摘要:

i . 54 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. The Formation of Ferments. IV. MARTIN JACOBY (Eiochenz. Zeitsch. 1917 83 74-80. Compare A. 1917 i 528).-In the last communication it was shown that urease is produced by bacteria which are grown 011 a medium containing inorganic salts and glycerol ammonium lactate sodium aspartate and leucine of which the last-named is indispensable. Further investigations 11 ave been undertaken to ascertain whether all the above-mentioned organic substances are indispensable for production of the ferment. On leucine alone a certain amount of ferment is produced but more satisfactory amounts are obtained when the medium con- tained in addition to leucine glycerol and sodium aspartate or ammonium lactate and sodium aspartate.When sodium lactate alone is employed even after transference of the bacteria to a medium containing leucine scarcely any urease is produced. It is to be recalled that bacteria will grow on a medium containing no leucine but produce no urease. On transference to a medium con- taining leucine however the ferment is formed. I n the experi- ments described in this paper the bacteria were first grown on media containing various mixtures of the abovenamed organic substances (sometimes with the additlion of leucine) and then after the second generation of growth transferred to a medium contain- ing this amino-acid. I n the control experiments where this acid was not present no urease was produced. S. B. S. The Extraction of Invertase and Maltare from the Permanent Yeast Preparations made by the Acetone Method.EDUARD BUCHNER and FERDINAND REISCH LE (Biochenz. Zeitsch. 1917 83 1-5) .-The preparations were washed and then allowed to act on sugars. No evolution of carbon dioxide took place unless boiled juice were added (to replace the co-enzyme which had been washed out). More carbon dioxide was evolved when dextrose and maltose were added than in the case when the same washed preparation was treated with sucrose and these experiments indicate that the invertase and maltase can be removed by washing. S. B. S. Formation of Hexosephosphate during Alcoholic Fermen- tation. HANS EULER OLOF SVANBERG GRETA HALLBERG and KARIN BRANDTING (Zeitsch. pkysiol. Chenz. 1917 100 203-208). -On estimating at intervals of fifteen minutes the amount of inorganic phosphate present in a fermenting mixture of dextrose yeast and disodium hydrogen phosphate it is found that during the first half of the fermentation the phosphate remains almost unchanged whilst subsequently rapid combination with dext,roseVEGETABLE PHYSIOLOGY AND AGRICULTURE. i.55 occurs. The acidity of the mixt,ure remains practically constaut throughout the whole period of fermentation It is suggested that' during the first half of the time of reaction a catalyst is formed which accelerates the combination of dextrose and phosphate during the later st'ages of fermentation. H. TV. B. Action of Sodium Phosphate on the Lactic Acid Fermen- tation. HANS EULER and OLOF SVANBERG (Zeitsch. physiol. Chew. 1917 100 148-158).-The lactic acid fermentatip of dextrose by the agency of Bacterium cosei E.is accelerated by sodium di- hydrogen phosphate and inhibited by trisodium phosphate but a conversion of the inorganic phosphate into hexosephosphate such as occurs during the fermentation of dextrose by yeast cannot he detected. The intermediate formation of lactic acid during the alcoholic fermentation of dextrose occurs therefore if i t occurs at all by a process which is probably different from thatl which is effected by the lactic acid bacilli. H. W. B. Amygdalin as Nutriment for Fusarium. H. J. WATERMAN (Yroc. K . Akad. Wetensch. Amsterdam 1917 20 185-188).- Rmygdalin is . assimilated by Pzcsa&m young mycelium being formed but the addition of emulsiii to the amygdalin solutioii entirely prevents growth. Amygdalin is as satisfactory a nutrient as dextrose in respect to t,he dry weight of mould obtained.W. G . The Chemistry of the Higher Fungi. XII. Lenzites sepiaria Sw. Panus stypticus BULL. and Exidia auricula Judae FR. Coni- pare A. 1915 i 1086).-Extraction of Lenzites sepiariu Sw. collected from pine trunks with light petroleum yielded a yellowish- brown fatty oil containing an ergosterol ; on extraction with ether an ergosterol was obbained together with a yellowish-red resin soluble in aqueous alkali hydroxide. The alcoholic extract was separated into constituents soluble in water these including mannitol and mycose [trehalose] with small quantities of choline and dextrose and a fraction insoluble in water containing brown nitrogen-free amorphous substances.The aqueous extract of the fungus contained a carbohydrate which did not' reduce Fehling's solution together with a trace of quinoline and mineral substances. Hydrolysis of the leathery residue insoluble in the above solvents gave rise to dextrose as the main product together with mannose and glucosamine ; indications of pentosans were also observed. Panus stypticus Bull. gave similar results except that two carbohydrates were observed in the aqueous extract which agreed in properties with Boudier's viscosin and mycet ide (these substances have never yet been obtained in a state of purity) and that glucosamine was the only definite substance isolated from the resi- dual insoluble tissue. With Exidin aiwiczila Judne Fr. similar observations were JULIUS ZELLNER (Monatsh.1 9 17 38 3 19-380.i. 56 ABSTRACTS OF CHEMICAL PAPERS. niade but 110 iiiaiiiiose or inycetide was detected in the alcoholic and aqueous extracts respectively ; the viscous constituent in the aqueous extract' on hydrolysis yielded mannose with a little dextrose and on oxidation with nitric acid produced only oxalic acid; it is therefore probable that' the mucous substance is a maniian. D. F. T. The Relationship which Exists in Plant Tissues between the Acid and Basic Elements. G. ANDRB (Bzdl. SOC. chiin. 1917 [iv] 21 258-271).-A more detailed account of work already published (compare A. 1912 ii 675 803; 1913 i 233 688 946). W. G. The Transient Red Colour given by certain Leaves when Treated with Nitric Acid in the Xanthoproteic Test.OTTO GERTZ (Biochem. Zeitsch. 1917 83 129-132).-The author is in agreement with Lakon (A. 1917 i 504) that the colour in question can be due to anthocyanin. I n certain plants however the colour is specific for nitric acid and is not given by other acids and in these cases it cannot be due to anthocyanin. The author ascribes i t t o a nitroso-derivative of some substance as yet unidentified. The nitroso-derivative is formed by reduction and on fnrther reduction i t becomes colourless. S. B. S. A New Plant containing Hydrogen Cyanide Isopyrum fumarioides L. MARCEL MIRANDE (Con@. rmd. 1917 165 71 7-718).-Zsopyrum fumarioides contains a cyanogenetic glucoside and an enzyme capable of hydrolysing its. The plant when in full flower and nearly in fruit yields 0.249 gram of hydrogen cyanide from 100 grams of fresh plant material.The green fruits contain 0.115% of hydrogen cyanide. The younger the plant the greater is the content of hydrogen cyanide. Vegetable and Animal Fats and Waxes. I. Fat from Rice Bran. ALBERT R. WEINHAGEN (Zeitsclz. plzysiol. Chem. 191 7 100 159-166) .-Rice bran contains 10.94% of fatty substances soluble in ether. They can be separated into a liquid oil (73%) and a solid fat (27%). The oil contains 5.3% of phytosterol and 91% of fatty acids of which 59% is oleic and 31.8% palmitic acid. The solid portion consists of 4.7% of phytosterol and 90.6% of fatty acid which is practically pure palmitic acid. A substance is also present which can be separated from the phytosterol by fractional crystallisation from alcohol in which it is only slightly soluble. Itl is found to be a satarated hydrocarbon C27H48 m. p. 79.5-80-5. Rice bran does not contain any glycerol or any phosphorus com- pounds soluble in ether and only a trace of alcohol-soluble phos- pholipoids. H. W. B. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9181400054

