i 53 Organic Chemistry. Absorption of Gasolene Vapours i n Natural Gas by Fuming Sulphuric Acid. R. P. ANDERSON and C. J. .hGEr,DER (J. I n d . Eng. Chem. 1914 6 989-992).-Fuming sulphuric acid has a distinct absorbing action on certain specimens of natural gas the absorption increasing with the amount of higher hydrocarbons particularly gasolene vapours present in the gas. The average number of carbon and hydrogen atoms per mol. of hydrocarbon absorbed by fuming sulphuric acid (and consequently the average molecular weight of the hydrocarbons) may be calculated from the composition of the gas before and aft*er absorption and from the decrease in volume which takes place. Application OF this reagent to the study of natural gases for the production of gasolene may be made by determining the absorption under certain uniform conditions ; the composition of the portion which is absorbed should also be ascerbained as a check on the indications obtained from the decrease in volume.w. P. s. Preparation of d h l o r o -E-bromopentan-P-ol and of a Ketone Therefrom. 1114734 and 11 14735 ; from J. Xoc. Chem. Ind. 1914 33 1 171).-Maguesium ( I atom.) is dissolved in an absolute ethereal solution of ethylene dibromide and epichlorohydrin (1 mol.) is added ; treatment with a suitable acid pro- d uces a-chZoro-E-bronzopentm-P-ol CH,Cl*C H (OH) * CH,*C H,*CH2Br. The ketone CH,CI*CO*CH,*CH,*CH,Br is obtained by the oxida- tion of the preceding carbinol for example with potassium dichromate ELI LILLY & Co. (U.S. Pat. and sulphuric acid. c.s. A Compkrison Between the Molecular Weights of Protagon and of the Phosphatide and Cerebrosides Obtainable from it. ALEXANDER LYALL PEARSON (Biochem. J. 1914 8 616-627).- The long-continued argument whether protagon is a mixture or a compound is approached by attempts to determine the molecular size of protagon and its constituents (cerebrosides and sphingomyelin). If it is a compound the molecular size of protagon would he greater than that of its constituents; it should therefore produce little or no elevation of the boiling point of a solvent. The solvent used was chloroform. In two experiments there was no alteration in the boil- ing point in one a lowering of 0.05O. Various mixtures of the cerebrosides with or without sphingomyelin produced elevations of the boiling point of the same solvent of 0.03O 0*13O 0.04' 0*07O 0*07* 0*03O and 0.02O in a series of experiments.The conclusion is drawn that the protagon molecule is very much larger than that of its constituents and therefore that protagon is a compound and not a mixture of them. It is termed a phospho-cerebroside. The question whether protagon is a mixture of several phospho-cerebrosides still remains to be settled. Cramer calculated that protagon has a molecular weight of 5778 from its sulphur-content. The molecular weights of cerebro- VQL. CVIII. i. fi. 54 ABSTRACTS OF CHEMICAL PAPERS. sides and of sphingomyelin are about 1000; one gram of a substance of this molecular weight would in a 4% solution in chloroforrri elevate the temperature of the boiling point of chloroform O*lOo.The smaller figures obtained in mobt of the experiments cited would rather tend to emphasise the author's admission that determinations of molecular weights of substances of high molecular weight can Gnly be approxi mate. W. D. H. The Dissociation of Cl-T;SO,Cl and C,H,*SO,Cl by Aluminium Chloride. J. BOESEKEN and H. W. VAN OCKENBURG (Izec. irctv. chirn. 1914 33 317-323. Compare A 1913 i 334).-Wheri methane- sulphonyl chloride is mixed with aluminium chloride a t t'he ordinary temperature in the absence of a solvent a crystalline additive ccrn- pound CH,-SO,Cl AlCl is formed. On warming this compound sulphur dioxide and methyl chloride are evolved and the aluminium chloride remains behind. If the methanesulphonyl chloride is added to the aluminium chloride in the presence of an excess of benzene hydrogen chloride is evolved and phenyl methyl sulphone m.p. 88* is f orrned. Ethanesulphonyl chloride behaves similarly with aluminium chloride in the absence of a solvent giving an additive cornpound G,H,*SO,CI,AlCJ which on warming gives ethyl chloride and sulphur dioxide and a t the same time a brown resinous product formed by the reaction of the aluminium chloride with hydrogen chloride and ethylene products of a secondary decomposition of the ethane- sulphon yl chloride. W. G. CECIL L. HORTON (Chem. News 1915 111 29-31).-1n a previous paper ( A . 1913 ii 743) attention has been drawn to the directive action of the carboxyl group in the Walden reactiofl This influence of the carboxyl group together with the fact that all the mbstituents and reagents are unsaturated is made the basis of a further attempt to explain the reaction in question.The theory assurses the formation of an intermediate compound in which the position of the addendum depends on the attractive or repulsive action of the carboxyl or ester group. This position determines the distri- bution of the valsncy and the resulting cleavage. The author illustrates the supposed action by reference to a number of special cases. Preparation and Hydrolyeis of Ethyl Hydrscrylate. The Walden Inversion. H. M. D. W. A. DRUSHEL (Amer. J. Sci. 1915 [iv] 39 113-121).