i. 61 Organic Chemistry. Methane. WILLIAM MALISOFF and GL'STAV EGLOFF (J. PhYsicaZ C'hem. 1918 22 529-575).--A summary is given of the work which has been published from all sources on the physical and chemical properties of methane and a number of important problems requiring investigation are enumerated. [See J . Soc. Chena. Id. 1919 35A.l E. H. R. Organic Chemical Reagents. 11. Amylene. tert.-Amy1 Alconol. KOCER ADAMS 0. KAUX and 0. S. MARVEL (J. Arum. Chem. Soc. 1918 40 1950-1955).-Dehydration of p h a r y alcohols by sulphuric acid generally proceeds less satisfactorily as the molecular weight of the alcohol increases. Amylene may how- ever be satisf actonly obtained from commercial amyl alcohol under the following conditions. Amy1 alcohol (1 -5 litres) and concen- trated sulphuric acid (100 c.G.) are heated to vigorous boiling under a reflux condenser in which the water is maintained a t such a tkmperature (60-90°) as t o allow a considerable amount of vapour to distil out of the apparatus; the top of the condenser is con- nected with a second eiliciently cooled condenser attached so as to permit downward distillation.The heating requires a maximum time of about eight hours. At first water and amyl alcohol pass over whilst subsequently amylene distils. The distillate is washed with sodium. hydroxide to remove sulphur dioxide and the amylene isolated by fractionation. It appears to consist of P-methyl-&- butylene and /3-methyl-Afi-butylene containing only a negligible amount of y-methyl-Aa-butylene. The residue in the original flask contains amyl alcohol and isoamyl ether which are recovered by distillation with steam and subsequent fractionation.*4bo.ut 250 C.C. of amylene 400 C.C. of istlarnyl ether and 500 C.C. of amyl alcohol are obtained from 1500 C.C. of the latter. Larger amounts of amylene are more conveniently obtained by the pyrogenic-catalytic method using aluminium oxide as catalyst a t 500-540O. A suitable electrically heated furnace is fully described. The general procedure is similar to that indicated by Ipatieff (A.y 1903 i 593). The yield of amylene is 70--80% of the theoretical and the product* is about 98-99% pentene. The catalyst retains its activity over lengt-hy periods. tert-Amy1 alcohol is prepared by the gradual addition of amylene to a mixture of concentrated sulphuric acid and ice.The product is diluted with ice-water (after removal of any unchanged amylene) rendered alkaline with sodium hydroxide and distilled. 275-300 Grams of a product b. p. 100-103° may be obtained from 325 grams of amylene. H. W Geometrical Isomerism. A. E. LACOMBL~B (Chem. ~ ~ e e ~ ~ l 1918 15 605-610) .-The inconsistencies which are introduced VOL. CXVI. i. 1i. 62 ABSTRACTS OF CIIERT1CA.L PAPEBS. by the attempts to explain the existence of the cis- and $ranis- isomerides of ethylenic compounds of the type (A,B)C = C(A,B) by the theories of Werner and Stark are pointed out. All such theories set out to explain how the existence of the double bond prevents free rotation of the two doubly-linked carbon atoms about the line joining their centres.The explanations of Werner and of Stark are shown t o be inconsistent with the hypotheses which they put forward as to the nature of the atoms and the mechanism by which the atoms are linked together. The author points out that it is hopeless to attemptl to base an hypothesis of the structure of the benzene ring for example 011 theories which are inadequate to Derivatives of Trihalogeno-tert.-butyl Alcohols. 11. The Propionic and Butyric Esters of Tribromo-teyt,-butyl Alcohol (Brometorae). T. B. ALDRICH ( J . Anze~. Clzem. SOL 1918 40 1948-1950. Compare Aldrich and Beckwith A. 1917 i 77) .-&Tribromomethylpropan-&oI is converted into the corre- sponding prop'oiznte white crystals in. p. 2 7 O by the action of propionyl chloride. The similarly prepared hiityrate is an oil b.p. 144-l45O/I 3 - 4 4 inni. Both are comparatively inactive phar~nacologically due probably to their notI being decomposed into soluble constituents having a typical physiological action and are rather slowly absorbed. Glyceryl Methyl Ether Dinitrate (a-Methylin Dinitrate). DAVID TREVOR JONES (T. 1919 115 76-81). The Action of Sodium Hydroxide on Carbon Monoxide Sodium Formate and Sodium Oxalate. MAITLAND C . BOSWELL and J. V. DICKSON (J. ilmer. CThem. Scre. 1918 40 1779-1786).-It has been shown (this vol. ii 63) that; fused sodium oxide is very active in effecting oxidations. It is now demonstrated that a t 410-430° carbon monoxide in contact with fused sodium hydroxide is oxidised t o carbon dioxide an equi- valent amount of hydrogen being produced a t the same time.Sodium forniate when fused with sodium hydroxide at 2 7 5 O a temperature much below its decomposition temperature is oxidised almost quantitatively t o carbon dioxide in a very short time an equivalent amount. of hydrogen also being formed. Sodium oxalate is similarly oxidised a t B O O . ln both these cases it is the water present in the fusion cat~alysed by the sodium hydroxide which is the effective oxidising agent. It is held that the general reaction involving the replacement of the carboxyl group by hydrogen in alkali fusions for example in the formation of benzene from sodium benzoate involves simultaneous oxidation and reduction by the oxygen and hydrogen of water. [See also J . SOC Chem. znd. 1919 February.] E.H. R. PAUL PFEIFFER and THEODOR B~TTLER (Ber. 1918 51 1819-1829. Compare Pratt and Perkins A 1918 i 167).-Maleic anhydride is related explain the mechanism of t,he double bond. s. I. L. H. W. Quinonoid Character of Maleic Anhydride.ORGaMC CHEMXSTRY. i. 63 Go furan in the same manner as quinone t o benzene; it may there- fore be regarded as a quinone of furan and in the present com- munication evidence is adduced to show that the formal analogy is reproduced in its properties. A characteristic property of quinones is their ability to yield more o r deeply coloured molecular compounds with aromatic hydro- carbons amines phenols and phenol ethers (A. 1914 i 551; 1917 i 205); this property is shared by maleic anhydride which although yielding colourless solutions in benzene toluene or m-xylene gives coloured solutions with durene hexamethylbenzene naphthalene 2 4 5 2' 4' 5/-hexamethylstilbene 0-tolyl methyl ether and quinol and dimethylaniline.The influence of sub- st'ituent~s in the molecule of the solute and solvent respectively is similar in hhe cases of p-benzoquinone and of maleic anhydride. Thus methylation in the quinone molecule exerts a hypsochromic netion on the colour of the quinhydrone; similarly solutions of citraconic anhydride are less intensely eoloured than corresponding solutions of maleic anhydride. Methylation in the benzenoid com- ponent produces a deepening of colour in the cases of p-benzo- quinone and 05 maleic anhydride. The introduction of an ortho- condensed benzene nucleus has a similar influence in each instance as is proved by the comparison of a-naphthaquinone with pbenzo- quinone on the one hand and of phthalic anhydride with maleic anhydride on the other.The deepening in colour caused by ths introduction of halogen atoms into the quinone molecule is remark- ably characteristic; the same effect is produced in the anhydrides as proved by examination of bromomaleic dibromomaleic and tetrachlorophthalic anhydrides. Attempts to isolate the additive compounds of maleic anhydride or its bromo- or methyl derivatives in the crystalline state were not successful but similar substances were readily obtained from tetrachlorophthalic anhydride and durene (long pale yellow needles) and hexamethylstilbene (orange- coloured shining feaflets m. p. 183-184") respectively.The effect of alteration in the structure of the anhydride has also been investigated. Succinic anhydride yields colourless solu- tions in all the media mentioned above whilst the solutions of itaconic anhydride are much less deeply mloured than those of citraconic anhydride. When dissohed in dimethylaniline it aconic anhydride is gradually isomerised to citraconic anhydride. On passing from the anhydride to the corresponding acid or its esters the quinonoid character is largely 1mt and the solutions are colsur- less or less intensely coloured as is shown a t the instances of maleic and dibromomaleic acids of methyl fumarate and of methyl tetra- chlorophthalate. The substance CO,H*CBr:CBr*CHO scarcely possesses any quinonoid characteristics but these are more marked with transdibenzoylethylene.y-Pyrone and the ketones of the distvryl ketone series are less nearly related to quinone than is maleic anhydride ; the former yields completely colourless solutions whilst those of the latter only show faint colorations. It was t o be expected that h i d e s of the type sf maleinhide d 2i. 64 ABSTRACTS OF CHEMICAL PAPERS. would also show quinonoid characteristics; this is actually the case but solutions of citraconanil and tetrachlorophthalimide are less deeply coioured than those of citraconic and tetrachlorophthalic anhydrides. Maleic citraconic phthalic and tetrachlorophthalic anhydrides do not exhibit halochromic phenomena when treated with concen- trated sulphuric acid trichloroacetic acid or tin tetrabromide.Further investigation of this problem has led to the conclusion that the carbonyl groups of the substances which yield quin- hydrones and of typical halochromic compounds must differ markedly in t'heir chemical nature. H. W. Oxidation of Organic Compounds by Silver Oxide. ROBERT BEIIREND and KARL DREYEH (dmnaterh 1918 416 203-225).-1t has long been known that many acids and alcohols are oxidised by silver oxide but hitherto a systematic investigation 'has not been made of the relation between the constitutions of substances and their tendency to oxidation or of the nature and quantity of the products of oxidation. The present paper deals with these points in the case of the simpler hydroxylic aliphatic compounds. In order that it substance may be oxidised by silver oxide in alkali hydroxide or ammoniacal solution it mustl contain a ;CH*OH (or CO or C[0HJ2) group combined with two *CH,*OH two :CH*OH or two *C02H groups? or with any two of these three groups.Tartronic tartaric dihydroxytartaric glyceric mucic saccharic and gluconic acids dextrose glycerol and mannitol are thus oxidised. For oxidation in neutral or acid solution it suffices that the :CH*OH group shall be combined with a carboxyl group and also with H CH or CH,. Glycollic lactic malic (and also formic) acids are thus oxidised. Propylene glycol ethyl alcohol isopropyl alcohol and oxalic acid suffer little or no oxidation. In alkali hydroxide solution substances of the group first mentioned are oxidised rapidly and completely; the rate of oxidation is accelerated but the relative quantities of the products of oxida- tion are unaffected by an increased concentration of the alkali hydroxide.In ammoniacal solution silver oxide oxidises the alkali salts of the acids completely in fifty minutes a t 90°. The acids are more easily oxidised in the form of alkali salts than in the form of ammonium salts. An excess of ammonia or of ammonium salt retards the oxidation. The products of oxidation in alkaline solution contain at most two atoms of carbon and are never obtained in simple molecular proportions. All the substances with the exception of glycerol yield carbon dioxide as one of the products of oxidation in acid or in alkaline solution. Formic acid is a product of oxidation in alkaline solution and then only if the oxidisable substance con- tains a :CH*OH group united with a :CE€-OH or *CH,*OH group as well as with a :CH*OR *CH,.OR or *CO,H group.Formic acid may be an intermediate producb of oxidation in acid solution but in such circumstances it undergoes further oxidation. Oxalicacid is almost always the chief product of oxidation in alkaline solution; in neutral or acid solution it is formed in much smaller quantity. I n neutral solution malic acid yields malonic acid and lactic acid and propylene glycol yield acetic acid. Tastronic Acid. ROBERT BEHRERD and AUUUST PRO WE (Annuten 1918 416 233-339),-Tartronic ,acid has been pre- pared by eleven investigators who record eight different m. p . ' ~ between 1 4 5 O and 1 8 5 O . The correct value appears to be 156-158O Preparation of Gulonolactone. F.B. LA FORCE ( J . Bid. Chem. 1918 36 34?-349).-To a solution of 150 grams of xylose in 300 C.C. of water 30 grams of hydrocyanic acid are added and then a few drops of ammonium hydroxide. The reaction com- mences a t once and is completed in about six hours a t 3 5 O . Slightly more than one equivalent (55 ,;rams) of sulphuric acid diluted with a small amount. of water is added t o the solution which is then concentrated a t once to a viscous syrup. Hydrolysis of the nitrile takes place and on cooling and keeping the lactone crystal'lises out. The yield after recrvstallisation from 60% alcohol amounts to 55 to 60% of the weight of xylose used. Crystallography and Optical Properties of Three Aldopentoses. EDGAR T. WHERRY (J.Amer. Chem.. Soc. 1918 40 1852-1858).-The optical properties of the crystals of the three sugars a-d-lyxose a-d-xylose and B-d-arabinose enable them to be readily distinguished and a determinative table is given for this purpose For the determination of the refractive indices by the immersion method suitable mixtares of turpentine oil (n 1-47) clove oil (n 1-53) and ~-bromonaphthalene (n 1.66) are used. ad-lgxose forms monoclinic probably sphenoidal crystals n b c= 1.608 1 1.828 ; B = 62O1Of mean refractive index n 1.541 ; D20 1.545 molecular refraction M 30.60. a-d-Xylose. rod-shaped monoclinic probablv sphenoidal crystals a h :c=l*655:1:1.776; B=62O55'; n 1.536; D20 1.525; M 30.67. P-J-Arahinuse rhombic. Drohahly Fphenoidal needles a b c= 1*497:1 :0*738; TL 1.568; Dm 1.605; M 30.61.Lvxoss and xvlose a re obviously very closely related crostallo- graphically and B-arahinnse although crystalliFing in a different svstem from the others shows dsselv similar inter-facial angles and the three stiPars form an essentially isomorphous group. The molecular refractivities Rre all slirht1-y lower than that calcnlated from the atomic refract9ivities. 31.2. The diverqence is nrobably due to some peculiarity of molecular configuration. Tetramethylammonium Azide. FRANK V. FRIEDLANDER ( J . A mer Chem. Soc. 1918 40 1945-1947).-Tetrarn(~~~~- nmmoni?tm azide NMe,N is prepared by the gradual addi- tion of a sohition of tetramethylammonium iodide to an aqueous suspension of a slight excess of silver azide The eryshls belong to the tetragmal system (ca:c=l :0*7245).It) is a fairly 6. S. (d ecomp.). c. s. F€. W. B. E. R. R.i. 66 ABSTRACTS OF CHEMICAL PAPERS stable substance which does not explode when struck with a hammer when ground in a mortar or when dropped on a hot plate; the dry salt begins to decompose a t about 1 2 5 O . Attempts t o transform it into the isomeric tetrarnethyltetrazons NM+*N:N*NM% have been unsuccessful up to the present. H. W. Glycosine. ROBERT BEHREND and HERMANN KOLLN (A?z?znle?t 1918 496 230-233).