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

i. 57 Organic Chemistry. Hydrolysis of Metals. HOWARD Organic Haloids and the Corrosion of WATERS DOUGHTY ( J . Amer. Chenz. Soc. 1917 39 2685-2692).-A qualitative study of the subject. The hydrolysis of carbon tetrachloride by water at ordinary tempera- tures is negligible but it is greatly accelerated by the presence of iron or copper the acceleration being accompanied by corrosion of the metal which is very well niarked with iron but very slight with copper. This corrosion is very greatly increased by the presence of ammonia but does not take place in the absence of water or carbon tetrachloride. The products are ferric hydroxide and cupric ammonium chloride. Certain other organic haloids behave in a manner similar t o carbon tetrachloride towards copper the action being most pro- nounced with compounds containing a trichloromethyl group.Monohalogen derivatives have practically no action on copper in the presence of water and ammonia and the presence of two halogen atoms gives no increased effect unless they are attached t o the same carbon atom. No effect is observed in the case of halogen substituted in the benzene nucleus. Tetrachloroethylene may be readily detected iii that when allowed to remain in contact with water ammonia and copper the aqueous layer develops a rich red colour. W. G. The Relative Stability of Halogen-substituted Aliphatic Acids in Aqueous Solution. W. A. DRUSHEL and G. S. SIMPSON ( J . Amer. Chem. SOC. 1917 39 2453-2460).-The authors are engaged on a study of the kinetics of the action of water on halogeno-aliphatic acids and have so far investigated the sodium salts of the halogeno-acetic acids.Decinormal solutions of the salts were heated in sealed tubes atl constant temperatures of 70-90° and after different intervals the free acid and also the sodium haloid were titrated or in the case of the trichloroacetate the sodium hydrogen carbonate formed according to the equation CC1,*C02Na + H20 = CHC1 + NaHCO,. With the exception of the case of the trihalogeno-acids the action of water is a true hydroxylation. It is probable that two reactions take place consecutively in the case of the dihalogeno-compounds thus CHCl,*CO,Na + H,O = CHO=CO,H + NaCl + HC1 and CHCl,*CO,Na + HC1= CHCl,*CO,H + NaC1. As the latter reac- tion is pract'ically instantaneous the hydroxylation of the dichloro- acetate should appear as a unimolecular reaction but the observed values do not agree with either a uni- or bi-molecular type.There is found to be more sodium chloride produced than free acid. The VOL. CXIV. i. ei. 58 ABS'l'RAC'kS OE' GHfiMICAL PAPI4RS. anoimly will be discussed in a later paper (compare also Johansseii Senter and others). The relative stability of these sodium salts in O*lN-solutions at 70° is of the order trichloroacetate 1 ; bromoacetate 1.2; iodo- acetate 3.6 ; chloroacetate 26 ; dichloroacetate 120. It is remark- able that the iodoacetate is more stable than the bromoacetate and that the dichloroacetate is so very stable compared with the mono- and tri-chloroacetates. J. C. W. a- and pcinenic Acids. H. RUPE and A.BLECHSCHMIDT ( J . pr. Chem. 1917 [ii] 96 59-64).-a-Cinenic acid when heated with dilute sulphuric acid is converted into an isomeric liquid P-cinenic acid (Rupe and Altenburg A. 1909 i 7). The isomeric nature of the two acids is now confirmed by careful analysis of some of the salts of the &acid (silver salt; mngizesizcm salt with AH,O; calcium salt with 2H,O) the results excluding the possi- klity of the &acid being in reality a hydroxy-lactone. The action of hydrogen bromide in acetic acid solution converts both a- and P-cinenic acids into the same bromo-derivative (compare Rupe and Altenburg Zoc. c i t . ) the B-isomeride undergoing the change more readily. As the bromo-product on treatment with magnesium carbonate and water yields cinogenic acid which on distillation gives a-cinenic acid it is possible to reconvert the P-acid into its a-isomeride. From these results it appears highly probable that the a- and P-acids are of similar structure.D. F. T. The Rdle of Atmospheric Oxygen and Alkali in the Oxidation of Acetone with Potassium Permanganate. Pyruvic Acid as an Intermediate Product. XDGAR J . WITZEMANN ( J . A m e r . Chena. SOC. 1917 39 2657-2671. Com- pare h. 1916 i 372).-A study of the oxiclatioii of acetone by potassium perinanganate in the presence of varying amounts of potassiuni hydroxide. I n the absence of alkali acetone is not per- ceptibly osidised by potassium permanganate a t the ordinary temperature. I n the presence of small amounts of alkali the oxidation is incomplete but in the presence of sufficient alkali the acetone is oxidised solely t o acetic and oxalic acids and carbon dioxide in such a way that one molecule of carbon dioxide is formed for each molecule of acetic and oxalic acids thus COMe + 40 = CH,*@O,H + CO + H,O.COMe + 7 0 = C,O,H + CO + 2H,O. The proportion of oxalic acid increases gradually but continually with increasing alkalinity indicating that the formation of oxalic acid is dependent on a molecular transformation that is catalysed by or dependent on the alkali. On the basis of Denis's work (com- pare A. 1907 i 997) and the intermediate formation of pyruvic acid as shown by Fournier (compare A. 1908 i 247) t8he authorgives the following series of changes for the osidatioii of acet'oiie by potassiuni yerrnanganate in the presence of alkali GOMe + CH,:CDle*OH -+- IIO.CH;CMe(OU),+ CHO-Chlt (OH) -+ CO,H*CJle(uH) + Cii3*CU2H 3.c'o /+- c €~;C'O*C@,E~ '-9 c~J,:c(oH)*co,TI -3- C,0*H2 + GO,. coinparable with the formation of iodof orm as explained by Pieroni and Tonnioli (compare A. 1914 i 6). The functioiis of the alkali in the oxidation are (1) to give rise to the active enol isoacetone; (2) to cause the enolisation of pyruvic acid; (3) to neutralise the acids formed and thus prevent their further oxidation; (4) to determine the velocity of oxidation; and (5) t o catalyse the absorp- tion of atmospheric oxygen. The Distillation of Cellulose and Starch in a Vacuum. AM^ PICTET and J. SAEASIN (Conzpt. rc/2a?. 1918 166 3S-S9).- When cellulose or starch is heated gradually under a pressure of 12-15 mni.ths fraction distilling between ZOOo and 300° amounts to about 45 per cent. of the original and consists of ail oily crystal- line paste froin which crystals have been separated corresponding in properties with Tanret's 7rccvogZucosn~a C,H,,O (A. 1894 i 6G4) (see further J . SOC. C'Iiem. Ind. 1918 37 Feh.). W. G . J. F. B. Pine-wood Lignin. PETER KJASON (Sz;ensl;. h i i . [Cidski.ift; 1917 29 5-16 47-52; from Chetri. Abstr. 1917 11 3482--2483).--The lignin was obtained from sulphite wvaste by two procedures ( n ) by saturating the waste liquors with calcium c-hloride and ( r ) ) by adding t o the filtered liquor iiaphthylainino hydrochloride. The sample ( ( I ) was purified as the barium salt aiid ( h ) as the calcium salt. These salts were analysed.The first liguiii had a composition suggesting that it' was composed of 1 mol. of coniferyl alcohol and 3 inols. of liydroxyconif cry1 alcohol C401348015 (MeO 11.55% found; 12.4% calc.). The second lignin ( b ) corresponds with 4 mols. of hydrosyconiferyl alcohol and G mols. of trihydroxycinnamyl alcohol C94H108040. Klason's conception of lignins is that they are formed by condensation of phenols with side-chains in positions 1 3 4 in a manner not unlike the proteins and dextrins. The sulphite process breaks up the larger molecules. Molecular weight determinations correspond with formulae twice the size of the above. Coniferyl alcohol is always the chief component o€ native lignin and this explains the formation of C6X3Me (OMe) *OH C,H,( C,H,) (OMe).OR.and @,R3(C3H,) (OMe) OH on destructive distillation of wood. Pure lignin and coniferyl alcohol both give several colour tests but the latter only on keeping. Freshly p w pared from an emulsion extracted with ether i t does not react. G . B. e 2i. 60 ABSTRACTS OF CHEMICAL PAPERS. Identity of Cyanuric Acid with so-called Tetracarbimide. E. H. WALTERS and LOUIS E. WISE ( J . Amer. Chem. Soc. 1917 39 2472-2477).-Scholtz described a product obtained by the oxidation of uric acid by hydrogen peroxide in alkaIine solutions as “tetracarbimide” (A. 1902 i 140) and this has not been called into question until recently when Venable and Moore sug- gested that the compound was really cyanuric acid ( J . Amer. Che.v)i. Suc. 1917 39 1750). The identity of the substance with cyanuric acid is now fully established optically titrirnetrically (thymol- phthalein as indicator) and by the characteristic copper salt.I n an application of Scholtz’s method with slight modifications a small amount of carbonyldicarbamide has been obtained from uric acid. It might’ be that this is an intermediate product between uric and cyanuric acids for i t readily loses ammonia and so produces the latter acid. Cyanuric acid has now been isolated from some eighteen different aoils (compare A. 1917 i 622). J. C. W. Conversion of Methyleneaminoacetonitsile into Imino- diacetonitrile. J. R. BAILEY and H. L. LOCHTE ( J . Anzer. Ckem. SOC. 1917 39 2443-2444).-Bailey and Snyder have re- ported that- inethyleneaminoacetonitrile unites directly with hydrogen cyanide to form irninodiacetonitrile NH( CH,*CN) (A.1915 i 389). DelBpine had previously stated that these com- pounds do not react together at all (Bull. SOC. chirrz. 1903 [iii] 29 1202) and the present authors have now found that a catalyst is necessary. Pure hydrogen cyanide does not combine with methyleneaminoacetonitrile’ but if a trace of hydrochloric acid is added to the mixture the reaction proceeds quickly t o completion. The original agent contained hydrochloric acid as a preservative. J. C. W. Hydrolysis of Sodium Cyanide. FREDERICK PALLISER WORLEY and VERE ROCHELLE BROWNE (T. 1917 111,1057-1062). -The degree of hydrolysis is measured by passing a current of air through the sodium cyanide solution and absorbing the hydrogen cyanide from the issuing gas by means of a solution con- taining 0.2% of picric acid and 2% of sodium cxbonate. This indicator solution is changed t o a reddish-brown colour which is matched against the colours produced when the same current of air is made to pass through aqueous solutions of hydrocyanic acid containing respectively slightly more and slightly less free acid than the solution of sodium cyanide under investigation. The strengths of the hydrocyanic mid solutions required are determined by preliminary tests.I n the actual determination the three flasks t o each of which is attached an absorption tube containing the same volume of indicator solution are arranged in series the sodium cyanide solution being in the middle. The results obtained are in very satisfactory agreement with the mass law expressed by the equation P2C/100(100-P)=k inORGANIC CHEMISTRY.i. 61 which C is the molar concentration of the cyanide and I’ the per- centage hydrolysis. The value of C was varied from 0.0073 to 5.2 mols. per litre. The influence of temperature on the hydro- lysis is shown by the fact’ that k x lo4 increases from 0.135 a t 0’ t o 0.484 a t 25O and 0.72 a t 30°. H. M. D. The Action of Aluminium Chloride on Cymene. A. W. SCHORGER ( J . Anzer. Chem. SOC. 1917 39 2671-2679. Compare Boedtker and Halse A. 1917 i 124).-When cymeens is heated with aluminium chloride a t from 60-150° the products are By-dimethylbutane benzene toluene m-xylene and 1-methyl-3 5- diisopropylbenzene. Small amounts of the catalyst favour the formation of toluene whilst thel formation of benzene increases with the amount! of catalyst used.1-Methyl-3 5-diisopropylbenzene7 as isolated has b. p. 215-21807 D20 0.8668 $’ 1.4950 and on oxidation with nitric acid (D 1-15) yields uvitic (s-methylisophthalic) acid giving a dimethyl ester m. p. 98O. With chlorosulphonic acid the hydrocarbon gave a t,hiochloride which with ammonia yielded a thioarnide m. p. 92O. W. G. Action of Benzenesulphonyl Chloride on Organic Bases in Anhydrous Ether. GEORGE L. SCHWARTZ AND WILLIAM M. DEHN ( J . Am,er. Chem. SOC. 1917 39 2444-2453).-In continua- tion of Dehn’s studies on the production of additive compounds of bases and haloids eypecially acid chlorides in anhydrous ether (A. 1912 i 833; 1914 i 1169; 1915 i 954 etc.) the behaviour of benzenesulphonyl chloride has been investigated. As before the reagents have been mixed in a large excess of ether and any precipitates formed immediately or after days or even months have been analysed. I n harmony with previous results it is found that (1) the initial reaction is additive (2) the reactions are non-ionic (3) and that light promotes reaction.With primary and secondary amines the additive product soon qives place to a greater or less extent’ to the hvdrochloride of the base thus C6H5*SQ2Cl + RNH = SO,Ph*RNH,HCl and this = SO,Ph*RNR + HCl -+ RNN,,HCI. The benzenesulphonyl derivative of the base remains in solution. The secondary reac- tions are promoted by heat traces of water and by the free bases. Thus aniline tho toluidines propylamine hexylamine benzidine phenylhvdrazine carbamide diethylamine dipropylamine diiso- butylamine.diisoamylamine methylanilinel ethylaniline piper- idine and dihenzylamine give mixtures of the additive compound and the hydroch’oride of the base. The appearance and analysis of the precipitates and the speed of the reactions are recorded. Phenylhpdrwine and carbamide qive precipitates which contain ats much as 82% and 94% of the additive compounds respectively but the other bases fall very short of this.i 62 ARS'FRACTS OF CHEMICAL PAPERS. With tertiary bases additive compounds of the types lB,C,H5~SO2C1 and B,,C,H,*SO,Cl are formed but these may be cont'aminated by other salts if traces of moisture are not excluded thus C,H,*SO,Cl,B + H,O -+ C,H5*S03H + B,HCl and sub- sequently C,H,* SO,H,B.Tribenzylamine gives a compound B2X microscopic prisms m. p. 174-176O ; tripropylamine yields a com- pound BX long needles m. p. 52O; pyridine forms compotinds BX microscopic prisms m. p. 110-112° and B,X large rect- angular plates ; a-picoliner gives a compozind B,X ; quinoline forms compounds BX needles and B,X stout rhombs ; quinaldine gives a mixture of mono- and di-derivatives ; acridinel gives a compound B,X golden prismatic needles m. p. 192O; antipyrine forms a compound BX needles. J. C. TV. Dichloroamine T and Chlorinated Eucalypt01 (D 1 a 2 ) . ROBERT B. KRAUSS and EDWARD CREDE ( J . Amer. Chenz. Soc. 1917 39 3720-2722).-An improved method is given for the preparation of dichloroamine T [toluene-psulphodichloroamide] on a large scale by which a stable product is obtained.When chlorine is passed into eucalypt01 in good daylight a t such a rate that' the temperature does not exceed 80° chlorinated oil (D 1.2) is obtained which can be used as a solvent for diphloroamine T for surgical purposes without requiring the addition of prepared paraffin oil as a diluent. By further chlorination of the oil (D 1*2) either directly a t looo or in boiling chloroform solution an amber- coloured oil (D 1.4) is obtained of the consistency of molasses. W. G . Solubilities of Anthracene Anthraquinone p-Dibromo- benzene Phenanthrene and Iodine in Various Solvents. JOEL H. HILDEBRAND E. T. ELLEFSON and c'. W. BEEBE ( J . A m r r . C h m . Soc. 1917 39 2301-2302. Compare this vol. ii 36).- The solubility of anthracene anthraquinone pl-dibromobenzene8 phen- anthrene and iodine has been determined at 25O in the solvents alcohol benzene carbon disulphide carbon tetrachloride ethyl ether and hexane.I n all cases except that of iodine the amou-lit dissolved was determined by evaporation of the solvent from a weighed portion of the saturated solution; in the case of iodine the estimation was effected by titration with sodium thiosulphate solution. The following values in grams of solute per 100 grams of solvent were obtained Alcohol solution 0.328 anthracene 0.437 anthraquinone. 10.35 wdibromohenzene. 4.91 phenanthrene. Benzene solution 1.86 anthracene 83.8 pdibromohenzene 59.5 phenanthrene. Carhon disulphide solution 2.58 anthracene 90.0 71-dibromohenzene 80.3 nhenanthrene. Carbon tetrachloride solu- tion 0.732 anthracene 36.6 ?i-dibromobenzene 26.3 phenanthrene.Ethvl ether solution 1.42 anthracene 0.104 anthraauinone 71.3 ?j-tlihromG~)enzene 42.9 phenanthrene. Hexaiie solution 0.37 anthracene. 35.9 ;7,-ctibro1llo~enzene 9.1 5 phenanthrene and 1.32 iodine. J. F. 8.ORGANIC CTTRMTSTRY . i . 63 Miscibility in the System Aniline -W a t er- G1 y cer 01. I. M. KOLTHOFF (Chem. TVeeEblad 1917 14 1081-1089).-At 1 8 O glycerol of 89% strength is miscible with aniline in all pro- portions a fact which affords a basis for a method of estimating the proportion of water in glycerol. Acid and Basic Properties of Various Compounds. H. I. WATERMAN (Chem. TVeekbZacZ 1917 14 1126-1131).-An investigation of the alkali and acid equivalents of various sub- stances determined by the effect produced on the decomposition of monoses by sodium hydroxide and the inversion of sucrose by hydrochloric acid Sulphanilic acid has no basic character and salicylic acid differs from its isomerides by displaying the proper- ties of a monobasic acid.Structural formuh to acount for these phenomena are suggested. A Catalytic Decomposition of certain Phenol Silver Salts. 11. Thermal Decompositions The Formula of the Unpolymerised Residues. W. H. HUNTER and F. E. JOYCE ( J . Amer.. Chem. SOC. 1917 39 2640-2646. Compare A. 1916 i 717).-When p-chlorophenol is brominated in glacial acetic acid solution it yields 4-chtloro-2 6-dibromophenoZ needles m. p. 92O giving a silver salt occurring in an orange and a white form. When this silver salt is boiled in benzene it yields a white amorphous solid which is a mixture of the two compounds (C,H,OClBr) and (C6H20Br,) in the proportion of 1 0.86.When the silver salt is treated with ethyl iodide in the cold it gives these two compounds together with some 4-chloro-2 6 4 - hrornophenetole m. p. 52.5O. If p-chlorophenol is dissolved in an excess of aqueous potassium hydroxide and t o the solution is added a solution of potassium iodate and another of iodine in potassium hydroxide on gradually acidifying this mixture with continual shaking 4-ckloro-2 6-di- iodophenol m. p. 107-108° is obtained giving a pale yellow silver salt. When boiled in benzene the silver salt< gives a mix- ture of the two compounds (C,H,OClI) and (C,H,Ol& in the proportion of 1 0.61.The silver salt of 2 6-dichloro-4-bromophenol is also decomposed by hot benzene giving the two compounds (C,H,OClBr) and (C,H,OCl,). in the proport'ion of 1 2.26. I n each of these cases it was found that the molecules of the silver salt split up losing some of their halogen from the ortho- nosition and some from the para-position the ratio varying widely between the different salts. There are slight indications that the halogen in the para-position is the more readily removed and that the ease of removal of the halogem is in the descending order iodine bromine chlorine. By the decomposition of the silver salt of 4-chloro-2 6-dihromo- phenol by ethyl iodide more of the molecules lost their hadogen from the ortho-position than iii the decomposition by h o t benzene.A. J. W. A. J . W. ?V. G.i. 64 ABSTRACTS OF CHEMICAL PAPERS. Basic Salts of the Metals of the Alkaline Earths. E. BELLONI and E. BACCI (Gazzeila 1917 47 ii 159-170).-The compouiid Ba,(S0,*C6H4*OH),*OH,8H,0 is obtained in prismatic crystals when a warm dilute solution of phenolsulphonic acid is neutralised with barium hydroxide until it becomes alkaline to phenolphthalein. Of the eight molecules of water contained in this salt four are lost when i t is kept over sulphuric acid three more at% 130° and the other only after proloiiged heating a t 1 7 0 O . When a dilute solution of the saltl is treated with carbon dioxide barium carbonate is precipitated and barium phenolsulphonate can be recovered from the solution. The compozcnd Ba2(S0,*C,H4*OH),(OR)2,4M,0 is produced by boiling a solution of 20 grams of barium phenolsulphonate in 200 C.C.of water with 15 grams of barium hydroxide. It' is a white powder very slightly soluble in water. When this solution is treated with carbon dioxide barium carbonate is precipitated but the filtrate on concentration yields the monobasic phenolsulphonate first described. The cornpozcnd Ca,(SO,*C,H,*OH),(OR),,4H,O is prepared by boiling a solution of phenolsulphonic acid with an excess of lime. The co mpozcn d B itg (CO,-C,H,* OH) (OH) (OH,) 4H,O is obtained by pouring a solution of sodium salicylate (6 grams) and sodium hydroxide (1 gram) in 50 C.C. of water into a boiling solu- tion of 6 grams of barium chloride in 50 C.C. of water. The constitution of these and other basic salts of the metals of the alkaline earths is discussed and formukt are assigned t o them derived from the theories of Werner.R. V. S. The SubstitutionProducts of the Aminophenols and of their Derivatives. WALTER FUCHS (Momtsh. 1917 38 331- 341).-The knowledge of the relative effect of the amino- and hydroxyl radicles in the aminophenols in directing the position of entry of a new substituent into the nucleus is not complete and the behaviour of p-aminophenol and its ortho-isomeride towards bromination has been examined. By the careful addition of a chloroform solution of bromine t o p-aminophenol dissolved in a mixture of chloroform and ether a green reaction product was obtained which from the fact that on treatment with ethyl sulphate and alkali it yielded a quantity of 3 5-dibromo-4-aminophenetole~ must have contained 3 5-dibromo-4-aminophenol ; the two bromine atoms had therefore been directed into the two ortho-positions t o the amino-group.p-Acetylaminophenol when treated with bromine in a similar manner gave rise to 2 6-dibromo-4-acety1aminopheno1 the influence of the hydroxyl group predominating over that of the acetylamino- radicle ; this product on ethylation gave 2 G-dibromo-4-acet~Zamino- phenctidine NHAc*C6H,Br?*OEt needles. m. p. 1 9 8 O . Attempts t o brominate o-aminophenol proved less satisfactory but itl is possible that some 3 5-dibromo-2-aminophenol was formed. As a result of this and earlier investiqations (Fuchs A . 1915 i 520;ORGANIC CHEMISTRY. i. 65 Reverdin and During A. 1899 i 266; Hodurek A.1897 i 276; Mohlau and Ohmichen A. 1882 395) the scheme NH > (OH,OAlk) > NHAc may be given to represent the relative directing power of the groups towards a new substituent the positions of the hydroxyl and alkyloxy-groups relative to one another remaining yet to be decided. D. F. T. Molecular Rearrangements in the Camphor Series. XIII. The Decomposition Products of the Methyl Ester of zsoAminocamphonanic Acid. A New Reaction Involv- ing the Formation of the Methyl Ether of a Hydroxy- acid. ~VILLIAM a. XOYES and GLENN S. SKINNER ( J . Amer. Chern. Soc. 1917 39 2692-2718).-It has been shown in an earlier paper (A. 1913 i 161) that isoaminocamphonanic acid is decom- posed by nitrous acid with the formation of cis-camphonolactone an unsaturated acid b.p. 150°/60 mm. (decornp.) and a saturated acid which decomposes a t 160O. The presen5 work was under- taken with tho object of studying the behaviour of the methyl ester of this acid towards nitrous acid. A much better yield of aj3-methyl Z-isocainphorate was obtained by doubling the amount of sulpliuric acid previously used (Zoc. (.if.) and reducing the time of heating to five hours. The follow- ing physical properties of the ester are given b. p. 130°/8 mm. 138O/13 mm. 141*5O/16 mm. 144O/19 mm. 146O/22 mm.; [a]F6- 65'5O and [u] - 6 6 . 5 O in 10.7% alcoholic solution. &Methyl a-Z-isocamphoramate has m. p. 127-128O (con .) and [a]$ -*55-4O in 10% absolute alcoholic solution (compare Zoc. cit.). From this ester a much better yield of methyl isoamino- camphonanate by the method previously described is obtained if the heating is reduced t o five minutes.The ester has b. p. 135-138°/10-12 mm.; [a]; -49O and [a] -41.2O in 10.5% alcoholic solution. Its hydrochloride has m. p. 179-180O (corr.). This hydrochloride when decomposed by nitrous acid yields a t least six products namely the methyl ether and the methyl ester of cic-camphonolic acid and the methyl esters of lauronolic acid 1 2 2-trimethyl-A4-cycZopentenel-carboxylic acid cis-2-hydroxy- 1 2 3-trimethylcyc7opentane-1-carboxylic acid and a secondary P-hvdroxy-acid . The methyl ether of cis-cnmphonolic acid has m. p. 87O (corr.) [al:? + 72*1° gives cis-camphonolsctone by treatment with hydrogen iodide and can be synthesised by the action of methyl iodide on the silver salt' of cis-camphonolic acid.It gives a s i t v e r s d t and a methyl ester m. p. 116-118°/25-29 mm.. [a] + 64.7O in 9% alcoholic solution. 1 3 2-Tr.imethz~l-~4-cyclope.i.ttel.te-l-c~r~o~~~l~c acid has b. p. 135*/ 14 mm. I37 1.0132 DY7 1.0088 ral + 105.3 and in 10% alcoholic solution rv1; + 83.4O ?z:! 147356 ?t;; 1.47560 ; 92; 1 48979; n:; 1.48887. The; wthyE ester has b. p. 75'/9 mm. 78*5O/15 mm. ; ralF5 + '76~6~. In 10% alcoholic solution it has [a] + 74.4" n 1.45454 ; 12; 1.45755 ; c*i. 66 ABSTRACTS OE’ CHEMICAL PAPERS. 12 1.46423 ; 7z.Z 1.4697. The structure of this acid was proved by its oxidation to an inactive tribasic acid which decomposed a t itb melting point giving off carbon dioxide. cis-2-HycFroxy-1 ; 2 3-trinzetkylcyclopenta~e-1-carboxylic acid has in.p. 101-102° [~t]Z+35*6~ in 7% alcoholic solution. It gives sodium calcium and silver salte. It is notl oxidised by Beckmann’s chromic acid mixture in the cold and does not givel a lactone by this treatment. It gives a comparatively stable crystalline iodide m. p. 85-87O which when treated a t once with sodium hydroxide yields lauronolic acid and no lactone. The methyl ester has b. p. 112-114°/18 min. The decomposition of the esters of aminocamphonanic and amino- dihydrocampholytic acids by nitrous acid was also examined but in neither case was an ether acid obtained. Methyl 6-camphorate b. p. 155O/25 mm. or 144O/15 mm. [a]:p +47*5O gives &methyl a-d-camphoramate m. p. 154-155O [a? + 23*1° in 9.7% alcoholic solution which yields methyl aminocamphonanate hydrochloride m.p. 237O [a]‘ +26*2O in lo.?.,! alcoholic solution. This hydro- chloride is decomposed by hydrochloric acid giving a methyl ester b. p. 78-85O/15 mm. [u]g5 +73*8O in 9.25% alcoholic solution of aJn unsaturated acid b. p. 125-130°/10 mm. [a]”,”‘”+ 108*1° ; DSo 1.0130. W. G. Pyro-condensations in the Aromatic Series. 111. HANS MEXER and ALICE HOFMANN (Monatsh. 1917 38 343-358. Com- pare A. 1917 i 641).-Azobenzene vapour when heated strongly is liable t o decompose suddenly. p-Toluidine when heated readily underwent decomposition with formation of pp’-diaminodibenzyl and a little resinous matter whereas o-toluidine was surprisingly resistant yielding only a small quantity of anthracene and of un- crystallisable resins ; benzonitrile also proved remarkably stable and remained unaltered unless the tFmperature was raised so high as to’ cause complete decomposition.Phthalimide a t 480° under- went rapid and almost quantitative conversion into benzonitrile isophthalimide probably occurring as an intermediate product. The presence of chlorine increases the stability of the phthalimide molecule and whereas the cl’ecomposition of phthalimide was already appreciable at’ 350° 4-chlorophthalimide formed pchlorobenzo- nitrile only very slowly a t 500O. whilst tetrachlorophthalimide even a t its temperature of carbonisation in the neighbourhood of 600° gave only sufficient nitrile to be detected by the odour. The gradual thermal decomposition of benzoic acid gave rise t o benzene. henzaldehyde diphenyl diphenyl-4-carboxylic acid and a small quantity of diphenyl-4 4/-dicarboxyiic acid ; the formation of benzaldehyde is probably due t o the reduction of benzoic acid by hydrogen already formed in the decomposition of part of the acid.Ethyl benzoste a t a dull red heat was rapidly converted into the free acid and ethylene b u t the methyl ester was much more stable and required a still higher temperature for its decomposition then yielding benzene diphenyl methyl diphen yl-3-carboxylate andOSGANIC CHEbIISTRY. i. 67 d iphenyl-4-carboxylate and trioxymethylene ; in a similar iiianiier the methyl group in toluene was retained by the benzene nucleus and in ethylbenzene only the end carbon atom of the ethyl group suffered scission the carbon atom adjacent t o the benzene ring remaining attached to the latter.The great stability of methyl benzoate rendered it likely that iii methyl toluate the ester group- ing might prove more resistant than the methyl radicle and this anticipation was realised the product being methyl diphenylethane- 4 4'-dicarboxylate accompanied by a little methyl stilbene-4 4/- dicnrboxylate m. p 226-227O and trioxymethylene. Phenol m7as strikingly resistant and after prolonged hesting yielded only a sinall quantity of decomposition products amongst which benzene and 4-hydroxydiphenyl were present ; anisole suffered eliininatiox of t'he methyl group with formation of phenol but no trioxy- methylene was observed. D. F. T. Organic Additive Compounds of Potassium Hydroxide. 1917 39 2646-2657).-When benzoic acid and potassium hydr- oxide are brought together in anhydrous ether the following suc- cessive additions and decompositions are recogiiised 2Ph*CO,H + 2KOH ++ CPh(OH),*O*COPh -+ TVILLIAM M.DEHN and RUTH E. MERLtNG (-7. dmer. Chen?. SOC. (1.1 CPh(OH,)*O*CPh(OH)*OK -+ 2Yh*CO,K -t 213,O. When beiizoic anhydride is used in place of benzoic acid the fiual salt (111) is the same as in the previous case but an intermediate salt different from that (11) in the first' case is formed COPh*O*COPh 4 COPh*O*CPh(OH)*OK 4 O[CPh(OH)*OK] + 2Ph*CO,K + 2H,O. A number of other acids were studied and salts were obtained the molecular proportions of acid and potassium hydroxide reacting being either 2 1 or 1 1 or 1 2. All these salts when first formed were additive compounds but later they mightl or might not yield the simple anhydrous salt.Initially all the water was found t o be present in the precipitate and the progressive loss of water from the precipitat'e was studied in most cases. That' the inter- mediate compounds were additive was also indicated by the fact that the final anhydrous salts did not take up a molecule of water from an et'hereal solution of it. This formation of additive coin- pounds with potassium hydroxide is not peculiar t o organic acids but is common to all organic compounds containing carbonyl groups. The types of compounds studied were acids acid anhydrides aldehydes ketones esters amides iinides alcohols and phenols and certain miscellaneous compounds. A few oxygen- containing compounds such as raffinose saccharin and camphor failed to show any reaction with potassium hydroxide.(11.1 (111.) W. G . ea 2i. 68 ABSTRAOTS OB UHEMICAL PAPERS. New Method of Preparing Aromatic Nitriles by Catalysis. ALPHONSE MAILHE (Corrzpt. rend. 1918 166 36-38).-When an ester of an organic acid is treated with ammonia it is decomposed yielding the alcohol and the amide of the acid and the latter on dehydration gives the nitrile. The reactions may be effected simultaneously by passing the vapour of an ester of an aromatic acid mixed with gaseous ammonia over heated thoria a t 450-470° (temperature measured in the channel supporting the catalysis tubs). A t the latter temperature the reaction is practic- ally complete and good yields of benzonitrile are obtained from methyl- ethyl- and isopropjjl-benzoates. The liquid product of the reaction separates into two layers the oily layer consisting almost entirely of benzonitrile which is purified by rectification (b.p. 189-191O). Aldehydic products and gases consisting of hydrogen and olefines are derived from the alkyl group of the ester. The nitriles of 0- and ptoluic acids may be prepared in exactly the same way and phenylacetonitrile is obtained from ethyl phenyl- acetate. The method appears to be of general application and gives good yields. Amides Carbamido-compounds and Carbamides containing an Aromatic Nucleus. WALTER A. JACOBS and MICHAEL HEIDELBERGER ( J . Smer. Chem. SOC. 1917 39 2418-2443. Compare A. 1917 i 552 559 695).-A large numbe? of compounds of the above classes are described.These and similar substances mentioned in the earlier papers have been collected as intermediate material in another investigation of which an early account is promised. A . AMIDES. (a) Amides of Substituted Benzoic Acids.- 3-A naino-6-hydroxybenzamide is best obtained by the action of aqueous ammonia a t l l O o on methyl aminosalicylate ; it crystallises in silky needles m. p. 194-197O (decomp.) and gives 3-chloro- acetylamino-6-hydroxy b enaamicle very pale purple platelets m. p. 225-227O when treated by the method already described (loc. cit. 552). Six other amides of this series have bem mentioned previously. (b) Amides of Aminophenylacetic Acids.-Methyl m-amino- phenylacetate hydrochloride crystallises in long thin glistening plates m.p. 167-170O (decomp.) ; m-aminol?henylacetnmide forms transparent prisms m. p. 164-166O (corr.) ; and m-chloroacetyl- arninophenylacetamide separates in prismatic needles m. p. 187-188O. (For the parent acid and amides of the para-series (c) Derivatives of the Aminopheiaoxyncetamides.-o-NitropherL- ospacetamide glistening needles m. p. 194.5-195-5O (corr.) yields o-aminophenoxyacetic anhydride when treated with ferrous snlphate and ammonia. 0-C hloroa ce t y lamiit opheno xya ce t i c acid CH?Cl*CO*NH C,H,-O*CH,* CO,H crystallises with 2H20 which it IOSPP at llOO/vac. and then melts a t 144*5-145*5O (corr.) the acid chloride forms colourless plates m. p. 52-59O and the amide crystallises in needles m. p. J. F. B. loc. cit.)ORGANIC CHEMISTRY. i. 69 15 8-1 6 I O.m - 8 minophenox yacet amide from the ethyl ester forms delicate cream-coloured needles m. p. 123*5-124O (corr.) and yields m-clzlol.oacetylumi11opheno~acetnniide radiating masses of lninute leaflets m. p. 235-238O (decornp.). p-A.minophe?zoxy- tccetnmide crystallises in creamy prisms m. p. 127.5-128'5O and the chloroacetyl conipound separates in colourless needles m. p. 195-196*6° (corr.) and forms a hexainethylerLetetrarn~~~i~~rn salt CH,@l.CO*NH.C,H,*O.CH~*CO.NH,,C,W,2N,. p - N i t r o P h e n 0 ~ ~ - acetpl chloride crystallises in hexagonal tablets m. p. 86-8'io (cGrr.) ; p?zitropheiioxyucetomethylap,Lide forms brilliant needles ni. p. 165.60 (corr.) ; and p-aminopkenoxyacetoineth?/lanzide NH,*C6€I,*0 C€I,*CO NHMe separates in creamy needles m.p. 1O9.5-11lo (corr.). The follow- ing 4-nminophenoz~acetnm~~es are obtained from the correspond- ing esters 2-methyZ- long flat glistening needles m. p. 155.5-156O (corr.) ; 3-methyZ- very pale pink filamentous masses m. p. 136-137O; 2:5-dinzethyl- silky needles m. p. 153-154' (corr.) ; 2-methyZ-5-isopopjZ- diamond-shaped plates m. p. 108-109° (corr.) ; 3-methyZ-6-isopopyZ- pointed leaflets m. p. 125-125-5O (corr.); 2-brmno- masses of long creamy needles m. p. 159-160° (corr.) ; 6-rnethoxy- glistening needles m. p. 177.5-178*5O (corr.) ; 6-carbethom~- minute leaflets m. p. 135-136O (corr.) ; Gacetyl- brownish-yellow leaflets rn. p. 138-139O. Colour reactions with ferric chloride and R-salt (after diazotisation) are described for most of these compounds. (For the parent acids or esters Zoc.cit.) (d) Derivo tives of Amino b enxen,esul;FPhonanaides.-Aniline-m- sulphonic acid is dissolved in an equivalent of N-sodium hydroxide shaken with acetic anhvdride the solution evaporated under reduced pressure 2nd the sodium m-acetylaminobenzenesu-lphonate left is triturated with phosphorus pentachloride. The crude sulphonyl chloride so formed is treated with ammonia and so converted into m - n c e t ~ ~ 7 n m i i ~ o b e n z e n ~ s ~ ~ l ~ ~ ~ ~ o n ~ r n ~ ~ e minute rhombs m. p. 216-219O. This is hydrolpsed by hydrochloric acid t o the known m-aminobenzenesulphonamide which forms a chloroacetyl corn- potind C~~T-T,CI*CO*NH*C,,3H,*S0,*N~ aggregates of minute needles. m. p. 1 6 5 O (clear). Sodium sdphanilate is acetylated in the same way and finallv converted into p-chloroacetylamino- bPnzenP~~ulphonnmide needles. m.p. 215-21 7 O . (a) Garbamides of Substituted Benzoic ,4cids. -0-A minobenzoylcarbamido (loc. cjt .) gives o-chloroncetlllnrnilzo- h~vzo~7cnrbnmide long glistening needles m. p. 222-2230 (decomp.) 2nd m-a,ininoheiizoylc~~,rhnmicle yields the chloronc~f?/7 comDound slender needles. decomp. 252-253O. p-Nitrohpnzo!ll- cflrbflm;dp microsconic prisms. m. p. 243-2450 gives rise t o p - n m i ? 7 o h P n z o ? / ! c n r b ~ ~ ~ ~ ~ minute plates partly decomposed but not molten. a t 285' and P - c h l o r o n c e t y ? a r n i ~ n o b e n z o v l c n r b ~ ~ ~ ~ ~ deconllo. 2 75-2 80'. O-HVdToz?/ b en z oy7cnrb nmide (,ya&o$carb - f/mide)9 microscoPic pale ~e110w crystals m. p.184-1860 (decolrlp.) is obtained by the intersction of carbamide and o-acetoxybenzoy] B. CARBAMIDES.chloride in benzene followed by agitation of the acebyl derivative with cold sodium hydroxide. m( ‘l)-Chloroacetyln~ninometh~l- 0 enzoyl car bantide a microcrystalline powder m. p. 225-228O (decomp.) is obtained by the action of methylolchloroacetamide on benzoylcar baniide i n sulphuric acid solution (compare Einhorn A 1906 i 245). (b) Derivatives of Y h eizylacetyl car bantide .-Phenylchloroacet yl chloride and carbamide yield a-chlorophenylacetylcurbamide CHPhCl*CO*NH*CO*NH needles m. p. 198O. p-Nztrophenyl- acetylcarbamide hair-like needles m. p. 260-252O (decornp.) gives ~ m i n o ~ ~ . e n ? l l a c e t ~ l c a r ~ a ~ L ~ ~ e felted needles m. p. 198-199’ (evolution of gas) and p-ck~loroncetylarr~ilzopJ~eizylneet~lcarbam~~~e m.p. 241O (decomp.). o f A m i I I o plb e no x ya c e t g 1 car b a rit ides .-o-Ni t TO- phenoayncetyl chloride long silky yellow needles m. P. 41-42’ (corr.) gives 0-nitrophenoxyncetylcarbamide cream-coloured irregular prisms m. p. 186-188O which is easily hydrolysed even by ammonia. p-~~itroplze~zoxyacetylcnrbarnz’cle m. p. 250’ (decomp.) yields p-anainophen oxynce tyl car bnmide long needles which melt a t 198-199O give off a gas resolidify and melt again evolving gas a t above 240° and p-chloroncet~lnmi?zophenoz~acetyZ- cnrbamide minute flat needles m. p. 238-240O (decomp.). A better yield of this compound is obtained from the corresponding acid chloride and carbamide. p-Chloroacetylanainophenoxyacetic acid irom the aminophenoxyacetic acid crystallises in rosettes of soft needles with lCH,*CO,H m.p. 170° (free from solvent of crystallisation) ; the chloride CH,Cl* CO*NH-C6H,*O*CH2*COCI forms aggregates of platelets m. p. 147-152O (decornp.) ant1 the n,rtli?yl ester forms flat needles m. p. 170-173O. carbainido-amides are generally prepared by the action of potassium cyaiiate on acetic acid solutions of the amino-amides. o-CInrh- ( i i n idoZ,enzamide NB,*CO*NH*C,H,*CO*NH crystallises in stout cream-coloured hexagoiial plates which melt at 184-185O evolviiig ammonia and changing thereby into solid benzoylenccarbamide ; m-cn?.I,(iniidobe?zsami~e forms flat needles m. p. 235O (decomp. ; resolidification) and gives m-chloroncetylcni.Fni,~ idob e m c m itle decomp .223-224O. p-Carb rc m idoh en znmicle forms aggregates of prisms m. p. 240-242O (gas evolved ; resolidifies; continues to evolve gas; finally molteii a t 276O) and yields a cJLloronccty2 com- pound hexagonal plates decomp. 236--237O. m-Cnsabccm ido;~llr PH?,?- awtnnritde ni. p. 201-202° gives a cl~loroirc~t.t/l comuoand CH,CI*CO*NII*CO.Plr’FT.C,H,.CH,.CO.NH very pale pillk aggregates of platelets and needles m. p. 1T9-l8l0 (deconip .). p-Cadmnidoph e,iyZacetom id? forms rectangular plate$ m. p. 333-23G0 (decoinp. ; resolidification) aiid gives a cJLloro- ncetyl corn pour id m . p. 200--201 O (decomp. ). p-Cai*ban? idophc I ) - oz.ycicPtniriitZe crystallises in radiating masses of loiig flat pale brown needles in. p. 230° (evolution oE gas ; resolidification ; secollt1 111.1’ 3F;Oo) ant1 its rl17o~nrrr~tyZ compound decomposes a t 2,300 C€i,Cl*CO NH*CH,*C,I-I,* CO*NH* CO *NH (c ) D e r iva ti v es (!. AROMATIC CARUAMIDES CONTAINING AN AMlDO-GROUP.-~heSeORGANIC! CHEMISTRY. i . 7 1 il.ietJbyl p-carbnirrido~riienoccycccet~~te m. p. 192-193° gives a ch Zoroa c e t y l compound flat prisms m. p. 181-183O (decomp.). I). CARBAMIDES WITH OTHER SUBSTITUENTS AND SIDE CHAINS.- p-Hydroxyphenylcarbamide yields p-cJdoi3oacetylcorbamidophelzyl chloroacetate needles and long thin plates m. p. 185*5-187.5' when boiled with chloroacetjrl chloride and benzene; p-acetylcarb- nniidophenyl acetate delicate pale pink needles m. p. 213.5-214O (corr.) when warmed with acetic anhydride and a little sulphuric acid ; and p-carbamidophenyl acetate m.p. 201-202*5° when treated with acetyl chloride and pyridine. The latter may be chloroacetylated ; p-chloroacetylcarbnmidophenyl ace t o t e forms spindles and plates m. p. 181-182m50 (corr.). CH2C1*CO*NH~CO~NH~C,H4*O*CH,*C02Me CH,Cl*CO*NH*CO*NH*C,II,. OAc p ( 1 )-Car b amido chl oroa c e t y 1 b e nz y lamin e NH,* CO*NH*C,H,*CH,*NH*CO*CH,C1 microscopic spears m. p. 173-174O is obtained by the action of methylolchloroacetamide on phenylcarbamide (Einhorn's method p( !)-Carba-midophenyZ chloromethyl ketone creamy nacreous plates m. p. 197-198O (decomp.) is prepared by the condensation of phenylcarbamide and chloroacetyl chloride under the influence OF aluminium chloride. p-Acetylaminophenoxyethyl bromide is readily hydrolysed by hydrobromic acid to P-bromoethoxyaniline hydrobromide thin plates m.p. 227-228O (gas evolution). The free base (described as p-nmin,ophenos?/etligl bromide) crystallises in minute glistening platelets m. p. 83-84.5O decomp. 260° and the crude salt reacts with potassium cyanate to give P-hron2oetho.x?/piheitylcnl.bnn7idc (~,-rn~hninidop~ie,ioal/eth?i?ll hromidr) m. p. 160-162O. zoc. cit.). J. C. W. The Behaviour of the Alkali Salts of the Polyhydroxy- benzoic Acids at Higher Temperatures. DANICA MRAZEK (Monntsh. 1917 38 211-218).-The alkali salts of the dihydroxy- and trihydroxy-benzoic acids when heated a t 200-300° do not undergo intramolecular rearrangement and therefore do not behave like the potassium and thallium salts of salicylic acid which give rise to the p-hydroxgbenzoates but resemble more closely the salicylates of sodium lithium and the alkaline earth metals which undergo decomposition with formation of carbon dioxide and phenol.I n an examination of the behaviour of the potassium salts of a- and P-resorcvlic acids protocatechuic acid gentisic acid gallic acid and pyrogallolcarboxylic acid i t was found that carbon dioxide was generally liberated below 300° whilst in the case of P-resorcylic acid protocatechuic acid and gallic acid a partial further substitution of carbon dioxide into the molecule with formation of the corresponding polyhydroxyphthalic acid was also observed. The lithium salt o i &resorcv?+ acid behaved sirnilarlr l o the potassium Salk hiit' wikh the sodium r;aitl the formatioll ofi.72 AESTRACTS OF CHEMICAL PAPERS. dicarboxylic acid was negligible and an amorphous substance C12H1,,03 was obtained. \&7ii5h the sodium salt of protocatechuic acid no formation of a dicarboxylic acid was observable. D. F. T. The cycZoPropane Series. 1x1. E. P. KoImm G. A. HILL and L. A. BIGELOW ( J . Bn2er. C'hem. Soc. 1917 39 2405-2418. Compare A. 1917 i 566-570).-In the earlier papers three reactions of cyclopropane derivatives were described which involved rupture of the ring in the three possible ways but the primary eff'ect of some of the reagents could only be surmised. New com- pounds of this series have therefore been sought out in the hope of isolating from them definite products to fill the gaps in the chain of evidence and a certain measure oE success has been achieved.Expel-iments with 3-p-l;rornoberr ~oyl-2-~he~~ylcyclop~opa~e-l 1- dicarb oxylic A cid.-pBromopheny1 styryl ketone condenses with the nialonic esters under the influerice oE the sodium alkyloxides to give the methyl ester (needles m. p. 96O) and ethyl ester (m. p. 7 5-7 6 O ) of y - p-b r om o b e n z oyl-,O-p lz en y 1 e t hy7 mn lo ni c c( (:id C,€I,Br*CO*CI3[,*CHPh.CH( CO,II),,H,,O which . crystallises in transparent plates. Thel methyl ester yields methyl y -b r'o mo- y-p-b romob e I Z Z oyl-&d? eny let kylmnlona t e on bromination; this exists in plates m. p. 9 P and needles m. p. 11 3O which are separated after many crystallisations from methyl alcohol. The condensation of this compound to methyl 3-p-b?wmo- benzoyl-2-phenylcyclop~opane-1 l d i c a r b oxylate proceeds smoothly.Two forms are produced ; with magnesium methoxide both bromo- compounds yield a product which crystallises in thin plates m. p. 1 0 4 O whilst with potassium acetate and boiling methyl alcohol both bromides give an isoineride which separates in compact tablets m. p. 1 1 3 O ; the former is converted into the latter by boiling with methyl alcohol and a trace of an acid. As usual with these compounds the ring is opened between 1 and 3 by treatment! with zinc dust and acetic acid the product being the above methyl ester m. p. 96O. Similarly alkaline agents effect hydrolysis and also open the ring between 1 and 2. With sodium alkyloxides in moist ether however it is possible to control hvdrolgsis so t h a t the rwthyl hydrogen ester (plates m.p. 175-176O) and ethyl hydrogen ester (small tablets in. p. 144O; the diethyl ester is not described) are produced. The ethyl hydrogen ester is the best material f o r the final hydrolysis by the ordinaq methods t o the free acid and it may be prepared from the original ketone and ethyl malonate in a day or so without purifying the intermediate products. S-p-B~ornohenzovl-2-phenyZ- cyclopmpcrne-1 l-dicctrboay7iic ncid crystallises with 1H,O or lEt,,O and changes on heatinq at 16U-180° into P-p-hrol:?ohe77zo?/7-y- 77 h c n ?/ 7 h 9 c t yr oln c t on e ,ORGANIC CHEMISTRY. i. 73 which crystallises in needles m. p. 1 1 6 O together with a trace of a-benzyliclene-y-p-bromophenylcrotonolactone lemon-yellow plates m. p. 180-183°. The butyrolactone is converted into 8-pb~omo- Z enz o y Z- y -phen y Zisocr o t oiiic CI cid CFIF h C( CO C,H,Br ) *CH,* CO,H m.p. 1 5 6 O when shaken with just sufficient sodium methoxide in ether. This unsaturated acid yields methyl y-bromo-P-p-bromo- benzoyZ-y-phen?/7bi~t~/r~t~ CHPhBr.CaI(CO.CGH,Br)*CM,.CO,Me m.. p. 1 4 0 O (decomp.) when esterified by means of hydrobromic acld; the same ester is also obtained by similar treatment' of the butyrolactone. The substituted iwcrotonic acid also gives benz- aldehyde and P-p-bromob eizsoylpropionic acid thin plates m. p. 140° when treated with alkalis so these are the products if the butyrolactone is l e f t in contact with alkaline agents in excess. 3-p-Bromobenzoyl-2-phenylcyclopropane-1 1-dicarboxylic acid also reacts with hydrogen bromide in acetic acid yielding y-byorno-P-p- bromobei?zoyZ-y-phen?ileth?~lmnlonic acid CHPhBr*CH( CO*C,H,Br)-CH(C0,H)2 which separates i n stout needles and crystallises from ether in lustrous plates containing combined solvent.This B cid suffers lass of hydrogea bromide when shaken with magnesium acetate in dry ether with the formation of u-cctrbory-P-p-bromoh enzoyl-y-pheny7- ,H,O in small flattened b utyrolactone needles which readily change on heating into the above butyro- lactone rn. p. 1 1 6 O . The metlzyl ester plates m. p. 1 0 4 O is easily obtained from the cyclopropane acid directly. A small quantity of P-bromo-~-phen7/1-pl -p-b rnmob enzo?ylclim e t 11 ylmalonic acid CI4 PhB r C( C O,H),* CR,*CO C,H4Br is also formed by the action of hydrogen bromide on the cyclo- propane acid.It crystallises in plates. When ths cyclonropane acid methyl ester is left with magnesium methoxide the ring is ruptured between 'I and 2 and methyl 8-p - b :.onao b en z oy !- y- 71 hen 7/17 l i n i j l m al on n t e @FfFh:C( CO.C,R,Br).Cn(G10,1V4e) is formed; this crvstallises in nced!es m. p. 1 0 4 O which change into a stereoisorneride (hard lustrous prisms? m. p. 92-93O) when left with hydrochloric acid. Erryrimmts with Be~zca~~~-m-izitropJien~~7c-yclop~o~nen7;icnrb- olryY7ic A cid.-m-Nitrostgryl phenyl ketone and the inalonic esters react to form methul ~ - b e n z o z ~ l - P - m - s k i t r o p h e n ? / 7 e ~ J ~ ~ ~ m a ~ o ? short needles with ;IMeOH. m. n. 9?O or silky needles m. p. 102O and the et2i?/7 estw M.n. 100-10c).5°. These yield the correspond- iiip y-hromo-eqters COPh*CHFTRr*CT-T(C,H,*hlO.,)*CH(CO,R) ; each ex-ists in two forms the mef-hvl ester in l o u ~ silky needles m. p. 149.5O. aiid s h o r t . lustrous needles. in. p. 1 9 9 . 3 O ; the ethvl ester in short brittle needles m. p. lolo and soft slender needles or hard prisms m. p. 98'5O. Theses brorno-esters are condensed to cvc7ovropsne derimtives hj7 the usual mild agents. as above. The follnwiny PP~PTS are mentioned rnpthyl! 3-hpnzo~ll-2-m-7i;trop~ rnl/T- (10--YH.CO?H o<CJLPh. C N a )*C,H,Bri. 74 A HSTRACTS OF' CHEMICAT PAPERS. cyclopropune-1 I-dicurboryltrte stable large prismatic plates m. p. 109*3O and labile slender needles m. p. 1 1 1 . 5 O ; the methyl hydrogen ester short hard prisms m.p. 154'5O; and the ethyl ester small plates m. p. 6 7 O . The methyl hydrogen ester is hydro- l y s d by the prolonged action of alcoholic potassium hydroxide t o 3-benzoyl-2-m-nit~op?~e~ty~cyclopl.opnne-l 1-dicnrb oxylic acid (I) which crystallises with 1H,O in lustrous plates and decomposes a t above 135O into a-m-nitro b e.rz z y Ziden e- y-phenylcrot onolact o ne (11) small yellow plates m. p. 2 0 8 O and /3- be?tzoyZ-P-rn-nitrobe,i.,ylidene- propionic acid NO,*CT,H CH CBz CH,* CO,H slender needles m. p. 1 7 2 O . The cyclopropane methyl ester m. p. 109*5O yields methyZ j3-b en zoyl-P-m-nit rob enzytidenemet h?ylmuZonat e NO,*CGH,*CH:CBz*@H( CO,Me) prisms; m. p. 139*5O when boiled for a long time with magnesium methoxide solution ; this ester gives m-nitrobenzoic acid when oxidised with permanganate in aqueous acetone but a compound m.p. 1 9 7 O of undetermined structure is formed in dry acetone. J. C. W. 4 4'-Dimethylbenzophenone and its Condensation with Phenol. M. GONBERG and J. D. TODD (J. Amer. Chem. SOC. 1917 39 2392-2396) .-Toluene and carbon tetrachloride con- dense under the influence of aluminium chloride t o give a mixture of ditolylmethylene dichlorides which suffer violent decomposition when distillation is attempted. On hydrolysis the mixture gives a 30-35% yield of di-ptolyl Iretone 3n. p. 93O and an oily residue of other tolophenones soluble ill light petroleum. The pure ketone reacts with phosphorus pentachloride a t looo t o form di-p-tolyl- inefhylene dichloride as a mobile green liquid which decomposes a t above 1 7 5 O .This behaves like diphenylmethylene dichloride towards phenol (A. 1916 i 29) giving diphenoxydi-p-tolyl- methane m. p. 1 3 2 - - 1 3 3 O if the agents are diluted with benzene or p-hyc~rox?/phen~ZcZi-ptoZyZcrrr2,inol if no diluent is used. Two forms of this carbinol are' described but no suitable medium for crystallisation has been found. O€I.C,~,*C(C,H,Me),*OH obtained by precipitation with carbon dioxide from a solution in sodium hydroxide is pale yellow turns red and melts a t about 70° and evolves water a t 125O; the quinonoid form (OH),:C,H,:C( Cc,HdMe)n obtained by pouring an acetic acid soIution into water is orange- red becomes dark red and melts at about 6SD and freely gives off water a t above 90°. The Action of Phosphorus Trichloride on Unsaturated Ketones.JAMES B. CONANT (J. A ~ Y . C?mie. Soc. 1917 39 3679- -2684).-Phosphorus tricliloride reacts with a@-unsaturated ketones in glacial acetic acid solution and 011 diliiting the piwlnct B Syntheses of these products are also described. The benzenoid form J. C . W.with water &ketonic phosphonic acids are obtained. It is best t o allow the reaction mixture to remain overnight before diluting ic with water. I n this way phenyl p-methoxystyryl ketone yields P-b en zoyl- a-4-metlz oxyphenyle thp?ph osp h o k c acid OMe*CGH~~CH(PO,H~)*CH,.COPh m. p. 1 8 9 O giving an ozz?ne 1x1. p. 156O (decomp.) a crystalline sodazcrn salt soluble calcium and barium salts and insoluble silver and leud salts. Phenyl styryl ketone yields P-b enzoyl-a-phenyl- ethylphosphonic acid m.p. 116O and distyryl ketone yields B- citi nnmo~y 1-a-ph e nyl e t I& ylph osphonic n cid P O,H - C H P h C H2 CO CI-I C R Ph . JV. G. Bromohydroxynaghthaquinones. A. S. WHEELER arid V. C. EDWARDS ( J . Anzer.. Chenz. Soc. 1917 39 2460-246s. Compare A. 1916 i 392) .-I 4 5 6-Tetrahydroxynapht"ha1ene is an interesting compound since it appears t o exist in only one form but reacts sometimes as a tetrahydric phenol and sometimes as a quinone. The brominatioii of the coixponnd and also of its oxida- tion product nsphthazarin in the cold has now revzaled another curious type of isonerism. Both substances yield quinone di- bromides thus 0 0 0 Naphthazarin -+ " a- " in. p. 1G1-152° Tstrahydro~iyn~pl~tl~tllene. but the iwo products are not identical a i d not interchangeable although they are isomeric a i d yield the same derivatives on treat- ment with alcohol which remov2s t h e elemelits of hydrogen bromide.It rnny be that in one both broiniiie atonis are outside the ring and the hydrogen atonis within whilst in the other form a different spatial arrangement is observed. Naphthazarin reacts with bromine in cold chloroform to give the " u "-form of 5 G-dihydrotxy-1 4-nctPhtILarliii~iOtLC 2 3-(libromitle crys tallisiiig in lemon-yellow prisms which beconie red and then grey between 1 3 5 O and 150° mcl have m. p. 151-152O. This l o s a hydrogen bromide when warmed with alcohol giving 2(or 3)-hrowo- 5 G-t71h?/dro.ry-l 4-uoph tlicrqzricioiie in reddish-brown prisms in. 1'. IS8 - - ! 8 9 O (after giving a coloured vapour a t 170°) and yields the tetrahvdr.oxgiiapht~ialeiie on reduction with slaiiiious chloride.It also forins a diacetnte C,,H,,O,Br when boiled for a 10119 time with acetyl chloride. This crystallises in colourless plates which turn red at l l O o and melt a t 16G-167° and also become deep red when kept and it reacts with alcohol to forin the dincclcifr of the inoBobromo-conipound bright yellow silky needles i l l . 13 191- 193" whit~li niay Ite nht:iiiir~l also I)y "IiwPI :)c'?tyl:it i o l l " 3- " 111. p. 180° +- Quinone form.i. 76 ABSTRACTS OF CHEMICAL PAPERS. Naphthazarin yields 5 6-diacetoxy-1 4-naphthaquinone m. p. 189-190° when boiled with acetyl chloride but the tetra-acetoxy- naphthalene m. p. 277-5279° is fornied if acetic anhydride is applied (compare Zincke and Schmidt A.1895 i 613). The diacetate yields 1 4-dihydroxy-5 6-diacetoxynaphthalene on reduc- tion with stannous chloride ; this forms colourless microscopic plates which turn red a t 230° and have m. p. 241-5243'. Tetrahydroxynaphthaleas reacts with bromine in cold acetic acid t o form the '' fl 7'-modifi~ati~n of 5 6-dihydroxy-1 4-naphtha- quinona 2 3-dibromide. This crystallises in lemon-yellow prisms which begin t o turn red a t 140° and have m. p. 180O. It loses hydrogen bromide in the sunlight becoming steely-blue and it yields all the products described above in connexion with the a-isomeride . If tetrahydroxynaphthalene is brominated in acetic acid a t 70° the product is 2 3-dibromo-5 6-dihydroxy-l 4- naphthapinone (annexed formula) ; this crystal- /\/\CRr lises in red leaflets m.p. 258O and yields a 5 6-diacetate yellow needles m. D. 200-201° which may be reduced to 2 3-dibromo-1 4-di- OH CO hydroxy-5 6-dime tox y napht halen e colourless needles m. p. 196-197O by means of The many inter-reactions which have been established anong CO OH(,\ 1 ,?Br stannous chloride. these compounds are illustrated by a chart. of formula. J. C. W. Oil of Artemisia Annua. K. ASAHINA and YOSHITOMI (J. Phnrm. SOC. Japan 1917 424 1 ; Perf. EPS. Oil Rec. 1917 8 353-354).-0il of Artemisin annun was freed from aldehydic con- stituents distilled with steam and fractionated. The lower frac- tions contained cineole and the higher 2-camphor. The fraction boiling between 1 8 1 O and 190°/10 mm.contained a new ketone C,,H,,O b. p. 18Z0 Dti 0.8906 121ft5 1.4695 mol. refraction 47-57 (calc. 47-45) yielding a semicnrbazone m. g. 95-96O. Reduc- tion by means of hydrogen in presence of platinum converted the ketone into tetrah.y~ro-arte?nlnisia ketone C,,,H,,,O b. p. 73O/15 mm. 173O/760 mm. Di''5 0.8262 n 1.42425 yielding a semicarbacone rn. p. 13&-13150. (See also J . h'oc. Ilhern. I d . 1918 37 Feb.) T. F. B. Constituents of Formosan Lemongrass Oil. KINZO KAFAKU ( J . Ghem. I d . TGhyc-i 1917 20 825-833).-Forniossn lemongrass oil contains an olefinic terpene which yields dihydro- myrcene and 2 6-dimethyloctane on treatment with hydrogen under different conditions and succinic and oxalic acids on oxida- tion; it' is therefore believed to be mgrcene. The oil also contains an aldehydic substance other than citral which however has not heen isolated.(See1 also ,7. SOC. Chem I n d . 1918 37 Feb.) T. F. R.ORGANIU CHEMISTRY. i. 71 Action of Alkyl Nitrites on Pyrrole. GUIDO CUSMANO ( A t t i R. Accad. Lincei 1917 [v] 26 ii 127-131).-The action of ethyl nitrite on pyrrole in the presence of sodium ethoxide a t 5-10O results in the production of nitrosopyrrole-black (A. 1917 i 413) and the ethyl ester of the oxime of maleiiaimide OH*N:Y-NH CH:CH >co which forms colourless needles m. p. aboutl looo. This compound is hydrolysed by water acids or alkalis with formation of the oxime C,H,O,N which decomposes a t 195O and melts at 205O. The oxime forms a sodium salt C4H,0,N,Na which when treated with ethyl iodide yields a derivative isomeric with the ethyl ester above described; it crystallises in pale yellow needles m.p. 55-60O. The oxime of maleinimide when treat’ed with bromine yields fumaric acid and monobromomaleinimide. R. v. s. Betakes and Alkyliodides. R. VON WALTHER and ALBERT B. WEINHAGEN ( J . pr. Chem. 1917 [ii] 86 50-58).- ctChlorophenylacetic acid reacts normally with quinoline giving rise to a betaine additive cornpound of the formula C,,H140,NCI (mercwichloride m. p. 140O; perchlorate decomp. a t 120°) but with pyridine a-picoline and nicotine the additive process is com- plicated by the liberation of carbon dioxide the products re- spectively being benzylpyridinium chloride b enzylp’colinium chloride (aurichloride m. p. 133-134O ; platinichloride m.p. 212-213O; dichromate m. p. 129”) and beiaz.ylnicotinivm chloride decomp. at 236O (diazcrichloride decomp. at 1 7 8 O ; picrate decomp. at 9 9 O ) . With quinaldine and s-collidine however no additive product is obtained probably owing t o steric hindrance but the latter base presumably on account of its greater basicity extracts hydrogen chloride) from the chlorophenylacetic acid Pyridine and a-chloropropionic acid when heated together give rise to ethyl- pyridinium chloride (aurichloride m. p. 190° decomp.) carbon dioxide being liberated. With benzyl chloride and nicotine the monobenzyl- or dibenzyl-nicotinium compound is obtained accord- ing to the proportions taken ; dibenzylnicotinizwz diaurichloride decomposes atl 183O and the pdatinichloride a t 211° whilst the picrate has m.p. 122O. With o-nitrobenzyl chloride the following products were obtained o-Nitrob enzylpyridinium chloride C,~,H,,O,N,Cl,l&H,O colourless needles m. p. 103O ; mercurichloride leaflets. m. p. 1 4 5 O ; dickromate m. p. 172O; percldorate with 1H,O m. p. 154O; platinichloride m. p. 223O decomp. a t 228O; pz’crate needles rn. p. 148O. o-Nitrobenz?/l-a-~colinium chloride C,,H,,O,N,Cl m. p. 1 1 5 O ; nurichloride m. p. 132-133O. o-1C’itrobenzyZ~?cinoli,iiicl? chloride ; dichromate carbonises a t 190-200° ; merczcrichloridp. o-Nitrob eizzylnicotinium chloride ; platinichloride C,,H2102N3PI;C1 m. p. 227-229O ; dicrurichloride ; dichromnfe m. p. 1 1 0 O . No reac- tion was observable between o-nitrobenzyl chloride and collidine,i.78 ABSTRACTS 02' CHEMICAL I'APEltS. probably on account of steric hindrance. m-Nitrobeiizyl chloride in a similar manner was made to yield m-nitrob enzylpyridinizcnh chloride crystalline spangles with l+H,O m. p. 97-99O (nzerczcri- chloride needles m. p. 117-119°; diclzromate in. p. l 8 9 O decomp.; perchlornte needles in p. 142O; picrote needles m. p. 142O ;. plati?zicldoride in. p. 213-215°) ; rn-nit rob enzyl-a-picoli,iizrnz. chlorzde needles in. p. 1 1 8 O (aurichloride in. p. 1 5 9 O ) ; In-nitro- b e,c?z?/lylrinoliiiizr?n chloride (dichromate carbonises at 190' ; n 7 ercu r ichloricle) ; slid m-nitro b en x ylnicot iiiium c hloinide (plat in& chloride m. p. 204-205O decornp.; atrrichloride m. p. 185O decomp .) . Similarly p-nitrobenzyl chloride yielded p-nitro- benzylppriclinium chloride with 1 $H,O in.p. 64-66O (merczcri- chloride needles or tablets m. p. 137O; perchlorate needles m. p. 1 3 1 O ; dichronzate ; picrate needles m. p. 171O; platinichloride spangles in. p. 21O-21lo) ; p-nitrobenzylnicotiniun~ chloride (auri- chloride decomp. near 80° ; plutinichloride m. p. 223O) ; p-nitro- besaxyl-a.-p~icolini~~~ii chloride (nurichloride m. p. 1 5 9 O ; plntini- clalorade needles m. p. 2 1 7 O ; naercurichloride needles m. 11. 139-14OO) ; and p-nitrob e?zz?/lcluiiaoEiniuiiz chloride (dic hronzcct e m. p. 1 T 6 O ; nzemcricliloride) ; 2-methylquiiioline and collidiiie did not form additive compounds with p-nitrobenzyl chloride. Collidine (perchlorate m. p. 2 3 3 O ) when heated with benz- aldehyde gives rise t o b e~zzylidenecollidin~ e an izndistillable oil (?i,erci~ricJrloride M.1). 226O; platinichloride with 1 H,O m. 11. 236-238O) but no reaction was observable with acetaldehyde nitrobenzaldehyde or chloral. Attempts t o prepare alkylaminoacetic acids by the decomposition of pyridinebetaine with the aid of nitric acid or of hydriodic acid and phosphorus were unsuccessful the only isolated product being ppridiii e . D. F. T. The Estersication of 2 4-Lutidinetricarboxylic Acid. ALFRED KIRPAL aJnd KARL REINANN (Jfonatsh. 1917 38 249-265. See A. 1906 i 697; 1907 i 722).-When 2 4-dimethyl- pyridine-3 5 6-tricarboxyiic acid (2 4-lutidinetricarboxylic acid) is esterified by means of alcohol and hydrogen chloride the sole product is the 6-et Jbyl ester C,,H130,N,2H,0 colourless prisms in.p. logo t o the formation of which there is least steric hindrance; the constitution of this ester is demonstrated by coilversion through the corresponding crmide C',,H,,O,N m. p. 240° (decomp.) into 6-amim-2 4-dimethylpyridine-3 ; 5dicurboxylic acid C,M,,0,N2 m. p. 242O (decomp.) which on treatment with nitrous acid and heating yields successively 6-hydro~y-2 4-dirnethylpyriditze-3 5- dicarhozylic acid C",H,O,N,H,O needles m. p. 232O and 6-hydroxp- 2 4-dimethylpyridine (y-lutidostyril ; Hantzsch A. 1885 397 j. If the dimethylpyridinetricarboxylic acid is esterified with alcohol only the above ester is obtained together with a small quantity of the isomeric 5-ethyZ ester C,,H,,O,N,ZH,O colourless prisms m. p. 80° and then a,t 170° (decomp.) the two esters being also obtain- able by the action of alcohol on the mIi,?ldride rhombic tablets,ORGANIC CHEMISTRY.i. 79 in. p. 2 3 2 O (decomp.) which was produced by heating the dilnethyl- pyridinetricarboxylic acid with acetic anhydride. The 6-ethyl ester unlike the 5-ethyl isomeride is rapidly hydrolysed by boiling with water and is inert towards alcoholic hydrogen chloride whereas the latter ester is converted into the 5 6-diethyZ ester short prisms m. p. 107O. By heating the ammonium salt of 2 :4- dimethylpyridiiietricarboxylic acid at 160-1 T O O it is possible to obtain the imide C,,H,04N,,H,0 m. p. above 300° (decornp.) which when heated in neutral aqueous solution gives the isomeric 5-amide and 6-amide in almost equal quantities.The electrical conductivity of the 5-ethyl 6-ethyl and 5 6-diethyl esters and of the parent 2 4-diniethylpyridinetricarboxylic acid was examined in aqueous solution; the acid is a stronger electrolyte than pyridine-2 3 4 5-tetracarboxylic acid. C14H1,06N7H20 9 D. F. T. Two New Bases from Coal Tar. ALFRED ECKERT and SOPHIE LORIA (Monatsh. 1917 38 225-247).-Weidel and Pick (A 1885 556) isolated from bone oil a base which they believed to be 4-methyl-2-ethylpyridine but the properties of this base when synthesised from y-picoline and ethyl iodide prove that' the base from bone oil was a t any rate not pure and possibly contained 110 ethyl-substituted pyridiiie whatever. Examination of the collidine fraction obtained from coal tar revealed the presence of s-trimethylpyridine 3 5-dimethylpyridine7 a sniall quantity of a collidine b.p. 165-1GS0 and of a base giving a picrate in. p. 114-116° together with 2 3 6-trimethyl- pyridine and 2 3 4-triniethylpyridine. These two bases have iiot been found previously in coal tar; the latter has already been pro- duced synthetically (Guareschi A 1900 i 558) whilst the former is now described for the first time. No indication of the presence ol any ethyl derivative of pyridine was observed. 2 3 6-Trimethylpyridine C5H2NMe3 b. p. 173-174O/734 mrn. fbrms a platinichloride with lHtT,O in. p. 250-252O (decornp.) nurichloride needles in. p. 106O picrate yellow needles in. p. 143-144O and on oxidation yields pyridine-2 3 6-tricarboxyZic acid C,H,N(C0,H),,2H20 m. p. approx 130° which a t a higher temperature undergoes decoinposition into pyridine-2 5-dicarboxylic acid.Z-Methyl-4-ethylpyridine prepared by the action of ethyl iodide on a-picoline was found to have b. p. 177-179O/751 nim. (Schultz A. 1888 64 gives 169-174') and t o give a platinichloride yellow cubes m. p. 203O and a picrate m. p 141-142O whilst the isomeric 2-methyl-6-ethylpyridine obtained in the same reaction had b. p. 160°/747 mm. gave a platinichloride m. p. 188-190° (decornp.) and a stcrnnichloride. m. p. 206-207O ; synthetic 4-meth?/l-2-ethyllE?/?.idilze b. p. 173-175O/748 mm. yielded a pZatinichloricZe ni. p 230° a picrate m . p. 115-116° and a 717~1'cZ~riChToi,ide m. p. 94-960. D. I?. 2'.i. 80 ABSTRACTS OF CHEMICAL PAPERS A New Synthesis of 2:4-Dioxythiazole and of its 3-Phenyl Derivative. RUDOLPH RNDREASCH (3!Io?zatsh.1917 38 203-209. Compare Andreasch A. 1880 877 ; Andreasch and Zipser A. 1903 i 855).-When potassium cyanate is added to a cold aqueous solution of equirnolecular quantities of thiolacetic and acetic acids the potassium salt of carbainylthiolacetic acid NN,CCO*S*C13[,*C0,H is produced ; on repeated recrystallisation from hot water this xicl undergoes dehydration into 2 4-dioxy- thiazole S<ce,.bo . Fhenylcarbimide and thiolacetic acid in CO-N H ethereal solution* react rea,dily with formation of 2 4-diosy-3- phenylthiazole S<cH,. ~~ and cerbanilide the formation of co-y Ph the latter being due toathe action of water on the phenylcarbimide. The obscrvcd conversion of 3-phenyli.colhiohydantoin into 3 4-dioxy-3-phenylthiazolc carbamyltl.liolacetic acid thiolacetic x i d and aniline under the influence of mineral acids is probably due t o the decomposition following two different courses one in- volving mere elimination of the imino-group and the other depend- ing on the disruption of the cyclic molecule; however the possi- bility t h a t the phenylisothiohydantoin contained some of the 2-phenyl isomeride is not excluded.D. F. T. Reduction of 4-Anisylidenehydantoin- 1 -acetic Acid qnd its Ethyl Ester. DOROTHY A. MAHN and @. PAULINE Bum 2468-2472. Compare A. 1917 i 475).-A variety of products is formed when this acid is reduced with sodium amalgam. Using one equivalent proportion of 274 amalgam and aqueous alcohol as the solvent and boiling for one hour keeping the mixture neutral by additions of acetic acid sodium 4-n 17 i!:y 2 ide nehydamt oi?i- 1-ace tn t e separates in well-defined greenjsh-yellow plates which become white on dehydration.After boiling €or two hours the salt which separates on cooling in needles is sodium 4-anisylh?~dnntoi~2-1- acetate whilst after boiling with an excess of amalgam the disodiunz salt CO,Na*CN,*NH*@Q *NM* CH ( CO,Na)*CI~,.~~H,*OMe is obtained as a crystalline precipitate which gives the corresponding open-chain acid ( h c . cit.) on acidifying wibh hydrochloric acid. Reduction with' zinc and aqueous acetic acid gives a small amount of a zinc salt of the formula [ W i t h TREAT B. JOHNSON] ( J . ,+imer. Chem. SOC. 1917 89 7 IC*CO*NH*CH,*CO*(I OXe* C,W,.CH C -CQ*O----- Zn This yields the original 4-anisylirlenehydantoin-1 -acetic acid on zcidifying.These salts do not melt below 3 1 5 O and when they were ciicouii- tered in the earlier work they were erroneously regarded as a geo- metric isomeride of the parent acid. J. C. W.ORGANIC CHEMISTRY. i. 81 Pyrimidines. EXXXVI. Production of Glyoxalones by Hydrolysis of Pyrimidine Nucleosides. TREAT B. JOHNSON (,7. Amm. Chcm. h‘oc. 1917 39 2396-2405. Coinpare R. 1916 i 754; 1917 i’ 585 667).-In recent papers i t has been shown that certain hydroxypyrimidine conlpounds can be converted into glyoxalones merely by hydrolysis wit11 acids ; thus the secondary uracil-nucleoside 4-a-hydroxyethyl-1 2 3 6-tetrahydropyrimid- 2 6-dione yields 4 5-dimethylglyoxalone This remarkable reaction presents therefore the expulsion of a carbon atom from a &membered ring with the formation of a 5 -membered nucleus.Somewhat analogous reactions of the pyrimidine ring have been known for a long time but these are the result of oxidation and not mere hydrolysis. Thus the oxidation in alkaline media of uric acid to allantoin and of 4-methyluracil to parabanic acid repre- sent such a removal of a carbon atom. I n both cases the accepted interpretation of the reaction is that given by Behrend who sup- poses that the glycols are first produced by oxidation and that sub- sequent rearrangements take placs within these volecules. Between these glycols and the uracil-nucleosides there is just one feature in common namely a hydroxyl group five places removed from the’ nitrogen atom numbered 1 ; thus (1 ILVH-C@(G) ‘NH-CO WH-CO A0 “b(OJ-T)*NH CO W(OH) 60 CH I I I I I 1 KH-I’(OR~NH >’* kH-CMeoOH NH-~-EHM~.OH Uric acid glycol.Trihydroxydihydro- Secondary Should the union between the nitrogen atom 1 and carbon atom 6 be broken for example by hydrolysis there would be a hydroxyl group available for a recondensation t o a 5-membered ring and this is the explanation offered of the glyosalone formation. The following scheme illustrates the probable course of the change methyluracil. uracil-nucleoside. Other activities of the above glycols are discussed; and the trend of future researches in this field is indicated. J. C. W. The Decamposition of the Three Et.hoxyphenylhydrazines by Hydrochloric Acid. HARTWIG FRANZEN and MORITZ SCHMIDT ( J .pr. Chem. 1917 [ii] 96 1-25).-Itl is already known that ini. 82 ABSTRACTS OF CHEMICAL PAPRRS. the aminophenylhydrazines the presence of the amino-group reduces the stability of the linking between the two nitrogen atoms (Franzen and von Furst A. 1914 i 206; 1917 i 58 59) and the results of the present investigation demonstrate tha't the ethoxy- radicle exerts a similar but less powerful influence. p-Ethoxyphenylhydrazine was obtained by Altschul's method ; the hydrochloride when pure has ni. p. 165O (decomp.); the base yields a benzylidene derivative C,,H,,ON rose-red needles m. p. 124-125O ; a pyruvic acid derivative OEt*C,HqNH*N:CMe*CO,H yellow needles m. p. 1 1 8 O ; and a dihenzoyl derivative C&ET2,03N2 colourless needles in. p. 1 4 6 O .OEt*CbH,*NH*NH was prepared by converting o-phenetidine into sodium o-ethozy- diazo b e nz en esulphonat e OE t *C,H4*N2*S03Na yellow cry st als decomp. with mild explosion a t 170° and reducing this with zinc dust and acetic acid to .sodium o-et?ioxyplzeizylh?/drazineszllphonate OEt*C,H,*NHNH-SO,Na colourless pearly leaflets m. p. 205O (decomp .) which on decomposition with aqueous-alcoholic hydro- chloric acid gave the h?/drochZoride needles m. p. 159-160° (decomp.) of the desired base ; benzylidene derivative C,,H,,ON pale yellow needles m. p. 98-99O; pyruvic acid derauative OEt*C,H,*NH*N:CMe*CO,H yellow needles m. p. 138O ; dibenzoyl derivative colourless crystals m. p. 1 5 8 O . m-Phenetidine prepared from m-nitroaniline by way of m-nitrophenol and m-nitrophenetole was by successive diazotisation and reduction converted into m-e t hoxyphenylhydrazine OE t*C,H4*NH *NHg ; hydroc h l o d p colourless ; benzylidene derivative colourless needles m.p. 80°. When heated with boiling 2N-hydrochloric acid o-ethoxyphenyl- hydrazine hydrochloride undergoes decomposition with formation of p-phenetidine phenetole p-azophenetole ethyl chloride ammonia and nitrogen and analogous products with the excention of the azo-compound were observed in the decomposition of the ortho-isomeride. The decomposition in each case probably involves a prijnary formation of chloroamine or of ethoxvphenylchloro- amine modiiced bv the reactions OEt*CoH,*NH*NFT + HCl = OEt*C,B,*NH + NH,Cl and OEt=C;,H,*NH*NH + HCI = OEt*C,H,*NHCl+ NH3 respectively the various isolated products resulting from the subsequent reactions of these primary products. By allowing the action of hydrochloric acid on these ethoxyphenyl- hydrazines t o occur in ths presence of a reducing agent such as stannous chloride the a,lvn7e mnciirren t reactions hecorre renlaced l w the sinple reaction OEt*CnH1*NH*NR9 + 2H= OEt*C,H,*NH + NH? so tha,t the cruantitv of ammonia formed supdies a convenient measure of the; relative rates of the reaction with the ortho-. meta- and para-compounds.By proceeding in this manner it is shown that pethoxyphenvlhydrazine is reduced most raDidly and the nieta- isomeride least rapidlv so that the weskenine effect of the ethov- qrour in various positions. on the stabilitv of the N-N linkinR f a l l s in the order 17 > o > nt.althouph the influence of the ethoxy-pup ia much less than that of the amino-group. o-Etlzoxypl~enl~Zh?ldl.niine,ORGANIC CHEMISTRY. 3. 83 The decomposition of the three plienetidines by boiling hydro- chloric acid with formation of ethyl chloride was also investigated with the result that the reaction was found to occur most rapidly with p-phenetidine and least rapidly with o-phenetidine. D. F. T. The Nitrogen Distribution in Protalbic and Lysalhic Acids. CORNELIA KENNEDY and Ross A ~ n m GORTNER ( J . 9 ?II er. Cheii2. SOC. 1917 39 2734-2736).-Lysalbic and prot,albic acids h a ~ e been prepared from egg-albumin by Paal’s method (conipare A. 1902 i 653) and their nitrogen distributions have been determined by Van Slyke’s method and coinpared with that of the origiiial albumin with the following results Percentages in Ammonia nitrogen ................................. Hiimin ...................................Cystine ................................. Arginine ................................... Histidine ................................. Lysine ,) ................................. Amino-nitrogen in filtrate from bases. ........ Non-amino-nit,rogen in filtrnto from bnces ... Total.. .......... Egg- albumin. 9.0s 4-71 0.72 6.05 6.48 10.09 61-20 4-55 102.97 Protalhic Lysalbic acid. acid. 5.0s 8.2 1 4-00 4.49 0.11 0.51 6-38 6.23 7.96 8-42 13-73 12-50 58.17 58.37 5.22 2-70 100.s9 94.43 W. G. - - Animal Globulin. I-VI. Confirmed and not Confirmed. JOHANNES STARKE’ (Zeitsch. Biol. 1917 68 147-159.Compare A. 1901 i 242).-The author points out that his views on globulin based on experiments with ovoglobulin have since been confirmed by Hekma’s work on fibrinogen (A. 1916 i 513). He also claims priority for the demonstration of the transformation of albumin into globulin usually ascribed to Moll (A 1904 i 356; but see Bywaters and Tasker A. 1913 i 1399). H. W. B. The Effect of Prolonged Acid Hydrolysis on the Nitrogen Distribution of Fibrin with Especial Reference to the Ammonia Fraction. Ross AIKEN GORTNER and GEORGE E. HOLM ( J . Amer. Chem. SOC. 1917 39 2736-2745).-Fibrin was hydrolysed by boiling with 20% hydrochloric acid for periods of time ranging from one hour to six weeks and the distribution of nitrogen in the products was determined by Van Siyks’s method.The figures for ammonia nitrogen in an acid hydrolysate include not only the aniide nitrogen in the protein molecule but also some ammonia derived from the deamination of certain of the amino- acids. The extent of this deamination depends on the length of hydrolysis the monoamino-acids being deaminised much more easily than the histone bases. Cystine is not the only amino-acid which undergoes (leamination when bailed with hydrochloric acid (com-i . 84 ABSTRACTS OF CHEMICAL PAPERS. pare Van Slyke A. 1912 i 735). The figures in a Van Slyke :1 nalysis for histidine arginine and lysine are not appreciably altered by a hydrolysis extending over six weeks providing that all tryptophan has been so altered that i t is not precipitated on the addition of pliosphotungstic acid.Increases in the insoluble humin nitrogen owing to proloiiged hydrolysis are probably due to carbon- isation. W. G . Origin of the Humin Formed by the Acid Hydrolysis of Proteins. 111. Hydrolysis in the Presence of Aldehydes. 11. Hydrolysis in the Presence of Formaldehyde. Ross AIKEN GORTNER and GEORGE E. HOLM ( J . Amer. Chem. Soc. 1917 39 2477-2501. Compare A. 1915 i 726; 1916 i 681).-The nitrogen distribution in the hydrolysates of fibrin and gelatin obtained by boiling these proteins with hydrochloric acid and vary- ing quantities of trioxymethylene has been determined by Van Slyke’s methods with the modification that the humin fraction has been differentiated into (a) “acid-insoluble ” humin ( b ) “acid- solublei” humin precipitated by calcium hydroxide and (c) ‘‘ phos- photungst<ate ” humin precipitated by phosphotungstic acid.With fibrin the addition of aldehyde increases the yield of black insoluble humin up to a maximum about 100% above the normal. Further quantities of aldehyde then cause a decrease in the amount of insoluble humin and an increase in the soluble humin up to a second maximum when the continued addition of aldehyde causes decreases in the humin fractions and an increase in ammonia. With gelatin formzldehyde has no influence on the humin fraction which is very small but causes a steady increase in the yield of ammonia. This difference between the two proteins is obviously t o be con- nected with the lack of cystine histidine tyrosine and tryptophan in gelatin. With which of these amino-acids the humin formation is connected can theref ore be ascertained by hydrolysing mixtures of gelatin and these acids in the presence of formaldehyde.Cystine and histidine are not the critical acids. Tyrosine causes no increase in insoluble humin but a considerable increase in soluble humin which is not the true humin of protein hydrolysis as i t is not black but reddish-yellow. Tryptophan. however is the all-important constituent.. I f this is added t o gelatin the hydrolysates correspond with those obtained from fibrin. As tryptophan does not’ give rise to humin when boiled with hydrochloric acid unless an aldehyde is present tho inference is that an aldehydic substance as vet unknown is produced during protein hydrolysis but notl in sufficient quantity to combine with all the tryptophan since added aldehyde gives a higher yield of humin.Indole aJone also yields humin when boiled with hydro- chloric acid and formaldehyde so the condensation does not involve the side chain in the case of tryptophan. PyrroIe also produces humin but not so pvridine which sizgpests that whilst the pvrrole ring is critical it is possiloly not the imino-group which is con- nected with the condensation. That the a-amino-group of trypto-ORGANIC CHEMISTRY. i. 86 phan remains intact in the humin is proved by the fact that the humin formed from tryptophan and trioxymethylene under the most favourable conditions contains half its nitrogen in the amino- condit4ion just as in the free acid. Most probably therefore it is position 2 of the indole complex which is concerned in humin formation.Further experiments on mixtures of the pure amino-acids are well in hand but the authors are already convinced that tryptophan and some aldehydic component of the protein molecule are the only factors involved and they adversely criticise Roxas’s results in the same field (A. 1916 i 797). J. c. w. Helicorubin. I 11. CH. D H I ~ R ~ and G . VEGEZZI (J. Physiol. Path. gtn. 1917 17 44-52 5 3 - 4 7 . Compare A. 1917 i 421). -The bile of the snail Helix ponzntia contains a dialysable red pigment helicorubin (Krukenberg = enterohematin of MacMunn) and a non-dialysable brown pigment for which the name helico- fuscin is suggested by the present authors. By means of acidified alcohol helicorubin is transformed into hamatin spectrometrically identical with the substance obtained from vertebrate hzmoglobin.Potassium permanganate changes helicorubin into the same pigment with absorption band in the yellow as is obtained from haematin and finally sodium hyposulphite reduces helicohzmatin to hemato- porphyrin (of vertebrates). The bile was obtained from hibernabing snails free from chlorophyll. These experiments show helicorubin to be an “embryonic or ancestral ” form of hzmoglobin as was already surmised by Sorby and by MacMunn. G . B. 11 Carbohydrate ” Group of the True Nucleic Acids. 11. R. FEULGEN (Zeitsch. physiol. Chem. 1917 100 241-258. Corn- pare A. 1914 i 1098) .-The elementary analysis of sodium nucleate prepared from the thymus indicates the empirical formula for the substance. A study of the hydrolytic products shows how- ever that if the carbohydrate groups present in the molecule consist of dextrose the molecular weight of sodium nucleate must be considerably larger than that indicated by the above formula.The author finds that as a mztter of fact the carbohydrate groups consist of glucal (compare Fischer h. 1914 i 252) instead of dextrose molecules the chief reactioiis of glucal being given by the carbohydrate isolated from the hydrolytic products of the nucleate. The assumption of glucal ( CGHl0Os) instead of dextrose (C,H,,O(;) molecules also stands in harmony with the above empirical formula. HOWARD T. GRABER ( J . Znd. Eng. Chem. 1917 9 1125-1126).-1n comparative esti- mations of the rennetic activity of calf rennet and of pepsin from the hog’s stomach it was found that whereas the former never failed ~*3H470,,N 24N24 H.W. B. The Rennetic Properties of Pepsin.i. 86 AQSTRACTS OF CHGMIOAL PAYERS. to coagulate fresh milk or to give comparable results when diluted the latter usually failed to coagulate fresh milk and did not show an activity proportional to its dilution. The pepsin was most active in milk of an acidity of 0.2% or more whilst the activity of the rennin was not promoted by such high concentration of acid. By bringing the acidity of fresh milk t o 0.185% by the addition of lactic acid the results were comparable with those produced in fresh milk by the rennet. These results support the view that the two enzymic activities of pepsin are associated in a single molecule and that on contact with milk and acid or protein and acid coagula- tion of the milk or hydrolysis of the protein is effected (see also J .SOC. Chem. Znd. 1918 37 Feb.). 3hmw w. ~ O C K ~ Y O O U ( J . Brner. Ckenz. SOC. 1917 39 2745-2752).-A-n examination of the effect of various nitrogenous substances on the hydrolytic activity of the amylases of the saliva on starch those whiSh increase the activity being called auxoamylases. a-Amino-acids whether aliphatic or cyclic act as auxoamylases this being true in the case of cyclic compounds whether the amino-group is in a side chain as in tyrosine or in the ring as in the aminobenzoic acids. The posi- tion of the amino-group in the beilzene ring with reference to the carboxyl group has no effect on the activit'y. Not only do the acid amides not' actl as auxoarnylases but the entry of an amino- group in the carboxyl group destroys the e h c t of an amino-group elsewhers in the molecule. Thus aspartic acid is an auxoamylase asparagine is not. The sulphonyl group if substituted for the carboxyl group in an amino-acid destroys ths stimulating effect of tjhe amino-group on the amylases. Replacement of one of the hydrogen atoms in an amino-group by an acyl group as in hippuric acid does n o t destroy its stimulatiiig action. Imides however am 110b auxoamylases. The proteins act as auxoamylases towards Ihyaliii the effect increasing as the number of free amiiio-groups increases by the Ikydrolysis of the protein. As far as the tests go they indicate that' amino-acids act as auxoamylases not only on Supposed Action of Potassium Permanganate with Plant Peroxydases. H. H. BUNZELL and H. HASSELLRING (Bot. Gaz. 1917 63 225-228; from Plzysiol. Abstr. 1917 2,544). -Permanganate reduced to a brown solution by excess of various organic substances can still oxidise guaiacum pyrogallol or potassium iodide and on the basis of these experiments the. authors criticise the conclusion drawn by Reed (compare A. 1917 i 423 4-24) when he observed this phenomenon with horse-radish extract that a specific interaction of peroxydase with perrnanganate was taking place t o give a high-grade oxygenating substance. C. A. 35. Some Nitrogenous Auxoamylases . ptyalin but also on the pancreatic amylase. w. G . G . B.