-A convenient method for the preparation of hydracrylic acid is described in which glycerol is oxidised by means of fuming nitric acid and glyceric acid liberated from the calcium salt by the addition of oxalic acid.The glyceric acid is converted into P-iodopropionic acid by treatment with iodine and solid yellow phosphorus and the concentrated solution of the sodium salt is then acted on in the cold with silver oxide using a mechanical stirrer Esterification of the acid with absolute alcohol leads to the formation of a mixture of acrylic and hydracrylic esters even if only very small quantities of mineral acid are present but ethyl hydracrylate isORGSNIC CHEMISTRY. i. 55 readily obtained if the acid is boiled with an excess .of absolute alcohol in presence of anhydrous copper sulphate and mineral acids are rigidly excluded. It has b. p. 95-96'/20 mm. D20 1.059 and is completely miscible with water.I n the absence of a catalyst it is hydrolysed only very slowly by water. In presence of O.1N-hydrochloric acid the velocity coefficient ( k . lo5) for the hydrolysis was found to be 16-25 at 2S0 40.65 at 35O and 98.75 at 45O. The influence of the hydroxyl group in the P-position on the rate of hydrolysis is shown by a comparison of the coefficients at 25' for ethyl propionate (71.2) ethyl lactate (76*1) ethyl hydra- crylate (16-25) and ethyl glycerate (18.5). Substitution of the hydroxyl group in the /?-position has therefore a marked retarding influence on the rate of hydrolysis i n presence of acids. The velocity of saponification of the ester by sodium hydroxide was also measured a t 0" and 25'. The velocity coeflicient 1.83 at Oo is compared with the corresponding values for ethyl propionate (1.1 6) ethyl lactate (14.6) and ethyl glycerate (9.02).From there numbers i t is evident that the relations differ in some respects from those exhibited by the coefficients for hydrolysis by acids but are i n general agreement with the results obtained in the saponification of the esters of other oxy-acids (compare Dean A. 1913 ii 187). H. X D. a-Sulphopropionic Acid and its Resolution into Optically Active Isomerides. A. P. N. FRANCHIMONT and H. J. BACKER (Pvoc. K. Akad. Weetensch. Amsterdam 19 14 17 653-658).-a- Sulphopropionic acid hitherto known only in the form of a viscous syrupy liquid has been obtained in the form of large hygroscopic crystals containing one molecule of water of crystallisation. When dried over phosphoric oxide it has m.p. 100.5O. Previous attempts to resolve the acids have given negativo results but it is found that if an aqueous solution of the acid is evaporated with an equimolecular quantity of strychnine crystals of the strych- nine hydrogen salt of the dextro-acid are obtained which may be purified by recrystallisation. From this the neutral barium sait is obtained by decomposition with barium hydroxide and an aqueous solution of t be free acid is obtained from this by addition of sulphuric acid. The solution concentrated in a vacuum over phosphoric oxide does not crystallise spontaneously but crystals were obtained on the addition of a trace of the racemic compound. The acid is exceedingly hygro- scopic m. p. 81-82' and contains one molecule of water.The measurement of the rotatory power of the acid and its salts gave the following values for [MI"," d-acid + 4 9 * 2 O potassium hydro- gen salt + 45.'7' barium hydrogen salt + 79.8' strychnine hydrogen salt - 71.4' normal barium salt - 14.4'. The ltxvo-acid was not ob- tained in perfectly pure condition but the following data are recorded I-acid - 45*8O strychnine hydrogen salt - 135O normal ammonium salt +- 14.8'. It is noted that the molecular rotatory power of a-sulphopropionic acid is greater than that of a-brornopropionic acid (44.4') although the weights of the substituents are practically identical. H. M. D. VOL. CVIII. i. gi. 56 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Acetaldehyde from Acetylene. FARBENFABRI- KEN VORM. FRIEDR. BAYER & Co.(Fr. Pat. 469497 ; from J. Xoc. Chem. Ijzd. 1915 34,49).-Acetylene is passed into a solution or suspension of a n organic sulphonic acid and a mercury compound or of a mercury salt of a sulphonic acid I n either case a free mineral acid may be added. For example 21.6 parts of mercuric oxide are heated with 417 parts of o-chlorophenolsulphonic acid and 583 parts of water and acetylene is passed into this solution a t 30-35" ; when the absorption of the gas has diminished considerably the aldehyde is removed by heating or by means of steam. Solu- tions of sulphonic acids have a high power of hydration considerably greater than t h a t of solutions of mineral acids of the same acidity. The yield is about 300 parts. c. s. Synthesis by means of Mixed Organo-metallic Derivatives of Zinc Polyhalogenated Ketones.E. E. BLAISE (Bull. SOC. chim. 1914 [iv] 15 728-737. Compare A 1914 i 1050 1051).- Certain dichloro- and trichloro-ketones have been prepared through the intermediary of cycloacetals. For the preparation of these cyclo- acetals lactic acid a-hydroxyhexoic acid and a-hydroxyisobutyric acid were tried the last-named being the most satisfactory. Dicbloroacetyl chloride condenses with lactic acid giving a-dichloroacetoxypropionic acid CHCl2*CO*O*CHMe*CO2H m. p. 67O b. p. 164-167'/17 mm. yielding an mid chloride b. p. llso/21 mm ; and with a-hydroxy- hexoic acid giving a-dichlorocccetoxy?