摘要:

56 LING SOME METALLIC DERIVATIVES XI.-Some Metallic Derivatives of Halogen Nitrophenols. By ARTHUR R. LING. HAVING in my experiments with the nitrohalogen-derivatives of phenol obtained some metallic salts which have not so far as I am aware been described and which appear t o be in t,hemselves of some little interest I have deemed it advisable t publish zt description of the same. Although I do not claim to have obtained results of any theoretical importance it must be granted that any addition to o u r knowledge of this most interesting class of compounds cannot be without some value. Bromination of Orthoc7Lloroparaizitro~henol. The orthochloroparanitrophenol obtained by chlorinating paranitro-phenol in acetic acid solution was separated from the small quantity of dichloroparanitrophenol formed at the same time by converting it into the barium salt and crystallising from water.On decomposing the aqueous solution of this salt [C6H3C1(X0,).0],Ba,7H20 with dilute hydrochloric acid and subsequent ciystallisation of the colour OF HALOGEN KITROPHEKOLS. 57 less chloronitrophenol from a large bulk of hot water it was obtained in long white satiny needles iiielting at l l O o as stated by other observers. The pure compound was dissolved in glacial acetic acid and treated with the theoretical quantity of bromine (1 mol.) in the usual way, after wlkli the solution was poured into water and the precipitated chlorobromo-derivative converted into the potassium salt which crystallises from water in golden-yellow needles. On decomposing the latter with dilute hydrochloric acid and crystallising the resulting compound from boiling water (in which it is but sparingly soluble), it was obtained in colourless crystals resembling in appearance dichloro- and dibromo-paranitrophsnol and melting sharply with instantaneous decomposition a t 137".A specimen of the pure com-pound dried a t 100" gave the following result on analysis :-0.4497 gram gave 0.5890 gram AgC1,AgBr. Theory. C6H,C1B r ( NOz) -OH. Found, 45.72 per cent. gb}. . 45.74 per cent. Potassium ch7orobromoparaizitro~l~enol forms long golden-yellow needles which contain I mol. H,O and are moderately soluble in cold water easily in hot. It is thus analogous in composition to potassium clichloroparanitrophenol (Kollrepp Annalen 234 8).Analysis of an air-dried specimen gave the following results :-0.3639 gram lost 0.0211 gram at 100-120" and gave 0.1036 gram KzSOd. Theory. c6H,C1Br(NO2).OK,H,O. Found. H,O 5-83 per cent. 5.79 per cent. K 12-64 , 12.74 ,, Calcium c7LZorobromoparnrtitrop~e~~ol appears to resemble calcium dichloropnranitrophenol (Armstrong this Journal 1871 111 7) ; thus it crystallises in long yellow glistening needles containing 9 mols. H20, but the following difference is to be noted the dichloro-derira-tive is completely dehydrated at; 160" whilst the chlorobromo-salt requires heating to 210". On exposing the above to the air the needles soon effloresce and become somewhat darker in colour and dull in appearance. After however losing 2 mols. H20 the hydrate [CGHzClBr(N02).0]2Ca,,~~,@ a'ppeared to remain perfectly constant.This efflorescence takes place so quickly that it was found advisable to make the analytical determinations as soon after the salt had been dried between filt'er-paper as possible. VOL. LV. 58 LING SOME METALLIC DERIVATIVES I. 0.2556 gram lost 0.0586 gram at 210" and gave 0.0488 gram 11. 0,5099 gram lost 0.1190 gram a t 210" and gave 0.0960 gram CaSO,. CaS04. Found. 7 Theory. (-A.-[C6H,C1Br (NO?) .0!2Ca,9H,0. T. 11. HJI 22.98 p. c. 22-92 p. c. 23.33 p. c. C a . . . 5.67 , 5.59 , 5.53 ,, It may be stated that in all cases in which duplicate determinations The I. 0.2543 gram lostl 0.0480 gram at 210" and gave 0.0506 gram are given they have been taken from different preparations.effloresced salt gave the following numbers :-CaS04. 11. 0.2983 gram gave 0.0592 gram CaS04. Found. Theory. r- 7 [C,R2C1Br( NO)2.0],C~,7H,0. I. 11. H,O 18-83 p. c . 18.87 p. c. -Ca . 5.97 , 5.85 , 5.83 p. c. If instead of allowing the supersaturated solution of the above salt in water to cool to the temperature of the room it is kept at about 70" the salt separates in an entirely diflerent form namely in dark-yellow rhombic plates which appear to contain 4 moIs. H,O. The analytical results were as follows :-I. 0.2557 gram lost 0.0301 gram at 210" and gave 0.0357 CaS04. 11. 0.8763 grani gave 0.0606 gram CaS04. Found. Theory . f--L -3 [C6H2C1Br(NO2) .O],Ca,PH,O. I. 11. H,O 11.70 p. c. 11-77 p. c. -Ca 6.50 , 6.41 , 6.44 p. c. I am not aware that a calcium salt analogous to the above has yet been described.Barium chlorobronaoparnizitro~l~enol forms long canary-yellow glistening needles and is similar in composition to barium dibromo-paranitrophenol [ CBH2Br,(N0,)~O],Ba,10H,0 Brunck (Zeit. 1867, 204). Analysis :-I. 0.2676 gram lost 0.0586 gram at 200" and gave 0.0758 gram BaS04. 11. 0.3558 gram gave 0.1024 gram BaS04 OF HALOGEN NITROPHER'OLS. 5 9 Found. Theory. 7- 7 [ C6H2C1Br (N 0,) - O],Ba,lOH,O. I. 11. HzO 21.97 p. c. 21.90 p. C. -B a . . . 16-70 , 16-62 , 16.91 p. c. Erunck mentions (Zoc. cit.) that when the compound, [ CGHzBr,(N02)*0]2Ba,10Hz0, before alluded to is placed over concentrated sulphuric acid in a desiccator it dries up to a red powder hut it was afterwards shown by Post (Annnlen 205 94) that the form of the crystals remains unaltered and that the change of colour from yellow to red is accom-panied by the loss of 64 mols.H20. the red needles having the com-position [ C6HzBr,(N02)*0]2Ba,3~H20. I may mention that I have described an analogous red barium salt of dichloroparanitrophenol (Trans. 1887 786). When the last-described yellow salt of chloro-bromoparanitrophenol is allowed to remain over sulphuric acid for several hours a precisely similar change takes place for example,-I. 0,4754 gram yellow salt lost 0.0691 gram in 64 hours and changed in colour to red. 11. 0.6351 gram lost 0.0904 gram in 60 hours. Found. -7 Theory. r-J-[C,H2C1Br(NO2).O],Ba,3+H20 + 6iAq. I. 11. H 2 0 . . 14.26 p. c. 14.53 p. c. 14.83 p. c.The following numbers were also obtained on analysing the red I. 02331 gram lost 0.0214 gram a t 200° and gave (3.0765 gram salt :-BaS04. IT. 0.2318 gram gave 0.0773 gram BaS04. Found. Theory. r---\ [C,H2C1Br (NO,) .0I2Ba,3iH20. I. 11. H20 8.96 p. c . 9.18 p. C. -Ba . 19-48 , 19.30 , 19.58 p. c. A red salt probably identical with the above was deposited from supersaturated aqueous solutions of barium chlorolwomoparanitro-phenol if the temperature was kept at about 70"; but after the needles had been dried between filter-paper they were in every experiment tried found to be partially converted into a yellow salt, and so were not further examined 60 LING SOME METALLIC DERIVATIVES Calcium Parach lorothobromorthon,itro~~~enol. This salt has already been described by me (Trans.1887 789) R S crystallising in orange-red glistening scales containing 24 mols. HzO, but I find that my analytical numbers were wrongly calculated and as another specimen lately prepared does not agree with the above description I have re-examined the compound. It forms small glistening plates of a dark red colour in fact it is of quite as dark a colour as the isomeric compound containing 7H,O (Zoc. cit. 791). It however becomes much lighter in colour on losing its water of crystallisation (orange when anhydrous) a fact which would seem to indicate that the specimen previously examined was partially de-hydrated. It appears to be generally characteristic of these calcinni salts that they retain some of their water of crystallisation a t high temperatures.I n the paper before referred to it was shown that in order to completely dehydrate calcium orthochloropnrabromortho-nitrophenol it was necessary to heat it for a Considerable time at 250". When I first re-examined the salt under consideration I con-cluded that it contained 3 mols. H20 as the following analysis seemed to indicate :-0.2715 gram lost 0.0244 gram a t 100-125" and gave 0.0602 gram CaS04. Theory. [C6H2C1Br (XO,) .O],Ca,3II,O. Found. H,O 9.04 per cent. 8.98 per cent. C a . . . 6.70 , 6.51 ,, On heating another specimen however st 200" till its weight remained constant I found that a further loss occurred and con-firmed as the result is t o a certain extent by the halogen determina-tion there is little doubt that the salt in reality contains 4 mols.H,O; for example :-I. 0.2911 'gram lost 0.0338 gram a t 200' and gave 0.0654 gram Ca SOJ. 11. 0.3634 gram gave 0.3850 gram AgC1,AgBr. Found. 7 Theory. r-"-[C6H2C1Br (50,) O],Ca,4H20. I. 11. l3,O 11.70 p.c. 11.61 p. c. -Ca. 6-49 , - 6.50 ,, . 37-56 - 36.99 p.c OF HALOGEN NITROPHESOLS. c; 1 Culciurn D ich lorort honitrop henol. This is deposited from its hot aqueous solution in orange fibrous 0.1537 gram dried a t 100" gave 0.0443 gram CaSOJ. needles which are sparingly soluble in boiling water. Analysis :-Theory. [ C6H2C12(N0,) *O]&h,H20. Found. Ca . 