--ln addition to glyoxaline very small quantities of glycosina are obtained by the action of ammonia on glyoxal. The yield of glycosine is considerably increased by the following procedure. In a tall cylinder are placed 20 C.C. of nitric acid D 2.4 containing ten to fifteen drops of fuming nitric acid 25 C.C.of water and 25 C.C. of paraldehyde the three liquids being introduced with as lit,kle intermixture as possible. The cylinder is immersed in water the level of which is higher thau that of the liquids in the cylinder. When the liquids have iuter- mixed after some days and the evolution of gas has ceased the mixture is repeatedly evaporated with wat'er to remove volatile acids as completely as possible and the residual syrup is diluted to 50 C.C. with water producing an approximately 20% solution of glyoxal. One-half of this solution is evaporated until the tempera- ture is 120° 25-30 grams of ammonium acetatle which has been heated a t this temperature are gradually added the resulting brownish-black liquid is dried a t 100-llOo and treated with water.The black residue of crude glycosine is dried in air and then at 70° dissolved in warm 35% hvdrochloric acid (which is added drop by drop) the solution is diluted with water boiled with animal charcoal (free from iron) filtered after keeping for twenty-four hours in the warm the brown filtrate is boiled again with animal charcoal? and the colourless filtrate is neutralised by ammonia whereby &cosine is obtained in 42.576 yisld. A modification of Pinner's method of preparing trichlorolactic acid from chloral is described. @. s. P-Aminoethyl Alcohol and its Derivatives. SIGMUND FRXNKEL and MARTEA CORNELIUS (Ber. 1918 51 1654-1662).- The following derivatives have been prepared to facilitate the identifi- cation of the amino-alcohol.NHBz*CH,*CH,-OH prepared by boiling an alcoholic solution of the dibenzoyl deriv- ative with t*he quantity of solid potassium hydroxide calculated t o eliminate one benzoyl group forms colourless leaflets m. 13. 66-67O. j3-A cetylaminoet hyt acetate NHAc*CH,*CH,-OAc b. p. 103O /0.049 mm. is obtained by boiling j3-arninoethyl alcohol with acetic anhydride. &A cetylaminoethyl alcohol prepared from the amino-alcohol and acetvl chloride at< Oo f o m s co'Iourless needles m. p. 63-65O. 13-Nn7?htt7talenes?rl.13hon?~lami?toethyl crlcoho! C,,R[,*SO,*NH*CHT,*CH~*OH asbestos-like crystals m. p. 86-87O is obtained by adding A7-sodium hydroxide to an ethereal solution B-Benxo?/lamiizoet~~~~ alcohol,ORGANIC CHEMISTRY. i. 07 of P-naphthalenesulphonyl chloride (2 mols.) and p-arninoethyl alcohol (1 mol.) and subsequently acidifying the aqueous solution.P-m-Nitro b enzoylamimoet hyl m-nitro b enzoate NO2*C,H4=CO *NH*CH,.CH,*O*CO*C,€I-I4.NO colourless needles m. p 152-153O obtained by heating &amino- ethyl alcohol (1 mol.) and m-nitrobenzoyl chloride on the water- bath is reduced by the calculated quantity of tin and hydrochlorio acid to @-m-aminobenzoyZarninoethyl m-aminobenzoate hydro- chloride C,,H,,0,N3,2HC1 crystals m. p. 232O. P-p-NitrobenzoyZ- anzinoethyl p-nitrobenxoate yellow needles m. p. 188-189O) and fl-p-amin obenzoylaminoethyl p-aminob enzoate crystals m. p. 206O are obtained by similar methods. P-Phenylcarbamidoethyl phenyl- carbamate NHPh*COgNH*CM,*CH,*O*CO*NNPh colourless crystals m. p. 19O-19lo is obtained by adding phenylcarbimide drop by drop to cold P-aminoethyl alcohol and then heating the mixture in a sealed tube a t looo.fLBmirzoethyl hydrogem stdphate NH,*CH,*CH,*O*SO,H colourless crystals m. p. 230° is obtained from the amino-alcohol and fuming sulphuric acid in a freezing mixture. /3-Glycylaminoet hyl glycine NH,*CH,*CO*NH*CH,*CH,.O.CO.CH,.NFI obtained by adding chloroacetyl chloride (2 mols.) t o a chloroform solution of 6-aminoethyl alcohol (1 mol.) a t Oo in the presence of lead carbonate warming the mixture for a nionient on the water- bath and after the cessation of the reaction and evaporation of the chloroform treating the residual yellow syrup with ccmcen- trated aqueous ammonia is a yellow syrup which is converted by the Schotten-Baumann method into P-hipprvlaminoethyt hippurat e NHBz*@H,=CO*NR* CH,*CH,*O*CO * CH,*NHBz colour- less leaflets.m. x). 144O. 7 m. p 88-90° is obtained by the prolonged action of carbony1 chloride on P-aminoet'hyl alcohol in chloroform solution in the presence of lead carbonate FAminoethyl alcohol in very dilute solution responds t o the iodoform test. By treating an aqueous solution of the aminor alcohol with sodium nitrite and Ehrlich's reagent (2% alcoholic p-dimethylaminobenzaldehyde and dilute hydrochloric acid) an intense canary-yellow coloration is produced which is notl destroyed by warming or by the addition of aqueous ammonia or potassium hydroxide. @-Benzoylaminoethyl alcohol ~-n2-aminobenzoylaminoetihyl ?it-aminobeuzoate hydrochloride and P-p-aniiiiobenzoylaminoethyl 12-aminobenzoate are not anzesthetics.P-Hydroxytrimethylenediglycine . HUGO KRAUSE (Ber. 1918 51 1556-1571. Compare A. 1918 i 156 337).-&Hydr- oxytrimethylenediglycine has D :j 1-348 by the swimming method. I t s solution in formalin or water produces on a pine shaving a greenish-yellow but not very intense coloratioii ; the reaction may c. s.i. 68 ABSTRACTS OF CHEMICAL PAPERS. be used as a sensitive method of detecting glycine. The colora- tion is destroyed by alkali hydroxide or carbonate and by ammonia. Esters of P-hydroxytrimethylenediglycine are obtained by the action of aqueous sodium hydroxide on a solution of the glycine ester hydrochloride in formalin. OH*CH(CH,*NH*CH,*CO,Me) a viscous colourless liquid still containing 10% of formaldehyde DI5 1-18 is obtained in only 19% yield but the ethyl ester is more readily obtained. When pure it has b.p. 140-150°/16 mm. (partial decomp.) D15 1.150 and a molecular weight in benzene or naphthalene corresponding with its formula. It is comparatively stable towards sodium hydroxide but is decomposed quantitatively by cold dilute hydrochloric acid yielding methyl alcohol form- aldehyde and ethyl glycine hydrochloride. When the ethyl ester (84% purity) is heated a t 16-18 mm. the distillate apart from formaldehyde and unchanged ester consists of a pale yellow oil b. p. 200°/16 mm. which appears to be ethyl ?nethylenaegZycine CH,:N*CH,*CO,Et or ethyl ethyleriedigly&ne C,H,(NH*CH,*C0,Et)2 more probably the former. I n the expectation of preparing the amide ethyl B-hydroxytri- rnethylenediglycine was heated with alcoholic ammonia a t 68-70° for twenty-four hours but the chief product was a substaace C,,H2,0,N3 which may have the formula NH:C( CH,*NH-CH,*CO,Et) The silver salt C3H60,NAg previously described (loc.cit .) can also be prepared by dissolving glycine in 30% formaldehyde solution in the cold neutralising this solution immediately with 4X-potassium hydroxide (phenolphthalein as indicator) and add- ing 20% silver nitrate solution. It is decomposed in aqueous suspension by hydrogen sulphide yielding formaldehyde and glycine. The acid corresponding with the silver salt is therefore probably AT-hydroxymethylgl ycine OH*CH,*NR CB,* C0,E. The methyl ester c. s. Comparisons and SimiIarities Water and Ammonia.G. CIAMICXAN (Atti R . Accad. Lincei 1918 [v] 27 ii 141-146). -Attention is directed to the chemical analogy between OH and NH3 between =OH and *NH and between :O and :NH (compare Angeli A. 1910 ii 844 948; 1915 i 847). Such analogy is clearly shown in the relation between C:O and C:NH the ready oxidation of cyanides to cyanates corresponding with that of carbon monoxide t o carbon dioxide and the reduction by zinc of cyanic acid with that of carbon dioxide. These relations are further rendered evident by the following. series of equations CO + H,O = CO(OR),; CO,+NH,=OH*CO*NH,; 0:C:NR +NR,=CO(NH,),; C(:NH) + H,O = CO(NH,) ; C(:NH) + ROH= OR*C(:NH)*NH ; C(:NH) + NH,= NH:C(NH,),. The polymerisation of cvanamide t o dicyanodiamide corresponds with the synthesis of guanidine and its derivatives the two tautomeric forms of cyanamide being reparded as reacting C(:NH) + C3T.NET = N€€,*C(:NH)-NH*CN.Other similar analogies are recorded. T. 3. P.ORGANIC CHEMISTRY. i. 69 Formation of Carbamide from Ammonium Carbonate and Related Substances. FR. FICHTER H EINRICH STEIGER and THEOPHIL STANISCH (Verb. S c h e r a . Nat. Ges. 1916 28 ii 66-103; from Ghem. Zemtr. 191t3 ii 444-446).-1n a previous communication (Fichter Stutz and Grieshaber A. 1913 i 713) the formation of carbamide by the electrolysis of ammonium carbamate was attributed to the intermediate production of formamide by the action of hydroxylamine on ammonium carbamate; this view can no longer be maintained since direct experiment shows that ammonium carbarnate is not reduced by hydroxylamine.On the other hand carbon dioxide reacts with hydroxylamine in the same mmner as with ammonia giving according to conditions hydroxylamine carbonate or the dihydr- oxylamine salt of hydroxycarbamic acid OH*NH CO,H 2NH2*OH. The expmiments on the electrolysis of ammonium carbamate solu- tion (Zoc. cit.) have therefore been repeated the same solution being used as in previous experiments but every care being taken to keep the anode and cathode solutions separate by enclosing the elect’rodes in porous pots immersed in it trough all vessels contain- ing the same solution. The results show that carbamide is pro- duced exclusively a t the anode but no trace of a corresponding reduction product such as formic acid or formamide could be detected a t the cathode.Under the experimental conditions Liebig’s method of detecting carbamide is unsuitable but Fmse’s method (A. 1914 ii 756) gives trustworthy results is not affected by the presence of ammonium salts and allows the isolation of carbamide by the action of alcoholic hydrogen chloride on the dixanthylcarbamide. Attempts have also been made t o effect the oxidation of ammonium carbarnate t o carbamide by purely chemical means ; hydrogen peroxide or calcium permanganate gives small but dis- tinctly recognisable quantities of carbamide. Oxidation may also be effected by ozone either by leading ozonised oxygen into ammonium carbamate solution or over powdered ammonium carbonate or by mixing ozonised oxygen ammonia and carbon dioxide. The yield depends on the concentration of ammonia and the temperature.The chemical and slectrochemical oxidations have the transformation of ammonia into ammonium nitrate as a common feature; also the local increase in temperature caused by the reaction is sufficient to cause a purely thermal transformation of ammonium carbamate into carbamide. The general explanation of the equilibrium between ammonium carbamate and carbamide is that the former passes into the latter by loss of a molecule of water. This however. is opposed to the law af mass action; the change is more probably represented by the scheme NH2*C0,NH + H20 (NTf,),CO CO(NH,) + 2H,O. Direct experiment shows that the rate of formation of carbamide is increased by water in the early stages of the reaction as is required by_the above hypothesis.The authors are therefore led t o the conclusion that normal ammonium carbonate is the d*i. $0 ABSTRACTS OF CHEMICAL PAPERS. actual source of carbainide ; since however the presence of water has an effect disadvantageous to the carbamide in the final eyuil- ibriurn (NH4)&03 := CO(NH,),+ f3H,O it is advisable to operate with substances containing the components of ammonium carbonate but having less water such as amnionium carbamate. At the temperature of the reaction the small quantity of hygroscopic moisture is sufficient+ to start the conversion of the carbamate into carbonate and as soon as the latter commences t o be transformed into carbamide water is liberated in amount sufficient to complete the hydration of the carbamate. I n the anhydrous condition ammonium carbamate is more stable than the carbonate; in the presence of water however it becomes unstable and above a certain temperature is incapable of existence.I n the region above 135O there is only the equilibrium between ammonium carbonate and carbamide in which the latter is favoured by further rise of temperature; below 135O on the other hand the complex equil- ibrium of the first scheme exists. The maximum yield obtained at 135O thus finds a simple explanation. The equilibrium (NH,),CO CO(NH,),+ 2H,O has been investigated a t 1 2 5 O looo 78O and 37*3S0 and the combined effects of temperature and dilution are explicable from t'he point of view of the complex equilibrium scheme. Lowering of temperature renders the carbamate and the carbamide more stable; increase in the quantity of water acts in the opposite direction in each case.According to the preponderance of one or the other factors the following effects may be observed at. temperatures below 1 3 5 O with a constant mole- cular ratio of carbamate to water (1) the second portion of the scheme may be so far favoured that the yield of carbamide is in- creased since the amount of water suffices to convert a larger pro- portion of carbamate into carbonate in spite of the actual increased stability of the former; (2) the yield may remain constant since the increase in stability of the carbamate balances the increased tendency to formation of carbamide; ( 3 ) the increased stability of the carbamate is not counterbalanced by the amount of water and the yield of carbamide sinks.All three possibilities have been experiment alIy realised. Free ammonia favours the carbamide in the equilibrium (NH,),C03 CO(NH,) + 2H,O in the absence of water but is without influence in presence of the latter. H. W. Acetylmethylcarbamide . ROBERT BEHREND and HANS ODENWALD (Annalem 1918 416 228-229).-Fifty-nine grams of acetamide (1 mol.) are dissolved in 88 grams of bromine (0.55 mol.) a 20% solution of potassium hydroxide (56 grams; 1 mol.) is added the solution is heated on the water-bath until it becomes yellow and is no longer alkaline and is then cooled when acetylmethyl- carbamide crystallises. Further quantities can be obtained from the mother liquor the total yield being 75% of the theoretical. With even a slight excess of alkali the yield falls t o zero.C. S.ORGANIC CHEMISTRY. i. '71 Substitution in Aromatic Compounds. 13. J. PRINS (Clzem. tf'cekbEad 1918 15 571-58O).