~exo?ll chlovide b. p. 147-1 49'1 26 mm. Dichloroacetyl chloride is best condensed with a-hydr- oxyisobutyric acid by heating the mixture on a water-babh until the action is complete when on cooling a-dich2oroacetoxyisobutyric acid m.p. 9 5 O crystallises out ; i t is moderately readily hydrolysed by water. It gives a n anilide needles m. p. 99-100' and a chloride a colourless denbe liquid b. p. 103'/12 mm. This chloride condenses with zinc ethyl iodide in dry toluene giving the cycloacetal CHCI,-CEt<O.&O 0 CMe m. p. 51" b. p. 236-239O or 124*5-125'/16 mm. On boiling this cpclo- acetal with a mixture of acetic and hydrochloric acids i t is decomposed giving a mixture of dichloromethyb ethgl ketone CHCl,*COEt b. p. 138.5 -1 39' or 56.5'/36 mm. yielding with hydroxylamine glyoxal- dioxime and chloroniethyl chloroethyl ketone CH,Cl-CO*CHClMe b. p. 60°/13 mm. (compare Vladesco A 1891 1183) the second ketone beirjg formed by migration of the chlorine atom after the formation of the first ketone.Trichloroacetyl chloride condenses with a-hydroxyisobutyric acid giving a-trichloroacetoxyi8oDut?/ric acid CC13*CO*O*CMe2*C02H m. p. 1 1 7 O giving a chloride b. p. 107'/13 mm. or 113"/18 mm. and a n anilide m. p. 100'. The chloride yields with ziuc methyl iodide the m. p. 98-99' with sublimation cycloacetal CCl,*CMe< which on boiling with the mixture of acetic and hydrochloric acids gives methyl trichloromethyl ketone a colourless mobile liquid b. p. O*$!Me 0-coORGANIC CHEMISTRY. i. 57 57"/48 mm. 60'154 mm. and 134' (compare Schlotterbeck A. 1909 i 533). The author agrees with Cloez that the ordinary trichloroacetone consists almost entirely of aay-trichloropropanone.W. G. I t yields a sernicarbazone m. p. 140". Structure of the Two Methylglucosides; a Third Methyl- glucoside. EMIL FISCHER (Ber. 1914 47 1980-1989).-Nof's statement (A 1914 i 490) that a- and P-methylglucosides are striic- turally different as also are the corresponding a- and P-penta-acetyl- dextroses is not in harmony with the following properties of the com- pounds (i) The penta-acetates are converted into the same p-aceto- chloro(or bromo)-dextrose by hydrogen chloride (or bromide). (ii) Treatment! of P-acetobromodextrose with silver nitrate and sodium yields an acetonitrodextrose which is converted merely by crystal- lisation into the isomeric stable well-known acetonitrodextrose. (iii) By hydrolysis Purdie and Irvine's tetramethyl a- and P-methyl- glucosides (T.1903 83 1081 ; 1904 85 1049; 1905 87 1022) are converted into the same tetramethyl glucose. The latter retains its methyl groups against the attack of hydrogen chloride in benzene a t 105-115O and yet is converted by methylation into the original tetramethyl a- and P-methylglucosides. A structural difference in the methylglucoside~ therefore appears t o be impossible a t all events in the sense of NeE's conception. The reaction between a-dextrose and methyl alcohol containing 1% of hydrogen chloride yields in addition t o the two crystalline methyl- glucosides a considerable amount of a syrup which has hitherto not been purified and has been regarded a s dextrose dimetbylacetal. It is now found that the syrup distils without decomposition in a high vacuum.The purified substance C7III4O b. p. 200-215°/0*2 mm. [a]E - 3.64' in about 10% aqueous solution is named y-methylylucoside (the prefix does not refer too the structure of the compound but is used simply t o differentiate it from the a- and P-isomerides). It is stable to alkalis Felrling's solution or hot water but is hydrolysed to dextrose and methyl alcohol by N-acetic acid a t loo" by N/lOO-hydro- chloric acid at looo and by N/lO-hydrochlaric acid a t 17-16". y-Methylglucoside is scarcely attacked by emulsin or by yeast extract a t 37'. c. s. New Compounds of the Choline Type. P r e p a r a t i o n of the Monoacetate of P-Methylbutane-up-diol. 111. G. A. MENGE (U. S. Hyg. Labop.. Bull. No. 96 37-50. Compare A 1912 i 74 949).-The physiological activity of choline and p- and y-homocholines and their derivatives indicates that the greatest activity and the least toxicity are obtained in those compounds which contain the trimethyl- amine nucleus and in which the alcoholic hydroxyl group is not further removed from the nitrogen than the P-position.Consequently the substitution of the hydrogen atoms in the a- and the @positions of the carbon chain by alkyl and other groups rather than the direct extension of the chain is indicated as the most promising development from the point of view of physiological activity. The preparation and properties of a-methylcholine I' P-homocholine," 9 2i. 58 ABSTRACTS OF CHEMLCAL. PAPERS. '' y-homocholine," and of some of their derivatives have been already recorded (Zoc.cit.). OH*CMeEt*CH,*Nllle,Cl has now been prepared from the crude substance by means of the platinichloyide. P-Phennyl -P-methylcholine chloride OH* CPhMe- CH,*NMe,CI colourless rhombohedra1 plates is prepared by heating P-chloro-a- hydroxyisopropy lbenzene with a small excess of 33% alcoholic tri- methylamine in a sealed tube in boiling water; it forms a platini- chloride (C,,H,,ON),PtC1 decomy. 