8.47 per cent. 8.45 per cent. If a saturated solution of the above salt be left over sulphuric acid t u evaporate slowly it will be obtained in small dark-red needles aiid plates which probably contain 4 mols.H,O. When heated a t 135O, they were found to lose 10.67 per cent. of their weight which agrees with the theory for 3 nwls. H20; the calcium determination is how-ever nearer that demanded for 4H20. 09566 gram gave 0.0664 CaS04. Theory. [C6H?C1,( N 0,)*0]2Ca,4HzO. Found. Ca . 7.60 per cent. 7.60 per cent. This salt could not be further examined as I had no more at my disposal. Calcium Dibromorthonitrdphenol. This forms red scales containing 7H20 and is analogous therefore, to calcium orthochloroparabromorthonitrophenol. It is impossible to remove all the water of crystallisation from the above below the temperature at which it decomposcs. I. 0.2352 gram gave 0,0423 gram CaS04* 11. 0.3065 , 0.0541 , CaS04.111. 0.2190 , 0.2178 , AgBr. Found. Theory. r-----. 7 [C6H2 Br2(N02) *OI2Ca,7H2O. I. 11. 111. Ca 5.28 p. c . 5.27 p. C. 5.18 p. C. -B Y . . 42.%1 , - - 42.41 p. c. Culciurn Parabronzod hiodorthonitrophenol. Parabromorthiodorthonitrophenol was first described by Korner (Jahrb. 1867 617) according to whom it melts a t 104*2" and next by Groth (,Jahrb. 1877 54!)) who states that the crystals are brownish-yellow and melt at ltld" ; he gives measurements of them 62 NETALLIC DERIVATIVES OF HALOGEIT NlTKOPHET\'OLS. This compound was prepared by me by iodising parnbromortlio-nitrophenol m. p. 88" in alcoholic solution with iodine and mercuric oxide. After purification by means of its potassium salt and snb-sequent decomposition of the latter arid crystallisation from alcohol, i t was obtained in yellow scales of a somewhat dirty appearance melting a t 104".The calcium salt forms dark-red plates containing 4 mols. H,O. Analysis :-I. 0.2295 gram lost 0.0204 gram a t 190" and gave 0.0397 gram I1 CaS04. 0.3441 gram gave 0,3652 gram Ag( Br,T). Found. Theory. T.-h- I [ C,H,BrI (NO?) * O],Ca,4H20. I. 11. H20 8.89 p. c. - 9.03 p.c. - Ca. 5.02 , 5.09 ,, . 51.82 ? - 51.93 p. c. I Of the foregoing calciuui salts of orthonitrophenol-derivatives it is to be IBemarked that they all pass from a red to an orange colour with the loss of their water of crystallisation; this is a t variance with the observations of Carnelley and Alexander who state (Proc. 1888, 64) that in the metallic derivatives of the nitrophenols the colour passes towards the red end of the spectrum as the water of crystalli-sation diminishes.It is also noteworthy that calcium dichlorortho-nitrophenol has less tendency to unite with water than the other calcium dihalogen orthoni trophenol-derivatives ; for example the monohydrate (an orange salt) is formed with ease whilst the red salt coritaining 4 mols. H,O is only obtained by slowly evaporating the solution over concentrated sulphuric acid. As regards the colour of the salts of the nitrophenols it is to be observed that those from the alkali metals potassium and sodium &c., of derivatives of orthonitropheiiol are red whilst those of para-nitrophenol are yellow ; also that those of ortho-orthodinitrophenol and its derivatives are red and those of orthoparadinitrophenol are jellow.In a paper by Nijltiiig and Pick published in a recent number of the Berichte (21 3158-3260) two isomeric dinitro-xylenols from ortho-xylene are described ; one melting at 127", having the N02-groups in the two ortho-positions with respect to the OH-group and the other melting at 82" and having the N02-groups in ortho-para-positions with respect to the same. Now, according to the authors the salts of both these compounds are yellow and thus it would seem that the introduction of two methyl-groups in the place of two hydrogen-atoms brings about a con W. H. PERKIN JUN. ON BEHBERINE. 6 3 siderable modification in the colour in the case of ortho-orthodinitro-phenol removing it further from the red end of the spectrum. Ortho-orthodinitrophenol and its halogen substitution-derivatives melt at a lower temperature than orthoparadinitrophenol and its correspnndiiig derivatives ; but t h i s state of things seems tmo be reversed by the introduction of the two methyl-groups into the molecule and the derirative of ortho-orthodinitrophenol then melts a t the higher temperature

ISSN:0368-1645    

DOI:10.1039/CT8895500056

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

W. H. PERKIN JUN. ON BEHBERINE. 6 3 XI1.-On Reyberine. (Part I.) ByW. H. PERKIN Jun. Ph.D. BERBKRTNE the yellow alkaloiid of Berberis vulgaris was discovered in the year 1826 by Chevallier and Pelletan (Journ. de Chim. Mkdicak, 2 314) in Xanthoxylum clava Herculis and described by them under the name of xaiithopicrit,. Subsequent researches have shown that this alkaloi‘d is a con-stituent of a large number of plants in some of which i t is present in considerable quantities. It has been found in CocculuspaZmatus or Columbo root (Boedecker, Annalen 6 6 384 ; 69 40) ; in Berberis vulgaris (Buchner Ann. 24, 228) ; in C d w l i n e polycaipa (Stenhouse Ann. 95 108 ; 105, 360) ; in the wood of Cosciniriin fenestratum from Ceylon and in Santliorrisn apii folia a North American plant of the Ranunculacea order (Perrins AnrL.83 276) ; in Hydrastis canadensis (Mahla Sill. ,lm. J. [2] 33 43 (1862)) ; andther North American plant of the Knnunculacea order which as it contains about 4 per cent. of crude iLlkiilO’id and is readily obtainable in England can be used as a source of the alkaloid (Perrins Ann. Suppl. 2 173). Berberine has also been found in Woodumpar a yellow wood from Upper Assain in the root of Coptis tecfa or Mahmira-a plant growing in Hindoostan and China and which is much valued in India on account of its tonic properties. Perriiis (loc. cit. p. 174) who examined this soimce obtained as much as 8; per cent. berberine from the root-a far larger quantity than has up to the present been found in any plant. The French chemists Chevallier and Pelletan the discoverers of berberine although they carefully and accurately described some of its properties do not appear to have made any analFses of thei 64 W.H. PERKI?; JUN. ON BERBERINE. product and it was not till 1835 that any attempts were made to ascertain the cnmposition of this interesting substance. I n this year, Buchner and Herberger (AnnaleiL 24 228) published the results of an important series of experiments on this alkalojid together with a number of analyses of the base itself and also of its compound with oxide of silver. These experiments led them to the supposition that berberine was represented by the tbrmula C33H36NL012 (C = 6 0 = 8). At a later date Fleitmann made a careful examination of berberine, and showed that instead of being a weak acid as Buchner had sug-gested it was in reality a strong base forming with acids stable salts, and in all respects showing the properties of a well-defined alkalo'id.Fleitmann analyscd not orily bwberine itself but also several of its salts and the results of his experiments led him to the conclusion that the formula proposed by Buchner was erroneous and that the composition of this base was C,,H,&O ( C = 6 0 = 8). In the year 1861 J. Djson Perrins jAm,aZen Suppl. 2 1'76) pub-lished the most accurate investigation of berberine which had up to that time been made in the course of which he analysed a large number of its salts and showed in a most coriclusive manner that Fleitmann's formula was inaccurate and that the true formula was C,,H,,NO (C = 12 0 = 16).Although the analytical results obtained by Perrins agree so closely with this formula I etilI thought it necessary before staitiiig an investigation on the constdntion of this interesting alkaloid to repeat some of these analyses with specially purified substances so as to leave no doubt as to the relation of the carbon hjdrogen nitrogen and oxygen-atoms in it. The berberine used in these experiments was purified in the following manner :-Crude herberine hydrochloride (from Merck in Darmstadt) was recrystallised twice from water acidified with hydrochloric acid the beautiful yellow silky needles dissolved in a little boiling water and the solution rendered alkaline by the addition of an excess of car-bonate of soda solution.On cooling the liquid became filled with brownish silky crystals. These were filtered from the dark brownish-red mother-liquor, washed with water till the washings were only slightly yellowish, arid dried on a porous plate. The beautiful silky mass thus obhained was next dissolved in boiling 80 per cent. alcohol (carefully purified methylated spirits may also be used) from which 011 slowly cooling, long yellowish-brown needles separated. After repented crys t allisa-tion from dilute alcohol these crystals entirely lose their original brownish colour and are a t length deposited in the form of long, silky needles of an intensely yellow colour. This substance was repeatecilg analysed under vaqing conditions but in spite of this n W. E. PERKIN JUN. ON BERBERINE.65 satisfactory results could be obtained. One reason for this is t h a t the substance contains several molecules of water of crystallisation, part of which is given of€ slowly a t ordinary temperatures and part a t 100". The substance dried a t 100" is however never free from water of crystallisation and if attempts are made to drive this off at a higher temperature slight decomposition invariably takes place sufficient t o spoil the analytical results. Another reason for the difficulty experienced i n obtaining concordant numbers with berberine pre-pared in this way is that the substance almost invariably contains traces of chlorine. Experience showed that the nitrat'e hydriodide and platinochloride of berberine were far more suitable f o r analytical examination than the base itself.Berberirie Nifrate CznH1,NO4,HNO,.