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It~ed17/12/1895. PROCEEDINGS OF THE CHEMICAL SOCIETY. EDITED BY THE SECRETARIES. No.157. Sesaion 1895-96. December 5th, 1895. Mr. 8..G. Vernon Harcourt,,President, in the Chair. Certificates were read for the first time in favour of Messrs. .Tohn Allan, 242,Moss Lane East, Mnnchester ; Herbert Lister Bowman, 13, Sheffield Gardens, Kensington, W. ; James Kerry Burbridge, Moor’s Lea, Winchmore Hill ; Frank Dixon, 73, King Edward Road, South Hackney, N.E. ; Joseph Edward Morrison, Montreal ; Harold Rostron, 70, Davenport Street, Bolton ; Peter B. Scotland, 30, Stirl-ing Street, Airdrie, N.B. ; Aitken Migget Simpson, 4,Kitto Road, St. Catherine’s Park, S.E. ; Henry G. Smith, Technological Museum, Sydney, N.S.W. Mr. OTTOHEHNERcalled the attention of the Society to what he regarded as unprofessional conduct on the part of a Fellow of the Society whose name appeared on the certificates of certain candidates who were to be balloted for that evening.Professor ARMSTRONG seconded, that then moved, and Mr. GROVES the Council be requested to consider this case. Professor TILDEN, having spoken in support of the motion, it was put to the meeting and carried. The following were duly elected Fellows of the Society :-George Percy Bailey, B.A., The Earl of Berkeley, Arthur Jenner Chapman, Wm. Chattaway, George Bertram Cockburn, B.A., Charles Crocker, Gurney Cuthbertson, William Dixon, Edward Henry Farr, Charles James Fauvel, Patrick Joseph D. Fielding, Jervis E. E’oakes, Stanley Fox, James Gardner, Edward Graham, B.Sc.206 Edward Henry Grossmann, The Rev. Henry Arthur Hall, M.A., Edgar Septimus Hanes, C. E. Harrison, B.A., James Henderson, B.Sc., Thomas Hawkins Percy Heriot, Frederick Arthur Hillard, B.A.,Arthur Edward Holme, M.A., Oxon., Alfred James: Frederick Edward Johnson, William Oakes Kibble, Leonard P. Kinnicut,, James McCreath, David James Morgan, William Henry Pennington, Martin Priest, W. T. B. Ridge, William Round, William Augustus Rugginz, Clarence Arthur Seyler, B.Sc., Mathew Smith, B.A., Frank R. Stephens, George Stone, W. J. Tibbals, John Williams, B.A.,Thomas Rowland Wingfield, and Harold E. Wright. Of the following papers those marked * were read :-“141. “Researches on the terpenes. VI. Products of the oxidation of camphene: camphoic acid and its derivatives.” By J.E.Marsh and J. A. Gardner. In this paper some of the oxidation products of cnmphene are de- scribed, among them being camphoic acid, CIOH140S,as chief product, camphoric acid in small quantity, tereph thalic acid, and succinic acid. From camphoric acid were obtained :-Anhydrocamphoic acid, C,oH,40,; cis- and trans-camphopyric acids, C,H1404; camphopyric chloride, C,H12C1,02; Chlorocamphopyric chloride, C,H,,C I3O2; chlorocalvphopyric anhydride, C,H1,C1O3; camphopyranilic acid, C,Hl,03(~HC,H,); and salts of camphoic and camphopyric acids. With camphopyric acid is compared comphoric acid in respect of their bohh existing as cis- and trans-isomers, and also as regards the acid chloride, chloroacid chloride, and chloroanhydride, producible from bot<h camphoric and camphopyric acids.Tho reduction of camphopyric acid to hexahyclrometaxylene has also been accomplished, while the constitution of camphene is dis-cussed from the general analogy of camphoric and ca,mphopyric acids, from the probability of their both containing a hexamethylene nucleus, from the fact of the production of both acids from campliene and from the probability that neither camphoic acid nor camphopyric acid is producible from camphoric acid. DISCUSSION. Professor ARMSTRONG inquired whether Mr. Marsh could give any further information as to the isomeric bromocamphor described by him on a previous occasion, siiice he (Professor Armstrong) had not been able to confirm Mr.Marsh’s results. If a molecular proportion of bromine be added to camphor heated 207 on the water bath, using 1or 2 per cent. in excess, so as to ensure the absence of camphoi*, an almost theoretical yield of bromocam-phor (m. p. 76") is obtained. If, to purify the product, it be dis- solved in hot alcohol, the greater part of the bromocamphor at once crystallises out as the solution cools, and if the small amount of oily residue obtained from the mother liquor-a mixture of mono-and dibromo-camphor-be digested with alcoholic potash, so as to reduce the dibromo-compound, this also ia converted into well-crystallised bromocarnphor. According t'o Marsh (Trans., 1890,€328): if camphor be brominated in presence of alcohol, almost half the product consists of an isomeric bromocamphor of ill-defined crystalline form and very low rotatory power.A product such as he describes can undoubtedly be obtained, but it is not difficult to separate bromocnmphor from it, and its pro-perties are certainly those