ISSN:0368-1769    

DOI:10.1039/CA9181400057

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. Inorganic Chemistry. .. 11. 75 The Crystalline System and the Axial Ratio of Ice. F. RINNE (Ber. K . Sachs. Ges. TViss. Math-phys. Klasse 1917 69 57-62; from Chem. Z e n t r . 1917 ii 671. Compare ibid. i 452). -Using the apparatus described earlier the statement of Nordens- kiold that ice is hexagonal-bipyramidal (hexagonal-hemimorphic a c = 1 1-6) is confirmed. This result is regarded as supporting the author's law of isotypism according to which ice follows the magnesium type. D. F. T. Black Phosphorus. 11. A. SMITS G. METER and R. TH. BECK (Proc. K. Akad. W e t e n s c h . Amsterdcim 1918 20 392-393. Compare A. 1916 ii 185).-Experiments in which black and violet phosphorus were heated for prolonged periods a t 480° and 450° indicate that' the black niodifica,tion is metastable a t these temperatures and in presence of 1% of iodine as catalyst is trans- formed into the violet form.Mistures of violet and black phos- phorus in the ratio 4 l heated for fourteen weeks at 380° showed complete transformation of the black into the violet form but no appreciable change took place when the proportion of violet t o black was 1 :4. [See J . SOC. Chent. Ind. 1918 March.] H. M. D. The Thermal Dissociation of Metaphosphoric Acid. D. BALAREFF (Zeitsclz. mzorg. Chenz. 1918 102 34-40).-The author studies the formation and thermal dissociation of metaphosphoric acid by heating orthophosphoric acid for varying lengths of time in a pear-shaped gold flask having a long neck A current of dry air. led into the Aask through a gold tube serves to carry away any water-vapour formed whilst the volatilised melaphosphoric acid and phosphoric oxide condenses in the neck of tlhe flask.A t the end of an experiment the flask is closed weighed and the residue analysed by estimating phosphoric oxide by the method of Schmitz. The product always contains less water than that required for met'aphos- phoric acid the deficiency being greater the more prolonged the heating. The thermal dissociation of metaphosphoric acid in the gaseous state is therefore established. The results of those ob- servers who have obtained metaphosphoric acid containing excess of water are to be explained by insufficient heating or by the presence of impurities in the phosphoric acid used (compare Holt ;tiid Myers T. 1913 103 532 The dehychtion of ortho phosphoric acid solutions by heating does not take place in dcfinit ti 536).ii.76 ABSTRACTS OF CHEMICAL PAPERS. stages but is iiifluenced by the rate of heating and by the vapour tensions of water and phosphoric oxide. Even a& 260-300° phos- phoric acid volatdlises with the water in appreciable quantities. The composition of the residue depends on the temperature and diiration of heating. [Compare J . SOC. Clzem. Itid- 1918 March.] E. H. R. The Existence of Basic Calcium Carbonates. ED. DONATH and A. LANG (Osterr. Clzem. Zeit. 1917 [ii] 20 1'75-176; from Cheni. Zentr. 1917 ii 672).-When brought into contact with water and liniel calcium carbonate becomes hardened due to a fixation of part of the lime; this result is adduced as evidence of the probable existence of basic carbonates of calcium (compare Busvold A.1917 ii 207). Glucinum Nitride. A. C. VOURNASOS (Bid1. S'oc. chim. 1917 [iv] 21 282-288. Compare A. 1911 ii 600; 1913 i 25).- Gluciiium nitride may be obtained by the direct action of cyano- gen on glucinum a t 8 0 0 O . The partial oxidation of a cyanide or of a carbide in the pres- euce of nitrogen will in certain cases yield nitrides. Thus i f zinc or copper cyanide or calcium carbide is heated with ammonium nitrate the corresponding nitride is formed 3Zn(CN)?+ 12NH,NO = Zn3N + 6C0 + 14N2 + 24H20. Barium cyanamide similarly reacts with ammonium nitrate t o give barium nitride. [See also J . Sor. Chmz. Ind. 1918 March.] A Silica-Glass Mercury Still J. C. HO~TETTER and R.B. SOSNAN ( J . Waskington A cad. Sci. 1918 8 ll-l5).-Vacuum mercury stills made of ordinary or combustion glass are liable to collapse when slightly overheated. This has led to the construction of a silica-glass still the design of which is of the simplest possible kind in order t o minimise the difficulties connectled with the work- ing of the fused silica. The distillation chamber is heated electri- cally and the pressure reduced to less than 10 mm. Mercury Ammonia Compounds I. MURIEL CATHERINK CANNING HOLMES (T. 1918 113 74-79).-By digesting infusible precipitate at l Q O o with solutions nearly saturated with respect t o am moniuin chloride and containing varying quantities of mercuric chloride and examining the crystals which separate on cooling it has been found that the product consists of the compound 3HgC1,,2NH3 or of HgC1,,2NH3.There is no evidence of the formation of any compound of intermediate composition. The product obtained under similar conditions by using solutions nearly saturated with mercuric chloride and variable small amounts of ammonium chloride has the composition HgC1,,NH2-HgCl. This compouiid has previously been obtained by Stromholm (A. 1906 i 93.5; Z e j f w l i . ( I I I O ~ ! / . CTi(t?i. 1908 57 72). Electrolysis of Solutions of the Rare Earths. 111. L. M. I)F;NNTS ;ind A. R. RAY ( J . I m ~ r . (IhPtn. Soc. 19t8 40 174--181). Tho fact that the electrolysis of solutions of rare earth salts leads D. F. T. W. G . H. M. D. H. M. D.INORGANIC~CHEMISTRY. ii. 77 1 o LLC fractional precipitatiou of the rare earth hydroxities ( c w t i i - 1,al.e A.1915 ii 775) has been attxibiited to tlie action ol' t l l t i hydroxyl ions set free a t the mercury cathode the hydroxide 01' [,tie weakest base being precipitated first. T n the expectatioii t h a t vigorous stirring of the mercury surface would facilitate the f r x - tionation esperiiiients have been made with neutral soIutions of the nitrates of the rare earths of the yttrium and erbium groups the average atomic weight of the metal being 106.95. The hydr- oxides precipitated a t different stages were removed and the average atomic weight of the metal in each fraction determined. Comparing the results obtained in two series of electrolytes in one of which the cathode was vigorously and in the other slightly agitated it is found that vigorous stirring causes a more rapid segregation of the earths of higher atomic weight in Ihe early fractions and a better concentration of the earths of lower atomic weight in the last fractions.Other experiments in which neutral solutions of the nitrates of the rare earths and thorium were electrolysed show that fraction- ation occurs the thorium being concentrated in the early frac- tions. A Thermoelectric Method for the Study of the Allotropic Transformations of Metals. R. DURRER (Stct ZiZ m d Eisen 1917 37 430-431; from Chem. Zent?.. 1917 ii 672. Compare Benedicks A. 1916 ii 172).-After a description of the appara- tus used by Benedicks a statement is made that the decision of the latter with respect to the discontinuity a t the point' A of the curve for iron and the absence of discontinuity at the point A is based on insufficient material.D. F. T. [See also J . SOC. C'It~nz. Znd. 1918 March.] H. M. D. Iso- and Hetero-poly Acids. XV. Heteropolytungstates and some Heteropolymolybdates . ABTHUR ROSENHEIM and JOHANNES JAENICKE (Zeitsclz. anorg. Chem. 1917 101 235-275.. Compare this vol. 191.-In this paper is given the new experimental data which the authors have used in the dedopment of their theory of the constitution of the heteropoly acids. The acids of the fundamental type have the constitution expressed by the formula H12-n[R?z(M207)6] where R is the non-metallic element and M the metallic. These acids form two series of hydrates one series crystallising in quadratic octahedra with 28H,O the other in rhombohedra with 22H20.They are the mostl stable of the heteropoly acids and are formed in presence of excess of the metallic acid. The 8- and 9-basic acids show isomerism of a type not under- stood. 12-Borotunystic acid H,[ 33 (\V20,),],28H,0 forms crystals of two kinds large transparent octahedra m. p. 45-51° and slender needles. A lower hydrate with lOH,O was isolated. An iso-12- borotungstic acid H,[B(W2O7),],22H20 was obtained in the form of hexagonal bipyramidal crystals. 12-Silicomolybdic acid H8[Si(Mo,0,),1,28H,0 forms transparent octahedra which melt' gradually a t 47-55O t o a uniform liquid.ii. 7 8 ABSTRACTS OF CHEMICAL PAPERS. Clrystdlised i m l l hot. iiitric acid it .forms a lower hydrate with 14H,O. 12-Silicotungstic acid forms both quadratic and rhombohedra1 hydrates with 28H,O and 22H,O respectively.The transition point determined by the dilatometer method is at 28*5O. In addi- tion a hydrate with 15H20 was obtained. Iso-l~-siZic~tzcngstic acid H,[Si(WzO7),],20H,O forms triclinic prisms. lZ-Phospho?izol~!Fclic acid was obtained in yellow octahedral crystals of the composition H7[P(Mo,O7 j6],28H,0 and by crystal- lisatioii from hot nitric acid the hitherto unknown hydrate with 22H20 was obtained in small yellow probably rhombohedra1 tables. The conductivity at 25O was studied and also the course of neutral- isation by mca iis of conductivity measurements. 12-Z’~~osp~~otzcnystic ucid forms crystals of the iiormal type with 28H20. I n presence of traces of acid these break down intominute rhombohedra of the hydrate with 22H,O melting at 89-94O to a homogeneous liquid.The highest metallic salts which could be prepared were tribasic for example Ba,H,[P(W2O7),1,,54H,O and Na,I3,[P(W20,),l,13H~0 but in the guanidine salt (CN3H,)7H7[P(W,07)s]2,12H,0? half the hydrogen is replaced. 12-Anenotungstic acid could only be obtained in the form of its ammonium salt (NH4)3H4[As(\.V207),],4H20. The unsaturated rnono-nucleic heteropoly acids are of the type H,2-n[RnO(M207)5JJ their basicity being the same as that of the sa t ur a ted acids. 10-Silicotzozgstic acid was obtained in the form of a potassium salt badly formed cube-like crystals of the composition The corresponding guanidine salt contains 9H,O. having an outer bridge H7[Rn*OH*(M207)5]*M207,[Rn*OH*(M207)5]H,,. whilst the 1 9 (luteo) acids have an inner bridge The acids of the last type it is suggested are in tautomeric equil- ibrium with the form They are always formed in presence of excess of the metalloid acid.Il-Pi-Los~hotungstntes are formed at an intermediate stage in the decomposition of 12-phosphotungstic acid by strong bases. They are stable salts which can be readily prepared from the barium salt to which the constitution is given. Strong mineral acids bring about decomposition of the ll-phosphotungstates with formation of 12- and 2 21-phospho- tungstates. The 1l-ur.s~izotztngstates are completely analogous to the corresponding phosphotungstates. 9-Pltosphotungstic acid P,0,,18W0,,42H20 forms thin six- sided tables which are very readily soluble and melt at 28O.All K7H[SiO( W207)&1 1H2O. The bi-nucleic heteropoly acids form two groups the 1 11 acids HI,- n[(M,07)4R10*M207*Rn0g(M~07!4]Hii - n. H10- ,[(M,07),RnOH*M,07*RnOH(M20,),1H - n . Ba7[ P (0 H ) (W20,) J-W207-[ ( W&) j (0 H) PI5 3 H,OINORGANIC CHEMlSTRY. ii. 79 attemphs to prepare salts of higher basicity t h i i 5 failed a i d il is concluded that the constitution of the acid .must be represented by the formula A study of the conductivity and neutralisation curves points to the same conclusion. The silver salt 5Ag,0,PZ05,1 8W0,,34H20 is precipitated as yellow amorphous flakes which quickly crystallise. It is almost insoluble. The corresponding guanidine salt with 18H,O forms bright yellow aggregates of small tables and is only slightly soluble. 9-A rsenotzcngstzc acid corresponds exactly with luteophospho- tungstic acid. Only the tribasic potassium and ammonium salts were prepared these having similar properties t o the tribasic salts of 9-phosphotungstic acid. Among the more complex heteropoly acids the authors have studied 2 21-phosphotungstic acid 2 17-phospho- and 2 17-arseno- tungstic acids. They probably contain four non-metallic acid nuclei but no constitutional forrnulze have yet been suggested for them. The preparation and properties of a number of salts of these acids are described. H ~ [ P ( o H ~ ( W 2 0 ~ ) ~ ~ w ~ 0 7 ~ ( W 2 0 7 ) ~ ( o H ) P]H,,36H20. E. H. R.

ISSN:0368-1769    

DOI:10.1039/CA9181405075

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

INORGANIC CHEMlSTRY. ii. 79 Miner alogic a1 Chemistry. Amblygonite-Tin Deposits at Caceres Spain. W. T. DORPINGHAUS (Jahrb Miiz. 1917 i Ref. 326-328; from Archiu Lagerstattenfomchung 1914 16 49 pp.) ,-Veins containing amblygonite and cassiterite intersect Silurian and Devonian slates in the neighbourhood of the well-known phosphate veins of Estremadura. The average composition of the amblygonite is given under I. Associated minerals are pyrophyllite (anal. 11) and a soda-muscovite (111). SiO,. P,O,. SO,. Al,O:,. Fe,O,,. CaO. MgO. I. - 46.35 - 34.29 0.79 - - 11. 67-01 trace trace 17-03 0.06 - - 111. 45.78 trace 0.08 36-49 0.15 0-0s 0.11 K,O. Na,O. Li,O. H,O. F. I. - 1.60 8.87 5.16 3.00 11. 6.27 2.23 - 6-69 - 111. 8-41 3-25 - 5.15 I L. J. S. Celestite from Galicia. STEFAN KREUTZ (Jcidzrb.illin. 1917 i Ref. 269-277; from Abh. Akad. H’iss.- Krakau 1915 55 [ A ] 1-24) .-An account is given of the minerals (aragonite rock-salt gypsum celestite calcite and dolomite) found in the salt-clays which are worked for ozocerite and sulphur in the mining districtii. $0 ABSTRACTS OF CHEMICAL PAPERS. of Poiii$arki near ilie village of Truskawiec in Galicia. ! o g r a p h tlescript,ion is given of the celestite; analysis gave SPO. Hat>. ChO. SO3. Ign. Total. Sp. gr. 54.41 0.69 0.67 43.54 0.22 99.53 3.965 A crystal coi.respuiiilitig with SrSO 97.38 CaSO 1.64 BaSO 0-98. Mixed crystals of these sulphates are discussed and the fact that the minerals celestite barytes and anhydrite always contain a pre- dominance of one metal is commented upon.The Existence of Bischofite Deposits and the Secondary Transformations of the Zechstein Potassium Salts. M. R(~ZSA (Zeztsch. aiaorg. Chenz. 1917 101 276-284. Compare A. 1916 ii 257 335; 1917 ii 97 214).-Fresh arguments are put forward in support of the author’s contention thst bischofite did notl form a primary deposit and therefore could not have psr- ticipated in the secondary metamorphoses of the salt deposits. The carnallite-kieserite salts of the 16 metres thick “ principal ” salt layers are the primary products. The mean composition of five borings through this deposit gave carnallite 56% kieserite 13*3% rock-salt 28.7%. The kieserite-carnallite layers are less rich in carnallite. The origin of this carnallite can be explained with- out the assumption of a primary bischofite deposit on the suppo- sition that the magnesium chloride appears as a decomposition product of the “ principal ” salt deposit.The thermal or hydrothermal decomposition of lcainite into kieserite and carnallite has been studied from the van’t Hoff equil- ibrium diagram and i t is concluded from the relative proportions of these two salts in the “ principal ” salt deposits that the last could not have been produced by thel decomposition of kainite. The occasional transformation of the ‘‘ principal ” deposits into a hard-salt rich in langbeinite can be explained qualitatively but quantitative data are wanting. [See also J . SOC. Chem. Ind. 1918. March .] E. H. R. Rock-forming Minerals from the Tatra Mountains. TIT. 1’AwLIcs (Jahrb. Min. 1917 i Ref. 278-282; Bull. Acad. Sci. C~.ncovie Cl. sci. math. ?ant. [ A ] 1915 52-76) .-Thirteen det,ailed analyses are given of minerals (muscovite biotite ortho- clase oligoclase amphibole garnet and tourmaline) isolated from L. J. S. granite pegmatite and gneiss. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9181405079

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

ii. 80 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. . Accurate Method for taking Aliquots of a Standard in Standardiskg Solutions. C. F. MILLER (J. Amer. C'hem SOC. 1917 39 2388).-About five times as much of the standard sub- stance is weighed out and dissolved in a quantity of water slightlyANALYTWAL CHEMISTRY. ii. 81 exceeding five times the capacity of the pipette to be used in taking the aliquot portions. (This pipette need not be staadardised.) Five portions of the solution are now pipetted into separate vessels and the remainder of the solution together with the rinsings from the pipette is transferred to a tared platinum basin evaporated the residue dried and weighed. A simple calcu- lation gives the quantity of substance taken for each titration The method can be used only for such substances as sodium carbonate sodium oxalate etc.which are soluble and separate from their solution in a weighable form on evaporation. A General Method €or the Analysis of Gaseous Mixtures. PAUL LEBEAU and A. DAMIENS (Ann. Chz.m. 1917 [ix] 8 221-264).-A more detailed account of work already published (compare A 1913 i 437; ii 253 349 700). The McLean-Van Slyke Iodometric Method for the Titra- tion of Small Amounts of Haloids. Its Application to Chlorides. ROBERT F. MCCRACKEN and MARY D. WALSH ( J . dmcr. Chern. SOC. 1917 39 2501-2506. Compare A. 1915 ii 479).- When the titration in this method is made very slowly a blue coloration which might be mistaken for the end-point sometimes develops before the titration is complete ; this coloration however disappears gradually as the end-point is approached.The end- point can be obtained in a clear solution by adding a further quantity of starch just before the titration is commenced. The method yields trustworthy results. [See further J . SOC. Chenz. W. P. 8. W. G. Ind. 1918 6 ~ . ] w. P. s. Applications of Gas Analysis. IV. The Haldane Gas Analyser. YANDELL HENDERSON (J. Biol. Chevz. 1918 33 31 -38) -Modifications of Haldane’s apparatus for the estimation of carbon dioxide in air and in blood are described by means of which the apparatus may be more readily taken apart and cleaned. A simpler form of the apparat’us suitable €or teaching purposes is also illus- trated. Applications oi Gas Analysis. V. The Gases of the Blood. YANDELL HENDERSON and ARTHUR H.SMITH ( J . Biol. Chem. 1918 33 39-46. Compare preceding abstract).-The authors describe a modification of Barcroft and Haldane’s method in which the oxygen from 1 C.C. of the blood is liberated by the action of potassium ferricyanide in a special “ diffusion tube,” which is sub- sequently rotated horizontally. During the rotation the contents of the tube spread in a thin film along the walls and allow com- plete diffusion of the liberated oxygen into the air of the tube to occur. The excess of oxygen in the air is then estimated by means of the analyser previously described (Zoc. cit.). Carbon dioxide in the blood is similarly estimated after treatment with tartaric acid a correction being made for the solubility of carbon dioxide in acidified solutions of blood.[See also J . SOC. Chenz. I E ~ . 1918 March.] H. W. B. H. W. B. YOL. CXTV. ii. 6ii. 82 ABSTRACTS OF CIIEMTCAL PAPERS. Gasometric Estimation of the Oxygen and Hemoglobin of Blood. DONALD I). VAN SLYKE ( J . B2oZ. Chem. 1918 33 127-132. Compare A. 1917 ii 422).-The apparatus previously described for the estimation of carbon dioxide in tbe blood is used with a similar technique for the estimation of oxygen. The oxygen is liberated from combination with haemoglobin within the apparatus by the addition of ferricyanide is extracted in a vacuum and measured a t atmospheric pressure a few minutes sufficing for an accurate estimation. H. W. B. Rapid Characterisation of the Sulphuric Ion in Insoluble Sulphates. Application to the Identification of this Ion in General.G. DENIG~S (Bull. SOC. chim. 1911 liv] 23 36-39).- The presence of the sulphuric ion in insoluble sulphates such as those of lead mercurous mercury calcium strontium and barium may readily be shown by adding to the sulphate a 10% solution of mercuric nitrate in nitric acid (1 in 100). Turpeth mineral is formed aiid may be detected if necessary microscopically. Calcium and mercuroup sulphates give the reaction immediately in the cold strontium and lead sulphates only slowly and barium sulphate only on boiling. I n a complex mixture the sulphate may be first precipitated as barium sulphate' and then detected as described. [See also t7. SOC. Chenz. Z?MJ. 1918 March.] W. G. The Adaptation of Truog's Method for the Estimation of Carbon Dioxide to Plant Respiration Studies.A. M. GURJAR (The Plant World 1917 20 288-293; from Physiol. A b s t ~ . 1918 2 641).-In the original paper an apparatus is described for the estimation of carbon dioxide by Truog's method the gas being absorbed in a known volume of N/4-barium hydr- oxide solution and the residual hydroxide titraied back with standard acid. The modification consists in the use of an auto- matic pipette for measuring and transferring the barium hydroxide solution without allowing it to come into contact with the air. There is also an arrangement for rendering the wash-water free from carbon dioxide without disconnecting the reservoir. Use of Sodium Paratungstate in the Estimation as Oxide of the Metal in Cyanides. S. B. KUZIRIAN (J. Snter. Chem. SOG. 1917 39 2356-2358.Compare A. 1913 ii 865).- Cyanides when heated with sodium paratungstate in the presence of an oxidising substance (ammonium nitrate) lose their acid radicle leaving a residual oxide in a definite and stable form for weighing together with the paratungstate. [See further J . SOC. F. H. MCCRUDDEN and C. S. SARGENT ( J . Biol. Chem. 1918 33 235-241).-Sodium and potassium are separated from other compounds as the com- bined chlorides and the amount of each is calculated from the chlorine content of a kiinwn weight of the mixturs. The authors 147. G. Chem. Ind. 1918 304.3 w. P. s. Estimation of Sodium and Potassium.ANALYTICAL CHEMISTRY. ii. 83 show that whtii the RfcLean-Van Slyke method is employed f o r estimating the chlorine the probable error in the estimation of the sodium increases as the ratio of sodium to potassium decreases and amounts usually to about 1%.H. 137. B. New Hydrogen Electrode for the Electrometric Titration of the Alkaline Reserve of Blood Plasma and other Froth- ing Fluids. J. F. McCr,~~mos ( J . Bid. Clicm. :91& 33 19-29).- The new electrode vessel is attached to a horizontal spindle in such a way as to perinit the introduction at the free end of acid and of hydrogen during rotation without disconnection from the potentio- meter. The addition of N/10-hydrochloric acid to the plasma is continued until the hydrogen-ion concentration is that of water (pH=7*00 a t 2 3 O ) . The amount of acid required is a measure of the alkaline reserve of the blood. H. W- B. Volumetric Method for the Estimation of Calcium.J. GROSSFELD ( C h e n t . Z e i t . 1917 41 842).-The calcium is precipi- tated from a solution slightly acidified with phosphoric acid by the addition of a definite quantity of ammonium oxalate the calcium oxalate is then separated by filtration through a “kiesel- guhr filter-paper,” and the excess of ammonium oxalate is titrated with permanganate in ’an aliquot portion of the filtrate. [See further ,7. ,SOP. Plrcm. It/(!. 1918 76.4.1 IV. P. s. Identification and Estimation of Lead in Water. I ~ O B E I ~ T MELDRUM (Chem. S e w s 1918 117 49-50).-In the colorimetric estimation of lead by means of hydrogen sulphide it is essential that the standard or comparison solution be prepared with the same water free from lead. The colouring matter’in the water and the proportion of saline constituents influence the intensity of the coloration due to lead sulphide the difference in some cases amount- ing to 100%.When distilled water is used for the standard solu- tion the lead may be underestiniated to the extent of 33%. [See further J . SOC. Chenz. Ind. 1918 March.] UT. P. s. A New Method of Estimating Copper. JAMES Mom ( J . Chem. M e t . Min. SOC. S. Jfricn 1917 18 133-135).-The sample is dissolved in concentrated nitric acid and the copper con- verted into faintly acid cupric acetate either by the usual method or by adding carbamide boiling nearly neutralising with sodium hydroxide and adding sodium acetate. A slight excess of sodium thiosulphate is added to the solution followed immediately by an excess of potassium thiocyanate.The precipitated copper thio- cyanate is filtered through filter-pulp and washed the filtrate is diluted sulphuric acid and a small quantity of starch solution are added and the excess of thiosulphate is titrated with iV/ 10-iodine solution. [For details see J . SOC. Chent. Znd. 1918 March 15th.l T. F. B.ii. 84 ABSTRACTS OF CHEMICAL PAPERS. Colorimetric Estimation of Manganese by Oxidation with Periodate. HOBART H. WILLARD aid LUCIEN H. GREATHOUSE (J. Amer. Chem. SOC. 1917 39 2366-2377).-Manganese salts are readily oxidised to permanganato by heating with an alkali periodate in acid solution. The quantity of free sulphuric acid present must be sufficient to prevent the precipitation of mangaoic periodates or oxides; a high concentration of acid prolonged heat- ing and the presence of ammonium salts are without effect on the results.Traces of chloride do not interfere and the common metals if they do not form coloured ions may be present. Reducing substances must be removed previously by treatment with nitric acid; phosphoric acid should be-added i f much iron is present. The quantity of permanganate formed is estimated calorimetrically. [See further J . SOC. Chem. Ind. 1918 4 1 ~ . ] w. P. s. Use of Cupferron (Ammonium Salt of Nitrosophenyl- hydroxylamine) in I. The Quantitative Separation of Zirconium Titanium Iron Manganese and Aluminium. IT. The Analysis of Zircon and Baddeleyite. JAMES BROWN ( J . Arner. Chem. SOC. 1917 39 2358-2366. Compare Thornton and Haydesn A. 1914 ii 779).-Cupferron reagent may be used for the precipitation and separation of iron tdtanium and zirconium from aluminium and manganese.The precipitation is made from a sulphuric acid solution. The iron titanium and zirconium are then separated from one another by the use of standard methods and the aluminium and manganese are estim- ated after the excess,of cupferron has been destroyed by treatment with concentrated nitric acid. The method yields trustworthy results either with niixtures of the pure salts or with minerals con- taining the elements. mentioned. [See further J . Soc. Chenz. Id. 1918 4 1 A . l TN. P s. Reagents for Use in Gas Analysis. VII. The Estimation of Benzene Vapour. R. P. ANDERSON ( J . Ind. Eng. Chem. 1918 10 25-26).-A method is proposed for the estimation of benzene vapour in gas in which a measured quantity of gas containing benzene vapour is placed in contact with benzene in a special apparatus and the increase in volume read.By determining what the increase would have been had there been no benzene vapour present the amount of benzene vapour present can be estimated. A standard apparatus has not yet been produced. L. A. C. Estimation of Phenol in the Presence of the Three Cresols. G . W. KNIGHT C. T. LINCOLN G . FORMANEK and H. L. FOLLETT ( J . Ind. E?zg Chenz. 1918 10 9-18).-From a series of deter- minations of the specific gravities and solidifying points of a number of mixtures of pure phenol and pure 0- rn- and pcresols the adthors have devised a method for determining the percentage of phenol present in unknown mixtures of these compounds.ASALYTICAL CHEXISTRY.ii. 86 Details are given for carrying out the method and obtaining the necesary measurements for solviiig the equation Per cent. phenol = lOOX [(To - Ts,)(0.366 + 0 702L,) + where L,= {lOOO(G,-G,,)}/{Tp- TA9} -0.842; G and G =D: of phenol used and phenol + distillate mixture respectively ; Go and G = D$ of o-cresol used and o-cresol + distillate mixture respectively; T Tsp To and T8,=solidifying points of the phenol phenol + distillate mixture o-cresol used and o-cresol+ distillate mixture respectively ; X = wt. of total distillate below 197O; lV=wt. of sample used. This equation does not give absolutely accurate results with all possible mixtures of the three isomerides or where both o-cresol and mcresol are present and p-cresol is absent or present only in very small quantities the results in this case being too low.The error increases as o-cresol increases and pcresol decreases being greattest where pcresol is absent and more than 50% of nz-cresol and less than 50% of o-cresol is present. In all cases ordinarily met with in commercial practice however? the probable error would amount to only a few tenths per cent. [See further J . SOC. ChenL. Ind. 1918 8 5 A . l (Gso - Go)(S970 - 609.Lr)]/s0 W. L. A. C. Estimation of Pentose in Urine. G. TESYONI (Polictii~ic~ 1917 24 641; cram Physiol. Abstr. 1918 2 598).-Ten C.C. of urine are decolorised by heating with blood charcoal and filtered. The filtrate is evaporated t o 5 c.c. and to i t is added 9 C.C.of a warm 0.25% solution of phloroglucinol in glacial acetic acid and 1 C.C. of hydrochloric acid. The mixture is allowed to remain at 50° for half an hour when the characteristic colour will have appeared. A quantitative estimation may be made by means of a colorimet,er. The method is applicable to diabetic urine. If pentose is the only sugar present the filtrate from the decolorising process need not be evaporated. W. G. Estimation of Dextrose in Urine. J. J. GURTOV (Xed. Record Wew Pork 1917 92 502-503 ; from Physiol. Abstr. 1917 2 497498).-If a solvent (potassium ferricyanide) is added to the copper solution in amount less than is necessary t o dissolve all t,he cuprous oxide the reagent will remain clear until all the cyanide has combined with the greater part of the oxide; then a bulky pre- cipit,ate occurs and this sign of the end of the reaction is easily recognised. G .B. ARapidMeChod for the Estimation of Sugar in Urine. OTTO MAYER (Mii?ich. wed. TITock. 1917 64 1222-1223; from Chem. Zentr. 1917 2 653-654).-A mixture of 10 C.C. of the urine with 10 C.C. of 15% sodium hydroxide solution is diluted t o 50 C.C. with water and a 2.5% solution of copper sulphate gradu- ally added with shaking until the precipitate has almost entirely redissolved and a just perceptible permanent turbidity remains,ii. SG AHSTRACXS OF UHEBIICAL PAPERS. which iiicreases somewhat 011 keepiug. Under these conditions each C.C. of the copper sulphate is equivalent to 0.1% of dextrose. If the urine contains more than 47L of dextrose oiily 5 C.C.should be used whilst if less than 0*5-1% is present 20 C.C. should be taken. Should the urine give a precipitate of calcium phosphate it should be previously treated with a measured proportion of sodium hydroxide solution and a suitable fraction of the filtrate submitted to the above titration. Very turbid urixies should be filtered and excessive quantities of albumin removed by boiling before a sample is submitted to the above analytical process. D. F. T. Acidosis. VII. Estimation of P-Hydroxybutyric Acid Acetoacetic Acid and Acetone in Urine. DONALD I). VAN SLYKE ( J . Biol. Cl~enz . 1917 32 455-493).-Dextrose and other interfering substances are first removed by treating 25 C.C. of the urine in a 250 C.C. measuring flask with 100 C.C. of water 50 C.C.of a 20% copper sulphate solution and after mixing 50 C.C. of 10% suspension of calcium hydroxide in water. After shaking and testing with litmus (if not alkaline more calcium hydroxide is added) the mixture is diluted to the mark and allowed to remain for at least one-half hour for dextrose to precipitate. It is then filtered through a dry filter paper. To estimate the totai acetone substances 25 C . C . of the urinary filtrate are placed in a 500 C.C. flask and boiled with 100 C.C. of water 10 C.C. of 50% sulphuric acid and 35 C.C. of 10% mercuric sulphate (73 grams of pure red mercuric oxide dissolved in 1 litre of 4iV-sulphuric acid) under a reflux condenser. After boiling has begun 5 C.C. of a 5% solution of potassium dichromate are added and the boiling continued for one and a-half hours.The yellow precipitate which forms consists of an acetone-mercury- sulphate-chromate compound and it is collected on a tared Gooch crucible washed with 200 C.C. of cold water and dried for an hour a t 110O. After cooling in the air it is weighed or the precipitate may be dissolved in hydrochloric acid and titrated with standard potassium iodide solution. The acetone plus the acetoacetic acid is estimated exactly as the total acetone substances except that (1) no dichromate is added and (2) the boiling is continued for not less than thirty and not more than forty-five minutes The hydroxybutyric acid may be estimated separately by first acidifying with sulphuric acid and boiling off the acetone and acetoacetic acid. The factors for calculating the results are 1 mg.acetone yields 20 mg. of pre- cipitate and 1 mg. hydroxybutyric acid yields 8.45 mg. of pre- cipitate. I n acetonuria hydroxybutyric acid usually represents 75% of the total acetone substances. H. W. B. Acidosis. VIII. Estimation of /3-Hydroxybutyric Acid Acetoacetic Acid and Acetone in Blood. DONALD D. v . 4 ~ SLYKE and REGINALD FITZ ( J . Rio7. Cltem. 1917 32 495-497. Compare preceding abstract).-The proteins are first removed byANALYTICAL CHEMISTRY. ii. S7 precipitatioii with uiercuric sulphat e siicl the acetone substauces are then estimated in the resulting filtrate exactly as described for urine (ZOC. cit.). H. W. B. A Biological Colour Reaction for Succinic Acid. T. THUNBERG (Sue nska Lakar e f Brenigen shandlingar 1917 43 996-1001; from Phylsiol.Abstr. 1918 2 655. Compare this vol. i 140).-The amount of succinic acid in tissues may be estimated as follows. The organ is extracted with ainyl alcohol and this is then extracted with ether. The ethereal extract is neutralised and its decolorisation effect in a solution containing methylene- blue and muscle is observed. By this means 0.02 mg. of succinic acid can be detected and estimated. W. 0. The Test for Tartrates Depending on the Formation of the Copper Tartrate Complex. 1,. J . CURTMAN A. III~w~s and B. R. HARRIS (,7. -1mer. C'lzem. ,(Ioc. 1917 39 2623-2630).-The test for tartrates which depends on the solubility of cupric hydr- oxide in alkaline solutions of the alkali tartrates has been sub- mitted to examination with the object of determining its sensitive- ness.By the use of pot'assium ferrocyanide instead of ammonia for the detection of the dissolved copper in the filtered solution it has been found possible to detect 0.3 mg. of tartrate. Solutions which contain ammonium salts arsenites Lorates or phosphates give a positive reaction in the absence of tartrates. Chromates ferrocyanides and ferricyanides interfere by masking the test colour whilst cyanides readily dissolve cupric hydroxide. One mg. of tartrate gives a negative result in the presence of 500 mg. of thiosulphate arsenate chromate fluoride thiocyanate flitrite or acetate and also in the presence 9f 250 mg. of thio- sulphate osalate thiocyanate. or nitrite. RIaiiy organic substances interfere with the application of the test.H. M. D. Comparison between the Bromide-Bromate Method and the Methods of Hubl and of Wys for the Estimation of the Iodine Number of Oils and Fats. C. KELEER and €1. RHEIN- HEIMER (Arch. Phnrm . 1917 255 417-424).-A11 three methods give concordant results for oils and fats having small iodine numbers including hydrogenised oils which before hardening had large iodine numbers but have been exteiisively saturated by the addition of the hydrogen. The bromide-bromate method always gives too low results in the case of oils having large iodine numbers. The authors prefer the method of Wys to that of Hubl. c. s. A Method for the Estimation of Uric Acid in Small Quantities of Blood Urine and other Body Fluids. A. KOWARSKY ( B e r l i n Klin. li'och.1917 54 987-989 ; from Physiol rl bstr. 1918 2 586) .-Proteins are first completely precipitated and removed and the filtrate is coiicentrated to 2 C.C. The urici. 88 ABSTRACTS OF CHEMICAL PAPERS. acid is precipitated by ammonium chloride and the ammonia in the precipitate estimated by the formalin method. Accurate results are reported. W. G . Estimation of Phytin Phosphorus in Plant Products. J. B. RATHER ( J . Amer. Chem. SOC. 1917 39 2506-2515).-The ferric chloride titration method described by Heubner and Stadler (A. 1914 ii 690) may be applied to the estimation of phytin in vegetable substances. Maximum extraction of the phytin phos- phorus is attained by extraction with 1.2% hydrochloric acid for three hours. Non-phosphorised substances and phosphorus com- pounds other than phytin do n o t interfere with the estimation.The largest amount of phytin phosphorus was found in wheat bran rice bran rice polish and cotton-seed meal (0.76 t o 1*26%) and the smallest in maize oats soja beans and clover seed (0.19 to 0.36%). [See further J . SOC. Chem. Ind. 1918 1 7 ~ . ] w. P. s. The Simplest and most Convenient Method for the Detection of Albumin in Urine. F. LENZ (Miinch. Med. 'CVoch. 1917 64 1267; from Physiol. ilbstr. 1918 2 613).-In this method only one reagent namely sulphosalicylic acid is used and heat is not necessary. Colorimetric Estimation of Haemoglobin. WALTER IT. PALMER ( J . Biol. Chem. 1918 33 119-126).-The blood is obtained in the usual manner by pricking the finger or lobe of the ear. It is diluted by drawing 0.05 C.C. into a special pipette and transferring into 5 C.C. of 0.4% ammonium hydroxide solution contained in a test-tube. After rinsing out the blood pipette by drawing the ammonium hydroxide solution into i t two or three times ordinary illuminating gas is bubbled rapidly through the ammonia-blood solution for thirty seconds. It is then compared in a Duboscq colorimeter with a standard carbon monoxide hzemo- globin solution set a t 10. For the preparation of the standard solution a quantity of human or ox blood is obtained and its oxygen capacity estimated (compare Van Slyke this vol. ii 82). The blood is diluted with 0.4% ammonium hydroxide solution so as to make a 2% solution of a blood with an oxygen capacity of 18*5% and it is then saturatled with carbon monoxide. This stock solution will keep for many months and the standard solution can be prepared from it a t any time by diluting 5 C.C. t o 100 C.C. with 0.4% ammonium hydroxide solution. The accuracy of the estima- tion is usually within 1%. [See also J . SOC. Chem. Ind. 1918 March.] H. W. B. W. G .