223*5-224* (corr.) and auri- chloyide m. p. 137*5-138*5O (corr.). In striking contrast to all other attempts to acylate /3P-disubstituted cholines the acetyl derivative of PP-dirnethylcholine chloride OAc*CMe2*CH2*NMe,C1 a colourless waxy substance is readily obtained by gently boiling PP- dimethylcholine chloride with acetic anhydride and pouring the cooled mixture into dry ether; theplatinichloride has decomp.233-234'. The acetyl derivative of P-phenyl-a-metbylcholine chloride prepared by means of acetyl chloride at looo forms a yellow platinichloride. For the preparation of a-mono- and di-substituted cholines chloro- hydrins of the types CHRCl*CH,-OH and CRR'Cl*CH,*OH are necessary Two methods of preparing the latter namely (i) the addition of bypochlorous acid to olefines and (ii) reactions indicated in the scheme Pure P-methyl-P-ethylcholine chloride CH,Cl*CRR'*OH -+ OAc*CH,*CRR'*OH -+ OAc*CH,*CRRCl -+ OH*CH,*CRR'CI have not been practically successful. However the first stage of the second method for example heating anhydrous potassium acetate and a-chloro-P-methylbutan-P-ol to gentle boiling readily yields the acetate OAc*CH,*CMeEt*OH b.p. 92*8-93'/15 mm. (Kling gives LUIGI ROLLA (Ann. Chim. Applicata 1914 2 301-304).-The author has analysed the gaseous products formed by the action of water vapour on barium cyanide at various temperatures ranging from 100' to 500O. A t temperatures below 200° the changes taking place are expressed by the equations (1) Ba(CN) + 3H,O = Ba(OH) + ZNH + 2CO and (2) Ba(OH) + 2CO = (H*CO,),Ba. I n accord with the thermochemical data the absorption of carbon monoxide by brtrium hydroxide occurs more readily at 100' than a t higher temperatures. A t ZSO' the barium formate begins to undergo partial decomposition thus (3) (H*CO,),Ba = BaCO + H + COY and the oxalate which is also formed to some extent is probably decomposed into barium carbonate and carbon monoxide.At 300-400° reactions occur similar t o those observed by Vignon (A. 1911 ii 391; 1914 i 917) in his investigation of the action of carbon monoxide on lime the corresponding equation being (4) 2(H-C02),Ba + BaO = 3BaC0 + CH or (5) 4(H*CO,),Ba + 2Ba0 = 6BaC0,+C2H,+2H,. That reaction (4) should take place at a higher temperature than (2) is indicated by thermochemical data but 145-147O/10 rnm.) DZ5 0.9989. c. s. Action of Water Vapour on Barium Cyanide.ORGANIC CHEMISTRY. i. 59 i t could not be foreseen that above 400' the predominating reactions are (3) and the decomposition of the oxalate into carbonate and carbon monoxide. At temperatures exceeding 250° carbon dioxide is formed in appreciable proportions ; combination of reactions (2) and (3) evidently results in a change analogous to the formation of water gas from carbon monoxide and water vapour.PIETRO FALCIOLA and ANTONIO MANNINO (Ann. Chim. Applicata 1914 2 351-356).- Treatment of olive oil with hydrazine hydrate renders the oil turbid and raises its melting point considerably. The reaction proceeds in the cold and without appreciable development of heat a slight ammoniacal odour being detectable in its early stages. The mass becomes whiter and the elevation of its melting point increases with the proportion of hydrazine hydrate employed. The solid substance separating from the oil is mostly soluble in hot alcohol which deposits a crystalline substance m. p. 110-112°. I t is also soluble in acetone which deposits a white substance m.p. 65-67'. A number of other oils both animal and vegetable exhibit similar behaviour. Such hardened oils and fats either alone or in conjunction with other substances such as naphthalene or anthracene are suitable for the manufacture of candles. Triolein behaves similarly with hydrazine hydrate the resultant product which contains C 74*32-74*47% H 23*56-13-64% and N' 9*03-9*07% having m. p. 110-112° about 76' and 106-108O when crystallised from alcohol acetone and alcohol successively. The iodine number of the substance is 166 and vapours alkaline towards litmus are evolved when i t is heated with potassium hydroxide. The similar substance m. p. 112-114' obtained from fused tristearin has a still higher iodine number ; its percentage composition is C 73.1 H 13.4 and N 9.1 and its molecular weight determined in freezing benzene varies from 178.8 to 320.4 as its concentration increases from 1.2% to 2.6%.Tripalmitin and hydrazine hydrate yield a similar product m. p. 108- logo. T. H. P. Nitration of Mixed Dihalogenbenzenes. A . F. HOLLEMAN (Proc. K. Akad. Wetensch. Amsterdam 19 14 1 7 846-849).-The author at tempts to express quantitatively the directing influence of each of two substituents in a benzene nucleus on a third entrant atom or group. [With W~~Au~.]-\vhen o-chlorotoluene is nitrated the chlorine atom directs the nitro-group to positions 3 and 5 whilst the methyl group directs it to positions 4 and 6. If the proportion is determined (by solidification curves) in which o-chloro-4(and 6)-nitrotoluenes are present in regard to the isomerides o-chloro-3 (and 5)-nitrotoluenes the ratio which is found t o be Mo :GI= 1 1.415 is also the proportion of the substitution velocities caused by methyl and by chlorine [With VAN DEN AREND.]-T~~ preceding ratio applied to the case of the nitration of p-chlorotoluene gives calculated quantities of the isomeric chloronitrotoluenes which agree approximately with those observed experimentally. T.H. P. Action of Hydrazine Hydrate on Fats.i. 60 ABSTRACTS OF CHEMICAL PAPERS. [In part with HEINEKEIT.]