-This salt has been described by both Fleitniann and Perrins. It is readily prepared by adding an excess of dilute nitric acid to a warm concentrated solution of the base. The nitrate is thus precipitated as a yellow crystalline mass, which is collected well washed with water and repeatedly recrystal-lised from this solvent. I n this way beautiful yellow needles were obtained which after drying first over sulpliuric acid in a vacuum. and then a t IOU" gave the followiiig results on analyhis :-I. 0.1724 gram substance gave 0.0782 gram H,O and 0.3808 11. 0.1638 gram substance gave 0.0679 gram H,O and 0.3621 111. 0.2056 gram substance gave 12.5 C.C. N. Bar = 760 mm. t = gram CO,. gram CO,.15". Found. Theory. 7-- 7 C2,H17N O,,HNO,. I. 11. 111. C 60.30 p. c. 60*24 60.27 - p. c. H . 4.52 , 4-65 4.52 - ,, N . 7-04 , - 7.16 ,, 0 . 28.14 ,, -- - - > ? These numbers agree well with those previously found by Fleit-mann and Perrins but not so well with those given by Henry. Fleit mann. Henry. 7 Perrins. (-A- 7-+ C 60.15 59.64 p. c. 60.19 p. c. 59.09 59.44 p. c . H . 4.75 4.62 , 4.60 , 4-85 4-84 ,, This salt is readily soluble in hot water sparingly in cold a,nd almost insoluble in dilute nitric acid 66 W. H. PERKIN JUN. ON BERBERINE. If the hot solution of berherine nitrate be mixed with a small quantity of ammonia on cooling a remarkable compound separates in sparingly soluble golden plates. I have not as yet been able to determine the nature of this substance but from the analyses already carried out it appears to have the formula C20H2,N20,.(Found C = 55.2. H = 4.8. N = 6.80. Theory requires C = I am a t present engaged in the investigation of this substance. Berberine Hydriodide C20H17N04,HI.-This very insoluble salt is obtained as a yellow precipitate when au aqueous solution of berbe-rine is acidified with a few divps of aqueous hydrogen iodide-or when potassic iodide is added to it solution of nitrat,e of berberine. The salt was collected well washed with water dried OIL a porous plate and recrystallised from a large quantity of boiling 80 per cent. alcohol. In this way heautiful satiny needles were obtained which on analysis gave the following numbers :-55.55.H = 4.63. N = 6.48.) I. 0.1460 gram substance gave 0,0523 gram H20 and 0.2767 11. 0,3561 gram snbstance gave 0.1795 gram AgI. gram CO,. Pound. Theory. r--- 7 C,,H,,NO HI. I. 11. p. c. - c 51-83 p. c. 5 1.68 H . . . . . . 3.88 , 3.98 9 , I . 27.43 , - 27.25 ,, -Perrins and Henry who also analysed this salt obtained numbers agreeing closely with the above. Perrins. r-h- 7 Henry. C 51.i2 51.77 p. c. 51-5Y p. c. H . . . . . . 3.92 3.96 , 4-23 ,, I . 27-02 27.12 , 25.71 ,, Beyb erine P Zat inoch Zo ride ( C?,,H l,N 0 ), H2Pt C I,.-T his douhl e salt has on account of its insolubility and suitability for determining the molecular weight of berberine been repeatedly examined. It is readily prepared by adding platinum chloride in excess to a slightly acid solution of berberine hydrochloride.The yellow precipitate thus thi-own down was collected well washed with water dried on IL porous plate over sulphuric acid and then at loo" and analysed with the following results : IT. H. PERKIN JUN. ON BERBERIKE. 67 I. 0.2251 gram substance gave 0.0708 gram H20 0.3657 gram C02 arid 0.0406 gram Pt. 11. 0.6807 gram substance gave 0.12.28 gram Pt. 111. 02T80 gram substarice gave 0.2192 gram AgCl. Found. Theory. c-.A- 7 (C,oH,,N O,),,H,PtC1,. I. 11. 111 c 44.47 p. c. 44.31 H . 333 , 3.49 7 9 Pt 18.02 , 18.03 18.08 9 9 Ci. 19.73 , - - 19-50 ,; p. c. - -- --Previous analyses of this salt by Fleitmann Perrins and Henry gave the following results which are in each case the mean of a number of experiments :-Flei tmann.Henry. Perrins. C 44.40 p. c. 44.38 p. c. 44-33 p. c. H . . . . . . . . . . 3.50 , 3.57 , 3.41 ,, Pt . 18.11 , 17.90 , 18-21 ,, This salt is almost insoluble in all the ordinary solvents. It crystal-lises from its solution in boiling amyl alcohol on cooling in small, yellow needles but it is extremely insoluble i n this solvent even on boiling. The analyses of these three salts show conclasively that the correct formula for berberine is C20H,,N04. For a complete list of the various berberine salts which have from time to time been analysed by different investigators I iiiust refer to a paper by Hlasiwetz and Gilm (Annulen Suppl. 2 197-201) ; and also to a recent paper by Ernst Schmidt (Mittheilungeit aus pharm. chem. Institut Murbuyg), which I have only lately had the opportunity of consulting.In his researches on berberine (loc. cit.) Fleitmann states that it crystallises from water with 4k mols. H,O. Sereral analyses which 1 made with different samples agree rather with the formula C,oH,,N04 + 5& H20. In these experiments the berberine used was prepared by Fleitmann's method very carefully purified by repeated recrystallisation from water and then dried in the air on a porous plate a t the ordinary temperature. Determinations of the amount of water of crystallisation given off at 100" gave the following results :-I. 1.5241 gram substance heated to 100" till coustant lost 0.1944 gram GS W. H. PEKKIS JUN. ON BERBERINE. 11. 0.5883 gram substance heated t o 100" till constant lost 0.0702 111.0.6444 gram substance heated to 100" till constant lost 0.0758 IV. 0.7017 gram substance heated t o 100" till constant lost 0.0851 gram. gram. gram. Found. T. IT. 111. IV. H,O . . . . 12.7 11.9 11.9 12.1 p. c. Complete analyses of different preparations of berberine dried at 100" till constant gave the following numbers :-I. 0.2385 gram substance gave 0.1239 gram H,O and 0.5550 gram 11 0.2095 gram substance gave 0 1041 gram H,O and 0.4577 gram 111. 0.1316 gram suhstance gave 0.0666 gram H,O and 0.3032 gram IV. 0*3,1.30 gram substance gave 11.4 C.C. N. t = 16.5". Bar. = CO,. co,. co,. 736 mm. Found. -. Theory. c-A-C?0H17N04 + 2:IIZO. I. 11. IIT. 1V. C . . . . . 6:3*16 p. C. 63-08 63-49 63.83 - p. c. H . . . . 5.78 , 5.77 5.52 5.66 - ,, - 3.72 , - - N .. . . 3.68 ., From these analyses it seems probable that berberine dried at 100" still contains 24 mols. H,O and that t'he air-dried substance originally contained 54 mols. H,O 3 of which are driven off at 100". This would require a loss of 12.4 per cent. which agrees approximately with the numbers given above. Kermann Schreiber (Dissertation Marburg 1888) is of opinion that berberine crystallises with 6 mols. H,O all of which is expelled at 100" in a stream of hydrogen. P r o p e r t i e s of Beyberine. Berberine crystallises from water in brilliant yellow needles which when dried in the air have a fine silky lustre. The base itself and also its salts are remarkable for their excessively bitter taste ; when warmed they emit a faint but peculiar odour strongly resembling that of ordinary quinone.When heated t o loo" the yellow berberine crystals gradually lose their lustre and become yellowish-brown at 110" the change is ver W. H. PERKIN JUK. ON BERBERISE. G9 rapid and a t temperatures above 160" total decomposition soon sets in with formation of a brownish-black mass from which I have not as yet been able to obtain anything of a ciystalline nature. On account of this behaviour of berberine wben heated I have not made any attempts to determine its meltinqg point. Fleitmann (ZOC. cit.) gives as the melting point of berberine 120° but this is certainly too low. If bromine-water be added to even very dilute solutions of bw-berine a yellow precipitate is produced which on standing rapidly becomes darker.If the product is collected and washed with dilute sulphurous acid a yellowish-orange mass is obtained crystallising from large quantities of boiling water in ncedles which appear to consist of the hydrobromide of a new base. Schreiber (Zoc. cit., p. 