of an impure material. It is desirable that this product should be more fully examined, and its nature definitely established, in view of the interest attaching to isomeric cis- and trans-modifications of camphor derivat,ives ; the account, given by Marsh is incomplete as it stands, and it is to be hoped that he will study further the action of bromine on camphor in presence of alcohol. Mi,. MARSH,in reply, said he had no doubt as to the existence of khe second bromocamphor. He regarded the action of bromine on camphor as very considerably modified by the presence of alcohol, which, by reacting at once with the hydrobromic acid to form ethyl bromide, favoured the existence of the unstable isobromocamphor.The isobromocarnphor has been obtained in crystals having a definite melting point. Its specific rotation is more than 100" lower than that of the ordinary modification, while it is also lower than that of camphor itself'. When distilled it is converted partially, without ap- preciable decomposition, into the ordir,ary modification, the rotatory power after one distillation being raised about 50°, whilst ordinary bromocamphor may be readily obtained from the distilled product by crjstallisation from alcohol. *142 " New derivatives from ~-dibromocamphor."By Martin 0.Forster, Ph.D. Early in this year a preliminary note was published in the Pro-medinga (p. 4), describing the behaviour of a-dibroniocamphor towards nitric acid, an investigatioii undertaken at the suggestion of Professor Armstrong. It appears desirable to place on record the results which have since been obtained in this connection. It has been already stated (Zoc. cit.) that a compound of the formula CIoHl2Br,O2is produced when a-dibromocamphor is acted on by fuming nitric acid (d. 1-52>,and that reduction wit,h zinc dust and alcoholic ammonia connrts this substance into a compound of the formula C,,H,,BrO,. A fuller investigation Iias shown that the com- position of these products is represented by the formula3 Cl,H14Brz0, and C,,H,,BrO, respectirely, which, in fact, correspond more closely to the analytical results already pnblished than do the formulae pre- viously chosen.The compounds C,oH,,Br20zand CloHl,BrO, having given rise to numerous derivatives, it has becii fouiicl necessary to adopt some system of nomenclature by means of which they may he designated and the sclieme which is now proposed has been selected because it aims at representing in the name of a derivative the class of corn-pounds to which it belongs. It having been found that the initial sompound C,,H,rBr202 has the properties of n lactone, this substance will be referred to as di~~'o~~~ocamp1~oZi~;the product of its reduc- tion, CIOHlBBrO2,is an unsaturated (carboxylic) acid, and will be called bronzocam,phoi-eiiic acid, the termination " olid "being significant of lactones, whilst ethylenic linking is represented by the syllable '' en." DibromocamphoZid, CI0HllI3r2O2,is obtained by the action of fuming aitric acid (d.1.52) on a-dibromocamphor in quantity nrrioirnting to about 10 per cent. of the material used; it crystallises in long, colourless, transparent needles, and melts at 152'. Alcoliolic potash converts it into the lactone, C10H1403, whicli melts at 174O, and yields the acid CloH,,OIon hydrolysis ; the lactone is readily converted by bromine into the bronzoZacto?ae, CloHISBr03, fromwhich ci~~stnllis~~s alcohol in lustrous, silky needles, and melts at 196-197'. Bronzocamphorenic acid, C10H15Br02,is formed when an alcoholic solution of dibromocampholid is reduced with zinc dust and am- monia ; it crystallises from alcohol in thin, lustrous, six-sided plates, and melts at 159".The ba~irimsalt contains 2H20, and the xiuc, Copper, and siZ2~salts are also crystalline ; the methylic salt is a fragrant oil, which boils at 255" under a pressure of 767.5 mm. The unsatu~ated character of bromocamphorenic acid is indicated by its behsviour towards potassium permangnnate, which is jmmeclintely c1ecQlorisecl by the solution in sodium carbonate, a dicarboxylic acid being produced having the formula C,,H,,O,, and melting at 1S4O; a cold solution of bromine in chloroform is at once decolorisecl by the acid in the same medium, hydrogen bromide and dibromocampholid being formed.Canzphorenic acid, C10H1602,is obtained by reducing a boiling nlka- line solution of bromocamphorenic acid with sodium amalgam ; it clytallises from alcohol in colourless needles, and melts at 161". The sodium salt crystallises from strongly alkaline solutions in silky needles ; the methylic salt is a colourless oil, which boils at 215" under a pressure of 767.5 mm., and has the odour of camphor. The anhy-dride, C,,H,,O,, melts at 84-85°. a-Bromocampholid,C,,HI,Br02,is obtained by the action of concen-trated sulphuric acid on