-It has been shown in an earlier paper (&id. 98) that substitution in aromatic compounds begins by addition to a carbon atom of the ring followed by reaction with the hydrogen atom attached to that carbon atom; the reactivity of the hydrogen atom depends therefore in the first place on the degree of unsaturation of the atom to which it is attached as is true also in the case of alcohols and ainines. Since unsaturation is distributed aver t"he whole nucleus addition can obviously occur a t more than one carbon atom. The analogy with alcohols and amines is shown not only in tha carbon atoms of the nucleus but in oxygen or nitrogen atoms in side-chains attached t o the nucleus and substitution can be brought about in all these cases by the same catalysts.Substitution may be no& w l y direct but indirect also as in the. case of chloroacetanilide ; the reaction here is uiiimolecular and may be ascribed to a disturbance of t.he equilibrium between the energy of the atoms (atom-energy) and the energy of combination between the atoms (link-energy). Substitution occurs then in the first place a t the least saturated carbon atom but this may not yield the most stable system and the substituting group may finally take up a different position. The entry of any substituent X into the benzene ring must cause a change in the relation between atomenergy and link- energy both in the substituent.and in the nucleus. Two cases may arise. I n the first in which the link-energy between X and C; the carbon atom tno which X becomes attached is greater than that between C and the hydrogen atom displaced; the atom-energy of C is therefore reduced and to restore this as far as possible the link-energy between C and its neighbours C2 and C3 is reduced with the consequence that the link-energy between C and C and between C3 and C5 is increased (C and C being the neighbours of C2 and C remote from (2,). and that between C and CB and c5 and C is diminished; C therefore by the diminution of it,s link-energy receives an increase of atom-energy and is therefore rendered more reactive. The effect of introducing X therefore is t o make the para-carbon atom more reactive. I n the second case in which the link-energy between C and the substituent is less than between Cl and hydrogen the redistribution of energy causes an increase in the atom energy of C4 and C5 that is of the carbon atnoms in the meta-position.The fact that a suhstituent which directs a second substituting ~ ~ O U ' P to the meta-position also causes a reduction in the velocity of substitlltion is taken to indicate that the atom-energy of the atoms of the snhstihted nucleus is less than t,hat of the atoms of the unsiibstituted benzene ring itself and hence it follows that the introduction into the rinq of a group which directs to the meta- position causes the transformation of atomenergy into link-energy throughout the ring as a whole.*i. 73 ABSTRAOTS OF CHEMIUBL PAPERS. It is shown that substitution iu the benzene ring cannot be ex- plained by the assumption of a conjugated system as attempted by Boeseken (A. 1912 i 430) and by Holleman (Chem. FVeekbZad 1913 10 615 61S) without postulating many other conditions. s. I. r,. Pyrogenic Acetylene Condensations. V. RICHARD &!EYER and WILHELM MEYER (BeT. 1918 51 1571-1587. Compare A. 1917 i 313).-In addition t a the substances previously identified in the product of the pyrogenic condensat.ion of acetylene o-xylem (identified as o-phthalic acid} and indene have been detected and the presence of mesitylene and q-cumene confirmed. Durene and isodurene could not be detected. The methylthiophen obtained by the condensation of acetylene methane! and hydrogen sulphide (Zoc.c i t . ) is proved to be a-thiotolen and thionaphthen has been found in the product of the condensation of acetylene and hydrogen sulphide. A complete list is given of all the products obtained by pyrogenic acetylene condensations. Hvdrindene brorninated in the cold in the presence of a little iodide yields 4 5 6 7-tetrabro.mor7lydr~~ene C,Br <gz>CX2 needles m. p 200° (which is converted into tetrabromo6hthalic acid by oxidation) but brominated in boiling chloroform yields 1 2 S-t~ibromoh~d;rindeme feathery crystals m. p. 134O which yields phthalic acid by oxidation and is also obtained by the further bromination of indene dibromide. About 0.5 C.C. of aniline was obtained when the vapour of 3 litxes of benzene mixed with ammonia was passed during twenty- four hours through a tube heated a t 550° initially and a t 700° finally; aniline could not be detected if the temperature was maintained a t 550° throughout.[See also J . Sac. Chem. Ind. The Optically Active moMethylhydrindamines . J OSEPH WALTER HARILIS (T. 1919 115 61-67). The Fusion of Sodium Hydroxide with Several Phenols and Sulphonic Acids. MAITLAND C. BOSWELL and J. V. DICKSON ( J . A m e r . Chem. Soc. 1918 40 1786-1793).-A number of experiments were carried out in which sodium benzene- sulphonate was fused wit'h sodium hydroxide a t temperatures of 30O-35Oo in a closed vessel in presence! or absence of air the gaseous contents of the tube being analysed before and after the experiments. It was found that when the fusion was carried out in presence of air a considerable quantity of hydrogen was formed and a much smaller quantity of methane or other gaseous hydro- carbon.At the same time some of the oxygen originally present disappeared the volume ratio of hydrogen formed to oxygen used up being approximately 1 2. When air is excluded from the fusion however no hydrogen or methane appears. It was found working on comparatively large quantities of material that by 1919 3 5 ~ . ] c. s.ORGANIC CHEMISTRY. i. 73 carrying out the fusion in an atmosphere of nitrogen instead of air the yield of phenol could be increased from 90% to 98% of the theoretical. In the presence of free oxygen secondary reactions evidently occur involving the absorption of oxygen followed by an oxida- tdon involving the elements of water.To determine whether any of the dihydroxy- or trihydroxy-benzenes are formed as secondary products the fusion of all six of these with sodium hydroxide in presence or absence of air was studied. I n the case of five of them hydrogen was formed in presence not in absence of air. In the case of hydroxyquinol much hydrogen is evolved even in absence of air and also considerable quantities of methane. It is not considered that any of these can be the direct cause of hydrogen formation in the benzenesulphonate fusion. Sodium hydroxide does not bring about catalytic oxidation of the dihydroxybenzenes of pyrogallol of P-naphthalenesulphonic acid or phenylglycine-o-carboxylic acid. With sodium anthra- quinone-6-sulphonate however oxidation occurs in absence of oxygen with format'ion of free hydrogen. REX& DUBRTSAY TRIPIER and TOQUET ( Compt.rend. 1918 167 1036-1038) .-The coefficient of reciprocal miscibility of phenol and water st"eadi1y increases with the addition of alkali hydroxides t o the water. Curves are given for sodinm hydroxide a t concen- trations varying from A7/Z0 to J77/3. The action of the alkaline earth hydroxides is similar but less marked On the other hand acids and salts of the strong acids cause a diminution in the coeffcient and the same holds good €or the alkali carbonates. E. R. R. The Miscibility of Phenol and Alkaline Solutions. W. G. Aromatic Derivatives of Orthosulphurous Acid. X. M. RICHTER (AnmaZen 1918 416 291-304. Compare A. 1917 i 34).-The attempt to prepare aryl sulphates in the same way as aryl sulphites (Zoc.cit.) by mean9 of sulphuryl chloride and nvridine failed chlorinated liquid products being obtained. Phenyl sulphate is obtained indirectly by dissolving phenyl sulphite in concentrated snlshuric acid with cooling and ponrinq the solit- tion into water. The amorphous precipitate obtained separates from formic acid solrxtion in plates with blunted angles n. p. 388O (decomp. ; rapidly heated) or 280-282° (decomp. ; slomlv heated). The srtbstance is regarded as it double salt of ctinhenyl su1phat.e (1 mol.) and diphenyl sidphite (3 mols.) havinq the formula SO,rO*S(OPh),l %,hat ic; i t is a wlphnte of tri~henv7- o7.Aho.~iclph?crozcs m2. It iR essilv solitble in formic sulphuric and phosphoric acids in methyl sitl~hate and in alkali hvdroxides and carbonates ammonia and alkali sulnhides dissolves slightly in warm methyl or ethyl alcohol and in boiling water and is insoliihle ilt all other Common solvents.It is converted by alcoholic hydro- chloric acid a t 70° into the rhloride of tri~honvbortho v ~ t p f i w o ~ ~ ~ nrk'. 8((3Ph),CT long. prismatic needles m. p. 356O (decamp.) snrl in clilntfi potassiirm hydroxide mltition by a soltition of Fyrirlinei. 74 ABSTRACTS OF CHEMICAL PAPERS. hydrochloride containing a11 excess of pyridine into trip7,eibylortito- sulphurous acid OH*S(OPh) an amorphous powder i n p. 233O. The last substaiice is amplioteric. Its acidic character is weaker than that of carbonic acid whilst it6 basic properties are such that a hot 50% alcoholic solution has an alkaline reaction towards litnius.The three phenyl groups are not eliminated by hydro- lysing agents. By treating an alcoholic suspension of the acid with the requisite acid the bromide S(OPh),Br needles m. p. 241-242O (decomp.) iodide short needles m. p. 194-195O (reddening) nitrate hair-like needles m. p. 160-161O (decomp.) acetate waxy mass and picmte yellow mass are obtained. Ethyl ti.iphcnylorthosulphite OEtt-S(OPh) amorphous powder m p. 244O (decornp.) is obt"ained from the chloride and alcoholic sodium ethoxide. The szclphate 80,[0*S(O*C,I-I,~~e),l crystals In. p. 296O (decomp.) prepared from di-o-tolyl sulphite and the correspond- ing sulplzate m. p. 3 1 5 O (decornp.) prepared from di-m-tolyl sulphite are obtained in the same way as the phenyl analogue; the latter yields tl.i-m-toZ?/lorthos~~l~~h~~.ous acid amorphaus powder m.p. 2 6 7 O (decornp.) by treatment with pyridine hydro- chloride as above. The colourless amorphous szrlphate m. p. 232O (decornp.) obtained by pouring a solution of dithymyl sulphite in concen- trated sulphuric acid into water is regarded as a mixed anhydride of sulphuric dithymvlortliosulphurous and trithpylortho- sulphurous acids (C,,l"i,,*O),S.0*S02*0.S(O*C,,R,3),.0H. It is soluble in alcohol but by treating its solution in aqueous-alcoholic potassium hydroxide with alcoholic sulphuric acid a szdphate SO,[O*S(O*C',,H,,),f amorphous powder m. p. 280-281* (decomp.) is precipitated which is insoluble in alcohol. The in- soluble sulphate yields trcth?/rn?/lort?~os?Ilplt.2lrolra acid amorphous powder m.p. 274-275O (decornp.). by ths pvridine hydrochloride method whilst t-he soluble sulphate by treatment with alcohol and the requisite acid yields the chloride SCl(O*@,,R,,) amorphous powder darkening at 295-300O without. melting bromide small crystals decornp. 330-340° iodide crvsta'ls. and nitrafe small rectangular plates blackening a t 285-290° without melting. c. s. Thiophenol in Synthetic Phenol. G. CAPPELLI (Gaxzetta 1918 48 ii 107-113).-The repulsive odour exhibited by some samdes of synthetic phenol is sometimes attributed to the presence of thioplien in the benzene used in the manufacture. The author shows that such odour is due to a small pronortion of thiophenol formed from particles of sodium benzenemlphanate which during the fusion with alkali. escape contact with t*he latter and underqo deoxidation a t the surface of the iron in the manner observed bv Stenhouse (,4n?zden.1866 148. 284 1869. 149 42). The phenol may be freed frcin this impuritv by fusing it adding a 'little alcohol to keep it liquid and then addinp per kilo. of Phenol about 50 C.C. (more if continued formation of !xscipitate shows it to he netes-ORGANIC CHEMISTRY. i. 75 sary) of 1076 alcoholic mercuric chloride solution. The excess of mercuric chloride is eliminated by leaving the clear liquid for a couple of days in contact with copper turnings o r foil; the mercury deposited on the latter may be recovered by distillation. Frac- tional distillatioii of the decanted solution gives (I) below 179* water and alcohol aiid (2) a t 179-183° pure phenol with its characteristic odour.T. H. P. Organic Salts of Bivalent Chromium. G. SCAGLIARINI (Atti R. ilccad. Liizcei 1918 [v] 27 ii 87-89; Gmzetta 1918 48 ii 148-150) .-The greyish-green salt obtained by Calcagni (A. 1913 i 1154) either from chrome alum and sodium salicylate or from chromic hydroxide and salicylic acid and regarded by him as a chromous compound is probably a salt of tervalent chromium in which also the phenolic hydroxyl groups take part in the salt- formation. All other chrornous salts of organic acids including those now described by the author are red. Cfhroinozcs salicylate C,,H.t<-O->Cr,3H20 coo0 prepared by re- ducing chrome alum solution with zinc and hydrochloric acid and adding sodiuni salicylate solution free from air.forms mall red crystals but rapidly oxidises and becomes greenish-grey in the air. Clzrornous propionate 2( C,H,O,),Cr,H,O was also prepared and analysed and the butyrate and valerate prepared. Nitro-2 4-phenylenedithioglycollic Acid and Some of its Colouring Derivatives. C. FINZI and N. BOTTIGLIERI (Gazztta 1918 48 ii 113-122).-The authors have prepared the nitro-derivative of ?r~-pheiiylenedithioglycollic [m-phenylene- dithiolacetic] acid and as this yields on reduction not an amino- acid but a ketothiazine derivative the conclusion is drawn that the nitro-group enters the benzene nucleus in the ortho-position to one of the substituents. The sulphone corresponding with the nitro-compound undergoes ring-closure on reduction still more easily the resultant compound being quite analogous to Clausz's sulphazone (A.1912 i 389) aiid being hence termed sulphazon- sulphonacetic acid. This acid has been coupled with various diazo- compounds the derivatives thus obtained CO,H*CH,*S being of different colours and serving as sub- (an- nexed formula) obtained from m-phenylene- dithiolacetic acid and gitric acid forms 2-Keto-2 3-cFihydrothiasine-6-thi~~~cetic acid (annexed formula) obtained by reducing the previous com- 8 pound forms tufts of silky white needles. m. p. 2 1 0 O ; its sodifcm salt (+ 3RaO) was prepared and analysed. 4-xitro - ni - nhPn?,tened~.~idnhonacetic NH acid NO,.C,H,( S0,*CH2*C0,H) pre- pared by the action of hydrogen per- T. H. P. /T stantive dyestuffs for silk.\ - / 4 -Nit yo- m-ph en y lenedit hiolac e ti c n cid CO,H*CH,*S NO slender yellow needles m. p. 174O. CO,H*CH,*S y \ y E 2 \/\ P oi. 76 ABSTRACTS OF CHEMICAL PAPERS. oxide on the nitro-acid forms long white needles m. p. 199O (decornp.). On reduction with tin and hydrochloric acid it yields S~clpl~azc~n-6-suI~horwtcetic acid so2 C0,HCHI*S02f\)/\FH \ / \ P O NH which forms white mammillary masses of slender needles m. p. 219O (decomp.). p-Sulp7~ o b en z e n ea z osutphaz on- 6-sul p It ona ce tic acid so " NH obtained by condensing the preceding acid with diazobenzene- sulphonic acid forms small needles of the colour of chromic anhydride. A t 40-50° in aqueous solution it is fixed directly on silk giving a brilliant orange-yellow colour stable against soap and light; wool fixes it with more difficulty but assumes a stable yellow coloration.4-Szclp~Lona~I~thnlenenzosulphazonace tic acid SO .. NH \-/ dyes silk an old-gold ysllow stable against soap and light. SaJicytic- acid- p -G odiphe I? y 1 - p -as osdphaa onszc1ph on nce tic a cid so* forms a brownish-black colouring matter almost insoluble in water and directly colours silk yelIow k i t h an olive-green tinge. T. H. P. 4-Aminoisophthalic Acid and its Derivatives. RUDOLF WEGSCHEIDER HANS MALLE ALFRED EHRLICH and ROBERT SKUTEZKY ( M o w tsk-. 