-T~~ relative quantities of mononitrated chlorobromobenzenes produced by the nitration of 0- or p-chlorobromo- benzene are determined by estimating the amount of chlorine and bromine displaced by treatment with sodium rnethoxide ; it is well known that only halogen atoms in the ortho- and para-positions to nitro-groups are eliminated by this rexgent. Experiments on the nitration of 0- and p-chlorobromobenzenes show that the ratio of the substitution velocities caused by chlorine and bromine when present together in the benzene nucleus is C1 Br= 1 0.88.The ratio obtained in the case of o-chloroiodobenzene is C1 I = 1 1.84. From these two ratios the authors calculate that the ratio for bromine and iodine should be Br I = 1 2.30 ; the experimental value obtained by the nitration of o-brornoiodobenzene is Br I = 1 1.75. c. s. Action of Potassium Hydroxide on the Nitroamine of 4 6-Dinitro-3-methylanisidine. F R ~ D ~ R I C REVERDIN and ARMAND DE Luc (Arch. Sci. phys. nut. 1914 [iv] 38 410-413).-The authors have determined the constitution of the substance m.p. 1 8 2 O previously obtained by them (compare A 1914 i 831) by heating 4 6-dinitro-3-methylnitroaminoanisole with potassium hydroxide solu- tion. This substance is now shown to be 4 6-dinitro-3-methylmino- phenol its constitution being proved by the fact that on heating its silver salt emulsified in methyl alchol with methyl iodide on a water- bath for fifteen minutep the methyl ether of 4 6-dinitro-3-methyl- arninophenol m. p. 198' (compare Blanksma Rec. truv. chim. 1889 8 276) is obtained. The original substance dissolves in nitric acid (D 1.5.2) giving a violet solution turning to yellow on addition of water and yielding by ex traction with ether a substance cry stallising in small prisms m.p. 173'. W. G. The Three Fluorobenxoic Acids and their Nitration. J. H. SLOTHOUWEB (Kec. trccv. chim. 1914 33 324-342).-The author has prepared the three fluorobenzoic acids by oxidation of the correspond- ing fluorotoluenes with aqueous potassium permanganate. H e has determined the solubility in water a t 32' and the electrical conduc- tivity at 25' of these acids and from them has prepared a number of derivatives. o-Fluorobenzoic acid m. p. 123O gives a chloride b. p. 206O an amide small white needles m. p. 1 1 6 O a rnetlhyl ester b. p. 209' a n ethyl ester b. p. 221' and the following salts sodium salt C,H,F* CO,Na basic magnesium salt CGE4F*CO,*Mg*OH 3H,O calciuin salt (C,H4F*C0J2Ca 2H,O barium salt (C,H,F*CO,),Ba H,O strontium salt (C,H,F* C0,),Sr,2H20 zinc salt (C,H,F*C0,),Zn,3H20 basic zinc salt C,H,F*CO,*Zn*OH cadmium salt ( C,H,F*C0,)2Cd,H,0 and 2iH,O basic coppei.salt C,H,F*CO,*Cu*OH silver salt C,H ,F*CO,Ag. m-Fluorobenzoic acid m. p. 123.6' yields a chloride b. p. 189' an arnide white leaflets m. p. 130° a methyl ester b. p. 1 9 7 O an ethyl ester b. p. 2 0 9 O and the following salts sodium salt C,H,F*CO,Na,ORGANIC CHEMISTRY. i. 61 potassium salt C,H,F'*CO,K calcium salt (C,H,F*C0,),Ca:3H20 barium salt (C,H,F*C02),Ba,3H,0 and 4E20 cadmium salt ( c6 H,F*CO,),Cd 2H20 basic coppev salt C,H,F'*CO,*Cu*O H silver salt C,H4F*C02 Ag. p-Fluorobenzoic acid m. p. 182O gives a chloride b. p. 193' a n amide white leaflets m. p. 154*5" a methyl ester b. p. 198" an ethy? ester b. p 210° m. p. 26" and the following salts sodium salt C,H,F*CO,Na ccclcium salt (C,H,P*CO,),Ca 3H,O barium salt (C6H4F*C02)2Ba and with 2H20 and 4H,O z i n c salt (C,H E'*C0,),Zn,3H20 cadmium salt (C,H4F*C0,),Cd,4H20 basic lead salt C,H,F*CO2=Pb*OH,3H,O copper salt (C6H4F*C0,!,Cu silver salt C,H,F*CO,Ag.o-Fluorobenzoic acid is readily nitrated when slowly added to nitric acid (D 1.52) at 0". The two isomeric nitro-compounds formed are separated by fractional crystallisation of their potassium salts from water the salts being then decomposed with dilute hydrochloric acid. The main product is 2-fluoro-5-nitrober~xoic acid m. p. 138-139' which is almost white and gives a potassium salt crystallising in long needles. I t s constitution was proved by heating it with alcoholic ammonia in a sealed tube at 130-140" the product being 5-nitro- 2-aminobenzoic acid rn.p. 265' (compare Hubner A. 1878 148). The other product of the nitration only present as a trace was 2;fluoro-3-nitrobeszxoic acid m. p. 160". m- Fluorobenzoic acid is nitrated under similar conditions giving 3-fEuoro-6-nitrobenxoic acid m. p. 134.5" which is converted by alcoholic ammonia into 6-nitro-3-aminobenzoic acid (compare Griess Ber. 1872 5 198). A certain amount of resinous products are formed during this nitration. p-Fluorobenzoic acid is nitrated by adding i t slowly to boiling nitric acid (D 1.52) and pouring the product into excess of cold water. The sole product is 4-f2uOrO-3-nitrOhenxOiC acid slender needles m. p. 121-1 22O which with alcoholic ammonia yields 3-nitro-4-amino- benzoic acid (compare Salkoweki this Journ.1875 72). Comparing the four series of fluoronitro- chloronitro- and bromo- nitrobenzoic acids they show in each case R steady rise in the ni. p. on passing from the fiuoro- through the chloro- t o the bromo-deriva- tives. The point of entrance of the nitro-group in all the above nitrations is in every case what would be expected from a knowledge of the behaviour of fluorobenzene and benzoic acid respectively on nitration. W. G. Preparation of Halogen-alkyl Esters of o-Acetoxybenzoic Acid. It. WOLFFENSTEIN (D.R.