38) considers this substance to be simply berberine hydrobro-mide. Berbwine not only combines with acids to form salts but i t also gives peculiar compounds with alkalis. The addition of methyl alco-holic potash to a strong solution of berberine in alcoholic potash produces a pinkish-white amorphous precipitate wliich contains con-siderable quantities of inorganic matter. The analyses of this compound have not as yet given satisfactory results. Berberine does not appear to combiue either with hydroxylamine o r phenylhydrazine and although the alknlo'id dissolves readily in a mixture of oxychloride and pentachloride of phosphorus no change seems to take place even when the mixture is allowed to remain for a long time a t ordinary temperatures.Before publishing the details of the experiments which have been made in this direction I propose to confirm the results already obtained by using instead of the alkaloi'd itself some salt such as the nitrate which contains no water of crystallisation. In its behaviour towards reagents berberine shows the following characteristic reactions :-It dissolves in concentrated sulphuric acid forming a yellow solu-tion which on warming turns olive-green, Very dilute solutions of berberine give with chlorine-water a decided brownish-red coloration whilst strong solutions are coloured intensely by this reagent.Reducing agents such as tin and hydro-chloric acid destroy this colour which however reappears on the further addition of chlorine- water. Concentrabed nitric acid dissolves berberine forniing a dark red-dish-brown solution from which water precipitates a yellow flocculent mass partly soluble in ammonia. If the brown-red solution in nitric acid be warmed oxidation rapidly sets in with evolution of almndance of red fumes and formation of a yellow solution which contains ber 'TO W H. PERKIN JUN. ON BERBERINE. beronic acid oxalic acid and other products. Potassium ferricyanide in alkalino solution gives with berberine a yellow precipitate being itself for the most.part reduced to ferrocyanide. If 5t trace of berberine be boiled for a short time with concentrated aqiieous hydrogen iodide the product diluted with water and ren-dered slightly alkaline by the addition of ammonia an intense blackish-violet coloration is produced. Berberine is also chnracterised by the insolubility of some of its compounds as for instance its hydriodide platinochloride auro-chloride chromate &c. whilst a number of soluble salts such a s the nitrate are rendered almost insoluble by the addition of a mineral acid. A solution of iodine in potassic iodide gives with extremely small quantities of berberine salts a brownish precipitate of the periodide, CZOH,7N0,,HI,12. If the precipit,ation be carefully conducted in warm alcoholic solution beautiful shining green plates separate.Berb erine Hydrochloride C20H17N04 H C 1 + 2H20 .-T h is beaut if ul salt crystallises from water in long yellow needles. As mentioned at the commencement of the paper this salt in spite of its beautiful appearance does not give very satisfactory results on analysis. If attempts are made to dry it a t loo" in a short time the yellow colour of the crystals gradually changes to brownish-yellow and then to brownish-red small quantities of hydrochloric acid being invariably lost during the operation. Analysis of the pure substance dried over sulphuric acid gave numbers agreeing fairly well with those required by the formula C20H17N04,HCl + 'LH,O. I. 0.2075 gram substance gave 0.1057 gram H,O and 0.4461 gram 11. 0.1557 gram substance gave 0.0792 gram H,O and 0.3383 gram Temp.= 17". Bar. coz. co,. 727 mm. 111. 0.5091 gram substance gave 16.5 C.C. N. Found. 7 Theory. r-L-C&,TNO,,HCl + 2H20. I. 11. 111. c 5&S9 p. c. 58.63 59.25 - p. c. H 5.39 , 5-66 5-63 - ,, N 3.43 , - 3.63 ,) -The difficulty in obtaining good results in the analysis of this siibstance is partly accounted for by the fact that the salt dried as above is so excessively hygroscopic as to render it very difficult to weigh it out with the necessary degree of accuracy. As the result of a number of careful analyses E. Schmidt (Zoc. cit. IT. H. PEKKIh' JUN. ON BERBER". 71 p. S4) has shown t h a t berberine hydrochloride crystallises from dilute alcohol with 4 mols. H,O. Oxidation of Berberine with Potassium Perrrcanganate.In most of the investigations on the constitution of the alkaloi'ds which have up t o the present time been carried out it has been found that the careful examination of the behaviour of this class of substances towards oxidising agents has almost invariably given interesting results and in some cases very important clues as to their structure. The molecule of the alkalojid is usually split up yielding acids of much simpler constitution such as hemipinic acid (from narcotine), c:arboxylic acids of pyridine quinolinc and their derivatives (in the case of quinine cinchonine &c.) &c. although in some cases acids containing nearly the same number of carbon-atoms as the alkaloid empioyed are obtained. One of the most remarkable examples of the ralue of careful Oxidation in investigating an alkaloid is that of papaverine from which by the use of potassium permanganate under various condi-tions Goldschniiedt was able to obtain among other substances papa-verinic veratric hemipink py~idinetricarboxylic and dimethyl-oxycinchoninic acids and papaveiddine.Experiments on the oxidation of berberiiie with potassic per-manganate have already been made by E. Schmidt and C. Schilbach (Arch. Pharm. [ 3 ] 25 164-170 ; Abstr. 1887 604)) who obtained thus considerable quantities of h emip inic acid. In some pyeliminary experiments on berberine made early in 1887 1 also obtained Lemipinic acid in considerable quantities by the oxidation of berberine with alkaline permanganate arid lately in view of the remarkable results obtained by Goldschmiedt in his examina-tion of hemipinic and isohemipinic acids (Monats.1888 86l) I have again very carefully studied t h i s decomposition partly with the object of determining whether the acid obtained is simply hemipinic acid or a mixture of this acid with metahemipinic acid, and partly from a desire to obtain some substance intermediate between berberine and this acid which might afford some clue to the constitution of the alkalojid. The first experiments were carried out almost exactly in the way Goldschmiedt recommends in his first paper on papaverine (Monats. 1885 1112). 30 grams of pure berberine hydrochloride were dissolved in 1 lit,rc of boiling water the salt decomposed by the addition of 6 grains of potassic carbonate and then oxidised by slowly runnin 72 W.H. PERKIN JUN. ON BERBERINE. in 150 grams of potassic permmganate dissolved in 3 litres of hot water. A t first the oxidation is very rapid but as SOOT\ as about two- t hircls of the permanganxtle have been added decolorisation takes place much more slowly continued boiling being uecessary to remove the last traces of the oxidiser. At the end of this operation the product was saturated with carboiiic acid filtered through a cloth filter and the manganese pre-cipitate well pressed ; this was then carefully extracted hy repented hoiling with water and pressing in a vice. The filtrate and wasliings were evaporated to dryness the residue pulverised and repeatedly exhausted with boilirig absolute alcohol (or purified methylated spirits), the alcoholic solution distilled :ind the residue after freeing it from the last traces of alcohol hy gently warming dn a water-bath was dis-solved in a little water and filtered.On acidifying with dilute aul-phuric acid the brown aqrieous solution deposits a small quantity of a resinous precipitate from which however nothing crystalline could be obtained. It was removed by tiltration the clear filtrate extracted 20 times with pure ether the ethereal solution dried over calcic chloride and evaporated and the brownish residue thus obtained was allowed to remain for some days over sulphuric acid in a vacuum. The crude semi-solid mass was then roughly purified by spreading it on a porous plate and afteru-arde repeatedly recrystallised from boiling water.I n this way beautiful transparent crystals were obtained, which on analysis gave numbers agreeing wit.11 those required for hemipinic acid :-0.1827 gram substance gave 0.0720 gram H,O and 0.3550 gram CO,. Theory. c l O J 1 10°6' Found. C 53.10 per cent. 52-99 per cent. H . . 4-42 , 4-38 ,, 0 42.48 , 42.73 ,, Determination of water of crystallisation :-0.8878 gram of substance heated to 100" till constant lost 0.1256 Theory for Cl0HIOO6 + H,O = 13.74 per Considerable difference of opinion exists as to the melting point of hemipinic acid. Wegscheider (Nonuts. 3 351) gives 175-1 79" for the acid from narcotine ; Liebermann (Ber. 19 2279) 180-181", and Griine (Bey. 19 230) 180" whereas E. Schmidt and Scliilbach (Arch.Pharm. 