19 18 39 3 15-41 7).-4-Acetylaminoiso- phthalic acid is conveniently prepared by oxidising 4-acetu-m- xylidide with a boiling aqueous solution of calcium pennanganate ; when rapidly heated it becomes yellow a t about 270° melts a t 295-296O (corr.; decomp.) immediately resolidifies and then remains unchanged up to 350° ; when slowly heated decomposit,ion frequently occurs without visible liquefaction. (The cdciam saltORGA.NIC CHEMISTRY. i. 77 [+3H,OJ is described.) During the heating one molecule of acid loses its acetyl group and the residue reacts as an amine with a second molecule of acid yielding thereby ri-keto-3-phe~~l-2-methyl- 3 4dihydropzcinazoline-6 2' ; 4t-tricarboxylic a*cicE (annexed formula) m. p. 416O CO,H (corr.). [Ethyl ester m. p. 332O (corr.) after 'co2K sintering a t 33OO.l The esters of 4-acetyl- aminoisophthalic acid were prepared by acetylation of the corresponding esters of the aminotacid methyl 4acetyl- c7*mimisophthdlate has m. p. 125-126"; 1-methyl 3-hydrogen 4-acetylaminoisophthalate melts a t 218-219O ; the corresponding normal and acid ethyl esters have m.p.'s 109-llOo and 193-5-194'5O respectively. Attempts to esterify the acetylamino- acid by methyl alcohol and mineral acids led as in the case of acetylaminoterephthalic acid (Wegscheider and Faltis A. 1912 i 463) to the deacetylation of the acid. 4-Aminoz'sophthalic acid is most conveniently prepared from its acetyl derivative by esterifying the latter with methyl alcohol and mineral acid and subsequent hydrolysis of the puri6ed amino- ester so formed; it has m. p. 336-337O (corr.; decomp.). The dimethyl and dietlzyl esters have m. p.'s 131*5O and 79-80° re- spectively whilst I-methyl 3-hydmgen $-aminuisophthalate and the corresponding ethyl ester melt a t 224-225O (decomp.) and 216-5-218O.The acid behaves contrary t o the usual rule since it yields the same ester by treatment with mineral acid and methyl alcohol and by half-hydrolysis of the normal ester. The methylation of the amino- and acetylaminoacids and their esters has been studied under varying conditions. 4-Dimethyl- aminoisapht hnilic acid is most conveniently prepared by treatment of the corresponding dimethyl ester with methyl sulphate a t looo and hydrolysis of the ester (m. p. 70°) with alcoholic potassium hydroxide; its m. p. depends greatly on the mode of heating. The silver s d t is described. Methylation of the free acid is very in- complete either by the action of methyl sulphate on the dry potassium salt in the presence of potassium hydroxide solut>ion or in the presence of water and barium carbonate.The use of methyl iodide and potassium hydroxide dues not lead t o better results. 4-Acetylaminoisophthalic acid is methylated with still greater difficulty yielding small amounts of dimethylaminoi.s~phtha1ic acid. Methyl sulphate does not act on dimethyl 4-acetylaminoi~o- phthalate below 1 1 5 O ; a t 120-124°. however trimethyl 4-heto-3- p?w?~yl-2-m e t 11&3 4-&78~1~?9-0q 7 1 in a OJ~TLC-6 3 f 4 !- tm-carh o my la8 4 m. p. 305'5O is produced. 4-A cetylmet 7~~ylnn-tinoisop~~tTtalic acid is prepared by the action of methyl iodide on the sodium or preferably the potassium salt of dimethyl 4-ncetylaminoiso~~t~a~a~e and subsequent hydrolysis with alcoholic potaPsiiim hydroxide solution ; it frsrms colourlew __- CO co,&/ AN-/ 1 \1 AM*\--/ \/\/ Ni.78 ABSTRACTS OF CHEMICAL PAPERS. needles the m. p. of which depends on the mode of heating. 4-Methy2aminoiso~~~thalic acid has m. p. 297.5-298'5O (carr.) after decomposition a t 29Go when placed in a bath preheated to 293O; the corresponding dintethyl ester melts a t 115O. l-Met?qZ 3 -It ydrog e n 4- nt e t h y laminoisop?s t hnla t e m. p . 2 38-2 3 (decom p. ) is obtained by the partial esterification of 4-methylaminoisophthalic H. w. Colour and Chemical Constitution. 111. Derivatives of the Unknown op-Phenolphthalein.. JAMES A1 OIR (I'ralzs. Roy. Soc. S. Africa 1918 7 123-127. Compare A. 1917 ii 349 557). -The preparation and absorption spectra of a number of phthalein derivatives containing one hydroxyl group in the o?*tho- and a second in the para-position to the central carbon atom are described. Thus phe~~ol-p-cresolpF,IhuEein is obtained by heating a mixture of p-cresol and phydroxybenzoylbenzoic acid in the presence of zinc chloride.The following substances are prepared in a similar manner op-phenolpWthalei~m-carboxylic acid and its methyl ether hydroxydipkeny1p~Lth~li~e carb oxylic acid m-amin 0- op-phenolph t ?salein* the corresponding m-me t h ylamin o - derivatives and its o-carboxylic acid m-phe~~l-op-phenolpTLth.aleil7 and m-nitro-op-phenol~hthalei~. Attempts to prepare op-phenol- phthalein by reduction of rn-iodo-op-27henolphth~lein did not yield the desired result and further work in this direction was aban- doned since it was discovered t-hat p-hydroxybenzoylbenzoic acid yields a phthalein-like substance when heated a t above ZOOo or a t a lower temperature in the presence of concentrated sulphuric acid; this substance which resembles phenolphthalein very closely can also be obtained by heating phenolphthaleinoxime with a mall quantity of sulphuric acid a t above ZOOo and it therefore appears probable that the so-called oxime is in reality the p-hydroxyanilide of p-hydroxybenzoylbenzoic acid.It is possible to find a particular strength of alkali in which any phthalein gives a colourless solution in the cold but which becomes coloured on heating to near the boiling point and again fades on cooling and keeping. For ordinary phenolphthalein the concentration of alkali is slightly above normal ; tetraiodo- phenolphthalein requires a much weaker alkali whilst a-naphthol- phthalein requires about 2N-alkali.Phenolphthalein-o-carboxylic acid is coloured faintly pink by ammonia and deep violet-pink by alkali hydroxide; as an indi- cator it resembles thymolphthalein but has a more favourable colour. The comesponding dicarboxvlic acid is useful in proving the presence of definite caustic alkalinity a t about N/100. acid with methyl alcohol and hydrogen chloride. H. W. Constitution of the Hydrazone of Benzaldehyde . J. SUREDA BLANES (Amal. Fis. Quim. 1918 16 707-718).-The author summarises the evidence for and against the cyclical formula of Curtins for the aliphatic diazo-comporrnds RR-C!<+ 8s corn- NORGANIC CHEMISTRY. i. 79 pared with the lineal formula RRCNiN suggested by Angeli and later by Thiele.The easy oxidation of hydrazones to diazecompounds suggests the investigation of the constitution of the former substances. The hydrazone chosen for preliminary examination is that of benz- aldehyde which on oxidation gives phenyldiazomethane. The alternative structures which may be assigned to benzaldehyde- hydrazone are CHPh<hH and CHPh:N*NH,. NH The following reactions establish the fatter formula (1) Benzaldehydehydrazoii e aEd phenylcarbimide CHPh:N*N€€ +- CONPh = NHPh*CO*NH*N:CHPh. (2) Benzaldehydehydrazone and phenylthiocarbimide CHPh:N*NH + SCNPh = NHPh*CS*NR*N:CHPh. (3) Benzaldehydehydrazone and diphenylketen CHPh:N*NH + CPh,:CO = CHPh,-CO*NH*N:CHPh. The product of the last reaction forms white crystals insoluble in alcohol ether o r benzene slightly soluble in light petroleum and glacial acetic acid m.p. 196O. These reactions are incom- patible with the cyclical formula for benzaldehydehydrazone and therefore the lineal formula must be assumed. W. S. M. Anilinoquinones . HERMANN SUIDA and WILHELM SUIDA (8nnden 1918 416 113-163).-The generally accepted view thatl anilinoquinones are always formed by trhe transformation of an additive compound of the type N HAr*CH<C('~~)'cH>CK.~HAr CH . C (OH) into NHAr*C<~~.~>C."HAr with the removal of four atoms of hydrogen which reduce two further molecules of the quinone is found not to hold. I n so'me cases the reaction recognisably passes through the monoanilide. I n the case of the simplest and most reactive components monoanilides are smoothly formed in accord- ance with the equation 2C,H,02 + NH,Ar = C,H30,-NHAr + C6H!(OH)%.The capacity of the group *CO-CH:CH-CO* to form anilincr-compounds must be connected in some way with the struc- ture of the benzene nucleus because maleic and fumaric esters and the cis- and trans-modifications of dibenzoylethylene in which this group occurs do not react in this way with aromatic amines. Under the conditions of the authors' experiments the following generalisations have been made. p-Benzoquinone in aqueous faintly acetic acid solution yields with all pronouncedly basic primary and secondary aromatic arnines anilinoquinones pre- dominantly and even sometimes exclusively monoanilinoquinones. The intensity of the reaction diminishes as the basic character of the amine is weakened by the entrance of acidic substituent,s.Thus the strongest bases (aniline and its homologues diamines etc.) yield mono- and di-anilides simultaneously the weaker bases (secondary amines iiitroanilines etc .) yield only monoanilides,i. 80 ABSTRACTS OB OHEMIUAL PAPERS. whilst the weakest bases do not react in aqueous solution. Tolu- quinone yields only monoanilides and s-xyloquinone does not react. I n alcoholio solution p-benzoquinone forms only dianilides ; monoanilides are present in the mother liquor only when the basic component contains acidic substituents. Tolu- and naphtha- quinones yield only monoanilides and s-xylquinone none. The reactions also proceed in glacial acetic acid solution. There- fore by a suitable selection of the solvent and of the temperature it is possible to make a quinone react once or twice with an amine or a monoanilinoquinone to react with a different base producing a mixed dianilinoquinone. The following new derivatives of p-benzoquinone have been pre- pared 5-anili.r~o-2-a-naphthylamin 0- CBH,,O,N yellowish-brown powder m.p. 278-280° ; 2-p-chlocr.oanilino- sepia crystals decomp. about 1 1 5 O ; 2 5-di-p-chioroaizilino- pale brown crystals ; 2-0-tolu- idino- dark violet-brown crystals m. p. 100-104° ; 2 5-di-o-tolu- idino- rust-red needles m. p. 250-252O ; 2-m-toZuidino- dark violet- brown crystals m. p. 90-100° (decomp.) ; 2 5-di-m-toZuidino- crimson-red needles m. p. 256-257O ; 2-p-toZuidino- aggregates of violebblack needles m.p. 134-137O (bath a t 134O) ; 2 5-di-p- toluidilzo- crystals m. p. 31W; 2-p-acetylaminmnili/no- dark crystals ; 2-as-m-xyZidino- reddish-brown crystals m. p. 1 0 2 O ; 2 5-di-as-m-zylidino- pale brown crystals M. p- 297-300° ; 2-$-cumidino- brick-red crystals m. p. 90-106' ; 2 5-di-$- cumidino- pale red crystals xn. p. 301-303" ; Z-o-anisidino- brownish-violet leaflets with metallic lustre m. p. 1 1 4 O (not sharp). With the object of preparing monoanilides soluble in water the aminobenzenesulphonic acids have been utilised. These do not react satisfactorily with p-benzoquinone but give good results with the less reactive 2 6-dichloro-~benzoquinone. By adding t o a hotl alcoholic solution of this a hot aqueous solution of sulphanilic acid (1 mol.) and subsequently an aqueous solution of sodium acetate (1 mol.) and then barium chloride barium 2 6-dichZoro- 5 -n n irin o -p-5 enz o pzt in one-p f -su2 phona t e ( C,HCI,O,oNR* c6134* SO,),Ba copper-red leaflets is obtained the mother liquor containing 2:6-dichloroquinol.If the temperature is about 60° at the beginning and about 30° a t the end of the experiment the pro- duct is mainly the barium hydrogen. salt. An aqueous solution of the barium salt a t looo rapidly acquires chlorine ions and deposits a blackish-brawn powder which appears to be the barium salt of ~-chlorcu-5-p-sulphoa7til~.no-6-hy~oxy-~-be~zoqu~none. By adding sulphanilic acid to a hot aqueous solution of the first-mentioned barium saltl the barium hydrogen salt of 6-chZoro-2 5-dianilino-p- b enzoqzcinone-p'pN-d~sul~~onic acid is obtained 8s a brovnish-black powder.2 -&Wet hyladino-p- h enz oqzcimmze c?6H,0,*NMePh prepared by adding a cold 50% acetic acid solution of methylaniline (1 mol.) to an aqueous solution of p-benzquiqane (2 mols.) foms dark redOR(XANI0 (;1HEMISTRY i. s1 ueedles LII. p. 125-130O. 2 5-L)imethyZan/ilino-p-ben~~p.u.iraone leaflets m. p. 205O is obtained from itx components in alcoholic solution. * 2-~lethylanilin~pbenzquinone like all other monoanilino- quinones of the same type yields mixed dianilinoquinones by tri- turation with an aromatic base or by warming with it in alcoholic solution. The following 2-methylanilino-p-benzoquinones of this kind have been prepared 5-am-Zino- NhlePh*C6H,020NHPh orange-red crystals ; 5-p-carboxyar~ilino- dark red leaflets ; 5-m-carb oxyanilino- brownish-red crystals ; 5-m-chloroaniZino- garnet-red needles ; 5-o-~~ydroxya?ailino- brown leaflets ; 5-m-hydr- oxyandino- brownish-yellow metallic crystals; 5-p-bromoandino- red crystals ; 5-p-suZphoanilino- prepared in the presence of sodium carbonate and 3% hydrogen peroxide and isolated as the sodium salt ; 5-a-naphthylamino- dark brown crystals ; 5-j3-naphthylamino- dark violet-brown crystals; 5-p-Benaeneazounilina- violet-brown crystals.2-Methylanilinepbenzoquinone (2 mols.) and p-phenylenedi- amine (1 mol.) react in boiling alcohol t o form a substance C&&aO4N4 brownish-green crystals probably (NMePh~C,H20,*NH),C,H4 whilst in the ratio of 4:1 in alcohol glacial acetic acid or nitro- benzene or by moistening the mixture of the two compmenb with a little solvent and warning on the water-bath a dark green crystalline substance [(NMePh*C6HzOz)zN],C,H4 is obtained 2-Methylanilino-p-benzoquinone and benzidine react in warm m.p. 250-260°. alcohol t o form the compound NMePh*CsH,O,*NH*C,H,*C,H,*NH brown needles m. p. 215-218° which is converted by chloranil in glacial acetic acid solution into the substance C1,Cl,O,( NH*C~H,°C,H,*NHo~6H,0,.NMePh)z crystals. 2-Methyl-ptoluidino-pbenzoquinone and pphenylene- diamine in hot alcoholic solution yield a dark green substance probably (C,R,*NMe* C,H,Os*NH),C,H,. 2-Ethzylanilino~p-benzoqui72.one forms dark needles m. p. 85' with previous sintering. 2-Renz?/ltznilino-p- b enzoquimone f o m s almost black needles m.p. 60-70° whilst 2 5dibenz?ylaniZino- p-bermspinme C,R,O,(NPh*CH,Ph) crystallises in blood-red needles m. p. 155-1560. 2 - M e t h y Z - p - t o Z ~ i ~ ~ o - p - b e n z o ~ ~ ~ ~ n o ~ a forms reddish-yellow needle9 m. p. 1 2 7 O and 2 5-dimethyl-p- fo.hidino-p-h enzoquinon e yellowish-brown rhombic plates m . p. 20 6O. OH*C,H,*NMe*C,H,O and 2 5-di-o-Ttpdroxymet hplanil~~o-p-benzol).?l.in~nc are described. 2-0 -Hydro xyme r5 hqlrnJin o-n-b en a nqilinone A table j s given of the colorations of the anilinoquinoneq in Polymerisation PhenomenR in the Simple 'Monoanilinn- benzouuinoaes . HERMANN SUIDA (AnmZen 191 8 4 16 I 164-181. Compare preceding abstract) .