-P. 276809 ; from J. SOC. C'hem. I d . 1914 33 1172. Compare A 1912 i 556).-Polyhaloidalkyl esters of salicylic acid are treated with acetylating agents. For example tert.-trichlorobutyl salicylate is heated with acetic anhydride and anhydrous sodium acetate at 160-180" and the product is treated with water and with aqueous sodium carbonate the ester being finally extracted by ether c.s.i. 62 ABSTRACTS OF CHEMICAL PAPERS. Preparation of Halogen-alkyl Esters of o-Acyloxybeneoic Acids. R. WOLFFENSTEIN (D.IC.-P. 276810 ; from J. Xoc. Chem. Ind. 19 14 33 11 72. Compare preceding abstract).-Polyhalogen-alkyl esters of salicylic acid are treated with acylating agents other than those which introduce the acetyl group. c. s. cis-Caronic Acid and Some of Its Derivatives. R. LOCQUIN (Bull. Xoc. chim 1914 [iv] 15 747-751. Compare Baeyer and Ipatiev A. 1897 i 83 ; and Perkin and Thorpe T. 1899 75 48),- cis-Caronic acid can readily be distinguished from its isomeride terebic acid by its instantaneous m.p. taken on mercury that of the former rising t o 186" and that of the latter remaining at 174'. Methyl cis- caronate C9H1404 is a colourlees mobile liquid b. p. 111-113°/ 14 mm. Ethyl cis-caronate C,,H,,O bas b. p. 129-330'/13 mm. The acid can be readilyregenerated from the esters by boiling with 15% aqueous hydrochloric acid under reflux until the oily layer dis- appears. Caronic anhydride is best prepared by boiling the cis-acid for some time with a n excess of acetyl chloride or thionyl chloride. 1x1 benzene solution with aniline i t yields an acid anilide CO,H*C,H,*CO*NHPh rn. p. 205' which if kept for some time at 180-190° is converted into the a d C,H,<CO>NPh co m. p. 143'. W. G. Glucosides of Chalkones [P henyl Styryl Ketones].G. BARGELLINI (Gazzetta 19 14 44 ii 520-528).-The author has prepared various glucosides of phenyl styryl ketones by condensation of the glucoside of salicylaldehyde helicin and of the glucoside of vanillin with different hydroxy-ketones. The condensations take place in alcoholic solution a t the ordinary temperature and in presence of either 40% sodium hydroxide solution or piperidioe. The glucosides are not resolved into their constituents by emulsin and therefore belong t o the a-series. They are not hydrolysed by acids but they dissolve in concentrated sulphuric acid giving first an intense red coloration and afterwards an orange-yellow or red solution. The gtucoside of 4-hydroxyphenyl 2-hydroxlystyryl ketone OH*C,H,*CO CH CH C,H,* O*C,H 1105 prepared from the glucoside of salicylaldehyde and p-hydroxyaceto- phenooe forms a felted mass of minute cream-yellow needles m.p. 26 7-25 9 O (decom p.). The glucoside of 2-hydroxy-4-rnethoxyphenyl 2-hydroxystyryl ketone O M e ~ C 6 H 3 ( 0 ~ ) * ~ O * C H C ~ * C H 4 * O * C ~ ~ ~ obtained from the glucoside of salicylaldehyde and 2-hydroxy-4-methoxyacetophenone forms flocks of canary-yellow needles xu. p. 213-215". The glucoside of 2-hydroxy-5-methoxyphenyl 2-hydroxysty~yl ketone C,,H,,O forms small orange-yellow needles m. p. 255-227'. The g Eucoside of 2-h y droxy - 3 4 -dime t hoxypheng l 2 -h y drox ystyry Z ketone OH*C,H,(OMe),* co CH:CH C,H,* o*C6H1,o5 forms bright yellow medles m. p. 195-196' (decornp.).ORGANIC CHEMISTRY. i. 63 The glucoside of 1 -hydroxy- /\A 2-naphthyl 2 - hydroxystyryl 1 I ,,!-GO* CH C H * C,H,*O* C,H1,O ketone (annexed formula) \A/ prepared from 2-acetyl-a- naphthol and the glucoside of salicylaldehydo forms flocculent aggregates of minute ormge-red needles m.p. 264-246' (decomp.). CHO-(~>-O*C6H,05A~ ~~tra-acetylglucovanillin (annexed formula) prepared from tetra-acetyl- bromoglucose and vanillin in presence of sodium hydroxide forms shining colourless prisms m. p. 143-144'. The glucoside of 2-lqdroxy-4-methoxyphenyl 4-hydroxy-3-methoxy- styryl ketone O?il[e* C,H,( OH)*CO* CH :CH*C,H,( OMe)* 0*C,H,,05 prepared from the preceding compound and 2-hydroxy-4-methoxyaceto- phenone forms canary-yellow crystals m. p. 220-225O. OH OMe T. H. P. Preparation of Anthraquinone. CHEMISCHE FABRTK GRIESHETM- ELEHTRON (U.S.Pat. 1119546; from J. Xoc. Chem. lnd. 1915 34 22).-Anthracene is treated with nitric acid in the presence of a mercury salt and an indifferent liquid below 60'. The product which is a mixture of unstable meso-nitro-derivatives of nnthracene is con- verted into anthraquinone by treatment with an oxidising agent in the presence of a mercury salt above 60'. c. s Preparation of Aminoanthraquinones. FARBWERKE VORM. MEISTER LUCIUS & BHUNING (Fr. Pat. 469741 ; from J. Soc. Chem. Ind. 1915 34 22. Compare this vol. i 20).-Organic amino- compounds may be used in place of ammonia. c. s. Constituents of Esential Oils. I. Galbanum Oil. 11. Syntheses in the Sesquiterpene and the Diterpene Series. F. W.SEMMLER and K. G. JONAS (Ber. 1914 47 2068-2082).