ISSN:0368-1769    

DOI:10.1039/CA9181405080

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

1’IIYSIOLOGlCAL CHEMISTRY. Physiological Chemistry. i. 87 The Chemistry of the Proteins. I. The Protein Fractions of Blood-plasma. 11. The Theory of the Agglutination of Bacteria. E. HERZFELD and R. KLINGER (Bzochewz. Zcitsch. 1917 83 228-243).-I The theory is put forward that the various protein fractions of the plasma such as fibrinogen globulin albumins etc. are not chemical individuals but form a series of which the individual members can pass one into another. The more complex proteins are assumed to be liberated from the cells in a state of low aggregation with comparatively small amounts of adsorbed simple substances t o keep them in a colloidally dis- persed state from which they can be readily flocculated by salts etc. In the course of time the state of aggregation is finer amd the amount of adsorbed substances is increased and the proteins are not then so readily precipitated.By alteration in the state of aggregation and aiiiount of adsorbed simpler substances variations in tke physical properties can be produced and a blood protein can thus be varied in its properties so as to pass from a readily aggre- gating substance like fibrinogen through a globulin to an albuniose. Experiments which are stated to substantiate this theory are quoted . 11. Bacteria are supposed to act like colloidal solutions of certain proteins which can be precipitated by neutral salts weak acids etc. and are changed in their properties as regards aggregation by adsorption of various substances from sera containing anti-sub- dances. I n this respect the theory of the authors does not’ differ niarkedly from that of others.It differs however in that they (lo not lay so much stress 011 the effect of electrical discharge on Ihc flocculation as on the effect of various adsorbed simpler sub- S ~ A ~ I C ~ S on the capacity of the bacteria for boldiiig water. The nptirnal conditions for flocculation often coincide with the point of clectrical discharge because a t this point the solubility of the adsorbed substances in water is smallest. Rate of Formation of Fibrin Ferment from Prothrombin by the Action of Thrombokinase and Calcium Chloride. JOHN MELLANBY ( J . Phgsiol. 1917 5 1 396-403).-The formation of fibrin ferment proceeds in a manner similar to that observed in the activation of trypsinogen by enterokinase (Mellanby and IVoolley A.1913 i 113 662) ; in both cases the velocity of the change is small a t the outset but the reaction proceeds with a constantly increasing acceleration It is suggested hypothetically that the uItimate agent in the activation is the calcium ion which does not act on pure prothrombin but on prothrombin which has adsorbed thrombokinase for the reaction is accelerated both by an increase in the cLzlciiim concentration and by an increase in the thrombokinase. G . B. s. B. s.i. 88 ABSTRACTS OF CHEMICAL PAPERS. Metabolism of Arginine. IV. Effect on the Secretion of Total Creatinine. W. W. T~IOBIPSON (J. PhysioL. 1917 51 347-376. Compare A. 1917 i 673).-Whereas arginine alone given hypodermically to dogs is converted into creatinine only to the exbent of 4*5% the addition of methyl citrate brings about a 7% conversion.When the substances are given by the mouth there is no increased methylation of the guanidine nucleus or when methyl benzoate replaces methyl citrate in the hypodermic experi- ments. Small hypodermic doses of guanidine carbonate gave an increase in the creatinine output up t o 10.8% of the guanidine injected. G. B. Oxydones. L. LOPEZ-P~REZ (Compt. r . e d SOC. Biol. 1917 $0 326-327).-The oxydones of Batelli and St’ern (which these authors consider responsible for the respiration of animal tissues and the oxidatio.n of citric fumaric m a h and succinic acids and of p-phenylenediamine) are not attacked by erepsin or by nuclease or takadiastase so that the oxydones are not albumoses or peptones or nucleic acid or polysaccharides.Changes in the Chemistry of the Brain as a Result of Intoxications. J. E. ABELOUS and L. C. SOULA ( J . Phzysiol. Path. gtrz. 1917 17 157-170).-Rabbits were poisoned non- fatally by crystalloids (strychnine cocaine chloroform) and colloids (serum-albumin egg-albumin urohypotensin) and twenty to thirty-five days afterwards their brains were aiialysed by deter- mining the protein nitrogen amino-nitrogen (formol titration) protein phosphorus lipoid phosphorus etc. This affords a measure of the fission of proteins and lipoids in the brain; the degree of fission is considerably increased as compared with normal controls. The brain the organ of psychical memory also has a “chemical memory” of previous intoxications. The bearing of this on anaphylaxis is considered.G. €3. Fower of Perfumes and their Solubility in Water and in Oil. E. LOUIS BACKNAN ( J . Physiol. Path. ge‘lz. 1917 17 1-4. Compare A. 1917 i 498).-In order that a substance may be odorous it must be sufficiently soluble both in water and in lipoids ,since the cells of the receptor organ for smell are covered wibh a watery fluid whilst they themselves contain lipoid granules. Thus the odours of the series of homologous alcohols rirst increase as the molecular weight rises and then decrease again. The lower ones are comparatively odourless because little soluble in fats cetyl alcohol because little soluble in water. Butyl alcohol soluble in water and fats has a powerful odour. The same applies t o benzene toluene xylene and q-cumene and to isomeric butyl and amyl alcohols ; also to the three nitrophenols and nitrotoluidines to the dimethgltoluidines bromoanilines naphthylamines etc.The changed solubility in water and in oil also explains why the intro- duction of an acetyl group renders alcohol odorous and Zrliline inodorous. 0. B. G. B.PHYSIOLOQICAL CHXiVISTBY. i. 89 The Imbibition of Water by Muscular Tissue with Special Reference to the Action of Caffeine. ALEXANDER BEL~K (Biochem. Zeitsch. 1917 83 165-217).-The rate of imbi- bition of various frogs' muscles was determined. The first stage is rapid increase in the water content of the tissue which is regarded as an osmotic phenomenon produced by the osmotic pressure of the inner contents of the tissue. The first stage is followed by a loss of water due to a diffusion outwards of the salts which process is accelerated by an increase of the permeability of the membranes.The third stage of the action of water is the ordinary imbibition by colloids which follows the laws of colloidal chemistry. The action of caffeine consists apparently in the first instance in caus- ing an increase in the permeability by water followed by a transient increase in the capacity for binding water. The toxic action con- sists in the coagulation of the proteins which leads to a release of water by the tissues. S. B. S. What Substance is the Source of the Light of the Firefly ? E. N. HARVEY (Science 1917 46 241-243; from Physiok. Abstr. 1917 2 460. Compare A. 1917 i 365-366 where in the secoiid abstract photophlein should be photophelein) .-Evidence is pre- sented for the following conception.A colloid (photogenin) is oxidised and made to emit light under the influence of a thermo- stable dialysable substance (photophelein). The latter is cytolytic in its nature and encourages oxidation by disintegrating the colloid aggregates and multiplying their surface relations. [Compare also GOSS J . Biol. Chem. 1917 31 271; Harvey ibid. 311.1 G . B. Saturated Hydrocarbons in Basking-shark Liver Oil. MITSUMARU TSUJIMOTO ( J . Znd. Eng. Chein. 1917 9 1098-1099). -The liver-oil of the basking-shark Cetorhinus nzaximus contains 41.92 to 55.51% of unsaponifiable matter of which the unsaturated hydrocarbon squale7te (Tsujimoto A. 1916 i 786) is a constituent (compare Chapman T.1917 56 111). On distillation under a pressure of 5 mm. of the unsaponifiable matter from one specimen of the oil 10% of a yellow liquid distilled between 170° and 190° whilst at' 244-260° squalene (257;) distilled. The first fraction was washed with sodium hydroxide solution and then distilled at 160-166O under 13 mm. pressure. It was a colourless mobile liquid which did not solidify when cooled below Oo. It' had Di5 0.8768 refractive index nEo 1.4398 and iodine value 4.4. It began to boil a t about 294O under 766 mm. pressure and distilled almost completely a t 296O. Its elementary composition (C = 84.39 ; 13 = 15.02%) and molecular weightl (mean 259) corresponded most closely with the formula C,8Hss. Since however normal octadecane is solid a t the ordinary temperature this hydrocarbon is probably an isooctadecane and its low boiling point may be due t o this cause.The specific refraction (722 formula) was 0.3283 and the molecular refraction 83.4. This hydrocarbon or mixture of hydro- f VOL. CXIV. i.i. 90 ABSTRACTS OF CHEMICAL PAPERS. carbons was not present in two other specimens of the oil (see also J . SOC. Chenz. I~G?. 1918 37 Feb.). Erepsin in Normal Urine and its Relation to other Proteases. S. G. HEDIN and Y. MASAI (Zeztsch. physiol. Cham. 1917 100 263-303).-The urine contains an enzyme which is capable of breaking down peptone and similar protein substances in alkaline solutions. It is isolated by saturating the urine with ammonium sulphate dissolving the precipitate in water and then dialysing until free from sulphate.The enzyme prepared in this way from human urine can sometimes digest caseinogen and some other proteins. It is suggested that this exalted ereptic action may be due to a true erepsin or more probably to a mixture of erepsin with another proteolytic enzyme. Other proteolytic enzymes are also found in normal urine namely enzymes which effect the degradation of serum globulin and fibrin. They act best in an alkaline medium; and the above proteins with the co-operation of the urinary erepsin may be completely degraded to amino-acids. The effect of the co-operative action of the proteo- lytic and ereptic enzymes is considerably greater than the sum of the effects produced by the two enzymes working separately. The exalted proteolysis is observed no matter whether the co-operating erepsin has been obtained from the urine the intestinal wall or from yeast cells. E. SAmo\vsm (Zaitsch. physiol. Chern. 1917 100 259-262).-The specimen of human gall-stones examined was free from fat b7xt contained a resinous substance resembling f a t in its solubility in ether and other solvents (compare A. 1917 i 716). The Relation between Chemical Constitution and Physiological Action. FRANK LEE PYMAN (T. 1917 111 1103-1 128) .-A lecture delivered before the Chemical Society 011 December 6th 1917. C. A. M. H. W. €3. Fat Content of Human Gall-stones. H. W. B. H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9181400087

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

ii. 89 General and Physical Chemistry. Drude’s Theory of Dispersion from the Point of View of Bohr’s Model and the Constitution of H O and N2. A. XOMMERFELD (Anr~. Physik 1917 [iv] 53 497-550).-A theoretical paper in which the author discusses the question of the dispersion and magnetic rotation of gases on the assumption that the structure of tlhe molecules is in accordance with Bohr’s hypo- theses. The theoretical considerations are applied t’o hydrogen oxygen and nitrogen for which certain structures are assumed and the calculated refractive dispersive and magnetic rotatory powers are compared with those found by experiment. The Spectra of Isotopes and the Vibration of Electrons in the Atom. WILLIAM I>. HARKINS and LESTER ARONBERG (Proc. iVat. Acad. Sci. 1917 3 710-714).-The wavelength of the line A4058 in the spectra of ordinary lead and of lead from radium (radium-G) has been measured with great accuracy by the use of a 10-in.plane grating giving a sixth order spectrum with a dis- persion of 0.359 8. per mm. The atomic weight of the specimen of radium-G employed had been found by Richards to be 206.34 compared with 201.18 for ordinary lead. I n order to avoid mechanical shifts the two spectra were photo- graphed simultaneously the vacuum arc lamps employed as sources of light being interchanged from time to time during the taking of the records. I n all seventeen experiments were made and the platies show in all cases that the wave-length of the line h 4058 in the spectrum of radium4 is greater than its is in ordinary lead the average difference being equal to 0.0043 A The observations are said to establish definitely the existence of a measurable difference between the wave-lengt-hs of corresponding lines in the spectra of isotopes.The photographs indicate clearly that the shift is real and cannot be explained by broadening. H. M. D. H. M. D. Arc Spectrum of Gadolinium. Josm MARIA E ~ E H . (A communication from YAotochem. Lab. d . B K . Graph. LeJir- 7 1 . Verszcchsnmtalt Wien 1467-1535 ; from Chem. Zeiatr. 1917 ii 362).-The author has investigated this spectrum with the aid of gadolinium products obtained by Auer by a fractionation which separated gadolinium from samarium and europium. The chloride gives a purer spectrum than the oxide. The tables of gadolinium lines measured occupy 62 quarto pages.The fractions contain- ing europium prepared by Auer give indications spectroscopically of the presence of an unknown element lying between europium and samarium. R. V. S. The Spectrum of Rickel. J. E. PAULSON (Physikal. Zeztsch. 1918 19 13-15).-An examination of the wavelengths of line? In cross references t o abstracts I d . will be used in place of J. SOC. Chem. Ittd. 1918,37. CXIV. ii. 7ii. OO ABSTRACTS OF CHEMICAL PAPXRS. in the arc spectrum of nickel has shown the existence of thirty- three groups of eight lines with constant differences between the corresponding wave-numbers. The lines in question are tabiilated and the relative intensities are shown. H. M. D. The Ultimate Rays of Great Sensitiveness of Columbium and Zirconium.A. DE GRAMONT (Conzpt. mzd. 1915 166 365-368).-Under the conditions previously described for titanium (compare this vol. ii 49) the ultimate rays of columbium which could be detected photographically were h =4101-0 4079.7 4059.0. None of these was visible t o the eye a t dilutions much above 1 100. The ult'imate rays of zirconium were h=3496.2 3438.2 3392.0. The sensitiveness of the group of five rays in the blue Zra was small. W. G. Resonance Spectra of Iodine. R. W. WOOD (Phzl. Xag. 1918 [vi] 35 236-252. Compare A. 1913 ii 994; 1914 ii 233). -An account is given of further observations on the resonance spectra which are emitted by iodine vapour when this is excited by the light from a Cooper-Hewitt mercury lamp. An improved method of illumination is described.The doublet series which is excited by the green mercury line has been found to extend towards the red end of the spectrum up to h'7685. The photographs obtained by means of plates semi- tised with dicyanine show most of the doublets of the series the last doublet a t A7685 being of the twenty-seventh order. It is probable that this represents the limit of the resonance spectrum for the plates used were highly sensitive to beyond h 8500. The position of the twenty-seventh order doublet is moreover approxim- ately ths same as the limit of the absorption spectrum. If the plates are exposed to the resonance radiation for louger periods the doublets are found to be accompanied by faint com- panion lines some of.which may be duel to excitation by the satel- lites of the green mercury line but the author considers that some are to be attributed to the stimulating influence of the green line itself.011 greatly prolonged exposure it is found that the doublets fuse together t o form a series of wide bands. If a gas of the helium group is introduced into the iodine tube the1 intensity of the doublets is greatly reduced and a series of fluted bands makes its appearance,. These bands which occupy positions between the doublets are not exhibited by the resonance spectrum of iodine in a vacuum. It' is probable that the lines forming the doublets are themselves constituents of the fluted bands and that the appear- ance of thel bands in presence of an inert gas is due t o a transfer of energy from one part of the vibrating system to another as a result of collisions between iodine molecules and molecules of the inert gas.It may in this way be possible t o account for the complicated system of bands in the absorption spectrum these bands being referred to simpler systems which can be excited separately.GENERAL AND PHYSICAL CHEMISTRY. ii. 91 If the iodine vapour in a vacuum is excited by means of a quartz mercury arc complicated groups of lines are obtained in place of the doublet series. This is attributed to the circumstance that under these conditions the green mercury line has broadened to such an extent that it covers a number of the iodine absorption lines. The intensity distribution amongst the groups of lines pro- duced by this multiplex excitation is approximately the same as the distribution in the doublet series.The complexity of the groups increases with the wrdth of the green exciting line. A short reference is made to the resonance spectra excited by the two yellow mercury lines but these have not yet been examined in detail. H. 31. D. Series Law of Resonance Spectra. R. W. WOOD arid hi. KIMUXA (Phil. Nag. 1918 [vi] 35 252-261. Compare pre- ceding abstract) .-The wave-lengths of lines in t.he resonance spec- tra of iodine are recorded and tlie law of distribution is discussed. The series of strong doublets excited by the green line of the Cooper-Hewitt lamp has been examined with particular care with the result that the frequency difference between the components is found t o be constant and equal tol 50. The spacing of the first member (shorter x component) of each doublet is represented by the formula l/h,=183075 -2131.414-t 12*734m(nz- l ) / Z in which A is the wave-length of the first member of the doublet of the mtlh order.The agreement between the calculated and observed values is quite good up to the doublet of the fifteenth order but as the order becomes greater the divergence increases. Other series of doublets with constant frequency differences may be approximately represeiiteld by a similar formula. The lines in the rosoiiance spectrum excited by tIhe yellow lines h5769.G and h 5790.7 have also been examined with reference t o the law of distribution. The doublets in these groups of lines are not cliaracterised by the same regularities as t'liose in the groups excited by the green mercury line.The frequency difference between the components has not a constant value but tlie spacing of the doublets in the groups of lines excited by the yellow line h 5769.6 is such that the difference between the successive values of l / h is nearly constant. The degree of constancy is not so pro- nounced for the case of the groups which are excited by h 5790.7. H. M. D. Absorption Spectrum of Oxyhaemoglobin in the Ultra- violet and Extreme Ultra-violet Regions. TOSHIKAZU MASHIMO (Mern. CoZZ. Sci. Kyoto 191'7 2 199-202).-0xyhaemo- globin purified by crystallisation was dissolved in water and the photographic records obtained by interposing layers of this soln- tion varying in thickness in the ratio of the integral numbers from 1 to 42 between a carbon arc and the photographic plate are com- pared.These records show an absorption band with the centre a t r\ 350 pp which is possibly the same as that described by Peyrega 7-2fi. 92 ABSTRACTS OF CHEMICAL PAPERS. and Vlbs as occurring a t A 3 3 3 p p (Colmpt. rend. 1912 154 133). No absorption could be detected in the Schumann region. H. M. D. The Fluorescence of Cyano-compounds. HUGO KAUFFMANX (Bey. 1917 50 1614-l623).-See this vol. i 113. Rotation Inversion and Anomalous Rotation Dispersion HhRMANN GROSSMANN and MARIE WRESCHNER ( J . pr. Chem. 1917 [ii] 96 125-165).-The dextrorotatory power of tartaric acid in aqueous solution is probably due tlo the dissociation of the acid because with increasing concentration of the solutions the rotation falls and indeed the molten or solid acid is lzevorotatory.Addi- tion of acids such as hydrochloric or nitric acid to the aqueous solution depresses the dissociation the normal rotatory dispersion curve which rises from red to violet becoming gradually altared by an increasing proportion of added acid until a falling curve results; during the inversion of the nature 'of the curve the latter exhibits a maximum which gradually moves in the direction of increased wave-length as the Concentration of added acid is raised. Acetic acid exerts a similar effect to hydrochloric and nitric acids but is less powerful. Sulphuric acid a t low concentrations gives an effect resenlbling that of nitric rtad hydrochloric acids but a t higher concentrations the curve again begins t o rise and in pure sul- phuric acid tartaric acid sliows rotation values [a] red +69 and [a1 violet +158*8 which are above those observed with any other solvent.With boric acid the rotatory dispersion curve of tartaric acid is unaffected in type probably because of the formation of complex compounds of the two acids (compare Grossmann and Wieneke A. 1906 ii 209). On adding increasing quantities of sodium hydroxide to the dextrorotatory aqueous solution of sodium tartrate the rising rotatory-dispersion curve gradually flattens and then after becom- ing coincident with the horizontal axis corresponding with zero rotation finally falls beIow on to the negative side of this axis; this alteration is attributed t o the reversible formation of a lzevorota- tory tetrabasic salt of the acid. The addition of a calcium stron- tium magnesium o r cerium salt to the solution of tartaric acid containing excess of sodium hydroxide causes the curve for the alkaline solution to alter its character and t o become wholly posi- tive doubtless clue to the formation of complex compounds; a zinc salt gives no such evidence of complex formation.Malic acid in the pure condition is dextrorotatory but in the ionised condition exhibits a lzevomtation ; the addition of acids t o the aqueous solution as with tartaric acid tends to repress disso- ciation and the rotatory dispersion curve f o r the solution which normally falls as it passes from red t o violet rapidly changes into a rising positive curve with the addition of increasing quantities of acid. Again sulphusic acid a t low concentration behaves like the other aqueous mineral acids b u t in pure sulphuric acid malic acid attains the extreme negative values [a] red - 2 7 O [a] violet - 60.4c.GENERAL AND PHYSTCAL CHEMISIUXY.ii. 93 The effect of excessive sodium hydroxide on the activity of sodium malate solution resembles that with aqueous so’dium tartrate ; the rotatory dispersion curve becomes gradually flattened and finally passes over to the other side of the horizontal axis representing zero- activity the transition in this case being upwards from the negative side to the positive. So-called anomalous rotatory dispersion as evidenced by maximum and minimum values or by achromatism occurs only in the neigh- bourhood of zero rotation and the evidence indicates that it is due t o the presence of two optically active components of different opti- cal activity.Lowry’s suggestion (A. 1914 ii 786) t o use the terms ‘‘ simple ” and ‘‘ complex ” rotatory dispersion in place of ‘‘ normal ” and ‘‘ anomalous,” is commended. n. F. T. The Relation of Position Isomerism to Optical Activity. XI. The Menthyl Alkyl Esters of Terephthalic Acid and its Nitro-derivatives . JULIUS BEREND COHEN and HANNAH SMITH DE PENNINGTON (T. 1918 113 57-66. Compare A. 1916 ii 206) .-The average molecular rotation of seven menthyl alkyl esters of terephthalic acid is found to be [MI? -254O and the rota- tion of menthyl hydrogen terephthalate to be [M]j;9 - 259*2O which may be compared with -239O for menthyl benzoate - 2 4 3 O for menthyl alkyl phthalates and - 3 3 2 O for menthyl hydrogen phthalate.It appears therefore that the carbalkoxyl ‘or carboxyl group has little influence in the para-position on the activity of the asymmetric carbon atom. In the case of some menthyl alkyl rdroterephthalates i t is likewise found that enhanced rotation is exhibited by those esters in which the nitro-group is adjacent t o the active group. A strange abnormality is met with among these particular o-nitro-esters ; the solutions in benzene have consideraljly higher rotations than the fused esters. F o r details of the preparation and constants of these esters see the original. J. C. W. Absorption of Hard Rontgen Rays in Gases. MINNA LAX; (Ann. Physill. 1917 fivl 53 279-319).-The experiments described were made with highly penetrating rays the absorptive powers of olxygen nitrogen air carbon dioxide hydrogen sulphur dioxide and methyl chloride being compared.The results obtained show the relative values of the absorption-coefficients for rays of varying penetrating power and the dependence of the absorptive power on the pressure ‘of the gas. A comparison is made of the absorptive capacity of air for Rontgen rays and y-rays. H. M. D. Interpretation of Rontgen Spectra. L. VEGARD (Ber. Deut. physikal. Ges. 1917 19 328-343).-A theoretical paper in which the authar discusses the origin of the several series of lines which have been recognised in the high frequency spectra. It is assumed that the atoms are built up in accordance with Bohr’s theory and that the high frequency emission is t o be explained on the lineE adopted by this author.ii.04 ABSTRACTS OF CHRMICAL PAPERS. According to Debys (A. 1917 ii 434) the emission of the X series of lines is due t o an inner ring of three electrons. This appears to be the most probable cause of the appearance of these lines but it is shown that changes in a four-ring system of electrons may also account f o r the series. The L and M series require the assumption of rings of electrons the disturbance of which is associated with two or more energy quanta and it is suggested that the origin of the L series is a seven-membered ring of electrons corresponding with two energy quanta the I series an eight-membered ring with two quanta and that! the Jf series is due t o a ring of nine electrons associated with three energy quanta.R. M.D. Atomic Structure on the Basis of Rijntgen Spectra. 1,. VEGAR~D (Ber. Deut. phlysikal. Ges. 1917 19 344-353).-The theoretical considerations advanced in explanation of the origin of the K L I and M series of high frequency lines (compare previonc; abstract) have led the author to devise models for the shructure ol the known elements. It is claimed that this system of models is in agreement with the periodicity in the properties of the elements. With increasing atomic number there is a gradual increase in the number of concentric electron rings but each ring appears to ret”ain its individual characteristics throughout the entire series of ele- ments. Such characteristics are the number of the constituent electrons and the energy quanta with which these are associated.Tlie number of quanta increases in general with the diameter of the ring. H. M. D. Resonance and Ionisation Potentials for Electrons in Cadmium Zinc and Potassium Vapours. JOHN T. TATE and PAUL D. FOOTE (Proc. N a t . Acad. Sci. 1918 4 9).-Accord- ing to the observations of Franck and Hertz there are certain definite potentials a t which electrons cause the emission of rays by the atoms ‘of a gas or vapour. Two types of collision occur one of which is accompanied by the emission of a single frequency whilst the other causes ionisation and gives rise to a composite spectrum. The corresponding potentials are distinguished as resonance and ionisation potentials and these critfical values of the potential have been determined for cadmium zinc and potassium vapours.Within the limits of experimental error the observed critical potentials agree with the values calculated from the quantum relation hv=eV in which v is the frequency of the single line in the case of the resonance radiation and the limiting frequency of the line series when the radiation is due to ionisation. Nomenclature of the Radio-elements. Sr. MEYER and E. VON SCHTVEIDLER (Zcitsch. Elektrochem. 1918,24,36-38 ; Phq/siknl. Zeitsch. 1918 19 3@-32).-The authors in a work published on radioactivity have made a number of changes in the symbolic representation of radioactive substances. The changes which have been assented t o by twenty-nine German and Austrian chemists and physicists consist. chiefly in the following (1) Isotopes are desig- H.M. D.CIENRRATJ AND PHYSICAT CHEMISTRY. ii. 95 nated by Roman indices f o r example U U,*. (2) Sucoessive dis- integration products are designated by Arabic indices for example UX U'X,. (3) Branched products are designated by dashes for example RaC' RaG" the single dash indicating that the sub- stances are like polonium and the double dash those like thallium. J. F. S. The Colloidal State of Radioactive Substances. HILARY ZACHS (Kolloid Zeitsch. 1917 21 165-176).-Many recorded observations show that certain radioactive substances in neutral or slightly alkaline solution exhibit properties which are usually regarded as characteristic of colloids although the concentration of the solution is very much smaller than that corresponding with saturation with respect t o the hydroxide.It has been suggested that the behaviour of these radioactive solutions is due to the pres- ence of colloidal impurities in the solution but certain facts cannot be reconciled with this hypothesis. In the attempt to obtain further information on the subject the author has investigated the properties of radium-A radium-B and radium4 in various solvents including water ethyl alcohol ethyl ether ethyl malonate and benzene. The nature of the solvent is of considerable influence on the behaviour of the solutions in an electric field. I n the case of water solutions for instance radium-A is deposited on the anode radium-B on the cathode and radium4 to a small extent on the anode whereas in alcoholic solution radium-A is deposited ,on the cathode and radium-B and -C on the anode.The sign of the change of the colloidal particles does not depend entirely on the nature of the solvent for in every case particles of opposite sign appear to be present. The results obtained with alcoholic solutions show moreover that the relative amounts of substance deposited on the two electrodes vary with the applied potential. This effect has been previously noted in the case of colloidal solutions of silver. The adsorption of the radioactive colloids by various adsorbents is also found t o exhibit a similar variation when the solvent is changed. The variability is said to afford evidence of the presence of particles of different degrees of dispersity and i t is suggested that the radioactive substances occur in the form of ions as well as in colloidal form.Although cellulose has but little adsorptive capacity f o r the radioactive substances it is found that comparatively large quanti- ties of the radioactive products remain on the filter when the above solutions are passed through an ordinary filter paper. This would seem to show that a considerable proportion of the radioactive dispersoid particles are of large dimensions and the suggestion is made that these particles contain a very large number of solvent molecules. The decay of radium emanation in a gas or vapour leads appar- ently t o the formation of gaseous ions by the combination of the particles of ratiium-.il -R and -C with the molecules of the gas orvapour present. This type of combination or condensation seems to be very different in kind however from that which occurs in liquid solvents in which apparently the degree of solvatation is such that colloidal properties are developed.H. M. D. Radioactive Minerals in Bavaria. 11. F. HENRICH ( J . p v Chem. 1917 [ii] 96 73-85).-The view that the fluorspar (so- called “ Stinkfluss ”) af Wolsenberg near Wolsendorf in the Upper Palatinate owes its colour and odour to radioactive influences has been experimentally tested. Crystallised colourless fluorspar can be coloured deep blue by the P- and y-rays of radium and then shows on gentle warming a beautiful green thermoluminescence which fades and changes into the pale violet light’ characteristic of all fluorspars. But neither by radium nor by positive rays (Kanalstrahlen) could the characteristic odour of Wolsenberg fluorspar be produced.Accord- ing to 0. Ruff this odour which is produced when the mineral is crushed is typical of free fluorine and indeed the mineral may be used to demonstrate conveniently the odour of this difficultly pre- pared element. The second part of the paper deals with the detailed analysis of copper-uranium mica (chalcolite or tobernite) from Steinbruch Fuchsbau near Leopldsdorf in the Fichtelgebirge the composi- tion of which agreed closely with the formula C U ( U O ~ ) ~ ( P O ) ~ ~ ~ ~ ~ H O . F. S. The Radioactivity of Archaan Rocks from the Mysore State South India. W. F. SMEETH sncl H. E. WATSON (Plid. M q . 1918 [vi] 35 206-214).-Some fifty radium estimations have been made of representat!ive samples from the various com- ponents of the ArchEan complex of Mysore in order to see how far the various formations or groups are distinguishable by their radioactivity. These are set forth in order of age of the rock in a table.The oldest the hornblende rocks (epidiorites and hornblende schists) of the Dharwar system are low in radium and uniform between 0.14 and 0-25 ( x 10-12 gram of radium per gram of rock) and the rocks of the chloritic series next in age do not differ much from them. Intrusions of the Champion gneiss and the related quartz veins of the Kolar Field which contain much more radium than the normal schists considerably increase the radium content whereas the basic intrusions of Dharwar age con- tain much less radium than the schists themselves.On radio- active evidence the original classification which correlated the Bellara trap with the Grey trap of Chitaldrug is correct rather than the newer correlation of the latter with the Santavari trap of the Kadur district which resembles i t closely but cont’ains three times as much radium as the other two. This affords an example of the possible use of such determinations in the correlation of the highly metamorphosed members of the Archzean camplex.GENERAL AND PHYSICAL CHEhIISTRY. ii. 97 The Champion gneiss Peninsular gneiss and Closepet granite next in age contain four to five tirhes as much radium as the Dharwar schists and twelve to fifteen times as much as the next' and following Charnockites which stand apart from the others in virtue of exceedingly low radium content.This confirms Holland's classification of Charnockites as a distinct petrographical province. The general conclusions are that these very ancient rocks all supposed to be of igneous origin contain remarkably little radium. For the fairly uniform hornblendic schists of the Kolar Field the radium content does not vary with the depth from the surface. Amongst magmas the more basic contain less radium than the more acid the Charnockite magma of intermediate composition being a striking exception. Influence of Heat Treatment on the Electrical and Thermal Resistivity and Thermo-electric Potential of some Steels EDWARD D. CAMPBELL and WILLIAM C. DOWD ( J . Iron Steel Inst. 1917 96 251-266).-In a series of annealed and hardened steels containing from 0.018 to 1.184% of carbon the ratio of the elec- trical resistivity to the relative thermal resistivity is in all cases higher than for pure iron.The effect of quenching is t o raise both values. The thermo-electric potential varies with the nature as well as with the concentration of the elements dissolved in the iron. [See further Znd. 1917 1051.1 C. H. D. A Permanganate Electric Cell. A. W. WARRINGTON (Chem. A!T~ws 1918 117 97-98).-Potassiuni permanganate is used as the depolarising agent in a t'wo-fluid electric cell in which the carbon plate is immersed in a dilute solution coii- taining 3-16 grams of potassium permanganate and 6 C.C. of concentrated sulphuric acid in 250 C.C. of liquid contained in a porous pot. The outer zinc compartment of 750 C.C.capacity contains a strong solution of zinc sulphate (14.55 grams). The cell gave et voltage of about 2. Two such cells were connected up t o a water voltaineter and tangent galvanometer in series and after the first ten minutes the fall in current in a run extending over three hours forty-six minutes was from 0.09 to 0.086 ampere only and the voltage a t the end was still 3.7. With a single-fluid per- manganate cell containing the same amounts of permanganate and sulphuric acid with amalgamated zinc and carbon the current after ten minutes fell from 0.0538 to 0.0358 ampere in 146 minutes whilst the voltage a t the end was 1.5. The yield of current with very dilute solutions in a two-fluid cell is very high and a cell containing 0.79 gram of potassium permaiiganate and 2.64 grams of sulphuric acid in 250 C.C.of liquid and 3.59 grams of crystal- lised zinc sulphate in 750 c.c.. deposited 0.48 gram of copper in three hours whilst nearly 75% of the energy was still available. A similar dichromate cell containing 5.88 grams of potassium dichrolnate and 13.72 grams of concentrated sulphuric acid in the carbon compartment gave an average current of 0.0632 ampere only. €3. N. F. S. 7 ,ii. 98 ABSTRACTS Oh' CHEMICAL PAPERY. The Magnetic Properties of Manganese and of some Manganese Steels. SIR ROBERT HADFIELD C. CHENEVEAU and CH. GENEAU (Proc. R o y . SOC. 1917 [A] 94 65-87; Contpt. rend. 1918 166 390-392).-Measurements have been made of the coefficient of magnetisation of manganese free from occluded gases and a number of manganese steels.Manganese is paramagnetic. [For numerical data see Ind. 128.1 W. G. Energy Theory of Matter. ELMER B. VLIET (C'henz. iVezcs 1918 117 118-119).-1t has been pointed out by Thornton (A 1917 ii 164) that the molecular heat of combustion of an organic compound is proportional to the number of oxygen atoms which is required for the complete combustion of one molecule of the organic substance. According to 'Redgrove (A 1917 ii 411) the molecular heatt of combustion can be represented by an additive series of terms which depend on the number and type of the valency bonds in the molecule. By applying these relations to the aliphatic hydrocarbons it is shown that the coefficients characteristic of the several terms in Redgrove's series may be calculated.The values so obtained differ from those calculated by Redgrove and the conclusion is drawn that the molecular heat of combustion cannot be regarded primarily as a function of the number and type of the valency bonds. I t is however still possible that the energy change accom- panying a reaction may depend on the valency changes. H. M. D. A High Temperature Thermostat. J . L. HAUGIITON and [D. HANSON ( J . Inst. Metals 1917 18 173-186).-The instru- ment consists in principle of a double-walled vessel like a Buiisen ice calorimeter made into a furnace by winding with nichrome wire. The vessel acts as a gas thermometer and the variations of pressure of the air contained in i t operate a contact-breaker con- sisting of a U-tube containing mercury with two platinum contacts through which passes a relatively small current.The latter by means of a solenoid pulls a fork out of or int'o two mercury cups so introducing an external resistance into the heating circuit or cutting it out. The other side of the U-tube is connected with a second thermostat of simpler construction which serves t o com- pensate for changes of external pressure and temperature. The furnace bulb is made of silica and may be used for tempera- tures of the order of 1OOOO. The U-tube has a tap for removing the mercury when fouled by sparking and is made sufficiently wide in the upper part of the limbs to prevent the mercury from being sucked back when the furnace is shut' off. The cold thermost,at consists of three concentric cylinders of which the inner one acts as the air-bulb and is surrounded by benzene contained in the middle vessel on which a fine resistance wire is wound.The benzene in expanding operates a mercury cont'act-breaker. The third cylinder contains insulating material. With this arrange-QENERAL AND PRY SlCAL CHEMISTRY. ii. 90 ineiit the temperature of this part of the apparatus is constant within less than O s l o . The main furnace is then kept constant within lo. By connecting another furnace such as a crucible furnace in series with the main regulating resistance but in parallel with a thermostat furnace the temperature of the former may be kept const'ant with about the same accuracy as the thermostat. By automatically reducing a resistance in parallel with the controlled furnace very regular cooling may be obtained such as is required in taking cooling curves.C. H. D. Adsorption Compounds and Adsorption. 111 The In- fluence of the Adsorption of certain Substances by Alcohol. L. BERCZELLER and ST. HETBNYI (Biochem. Zeitsch. 1917 84 137-148).-A number of measurements are given of the adsorp- tion of alkali hydroxides acetic acid iodine methylene-blue etc. by starch charcoal etc. and the influence of the additions of alcohols. The influences of isocapillary and equimolecular solu- tions of the alcohols on adsorption were compared. Generally the isocapillary solutions did notl exert the same amount of inhibition the solutions of lower alcohols which contain a relatively large amount of alcohol exerting a greater inhibition than isocapillary solutions of the higher alcohols.Those isomolecular solutions of which the surface tensions are lowest exert however a greater inhibitory action. S. B. S. Gliding Dialysis. 11. H. THOMS (Be?.. 1918 51 42-45. Compare A. 1917 ii 561).-Imtead of rotating the dialyser about the plane of the membrane it may be rotated or shaken in the same plane with equally good results. The new arrangement is an improvement inasmuch as i t imposes very little tearing strain on the membrane. [See further Z??ct. 1 9 0 ~ . ] J. C. ITT. Solubility and Dissociation of some Electrolytes in Ethylurethane. M. STUCKGOLD ( J . Chiin. Phys. 19 17 15 502-516) .-The author has determined the solubilities of the following salts in ethylurethane a t GOo ammonium rubidium potassium tetramethylammonium and tetraethylammonium iodides sodium potassium rubidium and tetramethylammonium bromides sodium potassium and ammonium chlorides.The conductivities of six electrolytes namely ammonium potassium and tetraethyl- ammonium iodides tetramethylammoiiium bromide cobalt nitrate and zinc nitrate have been determined those of the iodides being taken to the greatest dilutions suitable considering experimental errors. The cryoscopic constant of this solvent using naphthalene carbamide and nitrotoluene as solutes was found to be 53.2 and from this molecular weight determinations by the cryoscopic method indicated that ammonium potassium and rubidium iodides are dissociated in ethyl urethane. Moleciilar weight deterininations o n ethylurethane based on the 7*-2ii.100 ABSTRACTS OF CHEMICAL PAPERS. capillarity constant using the formula M = 0*6T(4*8 -log p)/a where T is the absolute b. p. at p mm. of mercury and a,=.h . T where1 h is the height of ascension and T the radius of the capillary in millimetres show that ethylurethane is strongly polymerised the factor of association being almost independent of the tempera- ture over the range 65-179O. The viscosities and densities of the urethane atl 60° 70° and 80° were also determined. W. G. Ultrafiltration of Supersaturated Solutions. L. HERCZELLER (Biochem. Zeitsch. 191 7 84 156-159).-Supersaturated solutions of menthol thymol and naphthol were filtered through collodion membranes and the surface tensions of filtrate and residue were determined by the stalagmometer.I n certain cases the results (lower surface tension of residue) indicated that some of the solute was retained on the filter from which fact the conclusion is drawn that the supersaturated solution is colloidal in character. S . B. S. Colloidal Nature of the 7-Alkali Resin Soaps. LUDWIG PAUL (Rolloid Zeitsch. 1917 21 176-191).-A general account is given of the properties of solutions of sodium and ammonia resin soaps in which particular attention is directed to the colloidal properties of the solutions and to differences between the resin and fatty acid soaps. Dilute solutions of the alkali resin soaps repre- sent highly disperse colloid systems of very pronounced stability. On the addition of basic dyes such as methyl-violet and magenta colloidal lakes are formed which can be kept without change for prolonged periods of time.The lakes are coagulated on the addi- tion of suitable electrolytes. On addition of hydrochloric acid to the y-alkali resin soaps y-pinic acid is obtained and this behaves very similarly to the soaps towards basic dyes. [See Ind. April.] H. M. D. Colour and Degree of Dispersity [of Colloidal Solutions]. I,. BERCZELLER (Biochem. Zeitsch. 1.917 84 156-174).-Gold sols have varying colours according to the size of the colloidal particles and Harrison (A 1912 ii 240) has directed attention t o the similarity of the colours of the adsorption complexes of iodine with starch and dextrins where similar variations of colour are produced by varying the size of the particles of the carbohydrate. The author shows that similar variations in the colour of the adsorption complelxes of lanthanum hydroxide can be produced by varying the size of the particles of the hydroxide.Atbention is also directed t o analogies in the colour variations in certain com- plex copper compounds in certain reactions of bile pigments in some furfuraldehyde reactions (XJdrinszky A. 1889 1024 ; 1891 350) and in the nuances of solutions of dyes when subjected to varying treatments (heating dilution taeatment with salts etc.). S. B. S.GENEML SND PHYSICAL CHEMISTRY. ii. 101 Anisotropic Colloidal Solutions. W. REINDERS (KoZZoicl Zeitsch. 1917 21 161-165. Compare Diesselhorstl and Freuncl- lich A. 1916 ii 65; Kruyt ihid. ii 486).-With a view t o the explanation of the double refraction which is exhibited by certain colloidal solutions further experiments have been made with vanadium pentoxide sols which seem t o show that the particles of such sols are crystalline.By varying the conditions of formation of the pentoxide it has been found that there is no clear line of demarcation between the particles which are present in the initially isotropic sols and those which can be microscopically identified as crystalline particles. Although the double refracting power of a sol is only developed very slowly a t the ordinary temperature the transformation takes place much more quickly at looo. I n the freshly prepared sols the ultra-microns are spherical but on heat- ing a t looo elongated ultra-microns make their appearance in a short time. These increase1 in size and number and the change is accompanied by a considerable increase in the vixosity.Experiments made with mercurous chloride and lead iodide gave similar results. If these substances are prepared by double decom- position in presence of a protective colloid doubly refracting sols are obtained but there is a continuous transition from the sol con- dition to that which is represented by crystalline suspensions of these substances. The anisotropic character of the sols in question appears there- fore t o be due t o the crystalline nature of the ultra-microns. H. M. D. Kinetics of the Reactions in the Formation and Floccula- 1917 84 175-182) .-Iodic acid accelerates the reduction of gold chloride solutions by sulphurous acid as do also mercuric sdts and the colour of the sols varies in the latter case with the salt used.Examples are given of the influence of capillary active substances (hexoic and decoic acids) on the flocculation of colloidaI gold and starch solutions which are cases of sensitisation of colloids t o salt' precipitation. as recently demonstrated by Freundlich and Rona (A. 1917 ii 365). Coagulation and the Attraction of Particles. RICHARD ZSIGMONDY (Nachr. R. Ges. Wiss. Gottingen 1917 1-43; from Chem. Zentr. 1917 ii 350-351 *).-The paper deals with the possi- bility of determining the attraction (if any) between discharged colloidal particles from measurements of the rate of coagulation. Experiments in which the changes of colour of gold hvdrosols were employed as an indicator of the progress of the coagulation showed that a pure colloidal gold solution of a given nature and concen- tration has a certain minimum time of coagulation.independent of the nature aiid to a great extent independent' of the concentra- tion of the electrolyte employed. The period of rapid coagulation is reached before the' particles are completely discharged but the * and Z ~ i f s c h . physikaZ.lChem. 1918,92 600-639. tion Of Colloidal Solutions. L. BERCZECLER (BiOCh e m . ZeitSCh. S. B. S.ii. 102 ABSTRACTS OF' CHEMTCATt PAPERS. remaining charges are small (compare Hardy am1 Powis X c i ~ s c I ~ . physiknl. Chern. 1915 89 179). The time of coagulation is approximately proportional to the gold concentration. A method of observing the progress of coagulation ultramicroscopically is given and by this means the diminution in the number of primary particles and the production of secondary particles (which shine more brightly) were determined.From these results i t is calcu- lated that the sphere of attraction of a primary particle is two or three times its radius. This is in agreement with the results obtained by other writers in other ways. It is proved therefore that the discharged particles do attract one another when they come within this distance of each other. Retardation of the Formation of Prussian Blue and other Reactions in Aluminium Hydroxide Sols. JOSEF REITST~TTER (Kolloid Zeitsck. 1917 21 197-200).-In the course of observations on the coagulation of aluminium hydroxide sols in presence of various alkali metal salts (Gann A.1916 ii 382) it was found that after coagulation by the addition of a very dilute solution of potassium ferrocyanide the solution gave no blue colora- tion on the addition of ferric ions until after the lapse of a con- siderable interval of time. To explain this effect it was suggested that the ferrocyanide ions are adsorbed and subsequently enveloped by the coagulate. Further experiments show that the retardation is very much less pronounced if some other coagulating electrolyte such as sodium citrate is added to the sol either before or after the addition of the ferrocyanide. I n these circumstances it is more probable that the retardation of the formation of Prussian blue is to be explained by the adsorption of both the ferrocyanide and the ferric ions.If either or both are then displaced by other ions conditions favour- able to the formation of Prussian blue are obtained. Similar retar(ation- phenomena have been found when a little of the blue sol obtained by acidifying Congo-red is mixed with a colloidal solution of aluminium hydroxide and a drop of sodium hydrogen carbonate solution is added t o the mixture. The blue sol may be replaced by Eerizopurpurin or rosolic acid. [See Ind. 7 1 A . l H. &I. D. General Curves for the Velocity of Complete Homo- geneous Reactions between Tw6 Substances at Constant Volume. GEORGE W. TODD (Phil. Mag. 1915 [vi] 35 281-286). -By choosing suitable quantities to represent the concentration of the reacting substances it is possible to plot curves showing the connexion between the rate of change and the time which are applicable to all reactions of the same type.The mode of repre- sentation may be illustrated by reference t o the birnolecular velocity equation d x / d t = k(a - r ) ( b - 2 ) . I f X = T / U R = ka and p = b / a this equation assumes the form d X / d t = K ( l - X ) ( p - X) and on integration this gives Kt=1/(1 -11) . {log p(1 - - - Y ) / ( p - I ) } . The curves referred t o are then obtained by plotting _Y against Kt for values of p r 1 . 5 2 3 etc. R. V. S.CIENERATI ,4ND PHYSTCATI CHEillTSTRIY. ii. 103 Correspoiiding series of curves are plotted for the termolecular reaction represented by ZL-l -I-B + for the three cases in which the initial concentration of A is equal to greater and less than that of B.Curves for the quadrimolecular reaction 3A + B e and 2A + 2B+ are also shown. These general curves may be applied in practice for the deter- mination of k of the value of X corresponding with a given time interval or for the determination of the order of a reaction. If the order of the reaction and the initial concentration are known i t is only necessary to measure X corresponding with a certain value of t and the curves then give K t and therefore k. The fraction X changed in a given time may be read off from the curves if the order of the reaction the coefficient k and the initial concentrations are known. To find the order of a reaction i t is necessary to know the initial concentrations and two correspond- ing values of X and t . The particular curve on which the two points (X t ) fit most exactly determines the order of the reaction.R. M. D. Relationship between the Saponification Velocity Con- stants of Esters. P. E. VERKADE (Chem. Weekblad. 1918 15 203-208).-The author finds that the ratio of the velocities of saponification of mixed anhydrides of acetic propionic etc. acids with different acids is always the same. Velocity of Saponification of certain Esters by Tenth- normal Potassium Hydroxide in Different Solvents at 25O. ERNEST ANDERSON and H. B. PIERCE ( J . Physical Chem. 1918 22 44-67) .-The object of these experiments was to determine whether the relative velocities of saponification of different esters are affected by the nature of the solvent and whether the relative rates of saponification of different esters containing the same alcohol (or acid) are independent of the nature of the alcohol (or acid).The rates of saponification of twenty-three esters were measured a t 25O in 90% methyl alcohol 90% ethyl alcohol isoamyl alcohol DT; 0.8166 and when possible in water. The results obtained show that the relative values of the velocity coefficients in the different solvents vary considerably with the nature of the ester. Esters containing the same alcohol (acid) are saponified at relative rates which depend on the nature of the alcohol (acid). A. J. W. H. M. D. Hydrolysis of Triethyl Citrate and the Ethyl Hydrogen Citrates. JOH. PINNOW (Zeitsch. Elektrochent. 19 18 24 21-36). -The hydrolysis of triethyl citrate symmetrical and unsymmetrical diethyl hydrogen citrate and symmetrical and unsymmetrical ethyl dihydrogen citrate by means of sodium hydroxide has been studied at a series of temperatures from Oo to looo. The hydrolysis of the various stages is shown to take place a t very different velocities between the temperatures of 8 O and 50°.Each step in the hydro- lysis may be separated from the others and goes to completion asii. 104 AJM’FRACTS OF CHEMICAL PAPERS. a strictly bimolecular reaction. The side ethyl groups are the first to be removed and in no circumstances do synimetrical diethyl hydrogen citratei or unsymmetrical ethyl dihydrogeii citrate appear in recognisable quantities as products of any of the hydrolyses. These products are only obtainable by the estsrification of citric acid. The preparative separation of the mono- and di-ethyl esters from one another and from citric acid can be effected by ether extraction from aqueous solution in a Partheil-Rose apparatus.The various esters were identified by measurements of their hydrogen ion concentration by means of the’ colorimetric process of Friedenthal Salesky and Salm. The temperature coefficient of the rate of hydrolysis is high for all five compounds at temperatures below 23O; in the case of the unsymmetrical diethyl ester and the monoethyl esters a minimum is shown between 23O and 30° and a second minimum for the monoethyl esters between 45O and 60° and 38O and 4 5 O respectively. The stepwise hydrolysis and the first minimum of the temperature coefficient are explained by the forma- tion of additive products between the.ester and the alkali these compounds undergoing decomposition as the hydrolysis proceeds into the original compounds. The following reaction constants and temperature coefficients have been found Hydrolysis of triethyl citrate M=37*8 at 8*1° 63.7 at 1 5 O 98.9 at 23O 149.8 a t 30° 253 at 40° and 443 a t 50°; increase of logk for loo between the successive temperatures is 0.328. 0.239 0.259 0.227 and 0.243. Unsymmetrical diethyl hydrogel citrate k = 1.725 at 8*1° 2.92 at 1 5 O 4.28 ati 23O 5.14 at 30° 9.38 a t 40° 16.17 a t 49O; increase of logk 0.330 0.208 0.114 0.262 and 0.263. Symmetrical diethyl hydrogen citrate k=0*474 a t 6*7O 0.841 at 15O 1.48 a t 23O 2-27 at 30° 4.16 a t 40° and 6-84 a t 50°; increase of log k 0.300 0.306 0.266 0.263 and 0.216.Symmetrical monoethyl hydrogen citrate k =0*0038 at Oo 0.0149 at 15O 0.0283 at 23O 0-0409 a t 30° 0.0743 at 38O 0.1153 at 45O 0.245 at 60° 0.584 at 75O and 2.86 at looo; increase of logk 0.395 0.349 0.229 0.324 0,273 0.218 0.251 and 0.276. Unsymmetrical monoethyl hydrogen citrate k = 0.0825 at So 0.132 a t 15O 0.238 at 23O 0.302 at 30° 0.511 a t 38O 0.654 at 45O 0.080 a t 55O. 1-76 aft 65O and 10.65 at looo; increase of logk 0.291 0.320 0.147 0-285 0.154 0-217 0.213 and 0.212. The figures in all cases refer t o the hydrolysis of a single ethyl group. J. F. S. Rate of Solution of Silver in Chromic Acid. R. G. VAN NAME and D. U. HILL (Amer. .7. S c i . 1918 [iv] 45 54-58).- The measurement of the rate at which silver dissolves in chromic acid solutions containing sulphuric acid has shown that the initial velocity is greater than the velocity which characterises the normal dissolution process.The anomaly indicates that the velocity depends on the physical state of the metal and this in turn suggests that the rate of dissolution of the metal is not entirely determined by diffusion process Previous experiments have shown that the rates of dissolution of different metals tend to become more nearly equal a8 the concentra-GENERAL AND PHYSICAL CH.E:MISTRS. ii. 105 tion of the sulphuric acid in the solution increases. The behaviour of cadmium and silver forms an exception to this rule in that the relative rates of dissolution diverge with increasing acid concen- tra tion. H. M. D. Contact Catalysis. IV. WILDER D. BANCROFT ( J .Physical Chem. 1918 22 22-43. -Compare this vol. ii 40).-A discussion of false equilibria in reference to the poisoning of catalysts by the adsorption of one or other of the products of reaction. Such adsorption will cause the reaction to slow down and it may be brought practically t o a standstill. I n these circumstances an apparent or false equilibrium is reached which will depend on the relative amount of the catalyst present. It is pyobable that molten sulphur catalyses. the reaction between hydrogen and sulphur and that hydrogen sulphide acts as a poison towards the catalyst. A similar effect is supposed to obtain in the reaction between hydrogen and selenium. Enzyme reactions are in many cases affected by the products of reaction in that a large quantity of enzyme is required to com- plete the reaction.I n such cases false equilibria are set up which may be explained in terms of the poisoning of the enzyme by one or other of the reaction products. H. M. D. The Variations in the International Tables of Atomic Weights TH. RENARD ( J . Chiwb. phys. 1917 15 541-548).- A brief discussion of the revisions made of the various atomic weights by the International Committee since 1903. The author advocates the use of the rounded-off values suggested by Guye (compare A. 1916 ii 386). W. G. Hydrogen Isotopy. A. E. LACOMBL~ ( C l ~ m . SFeekblnd 191 8 15 38-40).-Polemical. A criticism of the views expressed by Scheringa (ibid. 1917 14 953) on the relationship of Prout's hypothesis t o the periodic system. A. J. W.Prout 's Hypothesis and the Periodic System. K. SCHERIKGA (C'hem. Tt'eeliblcrd 1918 15 22l).-A reply t o Lacomb16 (preceding abstract). A. J. W. The Exchange of Energy in the Collisions between Slowly-moving Electrons and Molecules of Gases. G. HERTZ (Ber. Deut. pkysiknl. Ges. 1917 19 268-288).-A theoretical paper in which the laws governing the exchange of energy between colliding electrons and molecules are discussed in reference to atomic and molecular structure. From the available data for helium it is calculated that the loss of energy in the collision between an electron and a helium atom is 0.00027 times the energy of the electron. This result is very nearly the' same as that which is derived on the assumption that the laws of collision are those goveriiing collisions between elastic spheres and from the closeii I06 ABSTRACTS OF' CHERTTCAT PAPERS.agreement the conclusion is drawn that the energy lost by the electron is represented by the increase in the kinetic energy oi the helium atom. I n the case of hydrogen however the loss of energy is found to be much greater namely 0.06 of the energy of the electron and it would seem that the collision of an electron with a hydrogen molecule is accompanied by an increase in the internal energy of the molecule. The movement of electrons in gases a t higher pressures and the influence of small quantities of impurities on the effects produced are also discussed from the point of view of the author's theory. H. M. D. Valency Centres. 111. The Periodic System. 0. HINS- BERG ( J .pr. Chem. 1917 [ii] 96 166-173. Compare A. 1916 i 725; 1917 ii 173 461).-As explained in the earlier papers the atoms of the elements lithium glucinum boron and carbon are assumed to possess one valency centre the chemical valency of which ranges from one to four the maximuin being attained a t carbon; in the remaining elements of the first group the atoms contain two valency centres one being quadrivalent throughout and the other gradually increasing in valency from 1 to 4 so that the surplus or normal valency falls in the order 3 2 1 0 for nitrogen oxygen fluorine and neon respectively. Similar differences exist in the second series of the periodic system; a single valency centre or atomic nucleus is present in the first four members but atl the fifth element namely phosphorus a second valency centre enters and the remainder of the elements of the series up to argon con- tain the two atomic nuclei which in the last element just satisfy one another and leave the element without free valency; contrary to the earlier opinion chlorine probably contains only two valency centres this view receiving support from the similarity in the general properties of the chlorides and cyanides and the analogy between the intra-atomic structure of the chlorides and the intra- molecular structure of the cyanides for example *-*-Ag for silver chloride and N-C-Ag for silver cyanide.I n the next series a different' type is encountered; the assumption is made that in these elements a sexavalent atomic nucleus is present in which the active valency increases by units from potassium up to the maxi- mum of six which is attained a t chromium; the' atoms of the succeeding elements manganese iron cobalt and nickel include an additional valency centre which possesses an additional free valency a t each element named so that the maximum possible valency for these metals is 7 8 9 and 10 respectively the maxi- mum apparently being attained in iron carbonyl Fe(CO) with oct,avalent iron; in the case of cobalt the full possible nonavalency is never reached the differential valency or the difference between the valency of the sexavalent and tervalent nuclei supplying the maximum; with nickel also the differential valency has a value 3 in agreement with the composition of most of the compounds n W e -INORC ANIC CHEMISTRY.ii. 107 althougli in nickel carbonyl Ni(CO) the atom appears to attain octavalency but however is still short of decavalency. The metallic nature of the whole of the ten elements of this third series is ascribed to the presence of the sexavalent atomic nucleus. Copper is regarded as a transition element between the third and fourth series and therefore probably abnormal ; from zinc onwards the members of the fourth series fall into a normal group the valency of the first atomic nucleus gradually increasing in valency until quadrivalent germanium is reached ; after this point the atoms of this series contain a second atomic nucleus the valency of which gradually increases from unit value in arsenic to 4 in krypton the latter therefore being devoid of free valency. For the present the theory is extended only as far as the fifth and sixth groups ; the elements of the former contain as their essential charac- teristic a sevavaleiit atomic nucleus which exert's its full effect in molybdenum the last four elements of the group (one unknown) including an additional nucleus but the final elements namely rhodium and palladium exert only their cliff erential valency. Silver like copper is probably an abnormal transition element The sixth series from cadmium to xenon is normal and corresponds with the zinc-krypton group. D. F. T.