bromocaniphorenic acid, and is isomeric with that substance ;the production of an isomeric lactone under the influ- ence of sulphuric acid, and the formation of a bromolactone on treat-ment with bromine, are features which characterise &-unsaturated acids.a-BYOm ocampholid crys tdlises from alcoho I in lustrous plates, and melis at 92-93' ; it is indifferent tov:ards bromine, and is hydro-dysect by a boiling aqueous solution of barinni hydroxide. ~-BrornoccL1,?23lLoliclis isomeric with the foregoing substance, and is formed from camphorenic acid or the sodium salt and bromine ; it crystallises from ether in transparent prisms, and melts at 62". It is indifferent towards bromine, and when the alcoholic solution is rednced with zinc dust and ammonia, camphorenic acid is formed. C'ampholitl, CI0Hl6O2,is obtained by dissolviug camphorenic acid in concentrated sulphui-ic acid, the change being parallel with that attending the conversion oE bromocamphorenic acid into a-bromo- campholid ; it is very readily soluble in most organic solvents, but sepai.ates from petroleum in minute white crystals, and melts at, 176-1 77".Campholid is very volatile, and sublimes slowly below 100" ; it resembles camphor in appearance, and Ims the odour of that substance. It is indifferent towai3ds bromine, but yields an acid, CloHlaOa,on hydrolysis, which crystallises from ethylic acetate in magnificent lustrous needles, melting at 179". *143. ''Isomeric r-bromo-0-nitro camphors." By Arthur Lapworth, D.Sc., and F. Stanley Kipping, Ph.D., D.Sc. It has already been shown by one of the authors (Proc., 148, 39), that n--dibromo-camphor is attacked by concentrated nitric acid, and fhat hhe product consists partly of a bromocamphoric acid and partly of an oil, which, by the action of alcoholic potash, yields a bromo-nitro-camphor.It has now been found that if this oil be boiled with concentrated nitric acid until it is free from rr-dibromo-camphor, it subsequently solidifies to a crystalline cake, from which brornoizitro-camphor can be easily isolated. (Found C: = 34.05; H = 4.21 ;Br = 44.98 per cent. -Calc. C = 33.80 ; H = 3.67; Br = 45.05 per cent.). This compound separates from cold light petroleum in the form of long, flat needles, melting at 54O, and is insoluble in water, but soluble in most of the usual organic solvents. When boiled with alcoholic potash it loses 1atom of bromine, and affords the potassium salt of -the bromo-nitro-camphor previously described (Zoc.cit.). The further 210 investigation of this bromo-nitro- camphor leads to the conclusion that it is polymorphous. The crystals from chloroform and petroleum melt sharply at 133--134O, and solidify on cooling to a ci-ystalline mass, which fuses at 126O; this is also the melting point of crystals obtained from alcoholic or dilute acetic acid solutions, whereas large pyramidal crystals deposited from a mixture of ethylic acetate and chloroform melt at 108' immediately solidify, and melt once more at 126". A 6 per cent. solution gave La]D = +33.04. Reciuction of r-bromo-a-nitro-camphor with zinc dust and acetic 5ields an aniido-compound with a strong ammoniacal odonr, which is probably ordinary amido-camphor, as it contains no bromine, and agrees in properties with the compound described by Schiff (Bey., 13, 1 404). If, however, the bromo-nitro-camphor be carefully reduced with sodium amalgam in alkaline solution, it is converted into a new r-bromo-a-amido-camphor, C,oH,4BrONH,, the hydrochloride of which crystallises from water or acetone in colourless needles or plates.(Calculated for C,oH,4BrONH,*HC1.C = 42.46; H = 6.05; Br + C1 = 40.81. C1 = 12-56. Found C = 42.57; H = 6.05: Br + C1 = 40.36. C1 = 12.70). The oxalate is almost insoluble in water, and melts at 201"; the platinichloride forms silky, yellow needles, melting with decom-position about 219".rr-Bromo-a-nitro-camphor dissolves in hot hydrochloric acid, and the solution on cooling deposits erg-stds of a new compound, which is soluble in hot sodium carbonate solution, and separates from ben-zene in flat needles melting at 137". This substance is an isomeric rr-bromo-a-nitro-camphor. (Found C = 43.57; H = 5.32. Calc. C = 43.47; H = 5.07 per cent.). It differs from its isomeride inasmuch as it dissolves readily in hot water, crystallising from the solution in thin plates melting at 108O ; it is also much less soluble in ethylic acetate and in benzene, and it yields a, blue copper salt, that of its isomer being pink. Its specific rotation is also much greater, viz., [a]D = +52*7.That these two 7-bromo-a-nitro-camphor are structurally identical is probable from the fact that they both yield z--bromo-camphoric acid on oxidation with nitric acid ; it is concluded, therefore, that the difference between these two substances is of the same nature as that