225 164) found for the hemipinic acid prepared by them from berberine and also f o r the acid from narcotine the low melting point 160-161". Goldschmiedt who has lately most gram = 13.92per cent. cent W. H. PEREtN JUN. ON BERBERINE. 73 carefully re-examined the hemipinic acid from nnrcotine found that although when rapidly heated it melted a t 172-175" with decomposition into anhydride and water yet when slowly heated it melted a t 160-161". I have repeated these experiments with the hemipinic acid from berberine and although I can corroborate the experience of Goldschmiedt that the inel t i n g point varies considerably according to the rapidity of the heating still I have never been able to observe a melting point lower than 170". When heated moderately rapidly the acid obtained as above melts regularly a t 177-178" with decomposition.In studying the action of small quantities of permanganate on berberine I subsequently obtained an acid C10€11006 OE totally different appearance which melted a t 159-160" with decomposition and thus showed all the properties of hemipinic acid from nsrcotine. As 1 was therefore not quite satisfied that the acid obtained as described abcve melting a t 177-178" was hemipinic acid and not metahemipinic acid I carefully examined my product in the way suggested by Goldschmiedt (Monnts. 1888 870). In his researches on pnpaverine Goldschmiedt obtained by the oxi-clstion with alkaline permanganate an acid of the formula C,,H,,O,, which from its properties (m. p. 174-175" water of crystallisation &c.) he a t first supposed to be identical with the heniipinic acid from narco-tine.The further study of the constitution of papaverine however, showed that these two acids could not be identical but must be isorrieric merely a conclusion which was borne out by the further examination of their properties. As both these acids on fusion with potash give protocatechuic acid and both are orthocarboxylic acids, their constitution must. be represented by the formula-CH,O CH30/\COOH CH30ACOOH L)COOH Ctl,O!)COOH Hemipinic arid from Metahemipinic acid from narcotine. papaveri ne. In examiniug the hemipinic acid from berberine I first made a deterniination of the methoxyl-groups according to Zeisel's method (decomposition wit.h hydrogen iodide and determination of the amount of methyl iodide formed by leading into an alcoholic solutioil of silver nitrate and estimating the silver iodide precipitated (Monnts., 1883 704) with the following results :-0.2740 gram substance dried at 1.00" gave 0.7350 gram AgI.\'or,. LY. 74 W. H. PERKIX JUN. ON BERBERIXE. Theory for Found. ClOII,,06* OCH,. . 27.i4 per cent. 27.43 per cent. I n order then to prove that the acid from berbwine was a deriva-tive of pyrocntechol a small quantity was decomposed by fusion with potash. 2 grams of the pure acid was dissolved in a little potash, the solution evaporated to dryness and the residue fused in a silver dish with 50 grams of pure caustic potash and a little water for about half an hour. The resulting almost colourless melt was dissolved in water and acidified with dilute sulphuric acid during which operation the solution became first blue then violet and lastly reddish but rernaiiied clear.It was extracted several times with ether the ethereal solution dried over calcic chloride and the ether distilled off; in this way a crystalline residue was obtained which after recrystal-lising once or twice from a little water gave the following results on analysis :-0.1217 pram substance dried a t 100" gave 0,0442 gram H,O and 0.2436 gram CO,. Theory. C,H,O ,' Found. C 54.55 per cent. 54.59 per cent, H . . 3-89 , 4.03 ,, 0 4-56 , 4.48 ,, A determination of the water of cystallisation gave the following results :-0.3326 gram of air-dry substance dried at 100" lost 0.0347 gram.Theory. C7H,0 + H,O. Found. H,O 10.46 per cent. 10.43 per cent. This acid has therefore the composition of protocatechuic acid, with which it agrees in all it,s properties. It crystallised from hot water in needles melting at 195-196" The aqueous solution gives with ferric chloride a deep emerald-greeu coloration which on the careful additicn of sodic carbonate solution, beconies first blue then violet and at last red. It reduces an am-rnoniacal silver solution at. once gives with lead acetate a white precipitate soluble in acetic acid and on heating is decomposed into carbonic anhydride and a white crystalline sublimate which shows all the reactions of pyrocatechol. These react,ions however do not deter-mine whether the acid ohtained from herberine is hemipinic or meta-hemipinic acid as both these acids contain two methoxyl-groups an 'CV.H. PERKIN JUN. ON BERBERIXE. 75 both on fusion with potash yield protocatechuic acid. These two acids can however be readily distinguished by conversion into their ethyl-imides ; the ethylimide of hernipinic acid melting a t 96" whilst that of metahemipinic acid melts a t 226-227'. I n order to prepare the ethylimide of the acid from berberine the pure substance was dissolved in an aqueous solution of ethylamine, the solution evaporated to dryness on a water-bath and the residue distilled from a small retort. The solid distillate was dissolved in a little boiling methyl alcohol and allowed to stand when beautiful needle-shaped crystals were obtained which on analysis gave the following numbers :-t = 0.1753 pram substance gave 9.7 C.C.N. Bar. = 760 mm. 14.5". Theory. C12H,,NO,. Found. N . . . . . . . . . 5.96 per cent. 6-09 per cent. This ethylimide melts at 94-95' but when recrystallised from water at 96" and shows all the properties of ethylhemipinimide pre-paTed by Liebermaan by the action of ethyl iodide on the potassium-derivative of hemipinimide. It is therefore proved beyond doubt that hemipinic acid from berberine is identical with that obtained from narcotine.* Besides hemipinic acid there are small quantities of at least two other acids formed when berberine is oxidised with perman-ganate in the proportions given above both of which are present in the potassic carbonate residues from which the potash salt of hemipinic acid has been extracted with alcohol.These residues were dissolved in a small quantity of water neutralised with acetic acid and treated with acetate of copper. On long standing in a warm place the green solution thus produced deposited a sma11 qnantity of a light bluish -green precipitate. This was collected well washed with water and decomposed by passing sulphuretted hydrogen t,hrough the sall; suspended in boiling water ; the filtrate on evapora-tion gave a small quantity of a crystalline residue which on examina-tion was found to contain nitrogen. On recrystallisinq from water small nodular crystals were obtained, melting a t 238-242'. These gave on analysis the following numbers:-0.2629 gram substance gave 14.5 C.C. N. Bar = 759.t = 14". Theory. C,H,NO + H,O. Found. N . . . . . . . . . 6.11 per cent. 6-48 per cent. * This confirms the results obtained by E. Schmidt (ZOC. cit. 63-73). G 76 W. H. PERKIN JUN. ON BERBERIXE. Unfortunately the amount of this acid obt,ained by this reaction was too small to allow of further experiments being matle to determine its composition but from its melting point and analysis it would appear to be either carbocinchomeronic acid or berberonic acid. This is the more probable as berberine when oxidised by nitric acid yields berheronic acid. I t is interesting to notice that E. Smith and C. Schilbaqh (Arch. Pharm. [3] 25 164-170) in their experiments on the oxidation of berberine with permanganate also noticed the formation of a nitrogenous acid crystallisirig in nodular ci-ystals and nielting a t 218-22CIO.The silver salt however gave numbers showing this acid to be a pyridinemonocarboxylic acid (nicotinic acid ?). The mother-liquor from the copper salt was treated with sul-phuretted hydrogen filtered from the precipitated sulphide of copper, and subacetate of lead added so long as a precipitate was produced. The lead salt was collected well washed suspended in water decom-posed with sulphuretted hydrogen and the filtered solution evaporated to dryness. The residue when dissolved in a small quantity of boiling water, and the sulution allowed to cool slowly deposited after some time a quantity of crystals ; these on examination were found to consist of two distinct substances the one crystallising in thick brownish prisms and the other in long colourless needles.The brownish prisms were mechanically separated recrystallised several times from water and the colourless crystalline mass thus obtained dried at loo", and analysed with the following result :-0.1932 gram substance gave 0.0777 gram H,O and 0.3763 gram CO,. Theory CloH1,O6. Found. C . 