 281044 A i 645 281045 A i 654 281050 A. i 722 281051 A. i 653 281097 A. i 720 281134 A. ii 557 281136 A. i 720 281175 A. i 674 281176 A. i 674 281603 A. i 720 281902 A. i 768 281911 A. i 794 281912 A. i 839 282002 A. i 857 282133 A. i 813 282134 A. i 768 282264 A. i 845 282265 A i 816 282266 A. i 769 282374 A. i 842 282375 A. i 842 282412 A . i 815 282490 A. i 839 282492 A. i 796 282568 A. i 796 282818 A. i 794 282991 A. i 813 283105 A. i 784 283306 A. i 808 Swiss Patent. 6.5545 A. i 721 United States Patents. 1081079 A. i 32 1054581 A. i 2 1086294 A. i 8 1094296 A i 11 1098022 A. i 27 1098938 A.i 8 1101111 A. i 17 1101754 A. i 7 1103383 A. i 20 1103600 A ii 3 1104611 A. i 19 1104943 A. i 20 1106290 A i 1 1107019 A. i 5 1111821 A. i 33 1114734 A. i 53 1114735 A i 53 1119279 A. i 728 1119546 A. i 63 1122201 A. i 681 1123390 A. i 164 1125081 A. i 815 1133832 A. i 681 1138936 A. i 837 1138937 A. i 837 1140716 A. i 816 1149712 A. i 1050 1150251 A. i 1050 1150252 A . i 1051 1150253 A. i 1051 1150580 4.) i 1051 1151928 A. i 1050 1151929 A. i 1050

ISSN:0368-1769    

DOI:10.1039/CA9150806135

出版商:RSC    

年代:1915

数据来源: RSC

摘要:

ERRATA. VOL. CVI (ABSTR. 1914). (INDEX.) Page Col. Line ii 911 ii. 18 for ‘(Hartley Harold Brewer,” read “Hartley Harold.” Page i 190 i 193 i 193 i 346 i 472 i 520 i 525 i 562 i 634 i 646 i 674 i 692 i 708 i 714 i 732 i ’739 i 743 i 749 i 757 i 760 ii 251 ii 258 ii 280 ii 357 ii 357 ii 357 ii 452 VOL. CVIII (ABSTR. 1915). Line 11 for “ KEETOM ” read (‘ KEETON.” 6 “ some ” rend “ sour.” S* ‘‘360’) read “361.” 3” ‘‘ BKONNENFENNER” read ‘‘ BRONFENDILENNER.” 13* “ RATELLI ’) read ‘( BATTELLI.” 11* “ dibromo-” read (‘ tribromo-.” 18 “ Magnesium ethyl iodide ” read magnesium methyl iodide.” ly) “ a-bromoisobutyl ” read “ a-bromoisobutyryl. ” 11 }I “ gynocardinic ’’ read “ gynocardic. ” 2i ] ‘‘ gymcardinate ” read “ gynoeardate. ” 15*after “1267 ” insert “ ; from Oster. Chenz.Zcit. 1914 17 323-333.” 21* “473 ’) t y e r t “; from Philippine J. Xci. 1913 LA] 8 2* ‘( 1456 )) insert ‘‘ ; from Sitzzcngsber. Heidelberg. Akad. W~SS. Math. haturw. Klasse. [A] 1914 18.’’ “ 1165 ’’ insert ‘‘ ; from Sitmngsb;:. Muth. Nnturwiss. Klasse K. Akad. Wiss. Wicn 1914 reprint. ‘‘ 1447 ” insert “ ; from Apoth. Zeit. 1914 29 887-890.” “1280” insert “; from Zentr. Physiol. 1914 28 617-619.” ‘( Griebold ” read (‘ Griebel’s.” 3* 5* “ hydroxygynocardinic ’’ read ‘‘ hydroxygynocardic. ” 399-426. 19* 20 15” 16 (‘ 1074” insert ( ( ; from Arch. Anat. Physiol. Physiol. Abt. 19 ‘( 1279” insyt ‘( ; from Zeitsch. exper. Path. Ther. 1914 12 1170 insert ‘( ; from U.S. Dept. Agric. B d . 270.” 17* “1115 ’’ insert ‘‘ ; from Zeitsch. ges. Brauwcsen 1914 37 1914 585-594.” 16 4 8 4 ~ 4 9 2 .430-432 437-440.” 7* f o r ‘‘ HENDEN ’:,read ( ( HINDEN.” 20 ((maximum read “ minimum.” 5 “ not denied read ‘( denied.” 14 ( ( ?+-urtzite” read “Hauerite.” 21 29 ‘‘ Orahnite ” ‘‘ Gahnite.” “ V. J. VERNADSKI ” read “ V. I. VERNADSKI.” 8* ‘‘ Biol. Zentr. read “ Bied. Zentr. ’’ * From bottom. 1137ERRATA (continued). Page Line ii 497 ii 554 2 “1220” insert ( ( ; fsom Farb. Zeit. 1914 25 343-345 ii 557 17* “1421 ” insert ‘( ; from J. Gasbeleucht. 1914 57 941-943.’,’ ii 559 1 5 “1379” insert ‘ I ; from J. Gasbeleucht. 1914 57 733-740. ii 559 5* (‘1380” insert ‘( ; from J. Gasbeleucht. 1914 57 757-765 ii 570 11* “1082” insert ‘( ; from Atti R. Accad. s’ci. Napoli [xvi] ii 573 13 for ‘‘ an olive ” read “ a blue.” ii 574 15* ,) “ MISSON SERAINU’) read “ ISSON SON.'^ ii 574 13” ,) ‘( benzene ’’ read ‘‘ light petroleum.” ii 651 14* ‘( sodium ’’ read 66 hydrogen.” ii 651 4*after(‘ sulphate is ’’ insert ‘‘ ileutralised and.” ii 758 8* for ‘‘ molecular ” read <( unimolecular.” ii 828 4 “ VII ” read “ 111.” 1 2 after (‘ 1046 ” insert (‘ ; from Photo. Iztt,ndschau 1914 Heft. 3.” 361-382.” 781-787 805-810.” 2a No. 2.” * From bottom. 11 38

ISSN:0368-1769    

DOI:10.1039/CA9150806137

出版商:RSC    

年代:1915

数据来源: RSC