ISSN:0368-1769    

DOI:10.1039/CA9181405089

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

i. 90 ABSTRACTS OF CHEMICU PAPERS. Chemistry of Vegetable Physiology and Agriculture. Effects of Oxygen and Carbon Dioxide on Nitrification and Ammonification. J. K. PLUMMER (Cornell Univ. Agr. Expt. Stat. 1916 Bull. 384 305-330; Physiol. Abstr. 1917 2 569).-Nitrification takes place in Eealed flasks as long as there is a supply of oxygen; the optimum amount is 35-60%. Carbon dioxide is produced when lime is used; ammonium sulphate with- out' lime causes only a slight increase in nitrification. If oxygen is present carbon dioxide has no material effect. Under anaerobicVEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 91 conditions denitrification sets in until all nitrates are destroyed. There is no optimum content of oxygen for ammonia production but in its absence somewhat less is produced.Influence of the Chemical Structure of the Compounds to be Ammonified on the Rate of Ammonification. K. MIYAKE ( J . Amer. Chem. SOC 1917 39 2378-2382).-An in- vestigation on the relationship between the structure of organic nitrogen compounds and the rate a t which they are ccnverted into zmmonia in the soil. Quantities of 100 grams of various air-dried soils were mixed respectively with 100 C.C. of water and quantities of leucine tyrosine acetanilide benzanilide acetamide and benz- amide contsining 100 milligrams of nitrogen. The mixtures were allowed t o incuba,te for periods of two seven twelve and sixteen days and the amount of animoiiia formed was estimated. The rate a t which the conversion into ammonia took place followed the order acetamide > leucine > tyrosine > benzamide > acetanilide > benz- anilide. It is shown that aliphatic nitrogen compounds are more rapidly converted into ammonia than aromatic compounds and aromatic amino-compounds more rapidly than aromatic imino-com- pounds under the conditions of the experiment.Assimilation of Lactic Acid by Yeasts and the Production of Pyruvic Acid by Yeasts and Oidia. P. MAzF and M. RUOT (Compt. rend. SOC. biol. 1917 80 336-339. Compare A. 1917 i. 310).-Yeasts grown in a confined atmosphere in a solution containing mineral salts and 2% of calcium lactate qive about a 50% yield of pyruvic acid. By means of gas analyses and of the calcium carbonate formed it is shown t h a t the respiratory qnot;ent is the same as that of the controls without lactate (about 0.7) which may indicate that the yeast burned proteins and possible traces of f a t ; the combustion of carbohydrate reserves would give a quotient equal t o 1.The culture fluids contained also a small quantity of succinic and acetic acids but no alcohol or aldehyde. Six species of Oidium behaved similarly. The Culture of Yeast in Presence of Air with the Use of Carbamide as the Source of Nitrogen and with different sources of Carbon. The Quotient of Sugar Assimilation. TH. BOKORNY (Biochcm. Zeitsch. 1917 83 133-164).-A detailed account is given of a large number of ex- periments in which the increase in dry weight is determined when yeast is grown in diluted urine t o which various sugars glycerol etc. are added as the source of carbon.The quotient' of the sugar assimilation that is absolute increase in dry matter amount of sugar employed was determined in many cases. Hexose-diphosphoric Acid its Composition and its Role in Alcoholic Fermentation; the Behaviour of the Sugars with Three Carbon Atoms towards Yeast. CARL NEUBERG ADAM LEVITE and ERWIN SCHWENK (Biochem. Zeitsch. 1917 83 244-268).-The authors confirm the results of Harden and Young G . B. J. F. S. G . B. S. B. S.i. 92 ABSTRACTS OF CHRMTCAT PAPERS. in ascribing to 1iexose-phosp~lol.ic :Icid the formula C,R,,,0,(P0,B2)~. I t s rotation is [a]; + 3.55O and it yields lmmlose on hydrolysis. Neither it nor its salts can be fermented by living yeasts even in presence of co-ferments or artificial activators and this is not due to any toxic action on yeast cells The esterification of phosphates takes place to the extent of only about' 8% in presenca of living cells even when toluene has been added whereas the esterification of the phosphate by sugars is almost qxxantitative in presence of dried yeast or cell-free yeast juices.For these reasons the fornia- tion of hexose-phosphate is regarded as a pathological procws. There is no evidence therefore t h a t a hexose-phosphate forms an intermediate stage in the degradation of a six-carbon into a three- carbon sugar. Neither glyceraldehycle nor dih ydroxyacetone furthermore undergoes fermentation in the presence of yeaFt as does dextrose or lmmlose even in presence of activators and this is shotvn not t o be due t o any toxic action on the yeast.Furthermore trioses on distillation yield methylglyoxal which can be separated in the form of its p-nitrophenylosazone and this reac- tion is quantit'ative. On subjecting hexose-phosphoric acid pre- pared in different ways to this process no triose could be detected. All evidence therefore is against the theories t h a t t,he trioses are intermediary products of sugar fermentation and that hexose- phosphoric acids play a part in the production of such products (theory of Lebedev and others). S. B. S. Pharmacological Studies of the Ipecacuanha Alkaloids and some Synthetic Derivatives of Cephaeline. 111. Protazoocidal and Bactericidal Action. A. L. WALTERS W. F. BAKER and E. W. KOCH ( J . Pharm,. Eept. T h e y . 1917 10 341-364. Compare Walters Eckler and Koch A.1917 i 717). -When solutions of emetine hydrochloride of 0*0005% strength are in contact with cultures of amebas for an hour many of the! amebas are destroyed but* transplants from these cultures t o fresh agar plates show a certain amount of growth of amebas which is retarded or delayed due probably to the development of encysted or resistant forms. Stronger solutions of emetine hydrochloride are more toxic but even when a 1% solution is employed some amebas may still be living a t the end of an hour. The propyl and isoamyl ethers of cephaeline are more toxic towards amebas than emetine. Methylating cephaeline t o form emetine is known to increase the toxic action towards Endameba bucca2is and paramecia and the substitution of the methyl group by ethyl propyl butyl isoamyl or ally1 further intensifies this action.Cephaeline isoamyl ether phosphate is the most effective alkaloid of this group in killing paramecia being fifteen to twenty times as potent' as emetine phosphate. Tested on Staphylococcus aureus in the manner described cephaeline prop91 ether phosphate is bactericidal in solutions of fl*5'% drength and the corresponding isoamyl ether in golutiona oEO-O35'j/o strength. emetine in bactericidal action. Both these derivatives are rnuc.11 stxonger t l p l l 14. w. H . The Disinfectant Action of Quining Derivatives on Diph- theria Bacilli. HANS SCHAEFFER ( B i o c h e ~ ~ ~ Zeitsclz. 1917 83 269-314).-Quinine shows an inhibitory action towards diphtheria bacilli in a coiicentration of 1 10,000. This action is not greater in the cases of hydrocupreine and its inethyl ethyl and isopropyl derivatives.isoButylcupreine is however more active being anti- septic in a concentration of 1 50,000. i.coAniy1 hexyl heptyl and octyl dcrivatives show increased antiseptic activity with increasillg molecular weight the octyl derivative being active in the concen - tration 1 750,000. The decyl derivative is less active (1 500,0@0) and from this substance onwards the activity of the derivatives progressively diminishes with increasicg molecular weight until the cetyl derivative is active only in a concentration of 1 5000. The lethal action of the disinfectants runs for the most part parallel with their inhibitory action; an exception was found in the case of hexylhydrocupreine which has a greater antiseptic action than its next lower homologue (isoamylhydrocupreine) but a smaller disinfecting action.The monhydrochlorides of the alkaloid were more active than the dihydrochlorides. The hydrocupreine deriv- atives showed good disinfecting action in human serum. IX. G. CIAMICIAN and C. RAVENNA (Gazzettn 1917 47 ii 109-130. Compare A. 1917 i 681).-The experiments described in the first part of this paper were carried out by watering germinating seeds or plants with dilute solutions (0.1%) of various organic substances. IJ4and-elonitrile almost prevents germination but when i t is administered to seedlings their growth is not prevented although the mature plants have a habit of growth so abnormal as t o give the appearance of a new species.I n such plants hydrogen cyanide and benzaldehyde could not be detected either before or after the addition of emulsin. Normal adult plants are killed if mantlelo- nitrile is administered to them. Strychnine does not prevent germination but has poisonous effects afterwards. Nicotine hinders germination and affects growing plants adversely. Morphine and caffeine resemble strychnine in their action. I n the second part of the paper experiments are described deal- ing with the action of triturated spinach on solutions of various organic substances toluene being added to prevent putrefaction and a slow current of oxygen being passed to assist any oxidative processes. The escaping gas is passed through barium hydroxide solution and the precipitated barium carbonate is weighed.I n these conditions catechol and saligenin are acted on to a consider- able extent tartaric acid and salicylic acid to a lesser extent whilst Ivnzoic acid pyridine piperitline ant1 nicotine rm-iain unaltered . S. B. S. Behaviour of some Organic Substances in Plants. *4mygdalin does not prevent germination. R,. V. S.i. 94 ABSTRACTS OF CHEMICAL PAPERS. Permeability. V. The Swelling of Plant Tissue in Water and its Relation to Temperature and Various Dissolved Substances. W A L m i t STILES and TNGVAI~ J~RGENSEN (Ann. Bot. 1917 31 415-434).-Experiments with uniform disks of potatoes and carrots show that these vegetables u-hen immerssd in distilled water absorb water (swell) for some days before equil- ibrium is attained and then i t is maintained for several days.The rate of swelling of carrot is much greater than that of potato the amount of swelling being influenced by the previous history of the tissue. I n tap water the swelling is less than in distilled water and equilibrium is not maintained for so long a shrinkage of the tissue ultimately occurring. Rise of temperature causes an increase in the rate of swelling. I n solutiocs of sodium chloride or sucrose the swelling of potato or carrot diminishes with increase in the concentration of the solution and may become a shrinkage. For the potato the approximate concentrations of isotonic solutions are N / 8-sodium chloride and itl/ 4-sv.cross and for the carrot N / 3- sodium chloride. With the primary alcohols preliminary swelling takes place in solutions of much higher concentration than isotonic solutions and is followed by shrinkage in all concentrations.This shrinkage is due t o toxic action and not t o plasmolysis. Acids behave in a manner similar to the primary alcohols. W. G . Tuba an East Indian Poison for Fish. T. ISHIKAWA 1 7-8; from Ghem. Abstr. 1917 11 2371).-Tuba is the Malay name for the plant Derris elliptica Benth. and is used t o kill fish. Tubatoxin CI8Hl8O5 forms white crystals from alcohol m. p. 163*5O soluble in most organic solvents but not in water or in acids and alkalis ; it reduces amrnoniacal silver and alkaline copper solutions ; a sensitive colour test is described. Tubatoxin produces in fish frogs and mammals general motor paralysis. Thel lethal dose for a rabbit (intravenous) is 0.0009 gram per kilo. Coinpare also Greshoff -A.1891 335; van Sillevoldt A. 1900 i 109; Power A. 1903 ii 323. (Tok?/o 1 T g ~ ~ i i k ~ ~ l Znsshi 1916 30 45-46; .7ap. Med. Lit. 1917 G . B. Chemical Constituents of Uzara Root. W. HENNK (Arch. Pharm. 1917 255 382-405).-Uzara root the valuable anti-diarrhcetic properties of which have been described by Giirber (Miinch. med. W o c h . 1911 No. 40) appears t o be identical with Warsicky’s ithongua ( B e y . dcz~t. Phnrm. Ges. 191 6 26 266). The dried alcoholic extract of the root which is known as uzaron has been examined and only one of the three crystalline substances mentioned by Gtirber (Zoc. c i t . ) has been obtained. Uzaroii is shaken with hot water (4 parts) the clear aqueous solution when cold is separated from the upper layer of fatty and resinous sub- stances treated with freshly prepared 200L tannin solution so long as a precipitate is obtained (an excess i s to be avoided) the mis- ture is stirred for twenty-four hours the brown plastic mass which has separated is collected kneaded in a cnrrant of water.made intoVEGETABLE PHYSIOLOQY AND AGRICULTURE. i. 95 a viscous broth with zinc oxide and water and evaporated to dry- ness. The residual mass is finely powdered extracted with methyl alcohol in a Haussmann vacuum distillation apparatus the excess of alcohol is distilled from the extract and the residue which after being dried over sulphuric acid in a desiccator represents about 50% of the uzaron is shaken for many hours with cold water ; the insoluble portion is finally purified by repeated crystallisation from 50% alcohol and from hot water.The product is a glucoside uzarin the yield being about’ 10% of the uzaron or about 2.5% of the uzara root. l i z u r i n C75Hlo8030,9H20 slender colourless needles m. p. aboutl 210° decomp. about ZOOo is sparingly soluble in aqueous sodium hydroxide and in the usual solvents a t the ordinary temperature but dissolves comparatively easily in hot water. The solution has a neutral reaction gives a precipitate with tannic acid but not with neutral or basic lead acetate and exerts a slight reducing action on bismuth nitrate Fehling’s solu- iton and ammoniacal silver nitrate after prolonged boiling. The colour reactions of uzarin are described. The glucoside does not contain methoxyl groups.It is easily hydrolysed by hot 2% sulphuric acid yielding 1 mol. of propyl alcohol (identified in the form of barium propionate) and 3 mols. each of dextrose and uzaridin a portion of the latter being obtained as anhydrouzaridin (see below). Uzaridim C18H2405 forms colourless leaflets contain- ing $H,O and when anhydrous has decomp. about 246O. It is insoluble in water but dissolves in hot dilute alcohol the solution having an intensely bitter taste. The triacetyl derivative pre- pared by boiling with acetic anhydride forms large colourless needles m. p. 225-227O and when it is hydrolysed by boiling alcoholic N / 2-potassium hydroxide the amount of alkali neutralised is more than that corresponding with three acetyl groups. Under the same treatment uzaridin itself is found to neutralise potassium hydroxide although in what way cannot a t present be stated.An hydrousaridin C,,HzzO forms colourless needles containing $€I,O and when anhydrous has decomp. 208-214*. The alcoholic mother liquors obtained during the purification of urazin contain a small amount of a second glucoside which is amorphous and differs from uzarin in its physiological actdon and Toxicity of Galactose and Mannose for Green Plants and the Antagonistic Action of other Sugars towards these. L. KNUDSEN (Anzer. J. Bot. 1917 4 430-437; from PhysioZ. Abstr. 1917 2,56l).-Plants were grown in culture tubes on agar with a modified Pfeffer’s salt solution under conditions excluding micro-organisms. * Galactose and mannose in 0.025 molar solutions were very toxic to the roots of peas and wheat.Dextrose and sucrose act as antidotes. in its extremely bitter taste. c. s. G. R. Organic Plant Poisons. I. Hydrocyanic Acid. WINIFRED E. BRENCHLEY ( A tzn. Bot. 1917 31 447-456).-Hydrocyanic acid1 . '36 ABSTRACTS OP CHXMICAL PAPERS. is very toxic to peas and barley. Uown to a dilutioii of 1 iii 100,000 peas are killed either immediately or after a short interval of poor growth. I n the case of barley strong concentrations kill the plant but at' the above dilution there is a period during which no growth occurs after which there is slight progress but no normal growth. Sodium cyanide is just as toxic as hydrocyanic acid but formic acid except in very high concentrations is comparatively harmless to barley. I n no case was there any indication of stimu- lation in peas or barley even a t very great dilutions with any of the compounds tested.Pea plants killed by hydrocyanic acid shrivel from the cotyledons upwards and the roots contract' int,ensely. Barley roots will not enter strong solutions but often put out laterals which stop short atl the surface of the solution. W. G. Effect of Sulphur on Different Crops and Soils. 0. M. SHEDD ( J . Agric. Research 1917 11 91-103).-Soja beans clover oats lucerne and wheat were grown in pots on eight different types of soil which received applications of flowers of sulphur at the rates of 100 lb. and 200 lb. per acre together with calcium carbonate and other fertilisers as applied t o the controls. It was found that the sulphur increased the production of some crops had no effect on others and on some was injurious the results depending on the crop and soil.On the whole there was a majority of small increases. The sulphur increased the total sulphur and sulphate- sulphur of the crop. I n the cases of clover and lucerne the excess sulphur in the plants was in the form of sulphate but in soja beans part of the excess was in another form not necessarily protein since an increased protein content was not always found with an increased sulphur content. Germination tests with sixteen varieties of seeds showed that all except two formed a greater or less amount' of sulphate on germin- ating the increase varying from 0.0 t o 0.035% on the weight of seed. W. G. Nitrogen Chlorine and Sulphates in Rain and Snow. E. LYLE PECK (Chem. News 1917 116 283-284).-A continua- tion of the work of Artis (compare A. 1916 i 304). Porty-one samples of rain and snow were examined between October 1916 and June 1917. The following results expressed as parts per million were obtained sulphate 4.3-36.39 ; nitrate 0*10-0.50 ; nitrite 0~0005-0*208 ; nitrogen in free ammonia 0*097-0*8'(2 ; nitrogen in albuminoid ammonia 0*057-0*68 ; chlorine 2.84-18.62. The chlorine was most const,ant being 7.1 parts per million in twenty of the samples. The total fall*durixig the period amounted to 15.86 in. of rain and 22 in. of snow. W. G.