-The monmnilinoquin- concent'rated sulphuric acid. c. s.i. 82 ABSTRACTS OF CHEMICAL PAPERS.oues derived from priniary bases are only stable in the pure dry state ; they polymerise in solution. Dianilinoquinones and also monoanilinoquinones derived from secondary bases show no tendency to polymerise. The polymerisation is probably repre- sented thus 2C,H,0z*NHhr + C,H,O,*NAr-C,H,(OH),*NHAr ; the b e r i c meriquinoiioid form produced can undergo further polymerisation. The polymerisation is brought about by heating the monoanilinoquinone at its m. p. by heating with water or dilute acetic acid by prolonged boiling with alcohol o r by exposing its cold alcoholic solution to intense light. Thus 2-ptoluidino-p- benzoquinone yields the dimeride (C,3H,,0,N) m. p. 265-267O (in carbon dioxide) from which by reduction with alcoholic stannous chloride is produced the quinoL7 C,H,(OH),*N( C7H7) *CcH,(OH).7*NIIP.C,T~~ pale yellow crystals m.p. 236-237O (in carbon dioxide). Dimeric 11- tolziidino-p-71 enzoqzci?zone C,H,O,*N( C,H,)-~~H,O,*NH*C,H; produced by auto-oxidation by boiling the dimeric meriquiizone in glacial acetic acid or nitrobenzene forms violet-black crystals with green lustre which remain unchanged a t 400° ; the oxidation is also effected by ferric chloride in dilute alcoholic solution. c. s. Anilinoquinones from Benzoquinone and the Nitro- anilines . GUIDO MEYER and HERBIANN SUIDA (Annalm 1918 416 18l-l88~.-The nitroanilines do not react as easily as aniline with benzoquinone. I n cold aqueous solution a reaction between the nitroanilines and p-benzoquinone is only observed when the nitroaniline is used in the form of its hydro- chloride in the presence of an excess of hydrochloric acid; in all three cases reddish-brown crystalline additive compounds separate after some hours but if kept in contact with the mother Liquor for several weeks change into the mononitroanilino-p-benzoquinones. The latter are obtained immediately from the nitroanilines and p-b enzoquinone in boiling aqueous solution.2 -m-.lVi troanilin o - p - bemoquinorze and the p-nitro-compound are daik brown and do not crystallise well. The o-dro-compound is less readily obtained. All three compouiids have indefinite m. p.'s between 290' and 300° and develop with sulphuric acid a reddish-violet coloration which turns blue on warming. I n cold alcoholic solution a reaction occurs only between m-nitroanihe and p-benzoquinone whereby the additive com- pound is formed.I n hot alcoholic or better hot glacial acetic acid solution the 2 5-~~nitroanzililto-p-be?zzoqzti?zortes decomp. 310-360° are obtained. The nitroanilino- and dinitroanilino-p-benzoquinones are not attacked by mild reducing agents. Tin and hydrochloric acid con- vert the latter into phenylenediamines and aminoanilinoquinols which could not be isolated. p-Nitroianilinobenzoquinone was reduced by tin and hydrochloric acid to a base which was isolated as the sulpha te C,H,( OH),*NH* C6H,*NH,,2H,S0 prismatic needles; the base itself could not be isolated. @. s.ORGANIC CHEMTSTRY. i. 83 Action of the Isomeric Chloromethylanilifles on Benzo- and Tolu-quinones. HEINRICH TEUTSCHER (Aiznalen 1918 41 6 139-202.Compare Suida and Suida this vol. i 79).-The chloromethylanilines in aqueous faintly acetic acid solution yield exclusively monoanilinoquinones with p-benzo- and tolu-quinones ; as usual a second molecule of the quinoiie is reduced to the quinol. Additive products could not be isolated although they are un- doubtedly formed. I n alcoholic solution p-benzoquinone yields dianiliiioquirioiies whilst toluquiiroiie yields only the monoanilino- quinone; here again evidence (colour change) has been obtained of tahe intermediate formation of additive compounds. Toluquinone being a weaker oxidisiag agent than p-benzoquinone reacts more slowly with the aromatic bases. Of these o-chloroinethylaniline reacts most slowly and the p-ccmpouizd most rapidly.2-p-C Jdorome t h ylalzilino-p-b en z oquiizone C,H,O,*NniZe*C,H,Cl is a dark red crystalline powder in. p. 145O the m-chloro-compound a reddish-brown powder m. p. 1W0 sintering a t 120° and the o-chZw-0-compound crystallises in pale red needles m. p. 133O (decornp.) sintering a t 60°. 4-p-Chloro.meth?~Z~7iilz;rzotolzcquiiq~e forms a dark red crystalline powder with metallic lustre m. p. 156O (from aqueous solution) and dark red needles M. p. 184O (decornp.) (from alcoholic solution) and the o-chloro-compound red leaflets with metallic lustre m. p. 146O (decomp.). 2 5-Di-p-chlororrzet~~Za~z'l~no-p-beszeogzcinone forms deep bronze leaflets with metallic lustre m. p. 2 2 3 O the m-chloro-compound deep pellow leaflets m. p. 1 9 8 O and the o-ch7uro-compound reddish-bronze leaflets with metallic lustre m.p. 2 5 8 O . 2 5-Di-2' 4'-dz'chlorornerh?/1nrzilino-p-bensoguinone which re- quires the presence of hydrogen peroxide for its quick preparation forms brick-red leaflets m. p. 2400. c. s. Citronellol. H. J. PRIM (Chenz. Weekblad 1918 15 1378-1 380) .-Distillation of citronellol yields two fractions one with b. p. 217-219O and the other with b. p. 219-221O. The liquids probably contain isomerides but these cannot be separated by fractionation. When free from geraniol and other substances but containing these isomerides citronellol of maximum purity should have DIO 0-867-0.869 and its index of refraction should be 1-4586-1.4589. A. J. W. Constituents of Oil of Cassia. 11. FRANCIS D. DODGE (J Ind. Eng. Chern. 1918 10 1005-1006 Compare A.1916 i 155).- Oil of cassia was found to contain cinnamaldehyde (75 to go%) cinnamyl acetate phenylpropyl acetate ( a ) o-methoxycinnam- aldehyde salicylaldehyde (0.1 to 0*2:6) coumarin benzoic acid salicylic acid an unidentified liquid acid benzaldehyde and o-methoxybenzaldehyde. [See further J . Soc Chem. I d . 1919.1 w. P. s.i. 84 ABSTRACTS OF CHEltII(3AL PAPERS. Constitution of Substances from Guaiacum Resin. G. SCHROETER L. LICHTENSTADT and D. IRINEU (Ber. 1918 51 1587-1613).-!L'he milk test with extract of guaiacum resin is not entirely satisfactory since it depends on the quality of the extract. Before examining the chemistry of the blue compound it is neces- sary to determine the structure of the substance (or substances) in the resin which produces it.The two substances of unknown constitution obtained by the dry distillation of guaiacum resin are guaiene and pyroguaiacin. The latter is known to he a hydroxymethoxy-derivative of the former (Herzig and Schiff A 1897 i 254; 1898 i 327 530). Guaiene is now proved to be 2 3-dimethylnaphthalene by synthesis. P-Phenylisopropyl bromide CH,Ph*CHMeBr b. p. 107-109°/ 16 mm. D16a4 1.2908 obtained from the alcohol and hydrobromic acid (saturated a t 0.) a t looo reacts with ethyl malonate and alcoholic sodium ethoxide on the water-bath to form ethyl P-phercyl- iso~opyZmaZomnat e CH,Ph*CHMe*CH (CO,Et) b. p. 182-1 83O / 14 mm. D16.4 1.0673. This is converted in the usual manner into ethyl ~-pheizy~iso~opylmeth.ylmalonate b. p. 188O f 16 mm. Dl8.4 1.0505 which yields the acid CI3Hl6O4 colourless crystals m.p. 158-160O (decoxnp.) by hydrolysis. The acid heated a t 170-1 90° yields y-phenyl-aP-dimet hgylbutcyric acid CH,Ph* CHMe*C'HMe*CO,H b. p. 179-180-5°/13 mm. the acid chloride of which b. p. 136-143°/13 mm. is converted in light petroleum (b. p. 60-70°) by aluminium chloride into 1-&lo-2 3-dimethyZLl 2 3 4-tetra- h,ydrmaphthdene b. p. 148--150°/17 mm. m. p. -lo D21 1.019. This is reduced by sodium and alcohol t o 2 3-dirnethyltetrahydro- naphthol m. p. 110-114° h. p. 148-152O/18 m. which loses water a t above 200° and yields 2 3dimetkyl-~~-di~~yd.ronaphthalene b. p. 120-140°/16 mm. the dibronzid'e of which is converted by boiling methyl-alcoholic potassium hydroxide into 2 3-dimethyl- naphthalene m.p. 104-104.5° (picrate m. p. 123-124O) which is identical with guaiene. Pyroguaiacin is converted by boiling alcoholic potassium hydr- oxide and methyl sulphate into pyroguaict.cin methyl ether C,IH,,(OMe) leaflets m. p. 149-150° the oxidation of which by sodium dichromate and glacial acetic acid a t 95-115O yields pyro- guaiacinguinme methgl ether C,,H,,04 yellow needles m. p. 241-242O. For reasons given below pyroguaiacin is almost certainly 6-hydroxy-7-methoxy-2 3-dimethylnaphthalene. Guaiaretic acid the extraction of which from guaiacum resin by ether is described in detail has the formula C,,H,,O (Henig and Schiff koe. cif. give C,,H,,04) and is now found to be optic- ally active [alp - 9 4 O in alcohol and unsaturated. It is converted by methyl sulphate and hot aqu ems-alcoholic potassium hydroxide into R methy2 ether C,,R,,(OMy) cdourless needles m.p. 94-950 fa$ -92O in alcohol which is reduced by sodium and boiling alcohol or in solution in tetrahydronaphthalene at 180° by hydrogen and a nickel catalyst under a pressure of 40-50 Slog.ORGANIC CHEMISTRY. i. 85 to hychoyiiaiaretic acid metkyl ether C,8H,8(OMe) ; in both cases a mixture of the i-acid crystals m. p. 100-lO1° and the l-acid fiat prisms m. p. 86-87O [alp - 2 7 O in alcohol is obtained. Herzig and Schiff’s norguaiaretic acid (loc. cit.) obtained in poor yield from guaiaretic acid and boiling hydriodic acid is obtained in much better yield from hydroguaiaretic acid methyl ether and is reconverted ivtto this by methylation; it is therefore norhydroyuaiaretic acid.i-Dib7.ornoliydroguaiaretzc acid methyl ether C18H,,Br2(0Me) colourless needles m. p. 130-5-131.5° is obtained by the bromin- ation of i-hydroguaiaretic acid methyl ether or guaiaretic acid methyl ether in glacial acetic acid dehydroguaiaretic acid methyl ether (below) being also formed in the latter case. 1-Dibromo- hydroyuaiaretic acid methyl ether colourless crystals m. p. 121-122° [a] -420 in alcohol is obtained by brominating I-hydroguaiaretic acid methyl ether. i-Dinitro hydrogztaiare t i c acid methyl ether C,&f,,( NO,),( OMe) yellow crystals m. p. 150-151° obtained by adding nitric acid D 1.4 t o i-hydroguaiaretic acid methyl ether or guaiaretic acid methyl ether in glacial acetic acid solution is smoothly reduced in tetrahydronaphthalene solution by hydrogen and nickel t o i-diamiizohydroguaiaretic ucid methyl ether faintly violet needles m.p. 124-125O; attempts to resolve this base by means of d-t,artaric acid were unsuccessful. l-Dinitrohydroguaiaretic acid methyl et7zer yellow crystals m. p. 122-123O [a] - 4 9 ~ 5 ~ in glacial acetic acid is obtained by the nitration of I-hydroguainretic acid methyl ether. The reduction of I-guaiaretic acid and of its methyl ether yields a mixture of optically active and inactive hydro-derivatives and therefore possibly racemisation has occurred. Since it is shown however that the hydro-derivative. racemise with great &fficulty an alternative explanation of the formation of the inactive modif- cation is that a second carbon atom is rendered asymmetric by the reduction the inactive hydro-derivative being internally compen- sated.In favour of the symmetric structure thus postulated is the formation of the probably symmetrically substituted dibrorno- and dinitro-derivatives and the failure to resolve the diamina- derivative. Hydroguaiaretic acid methyl ether would therefore be a~-diveratrvl-fly-dimethylbut~ane C,R,(OMe),*CR,*CRMe*C~~~e*@n,*C,PI,(OMe) and guaiaretic acid methyl ether mould have the formula C,H,(OMe),=CB~CMe*CHMe~CH,*C,H,(U~le) the positions of the two methyl groups being determined by the fact that paiaretic acid can be converted through pyroguaiacin into guaiene (2 3-dimethylnaphthalene). An extraordinary transformation of guaiaretic acid methyl ether is its rechcction to hydroguaiaretic acid methyl ether by potassium pemanganate in acetone-glacial acetic acid solution veratric acid also being formed.The explanation is found in the action of Hubl’s iodine solution on guaiaretic acid methyl ether (1 mol.),i. 86 ABSTRACTS OF CHEMICAL PAPERS. whereby a mixture of i-hydroguaiaretic acid methyl ether and dehydroguaiaretic acid methyl ether C,,H2,O colourless crystals m. p. 178*5-179O optically inactive is obtained in the proportion of 1 2 by the consumption of 1 mol. of iodine. This change is represented by the equation 3 C H ( O M e ) * ~ H @ M e * ~ ~ M e * ~ ~ 2 * ~ ~ ~ ~ ( ~ M e ) 2 = C,H3(OMe),*CH,*C13N6e.CHMe.CH,.C,H,(OMe)~ + It is probable therefore that in the preceding reaction with potassium permanganate a portion of the guaiaretic acid methyl ether undergoes ring closure to a naphthalene derivative (which is then oxidised yielding veratric acid and other products) the hydrogen produced reducing another portion to hydroguaiaretic acid methyl ether which is stable towards pemanganate.By treatment with 2N-sodium hydroxide and methyl sulphate guaiaconic acid yields a methyl ether an amorphous yellow powder m. p. 94-10Z0 softening a t 82O which unlike guaiaconic acid does not develop a blue colour with lead peroxide. By oxida- tion with potassium permanganate in acetone-glacial acetic acid. solution the ether yields a comparatively large amount of veratric acid and other products which were not identified. Believing at first that guaiene was 1 2-dimethylnaphthalene the authors synthesised this substance as follows.By treatment of their sodio-derivatives with methyl iodide in warm benzene the P-phenylethylmalonic esters yield respectively methyl 8-phenyl- ethylmethylmlmate b. p. 178-180°/18 mm. and the-ethyl ester b. p. 182-184O/ 12 mm. from which B-gF~ienylethylmethylmalo~ic acid colourless crystals m. p. 150° (decomp.) is obtained. At 150-180° the acid is converted into y-~henyl-a-methylbutyric acid b. p. 167O/11 nun. the acid chloride of which b. p. 125*/12 mm. is converted in light petroleum solution by aluminium chloride into 1-keto-2-methyl-l 2 3 4-tetrahydro- naphthalene b. p. 127-131°/12 mm. This is converted by ethereal magnesium methyl iodide into I-hyd~oxy-1 2-dimethyl- 3 2 3 4 - t e t m h ? / ~ r o n c T ~ t T ~ ~ e n e b. p.135-140°/15 mm. m. p. 64-66O. which at 160-180° yields 1 Z-dimetTt?/l-Al-dihyd.ro- ?mnTztknlene b. p. 250-251°/atm. or 114-116°/15 xnm. D17 0.9885 q$n 1.5763. The dibromde of the latter a pale yellow oil is converted by boiling met.hyl-alcoholic potassium hydroxide into 2-met 7w2-l-nt e t T~?/lene-~"-dih,~4dro72arrTtffi.c~len c b. p. 157'1 15 mm. which yields 1 2-~~methvliiapktfi.nteite b. p. 139-140°/ 15 mm. (il)ic/xte oranpe-red crvstals m. p. 129*5-130'5°) by boiling with glacial acetic acid containing hydrogen chloride. c. s. Classification of Organic Colouring Matters. M. DOMINIKIEWICZ (Cheni. Z e i t . 1918 42 549-550 562-564) .- In the method of classification proposed the substances are arranged under chief types depending on the constitution of theORGANIC CHEMISTRY.i. 87 nucleus these types being subdivided into classes. The types include the quinone type the diphenylmethane type the safranine type t.he indigo t.ype etc. Sulphur derivatives and substances of Tannin and the Synthesis of Similar Substances. V. EMIL FISCHER and MAX BERGMANN (Ber. 1918 51 1760-1804. Compare A. 1912 i 471 887; 1913 i 479; 1915 i 437).