53.10 per cent. 5312 per cent. 0 . .42-48 , 42.41 ,, I1 4.42 , 4.47 ,, As this substance meltcd a t 177-178" there can be no doubt that it was simply hemipinic acid with which i t agreed in all its react ions. The needle-shaped crystals obtained from the lead salt together with the hemipinic acid after recrystallisation from water were found to consist of pure oxalic acid. It is very remarkable that in the oxidation of berberine with alkaline permanganate so little oxalic should be formed.The amount ac*tuxlly obtained from 60 grams of berberine was biit litt,le more than 3 grams. From the above it will be seen that 1 erberine when oxidised with an excess of potassium permangana te yields principally hemipini W. €3. PERK" JCX. ON BERBERIXE. 77 acid. the other oxidation products isolated being formed only in very small quantity. I n this respect berberine differs very widely from papaverine which under similar conditions yields a number of important decomposition products such as pnpaverinic acid C16H,3N0,, veratrinic acid C9Hl0O4 metahemipinio acid CloHlnOs a-pyridine-tricarboxylic acid CeH5N06 &c. all of which are found in consider-able quantity in the product of the oxidation.The reason for this IS that berberine and its derivatives are so very readily oxidised that unless a limited amount of permanganate is used and the oxidation very carefully carried out the whole molecule is split up yielding principally hemipinic acid. As the result of a very large number of experiments carried out under a great variety of conditions it has, however been found possible to arrest; the oxidation before it has gone as far as hemipinic acid and in this way several new substances have been isolated the study of which it is hoped will furnish some important clue as to the constitution of this interesting alkaloid. In experimenting on the Formation of these new derivatives I have found it necessary t o work with small quantities at a time (never more than 7 grams of berberine in one operation) as when large quantities are used even under precisely similar conditions of tem-perature and amount of oxidiser very small yields are obtained.The best results have been obtained with the following quan-tities :-5 grams berberine (dried a t the ordinary temperature), 9 , potassic permanganate. 9 , carbonate. The potassic permanganate and carbonate are dissolved in half a litre of water of go" and the solution very slowly run through R separating funnel or burette into a hot solution (90") of the berberine (in a quarter of a litre of water) the whole being well stirred during the operation. As soon as all the permanganate has been added (the oxidation requires about 10-15 minutes) the product is transferred to a flask cooled well under the tap and the manganese precipitate brought into solution by passing a slow stream of sulphurous acid into the mixture.In this way a slightly yellowish liquid is obtained, in which are suspended small yellow flocculent part'icles. These are collected well washed with water and freed from the last traces of mother-liquor by spreading them on a porous plate. The purification of the resulting amorphous jellow mass which contains at least three new substances is a very difficult operation and has up to the present, only been successfully carried out when the following conditions have been carefully observed. The well washed residue is suspended in water and well agitate $8 W. H. PERKIN JUN. ON BERBERINE.a t a temperature of about 40" with a slight excess of sodic carbonate, by which treatment the crude product is separated into two portions, the one soluble the other insoluble in carbonate of soda; these are separated by filtration. The new acid contained i n the brownish-coloured filtrate is de-posited on the addition of an acid in the form of an amorphous yellow precipitate which on account of the presence of a quantity of a resinous substance can mly with difficulty he obtained in a crystal-line condition. The method of purification which has given the best results is the following :-The solution in sodic carbonate is nearly neutralised with dilute sulphuric acid and the new acid fractionally precipitated in three fractions by running into the well-stirred solution a fine stream of very dilute sulphuric acid.The first fraction should be about one-fourth the second one-half the third one-fourt h of the whole. The second fraction is carefully washed dried on a porous plate dissolved in a little metliyl alcohol and the solution trans-ferred to a flat dish and allowed to evaporate completely a t the ordinary temperature. During the evaporation the new acid separates in yellow nodular masses covered with a trarispnrent resin which is invariably deposited along with the crystals. The resulting mixture of acid and resin is scraped off the sides of the dish and well kneaded between the fingers with a sniall quantity of methyl alcohol. I n this way the resin is removed leaving the warty masses almost entirely undissolved.The purified product is now dissolved in a small quantity of boiling methyl alcohol from which it is deposited on cooling in almost colourless nodular masses which after repeated recrystallisation gave the following results on analysis :-I. 0.1511 gram substance gave 0.0602 gram H,O and 0.3192 grain II. 0.1421 gram substance gave 0,0552 gram H20 and 0.3000 gram Bar. = CO,. CO,. 727 mm. 111. 0.3633 gram substance gave 10.4 C.C. N. i = 11". Theory. Found. f--&- 7 r-h- 7 C,,H,INOg. C2,H,gNO,. I. 11. 111. H . . . . 4.10 4-55 , 4-43 4.47 - 9 , - 3-40 , N . . . . 3.37 3.36 , -0 . . . . 34.70 34.53 , - - -C . . . . 57.83 57.35 per cent. 57.61 57.58 - per cent. 9 7 I t is as yet very difficult to decide whether this new substance has the formula C,oH,,N09 or C20H19N09 but for various reasons I a W.H. PERKIN JUK. ON BEHBERINE. 79 inclined in the meantime to adopt the latter formula leaving the definite settlement of this point t'o further experimental proof. This substance is readily soluble in ethyl arld methyl alcohol and in acetic acid but only sparingly in benzene toluene and ether and almost insoluble in light petroleum chloroform ethyl acetate and cold water. It is however best purified by recrystallisation from methyl alcohol from which it is deposited on long standing either in warty masses or in small plates. Considerable difficulty was experienced in determining the melting point of this new substance. When rapidly heated it softens at about 158-240" and then melts completely a t 141-142" with evolution of gas.At 150-155" it again becomes solid and on further heating melts again between 195" and 200". The pure compound C20H19N09 dissolves readily in alkalis and in alkaline carbonates. The barium salt was prepared bg dissolving the acid in baryta-water removing the excess of the latter by passing carbonic anhydride through the boiling solution filtering and evaporating on a water-bath. In this way a quantity of an almost coiourless crystalline barium salt was obtained which after washing with a little water and drying first over sulphuric acid in a vacuum and then a t looo, gave the following results on analysis :-0.4598 gram substance gave 0.1926 gram BaS04. Theory. Czo 11 I7NOgBa. Found. Ba . . 24-82 per cent. Ba . . 24.63 per cent.The neutral solution of the ammonium salt of this acid gives with nityate .f silver a white gelatinous precipitate soliible in a large quantity of boiling water with cupric acetate a beautiful hluish-green precipitate and with acetate of lead a white gelatinous pre-cipitate. Fused with a small quantity of pure caustic potash this substance is readily decomposed yielding an almost colourless melt which wheii dissolved in water acidified with sulphuric acid and extyacted with ether gives a crjstalline acid readily soluble in water. The solution of this acid gives with ferric chloride a deep-green coloration changing to violet and then to deep red on the addition of sodic carbonate. As it also gives with acetate of lead a white pre-cipitate and readily reduces ammoniacal silver solution it is probable that this substance is either berberiuic acid or protocatechuic acid.The residual product of the oxidation of berberine insoluble in sodic carbonate obtained as described above contains besides a quantity of a resinous substance two new compounds which are separated in the following way : 80 W. H. PERKIN JUN. OX BERBERINE. The crude brownish product is well washed first with ti dilute solution of sodic carbonate then several times with water dried on a porous plate and dissolved in a Pnisbll quantity of boiling 90 percent. acetic acid (5 grams of substance require about 20 grams of acetic acid). This solution on cooling gradually deposits a considerable quantity of R crystalline substance. At the end of 48 hours this is collected washed with a little glacial acetic acid and purified by repeated recrystallisation from tlliis solvent.