-1. The oil obtained by the distillation of Galbanum resin has b.p. 55-195O/15 mm. D25 0.9353 !nF 1.49395 and a t8'. By repeated fractional distillation it is separated into nine fractions of which the following have been examined. The fraction b. p. 56.5-75O/15 mm. obtained i n 29.506 yield contains pinene nopinene (P-pinene) and myrcene but no camphene. The fraction b. p. 100-120°/15 mm. (245%) contains a substance CloHl6.O (enolisible ketone?) which can be esterified and yields by oxidation a ketonic acid C,,,H,,O ; from the latter the dicarboxylic acid C9H1404 is obtained by the action of an alkaline solution of bromine. The fractions b. p. 120-150°/15 mm. (5%) contain cadinene. The fractions b. p. 150-170'/'15 mm. (36%) contain a tertiary sesquiterpene alcohol cadinol C,,H,60 which in a slightly impure state has b.p. 155-165°/15 mm. D20 0.9720 nD 1,50702 and uD +22O and yields an acetate C17H2,02 b. p. 160-170°/9 mm. DU 0.9916 nz 1.49870 and a' + 14'. By treatment with potassium hydrogen sulphate phthalic or succinic anhydride or formic acid,i. 64 ARSTRACTS OF CHEMTCAL PAPERS. cadinol is converted into I-cadinene. By reduction with hydrogen in the presence of platinum I-cadinene is converted into 1-tetrahydro- cadinene C15HB8 b. p. 125-128"/10 mm. D20'5 0.8838 ng'5 1.48045 I-Tetrahydrocadinene obtained by the reduction of I-cadi- nene dihydrochloride by sodium and alcohol has b. p. 125-12S0/ 10 mm. D21'5 0.8827 ng'5 1.48094 and ag'5-520. The colour re- actions of cadinene described by Wallach could not be obtained by the authors.11. Octahydro-a-camphorene (Semmler and Rosenberg A. 191 3 i 377) has b. p. 183-186'/14 mm. DzO 0.8331 n 1.46001 and From the liquid products obtained by the action of hydrogen chloride on the diterpene fraction of polymerised myrcene there is produced by the elimination of hydrogen chloride a bicyclic diterpene C,,H, for which the name iso-a-camphorene is proposed. It has b. p. 193-197"/19 mm. DZ1 0.9029 nD 1*50300 and [.]D+o" and is reduced by hydrogen and platinurn to hexahyclroiso-a-carnphorene C20H38 b. p. 180-186"/14 mm. DZ1 0.8588 nD 1.46800 and By heating with anhydrous oxalic acid in a sealed tube linalool has been converted directly into a-camphorene and citronellaldehyde into a diterpene oxide C,,H,,O b. p. 190-200°/17 mm. DZo 0.9193 nD 1,49156 al,+4" which is reduced by hydrogen and platinum to a saturated substance C,,H,,O b p.183-187°/17 mm. DZ0 0.8944 By reduction in dry ether by hydrogen and platinum cyclokoprene- myrcene (Semmler and Jonas A. 1913 i 742) yields hexahydrocyclo- isoprenemyrcene C15Hao b. p. 133-135"/15 mm. DZO 0.8245 nD 1.45497 an +-O' the formation of which is a complete proof of the monocyclic nature of cycloisoprenemyrcene. Since cadinene has a bicyclic structure of the naphthalene type and since the condensation of acyclic terpenes with isoprene yields mono- cyclic sesquiterpenes the authors hoped to synthesise bicyclic sesqui- terpenes for example cadinene by condensing monocyclic terpenes with isoprene. By heating I-a-phellandrene with isoprene in a sealed tube a sespuiterpene Cl5HZ4 is obtained which has b.p. 129-132'1 15 mm. DZ0 0.8976 12u 1,4949 and a - 1 5 O and is probably identical with P-santalene. Limonene and isoprene do not react by heating in a sealed tube but by their reaction in glacial acetic acid at 35" or by treating the two hydrocarbons in the proportion 2 1 with about three times the quantity of ethylsulphuric acid a t - 18' to - loo a sesquiterpene Cl5HZ4 b. p. 120-127°/10 mm. DZo 0.S89 n 1.502 otD +Lo is obtained which appears to be monocyclic. Similar results (and probably tho same sesquiterpene) are obtained with - 20". [.ID k O0* [a]D k 0'. nD 1.47319 a D + 3". isoprene and pinene or sabinene. c. s. The Synthesis of Colouring Mattens. E. NOELTTNG (Arch. Xci. phys. nat. 1914 [iv] 38 244-262 337-343).-An historical survey of the chemistry of dyes containing a classification of those used on a large scale into groups a brief account of the properties of each group being given.W G.ORUANIC CHEMISTRY. i. 65 Vat [Anthracene] Dyes and Intermediate Products for Use in their Preparation. BADISCHE ANILIN- & SODA-FABRIK (1st. Add. t o Pr. Pat. 458949 ; from J. SOC. Chem. Ind. 1915 34 22).- Imines of anthracene-1 9-dicarboxylic acid in which the hydrogen of the imino-group is replaced by a hydroxyl alkyl or aryl group are obtained by treating the acid or its anhydride with hydroxylamine or with an aliphatic or aromatic primary amine. For example the methylimine is obtained by heating anthracene-1 9-dicarhoxylic anhydride with ten times its weight of 13% aqueous methylamine a t 150" for 5 hours.The substituted imines are converted into vat dyes analogous t o those obtained according t o the principal patent by fusion with alkalis. The dyes may also be obtained by treating the dyes mentioned in the principal patent with alkylating or arylating agents. I n general the products dye rather bluer shades than do the substances c. s. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 276808; from J. SOC. Chem. Ind. 1914 33 1151).-Isatin is oxidised by potassium per- manganate in neutral aqueous suepension yielding a compound CI6H8O2N2 m. p. 262O yellow crystals which is converted into indigo- white by sodium hyposulphite and a n excess of alkali hydroxide and is very reactive and therefore suitable for the preparation of indigoid D i k e t o m e t h y l t r i a z i n e and its Derivatives.A. OETROGOVICH (Gazzettu 1914,44 ii 562-585).