- Previous attempts to prepare pentadigalloylglucose did not lead to the desired result owing to the unfavourable properties of tho methylcarbonat,o-compounds. Recently however it has been found possible to prepare the penta-acetyl derivatives of ?n- and p-digallic acids and the corresponding chlorides in the crystalline state (A. 1918 i 172) ; from these the pe~ta-(pent~-acetyldi~alloyl)-glucoses have now been prepared as well as the corresponding penta- (digalloy1)-glucoses.Penta-(m-digalloyl)-P-glltcose is shown to be remarkably similar to Chinese tannin the only point of difference noted being in the specific rotation in aqueous solution. Since however tlie solutions are colloidal in character and their optical activity is greatly influenced by sinall factors the authors do not consider the discrepancy is necessarily fundamental. The chemistry of the pentagalloylglucoses has been further studied (compare A. 1915 i 437) and through the triacetyl- galloyl derivatives i t has now been found possible to isolate pro- ducts which consist almost entirely of the pentagalloy1 derivatives of a- and &glucose respectively. unknown constitution form two separate classes.w. P. s. The preparation o€ 1-galloylglucose C,H,(OH),*CO*O*CH*(IH (OH)*CH(OR)*C H*CH(OH)*CH,*OH I 0 I is also described this being the first acyl derivative of glucose to which a definite structure can Is0 with certainty assigned. It is in all respects identical wit.h the gfucogallin isolated by Gilson from Chinese rhubarb (A. 1903 i 355). [pen ta-ace t my-m- b e n zo yloxy b e ncoyl] chloride @,I~,(OBC)~=CO~O~C,~~(OA~)~*COCI six-sided plates m. p. 18Q0 (corr.) after slight previous softening is obtained by the action of phosphorus pentachloride on m-digallic acid in the presence of chloroform and is converted by methyl alcohol in the presence of quinoline into met.hyl penta-acetyl-nz-digallate 1x1. p. 167-168O (corr.) (compare A 1918 i 174). It.reacts with P-glucose to yield i ~ e n t c c ( i M e i a t c c - n c e t y l - ~ ~ ~ a l ~ o ~ l ~ - P - ~ ~ u c ~ ~ ~ [C,I~,(OAc),-CO~O*C,H,(OAc)2*CO],C,13[,06~ two specirneiis of which had [a] -I-3.79O and [a] +2-60° i i i s-tetrachloroethane. [Pc rbta- (pert tn-ace tyl-p-digalZoyl)-~-glucose is obtained in a similar manner; it has [a]? + 1 . 5 4 O (in s-tetrachloro- ethane) and resexnbles the nz-derivative so closely that an analytic a1 distinction is alnios tr impossible.] Pen t a-( rn -digaZlqZ)- &glucose is prepared by deacetylation of the acetyl derivative with cold aqueous sodium hydroxide a t Oo and is purified by meam of the potmsizcnz salt; according t o the method of separatiion it forms I'enta-ace tyl-m-digalloyli. 88 ABSTRACTS OF CHEMICAL PAPERS.a pale brown light amorphous powder or a compact honey-yellow brittle mass. When hydrolysed by dilute sulphuric acid it gives approximately the same amount of dextrose and gallic acid as does Chinese tannin When treated with diazomethane i t yields penta-(penta~~thyldigalloyl)-glucose which like the earlier pre- parations is not perfectly uniform but which shows a very close analogy with the methyl derivative of the natural Chinese tannin. Reacetylation of penta-(m-digalloyl)-&glucose shows that a certain amount of change (possibly isomerisation of the &glucose to a-glucose derivative) occurs either during hydrolysis or on treat- ment with acetic anhydride. Penta-(pentu-ucetyl-m-digalloyZ)-a-glucose is prepared in the same mmner as the &derivative ; individual preparations had [a]= + 30*8O + 2 7 * 7 O and + 25’5O (in s-tetrachloroethane) point- ing to admixture with varying amounts of the @-isclmeride.[The corresponding penta-(pelcta-ucetyZ-p-G?~g~lloyl)-a-g~uc~se shows the closest analogy with the ,&compound 3 Penta-(m-~,~gaZZoyZ)-a- gZucose is a pale brown amorphous powder which can only be dis- tinguished from the &glucose derivative by its specific rotation ; it has [a] +43*8O (in water) [a] +35*8O (in alcohol) and [a] +40.1* (in acetone). Acetylation of Chinese tannin yields a penta-(penta-acetyldi- gallo y1)-glucose closely similar to penta-( pen t a-acetyl-m -digalloyl)- P-glucose; the regenerated tannin however is found t o differ some- what from the original specimen. Pen~ta-(tr~ucetylgulZoyl)-a-glucose ~C,B,(OAc),~CO~,C,”,OF is prepared in the usual manner from a-glucose and triacetylgalloyl- chloride; it forms an amorphous mass having [a] +42-7O to -t 46.95O in s-tetrachloroethane.Deacetylation is accomplished by means of sodium acetate in aqueous acetone solution; the penta- galloyl-a-glucme thus obtained is distinguished from the previous preparation (by hydrolysis of penta-[t rimethylcarbona t ogallo yl] -a- glucose by alkali) by a considerably higher specific rotation in aqueous and alcoholic solution but otherwise the resemblance is very close. On treatment with acetic anhydride the original acetyl derivative is regenerated. Diazomethane converts it into penta-(trimethylgalloy1)-a-glucose identical with that previously described (Zoc. cgt.).Pentn-( trincet?/l~aZlo?ll)-8-g~ucose is a pale yellow amorphous mass which has [a]; + 5*61° o r -I- 4.lo in s-tetrachloroet,hane; when deacetylated it yields pentagallo~l-~g.Iucose having ra]; + 23-3O (in alcohol) [a]; +13*6* and +13.lo in 10% and 1% aqueous solution. When treated with diazornethane it givee a penta-(tri- methvf~alIoyl)-~-~lucose which in its properties and optical activity closely resembles the preparation previously described (A. 1915 i 438\ but which unlike the latter could not be caused t o crystalhe. ReacetyIafion yields a produet closely resembling the original substance. Rydi-olysis of the two penta-(triacetyl- galloy1)-glucoses by alkali at Oo yields a- and /3-derivatives re- wectively which are quite distinct although less so than whenORGANIC CHEMISTRY.i. 89 sodium acetate is used. (In the case of the corresponding methyl- carbonatcmompounds practically identical products were obtained when the hydrolysis was effected by alkali a t the ordinary tempera- t u e . ) Yentu-(pace toxy b enzoy1)-a-glucose [CGH4(0Ac)*CO],C”,H706 forms fine needles m. p. 158-169O (corr.) [u] +124*7O in s-tetra- chloroethane ; during the preparation considerable quantities of the P-isomeride are formed which are removed during purification. The corresponding penta-(p-hydroxybenzoy1)-a-glucose could not be caused t o crystallise but the specific rotation of the product (+ 163-4O in alcohol) was considerably greater than that previously found ; on reacetylation it yielded the crystalline acetyl derivative in excellent yield. The preparation of penta-(p-acetozybenzoy1)- @-glucose and of penta-(p-hydrozyb enaoyl)-fl-glucose is also described but the substances could not be caused to crystallise and are probably admixed with the corresponding a-derivatives. 1-Triacetyigalloyl-2 3 5 6-tetra-acetylgiucose is prepared from acetobromoglucose and silver triacetylgallate ; it f oms microscopic needles or four-sided leaflets m.p. 125-126c (corr.) after slight softening [u]g -24.4O in s-tetrachloroethane. It may also be obtained from tetra-acetylglucwe and triacetylgalloyl chloride. When dissolved in alcohol and treated with ammonia a t 20° it yields 1 -monogalloyl-fl-glucose microscopic oblique prisms or plate- lets m. p. 214-215O (corr.; decomp.) when rapidly heated 202-203c (corr.; decomp.) when slowly heated; it has {a]:- 25’6’ in aqueous solution. The product is quite distinct from the gluco- gallic acid described by Feist (A 1912 i 566 888; 1913 i 70). When reacetylated it yields triacetylgalloyltetra-acetylglucose. Its action towards enzymes has been investigated. I t s identity with glucogallin is established both by chemical tests and by measurement of the crystals. l-Gall~yl-~-glucosemtrnoacetate forms colourless nwdles [u] +10-5O (in alcohol); it has no dis- tinct m. p. but when rapidly heated is converted into a viscous turbid liquid a t about 15OC after marked softening. 1-Gdloyl-@- gZulucosetetra-acetate ( 1 ) crystallises i n needles rn. p. about 136-137O [u]= +38-7O (in alcohol) but its isolation in the pure condition is not claimed.1-Benzoyltetra-acetylglucose is prepared from benzoyl chloride and 2 3 5 6-tetra-acetylglucose and agrees in its properties with the product described by Zernplh and Lfiszl6 (A. 1915 i 651) except in specific rotation ([aE - 26.6O in chloroform). 1-o-A cet- oxyb enzoyl-2 3 5 6-tetra-ncetyzg~ucose crystallises in microscopic flat prisms. It has m. p. 116-117O (corr.) [u] -41*Oo in s-tetra- chloroethane. H. W. Structure of P-Glucosidogallic Acid. EMIL FISCHER and MAX BERGMANN (Ber. 1918 51 1804-1808).-The work of Fischer and Strauss (A. 1913 i 180) has led to the supposition that P-glucosidogallic acid contains the sugar residue attached to the p-hydroxyl group of gallic acid; this hypothesis is confirmed by its conversion into glucosyringic acid (Mauthner A.1910 i 667).i. 90 ABSTBACTS OF CHEMICAL PAPEBS. Ethyl tetra-acetylglucosidogallate is converted by diazomethane into ethyl tetra-acetylglucosyringate from which glucosyringic acid is obtained by hydrolysis with barium hydroxide; the free acid has m. p. about 225O (decomp.) when moderately rapidly heated and [a]~-18*1S0 (as sodium salt) in water. Ethyl triacetylgallata has m. p. 138-139O (corr.) instead of 132-134* (A. 1915 i 683). Ethyl hexa-acetylglucosidoganate bas m. p. 176-177O (corr.) [u]’ - 19*Oo in tetrachloroethane solution. H. W. Digitalis Substances. XXXVIII. H. KILIANI (Bey. 1918 51 1613-1639. Compare A. 1916 i 493).-The pre- liminary cryst.allisation f rom 85% alcohol is nnnecessary in order to separate the digitonin from $he gitonin in “crude digibnin srnylate” (Bey. 1916 49 701).It suffices to dissolve the crude ainylate in ten parts of boiling 50% alcohol; o n cooling gitonin material separates first and pure digitonin subsequently. A sample of “ soluble digitonin ” supplied by Merck proved .Lo be identical with a new glucoside obtained from the final mot-her liquor of the crude digitonin (loc. cit.). The sugar syrup previously obtained (Zoc. c i t . ) could iiot be made t o crystallise because the sugars in the syrup which had beeu produced in an alcoholic medium are present chiefly in the form of ethyl glucosides. After a second hydrolysis with hydrochloric acid a partial crystallisation can be effected and d-galactose obtained by inoculation ; dextrose identified as d-gluconic acid is present and apparently also a third sugarJ 3 ketose since the syrup is shown to contain oxalic and glycollic acids. (The hydro- chloric acid was removed by silver oxide and it is known thatq silver oxide acts on hexoses particularly keto-hexoses t o produce these two acids.) During the conversion of digitogenin C31H5006 into digitogenic acid CBH4*08 three atoms of carbon are removed.Their fate has not been ascertained; it is shown that they do not appear as acetone acetaldehyde malonic propionic or carbonic acid. Digitogeiiic acid has [a] - 67-1O in aqueous potassium hydr- oxide and forms a magnesium salt C28H4,0,Mg,7H,0 small hard nodules of minute needles. P-Digitogenic acid has [afD - 6 0 ~ 2 ~ in aqueous potassium hydroxide and forms a magnesium salt micro- scopic prisms and needles with 7H20.The m. p. of digitogenic acid is altered by crystallisation and is therefore no safe criterion for identification. The acid is not reduced by hydrogen and colloidal palladium amalgamated zinc and hydrochloric acid or zinc dust and acetic acid. The acid CI6H2*O7 obtained by the oxidation of digitogenic acid in about 15% yield (loc. c i t . ) is obtained in about 27% yield by oxidising the amorphous precipitate thrown down by adding water t o the mother liquor of the crude digitogenic acid. It is oxidised by potassium permanganate in strongly alkaline solutionORGANIC CHEMISTRY. i. 91 yielding an amorphous acid C15H220,,Hz0 decomp. 120-130° softening a t about 70° which forms an amorphous maynesium salt (%.E3[1@7)&gdjH2O.The mother liquor of the crude acid CI6H,O (Zoc. cit.) con- tains in addition to other substances a t least two very easily soluble acids one of which has been identified as ethylsuccinic acid. The oxidation of gitogenic acid by hot chromic acetic and sulphuric acids yields an acid C18H2806 tufts of needles m. p. 210° sintering at about 206O (calciuni salt C18Hz606Ca,2H@) an acid C19H3000 m. p. 201-202° (calciunz salt; ClsHzsO6Ca amorphous) and ethylsuccinic acid. Digitoxigenin is not reduced by hydrogen and colloidal palladium and is oxidised by chromic and acetic acids yielding a neutral substance C1,H2,0 crystals m. p. 1 8 5 O . Digitaligenin forms an cccetyl derivative c2,H,80,Ac colourless prisms or needles m. p. 201-202O (digitaligenin also has m.p. 201-202° not 210-212O as stated previously) and is reduced in aqueous methyl-alcoliolic solution by hydrogen and colloidal palladium yielding a szcb.sta?z ce C1SH2ir(or3(1,03,H2Q crystals m. p. 182-184O sintering a t 1 7 5 O which is oxidisecl by chromic and acetic acids yielding a neutral szcbstmzce C1SH2ciurs)08 stout crystals m. p. 190-192O and an acid C,,H,,O (by analysis) or CllH1603 (by titration and by analysis of the calcizcm salt) colour- The Isomeric Lactones Caryophyllin and Urson. FRANCIS D. DODGE (J. Amer. Ckem. SOC. 1918 40 1917-1939).- Comparison of caryophyllin and urson shows a very close similarity of these compounds ; in strictly chemical properties no differences have been observed but the variations in the physical properties appear to warrant the conclusion that they are isomerides of very similar structure. The balance of evidence is in favour of a lactonic constitution but in certain respects (practically instantaneous neutralisation of alkali in alcoholic solution opening of lactone ring on acetylation) an unusual behaviour is exhibited. Caryophyllin is most readily obtained in the pure state through the potassium salt and crystallises in white needles (+ 2H20) ; the anhydrous substance has ni.p. about 310° (corr.) [a]= +54-5* in alcoholic solution; in a vacuuin t u b a t 280-300° it sublimes in characteristic rosettes. The potcrssiic m salt forms well-defined prisms (+ 1.5H20) ; the anhydrous salt has [a];k” + 63.4O in ethyl alcohol + 67.7O in methyl alcohol. Analyses lead to the formula C,,E,,O,K f o r the salt and hence to (C10H16.0)3 for caryo- phyllin.The calcizcm lead magnesium zinc and szlver salts are described. Acetylation of caryophyllin under various conditions leads t o the formation of diacetylcaryophylllinic acid and acetylcaryophyllin ; the former substance is somewhat unstable but can be obtained in the pure state by evaporation of an ethereal Eolution of the crude acetylation product a t the ordinary temperature. It slowly loses acetic acid a t the ordinary temperature; and is converted into less prisms sintering a t 240-245O without melting. c. s.i. 82 ABSTRACTS OF CHEMICAL PAPERS. acetylcaryophyllin by boiling ethyl alcohol or glacial acetic acid. The potassium salt is described. Acetylcaryophyllin forms white efflorescent needles m.p. 260-265° and yields a potassium salt which is readily soluble in alcohol. A very sparingly soluble sub- stance possibly a polymeric acetate is also obtained during the acetylation of caryophyllin. Qxida tion of caryophyllin with fuming nitric acid yields caryo- phyllic acid which is shown to be a somewhat unstable tribasic acid C27H,,03(C0,H)3 giving a characteristic sparingly soluble mono-potassizim salt. When heated with acetic anhydride it yields a compound m. p. 210-213O (slight decomp.) which appears to be an acetyl dilactone C31H4606 a molecule of carbon dioxide being eliminated during the process. Urson in its general properties is very similar to caryophyllin. The most striking difference is shown by t'he potassium salts that derived from urson being freely soluble in ethyl alcohol in which the caryophyllin salt is sparingly soluble; a method of separation is based on this dissimilarity The lead zinc magnesium and am- monium ( ?) salts of urson are described.Urson diacetata (diacetyl- ursonic acid) closely resembles the corresponding derivative of caryophyllin but is in general more soluble and less stable. Ds composition to the mono-acetate occurs so readily that it was found impossible to prepare a pure compound. Acetylurson separates from alcohol in plates or prisms (I- 5H20) quite different in appear- ance from the caryophyllin compound. It was not found possible to purify the product formed by the oxidation od umon with fuming nitric acid. H. W. 4-Phenylcounarins. 