subsisting between cis- and trans-modifications of cyclo'id deriva- tives. *144. ''Derivatives of rr-bromocamphoric acid." By F. Stanley Kipping,Ph.D., D.Sc. r-Bromocamphoric acid, CloHlaBrOa,prepared by oxidising r-di- 211 bromo-camphor (Proc., 148, 33), is readily acted on by alkalis giving, according to the conditions of the experiment, a lactonic acid, CloH14O4 (m. p. 164-165"), or n--hydroxycamphoric acid, C,,H,,O, (Proc., 151, S8j. The lactonic acid is the initial, and not the final, product of the action, as was at first supposed ; when heated with excess of aqueous potash it is converted into a salt of the n--hydroxy acid.The hydroxy-acid, treated with acetic chloride, yields an acetyl derivative of its anhydride ; this substance crystallises from ethereal petroleum in prisms melting at 89-96", and is dimorphous, another modification melting at 86-47". When the hydroxy-acid is distilled, it yields as principal product a lactonic acid, C,,H1404(m. p. about asso), iso- meric with the compound referred to above, and identical with that obtained by heating n--bromo-camphoric acid with qninoline (Zoc. cit.). The lactonic acid of lower melting point is also converted on dis- tillation into the isomeride of higher melting point, whereas the latter, on fusion with potash, gives tEe n--hydroxy-acid.n--Hydroxycamphoric acid and the lactonic acid melting at 164-165", are readily oxidised by nitric acid, giving an acid of the composition CloHla06(Zoc. cit.), but the lactonic acid of higher melting point is exceedingly stable, and seems not to be attacked by boiling nitric acid ; on prolonged treatment with alkaline permanganate, however, either at ordinary temperatures or at 100°, it yields, amongst other products not yet investigated, a small quantity of a derivative of dihydroxycamphoric acid, C10H1606,namely, a hydroxylactonecarb-oxylic acid of the composition CloH,,O,. This substance crystal- lises from hot water, in which it is readily soluble, in long, slender needles, and from a mixture of moist ether and etliylic acetate in well-defined, transparent prisms melting at about 265" ; these crystals lose 1H20, and become opaque when heated at loo", so that the substance is probably a monohydroxylactonic acid of the composition C10R,405+ H20, and not a dihydrosy compound. Its identity with the acid obtained from n--dibromocamphoric anhydride (see following note), and the fact that the lactone ring in the substance (m.p. 226') from which it is derived is very stabie, lead to the conclusion that it is the ir-hydroxy group which has taken part in the lactone forma- tion. It seems probable from the facts already established that the r-bromine atom in n--bromo-camphoric acid is a constituent of a -CHzBrgroup.145. '' r-Dibromocamphoric acid and its derivatives." By F. StanleyKipping, Ph.D., D.Sc. The derivatives of n--bromocamphoric acid, which have been referred 212 to in the preceding and in previous notes, are so stable that attempts to obtain from them sitnple oxidation products containing less than 10 atoms of carbon have so far been unsuccessful ; as they also 1-esist the action of bromine, or giye with it ill-defined substances, esperi- ments were made with the obj ecL of brominating rr-bromocamphoric acid itself, in the hope of obtaining a dibromo-derivative which, on treatment with alkalis, would yield products more easily oxidisable than those prepared from the monobrorno-acid. n--Dibromocantphol.ic ad ydride, C1,H1,BrZOs, is obtained on treahiiig dry n--bromocamphoric acid with bromine and amorphous phosphorus under the usual conditions ; it crjst)allises from chloroform in large, transparent plates, melts at about 210" without decomposing, and is readily soluble in warm chloroform but very sparingly in cold etlicr, and insoluble in cold water and cold sodium carbonate solution.n--DibromocampI~o~ic is deposited in small plates acid, C10Hf4BrZOJ, when the anhydride is dissolved in hot concentrated nitric acid and the solution evaporated on the water bath ; it melts and decomposes at 210-211°, and is readily soluble in cold ether, but insoluble, or nearly so, both in chloroform and in hot water. It dissolves in dilute sodium carbonate solution with effervescence, and on acidifying the solution after heating for a few minutes z--bromocamphanic acid (see Icelow) is precipitated.r-Dibromocamphoric acid is stable at loo", but when heated at its melting point part is reconverted into the dibromo-anhydride and part is transformed into z--bromocamphaiiic acid with liberation of hydrogen bromide. rr-Bron2ocuvnphanic acid, CIOHl3BrO4,is formed when the dibromo- anhydride is boiled for some hours with water aiid a little alcohol ;it separates from cold dilute alcoliol in fem-like crystals which contain water, but from hot water and from a mixture