* It is thus obtained in flat glittering plates with a remarkable silky lustre these after drying first on a porous plate and then at loo" gave the following results on ailalpis :-I.0.2001 gram substance gave 0.0800 gram HzO a.nd 0.4387 11. 0.1395 gram substance gave 0.0389 gram H,O and 0.3053 111. 0.1354 gram substance gave 0.0550 gram H,O and 0.2971 IV. 0.1560 gram substance gave 0.0620 gram H20 and 0.3433 V. 0.3773 gram substance gave 11.2 C.C. N (t = 13". Bar. = VI. 0.3372 gram substance gave 10.6 C.C. N ( t = 13.5". Bar. = pram CO,. gram CO,. gram CO,. gram CO,. 760 mm.). 737 mm.). Theory. Found. -7 --- h -I_- czo H1:N0* I.11. 111. LV. v. VI. C . . . . 60.15 p. c. -59.87 59.69 5 9 . i 7 60.02 - - p. c. H . . . . 4.26 , 4.44 4.53 4.51 4.41 - - ,, N . . . . 3 - 5 1 - - - - 3.50 3-58 ,, 0 . . . . 32.08 , - - - - - -This substance melts at 236-237". It is readily soluble i n hot acetic acid from which it crystallises on cooling in beautiful glitt,er-ing plates but is only sparingly soluble in et,hyl and methyl alcohol, benzene toluene light petroleum and acetone even on boiliug. Although insoluble in alkaline carbonates this substance dissolves readily in warm solutions of ammonia caustic potash &c. forming well-defined salts. If the solution in ammonin be allowed to evilPo-rate over snlphuric acid a very curious jelly-like animonium salt is deposited which gradually dries up to a mass resembling dried albumin.This dissolves readily in water and the solution gives with reagents some very characteristic salts. * The mother-liquors contain considerable quantities of a second neutral sub-stance which will be described f'urther on W. H. PERKIN JUN. OX BERBERISE. 82 Nitrate qf silver gives a white gelatinous precipitate which is readily soluble in hot water but only sparingly in cold ; it could not be recrystallised as it somewliat readily decomposes on warming with water. A small qua,nt,ity of this salt was prepared well washed with cold water dried on a piece of porous plate over sulphuric acid in a vacuum and arialysed with the following results :-I. 0.1996 gram subst,ance gave 0.0560 gram H,O 0.2547 gram GO2 and 0.0623 gram Ag, 11.0.3286 gram substance gave 0.1023 gram Ag. Found. Theory. +-7 C20Hi,N08Ag2 + 4H20. I. 11. c 35.04 p. c. 34.80 H 3.35 , :3*12 7 9 p. c. --Ag 31-40 , 31.22 32.13 ,, From this analysis it would appear as though the neutral substance, CmHlTN08 when dissolved in alkalis took up 4 mols. H,O forming a bibasic acid of the formula C2nH,N0,,. It is however much more probable that the silver salt when prepared as above contains water of crystallisation as is the case for example with the silver salt of papaverinic acid which crystallises with 2-2b mols. H,O. The formula of the acid formed by dissolving the substance C2,H,,NOe in alkalis can therefore only be accurately determined by the analysis of some other of its salts with the investigation of which 1 am at present engaged.The solution of the ammonium salt of this acid gives with acetate of copper a splendid light bluish-green precipitate and with acetate of lead a white gelatinous precipitate which dissolves somewhat sparingly in boiling water. The chlorides of barium and caZcium give no precipitate in the cold ; on boiling white amorphous salts are precipitated. The mother-liquors from the precipitation of the substance CZoHl,N08 contain besides small traces of this sparingly soluble sub-stance a considerable quantity of a second neutral substance which is much more readily soluble. To isolate this the dark-brown acetic acid solution is heated to boiling diluted with one-fourth of its bulk of boiling water and allowed to stand for 24 hours.The crystals which separate are collected the mother-liquor again treated as above, and the operation repeated until no more crystals separate. I n this way nearly the whole of the new substance crystallises out in yellowish plates whereas if too much water be added at first the crystals are invariably mixed with a black tarry substance which hinders their subsequent purification. The crude substance thus obtained can no 82 W. H. PERKIN JUN. ON BERBERINE. easily be purified by recrystallisation once from dilute acetic acid and twice from pure alcohol. From the hot alcoholic solution it is deposited on cooling in beautiful colourless plates with a pearly lustre. %'or analysis the substance was dried at 100". I. 0.1372 gram substance gave 0.0540 gram H,O and 0.31.55 gram GO2.11. 0.1792 gram substance gave 0.0741 gram H20 and 0.4093 gram COz. 111. 0.1395 gram substance gave 0.0584 gram H,O and 0.3213 gram C02. IV. 0.1680 gram substance gave 0.0720 gram H,O and 0.3832 gram CO,. V. 0.3070 gram substarce gnve 10.1 C.C. N ( t = 15". Bar. = 742 mm.). VI. 0.2493 gram substance gave 8.2 C.C. N ( 1 = 18.5". Bar. = 759 mm.). Theory. -- -.A---CsoH ;NO 7. I. $1. 111. IV. v. VI. Found. -3 C . . . . 62.66 p. C. 62.71 62-61 62.81 62.53 - - p. c. K . . 3-66 , - -H . . . . 4.43 , 4.38 4-70 4.65 4.76 - - ,, - - 3.75 3-80 ,, - - - - - - 0 . . . . 29-34 ,, This new compound which from the analysis appears to have the formula C2,,H,,N0, melts at 150". I t is readily soluble in hot methyl and ethyl alcbhol but only sparingly soluble in these liquids in the cold.It dissolves with dificulty in boiling water and the solution on slowly cooling deposits the substance in beautiful glittering plates, which resemble anthracene in appearance ; if rapidly cooled however, the aqueous solution becomes milky before crystallising. I t is also readily soluble in hot but almost insoluble in cold benzene and toluene. If this substance is not quite pure its solutions fluoresce in a most beautiful way reminding one strongly of a dilute solution of fluoresceln. The substance C,,,H,,NO does not dissolve in alkalis in the cold arld only very slowly on boiling. The solution in hot strong caustic potash on cooling deposits what appears to be the unchanged substance, but as the substance is more soluble in caustic potash than in water it is possible that it forms with alkalis very unstable salts.Fused with a little potash the substance C,,H,iK07 yields what appears to be protocatechuic acid (? berberinic acid). In studying this decomposition about 4 of a gram of substance was gently fused with 2 grams of potash and a little water in a thick test-tube. The crystals dissolved at once with evolution of quantities of a pungen W. H. PERRIN JUII'. ON BERBERIKE. 83 gas which resembled methylamine or ethylamine rather than ammonia. 'l'he colourless residue dissolved in water with R redtlish colour arid on acidifying and extracting with ether a colourless crystalline sub-stance was obtained which showed all the properties of protocatechuic acid.The aqueous solution gave with ferric chloride a deep-green coloration which on the addition of sodic carbonate became first blue then violet and at last red. On the addition of acetate of lead to the aqueous solution a white precipitate was obtained soluble in acetic acid. The substance C2,,H17N07 dissolves in strong nit,ric acid with a deep orange colour and in warm sulpliuric acid forming a deep violet-black solution. The addition of strong hydrochloric acid causes the crystals to turn yellow without dissolvirig them and if a drop of hydrochloric acid be added to the alcoholic solution of the substance the solution is coloured slightly yellow and acquires a bluish-green fluorescence. In order to further control the formula of the substance C20H,7N07, its molecular weight was determined by Raoult's method with bhe following result :-Substance taken 0.7558 gram.Acetic acid . 42.1296 ,, Meiting point of acetic acid 16.447" , of mixture 16.263 Depression of melting point 0.184 Molecular weight of substance found from the above data 380 Theory for C,,H,,N07 383 The yield of crude dry yellow substance obtained by the oxidation of 'LOO grams of berberine as described above is about 70 grams of which 12 grams are insoluble and 55 grams soluble in a solction of sodic carbonate. These numbers show clearly t.hat a large portion of the products of the oxidation must be contained in the filtrate from the yellow substance. In order to test this the yellow solution was evaporated over a free flame with occasional addition of a little aqueous sulphurous acid until the inorganic salts commenced to separate as a crust on the surface.The liquid was then allowed to cool filtered from the crystalline matter and again evaporated the operation being repeated until the soliltion from the oxidation of 200 grams of berberine was reduced in bulk to 1 litre. The brownish product was then extracted 20 times with ether the ethereal solu-tion dried over calcic chloride and the ether distilled off until about 150 C.C. remained. During this operation a quantity of a white crystalline substance separates which after collecting washing with a little ether an 84 W. H. PERKIS JUN. ON BERBERINE. drying on a porous plate presented the appearance of hard sandy crystals. Subsequent examination showed that this product was a, mixture of two substances which are readily separated from each other by recrystaUisation from water.The solution in a small quan-tity of boiling water deposits on cooling first of all a quantity of glittering plates which are rapidly filtered off. On standing the second substance separates from the mother-liquor in hard prisms. The more insoluble substance which is formed only in very small quantity was purified by recrystallisation from water ; the crystals, dried first over sulphuric acid in a vacuum and then at loo" gave the following nurribers on analysis :-I. 0,1493 gram substance gave 0.0618 gram H,O. 11. 