11. ADOLF SONN (Ber. 1918 5 1 1829-1832.Compare A. 1918 i 4Ol).-Further examples of the formation of 4-phenylcouznarins are given. Chloroacetylresorcinol dimethyl ether m. p. 114-115O after softening a t 112O [Tambor and du Bois (A. 1918 i 395) give 119O1 is obtained by the action of hydrogen chloride on an ethereal sotu- tion of resorcinol dimethyl ether and chloroacetonitrile in the pres- ence of zinc chloride and is converted by potassium cyanide into cy~noacetytresorcinoz dimethyZ ether prisms or plates m. p. P52-153O. The latter condenses with phloroglucinol in glacial acetic acid solution under the influence of zinc chloride and hydro- gen chloride yielding 5 7-dihydroxy-2/ 4 ' ~ ~ r n e t h o x ? i - 4 - ~ h e ~ ~ ~ c o z l - marin hexagonal prisms m. p. 2 3 2 O (decomp.). Similarly c~~arcoacety2catechol m.p. 222O (decomp.) after previous softening condenses with phloroglucinol to 3' 4' 5 7-tetrahydraxy- 4-phenylcozcmarin which after being purified through the acetyl derivative forms platelets (-t 2H,O) m. p. about 270° (decomp.). H. W. Improvements in and Relating to Synthetic Drugs [Mydriatic Alkaloids]. NAGAYOSHI NAGAI (Brit. Pat. 120936). -Synthetic racemic N-methylmydriatine OH*CHPh*CHMe*NHMe,ORQAMC CHEMISTRY. i. 93 or its salts is prepared by the condensation of benzaldeliyde with nitroethane by agitation for several hours a t the ordinary tempera- ture in the presence of a small quantity of a solution of a weak alkali such as an alkali carbonate or hydrogen carbonate or phos- phate or pyridine etc. The condensation product phenylnitro- propanol OH*CHPh*CHMe*NO is separated by extraction with sther and freed from benzaldehyde by shaking the ethereal solution with aqueous sodium hydrogen sulphite.The oily residue is dis- solved in dilute alcohol the calculated quantity of formaldehyde is added and the mixture is reduced a t a low temperature by adding dilute acetic acid and zinc dust The liquid is filtered and the zinc precipitated by hydrogen sulphide; the solution is evaporated in a vacuum and the resinous residue is shaken with dilute hydrochloric. acid and ether. The hydrochloride of tlie base is obtained by eva- porating the aqueous layer and is recrystallised from absolute alcohol. This synthetic ephedrine differs in constitution from Fourneau’s ephedrine (A.? 1907 i 762) and is the racemic form of natural ephedrine. J.F. B. Alkaloids of the Betel Nut. KARL FREUDENBERG (Bey. 1918,5 1 1668-1682).-Guvacine is 1 2 5 6-tetralnydropyridine-3-carboxylic acid according to the author (A 1918 i 403) and 1 2 5 6-tetra- liydropyridine-4-carboxylic acid according to Hess and Liebbrandt (A*? 1918 i 401). The author now shows that his view is the correct one by (i) tlie direct comparison (mixed m. p.’s etc.) of corresponding derivatives of guvacine and Wohl and Johnson’s 1 2 5 6-tetrahydropyridine-3-carboxylic acid (2) by the identity of N-methylguvacine with natural arecaidine and (3) by a compari- son of dihydroguvacine with nipecotinic acid and isonipecotinic acid. Contrary to the statement of Hess and Leibbrandt dihydroguvacine differs in every way from isonipecotinic acid and is completely identical with nipecotinic acid (piperidine-3-carboxylic acid).Di- hydroguvacine has m. p. 261O (decomp.; corr.) not above 320° as stated by Hess and Leibbrandt (Zoc. cit.). The nipecotinic acid used by Hess and Leibbrandt was in reality almost pure isonipeco- tinic acid. Several other errors in their paper are corrected; for example N-methylguvacine (arecaidine arecaine) when esterified by alcoholic hydrogen chloride is not demethylated a t the nitrogen atom. c. s. The Physical Constants of Nicotine. I. Specific Rotatory HARRY JEPHCOTT Power of Nicotine in Aqueous Solution. (T. 1919 115 104-108). Some Derivatives of Pyrrole. IV. G. KARL ALMSTROM (AnnuEen 1918 416 279-290. Compare A. 1913 i 1240; 1915 1 989 ; 1916 i 568).-In some reactions 5-hydroxy-4-acetyl-1 3-di- phenylpyrrole (A.? 1916 i 568) behaves as though it were the s-keto- compound. It is not attacked by boiling alkali hydroxide and benz- aldehyde but by heating with methyl iodide and alcoholic sodium methoxide a t 100° yields a mixture of 4-acetyt-1 3-diphenyl-4- VOL.CXVI. i. ei. 94 ABSTRACTS OF CIIERIfCAL PAPERS. ~ i e t J ~ y 1 - 5 - 1 ~ ~ r ? ' o ~ o t ~ ~ colourless crystals ni. p. 115-116O (semicc11.7~ cmme m. p. 2 1 7 O [decomp.]) and 1 S-cCiphetiyl-4-meI?~yl-5-ir?/l.roEo~~ e colourless needles m. p. 113-114O. The latter of these is also obtained by heating the former with moderately concentrated sul- phuric acid and is oxidised by chromic and acetic acids t o yrhenj/l- >NPh pale yellow quadratic 11 r t Jt,yIttialeit~pJ~ ejiy1 imide l'lates m. p.106-10'i0 from which aniline and plAe/iyZnLetlbyl- rrinleic cmhyd~ide m. p. 94-9rio are obtained by boiling with alcoholic sodium ethoxide. By heating on the water-bath with 2N-sodium hydroxide and a large excess of methyl sulphate 5-lnydroxy-4-acetyl-l 3-diphenyl- pyrrole yields 1 3-diphenyl-4-methyl-5-pyrrolone and 4-uce tyl-5- rihethozy-1 3-diphenyZpyrrole7 colourless crystals m. p. lolo which forms a semicarbnzone pale yellow crystals m. p. 215O (decomp.) yields 1 3-diphenyl-5-pyrrolone by heating with moderately concen . trated sulphuric acid and is converted into 4-cinnamoyZ-5-metJioxy- 1 3-dip?heiLylpjrrole7 yellow crystals m. p. 111-112° by heating with aqueous-alcoholic sodium hydroxide and benzaldehyde.1 3-L)iphenyl- 4 - etlzyl - 5 - pyrrolone colourless plates m. p. 118-119° yields pJ~e.nylethyZmaleii~phenyl~m~~e yellow rhombic plates in. p. 79-80° by oxidatlion from which aniline and phenyrll- etliylmaleic uithydride m. p. 46O are obtained by the action of sodium ethoxide. 5-€Iydroxy4-acetyI-l 3-diphenylpyrrole does not yield crystalline products by treatment with acetic anhydride diazometliane or acetyl chloride but it reacts wit,h magnesium methyl iodide and tlien with acetyl chloride t o form a szLbstnncu CI8HlGO3N colourless EMe-CO CPh*CO Iieedles m. p. 119-120°. c. s. General Reaction of Ketones. I GUARESCHI (Gazxetta 1918 48 ii 83-98).-The author has extended his work on the condensation of ketones with ethyl cyanoacetate in presence of ammonia o r an amine (A.1902 i 819) to benzyl methyl ketone and its homologues in order to ascertain which ketones react incom- pletely or not a t all with the cyanoacetate and to study the manner in which the new compounds decompose with formation of hydro- carbons. 3 5 -Dicyan o - 2 6-dik et o -4-7 P 11 zyl-4 - m e t Ji y l i i pe r'idin e tlie 1-ammonium derivative of which is formed from benzyl methyl ketone ethyl cyanoacetate and ammonia crystallises in shining needles or prisms m. p. 255-257* and has an acid reaction in aqueous solution; its ammonium salt is crystalline and in aqueous solution decomposes with difficulty into toluene and the ammonium derivative of 3 :A5-dicyano-2 6-dik&o-4-methyl-A3-tstrahydropyridine7 ~ ~ O g C ( ~ ~ ) ' - ' c * > " ~ * .CH(CN)*COORGANIC CHEMISTRY. i. 05 With bromine water 3 5-dicyano-2 6-dil;et0-4-benzyll-iriethyl- piperidine gives a dibromo-derivative which when boiled with alco- hol best with addition of a little formic acid rapidly loses bromine yielding 3 5-dicyano-4-t~,zz;?/l-4-~tiethyltrimet7~~7e1eec~icarborfLz’.nzi~r v >NH IY~. p. 266-268’. C( CN)*CO C( CN)*CO CH,Pli*CMe < I p-P henylet’hyl ‘methyl ketone yields 3 5-dicyano-3 6-diketo-4-6- 3 5-Dicyuti 0-2 6di/kto-4- betiz;?/l-4-etZi?lll”’periclin e phenylethyl-4-methylpiperidine which has been already described. obtained from benzyl ethyl ketone forms crystals in. p. 222-226O wliich absorb bromine giving the dibromo-derivative. The latter loses its bromine when boiled with alcohol and formic acid yielding 3 5-clicyuno-4-bett syl-4-met h yltrimethylen eclicnrboni~ri ide >NH C(CN)*CO C(CN)* co CH,Ph*CEt< I m.~ 4 . 226-228O. 3 & 5 -1) icycr n o - 2 6 -cli?c e t 0-4-/3-ph e IZ yle t lql-4-e t hylpz*pe ridin e prepared from /3-phenylethyl ethyl ketone forms crystals ni. p. 181-183O. forms colourless needles m. p. 248.5-249.5O. When treated with alcohol and formic acid its dibromo-derivative decomposes yielding a colourless crystalline compound m. p. 255-257O which is prob- ably 3 5-dicyan~-4-benzyl-4-isopropyltrimethylenedicarbonimide. Benzyl isobutyl ketone condenses with ethyl cyanoacetate and ammonia giving a small quantity of a compound which crystallises in needles m. p. 223-225O but was not analysed. With d i u r n hydrogen sulplGte benzyl methyl ketone B-phenyl- ethyl methyl ketone and benzyl ethyl ketone form crystalline coin- pounds but this is apparently not the case with @-phenylethyl ethyt ketone or benzyl isobutyl ketone.T. H. P. The Three Phenacylaminobenzoic Acids. M. SCHOLTZ (Ber. 1918 51 1645-1653).-The t‘hree aminobenzoic acids reack with w-bromoacetophenone in boiling alcohol to f o m o-phenacyl- aminobenzoic acid COPh*CH2*NH*C,H,*C0,H yellow leaflets m. p. f90° (phenylhydrazone yellow needles m. p. ISSO) the m-isomeride e 2 :i. 96 ABSTRACTS Oh’ (THJ3MICAI; PAPERS. colourless crystals in. p. 20Z0 and the pisomeride colourless needles m. p. 2 1 1 O respectively. If alkali hydroxide or carbonate also is present in the reaction in the case of the ortho- and para- compounds a by-product is the phenucyl ester COPh*CH2-NH*CGH4*CO*O*CH2*COPh (0-ester hair-like crystals m.p. 180O; p-ester colourless needles m. p. 186O). By treatment with boiling acetic anhydride wt- and p-phenacylaminobenzoic acids are converted into the corresponding N-acetyl derivatives pointed prisms m. p. 2 1 7 O and leaflets m. p. 1 76* i*espectively but the ortho-conipound is converted into a sub- stance C17€€!,02N colourless needles m. p. OH Ph 288O which is regarded as 8-liydroxy-3-keto- b i y I - phenylpropenylene - 2 1 - i d o l e (annexed formula). It develops a blood-red coloration /‘”’’‘~’’\~~~ with alcoholic ferric chloride forms a di- rn. p. 265O and is converted by hot aqueous alcoholic potassium hydroxide into the potassium salt of an acid C(17H@3N colourless needles m.p. 300O (decomp.) which does not give a coloration with ferric chloride forms a dibromide pale yellow needles and yields a phenylhydrazone yellow needles m. p. 221° anti is therefore regarded as indo~~l-2-P-cznnamic acid a l ’ \</-- 3- ”0 hromide C17Hl102NBr2 pale yellow needles I t is acetylated by warming with acetic anhydride but the product C‘17H1203NAc rhombie crystals m. p. 1 6 7 O no longer exhibits the properties of an acid ; it regenerates indoxylcinnainic acid after pro- longed boiling with aqueous sodium hydroxide. By boiling with phenylhydrazine in glacial acetic acid all three phenacylaminobenzoic acids yield the phenylhydrazmze of s-phen- acylphenylhydrazine NHPh*N:CPh*CH,*NH*NHPh yellow needles m. p. 1 4 7 O (acetyl derivative C2,Hl,N4Ac yellow crystals m.p. o-Bromoacetoplienone and phenylhydrazine react in boiling alco- 1.10~1 to form not the preceding compound but a substance CZ8Hz4N4 colourless needles m. p. 174O which is regarded as tetw- and is isomeric with fi Ph*CH2*NPh*n N-NPh-CH2-C Ph’ 1’7Le~~E-P-tetracarbazo~~ the substance m. p. 137O obtained by Hess in 1886 from the same Aldehyde Derivatives of Rhodaniaes and their Fission Products. I. RUDOLF ANDREASCH (Nonatsh. 1918,39 419-440). -A stildy of the oxidation reduction and fission of various con- densation products of aldehydes and r’hsdanines. A solution of phenylbenzylidenerhodanine in boiling glacial acetic acid is oxidised by bromine t o phenylbenzylidenethiocarbimideglycol- lide m. p. 209O (compare A. 1917 i 663 in which the m.p. is given as 239O in error) ; similarly phenyl-o-nitrobenzylidenerhodanine yields phenyl - o - nitrobelz~!ylidertethiocarbimideglycoE~de woolly needles m. p. 204O. 2010). two reagents in alcoholic solution a t Oo. c. s.ORGANIC CHEMISTRY. i. 97 The followilrg substances have been prepared with a view to the study of their reduction 5-ethylrhodanine (from ethyl a-bromo- butyrate and ammonium dit'hiocarbamate) yellowish-white crystal- line powder m. p. 1 0 5 O ; 3-phenyl-5-ethylidenerh&anime thin pale yellow plates m. p. 123O ; 3-~henyl-5-ethylrhodanine pale yellow needles m. p. 83O ; o-nitrobenzyl p~~enyldit?Liocarhamate NHPhm CS*S CH,. CGH4*N0 sulphur-yellow needles m. p. 120-121O. Attempts to reduce ethyl- idenerhodanine and phenyletjhylidenerhodanine have not yielded satisfactory results u p t o the present.The various aldehyde condensation products of the shodanines are found to be decompossd with widely differing velocities by alkali ; those containing a hydroxy-group in the phenyl residue are particu- larly resistant so that in general they are only decomposed under conditions which lead to the further degradation of their fission products. The most suitable reagent is a solution of sodium amyl- oxide in amyl alcohol probably by reason of the higher temperature which can be attained. Under these conditions phenplpiperonyl- idenerhodanine yields phenylthiocarbimide and rnethylenedioxy-a- thiolcinndmic acid CH,O,:CGH,*CH:C(SH)*CO,H yellow micro- scopic needles which begin to decompose a t ca.170° and are com- pletely molten a t 208-210°. The latter acid is transformed bv iodine into ~iSUlZJhidObiSnzethylene~~ox~ci?7ltctmic acid m. p. 228O. Sirnil arl y p-hyderow/-m -m e t hozy-a- thiol cinnamic acid OH*C,H,(OMe)*CH:C( SH) *C09H palo rlirome-yellow rlioinbic plates m. I). 