of chloroform and ethyl acetate anhydrous crybtals are deposited ; it melts at 176--177O, and is soluble in sodium carbonate solution with effervescence.On prolonged boiling with water, or on heating with aqueous alkalis, r-dibrornocamphoric acid is converted into an acid melting at about 265", and identical with the oxidation product described in the preceding note. 146. "20-Bromocamphoric acid." By F. Stanley Kipping, Ph.D., D.Sc. The fact that rr-bromocamphoric acid is obtained directly on oxidis- ing a-dibromocamphor, whereas the rr-dibromocamphoric acid can be prepared from the corresponding anhydride (see preceding abstract) led the author to try and isolate the unknown bromocamphoric acid corresponding with Wreden's bromocamphoric anhydride : this was accomplished by hydrolysing the anhydride with concentrated nitric acid under suitable conditions, but the yield was comparatively small, most of the anhydride being recovered. 213 The bromocamphoric acid, which, it is proposed, should be dis- tinguished from the isomeric r-acid by using the initial letter of Wreden's name (he having first prepared the anhydride), crystallises from a mixture of chloroform and ether in large, transparent, ortho- rhombic pyramids, having the cornpositmionCloH,,BrOa.(Fonnd C = 48.9, H = 5.4 : theory C = 439,H = 5.4per cent.) It dis-solves freely in ether, but is almost insoluble in benzene and chloro- form, and melts at 195-196', charring slightly and effervescing : it is readily soluble in sodium carbonate solution, by which it is rapidly decomposed, yielding ordinary camphanic acid.When heated for a short time with acetic chloride the acid is reconverted into the anhrdride from which it is derived. Sschan (Be,.., 27, 2112, and 28 ; Ref. 922), has recently isolated an acid, which he desiqnates Z-bromisocamphoric acid ; this compound appears to be different from the acid which forms the subject of the present communication, but' Aschan's original paper being at present inaccessible, this point cannot be finally- settled. The author also refers to a curious phenomenon observed in crys-tallising zc-bromocamphoric aohydride from chloroform ; in some cases the solution becomes highly supersaturated, and cry stallisation ultimately takes place with almost explosive violence. 147. r-Chlorocamphoric acid." By F.Stanley Kipping, Ph.D., D.Sc., and William J. Pope. Optically inactive camphor sulphonic chloride (Kipping and Yope, Trans., 1893, 63,548) yields, on distillation, two products, namely, a crystalline iiiactive rr-chlorocamphor and an oil (Trans., 4895, 67, 371). When the mixture of these two compounds is heated with nitric acid the oil is rapidly oxidiscd and passes into solution, but n--chloro- camphor, like rr-dibromocamphor is at,tacked and dissolved rather slowly. On cooling the solution, crystals and an oil are deposited. The crystalline substance is rr-chlorocamphoric acid, the oil being prob- ably n--chloro-a-nitrocamphor, the formation of which, under the above condition, would be analogous to that of n-a-dibromo-a-nitro-camphor from rra-diloromocamphor (see preceding note by Lapworth and Kipping) ; other substances are present in the filtrate from nitric acid, but they have not yet bcen examined.Inactive rr-chlorocamphoric acid, C,oHljC'lO, resembles n--bromo- camphoric acid very closely in ordinary properties. It is very sparingly soluble in hot water, from which it cryvstallises in small, lustrous prisms melting at about 195". It is almost insoluble iii chloroform, but dissolves freely in ether, methyl alcohol, and acetone. 214 This chloro-acid is doubless structurally similar to 7ic-bromocam-phoric acid, but whereas the latter is ft derivative of an optically active z--bromocamphor, the chloro-acid is derived from an inactive or racemic halogen derivative of camphor.A chlorocamphoric anhydride has been recently described by Aschan (Be,.? 28, Ref., 9.22), but this substance is derived from an acid structurally as well as optically different from rr-chlorocamphoric acid. 148. "Derivatives of a-hydrindone." By C. Revis and F. StanleyKipping, Ph.D., D.Sc. The study of a-hydrindone (Trans., 1894, 4SO) has been con-tinued, and arttempts have been made to convert it into ap-diketo- hydrindone ; up to the present, however, this substance has not been obtained. Two compounds are formed on treating a-hydrindoiie with a solution of bromine in soda accordiug to the conditions of the experiment; if the ketone be simply shaken with the alkaline solu-tion at ordinary temperatures, it is slowly converted into a bulky mass consisting of ordinary dibromohydrindone (m.p. 132"), whereas if the mixture be heated on the water bath, a heavy crystalline powder is formed, apparently by further action on the dribrom-compound. The latter is very sparingly soluble