-4 6-Diketo-2-methyl-1 3 :5-triazine (compare A 1911 i 1036) may be conveniently prepared by heating biuret with acetyl chloride in a sealed tube the isolation and purification of the acetylbiuret being thus avoided The free base crystallises either i n the anhydrous state or with 1H,O and has m. p. 276-277" (decomp.). The marked acidity of the compound shown by the ability of its aqueous solution to decompose carbonates and the fact t h a t all i t s metallic derivatives contain only one equivalent of metal are in from which they are derived. Preparation of an Oxidation Product of Isatin. dyes. c. s. better accord with the enolic structure NH<gf:i?>C*OH than with the diketonic formula previously given.The hydrochloride C,I'I,O,N,,HCl was prepared but the correspond- ing sulphate and selenate could not be obtained the hydrogen sulphate C,H,O,N,H,SO (or + H,O) and hydrogen selerzate C,H ,02N,,H2Se0,,&H,0 being formed under all the conditions employed. When heated a t above 100' or when repeatedly evaporated in aqueous solution on a water-bath the platinichIoride (C,H,O,N,) H2PtCI6,4H2O (compare Nencki Ber. 1876 9 234) loses hydrogen chloride with formation of dichloroplatodiketomethyltriazine C,H,O,N,*PtCl,* C4H402N3 which separates a s a pale yellow powder. Attempts to prepare the aurichloride resulted in the reduction of the auric chloride t o metallic gold which was deposited in shining leaflets.This reaction is very sensitive and may be employed t o detect small quantities of the base either in the pure state or ini. 66 ABSTRACTS OF CHEMICAL PAPERS. admixture with a large proportion of acetylbiuret which does not reduce auric chloride. Diketomethyltriaxilns phosphonaolybdate forms minute lemon-yellow acicular prisms. The sodium derivative of diketomethyltriazine C,H,ON,*ONa crystallises with 14H20 or 2H,O. The silver +&H20 and +H,O the barium + 7H20 and the basic Zeud derivatives O( *Pb*C4H402N3)2 + 8H,O were prepared. T. H. P. Mechanism of F o r m a t i o n of Azo.compounds by the Action of Diazonium Salts on Phenols and on Amines. G. CHARRIER (Gazzetta 19 14 44 ii 503-51 6). -The author discusses the various theories which have been advanced to explain the formation of hydroxy- and amino-azo-compounds by the action of diazonium salts on phenols and on amines.None of these theories explains however the varying reactivity in this respect shown by diazouium salts of phenols and of their ethers. The most secure basis for any explanation of the mechanism of this combination is furnished by the very general diazo-decomposition of the nitrates of (1) hydroxyazo-compounds and of their etherp and (2) aminoazo-compounds and of their alkyl derivatives (compare Charrier and Ferreri A. 1922 i 812; 1913 i 535 1111 1112,1113; 1914 i 597 599 748 1178). One advantage of such an explanation is that i t allows of the reconciliation of Blomstrand’s structural formulae for diazonium salts with certain of their more important reactione such as the formation of hydroxy- and amino-azo.compounds. In the light of the author’s experimental results it is probable that the formation of the so-called diazoamino-compounds or aryldiazoanilideq to which the nitrates of hydroxyazo-compounds show certain analogies in behaviour may be regarded as taking place according to the scheme Ar-NH + NiNAr’Clz N/HAr-..-.NI!YAr’Cl= NHAr*N:NHAr‘C‘l= =NHAr*N:NAr‘+HCl. T. H. P. ,,H .._______.._._ The c o a g u l a t i o n of Albumin by Pressure. P. w. BRIDGMAN (J. Biol. Chem. 1914 19 511-512).-Egg-albnmin was enclosed i n a nickel-steel case and pressure transmitted t o it by mercury. If the pressure is applied slowly any rise of temperature is negligible; a pressure of 5000 atmospheres for thirty minutes rendered the white of egg a little stiff ; 6000 produced coagulation like curded milk ; 7000 made it like a hard-boiled egg.The rate of coagulation is increased at low temperatures. J. A. MENZIES (Proc. physiol. Xoc. 1914; J. Physiol. 49 iv-v).-The blood is mixed with a quarter of its volume of a syrupy solution of potassium carbonate and heated on the water-bath until it sets into a brown coagulum. This is thrown into twice its volume of alcohol and left overnight for thorough extraction of the bEmatin ; on neutralising this dark brown extract with hydrochloric acid hsematin is precipitated and is W. D. H. The Preparation of Haematin.PHYSIOLOGICAL CHEMISTRY. i. 67 purified by washing with distilled water alcohol and ether. Hsma- tin may also be precipitated by ether or by calcium chloride and ammonia or baryta mixture. Calcium and barium compounds respectively are thus obtained. W. D. H. Hzematin Compounds. J. A. MENZIES (Proc. physiol. Xoc. 1914; J. Phyoiol. 49 v-vi).-Hzmatin exists in two forms one which occurs in solutions and moist precipitates is soluble in dilute hydrochloric acid. The other the dry substance is insoluble in dilute acid but is readily soluble in alkali. The first may be a hydrated aubstance and is changed by drying in the same way that a lactone is formed from a hydroxy-acid. Haematin in acid solution is precipitated by dialysis the acid acting as a solvent and not forming a compound. I n alkaline solution it is not precipitated on dialysis although the solution becomes neutral to litmus. Sodium and potassium therefore form compounds with hsmatin which are soluble in water. The calcium and barium compounds are insoluble in water but dissolve in alkali with the formation of the alkali compound. Hsmoglobin is analogous to a salt globin playing the part of a base and hsmatin that of an acid. W. D. H.