ISSN:0368-1769    

DOI:10.1039/CA9181400090

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

i. 97 Organic Chemistry. A System of Organic Nomenclature. AUSTIN M. PATTERSON and CARLETON E. CURRAN ( J . Amer. Chem. SOC. 1917 39 1623-1638).-An account with examples of the principles observed by the authors in their work of indexing organic com- pounds for the forthcoming Decennial Index of Chemical Abstracts. J. C. W. Solubiliby of Iodoform in Glycerol. CHIARIA (Gfiorn. Farm. Chim. 1917 66 94-96; from Chem. Zentr. 1917 ii 483).-The solubility of iodoform in glycerol (D16 1.256) is 0.123%. R. V. S. The Cause of the Anomalies shown in the Dissociation of Arnylene Egdrobromide and its Consequences. ALB. COLSON (Compt. rend. 1918 166 71-73).-The irregularities occurring in the dissociation of amylene hydrobromide b. p. 107O when heated for a long time a t 184O under different pressures (compare Lemoine A.1891 970) are shown to be due to the partial con- version of this hydrobromide CMe2Br*CH2Me into its isomeride CHMqCHMeBr b. p. 124O. W. G . An Alcohol Receipt of the Eighth Century. H. DEGERING (Siteungsber. K . Akad. Wiss. Berlin 1917 503-515 ; from Chem. Zentr. 1917 ii 366-367) .-A manuscript of the twelfth century lately received by the Royal Library in Berlin gives a recipe for the preparation of “aquu ardens” which agrees with another made known by Puccinotti from a manuscript a t San Gimignano. Both texts are probably derived from an original belonging to the eighth century. The process described must have yielded a t least 35 vol. % for the sulphur test is described and burning sulphur cannot be extinguished with a more watery liquid.R. V. S. The Action of Phosphoryl Chloride on Methyl or Ethyl Alcohol. D. BALAREFF (Zeitsch. anorg. Chem. 19 17 10 1 225-228. Compare A. 1917 i 625).-Experiments have now been made to determine what by-products are formed during this reaction. If excess of ethyl alcohol is used and the reaction mix- ture distilled a t 215-220° a small quantity of distillate (3-5% of the weight of the mixture) is obt’ained containing normal pyro- and ortho-esters. By neutralising the product from the action of excess of alcohol on phosphoryl chloride with barium hydroxide using phenolphthalein as indicator from 50-70% of the product is obtained as the salt BaC,H,PO,. It is shown experimentally that the tri-ester Et,PO is decomposed a t looo by dry hydrogen chloride with formation of the monwster according to the equa- VOL.CXIV. i. gi. 98 ABSTRACTS OF CHEMICAL PAPERS. tion EbPO + 2HC1= 2EtCl+ EtH,PO and it is suggested that the hydrochloric acid formed by the interaction of alcohol and phosphoryl chloride may have an important influence on the final products. The experiments fail to determine whether ortho-esters are produced by the repIacement of the third chlorine atom in the phosphoryl chloride molecule by the alcohol radicle or synthetically from the meta-ester and alcohol according to the equation 3EtP0 + 3EtOH = Et,PO? + EtH,PO + Et,HPO,. The reaction is complicated by the presence of different solvents. For instance in presence of ether practically no ethyl chloride is formed. E. H. R. [Preparation of] Paraffin Ethers.THE. ROESSLER AND HASSLACHER CHEMICAL Co. NEW YORK (U.S. Pat. 1245742 1917; from J. SOC. Chem. Ind. 1918 20~).-A vaporised mixture of a chlorine derivative of a hydrocarbon with an inert gas is passed over a basic oxide such as lime at 250-450O; thus for the pre- paration of ethyl ether a mixture of chlorine (1 vol.) with ethane (3 vols.) is caused to react a t 300-550° and after the removal of hydrogen chloride the rnixt,ure of ethyl chloride and ethane is dried and then submitted to the action of lime. D. F. T. Action of [Sodium] Arsenite and [Mixtures of Potassium] Sulphide and Cyanide on Hypochlorous Esters. A. GUTMAXN (Ber. 1917 50 1717-1718).-Ethyl hypochlorite reacts with sodium arsenite solution t o form normal sodium arsenate and ethyl alcohol and with a mixture of potassium cyanide and hydrosulphide according to the equation EtOCl+ KCN + KSH = KCNS + KC1 + EtOH.J. @. W. Lecithin. I. 1i Hydrolecithin " and its Bearing on the Constitution of Kephalin. P. A. LEVENE and C. J . WEST ( J . Riol. Chcm. 1918 33 111-117).-Hydrolecithin is readily produced by the reduction of lecithin with hydrogen in the presenco of palladium. After recrystallisation from methyl ethyl ketone it' softens on heating between 80° and 90° turns brown about looo starts to melt about 200° and runs down the tube giving a dark red liquid at 235O. According to Paal and Oehme (A. 1913 i 584) it sinters a t 83-84O and decomposes above 150'". The optical rotlation is [u]? + 5 ' 3 O . As thus prepared the hydrolecithin is not pure but3 contains 20% of a substance containing amino- nitrogen which from a consideration of the results of the elementary analysis and the isolation after hydrolysis of the auri- chloride of aminoethyl alcohol the authors believe to be hydro- kephalin.Drying Oils. I. The Properties of some Cerium Salts obtained from Drying Oils. ROBERT SELBY MORRELL (T. 1918 113 lll-l24).-Cerous salts of the normal type CeX have been prepared from palmitic stearic oleic elaidic linoleic a- and P-elEost earic linolenic and abieiic acids. When [See also J . SOC. Chem. I d . 1918 136~.] H. W. B.ORGANIC CHEMISTRY. i. 99 freshly prepared the oleate linoleate linolenate a-elseostearate and abietate are soluble in ether or turpentine but the other salts are insoluble. The ethereal solutions of the salts of the un- saturated acids darken on exposure to air the linolenate reacting according to the equation 4CeX3 + 30,= 2CeO(XO,) (a buff precipi- tate) +2CeX (soluble).Normal salts may also be obtained from raw oils (olive poppy-seed linseed) but after thickening by the author's heat treatment (A. 1915 i 75) and removing polyrnerides if any by mealis of acetone the oils give insoluble basic salts of the type CeOX and also soluble ceric salts CeX,. Cerous a-elaeostearate absorbs oxygen a t a rate which is easily measured giving a basic salt of the formula C~O(XO,),. The corresponding acid has peroxidic properties and gradually sets through polynierisstion to a varnish. This oxidation of the a-elaeostearate shows that the function of the salt as a drier can be represented by the scheme CeX -+ Ce,O(XO,) and this + a drying oil -+ CeX + peroxidised oil.It is probable in the light of the resu1t.s now presented that oxidation t o peroxidic acids pre- cedes polymerisation in the "drying " of oils. As the polymeriss- tion may be catalysed by other agents than the oxidation this would account for the comimoii practice in the trade of using two different driers. For experimental details and for discussions of other problems connected with the drying of oils see the original. J. C. W. Resolution of the Diamminodinitro-oxalatocobalt Com- plex and Determination of the Configurations of this Complex and of the Tetranitrodiamminocobalt Complex. YUJI SHIBATA and TOSHIO MARVKI ( J . CoZZ. Sci. Tokyo 1917 41 [2] 1-12).-In a previous paper (Shibata A.1916 i 277) i t has been shown that the two nitro-groups in the dinitrodiammino- oxalatocobalt complex [CO(NH~)~(NO,),C,O,]M are in the cis- position with respect to each other. If the relative positions of the two ammonia molecules can now be determined the whole con- figuration of the molecule is elucidated the oxalato-residue neces- sarily occupying the cis-position. Two space formulse are possible for this configuration namely NH NH NO ____ 1 NO? ,-LNR NO,!- I / No,!-.- . I - ( 1 ) 1 I I\C,C) and (2) / I f I i I Of these two formulz (2) represents a compound which should be capable of being resolved into optical isomerides so that the desired determination of the configuration should be possible. Experiments with barium dinitrodiammino-oxalatocobdtiate showed that it could readily be resolved in the usual way by means of brucine strychnine or cinchonine the alkaloid salt of the corn- 9 2i.100 ABSTRBUTS OB CmmOAL PAPER$. plex being prepared from the sulphate of the alkaloid and then fractionally crystallised. The potassium afid ammonium salts of the active complex could then be obtained by the action of potassium or ammonium iodide. The asymmetry of the complex in question is not due to the asymmetry of the cobalt atom but to a molecular asymmetry which is different from Werner's types I and 11; it is therefore called type 111 of molecular asymmetry. Since the dinitrodiammino-oxalatocobalt compound is readily obtained from the tetranitrodiamminocobalt compound by the action of oxalic acid it follows that the two ammonia groups in the latter compound are in the cis-position.The least soluble fraction of the brudine salt [Co(NH3)2(N02)2C,041H ,C23H2&)4N2,H20 crystallised in brown needles aggregating in radial form and had [Q]E'~ -70.7O; its solution in water was not stable the free alkaloid gradually being deposited. The mostl soluble fraction gave crystals having [a12 + 68.3O. obtained from the respective brucine salts gave [a]:+- 115O. gave a potassium salt having [&ID -104* but the strychnine salt could not be prepared pure owing to its instability. The dextro- potassium salt could not be obtained from the strychnine salt. With cinchonine the least soluble fraction separated as pale brown needles having the formula and [a]; + 149O; the potassium salt derived from it had [a] + 1 1 1 O .The more soluble fraction could not be isolated. Ammomiam salts were similarly obtained having [a] - 107O and + 116O respectively. Method of Producing Acetaldehyde. E. F. SCHELLER (U.S. Pats. 1244901 and 1244902 1917; from J . Soc. Chem. Znd. 1918 20a).-Purified acetylene mixed with steam is passed over a heated catalyst consisting of oxides or combinations of oxides; the exhausted or poisoned catalyst for example molybdic acid may be regenerated by heating in a current of gas containing oxygen for example air. D. F. T. The Method of Oxidation and the Oxidation Products of I-Arabinose and E-Xylose in Alkaline Solutions with Air and with Cupric Hydroxide. J. 17. NEF OSCAR F. HEDENBURG and J. W. E. GLATTFELD ( J .Amer. Chem. SOC. 1917 39 1638-1652. Compare A. 1914 i 490).-An account with full experimental details of the identification of the products formed by the oxidation of I-arabinose and I-xylose in alkaline solutions. Formic acid calcium glycollate I-erythroncly-lactone d-threono- phenylhydrazide quinine I-glycerate and calcium d-glycerate were actually obtained from Farabinose after oxidation with air and The potassium salts [Co(NH,)2(N02)2C,041K,1~H20 The least soluble strychnine salt [Co(NH3)2(N02)2C204~~~c21H2202N2~H20~ [Co(NH3)2(N02)2C20d H,C19H220N2 T. S. P.ORGANIC CHEMISTRY. i. 101 glycollic acid oxalic acid and I-arabono-y-lactoue after oxidation with cupric hydroxide. I-Xylose gave formic acid Lthreono- phenylhydrazide d-er y t hrono- y-lact one calcium glycollate and calcium I-glycerate when oxidised by air and I-xylono-y-lactone d-xylono-y-lactone glycollic acid and oxalic acid when heated with alkaline cupric hydroxide.J. C. W. The Auto-oxidation of Sugars. I,. BERCZELLER and E. Sz~aij (Biochem. Zeitsch. 1917 84 1-36).-Sugar in alkaline solution was shaken in the presence of air and the influence of various substances added to the solution on the rate of oxidation was ascertained. The oxidation was measured by determining the diminution of pressure in the reaction flask after varying intervals. Some substances such as niethyleneblue promote oxidation. The influence of tartrate and other substances on the oxidation of sugar in alkaline copper solutions was investigated. Charcoal was found to promote oxidation.S. B. S. Lactose. A. SMITS and J. GILLIS (PIOC. K. Akad. Wetensch. Amsterdam 1918 20 520-532. Compare Hudson A. 1908 i 952; ii 665).-The a-anhydrous form of lactose is metastable not only below 93O but also up to its m. p. 222.8O. The hydrate when heated a t 1 2 5 O in the dry condition gives the a-anhydrous form but in the presence of its saturated solution a t the same temperature always gives the &form. The authors consider that lactose hydrate is the hydrate of the a-form and that consequently its dehydration is accompanied by a transition of the a- into the &anhydrous form the transformation temperature 93.5O being really a transformation-dehydration point. As a consequence of this the system water-lactose must be considered as a pseudo- ternary system for which the authors have derived the isotherm diagram.[See also J . SOC. Chem. Znd. 1918 133~.1 W. G. Influence of different Compounds on the Destruction of Monosaccharides by Sodium Hydroxide and on the Inver- sion of Sucrose by Hydrochloric Acid. 11. H. I. WATERMAN (Proc. E. Akad. Wetensch. Amsterdam 1918 20 382-391. Com- pare A. 1917 i 195 631).-An extension of the study to the influence of a-aminobutyric acid valine leucine asparagine glutamic acid and tyrosine. The results in every case agree with those obtained from the amino-acids previously studied. Aniline and pyridiue have no influence on the action of sodium hydroxide on dextrose but they retard the inversion of sucrose by hydrochloric acid. [See also J . SOC. Chem. Znd. 1918 133A.l W.G. Adsorption Compounds and Adsorption. I. The Starch- Iodine Complex. L. BERCZELLER (Biochem. Zeitsch. 191 7 84 106-117).-It is shown that the presence of potassium iodide is not necessary for the formation of the complex. The imbibition temperat'ure of the stasch iodine complex is about lo above thati. 102 ABSTRACTS OF CHEMICAL PAPERS. of pure starch. Starch takes up more iodine a t a lower than at a higher temperature. A secondary adsorption of iodine by starch can be demonstrated. Adsorption equilibrium between starch and iodine t,akes place 11701‘e rapidly in dilute than jn concentrated solutions. S. B. S. Action of Methylene Iodide on Des-dimethylPiperidie (E-Dimethylamino-Aa-pentene) AM AND VALEUR and EWLE LUCE (Compt. rend. 1918 166 163-164).-Methylene iodide does not cause cyclisa tion when it acts on E-dimethylamino-Aa-pentene but the compound C,H17NI obtained (compare Ladenberg A.1882 534) is shown to be methylene-des-dimethyl@peridine iodide [dim e t hyliodomet hyl-a “-pen ten ylummonizt m iodide] CH2:CH*[CH,],*NMe21*CH21 m. p. 163O which when boiled with hydriodic acid in the presence of phosphorus gives cli m et?hyliodonzet hyl-b-iodo pen tylammonium iodide CH,*CHI*[CH2],*NMe,I* CHJ m. p. 136.5-1 37’5O. This compound with moist silver oxide gives a quaternary ammonium hydroxide which on treatment with potassium iodide yields a com- pound C8HI7NI2 m. p. 143-144O isomeric with the one described above. w. a. The Free Affinity of the Copper Salts of the Imino-acids. J. V. DUBSKY and WI. SPRZTZMANN ( J .pr. Chem,. 1917 [ii] 96 112-122).-The copper salt of iminodiacotic acid (Heintz AmnuZen 1862 124 297; 1870 156 51) in aqueous ammonia gives a deep blue1 solution which on evaporation deposits violet- blue needles of an additive compound of the composition C,H8O,N,Cu,3H,O ; in view of the composition of the correspond- ing compouiid derived from nitrosoiminodiacetic acid (see below) the constitution is probably NH ‘cu.. . .NH,. I n a similar manner the bluish-green microcrystalline copper salt C,H,O,N,Cu,2~H,O of nitrosoiininodiacetic acid yields a violet- blue ammonia addit ice compound of t,he probable constitution > C U < - . ~ ~ ~ Z H ~ O and the green copper salt of N*’%H,.CO 0 nitroimiiiodiacetic acid forms a riolet-blue additive compound to which is ascribed the formula N02*N< CH CO ,I K c 0 f ‘- C H B.C 01/ /NH CH;CO CH,*i’O,>C,,,...-N H ‘-NH H,O. The copper salt C,,H,O,NCu,H,O (green needles) of phenylimino- diacetic acid and the copper salts of iminodipropionic and nitro- iminodipropionic acids with arninonia forin respectively the com- pounds C,,H,O,NCu ,NH (bluish-green needles and prisms) C,H,,O,N2Cu,1kH,O (pale blue crystals) and C6H,,0,N,Cu,2H,0 (violet-blue). I n all these ammonia derivatives the copper atow is regarded as assuming a maximum valency of four. With the salts of nitrilotriacetic acid N(CH,*C02H)3 the behaviour was less regular ; the bluish-green normal copper salt C,,H,,0,,N2Cu,,7H,0,ORGANIC CHEMISTRY. i. LO3 yielded pale blue crystals of a violebblue ammonia compound C,,H2,0,,N,Cu,,4H,0 whereas the pale blue acid copper salt C,H,O,NCu gave no definite product with ammonia.Salt Formation with Nitroso- Nitro- and Phenylimino- J. V. DUBSKY and M. SPRITZMANN (J. pr. Chew&. D. F. T. diacetic Acids. 1917 [ii] 96 105-111) .-Nitrosoiminodiacetic acid NOON ( CH,-CO,H) is conveniently prepared by the action of nitrous fumes on an aqueous suspension of iminodiacetic acid ; the nitroso-acid is dibasic and forms an animoniu,m salt a colourless microcryst'alline powder with $H,O and a colourless crystalline zwzc salt with 2H,O. Nitroiminodiacetic acid N0,*N(CH2=C0,H) (Franchi- niokt and Dubsky A. 1916 i 467) which is also dibasic was con- verted through its ammonium salt colourless leaflets with 1H,O into the colourless .silver salt barium salt crystalline mass with 2H20 and zinc salt an explosive crystalline mass.Phenylimino- diacetic acid in aqueous solution reacts with silver nitrate giving a silver salt C,,H,,O,NAg needles but the interaction of the diammonium salt with silver nitrate yields a disilver salt C,,H,0,NAg2 tho precipitate which is white a t first rapidly becoming yellow ; the zinc salt C,,H9O,NZn,3H,O was also pre- pared from the ammonium saltl by double decomposition with zinc sulnhate. With these acids. no double salts were observed of the ty{e yielded by iminodiacetic and iminodipropionic acids. D. F. T. Constitution of Carbamides. V. Mechanism of the Decomposition of Urea when Heated in Solution with Alkalis and with Acids respectively. The Hydrolysis of Metallic Cyanates. EMIL ALPHONSE WERNER (T.1918 113 84-99. Compare T. 1913 103 1013).-If a solution of urea in aqueous barium hydroxide is heated ammonia can be detected in the vapour as soon as the boiling point is reached but some minutes elapse before any barium carbonate appears. It follows therefore that the equation CH,ON + Ba(OH)2 = BaCO + 2NH3 does not represent the facts and that urea is not hydrolysed in this sense. The decomposition of urea by hydrolytic agents is more correctly represented in two stages first the dissociation of urea which is the ammonium salt of ketonic cyanic acid into ammonia and cyanic acid and secondly the hydrolysis of the cyanic acid or alkali cyanate. Under comparable conditions the rate a t which urea is decomposed is greater in the presence of sodium hydroxide than in the presence of hydrochloric acid because the proportion of free urea is greater in alkaline solutions than in acid and only free urea suffers decomposition.Thus in N-solutions 55% of urea hydrochloride is dissociated into its components NH:C(OH)*NH,,HCl -+ NH:C<XK3 + HCl whilst the acidic property of urea is so slight that a salt of thei. 104 ABSTRACTS OF CHEMICAL PAPERS. formula NH:C(ONa)*NH would only exist in solutions containing much urea and much alkali. The dissociation of urea into ammonia and cyanic acid does not take place in sterile solutions either acid or alkaline t o any appreciable extent beIow 90°. Thus the velocity of the decom- position of urea a t 98*2O 71'25O and 61'05O respectively is as 83.6 2.77 0.715. This can be verified by testing the solution from time to tims with silver nitrate or barium hydroxide.The enzyme urease which brings about speedy decomposition a t ordinary temperatures apparently promotes direct hydrolysis of undissociated urea for it has no influence on potassium cyanate. The well-known fact that alcohol retards the decomposition of urea in solution but accelerates the transformation of ammonium cyanate into urea can only be explained satisfactorily in the light of these dissociation theories. I n the first case alcohol really ret'ards the hydrolysis of the cyanic acid formed by dissociation of the urea and in the second it promotes the dissociation of ammonium cyanate into ammonia and enolic cyanic acid but does not interfere with the tautomerisation of the acid and its reunion in the ketonic form with ammonia to give urea.The formation of urea from other cyanates than ammonium cyanate can be explained in a similar manner. Thus the hydre lysis of potassium cyanate a t ordinary temperatures is indicated by the equations (1) ROCN+H,O ROH+(HO.CN z= HNZCO) (2) HO*CN + H,O = NH + CO (3) CO + KOH = KHCO (4) HN:CO + NH,= HN:C<xHs and HO*CN + NH = NH,O.CN. A t higher temperatures than 80° no ammonium cyanate would be formed. For experimental details see the original. Preparation of Cyanamide. A. E. OSTERBERG and E. C. KENDALL ( J . Biol. Chem. 1917 82 297-298).-Calcium cyan- amide is mixed with water and carbon dioxide passed in until a neutral or only slightly alkaline reaction is reached. The tempera- ture must be maintained below 40°.I n these circumstances the calcium cyanamide is quantitatively decomposed ; and after filter- ing off the precipitated calcium carbonate the cyanamide is recovered from the filtrate by concentrating in a vacuum and sub- sequently extracting with ether. I n this way 55 grams of pure crystallised cyanamide are obtained from 200 grams of the calcium salt corresponding with a yield of 92% of the theoretical. [Com- pare J . Soc. Chem. znd. 1918 37 IOTA.] H. W. B. Cyanuric Acid as an Oxidation Product of Uric Acid. Its probable Identity with Tetracarbimide C. S. VERABLE and F. J. MOORE ( J . Amer. Chem. SOC. 1917 39 1750-1755).- Under the conditions described by Scholtz (A. 1902 i 140) uric acid may be oxidised to cyanuric acid. With slight modifications the yield of this product may be nearly 50% of the theoretical amount.The cyanuric acid prepared by this method has been J. C. W.ORGANIC CHEMISTRY. i. 106 thoroughly identified and it is more than likely that' Scholtz was wrong in regarding his product as tetracarbimide. J. C. W. New Preparation of Aliphatic Nitriles by Catalysis. ALPHONSE MAILHE (Csmpt. rend. 1918 166 121-123).- Aluminium oxide can be used as a catalyst in place of thorium oxide for the preparation of nitriles from the esters of cyclic acids by the action of ammonia (compare this vol. i 68) only in this case the gas evolved consists of ethylene and hydrogen in the pro- portion of 2 l if ethyl esters are used. The reaction may be applied to aliphatic esters with equal success but in this case with thorium oxide a certain amount of aldehyde-ammonia is produced and with aluminium oxide some amide corresponding with the nitrile.New Method of Formation of Nitriles by Catalysis. ALPH. MAILHE and F. DE GODON (Compt. rend. 1918 166 215-217. Compare preceding abstract).-When the mixed vapours of an aldehyde and ammonia are passed over thorium oxide a t 420--440° the products are the corresponding nitrile water and some products of condensatipn of the aldehyde and ammonia. The method has been applied with success both to aliphatic and aromatic nitriles. [See also .7. SOC. Chem. Ind. 1918 13 7~.] W. G. [See also J . SOC. Chem. I d . 1918 1 3 7 ~ ~ 1 W. G. A New Method of Dehydration of Oximes by Catalysis. ALPH. MAILHE and F. DIG GODON (Bull.SOC. chim. 1918 [iv] 23 18-20) .-Aldoxirnes were dehydrated by passing their vapour over aluminium oxide or thorium oxide heated a t 340-360° the corresponding nitrile being obtained. Dehydration also occurred under similar conditions with two ketoximes isobutyronoxime and isovaleronoxime the products in these cases being nitriles less rich in carbon. W. G . The Action of Trioxymethylene on the Various Hydro- carbons in the Presence of Aluminium chloride. G. B. FRANKFORTER ( J . Amer. Chem. SOC. 1918 40 329).-A question of priority between Nastjukov and the author. [See A. 1915 i 227 953.1 L. A. C Extraction of Pure Dimethylnaphthalenes from Coal Tar Oils. GESELLSCHAFT FUR TEERVERWERTUNG (D.R.-P. 301079 1916 ; from Chem. Zentr. 1917 ii 713-714).-The neutral purified frac- tion of the oil b.p. 260-265O or the solid hydrocarbon mixture obtainable from this is sulphopated by sulphuric acid and the resulting sulphonic acids are reconverted into the corresponding parent hydrocarbons. 1 6-Dimethylnaphthalene obtained in this way is a colourless oil of faint characteristic odour b. p. 265O (picrate needles m. p. 114O); the sulphonic acid forms a sulphonamide needles m. p. 185O on fusion with potassium hydroxide yields a dimethyl- 9*i. 106 ABSTRACTS OF CHEMICAL PAPERS. naphthol m. p. 82O and on reduction with sodium amalgam undergoes scission of the sulphonyl group. Oxidation with dilute nitric acid converts the hydrocarbon into a carboxylic and a dicarb- oxylic acid the latter being identical with 1 6-naphthalenedicarb- oxylic acid prepared from 1 6-naphthylaminesulphonic acid whilst the former when heated with hydrochloric acid loses carbon dioxide with formation of 2-methylnaphthalene.Chromic acid oxidises the dimet h ylnapht halene t o dimet hyl-u-n ap hthaquinone m. p. 9 5 O which is further oxidisable by potassium permanganate to o-methylphthalic acid. 2 6-Dimetthylnaphthalene leaflets m. p. 109-llOo b. p. 260-261° is oxidised by chromic acid to 2 6-dimethyl-maphtha- p i n o n e m. p. 136-137O and is convertible through the sulphonic acid into a dimethyl-&naphthol m. p. 172O. 2 7-Dimethylnaphthalene leaflets m. p. 96-97O b. p. 262O forms a solid sulphonic acid (sodium salt needles) and on oxida- tion with chromic acid yields a dimethyl-a-naphthapinone m.p. 114-115O which is further oxidisable by permanganate to tri- mellitic acid. D. F. T. Separation of Secondary Amines produced in the Catalytic Hydrogenation of Aniline. G. FOUQUE (Conzpt. rend. 19 17 165 1062-1065) .-Catalytic hydrogenation of aniline yields cyclo- hexylamine dicyclohexylamine cyclohexylaniline and diphenyl- amine together with smaller quantities of benzene cyclohexane and tar. For the separation of the secondary amines a method has been based on the following facts. ( a ) Dicyclohexylamine hydrate forms a solid carbonate and three non-hydrolysable sulphates; ( b ) cyclohexylaniline does not form a carbonate but yields a normal sulphate a sesquisulphate and a hydrogen sulphate which are hydrolysable but dissolve in water acidified with sulphuric acid; ( c ) aniline does not form a carbonate; (d) di- phenylamine sulphate has not been isolated.By repeated frac- tional distillation under ordinary and reduced pressure the pro- ducts are separated into fractions one of which contains only aniline and dicyclohexylamine and another consists of a mixture of dicyclohexylamine cyclohexylaniline and diphenylamine. Each fraction after the addition of water and ether is saturated for several hours with carbon dioxide and the aqueous solution of dicyclohexylamine carbonate is separated filtered and neutralised with sulphuric acid. On evaporating the liquid octahedral crystals of the normal sulphat e of dicyclohexylamine separate whilst the hydrogen sulphate separates on treating the mother liquors with excess of sulphuric acid.The amine is obtained by dissolving the successive deposits of crystals in water and distilling the solution with sodium hydroxide under reduced pressure. It is a colourless oily liquid boiling a t 135O (under pressure of 20 mm.). The residue from which the dicyclohexylamine carbonate was separated may consist of an ethereal solution of aniline or of a mixture of cyclohexylaniline and diphenylamine wiLh ether. After evaporation of the ether it is heated with dilute aulphuricORGANIC CHEMISTRY. i. 107 acid cooled and filtered the process being continued so long as the filtrate gives an orange coloration with a mixture of dilute sulphuric and nitric acids. Evaporation of the united filtrates yields deposits of crystals of cyclohexylaniline sesquisulphate whilst a little dicyclohexylamine hydrogen sulphate may be obtained from the mother liquor.cycloHexylaiiiline may be separated from its sesquisulphate by means of warm dilute ammonia solution and decanting and distilling the oily layer under reduced pressure. It is a strongly refractive liquid boiling at 157O,'20 mm. The solid residue of impure diphenylamine is purified by distillation and crystallisation from ether. C . A. M. Intermediate Products (Formomethylanilide Derivatives) suitable for the Manufacture of Colouring Matters. H. LEVINSTEIN and G. T. MORGAN (Eng. Pat. 111321 1916; from J . SOC. Chem. Z d . 1918 5~).-Formomethylanilide also its halogen or alkyloxy-derivatives and homologues with a free para- position to the amino-group may be nitrated a t - 5 O to +20° with formation of the corresponding p-nitroformomethylanilide compounds ; p-n itro f ormomethyZaniZide forms pale yellow prisms or needles m.p. 119-120°. These products on reduction with iron borings and dilute formic or acetic acid a t 85-looo are converted into the corresponding pamino-compounds ; the unsub- stituted pamino f or mom e t h ylanilide HCO*NMe*C6H,*NH forms almost colourless needles m. p 11 5-1 1 6 O . Reduction of Phenylethylamine. ALBERT WEISHAGEN (Biochem. J. 1917 11 272-276) .-Phenylethylamine prepared from phenylalanine differs from the synthetic product in that the latter resists reduction by the method of Willstatter and Hatt (A. 1912 i 545) whilst the former is completely reduced to the hexa- hydro-compound (cyclohexylethylamine) .The synthetic product decolorises permanganate solution very slowly whilst the other acts almost instantaneously. It is pointed out that Bernthsen re- marked certain minor differences between synthetic phenylethyl- amine and that produced from phenylalanine. [See also J . SOC. Chern. Ind. 1918 March.] Bromo-alkylated Aromatic Amines. I. J. VON BRAUN K. HEIDER and E. MULLER (Ber. 1917 50 1637-1651).-When methylaniline is heated with ethylene dibromide at looo diphenyl- diethylethylenediamine is not the only product. The first runnings of the basic distillate contain methyl-j3-bromoethylaniline NMePh*CHe*CH2Br and the yield of this may be increased to 35% of the methylaniline employed if the pro-portion of bromide to base is 3 mols. to 2 mols. The new bromGalkylated base is most remarkably reactive; i t can be brominated nitrated etc in the ring like any other tertiary aromatic amine; i t has the reactions of tertiary amines in general. but most important of all it is capable of all the reactions 01 ethyl bromide. D.F. T. J. H. L. g' 2i. 108 ABSTRACTS OF CHEMICAL PAPERS. Full details of the economical production of the bass are given together with notes on the recovery of the unchanged ethylene dibromide and methylaniline and the tert .-ethylenediamine. Methyl-8-bromoet hylaniline is a very pale yellow somewhat heavy oil b. p. 140-144°/13 mm. which becomes dark in the air with- out really suffering much change. The p*crate has m. p. 125O and the methiodide m. p. 1 2 2 O . It reacts with bases as follows methylaniline gives diphenyldimethylethylenediamine C2H4(NMePh)2 m.p. 51O; dimethylamine gives plzenyltrimet~yleth~lenediamine b. p. 144-146O/23 mm. which forms a dip-crate yellow leaflets m. p. 171O ; trimethylamine yields &=henylrnethtylaminoethyltri- methylammonium bromide NMePh*CH,*CH,*NMe,Br as a very hygroscopic white mass m. p. 165O. The base may also be brominated or nitrated giving oily products but' pnitrosomethyl- 8-bromoethylaniline which is prepared exactly like pnitrosodi- methylaniline is a stable green mass m. p. 70°. This reacts with trimethylamine to form a p-nitrosodialkylaniline derivative NODC,H4.*NMeoC,H4*NMesBr which is soluble in water the solu- tion having the same green colour as the ethereal solution of pnitr osodimethylaniline. Under the influence of aluminium chloride the base suffers con- densation t o 1-methyl-2 3-dihydroindole7 the yield being about 35%.This is the first instance of the production of a dihydro- indole by ring formation and the method may prove to be of great service in the case of substituted dihydroindoles. By Fittig's met$hod the base mag be converted into diphenyldimet hyltetra- methylenediamine C4H,(NMePh) m. p. 81° b. p. 186-190°/ 5 mm..(picrate rn. p. 173O; dimethiodide m. p. 180°) which gives a brilliant greenish-blue coloration with oxidising agents (compare A. 1917 i 175). The base condenses with p-acetylaminophenol under the influence of sodium ethoxide to form o-phenylmethylaiminophenacetin NHAc*C,H4*O*CH,*CH,*NMePh in glistening leaflets m. p. 102O and with morphine to give w-phenylmet hylaminodiomhe NMe:Cl,H,,0(OH)*O~C2H4*NMePh as a yellow oil which yields a hyycFrochEoricFe m.p. l l O o . These are practically without the physiological action of unsubstituted phenacetin or dionine. On boiling with aqueous-alcoholic potassium cyanide the base yields O-ph eny lm e thy laminopr o pionit ril e NMePh* CH CH,* CN a pleasant-smelling oil b. p. 186O/23 mm. together with a small quantity of the corresponding nmide m. p. 85O. This nitrile is interesting compared with phenylmethylaminoacetonitrile and other derivatives of aromatic amines containing the grouping =N*CH,*CN for the basic properties are not masked by the cyano- group and the methiodide m. p. 1 3 2 O (decomp.) is stable. The base reacts with magnesium quite as readily as bromo- bmzene.When the magnesium compound is decomposed with ammonia and ammonium chloride it yields methylethylaniline (6 5 %) and diphenyldimethyl t et ramethylenediamine (3 5 %) and,ORGANIC CHEMISTRY. i. 109 strange to say these are the only products which can be obtained after treating the Grignard compound with ketones although a vigorous reaction is observed to take place. Aldehydes react in a more normal manner however giving bases of the formula NMePh*CH2*CH,*CHR*OH. The separation of these from the mixture of products is a matter of considerable difficulty requiring special methods from case to case. An account is given of the production of the compound NMePh*C,H,*CHPra*OH from n-butaldehyde and its isolation in the form of a picrate long red needles m.p. 120° and pZatini- chloride m. p. 214O (decomp.). The failure of the reaction with ketones recalls the fact that' disubstituted amides R*CO*NR react vigorously with organomagnesium compounds but are regenerated if the products are treated with dilute acids whilst formamides H*CO*NR give aldehydes. It is suggested that the primary pro- ducts are additive compounds wit'h quadrivalent oxygen thus R,:C:O<ggX and that in the case of the above base there are steric hindrances against rearrangement into compounds R,C*MgX. J. C. W. Di- wbut y laniline. JOSEPH R EI L rAp and W LLFR ED J o HN HICKIN- BOTTOM (T 1918 113 99-111. Compare this vol. i lo).-If qzcbutyl chloride is heated with aniline in an autoclave a t 130-140° a very high yield of mono-n-butylaniline is soon obtained and if this is heated with more n-butyl chloride a t 180° under pressure a good yield of di-n-butylaniline is produced. This has been con- verted by normal methods into the following series of compounds A pnitrosodi-n-butylaniline and pphenylenedi-n-butyldiamine B 4di-n-butylaminoazobenzene-4'-sulphonate by means of diazo- tised sulphanilic acid and this by reduction into the above diamine.Similarly mono-n-butylaniline has been coupled with diazotised sulphanilic acid and t%e azo-compound reduced to p-phenylene-rz-buty ldiamine. For some unaccountable reason Karrer was unable to obtain the p-nitroso-compound or to couple the tertiary base with diazotised sulphanilic acid (A. 1915 i 1073). Typical salts and other derivatives of these compounds are also described but the original should be consulted for the details.CGH,*N(C*H,) + NO*CcH4*N(C4Hg) + NH2*CcH**N( C4Hg) ; J. C. W. Phototropy and Thermofropy. VIII. Cinnamyl- ideneamines. 2 4-Dihydroxybenzylideneamines. ALFRED SENIER and PATRICK HUGH GALLAGHER (T. 1918 118 28-35. Compare A. 1915 i 397 877 and earlier).-Various amines have been condensed with cinnamaldehyde and 2 4-dihydroxybenz- aldehyde in order to gather if possible new material for studies on phototropy and thermotropy. Of the many new Schiff's bases thus obt'ained nearly all are found to exhibit thermotropic changes but none are phototropic. Many of them however,i. 110 ABSTRACTS OF CHEMICAL PAPERS. change permanently iiito polymorphic forms on exposure t o actinic light. Solutions in acetic acid or chloroform are usually deeper in colour than those in light petroleum benzene or acetone and the 2 4-dihydroxybenzylidene compounds are green in dilute solu- tions and yellow in concentrated solutions.For experimental details see the original. J. C. W. The Sulphonation of P-Naphthylamine. ARriiun GEORGE GREEN and KAPILRAM H. VAKIL (T. 1918 113 35-44).-1t is well known that the 5- 6- 7- and 8-sulphonic acids can be obtained by the direct sulphonation of P-naphthylamine but it appeared to be of importance in the dye industry to learn something of the mechanism of the reactions the circumstances favouring the pro- duction of the individual isomerides and the coiiditions under which one may be converted into another. The present work therefore is a detailed study with those aims.Within temperatures from ZOO to 80° the product contains 97-99*5% of the 5- and 8-acids. The ratio between these does not vary very much from about two parts of the 8-isomeride to three of the !&acid neither has time (one to ten hours) nor con- centration of the acid (920/ H2S0 to an acid with 20% SO,) much ‘influence on this ratio except that the lowest temperatures and shortest time are favourable to the production of the 5-acid. At temperatures below 80° it follows that the sulphonation takes place simultaneously a t positions 5 and 8. At higher temperatures and with longer periods of heating there is a falling off in the propor- tion of the 8-acid and an increased production of the 5-isomeride. This is explained by assuming that the 8-acid suffers hydrolysis t o the free 8-naphthylamine which is then resulphonated mainly to the 5-compound as above.Simultaneously the yield of the 6- and 7-isomerides increases also reaching 7.5% with 96% sulphuric acid at 120° in five hours. It appears probable that disulphonic acids are produced and that these suffer hydrolysis t o mono- sulphonic acids the 5-acid giving the 5:7- and then the 7-acid and the 8-isomeride producing the 6 8- and then the 6-acid. For ddails of the methods of separation and analysis the original should be consulted. J. C . W. Aspirin. V. Action of Salicylraalicylic Acid on the Solidifica- tion of Aspirin in Concentric Rings. D. E. TSAKALOTOS and S . HORSCH ( B d l . SOC. clzinz. 1918 [iv! 23 16-18).-Salicyl- salicylic acid facilitates but is not essential for the formation of concentric rings during the crpstallisation of aspirin from alcohol W.G. The Indene Series. V. J . VON BRAUK (Ber. 1917 50 1659-1 661) .-Hydrindone reacts with magnesium methyl iodide t o form 1-hydroxy-1-methylhydrindene (A. 1913 i 1364). This is reconverted into the original ketone by the action of alkalis which is best demonstrated by leaving methyl-alcoholic solutions of the carbinol with anisaldehyde or pdimethylamino-ORGANIC CHEMISTRY. i. 111 bsnzaldebyde in contact with a few drops of sodium hydroxide when the known condensation products of hydrindone and the aldehydes soon crystallise out. a plea- sant-smelling syrup b. p. 123-135O/9 mm. D:O 1.063 behaves similarly. The tendency to part with the elements of water in- creases with increasing magnitude of the 1-alkyl group.The methyl compound may be distilled under atmospheric pressure but the ethyl honiologue changes thereby into 1-ethylindene a mobile liquid b. p. 226O DY 0.9732. With larger radicles the indenes are already produced during the Grignard reaction and may be purified by distillation under ordinary pressures. 1-11-BzrtyZindene a very pleasant-smelling liquid b. p. 252-255O 120°/ 10 mm'. D:d 0-9552 and l-pJzeny/incZene C,H,<cFi>CH a pale yellow syrup b. p. 200-201°/29 mm. Dy 1.0829 may be obtained directly from hydrindone in this way. l-Hydroxy-l-et?Lylhydrindene C 6 H 4Lc&((jH)>CH'2> /CH - CH J. C. W. Preparation of 1-Hydroxyanthranol. FAHUENFABRIKEN vom.FRIEDR. BAYER & Co. (D.R.-P. 301452 1916; from Chem. Zentr. 1917 ii 715).-By reducing 1-hydroxyanthraquinone with zinc in acid solution it is possible to obtain 1-hydroxyanthranol which is of value as a remedy for psoriasis. D. F. T. Triphenylmethgl. XXVIII. Tautomerism of Triaryl- carbinols. 31. G o m E R G and L. c'. JOHNSON ( J . Aincr. Chcnz. SOP. 1917 39 16'?&-1688. Compare A. 1916 i 639).-The condensa- tion of diphenylinethyleiie dichloride with phenols is a convenient method for the preparation of p-hydroxytriarylcarbinols. It has already been shown that compounds of this class even if they con- tain certain substituents in the ortho-position with respect to the phenolic group exist in two desmotropic forms benzenoid and quinonoid. From a preliminary survey however it appears that substituents in the meta-position in these carbinols (ortho to the central carbon atom) often hinder tautomerism to quinonoid forms.Thus diphenylmethylene dichloride combines with m-cresol t o for in 0 H CP h2 C6H,Me OH which can only be obtained in the colourless benzenoid form m. p. 114O. This has also been synthesised as follows m-cresol and carbon tetrachloride are converted by the Tiemann and Reimer method into 5-hydroxy-o-toluic acid and the ethyl ester of this is treated with magnesium phenyl bromide. The carbinol combines with many solvents in molecular proportions ; compounds with acetic acid alcohol benzene chloroform and carbon tetrachloride are described. OH*CPh,*C6H,Me*O0CO2Me from methyl chloroformate has m. p. 118 ; the 5-ethylcarbonato- derivative has m.p. 1 2 8 O ; the 5-benzoyloxy-derivative has m. p. 1 0 3 O ; and the Fi-acetosy-compound has m. p. 136O. The carbinol loses water a t about its m. p. forming diphen~/l-3-methylpzcino- d i l h e ?i y Z-5 -hydro ,x!/-O-t 01 y I ca r b i n ol The 5 -me thylcar b onat o-derivativei. 112 ABSTRAOTS OF CHEMICAL PAPERS. methane CPh&,H,Me:O in red needles m p. 183O. This fuchsone absorbs two molecular proportions of hydrogen chloride one of which is removed by evacuation. The carbinol is also transformed into the fuchsone hydrochloride when treated with hydrogen chloride so the triarylmethyl chloride required for the preparation of the free radicle cannot be obtained. The above ethylcarbonato-derivative however can be converted into diphen YE-5-e t h y lcar b o m t o-o-t 0191 car bin yl chloride CO,E t*O*C,H,Me-CP h,Cl m.p. 96-9707 from which the chloriiie can be removed by means of finely divided silver as usual. The authors have not been able to isolate the free radicle as a solid but have obtained its peroxide R,O m. p. 141-14207 by exposing the deep cherry-red benzene solution to the air until almost bleached an! then evaporating. If the original carbinol is brominated in acetic acid solution it yields diphenyl-4 6-dibromo-5-hydroxy-o-tolylcarbinol; this exists as an almost colourless benzenoid modification m. p. 146-5-147*5° and in the yellowish-red quinonoid form m. p. 147-148O. The latter loses water more rapidly than the former on heating but both ultimately change a t 150° into the dark red diphenyl-2:6- d~bromo-3-rneth~lpuinomethane CPh2:C6HMeBr2:0.The corre- sponding colourless and yellow diphenyl-4 6-dichloro-5-hyc€~oxy-o- tolylcarbinols have m. p. 135-137O. m-Met hoxyphenol also reacts with diphenylmethylene dichloride giving 4-hydroxy-2-methozytriphenylcarbinol of which only a colourless form m. p. 132O (decomp.) has been obtained. This crystallises with demi-molecular proportions of benzene and carbon tetrachloride. Its constitution is established by proving that it is not the other possible product namely 2-hydrozv-4-met hoxytri- phenylcarbinol which has m. p. 154O decomp. 158O. This has been synthesised as follows reRorcylic acid is converted by methyl- ation into 2-hydroxy-4-methoxybenzoic acid and the ethyl ester of this is treated with magnesium phenyl bromide.J. C. W. The State of Saturation of Chromophores. HUGO KAUFFMANN Compare A . 1917 i 391).-A reply (Ber. 1917 50 1623-1625. t o Lifschitz (A. 1917 i 558). J. C. W. Production of Aminoalkyl Esters and Alkylaminoalkyl Esters of p-Aminobenzoic Acid. W. BADER and LEVINSTEIN LTD. (Eng. Pat. 111328 1916; from J . Soc. Chem. Ind. 1918 4-5~).- Alkyl esters of p-aminobenzoic acid are heated a t 150-180° with an amino- or alkylamino-alcohol in the presence of the aluminium compound of the amino-alcohol when the simple alcohol is dis- placed from the ester and distils off; the excess of amino-alcohol may then be removed by distillation in a vacuum. Instead of adding the aluminium derivative of the amino-alcohol as such it can be formed in the mixture by the addition of aluminium amalgam.Diethylaminoethyl p-aminobenzoate prepared in this way forms a colourless hyd~ochloride. D. F. T.ORGANIC CHEMISTRY. i. 113 Process for Producing Carbarnides and Thiocarbamides of the Aromatic (Benzene or Carbazole) Series. FARBEN- FABRIKEN VORM. F. BAYER & Co. (Eng. Pat. 8591 1916; from J . SOC. Chem. Zltd. 1918 2 0 ~ ) . Carbamide or thiocarbamide compounds can be obtained by the action of carbonyl chloride or thiocarbonyl chloride on aminoacylaminosulphonic acids of the benzene or carbazole series. m-Nitrobenzoyl-m-aminobenzoyl- aminosulphosalicylic acid N0,.CGE[4*COoNH*C6H,*COoNH*~6H,( OH) (SO,H)*CO,H obtained by the action of m-nitrobenzoyl chloride on m-amino- benzoylaminosulphosalicylic acid on reduction yields m-umi?zo- b enzoyl-m-amino b enzoylaminoszJpho.salicytic acid NH,*C,H,*CO*NH*C,H,*CO=NH*C,H,( OH)( SO,H) *CO,H and this like bis[m-aminobenzoylJ-aminocarbazoledisulphonic acid can by means of the named reagents be converted into carbamide derivatives possessing valuable therapeutic properties. D.F. T. The FIuorescence of Cyano-compounds. HUGO KAUFFMANN (Ber. 1917 50 1614-1623).-The remarkable fluorescence ex- hibited by the platinocyanides would lead t o the supposition that the cyanogen radicle has a favourable influence on this phenomenon and makes a study of organic cyanogen compounds particularly interesting. Quite simple nitriles are found to be fluorescent; benzonitrile for example is strongly reactive in the ultra-violet. 2 5-Dimethoxybenzonitrile might therefore be expected to be very fluorescent as it combines the properties of very fluorescent p-di- methoxybenzene with those of the cyano-group. As a matter of fact the eye can scarcely detect any fluorescence (compare Grig- nard Bellet and Courtot A.1916 i 487) but in the ultra-violet .IT / 1000-alcoholic solutions are most strongly fluorescent. o-Amino- benzonitrile should also be very active but no mention of the property has been made in the literature. Alcoholic solutions exhibit a powerful violet fluorescence which is displaced towards the ultra-violet in indifferent solvents. Among more complicated nitriles a number of striking examples have recently been described (A. 1917 i 394). It is remarkable that many organic cyanogen compounds are only fluorescent in the solid state like barium platinocyanide.The compound NMe,*C,H,*CH:CPh*CN ((ibid.) is an example of this. The corresponding free amino-compound NH3-c6E4*CH:CPh*CN is also only fluorescent' in the solid state but the isomeride NH C,H,*C( CN) C HPh is strongly active both in the solid form and in solution. The intimate connexion between fluorescence and constitution is here exemplified in a new way. The last-named compound is a representative of a new class nf substances which are strongly fluorescent in solution namely corn- pounds containing the group -CH:C(CN)*C,H,*N& of which examples are now given. Nitro-groups are generally a hindrance to fluorescence but thei. 114 ABSTRACTS OF CHEMICAL PAPERS. cyano-group can ofteii overcome this influence. Thus the COTII- pounds OMe*C,H4*CH:C(CN)*C,H4*N0 and are fluorescent at any rate in the solid state whilst the analogous substances free from the cyano-group are very feebly active Red compounds as a rule are likewise seldom fluorescent but even red nitriles are knowii which are brilliantly fluorescent.When viewed in the light of a mercury lamp behind a blue screen so arranged that substances like lead chromat'e or ciunabar appear t o be black the red cornpound NMe,*C,lI,*CH:C(CN)*S02Ph (Troger and Breiner A. 1910 i 113) shines with a vermillioii light; the red nitrile NMe2*@,H,*CH:CBz*CN (Zoc. cit.) appears to be brick-red ; pdimethylaminobenzylidenemalonitrile is orange- red and the compound NMe,*C6Hq*N:CPh*CN (Ehrlich and Sachs A.1899 i 883) appears to be bright brick-red. [With AD. JEUTTER . 1-a-p-A ??%in ophe nyl ci?zmmo&tril e (p-u )IL ii? o- a-cyanostilberze) yellow crystals m. p. 1 2 2 O blue fliioresceiice in benzene ether or chloroform green in alcohol bluish-violet in carbon tetrachloride or light petroleum is obtained by reduction of the nitro-compound which is prepared by the condensation of pnitrobenzyl cyanide with benzaldehyde. (a-cyn tLo-a-mi i l l o- phenyl-8-~heltylbzrtadiene) which forms pale brown crystals m. p. 153O is obtained by reduction of the product of the condensation of cinnanialdehyde with p-nitrobenzyl cyanide. The fluorescence exhibited is as follows solid feebly red behind the blue screen; solution in pyridiiie or acetone bright green; in glacial acetic acid.ether or chloroform greenish-blue ; in alcohol yellowish-green ; in light petroleum violet-blue ; even iii such a n unfavourable solvent as carbon disulphide a blue fluorescence is still manifest. CGH,[CH:C( CN) *C,H,*N0,12 a-p-A minoph en& y-b enzylicleneacrylonitrile Dinifro-a af-d~ccyu.trodist~/ry2/1-4 4/-henzene C,H,[CH:C( CN)*C6H4*NOJ2 yellow crystals m. p. above 300° is formed by condensing p-nitro- benzyl cyanide with terephthalaldehyde . [With (FRL.) LILLY L~~~.]-p-A?nino-a-phenylcinnam~nitrile (p-ami?~o-o-cyanostilb eiie) from the nitro-compound forms yellow crystals m. p . 143O. a-p- A n z inop h P I ) yI-2-nzet hosy cinnamo nitril e stout yellow needles m. p. 1 0 5 O is obtained from the nitro-com- pound OMe-C,H4*CH:C(CN)*C,H,*N0 (lemon-yellow needles m.p. 190° brilliant lemon-yellow fluorescence behind the blue screen) which is prepared by the action of p-nitrobenzyl cyanide on o-methoxybenzalde h yde. a-p-.4 niino p h e n y l-4-m P t 11 o cy cinna m o- nitrile forms yellow needles m. p. 151° and its fluorescence is as follows solid moderate greenish-yellow ; solutions in pyridine and alcohol green in acetone blue and in ether violet-blue. a-p-A minop he ~ y l - 3 4-me t h yle nedioxy cinnamonitrile CH2:0, C&?,*CH:C( CN)*C,H,*NHz yelrow needles m. p. 174O (intense blixish-green fluorescence in pyridine) is obtained from the corresponding nitro-compound yellow needles m. p. 1 8 8 O (strong orange-yellow fliiqrescence,),ORGANIC CHEMISTRY. 3 . 115 which is prepared by the condensation of pnitrobenzyl cyanide and piperonaidehyde.J. C. W. Mandeliminohydrin. JOHN EDWIX NACKENZIE (T. 1918 113 l-3).-Following Eschweiler’s method for the preparation of ‘‘ iminohydrins ” of a-hydroxy-acids (A. 1897 i 399) the author has converted benzaldehydecyaiiohydrin into the iminoalkyl ether hydrochloride OH*CHPh*C(OEt):NH,HCl and this by means of silver hydroxide into (’ nzcrndelini inohydritz,” in. 11. 173-179O (decoinp. ) (see f olloming abstract). J. C. IT’. Amidine Salts and the Constitution of the so-called Iminohydrins. HAROLLJ GORDON RULE (T. 1918 113 3-20).- The iminohydrins or isoamides which are usually prepared by the action of moist silver oxide on imino-ether hydrochlorides or water on the free imino-ethers were formulated by Eschweiler as OH*CR:NH (A.1897 i 399) and by Hantzsch as NH:CR*O-NH,:CR*OH (A. 1901 i 676). Hantasch showed that the compounds are com- paratively strong electrolytes with molecular weights twice as great as Eschweiler supposed. “ Glycolliininohydrin ” hydrochloride and the sodium salt of “ glycolliminohydrin ” are moreover known to be considerably hydrolysed in aqueous solutions and Walker under whose inspiration the present payer and Mackenzie’s note (pre- ceding abstract) have been presented finds that the degree of hydrolysis for ;T/8-solutioiis is about 50%. On the theory of amphoteric electrolytes therefore free ‘‘ iminohydrins ” should he very feeble conductors but their conductivities are really as high as that of a salt which is in conflict with Hantzsch’s formula. Hantzsch and Walker were both impressed with the fact that all “ iminohydpins ” described so far have been those of .a-hydroxy- acids.The hydroxyl group is not a critical part of the molecule however for the methoxyacetic and phenylacetic derivatives have now been obtained and the discovery has been made tlhat the corn- pouiids are really amidine salts of the formula N€€,*CR:NH,R*C02H. Thus * * glycollimiiiohydriii ‘’ is g.ly.collainidine glycollate. aiid “ mandeliminohydrin ” is maiidelamidiiie niaiidelate OH*CHPh*C(NH,):NH,CO,H-CHPh-OH. These two salts have been synthesisecl by the interaction of the amidine hydrochlorides and sodium glycollate or mandelate as the case may be. The hydrolysis of the imino-ethers by water is formulated thus (I) OEt*CR:NH + 2H20 = R*CO,NR,+EtOH; (2) R*CO,NH,+ OEt*CR:NH = NH,’*CR:NH,R*CO,H + EtOH.In this connexion it is interesting to note that imino-ethers react with ammonium chloride but not ammonia t o form amidiiie hydrochlorides (Knorr A. 1917 i 255).i. 116 ABSTRACTS OF CHEMICAL PAPERS. In examining amidine salts of the hydrosy-acids a iiumber of For experimental details see the original. Influence of the Replacement of a ,@Hydrogen Atom by a Phenyl Group in a-Hydroxy- 1-phenylcrotonic and y-Hydroxy-7-phenylcrotonic Acids. J . BOUGAULT (BUZZ. SOC. chim. 1918 [iv] 23 20-24).-The introduction of a B-phenyl- group into these acids considerably modifies the molecule in that it prevents the reactions which are apparently the most character- istic of the groupings *CH:CH*CH(OH)*CO,H a i d *CH(OH)*CH:CH*CO,H. Thus the reactions with alkalis mineral acids oxalic acid iodine in excess and sodium carbonate are all modified.Nitration of 5- and 6-Acetylamino-3 4-dimethoxybenzoic Acids and 4-Acetylaminoveratrole. JOHN LIONEL SIMONSEN and MADYAR GOPALA RAU (T. 1918 113 22-28).-The authors have recently been associated with Gibson in a study of the nitra- tion of 2-acetylamino-3 4-dimethoxybenzoic acid and S-acetylamino- veratrole (A. 1917 i 203) and the present work is a natural sequel. 