in most ordinary solvents, but may be crystallised from boiling acetic acid, from which it separates in long, colourless needles decomposing bet ween 250" and 260". Analyses show it to be a conderisation product of the composition CleH1203,but its constitution has not yet been established. When monobromohydrindone is dissolved in alcoholic potash at ordinary temperatures it furnishes a substance which crystallises from chloroform in large, transparent, well-defined prisms. This com-pound is a condensation product of the composition C1,H,,Br02. Dibrouzohydrindone (m.p., 132') is readily acted on by alcoholic potash yielding various products according to the conditions of the experiment. If the potash be added gradually until the solution becomes per- manently alkaline, the dibromo-derivative is converted into a new substance which crystallises from benzene in lustrous needles of indefinite melting point (decomposing from 150--160"). 149. "The alkaline reciuction of metanitraniline." By Raphael Meldola and Ernest R. Andrews. On heating an aqueous solution of metanitraniline with alkaline 215 reducing agent's, such as sodium stannitc, the azoxy-compound, NH2.C6H4*N-N*C6H4*NH2,separates out on cooling.It forms yellow \o/scales (from toluene) or needles (from boiling water or dilute alcohol) ; m. p. 146-148'. The diacetyl-derivative (m. p. 254)",the disazimide (m. p. S6--8S0), the disazo-/3-naphthol derivative (m. p. 244-245"), and the meta.diiodoazoxybenzene (m. p. 118-119") have been prepared from the diamidoazoxy-compound. The correspond- ing azo-compound, having the constitution- NH2 NH, /-\N /-\\-/ 2\-/' has been prepared by the complete reduction of the azoxy-compound to a hydrazo-compound by the action of zinc dust and alkali, and subsequent reoxidation. This has been found the most effectii-e way of obtaining the azo-compound in a, stake of purity. It consists of dull orange needles when crystallised from boiling water; m.p. 150-151". The diacetyl-derivative (m. p. 272"), the dibenzoS1-derivative (m. p. 284-285), the disazo-/3-naphthol (m. p. 282"), aiid the oxalnte of the base have been prepared, and are described in the paper. The constitution was codirmed by conversion into the meta- diiodoazobenzene (m. p. 150-151") of Gabriel (Ber., 1876, 9, 1410). Both the azoxy- and azo-compounds are well characterised bases forming diacid salts. The paper concludes with a theoretical discus- sion by one of the authors (Meldola) of the process of reduction of nitro-compounds, 150. ''The chemistry of dibromopropylthiocarbimide ; and the action of bromine and iodine upon allylthiourea." By Augustus E. Dixon,M.D. Having failed LO obtain dibromopropylthiourea from pydibromo- propylthiocarbiniide and ammonia (Trans., 1892, 61, 548), the author proceeded to re-examine a compound obtained by Mnly (Zeits.f. Chenz., 1867, 42) from allythiourea and bromine. This compound, " thiosinnamine dibromide," C4H8N2SBr2, is, however, not dibromo- propylthiourea, but proves to be the hydrobromide of a well-marked base, C4H,NzSBr,which is precipitated, on the addition of caustic alkali, as a dense, almost colourless, strongly alkaline oil. The oil is sparingly soluble in water; it combines with hydrochloric acid to form the hydrochloride, C4H7N2SBr,HCl, hard white prisms melting at 129-130°, and identical with the "bromochloride " obtained by Maly from "t,hiosinnamine dibromide '' and moist AgC1. The hydrobromide, C4H,N2SBr,HBr, from the base and HBr, is identical 216 with the dibromide ; it was found to melt at 139-140O.By treat- ment of either the free base or its hydrobromide with picric acid, the salt C,H,N,SBr,C,H,(NO,),OH is precipitated ; when recrystallisecl from dilute spirit it forms minute, glittering prisms, pale yellow in colour, and melting at 187-188O. Heat is evolved on mixing dibromopropylthiocarbin~ide with alco- holic ammonia, ; ammonium bromide separates, arid is left, together with a brownidh sjmp, when the alcohol is evaporated ; this syrup is the byominated base C4H7N,SBr,somewhat impure. CH,Br-CHBr*C€I2.NCS+ 2NH3= NH4E(r + C4H7NzSBr. R’easoning from the conditions qrider which the base is produced, from its alkaline character, and froin the fact that it is not desulphur- isecl by treatment with alkaline lead. 01’ammoniacal silver solutions, the author regards it as having the probable constitution i.e., ~~-arnido-~-brornpenthiazoline,otheywise P-broniotrimethylene-912-thiourea. This view also receives support, from the results of ex-periments by Gabriel and others, on the interactioii of brominated fatty bases with thiocaybimides, whereby the tendency has been shown of monohalogenised fatty thioureas to lose, at the moment of formation, their contained halogen, with pi-oduction of the corre-sponding haloiid salts of closed-chain bases