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.