5-Acetylamino-3 4-dimethoxybenzoic acid prepared f roni 5-nitrovanillin yields the 6-nitro-compound which may be con- verted into the known 6-nitroveratric acid and also some 4 5-di- nitro-3-acetylaminoveratrole (ibid.). I n the case of 6-acetylamino- 3 4-dimethoxybenzoic acid the carboxyl group is displaced on nitration the sole product being S-nitro-4-acetylaminoveratrole which may also be prepared by nitrating 4-acetylaminoveratrole and can be converted into 4-nitroveratrole.Eschweiler’s statements have been revised. J. C. W. W. G . For experimental details see the original. Camphoceanaldehydic Acid (tert.-sec.) (Camphoric Acid Semialdehyde,. 11. J. BREDT ( J . pr. Chem. 1917 [ii] 96 65-72. See also A. 1917 i 560).-Camphoraldehydic acid is unstable both in its active and inactive modifications; not only does it readily undergo atmospheric oxidation but also when kept out of contact with air the crystalline acid gradually becomes liquid the alteration apparently being one of polymerisation. The aldehydic acid is therefore conveniently kept in the form of its acetyl derivatdve viz.acetoxy-P-campholide from which it is easily reobtained by hydrolysis with aqueous sodium carbonate. [With L. ACKERMANN and J. DoRREN.]-I~ d-camphoraldehydic acid is heated for eight hours a t 100 in a sealed tube with acetic anhydride the normal Z-acetoxy-B-campholide m. p. 126-128O is obtained together with an isonzeride prisms or tablets m. p. 81-83O [a];’ +95*77O in benzene; both products on hydrolysis with sodium carbonate yield the original aldehydic acid. I n a similar manner dZ-camphoraldehydic acid on prolonged heating with acetic anhydride gives rise to a mixture of the dl-acetoxy- campholide m. p. 97-98O already described (Zoc. cit .) together with an isomeride tablets m. p. 73-74O. The active and inactive compounds already known together with their isomerides now J.C. W.ORGANIC CHEMISTRY. i. 117 described do not reduce potassium permanganate in neutral aqueous solution and therefore are all free from the aldehydic group; the isomerism is therefore regarded as similar to that of the endo- and em-borneols and due to the position of the acetoxy- group with respect to the plane of the six-atom ring. The failure of Rupe and Splittgerber (A. 1907 i 1016) t o obtain P-campholide by the action of nitrous acid on B-aminocampholic acid is ascrhed to the conversion of the four-atom ring into a five atom ring during the reaction according to which view the liquid product of this reaction is to be regarded as the lactone of hydroxy- trimethylcy clohexanecarboxylic acid ; such enlargements of the four-atom ring have already been observed (Demjanoff and Luschnikoff A.1903 i 403; Errera A. 1893 i 108; 1894 i 202). I n order to avoid the inconveniently high temperature (erroneously quoted as 600° instead of 400° in the earlier paper) necessary for the production of sodamide a mixture of sodamide and potassamide is prepared by passing ammonia on to a mixture of the metals (2 1 by weight) at 270-280O. Preparation of a-Naphtholphthalein. EMIL ALPHONSE WERNER (T. 1918 113 20-21).-A mixture of a-naphthol phthalic anhydride and a small quantity of sulphuric acid is carefully heated at 60-65O. The yield is about 33% of the weight of a-naphthol but is seriously diminished if the temperature rises above 6 5 O . D. F. T. J. C.W. Production of Anils of Hydroaromatic Ketones. GUSTAV REDDELIEN (D.R.-P. 301121 1915 ; from Chem. Zcntr. 1917 ii 714) .-Anils are easily obtained by heating the hydroaromatic ketones with amino-compounds at 160-180° in the presence of a small quantity of a strong acid for example hydrochloric acid as catalyst; instead of the acid the corresponding salt of the amincl compound may be used or if the reaction is vigorous even a metallic salt for example the zinc salt of the acid may be applied. Camphor when heated with aniline and aniline hydrochloride yields camphoranil colourless needles m. p. 13'5O b. p. 164-165O/ 15 mm.; menthone and aniline react in the presence of the additive compound of zinc chloride and aniline giving menthoneanil a pale yellow oil b. p.162-172O/16 mm. whilst with panisidine rnenthone-p-anisil m. p. 61-62O is formed ; carvoneanil obtained similarly is a yellow oil b. p. 179-181°/15 mm. which forms an exceptionally sensitive reagent for nitric acid giving a deep blue coloration with this substance. Decomposition of Oximinocamphor when Heated. E. SERNAGIOTTI (Atti R . Accad. Lincei 1917 [v] 26 ii 221-223). -Beckmann and Koster (A. 1893 i 474) showed that on fusion a-benziloxime is converted into benzoic acid and benzonitrile the hydroxyl of the :C:N*OH group passing t o the adjacent carbonyl group. On the other hand Kotz and Wunstorf (A. 1913 i 1361) found that at 240° oximinocamphor is decomposed in a different manner the products formed being dimethylheptenonitrile and D. F. T.i. 118 ABSTRACTS OF CHEMICAL PAPEHS.camphoric anhydride although the grouping undergoing change is th0 same as in the previous case namely iC*CO*C(:NOH)*Ci. The authors find however that a t 206-207O oximinocamphor is rapidly decomposed with formation of the a-nitrile of camphoric acid together with a green oil of ketonic or aldehydic character; the nitrile resu1t.s from a reaction similar t o that occurring with a-benziloxime. T. H. P. Constituents of Ethereal Oils. Synthetical Experiments in the Unicyclic Sesquiterpene Series. F. W. SEMMLER I<. G. JONAS and K. OELSNEK. (Ber. 1917 50 1838-1842).-The pro- duct of the action of magnesiuni isoamyl iodide on carvone con- tains not only isoamyl-a-dehydrophellandrene (following abstract) but small quantities of oxygenated compounds with higher b.p.'s. One of these is the normal carbinol CMe:CH tert-isoamylcarveol (annexed formula) which has b. p. 155-170°/12 mm. DZo 0.9217 72;' 1.4917 a; - 4 O and is the first synthetic unicyclic sesqui- terpene alcohol. It loses water when sulphate and may be hydrogenated to form t ert .-iso<r?nylt e t rah ydro- cawed b. p. 154-160°/17 mm. DZo 0.8908 nz 1.4632 aio -1.5O. The other compound which is formed in larger quantity i f ether is used instead of benzene as the solvent is the first synthetic sesquiterpene ketone. The isoamyl group is introduced at the double linking in the carvom ring instead of a t the carboiiyl group. isoL4 rn;7/Zdil~ydrocarvo?ie (annexed formula) has b. p. 144-148°/10 mm. D20 0.9022 9 ) ; 1.47694 t$ -8O forms an oxime m.p. 1 3 5 O and may be /\ reduced by sodium and alcohol to sec- CH CH I isoanzyld~hyd~ocarued This has b0 CH*CH,*CH,*C'HRle b. p. 150-155°/10 mm. DZ0 0.8993 r$ 1.47449 a:' +lo forms an acetate b. p. 155-160°/11 mm. D20 0.9227 7 2 2 1.46711 a," +5O and may be hydrogenated to sec .-isoarnylte tmhydrocavveol b. p. 145-1 52O/ 12 mm. D20 0.8906 ?iEo 1.46855 # +lo. [See also J . SOC. Chcm. I?&. 1918 137A.l J. C. IT. Gum Ammoniac Oil and Synthetical Experiments on the Nature of its Constituents. F. W. SEMMLER K. G. JONAS and PAUL ROENISCH (Ber. 1927 50 1823-1837).-I. Incestiyation of Gum Ammoninc Oil.-The gum- resin which is obtained in the first instance as a milky juice from the umbelliferous plant Dorema nmmoniacum and several FeriiZa species yields about 0.3% of an oil on distillation.A sample of this with D20 0.8855 nio 1.47233 and a," +-le70 has been sub- mitted to a thorough investigation along the usual lines. The first two fractions b. 1). 6O-13Oo/10 mm. 19% of the oil. contain linalyl and cit1mnellvl acetates. The third fraction 13. p. 130--140",' f!M /\ CH CH OH ' ':\OH ' ##CH2*CH2*CH treated .with potassium hydrogen \/ U Me CMe:CH b H \/ CHMe Constituents of Ethereal Oils.ORGANIC CHEMISTRY. i. 119 10 mm. 2074 of the oil consists chiefly of a unicyclic dihydro- sesquiterpene Cl5H% to which the name ferulene is given; this has not been obtained pure as the sample contains about 25% of a bicyclic sesquiterpene C15HB the constants b. p. 124-126O/ 7 mm. D20 0.8698 n2 1.48423 +6O beiiig in agreement with such a mixture; on reduction it' yielded tetrahydroferulene b.p. 118-120°/10 mm. D20 0.8400 qz? 1.45810 a:' +4*2O. About 22% of the oil was found to have b. p. 145-155°/12 mm. D20 0.8765 n 1.47160 aio + 3 . 5 O and to consist of an ethylenic sesquiterpene ketone to which the name doremone is assigned. This is the first record of a ketone of this class either among natural or synthetic compounds. Doremone C,,H,,O forms an oxime m. p. 88O b. p. 160-185°/10 mm. D20 0.8995 n 1.47914 a," + 2 O (acetate b. p. 180-195O/9 mm. D20 0.9283 n 1.47370 a:' + l o ) and a semicarbazone m. p. 124O. It may be reduced by means of platinum and hydrogen to tetra- hydrodorenzone CI5Hm0 b. p. 142-144O/ 12 mm. D20 0.8434 n2 1,44803 aio + 1.4O and by means of sodium and alcohol to the ethylenic alcohol doremol C,,H,,O b.p. 145-150°/ 12 mm. D20 0.8702 n? 1.47130 4' + 3 O which may be further reduced by platinum and hydrogen to tetrwhydrodoremol ClSHZ0 b. p. 140-145°/12 nim. D20 0.8403 ni' 1.44818 a;' + 2 . 8 O a paraffin alcohol with abnormal carbon chain. Doi*emyl acetate b. p. 155-165O/12 mm. D20 0.8896 12," 1.46596 a:' +4*8O is also present in the higher fractions. The highest fraction b. p. above 175O/ 12 mm. contains cetyl alcohol which has not hitherto been found in plants. I I . Experiments o n the Synthesis an$ Charncterisataon of Uni- cyclic and Dlefirzic Compounds of t he Sespuit erpene Series.-When carvone is treated with magnesium isoamyl iodide in benzene it yields a unicyclic sesquiterpene the intermediate carbinol readily losing the elements of water thus CM e C H ChKCB I c' r3 &H /\ /\ CH CH 6H 60 CH & C H ~ ~ C H ~ ~ C H M ~ \/ \/ CHMe2'C2Hd'Mgl CH CH + I CMe CMe The hydrocarbon isoamyl-a-dehydrophellandrene has b.p. 130-132O/11 mm. D2O 0.8679 rz; 1.49478 +18*5O does not. form a solid compound with hydrogen chloride or suffer condensa- tion to a bicyclic compound which shows the absence of conjugated double linkings in the side chain but it combines with six atomic proportions of hydrogen to form isoamylmenthane C15HN b. p. 131-133°/14 mm. DX2 0.8250 n 1.45562 a - 1-5O. Farnesol may be hydrogenated in the presence of platinum to form inactive hexnhydrofarnesol C,,H,,O b. p. 145-155O/ 15 mm. Dz2 0.8387 n? 1.44525 with which the above doremol is obviously closely connected. [See also J.SOC. Chem. Znd. 1918 137a.l J. c". W.i. 120 ABSTRACTS OF CHEMICAL PAPERS. The Essential Oil of Sea-samphire from different parts of France. MARCEL DEL~PINE and GASTON DE RELSUNCE (Bull. SOC. c h h 1918 [iv] 23 24-35. Compare A. 1909 i 642; 1910 i 401).-The results of the analyses of oil of samphire (Crithmum mritirnrn) obtained from plants grown in different parts of France show that they all contain the characteristic constituents namely 5 6-dimethoxy-3 4-methylenedioxy-l-allylbenzene the methyl ether of thymol and crithmene. I n some cases pcymene and d-pinene and a paraffin m. p. 63O were also obtained. [See also J . SOC. Chem. Znd. 1918 137~.] The Colloidal Nature of Colophony. 11. LUDWIG PAUL (Kolloid Zeitsch. 1917 21 148-154. Compare this vol. i 25).-Further observations which are said to be of interest in refer- ence to the colloidal nature of resin. [See further J . SOC. Chem. Ind. 1918 130a.l Natural Resins [Uberwallungsharze]. IX. MAX BAMBERGER and HERBERT VON KLIMBURG (Monatsh. 1917 38 457. See also Bamberger and Renezeder A. 1903 i 643; 1899 i 929; 1898 i @).-The resin obtained from the stone pine (Pinus cembra) possesses an odour recalling vanillin becoma reddened on ex- posure to light and has m. p. about 70° acid number 127 and iodine number 112 but4 the value for the last is as low as 78.4 if the resin is previously purified by dissolving in alcohol and pour- ing into water acidified with hydrochloric acid ; the methoxyl con- tent is lower than in other natural resins amounting only to 13 parts per 1000.Boiling water extracts from the resin caffeic acid and also small quantities of ferulic acid and vanillin whilst the residual molten resin on fusion with potassium hydroxide yields p-hydroxybenzoic acid catechol protocatechuic acid acetic acid and a trace of butyric acid. As with the resins investigated earlier stone pine resin after extraction with water can be separated into an a-resin soluble in ether and a 8-resin insoluble in the same solvent the a-resin which has a much lower methoxyl content than the &resin predominating. Attempts to produce a resinol analogous to pinoresinol or lariciresinol (Bamberger A. 1894 i 109) were unsuccessful. Lariciresinol when heated with zinc dust in a stream of hydrogen yields a distillate containing toluene xylene naphthalene methyl- naphthalene a trace of guaiacol and probably also cumene.Lariciresinol also gives a resinous ozonide but the only decomposi- tion product identified after shaking with water was hydrogen peroxide. Pinoresinol is already known to coiitain two hydroxyl groups; by heating with alcohol and a little sulphuric acid it can be con- verted into an amorphous anhydro-compound ClgHl8O5 which resists the action of methyl sulphate in alkaline solution but on treatment with acetyl chloride yield diacetylpinoresinol. W. G. H. M. D. D. F. T. The Aloins. 11. E. LBGER ( A m . Chim. 1917 [ix] 8,265-302. Compare A. 1917 i 276).-A resume of work already publishedORQANIC CHEMISTRY. i. 121 (compare A. 1912 i 708; 1914 i 309 707; 1915 i 889; 1916 i 413).W. G . Synthesis in the Pyran Series. J. VON BRAUN and Z. KOHLER (Ber. 1917 50 1657-l658).-PPr-Di-iodoethyl ether has already been used in the synthesis of compounds containing the morpholine ring.(I) (compare Clarke T. 1912 101 1788). It may also be applied to the preparation of pyran derivatives of the type (11). CH,*CH. O<CH2*C H L>c< (1.1 (11.1 Thus ethyl disodiomalonate and B@-di-iodoethyl ether react to form ethyl tetrahydropyran-4 4dicarboxylate b. p. 152-155O/ 21 mm. The free acid crystallises in colourless leaflets m. p. 172-173O and yields tetrahydr.opyran-4-cair.boxyZic acid m. p. 8 7 O when heated above its m. p. J. C. W. Action of Hydrobromic Acid on Cinchonine and its Isomerides Cinchoniline Cinchonigine and upoCinchonine. E. LEGER (Compt.rend. 1918 166 76-79. Compare Cordier von Lowenhaupt A. 1899 i 176).-When cinchonine or its isomerides are heated on a water-bath with hydrobromic acid (D 1-49) there is addition of hydrogen bromide but at the same time isomerisation occurs. Thus in the case of cinchonine the mother liquors after the separation of hydrobromocinchonine contain cinchonigine 6-cinchonine apocinchonine cinchoniline in small amount and an amorphous base which the author names cinchoniretine which is isomeric with cinchonine. From cinchonigine and apocinchonine no cinchoniline was obtained. Further although the four isomeric bases give the same hydro- bromocinchonine with cinchonigine and apocinchonine there is a simultaneous formation of hydrobromoapocinchonine. Preparation of Derivatives of Alkaloids of the Cocaine Group.CHEMISCHE WERKE GRENZACH ID.R.-P. 301 139 1915 ; from Chem. Zentr. 1917 ii 714-715).-The compounds derived from alkaloids of the cocaine group by demethylation a t the nitrogen atom for example anhydronorecgonine (tropene2- carboxylic acid annexed formula) and anhydrodihydronorecgonine (tropane-2-carboxylic acid) and their esters on alkylatioii a t the nitrogen atom by means PH\ H.CO,H of halogen-alkyl benzoatesJ yield compounds of CH,I marked pharmacological activity showing I NH dH similar properties to cocaine ; they possess I great local anmthetic power and are also sterilisable and less poisonous than cocaine. CH,I b.’K \CH/ The ethyl ester of anhydroecgonine on treat- ment with cyanogen bromide and subsequent hydrolysis is convertible into anhydronorscgonine of which the ethyl ester b p.148-151°/20 mm. reacts with y-bromopropyl benzoate with formation of oily 6 ensoxpypropylanhydronorecgQnhze W. G.i. 122 ABSTRAWS OP CHEMICAL PAPERS. ethyl ester; liydrochlori.de crystals m. p . 116-117O. y-Bromo- propyl p-nitrobenzoate m. p. 42O b. p. 229-233O/17 mm. reacts with the ethyl ester of anhydronorecgonine yielding p-nitrobeni- oxypropyZanhydrwnorecgonine ethyl ester CZOH,,O,N ; hydro- chloride hygroscopic crystals m. p. 154O ; picrate difficulty crystal- lisable. On reduction with tin and hydrochloric acid the nitro- compound is converted into p-uminob enzoxypropyZanJ~ydr(~- norecgonine ethyl ester C,,H,,O,N 3 hydrochloride hygroscopic and of no definite m. p.; platinzchlorade m.p. 297O; aurichloricle m. p. 93O. c-Bromoamyl benzoate and anhydronorecgonine ethyl ester react with formation of benzoxyarnylanhydronorecgonine ethyl ester (hydrochloride oily). Anhydrodihydronorecgonine ethyl ester b. p. 135-138O obtained by the reduction of anhydronor- ecgonine ethyl ester with hydrogen in the presence of a catalyst reacts with y-bromopropyl benzoate giving b P?LzoxyZrropyZanJz~~ro- dihydronorecgonine ethyl ester C,,H,,O,N ; hy&-ochloride m. p. 1 4 2 O ; ~citim*chloride m. p. 94-95O; mrichlorid'e m. p. 127-128O. The Rotatory Power and Molecular Weight of Gitaline (+-Digitoxine) JAMES BURMANN (Bzd2. SOC. chim. 191 7 [iv] 21 290-293) .-The author finds for gitaline carefully prepared and purified the values [a] -25'2O (in chloroform) and - 1 8 .8 O (in alcohol) and for the molecular weight 539 by the ebullioscopic method chloroform being the solvent. [See also J . SOC. Chem. Id. 1918 136~.] W. G. Synthesis of isoQuinoline Derivatives. 11. ADOLF KAUFMAWN and NICLAUS D ~ R S T (Ber. 1917 58 1630-1637. Compare A. 1916 i 502).- According . t o Knorr's researches on the morphine alkaloids they are not isoquinoliiie derivatives but yield such whsn heated with concentrated hydrochloric acid or zinc chloride solution that is by the rupture of tha seven-membered nitrogen ring and closure of a new ring. This is illustrated by the change from morphine to apomorphine thus D. F. T. Constitution of the Morphine Alkaloids. CH,ORGANIC CHEMISTRY. i. 123 After rupture of the " morphine " ring and before closure to the isoquinoline nucleus one of the three chains *NMe.CH,*CH,*OH *NMe*CH2*CH,C1 or =NMe*CH:CH might be present.In order to gain some idea as to the possibility of the first of these being formed the authors have synthesised piperonyl-fl-hydroxyethyl- methylamine {I) and attempted to condense it to dihydro- hydrastinine (11). Unlike the tertiary phenylethylamine (III) however the t ert .-bemylamine does not yield an isoquinoline. CH,:0,:esH,*CH,*NMe*C€€~*CH2*O~ *nc,f CH2 /'\ C H 3. (1.) - CH&JI I IN& \/\/' CH ;7 OH2:0,:C,,Hs*CH,.CB2*~~e.CK;OH ' This is probably due to the ease with which tert.-benzylamines decompose into benzyl alcohol and sec.-mines (Tiff eneau and Fuhrer A. 1914 i. 517) for the present base is broken down on boiling with acetic anhydride into the compounds CH,:O,:C,H,*CH,*OAc and NMeAc*C,H,*OAc.Piperonaldehyde and methylamine are condensed to piperonyl- idenemethylamine b. p. 128-129O/ 10.5 mm. (Andree A. 1902 i 210); this is reduced t o piperonylmethylamine b. p. 126.5O/ 10 mm. by means of hydrogen and spongy platinum and this is condensed with ethylene oxide to 3 4-methyleuedioxybenzylmet??yl- fl-h~dro,.t.YetkyZalrzine (I) b. p. 172-173°/10 mm. No agents have been found which can bring about the condensation of this base to dihydrohydrastinine (11). Hydrochloric acid a t looo converts it into the saIt CH2:02:C,H,*CH2*NMe*CH2*CH,Cl,HC1 and this also yields no dihydrohydrastinine even when treated with zinc dust or aluminium chloride. On heating at) looo the free chloro- base changes into dip'y e r o n y lpipe raz in e din? e t 73 o c ?do ride (11.) (111.) ni.p. 221O (decomp.) (picrate m. p. 212O). Ch.em. Id. 1918 136n.I [See also J . SOC. J. CT. W. Reactions of Piperidine with Organic Halogen Com- pounds in Ethereal Solutions. SAROENT G. POWELL and WILLIAM M. DEHN { J . Amer. Chent. Soc. 1917 39 1717-1723).-When reaction takes place between piperidine and organic haloids in dry ether the primary products are additive compounds being in fact the halogen hydracid salts of the AT-derivatives of piperidine. These differ in stability towards water heat and bases and decompose ultimately into the piperidine salt and substituted bases thus C,H,,NH + RX C,H,,NR,HX + C5HloNR + HX ; C$I&H + HX -+ C,HI,NH,HX. The salt+? are obviouslyi. 124 ABSTRAUTS OF CHEMICAL PAPERS. obtained a8 precipitates which are sometimes nearly pure additive products sometimes nearly pure piperidine salts but usually mix- tures.The lower alkyl haloids react so quickly and in the dark that they give the purest additive compounds; iodides react more smoothly than bromides and these more readily than chlorides. From the halogen estimation the percentage of additive compound ( A . C . ) in the precipitate can be roughly estimated. Methyl iodide gave pure l-methylpiperidine hydriodide ; iso- propyl bromide gave piperidine hydrobromide ; isobutyl iodide gave l-isobutylpiperidine hydriodide stout prismatic needles m. p. 131O; isoamyl chloride gave a precipitate containing 84% of A.C. ; isoamyl bromide gave A.C. 0.87L; isoamyl iodide gave A.C.61.57i; cetyl iodide gave A.C. 58.5%; benzyl chloride gave A . C . 66.8%; epichlorohydrin gave A .C. 74.3% ; ethyl chloroformate gave A .C. 8%. PP-Dichloropropane yielded piperidine hydrochloride accord- ing to the equation C5RiONH + CMs,C12 = C5H,,NH,HCl + CH,:CMeCl ; tetrachloroethane reacted according to the equation B + C,H2C1 = B,HC1 + CHCKCCl,; carbonyl chloride yielded the unstable compound CO( C,H1,N),,2HCl ; acetyl thiocyanate gave nearly pure l-acptylp-peridine thiocyanate m. p. 83-85O ; phenyl- propionyl chloride benzenesulphonyl chloride arsenic trichloride antimony trichloride chromyl chloride pentachloroethane liexa- chloroethane and carbon tetrachloride yielded only piperidine hydrochloride ; s-dibromoethane gave piperidine hydrobromide ; bromoform yielded A.C.4 41%; acetyl bromide yielded A.C.72%; and isobutyryl bromide gave ,4 .C. 86.7%. ADOLF KAUPMANN and OTTO ZELLER [with JULES MARTON] (Ber. 1917 50 1626-1630).-The p-toluenesulphonyl derivatives of aminoquinolines can very readily be nitrated and the products are easily hydrolysed to the nitro- amines by means of concentrated sulphuric acid. 5-Aminoquinoline b. p. 184O/10 mm. m. p. 109-llOo forms a ptoluenesulphonyl compound in stout white needles m. p. 203-204° which reacts with nitric acid (D 1.5) a t 60° to give 6 ; 8-dinitro-5-p-to1uenesu1pZLonylana~noqu~no1~ne7 m. p. 2 1 5 O . 6-Aminoquinoline b. p. 187O/11 mm. m. p. 1 1 8 O yields a ptoluenesulphonyl derivative glistening white crystals m. p. 195O which reacts with 60% nitric acid at 70° to form 5-nitro-6-p- toluenesulphon ylaminoquinoline glistening yellow crystals m.p. 168-1 69O and this may be hydrolysed to 5-nitro-6-aminoquinoline7 yellow needles m. p. 1 7 8 O (picrate m. p. 270O). The position of the nitro-group follows from the factl that the product of the action of iron and hydrochloric acid 5 6diaminoquinoline pale brown bundles of needles m. p. 95O reacts with phenanthraquinone to form a yellow azine m. p. 287-288O. 8-Aminoquinoline b. p. 157-162O/20-24 mm. m. p. 65O yields a p-tolzrenesulphonyl compound hard white needles P. 154-1560 which reacts with 60% nitric acid a t 50° t o form 5:7- dinitro-8-p-tolwenes~l~hon~lami~uqu~nol~ne silky crystals m. p. 239-240°*(decomp.) and a small amount of a mom soluble mone- J. C'. W Nitroaminoquinolines.ORGANIC CHE&ISTRY.i. 125 mtro-derivative m. p. 199-200O. These yield Claue’s 5 7- dinitro-8-aminoquinoline m. p. 187-1 88O on hydrolpeis. J. C. W. Phenazoxonium and its Simplest Derivatives. F. KEHRMANN and A. BOUBIS (Ber. 1917 50 1662-1667. Compare A. 1914 i 868; 1915 i 586).-As an outcome of the discovery that phenazo- thionium forms both meri- and holo-quinonoid salts it was sug- gested that a new investigation of the azoxoniums would prove that these are also normal in their behaviour t’owards acids. The present chemical and optical notices (following abstracts) show that the supposition was well founded. The reddish-violet salts obtained by dissolving phenazoxine in sulphuric acid whether dilute or concentrated are meri-quinonoid mono-acid salts.If hydrogen peroxide is added to the solutions in concentrated sulphuric or perchloric acid yellow holo-quinonoid di-acid salts are formed. These are unstable but can be pre- served for a short time a t 0-loo. On diluting the yellow solutions with glacial acetic acid the colour changes to wine-red h o b quinonoid mono-acid salts being formed. The holoquinonoid monoperchlorate (annexed formula) can even be isolated as an explosive brown glistening cf3H4gE>C6H4 powder butl the successful preparation is a matter of chance as the salt readily changes to the meri-quinonoid compound. In the case of 3 9-dimethylphenazoxonium dark red solutions of the holo-quinonoid di-acid sulphate may be obtained by dis- solving the base in a mixture of the concentrated acid and hydrogen peroxide; on dilution with glacial acetic acid orange-coloured solutions of the holo-quinonoid mono-acid salt result.A brownish- red holo-quinonoid pkrate C2,Hi4O8N4 and a dark violet meri- quinonoid monoperchlorate may be isolated as crystalline powders. 5-Aminophenazoxonium yields an explosive very dark green bolo-quinonoid perchlorat e N€I~C~,H,Ni0*C104 which gives a blood-red solution of the holo-quinonoid di-acid salt in concentrated sulphuric acid. 3-Aminophenazoxonium perchlorate is a dark red para- quinonoid salt and not ortho-quinonoid thus C,,H,ON:NR,*C?lO,. [See also J . SOC. Chem. Ind. 1918 119A.] Quinoneimide Dyes. VII. Spectra of the Simplest Azoxine Dyes. F. KEHRMANN and MAURICE SANDOZ (Ber. 1917 50 1667-1673) .-An account with tables and reproductions of the curves of the absorption spectra of the salts of phenazoxonium 3 9dimethyl- and 5- and 3-amino-phenazoxoniums (compare p r s ceding abstract).%em’-Quinonoid phenazoxonium salts exhibit a band with maxi- mum a t h 530 pp; the holo-quinonoid di-acid salts give a maximum a t 460 ,up and the mono-acid salts show two maxima the principal one being a t 530pp. For the dimethylphenazoxonium salts the maxima are meri-quinonoid 570,u,u and faint bands a t 450pp 610 No tri-acid salt is formed. J. C. W.i. 126 ABSTRACTS OF CHEMICAL PAPERS. and in the extreme violet ; holo-quinonoid di-acid salts 500 pp and mono-acid salt8 560 pp. The holo-quinonoid mono-acid salts of 5-aminophenazoxonium give a maximum in the infra-red whilst the di-acid salts have maxima a t 535pp and 430pp; the salts are therefore ortho- quinonoid. The mono-acid salts of 3-aminophenazoxonium have maxima a t 492 and 395pp; the di-acid salts give maxima a t 640 and 590pp which proves that these salts are para-quinonoid.In the ultra-violet all these salts give absorption bands with maxima a t 265 and 285 pp. Phenazothionium salts on the other hand give one band at 290ppu. [See also J. SOC. Chem. Id. 1918 119A.I J. C. W. Quinoneimide Dyes. VIII. Supplementary Observations OR the Absorption Spectra of the Simplest Azothionium Compounds. F. KEHRMANN and M. SANDOZ (Ber. 1917 50 1673-1682. Compare A. 1915 i 586).-The absorption spectra of the following phenazothionium salts are reproduced by curves and tables phenazothionium di-acid salts yellowish-green maxima in infra-red a t h 520pp and 460 p p ; mono-acid salts blood-red h 518 and 435 pp ; 6-methylphenazothionium di-acid salts yellowish-green A 460 pp and in iufra-red; mono-acid salts constitution in doubt blood-red h 515pp and border of ultra- violet ; 5-aminoph enazothionium di-acid salts yellowish-blood-red h 540 and 440 pp; mono-acid salts yellowish-green h 410 pp and infra-red.[With A. Bou~1s.~-5-An~inophenazothion~um perchlorate (annexed formula) may be obtained in moss-green slender explosive needles by NH2*c6H3g:>p6H4 oxidising 5-aminothiodiphenylamine with ferric chloride and perchloric acid. It gives solutions of the di-acid salt in concen- trated sulphuric acid. [With G . ROCHAT and A. B o u ~ ~ s -1-Thiodipheiiylmethylamine is oxidised by means of sodium nitrite in glacial acetic acid to the sulphoxide which gives a green solution of the di-acid salt of 6-methylphenazothionium in 70% perchloric acid.[See also J . SOC. Chem. Ind.? 1918 119~.] Quinoneimide Dyes. 'IX. Absorption Spectra of the Mono- acid Salts of Phenyl Derivatives of 3 9-Diaminophen- azoxonium. F. KEHRMANN and M. SANDOZ (Bet-. 1917 50 1682-1683).-The tables referred to in the preceding abstract also contain the following data 3 9-diaminophenazoxonium mono- hydrochloride solutions in alcohol bluish-violet h 593 570 5 45 pp ; (9) -I? y dr o chl oride blue .A 605 pp ; 3 9-dianilinophenazoxonium monohydrochloride greenish- blue X 664 p p ; 3 9-tetrarnethyldiaminophenazoxonium nitrite greenish-blue X 645 588 pp ; and 3-dimethylamino-9-anilinophemz- oxonium (9)-monohydrochloride greenish-blue h 651 pp.The fact is again emphasised that all the phenazothioniums 'ld4 J. C. W. 3-am in o-9-a nilin o ph ena z oxoniu mORGANIC CHEMISTRY. i . 127 behave alike in the ultra-violet spectrum exhibiting an absorption band at h 290 ,up whilst the phenazoxoniums are all alike in giving two maxima h 265 and 285 pp. [See also ,7. SOC. Chem. Znd. 1918 1 19A.I J. C. W. Steric Hindrance. 111. J. VON BRAUN and 31. MINTZ (BET. 1917 50 1651-1656. Compare A. 1913 i 1333; 1916 i 647). -In the first paper of this series on tetramethyldiaminodiaryl- inethanes it was shown that if both basic groups are encumbered by hindering neighbours the compounds do not react a t all readily with cyanogen bromide or iodoacetonitrile but if only one group is sterically hindered then reactions can take place a t both tertiary amino-groups.Another example is now given; the compound (I) is inactive but the base (IT) reacts at both nitrogen atoms. (1.) (119) Tetramethyl-o-tolidine (I) prepared by heating o-tolidine with methyl iodide and sodium carbonate solution reacts sluggishly with iodoacet onitrile to form dim e f hyldic y an om e t h y 1-0- t olidin e CN*CH,*NMe*C,H3Me.C6H~~~e*NMe.CH,.CN in. p. 163O. 3-Me thylbenzidiue from the re’du cti on of o-methylazobenzen e forms a glassy mass b. p. 225O/4 mm. and yields a @rate m. p. 2 0 4 O . If this is methylated by the above method it gives the methiodide NMe~*C,H3~~e*C6H,*Nnle,I m. p. 155-156O which is converted by heating a t 180-200°/4 mm.into tetramethyl-3- wrt?iyZbe?j zidiiie @I) m. p. indefinite 63-70O. This base forms a ylcrcrte m. .p. 193O and a 6:6/-dinitro-compound m. p. l l O o and reacts with cyanogen bromide to give dh~anodimethyl-3- ethyibenzidine CN.NMe*C,H4.C,H31e*NMe*~ m. p. 138- 139O which may be hydrolysed to the oily clz’rncthyl-3-metJt,yT- he11 ?iJine this yielding a di?Litroso-cierivative in. p. 195O. When the tertiary base (11) is warmed with iodoacetonitrile three pro- ducts are formed one being insoluble in hot water another in- soluble in cold water and the third very soluble. The first is tlinaeth.yldicyn,zo?nethyl-3-naet?z yl b en zidine m. p. 93-94O ; the second is a quaternary iodide of the formula CN* CH,-NMe*C,H3Me*C6H,*NMe31 m. p. 145-148O; and the third is the diquaternary di-iodide of the briginal base,- I*NMe3*C,H,*C6H,Me-NM-e31 m.p. 155O. J. C. W. Nitro-derivatives of isooxadiazole Oxides knd of isoOra- $iazoles. ARTHUR G. GREEN and FREDERICK MAURICE ROWE (T. 1918 113 67-74. Compare T. 1913 103 2025)-Attention has already been directed to the acidic nature of 4:Bdinitrobenz- isooxadiazole oxide. This acidity is either t o be at4tributed to thei. 128 ABSTRAOTS OF UHEWCAL PAPERS. hydrogen atom a t position 5 or possibly the compound is really 4 6-dinitro-5-hydroxybenzisooxadiazole thus No N NO2 OH/\-V NO) I 0 >o 01' ' XO,!\)_$>O /\/I\ \ / \ I / N 0.) (11.1 A compound of the formula (I) would require 20 atoms of hydrogen per molecule for reduction whilst a substance of the alternate type.(II).would absorb 18 atoms. As a matter of fact it is found on titration with titanous chloride that 20 atoms are used. Nitrederivatives of naphthisooxadiazole and its oxide (A 1917 i 518) have been prepared. They probably have the formula s-0 I \ N- 0 ' " ' and (4 and 5 ) N02-C,,B,<r>0 ().')-LN ' 1 1 \ 5 \ 4 I N \/ \/ n 0 NO \/\/ NO NO For experimental details see the original. Mechanism of the Coupling Reaction. OTTO DIYROTR HELMUT LEICHTLIN and OTTO FRIEDEMANN (Ber. 1917 50 1534-1588).-The first stage in the coupling of a diazonium salt with a phenol was supposed by Dimroth to consist in the formation of a diazo-ether which would subsequently undergo rearrangement into the ordinary azo-compound. It was found for example that pnitrophenol and pbromobenzene- diazonium chloride gave an unstable intermediate compound of the constitution NO,*C,H,-O*N,*C,H,Br which changed into the normal compound NO,*C,H,(OE[)*N,=C,H,Br (A.1907 i 662). Two criticisms of this theory have appeared. One is based on the fact that phenolic ethers also form am-compounds which has led to the view that addition of the diazonium compound takes place a t the conjugated double linkings (Meyer and others A. 1914 i 882). On the other hand Auwers has suggested that the first products are not ethers R-O*N:N*R' but diazonium salts R-O-NRGN (A. 1915 i 85). An answer to the second criticism is now given. Morgan and Wootton's stable diazonium salts 4-benzoylamino- naphthalene-1-diazonium chloride and pacetylaminobenzene- diazonium chloride have been treated with phenols ranging in strength from picric acid to pentamethylphenol.The molecular conductivities of the product? in 80% acetone a t Oo have been measured and ,the results show that the compounds with picric acid and dinitrophenol are true diazonium salts with the same conductivities as the chlorides or trichloroacetates whereas the weaker phenols and enols give true ethers with conductivities as low as that of p-nitrobenzeneazomethyl ether. Benzoyl-1 4-naphthalenediamine is obtained from the 4nitro- J. C. W.ORGANIC CHEMISTRY. i. 129 compound by a slight niodification of Morgan’s method (T. 1907 91 13161 and converted into the diazonium chloride. This reacts with dilute sodium hydroxide to form not the nitrosoamine NHBz*Cl,H6*NH*N0 as Morgan supposed but the quiplonediazide NBz:C,,H,<.which crystallises from diluted acetone as a brownish-yellow substance. 4-Benzoylamiizonaphthalene-1-di- uzoniuni trichloroacetnte m. p. 124’ (decomp.) picrate m. pa 141-142* and 2 4~ir~itrophe,zoxide m. p. 7 5 O (decomp.) are prepared by precipitation from the chloride and the acid or phenol with or without the addition of sodium acetate. The diazonium chloride couples with y-nitrophenol to form 4-benzoylarnino- 71 n pli t h a1 e n e-I -0 zo- p-ni t r oph e n yl e t her NHBz.@,,H,*N:N*O~C,H,*NO ni. p. 115-120° (decomp.) which has a somewhat higher con- ductivity thari the other diazo-ethers. The enolic form of dibenzoyl- acetylmethane yields 4-benzoylaminonnpht halene-l-azo-aa-dibenzoy?- 6-Aa-propenyl ether NHBz*C,,H,*N:N*O*CMe:~Bz~ m.p. 134-135O ; this is completely hydrolysed by ethereal hydrochloric acid only after some hours ths components being formed on the one hand and acetyl chloride and the compound NHBZ*C,~H,*NH-N:CBZ brownish-yellow crystals i n p. 225’ on the other. p-d cetybmino- henzeneazo-aa-d~benzo~l-P-4”-27.ropc.n~Z ether forins large yellow crystals m. p. 145-146O. For the preparation of pentamethylphenol s.-m-xylidine hydro- chloride is heated with methyl alcohol a t 250° and the penta- methylaniline is diazotised. Pentamethylphenol is so feebly acidic that the alternative quinonoid formula has to be considered thus H*C,Me,:O -+ C,Me,*OH. It. dissolves more freely in alkalis than in water (1 litre of boiling water dissolves 1.5 grams; 1 litre of boiling O’8iT-potassiurn hydroxide dissolves 1 2 grams) but the free phenol and not the salt crystallises from saturated soliitions.Furthermore the conductivity of a mixture of the phenol and sodium hydroxide in 50% alcohol does not vary with time. The phenol is therefore not an enolisable ketone but a true but very weak hydroxy-compound comparable with amyl alcohol. Renzeneazo pentamethylphen!yl ether C6Me,*O-N:NPh is a very unstable brownish-yellow substance which may even explode spontaneously a t the ordinary temperature. 4-Benzoylamino- naphthalene-1-azo pentamethylphenyl ether is quite harmless t o handle but the pale yellow granules explode at 8 1 O . ~-~4cetr/Z- nminobenzenenzo pentarnethyly7i enyl ether is a straw-yellow powder which detonates a t 69O.Mesitol and isodurenol also give precipitates of diazo-ethers when mixed with neutralised diazonium salt solutions of the above types but the products decompose before they can be dried. [See also J . Soc. Chem. Ind. 1918 118A.7 Swelling of Fibrin in Polybasic Acids and their Salts. MARTIN H. FISCHER and MARTIN BENZINGER ( J . Amer. Chem. Soc. 1918 40 292-303).-Experiments on the absorption o€ N ” J. C. W. VOL. CXIV. i. hi. 130 ABSTRACTS OF CHEMICAL PAPERS. water by fibrin in acid ahd alkaline solutions containing the acid salts (using phosphoric and citric acids) gave essentially the same results as when gelatin was used (see below) with the exception that the points of minimum absorption corresponded with a different acid content in the solution. [See also J .SOC. Chem. I d . 1918 1 3 1 ~ . ] GEORGE CLARKE and SAMUEL BARNETT SCHRYVER (Biochem. J . 1917 11 319-324).- Nucleic acid is extracted from plant tissues by 1076 sodium chloride solution in the form of nucleates of proteins and is precipitated in this form from the extract by hydrochloric acid. If the plant material is first boiled with strong alcohol subsequent extraction with salt solution and precipitation with acid yields a product free from proteins. Methods for the preparation of nucleic acid from yeast and from wheat embryos are described. The purified pro- ducts from both sources contain the proportions of nitrogen and phosphorus required by Levene’s formula C3RH50029N15P4 (A. 1909 i 541). L. A. C. Preparation of Plant Nucleic Acids. [See also 3.SOC. C h ~ m . I d . 1918 March.] J. H. I,. Structure of Yeast-nucleic Acid. 11. Uridinephosphoric Acid. P. A. LEVENE ( J . Biol. Chenz. 1915 33 229-3334. Compare Levene A. 1917 i 670).-The previously described cytosine- uracil-dinucleotide is now shown to be a mixture of the two simple mononucleotides the brucine salts of which can be separated by fractional crystallisation from 35% alcohol. The less soluble frac- tion consist8 of b rucine uridinephosphat e C,,H6,0,N6P,7H,0 which contracts a t 183* then melts and finally decomposes a t 198O (corr.). It is converted into the barium salt C9Hl1O,N2PBa crystal- lising from water in rosettes of long needles [.] + 3 * 5 O in a 2.5% solution of hydrochloric acid. After hydrolysis the only pyrimidine which can be detected is uracil.The more soluble fraction consists of brzccine cytidinephosphat e but the corresponding barium saltl has not yet been obtained in a crystalline form I n the light of these results the presence of a tetraribose nucleus in yeast-nucleic acid (see Jones and Read A. 1917 i 233) cannot yet be regarded as established. H. W. B. Swelling of Gelatin in Polybasic Acids and their Salts. MARTIN H. FISCHER MAR MARIAN 0. HOOKER ( J . Amer. Chem. SOC. 1918 40 272-292).-The absorption of water by gelatin was determined in different. concentrations of the primary binary and ternary salts of phosphoric citric and carbonic acids and in solutions varying from pure acid to pure alkali (sodium hydroxide) for the same three acids. The absorption is greatest in pure acids and alkali decreasing considerably in the presence of salts and with certain salts at’ high concentrations is less than in pure water.Froin a certain minimum there is a progressive increase in the absorption with increase of the acid or alkali content of the mix- ture. The results are held t o be applicable to absorption by proto-ORGANIC CHEX ISTRY. i. 131 plasm iii living cells there being iizcreasod turgor or edema with every increase in the acid or alkali content of the cell even in the presence of (‘buffer” salts. [See also J . SOC. Chem. Z d . 1918 131A.l L. A. C. The Liquefaction or “Solution ” of Gelatin in Polybasic Acids and their Salts. MARTIN €3. FISCIIER and WARD D. COFFMAN ( J . Amer. Cltem. SOC. 1918 40 303-312).-Experi- iiients showed that there is a progressive increase in th3 tendency of gelatin to go into solution in mixtures of the salts of polybasic acids as the amount of acid or alkali in these mixtures is increased from a given low point. This shows that hydration and ‘(solu- tion” of a protein are not the same thing for if ’they were the addition of an acid or an alkali t o a solution should cause it to gel for this causes increased hydration (see previous abstracts). The results have an important bearing on many physiological problems such as acid intoxication digestion etc.[See also J . 80c. Chem. Ind. 1918 1318.3 L. A. C. Chemical Composition and Biological Availability of Peptone. L. DAVIS ( J . Lab. Cliii. X e d . St. Loiizs 1917 3 75-86; from Physio7. -4 bstr. 1918 2 662).-A comparison of domestic peptones with VCTitte’s product.It is most important t o deter- mine the products of hydrolysis physical properties and elementary chemical analysis being secondary to this. Tyrosine and trypto- phan are important constituents. The best comparison is given by quantitative biochemical tests such as the elaboration of diphtheria and tetanus toxins and the production of indole. Domestic peptones do not. give a potent diphtheria toxin although furnishing good tetanus toxin and frequently yielding indole. W. G . The Surface Tension of Solutions of Ferments. 1,. BERCZELLER (Biochem. Zeitsch. 1917 84 50-58).-Stalagmo- metric measurements of solutions of various enzymes. S. B. S. The 11 Reversion of Diastatic Action. ” L. BERCZELLER (Biochem. Zeitsch. 1917 84 3741).-The amount of starch precipitated when its solutions are treated with diastase depends on their previous treatment.If soluble starch solutions of vary- ing concentrations are treated with the same amount of diastase it will be found that within a given time starch precipitation will appear first in lower concentrations of those solutions which have been cooled before being submitted to the ferment’ (at the ordinary temperature) and in higher concentrations of solutions which have been heated. The action of the diastase is ascribed by the author to the aggregation of colloidal particles. The action of diastase diminishes the viscosity and thus promotes the precipitation of the larger particles as they are formed. The cooled solution of starch will before treatment with diastase contain more of the larger h 2i.132 AISSTRSCTS OF CHEMICAL PSPERS I aggregates than the heated solution. [See also J . SOC. C'hem. I d . 1918 133A.l S. B. 8. Action of Oxidising and Reducing Substances on Diastases. L. BERCZELLER and E. FODOR (Biochem. Zeitsch. 1917 84,42-49). -Potassium permanganate hydrogen peroxide and iodine in very small concentrations iuhibit the action of diast'ase. Ordinary formaldehyde (" formalin ") accelerates slightly the diastatic action b u t this acceleration is due t o the formic acid itl contains. If neutralised it has a slight inhibitory action. Enzyme Action. XVI. Formation of Ester-hydrolysing Substances by the Action of Alkali on Proteins. FLORENCE HULTON-FRANKEL ( J . B i d . Chc m. 1917 32 395-407. Compare Falk A.1917 i 598).-Proteins (caseinogen gelatin etc.) are shaken with alkali solutions and after twenty-four hours the turbid liquids are treated with hydrochloric acid until only a slightly alkaline reaction is obtained. Portions then incubated with ethyl butyrate or other esters cause a distinctly greater hydrolysis to occur than is observed in control solutions of the same hydroxyl- ion concentration. The most active solutions are obtained when the concentration of the alkali acting on the protein is about 3 N . RaisiEg the temperature to 80° increases the activity of the result- ing lipolytic solution. When treated with acid instead of alkali the protein solutions are devoid of ester-hydrolysing properties. Dialysis only partly removes the lipolytic property of the alkali- protein solutions whilst boiling does not exert the slightest in- activating action.[See further ,7. Roc. Chpn?. Iiid. 1918 1 3 5 ~ . ] H. W. B. MARTIN JACOBY (Riochem. Z e i f s c h . 1917 84 354-357).-The bacteria are removed from the culture on agar and dried on porous porcelain. A preparation is thus obtained which can be preswved for a long time and is active in the presence of toluene. The Formation of Ferments. V. MARTIN JACOBY (Biochem. %uifsch. 1917 84 358).-The addition of leucine does not increase the activity of the permanent ureass preparation (see preceding abstract) but rather inhibits it. This fact indicates taken in conjunction with the author's previous work t h a t this amino-acid is necessary for the formation of the enzyme but has no effect on its activity.S. B. S. Silicon-Hydrocarbons with Nuclei containing Halogens and their Us0 in Syntheses. GERHARD GRUTTNER and ERICH KRAUSE (Ber. 1917 50 1559-1568).-p-Ch1orobromo- and p-dibromo-benzene react with magnesium to form the magnesiuni phalogenophenyl bromides. When these are treated with silicon tetrachloride they yield the trichloro-phalogenophenylmonosilanes SiC1 C,H,X which react with magnesium alkyl haloids t o form phalogenophenyltrialkylnioiiosilanes. Compounds of this type S . B. S. The Preparation of Urease from Bacteria. S. B. S.ORGANIC CHl3MISTRY. i. 1x3 react most readily with magnesium but not very snioothly with sodium but they may be applied very extensively in Grignard and Fittig syntheses. Magnesium p-bromophenyl broniide and silicon tetrachloride yield trichloro-pb ro moph c nylni on osila n e (p-b romoplz e n?y7.c chboride) a colourless oil b.p . 12U-125°/ 15 inni. which is immedi- ately hydrolysed by water t o p-b~ornophen?llsilicic acid (" hyCF.ro:~y- cl~o-pbromoylzenylmonosiln?7 r," according to Stock's nomenclature) C6H,Br*SiO*OH a white powder and also clichlol.odi-p-broni o- phenylmono.silane SiC1,(C6T-I,3r) snow-white prisms m. p. 60° b. p. 238-240°/ 21 nim. The trichloride reacts with magnesil-xi ethyl bromide to form p-b ro ,?iopke?iyltriethylni onosilane Some very unusual examples are now described. SiE t,*C,H,Br b. p. 149O/14 nim. D," 1.1643 1zHp 1.5283S ? l n 1.53280 nHIg 1.54411 ukl 1.55395 a t 21'. From p-chlorobromolsenzene the following compounds may be obtained by the same react ions.Trichloro-~-cl~lorophelzyl- monodame b. p. 103O/ 1.5 mm. ; p-ch7orophe?a?/lsilicic acid a colourless powder ; p-chloropli c i i y l t r i r t h ylmonosilnne b. p. 261-262O/760 mm. 137O/14'5 mm. D;"6 I *0056 n 1.51777 t i D 1.52193 ntrS 1.53255 ? i i i 7 1.54168 a t 9.6O ; p-chlorophenyltri- n-lrrolrylmonosila,ie b. p. 160°/ 14 mm. 0.9708 nHn 1.50835 itD 1.51234 ntIB 1.52225 n, 1.53059 a t go. pBromophenyltriethy1monosilane reacts readily with magnesium that has be.en etched by iodine to give the organo-magnesium com- pound in about 90% yield. This is ascertained froni the weight of phenyltriethylinonosilane b. p. 230-240° left on decomposing the compouiid with water. The following products have' been obtained from the magnesium compound by means of iodine p-iodopherL?Jlt7.iethylrrro.~o.ci~crrre a colourless liquid b.p. 165'/ 23 mm. D$ 1.3304 v,,? 1.53711 ?rn 1.56233 i t t I g 1-57578 H y 1.58709 a t 20' ; with lead trimethyl bromide p-triethy7silyl- f r i m c t hylplz(nzb,yy7b e n zetz e SiEt,*C,,H,*PhMe a stable viscous oil b. p. 191°/17 mni. DY 1.3997 1.54379 n 1.34937 / t L I 3 1.56240 n,, 1.57417 a t 23*8' which is resolved by bromine a t - 75' into lead trimethyl bromide and y-bromophenyltriethyl- monosilane ; by means of tin triethyl bromide p-triefhylsilyltr I- PthyZstarircyZberz,.ene SiEt,,*C6H,*SiiEt,. a colourless viscous oil 1,. p. 214'/18 mm. DP' 1.1216 71 * 1.52316 / i n 1.32756 I ? chloro di phen yl- ;Lrsine in the presence of sodium to form p-diphexylars~lltr;ethcvl- qilyylbenzene SiEt,-C,H,*AsPh as a colonrless viscous oil 11.p. 379-281°/17 mm. 1.1661 nbr 1.60784 n 1.61455 t / H p 1.63181 3LIly 1'64718 a t 21-3' which fornis crystalhe nclditive compounds with mercuric salts ( c h l o r i d ~ m. p. 188O ; bro112ide in. p. 181O; iodide m. p. 139.5O). From the optical data the moleculir refractions and dispersions of the above ~~halogenophenyltr.ialkyln302lnsilanes have been calcu- lated and the atomic refractions and clispersioiis of the silicon atom ha\7e besii wor1re:l out. Thew are t3lsulatect u7ith Rygtikn's 1.53853 ?2Hr 1.54864 a t 21.2'. p-C hlor ophenyl t rieth ylm onosilaiie r es c t s withi. 134 ABSTRACTS OF CHEMICAL PAPERS. values for phenyltriethylmoiiosilarie (A. 1915 ii SOS) and it is obvious t h a t the coiitribution of the silicon atom rises with the mass of the groups attached to it.All densities are reduced to vacuum standard. J. C. W. Benzyltrimethylsilicane-p-sulphonic Acid and some of its Derivatives. XwrrIuR BYGDBN ( J . pr. Chon. 1917 [ii] 96 86-104) .-Benzyltrimethylsilicane (BygdQn A. 1912 i 341) can be fairly easily converted into a sulphonic acid which unlike most of the organic silicane sulphonic acids described previously is easily isolated and convertible into crystalline salts. When treat ed in chloroforni solution with an equimolecular quantity of chlorosulphonic acid benzyltrimethylsilicaue yields benz?lltrirnetlLylsilicnne-ps.zLlphol.lic acid. SiMe,*CH,*C,H,.SO,H rectangular tablets with 2H20 which melt in their water of crystal- lisation a t 99-114O; the monohydrated acid has m.p. 116.0- 116-5O ; the position of the sulphonic acid group is demonstrated by the formation of phydroxybenzoic acid on fusing with potassium hydroxide and of toluene-psulphonic acid on boiling with aqueous potassium hydroxide. The following salts were prepared ptassizirn. salt rectengular or rhombic leaflets with 1H,O ; rubidium salt rectaiigular leaflets with lH,O ; caesium salt hexagonal leaflets with $H,O ; sodiirn7 salt leaflets with 2H,O ; Zithiunz salt' crystals with 2H,O ; calcium salt rhombic tablets with 2H,O ; stro?ztium salt needles with 2 H,O ; TICII'L'U~P salt needles with 2H,O ; magnesizrm salt rhombic leaflets with 7.1,H20 ; :ii)ic salt platelets or needles with 6€€,0; cndwzizcrn salt platelets or needles with 6H,O ; ferrous salt almost colourless leaflets with 'iH,O; nichel salt green leaflets or needles with 7H,O; cobult salt red lesflets with 8H,O; lend salt needles with 2H,O; copper salt blue leaflets with 6H,O ; siloer salt rectangular leaflets with 3H20 ; iimntonlzcin salt tablets with 1H,O ; metJi!/lammo~tr,unz.salt elongated tablets m. p. 144--l'i2° ; ethylurnrnonizim salt leaflets prisms or tablets m. p. 110.5 -111.5O (corr.) ; hiwcine salt rhombic tahlets m. p. 215~5-21T.~5° (corr.). The potassium salt of the sulphonic acid on treatment with phosphorus pentachloride yielded b eti r.yltrimet hylsilicane-p-sttl phony1 chloride &Me,* CH,*C,,H,*SO,Cl tablets in. 13. 45.5-46.5O (corr.) and the corresponding tromide. RiMe,*CH,*C,,€~,*SO,Br rectanqular tablets m.p . 60-60.5O (corr.) was obtained in a similar manner with the use of phos- phorus pentabromide. By allowing the acid chloride t o react in ethereal solution with various bases beili;~ltrintet7t;ylsilica~e-p- srrlphonamide SiMe,3*CH,*CGH,*S0,.NH tablets or prisms m. p. 81-81*S0 (corr.) and the corresponding methylamide prisms m. p. 7 6 . 4 ~ 7 7 ~ 2 ~ (corr.) be?az?,dnmide leaflets m. p. 130*5-131° (corr.) anilide hexagonal or rhombic tablets m. p. 124.2-125O (corr.) methyllrnilid~. needles rn. p. 71.5-72p50 (corr.) o-toluidide tablets m. D. 153-153.5O (corr.). and p-toTiridirZe rhombic tablets m. p. 97-98O (corr.) were also prepared. D. F. T.ORCIAYIC CHEMISTRY. i. 135 New Heterocyclic Systems. IV. Dimethyl- and Diefhyl- cyczopentamethylenestannine and their Scission Products.GERHARD GRUTTNER ERICH KRAUSE and MAXIMILIAN WIERNIK (Ber. 1917 50 1549-1558. Compare A. 1917 i 122).-Cyclic com- pounds containing five carbon atoms and one tin atom in the ring hale now been obtained by me1 hods analogous to those employed in the case of lead. Tin diethyl dibromide which is readily prepared by heating tin filings with ethyl bromide at 175-180" reacts with the magnesium corn pound of or-dichloropentane to form dzethylcyclopentamethylene- stannine,. C,H,,:SnEt which is a colourless mobile oil with the odour of fir-needle extract and has b. p. 95'1 i 4 mm. 1.2693 I ? ~ ~ 1.50398 n 1.50673 nHa 1.51586 n 1-523.57 a t 19.9'. The oil is htable in the absence of air but otherwise it gradually deposits a white resin. The ring is opened by means of bromine diluted with ethyl acetate a t O' when tin diethyl-r bromoamyl bromide C,H,,Br *SnEt,Br is formed as a very yiscous oil b.p. 190*5O/16 mm. Di0 1.7113 7% 1.54270 n 1.54707 ?zHP 1.55768 nHY 1.56675 at 20-3'. This reacts sith magnesium ethyl bromide to form tin triethyZ-eb?.omoamyl SnEt,*C,H,,Br which is a stable almost odourless mobile oil b. p. 155*5O/15 mm. D;" 1.3723 tztla 1-50304 ?L 1.50563 nHB 1.51457 nHy 1.52213 at 19.1'. The halogen is removed from this substance by converting it iiito its magnesium compound and decomposing this with water ; the main product is tin trzethgl-n-amyl b. p. 110°/15 mni. DY 1.1258 1 1 ~ 1.47070 n 1.47400 nHa 1.48216 n, 1.48906 at SOo but there is formed as well some a~-Zr~~aet~iyldistn?~izyldecir ) 2 ~ SnEt,*[CH2] ,,*SnEt nhich distils without decomposition and has b. p. 248'/15 ~ U I U . U?. 1.1887 nIIa 1.49480 u 1-4983.5 12Ha 1.50637 nay 1.51421 at 20.7". Tin diethyl-n-amyl bromzde C,Hll*SnEt,Br an unpleasant- smelling viwous oil b. p. 135"/15 mm. DF3 1.1365 n 1.50484 n 1.50866 ?zHB 1.51825 nIi 1.52657 at 22.3O is formed by the action of bromine on the tin tetra-alkyl. Dimethylcyclopentilmet hylenestannirze is obtained from tin dimethyl di-iodide as above; it closely resembles the homologue and has b. p. &l3/16 mm. 1):' 1.3357 iiHo 1.49861 ?L 1.50342 nHB 1.51184 n 1.51993 at 23.1'. Tin dii72eth~l-r-bronzoarnyl bromzde has b. p. 168'/14*5 mm. DY 1.8385 n 1.54548 n 1.54983 ?zHB 1.56085 l L H y 1.57019 at 24' and tzn tl.271~ethyE-~-bl.onwamyl has b. p. 124'/18 mm DF''4 1-4659 n 1.49604 n 1.49976 nHp 1.R0895 nllY 1.51677 at 23.4'. The magnesium compound of the latter reacts with lead trimethyl bromide to form a-trimethy~sta?zizyGr-trinzethylplumbyl- pentane SnMe;[ CH,J,*YbMe as a colourless viscous oil b. p. 162O/17.5 mm. D:3f! 1.6482 I Y L ~ ~ ~ 1.51S23 n 1.52383 ?zHB 1.53452 I L ~ 1,54473 at 2 3 ~ 2 ~ . Tin triethyl bromide reacts with the magnesium compound of aedi- chloropentane to form ac-hexnethyldistannylpentane b. p. 205-5"/14*8 mm. Dp 1.2654 n 1-5053 ?zF - nc 0.01312. Similarly lead trimethyl bromide gives a r - l i e x ~ n z e t l ~ y l d i p l ~ ~ ~ 2 ~i. 136 ABSTRACTS OF CHEMICAL PAPERS. pentane PbMe*[CH,~;PbMe b. p. 166.5'114 rnm. l):i5 1.9448 nz'5 1.55'71 nF - 7 1 ~ 0.0 i 940. All the densities are reduced to vacuum standard and in many cases sets of refractive indices at higher temperatures are recorded J. C. W.