of the above tFpe.Iodine appears not to combine with allylthiocarbaniide, but acts similarly to bromine on allylthiourea, giving the hydriodide of an iodised base, C4H7N2SI,HI.The salt is fyeely soluble in water or spirit, and melts at l~E?.5-13:3-5.When treated with caustic potash the base is thrown down as a dense, sticky oil, alkaline to litmus, nearly insoluble in water, reacting (like its brominated analogue) for halogen with chlorine water, and yielding a picrate of ni. p., CH2*S1’76-177O. Tlis constitution assigned to it’ is CHI< CH,.Jg>C *NHz = p-arnido-rpiodpenthiazoline. Similar compounds were obtained by acting with organic bases upon dibiomopropylthiocarbimide. from the thiocarbimide and o-toluidine, was deposited from alcohol in rhombic plates, m. p. 134*5--135*5O. It is insoluble in water, rather difficultly soluble in alcohol, feebly alkaline to litmus, and-like the other compounds of its class-retains its sulphur, even when boiled with alkaline lead, or ammoniacal silver salts.The hydrobromide is .n clear, pale brown, apparently uncrystallisable, acid syrup. p-Pn~ntolylamido-.(-bi.ompenthictzoline hydrobronzide foi-med a thick, 217 acid syrup ; the free base occurred in rosettes of pointed white prisms melting at 124-125". p-Napht722Jlanzido-.J-bl.ompen~l~iazoline7like its hydrobronzide, could onlj- be obtained as a liquid. The hydrobromide of the correspond- ing P-izaphthyl-c0112po1d?2dwas a brownish, tenacious acid syrup ; its base occurred in brilliant prisms, neutral at litmus, and melting at 190-191O. p-Met k 2/11312€nylamido-.y-b~.ompenthinzol.ille, CHBr<::::!> C.Nl4ePh (from the thiocarbimide and metliylaniline, with evolution of heat), separated as a colourless oil ; its hydrobromide is crystalline, easily soluble in hot water, and melts at 283-184'.duced with evolution of heat ; the HBr salt forms colourless, vitreous prisms, soluble in cold water, with neutral reaction ; m. p., 189-190". The base is a nearly colourless syrup, which does not afford bromine w7hen mixed with chlorine water; it is so strongly alkaline as to allow of titration by standard acid. By acting with methylic, ethylic, and propylic alcohols respec- tively at a little over 100' on the thiocarbimide, the three following compounds were obtained, together with (free) hydrogen bromide. ~-~etho~y--~-b~nm~e~~tl~iazoline, -WhiteC HBi*<~~:~>C*OMe. crystals easily soluble in hot water ; not desulphurised by silver or lead salts ; ni.p. 95-96'. The silver compound becomes purple on short exposure to actinic light. -Ethoxy-y-2, rompenthiuzolin e.-s mall, white prism8, moderately soluble in hot water; m. p. 96-97'. Forms a silvei compound which is very markedly light-sensitive. p -P~opoxy--brompenthiazolinr. -Pyramidal crystals ; ni, p., 96-97" ; closely resembling the preceding coinpound in properties. Phenyl and ortbotolylthiocsrbimides respectively combine, evolving $IH2*NHheat, wit8h u-methFliniidazoline, >C*CHs (ethenylethyleiieCHZ-N diamine), thereby affording PhN:C(SH).N<C~~.~~~~~N. C(CH )-~-MethyEimidnso1ylpheny7thiourea.-Thick7 lustrous prisms, diffi-cultly soluble in cold water or alcohol ; clesulphurised by lead and silver salts ; m.p., 173-174'. p-Methylimidazolyl-0-toly ItIiiozwea.-White crystals melting at 159-159.5', and generally resembling the corresponding pllenyl-. 11 eriv a tivea. 2 18 ADDITIONS TO THE LIBRARY. I. Pamphlets. On the Colour Reactions of Atoms, Ions, and Molecules. By 31. Carey Lea. Part I with Plate. The causes and nature of Fermentative Changes in Natural and Polluted Waters, and in Artificial solutions, as indicated by the Composition of the Dissolved Gases (Parts I, IT, and 111). By W. E. Adeney, Assoc. R.C.Sc.I., F.I.C. Pp. 539--620. 440. Dublin 1895. From the Author. On the Multiple Propoytions of the Atomic Weights of Elementary Substances in relation to the Unit of Hydrogen.By Henry Wilde, P.R.S. On the Evidence afforded by Bode’s Law of a Permanent Contrac- tion of the Radii ‘Vectows of the Planetary Orbits. BJ Henry Wilde, F.R.S. Ricerche sull’ Essenza di Bergamotto e sulle sue Sofisticszioni del dott Ignazio Campolo. The Volcanic Rock of Alum Hill, Boulder County, Colorado. ByC. I. Andrews. The recent History and present Status of Chemistry. By Pro-fessor Charles s.Palmer. Vein Structure in the Enterprise Mine. By 1’.A. Rickard. Notes on the Precipitation of the Precious Metals from Cyanide Solutions by means of Zinc. No. I. The Non-existence of Cyanide of Zinc in Alkaline Solutions. By Nicholai Anderson, Denver. The Determination of Bismuth in Refined Lead and in Lead Bul-lion. By L.G. Eakins. The Contributiocs of Chemistry to the Methods of Preventing and Edinguishing Conflagration. By Thos. H. Norton. Michigan Mining School, Houghton, Michigan. Prospectus of Elective Studies. May, 1895. A Contribution to the Chemistry of Australian Myrtaceous Kinos. By J. H, Maiden, F.L.S., and H. G Smith. June, 1895. Estudios Ijieniqos del Aire. Por A. E. Salazor 1. Q. Newman. Santiago 1895. The Philosophy of Substaiitialism, or Matter, Force, and Energy. By Henry A. Mott, Ph.D., LL.D. The Oximes of Benzaldehyde and their Derivatives. By C. M. Luxmoore, B.Sc. A Thesis accepted for the Degree of D.Sc. of the University of London. Snalysis of Commercial Fertilisers.By F. B. Guthyie Depart-ment of Agriculture. Sydnej, N.S.W., 1895. Notes on the Milling Qualities of Different Varieties of Wheat. 