183O after softening at! 1 70° is obtained from the condensation product of vanillin and pheuylrhodanine whilst the anhydride of o-hydroxy-a-thiolcinnamic acid (m. p- of benzyl derivative 164-165O) is prepared from phenyl-o-hydroxybenzylideiiethiocarbimide~lycollide. Phenylfuryl- id enerhodanine yields f u r y It hio la crqlic acid C,H,O*CH :C(SH)*CO,H fine needles m. p. 102-103° which is transformed by iodine into the corresponding disdphido-acid lemon-yellow needles or hexagonal plates m.p. 190-1 91 O. Fission of p-hydroxybenzylidenerhodanine m. p. 2 7 4 O after softening a t 260° did not lead t o the isolation of p-hydroxy-a-thiolcinnarnic acid but its formation was proved by the separation of its h ei?uyZ derivative colourless microscopic needles m. p 1 8 3 O . The free acid chrome-yellow needles m. p. 1860 was prepared by the action of a solution of sodium amyl oxide in hot amyl alcohol on ph en?/l-p-hy~ro~ybenzylide~erh.oda~i?~~ cadmiuni-yeIIow needles m. p. 285O. The corresponding disulpltido- c~cid is a yellow crystalline powder m. p. 197O. pDimethyZamino- a-thiolcinnarnic acid has rn. p. 160° ; the corresponding disutphido- acid is a scarlet powder m. p. 198O. PCAminobenzylidenerhodaniize forms fine woolly needles rescm- bling chromium trioxide which soften a t about ZOOo and are not completely melted a t 290° ; 2 4-diEeto-5-p-aminobenzylidenethiazol- iditbe 7 o-s>C:~H-C,H,*NH is a dark reddish-brown powder NH*COi .98 ABSTRACTS OF CHEMICAL PAPEltS. which further darkens from about 200° and has 110 definite H I . p. Attempts to decompose these sdbstances as also phenyl-o-nitrobeiizyl- idenerliodanine by alkali led to negative results. H. W. Parabanic Acid. BQBERT BEHREND and ADOLF ASCHE (Amalen 1918 416 226-228).-Parabanic acid can be obtained in about 33% yield by rapidly adding 8.4 g a i m of uric acid to 39 C.C. of nitric acid D 1.3 heated at 70° evaporating the solution ti0 dry- ness and evaporating the residue two or three times with nitric acid D 1.4 until the evolution of gas ceases. The product is New Compounds to be employed as Colouring Matters or in the Production of Colouring Matters.ANJX~EA ANGEL (Eiig. Pat,. 121347 1917).-R new type of compoiiiids for which 1 he iianie of “ parazones ” is suggested coiitains two benzene iiiiclei (or nuclei of benzene derivatives or other cyclic groups) linked togekher through four para-carbon atoms of the nuclei by two nitrogen atoms. Of the three phases of the foimula which may be assigned to parazene two (I and TIT) become identic&l in the absence of uiisyminetrical substitution crystallised from boiling water. c. s. -+ (111.) Parazelies are prepared by heating a parahalogen substituted aniline or a-naphthylamine or derivatives of either containing indifferent groups in the nuclei with a condensing agent such as zinc chloride ferric chloride aluminium chloride or phosphoric oxide.The product oi the reaction is a hydroxyparazene which is converted by reduction into para- zene. The parazene thus obtained from 2,-chloroaniline is a dark blue powder -which when dissolved in dilute acetic acid may be used for dyeing wool or silk. Special colouring matters may be produced by introducing auxochromic groups by t,he ordinary methods. Parazelies mill form salts with acids by addition to one 0% both of the nitrogen atoms. [See further ,7. SOC. Cham Ind. 1919 February.] C. A. M. Interaction of Aliphatic Diazo-compounds and Diphenyl- keten. J. SUREDA Y BLANES ( A m l . Fis. (Jziiin. 1918 16 611-624). -With phenyldiazomethane diphenylketen produces a substance C,,H,,ON white crystals m.p. 1 9 6 O . Diphenyldiazomethane and diphenylketen yield yeIlow crystals m. p. 133-135O (decomp.). The product from diphenylenediazomethane arid diphenylketen is a dark yellow powder m. p. 1 5 7 O (decomp.). The constitution of these sribstances is being farther investigated. A. J. W,ORGANIC CHEMISTRY. i. 99 Preparation of True Vat Dyes from Di- and Tri-aryl- methane Dyes. HEINRICH WIELAND (D.R.-P. 308298 fro111 Clwni. Zentr. 1918 ii 782-783).-33y treatment of the dyes with alkali hyposulphite solution colourless alkali salts are obtained which are soluble in water and are reoxidised to the original dyes with extraordinary rapidity by atmospheric oxygen. For example crystal violet yields sodiu-m hexamethyltriamiiiotriphenyl- niethanesulphonate C(C,II,*NMe,)3*S0,Na crystallising in glisten ing needles.H TV. B. Some Derivatives of Isatin. ANDRB MEYER (Conzpt. ?-e?zd. 1918 167 1070-1073) .-When the amino-oxindole obtained by the reduction of isatoxims with tin and hydrochloric acid ii oxidised by potassium f erricyanide in dilute solution in additioii to isatin a small amount of a red compound is obtained. If the isatosime is reduced by zinc and acetic acid the z i n c salt C,,H,O,N,Zn of this red compound is obtained. From its behariour on reduction with sodium hyposulphite or when dis- solved in sulphuric acid the author considers that the red com- pound is probably identical with Me F -C-N=C' " Wahl and Bagard's isoindigotin. 3XeN 60 1 Mixed rubazonic acids of the isatiii %<\/ series may be prepared by condensing in alcoholic solution amino-anti- pyrine with isatiii 5-bromoisatii7 5 7-dibromoisalin and naplithisatin.They have the general COII- stitulion (annexed formula). where X represents the substituted \/ NPh benzene 01- naphthalene nucleus. 117. G. Derivatives of the Iadole and Indigotin Groups Sub- stituted at the Nitrogen Atom. AUGUST ALBERT (Aitsznlciz 1918 416 240-278. Compare A. 191G i 821).-l-IIydroxy-2- t~hio-3-benzoyloxyoxindole (A.? 1915 i 595) only reacts in the thioii form in forming the acetyl derivative. In all other cases it reacts in the thiol-form C,H,<CH'*~~>C*SH. For example it reacts with phenylhydrazine in cold alcoholic or glacial acetic acid solution to form 2-thiol-3-b e?izrr?/lox?/ocinclolepir cnylii ydrnsoir I - I - .. C H - J/,yclrnte NHPh*NH*N(OH) <c~s&>CI?l*OB~ pale yellow plates 111. p. 123-126° (decoinp.). whi'ch is also formed from the acetyl derivative acetic acid being eliminated. The phenylhydrazone hydrate is interesting in that the sulphur can be extraordinarily easily eliminated. LY/ 2-Sodium hydroxide converts it into 1 I' - bisphei2?/2hydrazi.II oindigo t in,i. 100 ABSTRACTS OF CHEMICAL PAPERS. which the presence of the tlwo carbonyl groups is shown (1) by heating on the water-bath with aniline or ptoluidine and its hydrochloride whereby the hydrochloiide of the and steel-blue needles decomp. 240° or of the p-tolil greenish-blue crystals decomp. 218-223* is obtained and (2) by heating with phenylhydrazine and its hydrochloride whereby the bisphenyl- hydrazone C40H34N10 yellow plates decomp.200-206° is obtained. Certain reactions indicate that 1 1'-bisphenylhydrazinoindigotin is able to react in the tautomeric enolic form Ck,H,,N,,2HC4 C (OH)-- c (OH)-- C6H4<h(:N.NHPh) )c:Q<g( :* .N Hph)>CBH 3 Thus the substance is insoluble in dilute aqueous sodium hydr- oxide and is only sparingly soluble in alcohol but dissolves extremely easily in alcoholic sodium hydroxide the colour of the solution changing from yellow t o blood-red; the yellow colour is regenerated by the addition of water. These colour changes are still more pronounced in the case of the 1 1'-bisphenylmethyl- hydrazinoindigotin mentioned below ; the yellow colour of its alcoholic solution is changed t o dark green by alcoholic potassium hydroxide and is regenerated by the addition of water.The presence of two hydroxyl groups is proved by means of benzoyl chloride. I 1'-Bisph enylhydrazinoindigotin is boiled with 10N- sodium hydroxide unt"i1 t,he dark red sodium derivative is formed the mixture is then cooled and treated with benzoyl chloride whereby according to the conditions the dib enzod derivative. plates containing 2Hi0 m. p. 140-145O [hydrated] or 186-189O [decomp. ; anhydrous]) or the tetrnbenzoyl derivative yellow or yellowish-brown rhombic plates m. p. 158-159* i s obtained. The tetrabenzoyl derivative is converted into the dibenzoyl derivative by careful treatment with sodium ethoxide and into the bisphenylhydrazone of the latter by warming with phenylhydrazine and its hydrochloride a t 50°.By treatment with as-phenylmethylhy drazine I-hydroxy-3 - benzoyloxy-2-thio-oxindole is converted into a phenylmethylhydr- azone which could not be obtained crystalline and is readily changed by N/2-sodium hydroxide into 1 1 -6isphenylmethtyZ- hydrazinoindzgotin C3,H,602N6 yellow or yellowish-red needles m. p. 2 0 2 O (bisphenylhyd'razo~ne C42H38N10 yellowish-brown plates,ORGANIC CHEMISTRY. i. 101 decomp. 1 6 5 O ) . and methyl sulphate to form the dimethyl ether This reacts with cold alcoholic potassium ethoxide dark bluish-red plates m. p. 105O and its sodium derivative reacts with benzoyl chloride to form only a dihenzoyl derivative yellow quadratic plates M. p. 150-151°. The dibenzoyl deriv- ative is converted into the preceding bisphenylhydrazone decomp.165O by warming with phenylhydrazine the two benzoyl groups being eliminated 1 1 f-Bis-p - 71 rom oph e ti yl hydra einoindig ot in C,,R2,,0,N,Br2 f o m s orange-yellow rectangular plates m. p. 2 4 7 O (decomp.) and is converted by warm aniline and aniline hydrochloride into the Jtydrochloride of the anil C,,,H,N8Br2,2HCl blackish-blue micro- scopic plates m. p. 227-231O (decmp.). The preceding bisphenylhydrazino- and substituted bisphenyl- hydrazino-indigotins do not yield vat dyes on reduction but undergo profound decomposition the products depending on the nature of the reducing agent. The course of the reduction in acid media will be described in a later paper. The reduction of I 1 '-bisphenylhvdrazinoindiqotin suspended in benzene by alcoholic ammonium sulphide yields dihydroindigotin aniline and ammonia.Its reduction by N-sodium hydroxide and zinc dust in an atmo- sphere of coal gas for six days yields a pale yellow solution from which is precipitated by means of atmospheric oxyqen a dark blue zinc salt- probably of 1 1'-diaminoindigotin from which is liberat,etl by dilute hydrochloric acid the Jw/drochZoride of indigotin-1 1'- CQ--Q==zC ,or) imide I I I violet rectangular plates decornp. C,H,*N*NH*N-C,H ' 1 8 5 O . This' base forms an acetyZ derivat'ive a very sparingly soluble s u l p h t e 2C,GJ390?N3,H,S0 needles and other crystalline salts and is a true vat dye yielding with alkaline sodium hypo- sulphite a yellow vat from which the imide is regenerated by means of oxygen. The preceding zinc salt yields dihydroindigotin by reduction.c. s. Compounds Derived from Proteins by Energetic Treat- ment with Nitric Acid. VII. CARL TH. M~RNER (Zeitsch. physiol. Chem. 1918 103 80-83. Compare A. 1918 i 198).- The occurrence of 5-nitroglyoxaline-kcarboxylic and glyoxaline-4- glyoxylic acids both oxidation products of histidine among the products of the oxidation of protein is confirmed (see Knoop A. 1918 i 412). D. BREESE JONES and CARL 0. JOHNS ( J . Biol. Chem. 1918 36 323-334).-Kafirin the alcohol- soliible protein of kafir ( A ndropogon ~or~yhzcm) contains 21 -a?/ H. W. B. Hydrolysis of Kafirin.i. 102 ABSTEACTS OF CHEMICAL PAPERS. gliitairric acid 15.4% leucine 8.1 y6 alanine 7.8% proline 5*5() tyrosine 4.3% valine 3.5% ammonia 2-37; phenylalanine 2*3”/ aspartic acid 1 *S% arginine 1.1% histidine 0.9576 lysine and 0*84’j cystine.Tryptophan is also present but glycine is absent. liafirin theref ore closely resembles zein the alcohol-soluble protein of maize except in regard t o its content of tryptophan. H. W. B. Froteins of the Peanut Arachis hypogzea. 111. The Hydrolysis of Arachin. CARL 0. J o m s and D. BREESC JONES ( J . Bio?. Ciiem. 191 8 36 491-500. Compare preceding abstract). -Arachin contains 16.7% glutamic acid 13.5% arginine 5.5% Lyrosine 5.3% aspartic acid 5.076 lysine 4*1°4 alanine 3.9% leucine ?6(jL pIienylalanine 3.0°! aiiimonia 1*97& liisthicline 1 ‘4% proliiie absent. H. W. B. 1 .] n/ ,* valine and 0.9:; cystine. Tryptophan is present glyciue Chemical Study of Enzyme Action.I!. G . FALK (Scieizcc 1918 47 423-429; from Ph,?,ts~oI. A hsfr. 1918 3 407).-The chemical nature of enzymes is discussed in the light of the results od experiments previously published (compare A. 191’7 i 598). H. W. B. Studies in Fermentation. 111. Pepsin and Peptic Digestion. W. BIEDERMARN (_Zicn7~ciztforsc7. 1917 2 1-57 ; from Cfrem. %;elit?*. 1918 ii 741-742. Compare A 1917 i 62).-A suspension of coagulated egg white in water can be employed €or detecting a small amount of pepsin. The former is prepared from dried commercial egg albumin by dissolving in water acidifying with acetic acid adding sodium chloride and then heating to the Foiling point with continua1 stirring. The protein separates in very finely divided flocks which after washing and pressing can be rubbed u p with a little glycerol t o form a paste in which form it can be preserved indefinitely. A small fragment about the size of a pea in 10 C.C. of water forms a milky fluid which does not yield a perceptible sediment for several hours. On digestion with a trace of pepsin and hydro’chloric acid the turbidity quickly disappears. Fibrin is dissolved by dilute hydrochloric acid even in the absence of pepsin. Repeated addition of fibrin results in an increased rate of solution which appears t o indicate that an autolytic or peptic e:izyme is closely associated wit,li fibrin o r is formed from the fibrin by liydrolysis. If the fibrin is boiled prior to tlie experiment it doe. not dissolve so readily in the dilute acid. R. W. B. Trypsin and a New Method of Purifying Enzymes. JOSEPH T. WOOD ( J . SOC. t l h e m . Ind. 1918 37 313-315~).-1t has been stated by Holzberg (A. 1913 i 662) that when a saturated solution of safranine is added t o a neutral or very faintly alkaline sol11 tion of trypsin a precipitate is form etl which possesses proteo- lyiic. properties. This diitellleiit is coiifinirctl by tlie autlior. and it,PI~YSIOLOGICAL CHEMISTRY. i. 103 is shown that the precipitated inaterial consists of protein matter with the safraniiie and the enzyme in an adsorbed condition. Trypsin or other enzyme can be purified by dissolving in a small quantity of water and allowing the solution t o soak into filter or blotting paper. After rapid drying a t a low temperature the pro- teins are retained more tenaciously by the paper than the enzyme and on placing in water for a few minutes and then filtering a soln- tioii of the enzyme is obtained practically free from protein. Such a protein-free trypsin solution does not give any precipitate with safraniiie. H. W. B. Action of Mercuric Acetate on p-Toluidine. I. L. VECCHIOTTI (Gazzetttr. 1938 48 ii; 78-83. Compare A. 1914 i lT)G3).-The interaction of mercuric acetate (I mol.) aiirl gi4olu- i tl i t t e (I ni of. ) y i el cl s 11- f o 7u idi n c nz e rc I I ria cc f u f c NH2*C,H,Me*Hg*ORc which foims shining white crystals rn. p. 184O ; the mercuriacetato group probably occupies tlie ortho-position to tlie amino-group. Tlie corresponding hydroxide NH,*C,H,Me*Hg*OH crystallises in pale yellow plates m. I). 212-213O which begin t o turn brown a t about 1 20° ; it renders water strongly alkaline. The chZor2'cZ~ C,H,NClHg forms prismatic need!es m. I). 170°. T. H. P.