ISSN:0368-1769    

DOI:10.1039/CA9181400097

出版商:RSC    

年代:1918

数据来源: RSC

摘要:

INORC ANIC CHEMISTRY. ii. 107 Inorganic C hernist ry. The Hydrides of the Metalloids. R. DE FORCRAND (J. Chim. phys. 1917 15 517-540).-An elaboration of work already pub- lished (compare A. 1905 ii 696) and a discussion of Berthoud’s work on this subject (compare A. 1917 ii 237). M. KLEIKSTUCK (Rer. 1918 51 lO&-lll).-SiIver chloride suspended in potassium hydroxide solution is quickly reduced by hydrogen peroxide accord- ing to the equation 2AgC1+ H,O + 2KOH = 2Ag + 0 + 2KCI + H,O. Carbonyl chloride and phenyl carbonate also react with alkaline hydrogen peroxide and so does a saturated solution of potassium hydrogen carbonate if kept a t looo in a pressure bottle. The dis- tillate obtained by passing steam through the products reduces ammoniacal silver oxide and is therefore said to contain form- aldehyde.The author sees in these reactions a new interpretation of the assimilation of carbon dioxide by plants thus H,CO + H,O - CB,O + H,O + 3 0 . [See also T)2TJ. April.] Variations of the Density of Air and the Loomis-Morley Law. PH. A. GUYE (J. Chim. phys. l917,15,561-566).-A study of the results obtained by various workers f o r the weight of a normal litre of air in which i t is shown that the results taken its W. G. Hydrogen Peroxide as a Reducing Agent. J. C . W.ii. 108 ABSTRACTS OF CHEMICAL PAPERS. a whole verify the qualitative experimental relation stated by Loomis and Morley between the density of the air and the baro- metric pressure. The most probable explanation of such varia- tions in density is based on the presence in the air of varying quantities of dust invisible under the ultramicroscope. The mean of the most modern determinations gives the value 1.2928 grams as w.G . Portable Hydrogen Sulphide Generator. W. F,PITOUTE MUNN ( J . I d . Eng. Chem. 1918 10 130-131).-A wide glass tube has two bulbs formed a t its lower end the bottom bulb being provided with a draw-off tap. A perforated lead plate is fitted a t the constriction between the bulbs (a piece of glass tubing in the lower bulb acts as a support for the plate) and ferrous sulphide is filled into the UP er bulb. The acid reservoir consists of a large the wide glass tube and extends to the bottom of the lower bulb. A tapped exit tube for the gas is placed near the top of the wide] tube and this exit tube is fitted with a small washing tube.the weight of a normal litre of air. bulb the stem o f which passes through a cork closing the top of w. P. s. Automatic Hydrogen Sulphide Stopcock. CARL H. CLASSEN ( J . Ind. Etzg. Chem. 1918 10 131-132).-To the delivery tube of the hydrogen sulphide apparatus is attached a length of rubber tubing in which is inserted a glass '' pearl " made from glass tubing having a diameter slightly larger than that of the rubber tubing. When the rubber tubing over the " pearl" is compressed between the finger and thumb a channel for the flow of the gas is formed Chlor o- and B rorn o-aminosulphonic Acids. W ILH ELM TRAUBE and E. VON DRATHEN (Ber. 1918 51 lll-115).-Solu- tions of potassium aminosulphonate and hypochlorous acid in equi- valent proportions react in the cold to form potassium chloroamino- stclphonate NHCl*SO,K which may bel isolated by evaporating the mixture t o a small bulk in a high vacuuni a t as low a tempera- ture as possible and precipitating with alcohol.The salt forms limpid hygroscopic crystals and is comparatively stable. When warmed with mineral acids hydrolysis takes place according to the equation NHCl*SO,H + H,O = NH,CZ + H,SO,. The corre- sponding barium salt is not so stable but potnssiicm bromoamino- sulphoncxte is very similar. Similar salts may be prepared by the interaction of free amino- sulphonic acid and metallic hypochlorites. Alkylaminosulphonates apparently give very unstable products for evolution of gas is noticed as soon as hypochlorous acid is added.There are indications that a double amount of hypochlorous acid produces less stable dichloroaminosulphunates. Rate of Hydrolysis and Electrical Conductivity of Hypo- phosphoric Acid Solutions. R. G. VAN NAVE and WILRERT J' HVFF ('4 mer. ,7. S c i . 1918 [iv] 45 103-118).-The idometric between the glass and the rubber. w. P. s. J. C. W.INORGANIC CHEMISTRY. ii. 109 method for the estimation of phosphorous acid in presence of hypo- phosphoric acid (this vol. ii 128) has enabled the authors t o in- vestigate the rate of hydrolysis of the latter acid. The data obt,ained at' 2 5 O and 600 show that' in dilute solutdons containing hydrochloric acid as catalyst the hydrolysis proceeds in accordance with the equation for a unimolecular change. The velocity co- efficient increases much more rapidly than the hydrogen ion con- centration.The temperature coefficient for loo is 2.7. The fact that the hydrolysis follows a unimolecular law is in favour of the formula H4P90 rather than H,PO for hypophosphoric acid for the production of phosphorous and phosphoric acids would require the interaction of two molecules of acid if it had the simpler formula. For the conductivity measurements pure solutions of the acid were prepared from lead and copper hypophosphate by the action of hydrogen sulphide a t low temperatures. The metallic sulphides were filtered off and the excess of hydrogen sulphide removed by a current of air. The conductivity of the solutions after complete hydrolysis was also determined. The molecular conductivity a t 2 5 O referred to the formula H4P,0 increases from A = 384.7 at' E = 32 to A = 629-3 at 'u = 1024.After hydrolysis the conductdvity of the stronger solutions is diminished whilst that of the more dilute solutions is increased. Attention is directed to the resemblqnce between thel properties of hypophosphoric acid and pyrophosphoric acid. This resemblance is found in the conductivity of the solutions in the behaviour towards indicators and in their solubility relations and may be adduced in support' of the formula H,P,O for hypophosphoric acid. R. M. D. Preparation of Amorphous Boron WILHELM KROLL (Zeitsch. nnorg. Chem. 1918 102 1-33).-The paper gives t8he results of numerous experiments on the reduction of boron compounds. Aluminium is unsuitable. Sodium yields mixtures of the lower oxides of boron mixed with boride.Calcium produces only borides. Magnesium may be used for the reduction of boric acid but the product contains more than 3% Mg in the form of in- soluble boride. The halogen compounds of boron can be reduced by potassium sodium magnesium and aluminium; in each case borides of the metal are formed as well as free boron. The purest boron is obtained by the reduction of boron chloride with hydrogen in the high tension electric arc. Red phosphorus does not reduce boric acid. When boric acid is heated with magnesium nitride a boron n,itride probably B,N is produced. Boron nitride BN can be conveniently prepared from boric acid and calcium cyanamide. When boron chloride is passed over red phosphorus in the presence of oxygen a yhocphntP 5?B,O,P,O is formed.Other phosphates appear to exist. The original contains details as t o analytical processes regarding compounds of boron. [See further Izd. 1484.1 R. V. S.ii. 110 ABSTRACTS OF CHEMICAL PAPERS. Nomenclature of Silicon Compounds. ALFRED SrocK (h’er. 1917 50 1769-1771. Compare A. 1917 ii 204).-The author again emphasises the fact that very little chemical similarity exists between silicon and carbon compounds of the same structure and proposes to abandon the nomenclature of carbon chemistry as far as possible. For example the radicle -SiO*OH in no way resembles a carboxyl group and therefore the term “hydroxyoxo” is sug- gested in such a case. J. C. TY. Silicon Hydrides. 11. Bromination of Monosilane SiH4. SiH,Br and SiH,Br,.ALFRED STOCK and CARL SOJIIESKI (Ber. 1917 50 1739-1754. Compare A. 1916 ii 319). -The experiments fully described in this paper had for their object the bromination of pure silane under conditions favourable to the production of the lower bromides. Under ordinary condi- tions the reaction betwemen bromine and silane is very violent but if an excess of the gas is led into a large vessel on the walls of which solid bromine is deposited and the temperature is main- tained at about - 80° to - 70° the mono- and di-substitution pro- ducts can be obtained comparatively free from SiHBr and SiBr,. The apparatus employed is very elaborate (see A. 1917 ii 442) and the manipulation is a matter of considerable difficulty. For details of the preparations and final fractionations the original should be consulted.Bronzomonosilane SiH3Br is a colourless gas with a pungent odour a t the same time reminiscent of monosilane. It has m. p. -94O b. p. +1-9O/760 mm. DO 1.533 and molecular latent heat of vaporisation 5.83 Cal. It may be preserved over mercury for some time but it detonates on exposure to the air giving silicic acid and brown silicon. It reacts with cold water according to the equation 2SiH,Br + H,O = 2HBr + (SiH,),O (see following abstract) whilst’ it may be aiialysed by measuring the volume of hydrogen produced under treatment with 30% sodium hydroxide according to the equation SiH,Br + 3NaOH = 3H2 + NaBr+ Na,SiO,. ~ihro?~zomo,iosiZni~e SiH,Br is a colourless mobile highly re- fractive liquid m. p. -70*1° b. p. 66O/760 mm.(extrapolation; highest recorded value 18O/123 mm.) Do 2-17 molecular latent heat of vaporisatJim 7.41 Cal. I n carefully dried vessels it may be kept for a long time but i t inflames in the air. It is very sensitive to moisture being decomposed into hydrogen bromide and a solid (SiH,O),. Alkalis decompose it according to the equa,tioii SiH,Br + 4NaOH = 2H + 2NaBr + Na,Si03 + H,O. J. C . W. Silicon Hydrides. 111. Disiloxane (SiH,),O ; Tetra- chloromonosilane SiCl ; Hexachlorodisiloxane (SiCl,),O. ALFRED STOCK CARL SOMIESHI and ROBERT WINTGEN (Ber. 1917 50 1754-1764) .-When bromomonosilane is shaken with water it changes into disiToxnue (SiH,),O the preparation and purifica-INORGANIC CHEMISTRY. ii. 111 tion of which are now described. It is a colourless odourless gas which does not inflame spontaneously but burns with a brilliant light giving a white smoke and a deposit of brown silicon.It has m. p. -144O b. p. -15*2O D-80 0.881 molecular latent heat of vaporisation 5-63 Cal. (compare SiH 3.03; Si,H 5.18; Si,H8 7.13; Si,H, 9-18 Cal.). The m. p. and b. p. are lower than the constants for the parent hydride Si,H (m. p. -132.5O b. p. - 1 5 O ) which is the reverse of the relationships between ethane and dimethyl ether. It only decomposes rapidly under the influence of heat when raised to redness. Submitted to a discharge of electric sparks it slowly yields pure hydrogen. When mixed with oxygen it inflames or explodes at once the alteration in volume being in accordance with the equation (SiH,),O + So,= 2Si0 + 3H20.It is not appreciably soluble in water but soon decomposes into hydrogen and insoluble products like (SiH,O) etc. With sodium hydroxide however decomposition is complete according to the equation (SiH,),O + H,O + 4NaOH = 2Na,SiO + 6H which may be applied in the analysis of the gas. Disiloxane and chlorine react very vigorously a t - 125O; the primary product hexachlorodisiloxane may be isblated but most of i t decomposes according to the equation 4(SiCl3),O = 2Si0 + GSiCl and some brown silicon is even formed as well. “ Tetrrr- cJ~ZorominosiZane ” (silicon tetrachloride) has m. p. - 68*7O b. p. 56*8O/760 mm. molecular latent heat of vaporisation 7.19 Cal. and “T~exacJ~Zo~odisiZoxane” is now found to have m. p. -33O and b. p. 137O/760 mm. It is an interesting fact that disiloxane is the first volatile com- pound of silicon hydrogen and oxygen.Many derivatives with the same elements are known such as “ silicoformic anhydride,” (O:SiH),O but these must assuredly be polymerides whereas alkyl alkoxyl and similar derivatives of the true monomeric type for example (SiR,),O and rSi( OR),],O have frequently been prepared (compare Martin and Kipping). Apparently the compound SiH,*OH which would be the primary product of the action of water on SiHR,Br is very unstable. It is noteworthy that the alkyl derivatives SiR,*OH also change into oxides readily but the alkyl groups do confer a measure of stability on them for hexaphenyldisiloxane (SiPh,),O changes back into SiPh,*OH on boiling with alcoholic potassium hydroxide (Kipping and Lloyd T.1901 79 455). J. c“. W. Silicon Hydrides. IV. Oxomonosilane (Protosiloxane) . ALFRED STOCK CARL SOMIESKI and ROBERT WINTGEN (Ber. 1917 50 1764-1769).-Dibromomonosiloxane reacts with water to form hydrogen bromide and a volatile compound which is very probably oxomonosdnne (poto.siZoxane) SiH,O. The authors have not been able to isolate this as it is about as volatile as the hydrogen bromide solution and furthermore polymerises most readily so’ that after a few distillations the whole of the origiiial silicon is found in the insoluble residues. The ldynzericle is ail amorphous white solid,ii. 112 ABSTRACTS OF CHEMICAL PAPERS. which is stable a t 300° (vacuum) or in contact with boiling water but inflames in the air or chlorine and reacts with sodium hydr- oxide according t o the equation (SiH,O) + 2NaOH -+ 2H2 J,- Na,SiOs.J. C. W. Proof of the Production of Water in the Formation of Salts from Acid and Base. W. FRANCK (Zeitsch. physiknl Chern. Unterr. 30 147; from Chena. Zentr. 1917 ii 358-359). -In the experiment described by Zeitler (A. 1917 ii 463) calcium or barium hydroxide should be used as the alkali hydr- oxides are never anhydrous. The System Lithium Sulphate-Lithium Chloride-Water at 303. F. A. €I. SCHREINEHAKERS and G. M. A. KAYSER (Chent. WeekbZacZ 1918 15 120-121).-The solubility of lithium sulphate in water is much diminished by the presence of lithium chloride. A. J. W. R. V. S. The Necessity for Applying a New Correction to the Atomic Weight of Silver. PH. A. GUYE (J. C h h i ~ . phys.1917 15 549-560).-The author discusses the various sources of error due to the presence of occluded gases and the adherent pellicle of moisture on the metal in the atomic weight determinations of silver. On the basis of recent work (compare A. 1916 ii 432) he considers that the atomic wedght of silver should be revised to 107.87 and that the correct values for the halogens should be C1= 35.461 Br = 79.925 I = 126.915. W. G. Metallographic Investigation of the System Zinc and Selenium MASUMI CHIKASHIGE and ROKURO KUROSAWA (Me7n. CoZZ. Sci. Kyoto 1917 2 245-248).-When zinc and selenium are heated together at a sufficiently high temperature the com- pound ZnSe is formed. Zinc selenide has a brilliant yellow colour DZ1 5.29 and does not fuse up to 1 1 0 0 O . The fused elements are not appreciably miscible and the selenide does not dis- solve in either.If a fused mixture is allowed to cool the two free elements and the compound are detectable in the solidified product when examined under the microscope. [See Ind. 153A.I H. M. D. Metallographic Investigation of the System Cadmium and Selenium. MASUMI CHIKASHIGE and RIICHI HIKOSAKA (Mem. CoZZ. Sci. Kyoto 1917 2 239-244).-Cadmium and selenium combine to form the compound CdSe which is infusible up to 1350O and has D16 5-81. The reaction between the elements begins t o be appreciable at about 360° and its velocity increases with rise of temperature. The cadmium selenide does not dissolve in either of the molten elements which are themselves practically immiscible. When therefore a mixture of thel two elements is fused and cooled the product consists of a mixture of cadmium selenide cadmium and selenium which are readily recognised under theINORGANIC CITEMTSTRP.ii. 113 microscope. The proportion of the compound in the product denends on the temDerat’ure to which the mixture has been heated agd on the length i f the period of heating. [See Irtd. 153~..] H. M. D. The System Copper Chloride-Lithium Chloride-Water at 30°. F. 9. H. SCHREINEMAKERS and (MISS) A. C. NOORDUYN (Chenz,. IT7pcX:hlcrd 191 8 15 118 --I 20).-An application of Schreine- makers’s graphic method t o solutions containing cupric and lithium chlorides. A J. W. The Critical Constants of Mercury. E. ARIES (Conzpt. retad. 1918 166 334-337).-Using the formula previously given (compare this vol.ii 61) for monatomic vapours and taking the known vapour pressures of mercury a t different temperatures the author calculates the critical temperature of mercury as 1077O and the critical pressure as 420 atmos. these values being a close approximation to the correct figures. W. G . White Pre- cipitate.” I. M. KOLTHOFF (Phamz. Weekblnd 1918 5 5 208-!218).-A comparison of the methods for preparing white precipitate” given in the Dutch German English Belgian Swiss and U.S.A. pharmacopaeias. The author is of opinion that the Dutch method is the most satisfactory. [See further Ind. April.] Preparation Properties and Analysis of A. J. W. The Space Lattice of Aluminium. P. SCHERRER (Physikul. Zeitsch. 1918 19 23-27).-The method described by Debye and Scherrer (A.1917 ii 437) for the X-ray examination of crystal structure has been applied to finely powdered aluminium. The interference photographs afford evideiice that aluminium forms cubic crystals and that the atoms are arranged according t o a simple face-centred lattice. Measurements of the interference patterns give 4.07 x cm. for the length of the edge of the elementary cube. The corresponding values obtained from previous investigations are copper 3.61 silver 4.06 gold 4.07 and lead 4.91 x 10-8 cm. I n spite of the close agreement between the values of the lat’tice constants and of the atdmic volumes for aluminium and gold the two metals do not form a complete series of mixed crystals. This is attributed to the preponderating influence of chemical affinity.H. M. D. The Effect of Great Hydrostatic Pressure on the Physical Properties of Metals. ZAY JBFFRIES (J. Inst. Metals 1917 18 243-252).-The statement of Hanriot (A. 1913 ii 112) that metals subjected to hydrastatic pressures of the order of 10,000 kilos. per sq. crn. are permanently hardened without deformation is contrary t o modern views on hardness. A repetition of the experi- ments using aluminium and an alloy of aluminium and copper,Ei. 114 ABSTRACTS OF CXEMTCATJ PAPERS. immersed in light petroleum under pressures up to 12,400 kilo. per sq. cm. shows that no increase in hardness is produced. Hanriot used vaselin which becomes solid under very high pressures so that the pressure applied is not hydrostatic. Experi- ments with the same metals show that a degree of cold deforma- tion insufficient to cause a noticeable change in the dimensions produces a marked increase in the hardness as determined by the scleroscope.This explanation is more probable than that of the occurrence of allotropic change in the metal. [See Ind. April.) C. H. D. Metallographic Investigation of the System Aluminium and Selenium. MASUMI CIIIKASHIGE and TSUW.JI AOKI ( X e m CoZZ. S c i . Kyoto 1917 2 249-254).-Cooling curve observations show the forniation of a compound AI,Se which melts at about 950°. The formation of this compound by heating the two elements together is frequently accompanied by an explosion unless the mixture contains more than 90% of selenium. The compound crystallises out from all fused mixtures of the two elements and in accordance with this the two branches of the compound curve on t'he freezing-point diagram cover the whole of the region from pure aluminium to pure selenium.The eutectics are therefore very nearly coincident with the freezing points of the two elements. The microcrystalline structure of solidified mixtures is in agree- ment with the thermal data. Aluminium selenide decomposes in contact with moist air with the formation of hydrogen selenide and aluminium hydroxide. [See Znd. 1 5 3 ~ . ] H. M. D. Metallographic Investigation of the System Tellurium and Aluminium. MASUMI CHIKASHIGE and JITSUZO NOS& (Menz. CoZZ. S c i . Kyoto 1917 2 227-232).-When aluminium and tellurium are heated together combination takes placel with ex- plosive violence and the compound Al,Te m.p. 895O is formed. This telluride forms mixed crystals with tellurium the series extending from the pure compound (12.4% by weight of aluminium) t o a mixture which contains 4.4% of aluminium. On cooling the a-mixed crystals undergo transformation into &mixed crystals. The temperature atl which this conversion takes place diminishes with increase in the tellurium content and for the saturated &mixed crystals falls to 541O. The j3-mixed crystals and tellurium co-exist a t the eutectic temperature 414O the eutectic mixture containing 2.8% of aluminium. The freezing-point curve of the compound A1,Te3 on the aluminium side is terminated by a eutectic point in which the telluride and aluminium co-exist in equilibrium. The eutectic mixture contains 970L of 'aluminium and the eutectic temperature is 621O.The conglomerates consisting of the telluride or aluminium and the enkectic undergo transformation when ths temperature hasTNORGANTC CHEMISTRY. ii. 11.5 fallen to 551° with the formation of AljTe according to the equa- tion A1,Te3 + 13A1= 3A1,Te. The telluride Al,Te is energetically decomposed by water or by contact with moist air with the formation of hydrogen telluride and aluminium hydroxide according t o the equation Al,Te3 + 3H20 = 3TeH + Al,03. The compound A1,Te is less readily decomposed but hydrogen telluride is liberated in contact with water the reaction being possibly represented by A15Te + H,O + 0 = TeH + A1203 + 3A1. Microphotographs are given which afford evidence in support of the results obtained by the thermal analysis of the system.[See I d . 15 3h.l A Criterion for Allotropic Transformations of Iron at High Temperatures. K~TARG HOWDA (Sci. Rep. TohoIm Imp. 77nizl. 1917 6 213-2117).-The transformations of iron consist in part of allotropic changes which take place at a definite temperature and of gradual changes in which the equilibrium con- dition is a continuous function of the temperature. The available data relating to these transformations show that A is of the second type whilst A and A are allotropic changes. I n the case of carbon steels there are in addition the changes designated by A and A the former representing a gradual change in cementite and the latter a eutectic transformation of cementite and ferrite which occurs a t a definite temperature.The Micro-structure of Commercially Pure Iron between Ar and Ar,. W. J. BROOKE and F. F. HUNTING ( J . I r o n Steel Znst. 1917 96 233-250).-Armco iron a basic open-hearth pro- duct containing as much as 99.84% Fe passes through a character- istic brittle range between 900° and 800° but only during cooling no change being observed within this range during heating. Quenching experiments show that a eutectic or eutectoid structure appears between these temperatures but is absent' either above or below the brittle range. This constituent resembles pearlite in structure but is not related to the carbon content and is also independent of the quantity of oxide in the iron. Heating in hydrogen is without influence on the structure. Similar results are obtained with Swedish iron containing about 0.04% of carbon.[See further Znd. 1917 1096.1 C. H. D. R. M. D. H. M. D. The Nature of Subsidiary Valencies. XVII. Prediction of the Decomposition Temperatures of Ammines. FRITZ EPHRAIM and ELIAS ROSENBERG (Ber. 1918 51 130-136).-1t was recently shown that the ratio of the temperatures cf dissocia- tion for certain pairs of compounds of two elements is roughly constant (A. 1917 ii 531). If the dissociation points of a number of compounds of one element are known and the ratio has been determined in the case of one pair of corresponding compounds for another element then the; dissociation temperatures of all the other compounds of the second element can be predicted. This is illus-ii. 1 1 6 ABSTRACTS OF CENMICAL PAPXRS.trated further in the case of the hexammines of nickel and cobalt salts. The ratio or I' temperature-modulus of the tension," calcu- lated from the dissociation temperatures of the iodides is NiICo 1/1*075 (A. 1912 ii 546). Dividing the known temperatures for other nickel salts by 1.0'75 therefore gives approximately the dis- sociation points for the corresponding cobalt salts I n the cases of the hexammines of ths bromides nitrates dithionates chlorides sulphates acetates and hydrogen carbonates (descending order of stability) the calculated values agree with the observed ones within thel limits of the experimental errors. Most' of the hexammines mentioned have been described before (A. 1913 ii 496 1061) but the following are new cobalt- hexnmmine nitrate by warming the crystalline nitrate in ammonia gas dithionate hypophosphite formate and acetate ; the dissocia- tion temperatures are respectively 160° 157*5O 51° 21*5=' and 55.5O. J. C. W. Metallographic Investigatiw of the System Selenium and Antimony. MASUMI CHI~ASHIGE and' MASASUKE FUJITA (Mem. (2011. Sci. Kyoto 1917 2 233-237).-Cooling-curve data show that' antimony and selenium form a compoupd SbnSes melt- ing at' 5 7 2 O . With antimony the cornpoupd forms a eutectic mix- ture containing 46.5% of selenium the eutectic temperature being 4 9 7 O . The eutectic on the selenium side of the compound corre- sponds very nearly with pure selenipm melting a t 2 1 1 O . Microscopic investigation of solidified mixtures of the two elements confirm the results obtained in the thermal analysis. [See h d . 1 5 3 ~ . ] H. M. D.

ISSN:0368-1769    

DOI:10.1039/CA9181405107

出版商:RSC    

年代:1918

数据来源: RSC