219 By F. B. Guthrie and E. H. Gurney. Department of Agriculture. Sydney, N.S.W., 1895. On the Choice and Use of Artificial Manures. By F. B. Guthrie, F.C.S. Department of Agriculture. Sydney, K.S.W., 1894. Australian Honey. By F. B. Guthrie. Department of Agriculture. Sydney, N.S.W., 1894. Analysis of Tumut Tobacco. By F. B. Guthrie. Department of Agriculture. Sydney, N.S.W., 1894. Ostwald, Pr. Wilhelm. Dietuberwindung des Wissenschsftlichen Materialismus Pp. 36. Leipzig 1895. Meyer, Dr. Victor. Probleme der Atomistik. Zweite Auflage. Pp. 45. Heidelberg 1896. Meyer, Dr. Victor. Cbemische Probleme der Gegenwart.Zweite Auflage. Pp. 46. Heidelberg 1890. 11. By Purchase. Ostwald, Dr. Wilhelm. Elektrochemie;ihre Geschichte und Lehre. Mit 260 Nachbildungen geschichtlicher Originalfiguren. Pp. xvi +1151. 8vo. Leipzig 1896. Neumeister, Richard. Lehrbuch der physiologischen Chemie : mit Beriicksichtignng der pa,thologischen Verhaltnisse : fur Studierende und Aerz te. Zweiter Teil. Die tierischen Gewebe und Flussigkeit’en. Pp. x +42O. Jena 1895. Jahn, Hans. Grundriss der Elektrochemie. Pp. x +3U. Wien 1895. Nernst, W., und Schonflies, A. Einfuhrung in die mathematische Behandlung der Naturwissenschaften. Kurzgefasstes Lehrbuch der Diff erentinl- und Integralrechung mit besonderer Beriicksichtigung der Chemie mit 61 im Text befindlichen Figuren.Pp. xi+309. Munchen and Leipzig 1895. Hammarsten, Olof. Lehrbuch der physiologischen Chemie. Dritte vollig umgearbeitete Auflage. Pp. x +647. Weisbaden 1895. Tiemann, Dr., Walter, G., und Gartner, Dr. A. Tiemann Gartner’s Hand buch der Untersuchung and Beurtheilung der Wasser zum Gebrauch fur Apotheker, Arzte, Chemiker, fabrikanten Medicinal- beamte und Techniker. Vierte vollstandig umgearbeitete und vermehrte Auflage. Pp. xxxvi +841. Braunschweig 1895. Schoop, 3aul. Die Sekundar-Elemente : auf Grundlage der Erfahrung dargestellt. I. Teil. Die Theorie des Blei-Sammlers und Construktion von Plant&-Batterien. Pp. viii+210. 11. Teil. Die Fabrikation von Blei-Sammlern. Pp. vii+ 211. Halle. 1895. Le Blanc, Max. Lehrbiich der Elektrochemie : mit 32 Figuren.Pp. viii +226. Leipzig 1896. 2 20 Dragendorff, Georg. Die gerichtlich-chemisclie Ermittelung von Giften in Nahrungsmitteln, Luftgemischen, Speiseresteii, Korper- fheilen, etc. Vierte, vollig umgearbeitete Adage. Pp. siv +532 Gottingen 1895. HELMHOLTZ MEMORIAL LECTURE. The Helmholtz Memorial Lecture will be delivered by Professor G.F. Fitzgerald, F.R.S., at an extra, meeting of the Societ,y to be held on Thursday, Januavy 23, 1896, at 8 P.M. COLLECTIVE INDEX OF THE TRANSACTIONS, ABSTRACTS, AND PROCEEDINGS OF THE CHEMICAL SOCIETY. Volume 11,1873 to 1882. Volume 111, 1883 to 1892. The Council, having determined to publish a Collective Index of their publicetiom from 1873 to 1892 inclusive, will issue copies to Fellows who may noti€y their wish to receive them.Both volumes will b3 sent to those who were Fellows of the Society before the end of 1882. Volume IlJ will be sent to l?ellows who have joined the Society between 1st January, 1883, and 31st December, 1892. Fellows who are ineligible to receive copies gmtis, and those who may have neglected to apply for them within the prescribed period, may obtain them by purchase at a price to be hereafter fixed. Fellows who desire the Index should notify their wish by letter, enclosing Is. for cost of distribution, &c., to the Assistant- Secretary, Mr. Robert Steele, Chemical Society, Buriington House, W., before 31st December, 1895. For Fellows resident abroad, who should remit 2s., which may be paid with their anaual contribution, the time will be extended to 1st March, 1896. A few copies of Vol. ‘I (1841-72) can still be obtained, price 3s., post free. --__~ -~ Ai, the next meeting, on Thursday, December 19th, the following papers will be read :-“ The liquefaction of Air and its emplojment in researches at low Temperatures ” (experimentally illustrated), by Professor Dewar,. F.R.S. ‘‘ Constitution of Terpenes and Camphor ” (Discussion). “ Derivatives of Dirnethylaniline,” by Miss Evans, B.Sc. BARBISON AND SONS,PRINTERS IN ORDINARY TO HER NAJESTY’,ST.MARTIN’SLANE.

ISSN:0369-8718    

DOI:10.1039/PL8951100205

出版商:RSC    

年代:1895

数据来源: RSC