0.2907 , , 8.8 C.C. N; t = 17". Bar. = 757 mm. Theory. C2oH1909. Found. C 57.55 per cent. 57.54 per cent.H 4.55 , 4-60 ,, N . . 3.35 , 3.50 ,, 0 34.53 , 34.36 ,, This interesting substance which from the above analysis appears to have the constitution C,,,HI9NO9 melts at 178-179" with decom-position due probably to loss of water. It is sparingly soluble in alcohol and ether fairly soluble in boiling water from which i t crystallises on cooling either in small plates o r in very small warty masses. At present only sufficient of this substrance has been obtained for the above analyses and subsequent investigation must show whether the constitution assigned to it is correct. This acid has the same formula as the acid obtained from the yellow precipitate (p. 78) but as it melts 38" higher it must be isomeric and not identical with this substance. The crude crystals of the more soluble substance obtained as described above were separated from the substance CzoHI7NO9 by repeated recrystallisation from water from which they were invariably deposited as a hard crystalline crust on the bottom of the beaker.The air-dried crystals when heated on a water-bath lost scarcely any weight showing the absence of water of crystallisation. On analysis the following numbers were obtained :-I. 0.1.518 gram substance gave 0.0608 gram H,O and 0.2970 gram 11. 0.1720 gram substance gave 0.0701 gram H20 and 0.3361 gram CO*. co, W. H. PERKIN JUN. ON BERBERJSE. 83 Found. Theory. r-h--7 CIOHIUOG- I. 11. C 53-10 p. c. 53.36 53.28 p. c. H . . 4.42 , 4.45 4.52 ,, 0 42.48 , 42.19 42.20 ,, This substance melts at 159-160" with decomposition and as it gives protocatechuic acid on fnsion with potash there can scarcely be a doubt that i t is heniipinic acid.It is however in appearance totally different from the hemipinic acid previously obtained (see p. 73). The crystals which contain no water of crystallisation, are very soluble in hot water and separate from the solution very slowly iiideed the deposition often being incomplete after standing for 24 hours. The hemipinic acid obtained as describpd a t the commencement of this chapter and also a sample of the same substance prepared from narcotine (for which I am indebted to Dr. Goldschmiedt) crystallise rapidly with 2 mols. H,O of crystallisation when the hot aqueous solution is allowed to cool moderately slowly. The crjstals dried a t lOO" and heated under the same conditions as the above melt a t 177-178" with decompositiou.The great difference in the properties of the two preparations lead me t o doubt their identity and in order to establish this the silver salt of the acid melting a t 159-160" was prepared and examined. This salt is thrown down on the addition of silver nitrate to the ammonium salt as a heavy white precipitate. It was well washed with water dried over sulphuric acid in a vacuum and then annlysed with the following result :-T. 0.2928 gram substance gave 0.1430 gram Ag. 11. 0.2505 , , 0.1222 ,, Found. Theory. +-7 C,H,O ASP I. 11. Ag 49-09 p. c. 48.83 48-78 p. c. This salt gives therefore the sa,me numbers as those required for the silver salt of hemipinic acid.Subseqnent experiments on these two preparations of hemipinic acid make it appear probable that this substance exists in two distinct forms the one melting a t 159-160" and the other a t 177-178". If a crystal of the latter acid be added to a warm saturated solution of the former in some cases at least the one modification is completely converted into the other but this change appears only to take place under certain conditions of cunc ntration &c 86 W. H. PERKIN JUN. ON BERBERINE. I hope to be able to investigate this point more completely a t an early date. Actiou of Hydrogen Iodide on Berherine. When heated with fuming aqueous hydrogen iodide berberine is readily decomposed with evolution of methyl iodide and formation of a new substance which dissolves in alkalis with a blackish-violet coloration.This preliminary experiment led me t o suppose that berberine is decomposed by hydrogen iodide in a way similar to papa-verine which under this treatment is split iip into papaveroline, C16H13N04 and 4 mols. of methyl iodide. In determining the con-stitution of berberine it was a matter of great importance to discover the number of OCH groups contained in the formula C2,H,7N04, and this is readily done by Zeisel's method (Monats. 6 995) which consists in decomposing the alkijfloi'd with fuming hydrogen iodide, and determining the amount of methyl iodide formed by means of alcoholic silver nitrate. The first experiments in this direction were made with berberine itself with the following results :-I.0.2930 gram of berberine 11. 0.3315 gram of berberine 111. 0.3290 gram of berberine 0.3990 gram AgI. 0.4440 gram AgI. 0.4430 gram AgI. Theory for 2(0CH3) groups in C,oHljNO + H20. (OCH,) . . . . 17.56 p. c. (dried at 100-110") gave (dried at 100-110") gave (dried a t 100-110") gave Found. r--*- 7 'I. 11. 111. 18.03 17.72 lT.83 p. c. These experiments show that berberine contains only two OCH, groups in its molecule these two being present in the portion which on oxidation yields hemipiiiic acid. Owing however to the diffi-culty i n determining accurately the amount of water of crystallisation present in the samples of berberine used these results were not considered perfectly trustworthy and in order to be quite certain similar experiments were instituted with the nitrate and hydriodide of the base these salts being so readily obtained pure and free from water of crystallisation.1. 0.3903 gram berberine nitrate dried at loo" gave 0.4669 gram AgI. Theory for 2(OCH:,) groups in C,loHliN04,HN03. Found. (OCH',) . . . . 15.59 per cent. 15-74 per cent W. H. PERKZX JUN. ON BERBERINX. 87 IT. 0.4901 gram berberine hydriodide gave 0.4520 gram AgI. Theory for 2(OCH,) groups in C20H,iN04,HI. Found. (OCH,) . . . . 13-39 per cent. 13.61 per cent. I n order if possible to isolate the phenolic substance formed during this reaction the experiment was carried o u t with larger quantities. 25 grams of pure berberine were boiled with a con-siderable excess of fuming aqueous hydrogen iodide in a flask con-nected with a reflux condenser until evolution of methyl iodide had cei1 sed.The dark-coloured solution on cooling deposited a small quantity of the new substance in the form of blackish-coloured nodules. These were collected the solution dihlied from a small retort until half had passed over and again allowed to cool when a further quantity of solid was obtained. The crude product was well washed with water till free from hjctrogen iodide and ground to a paste in a mortar with a weak solution of sulphurous acid to remove a small quantity of iodine. The yellowish-brown emulsion was now collected on a filter-pump well washed with water and extracted with boiling water containing a little sulphurous and sulphuric acids. The hot solution, after filtering from a quantity of a brown insoluble residue deposited the new substaiice on cooling in beautiful orange-coloured amorphous flocks which entirely filled the liquid.Tliese were collected repre-cipitated twice from hot water containing sulphurous acid dried over sulphuric acid in a vacuum and analysed with the following result :-I. 0.1478 gram substance gave 0.0582 gram H,O and 0.3097 gram IT. 0.1546 gram substance gave 0.0631 gram H,O and 0.3244 gram 111. 6.4354 gram substance gave 15.2 C.C. N ; t = 0.12. Bar. = IV. 0.4086 gram decomposed by nitric acid according to Carius' V. 0.4401 gram decomposed by nitric acid according to Carius' Ia. 0.2784 gram substance heated to 100" till constant lost IIa. 0.2.502 gram substance heated to 100" till constant lost CO?.c 0,. 740 mm. method gave 0.1314 gram BaSOJ. method gave 0.1412 gram BaSOa. 0.0123 gram. 0.0112 gram 88 W. H PERKIN JUN. ON BERBERINE. Found, 7 Theorv. r-A-_ (C,,H,,YOJ,,H2S04 + 2H@. 1. 11. 111. IT. v. p. c. - - C . . 57.75 p. C. 57.12 57.22 -H 4-23 , 4.37 4.60 - -- 4-01 - - N 3-74 , 9 9 H,SO,. . 1310 , - - - 13-58 13.45 ,, 4.43 4.47 - - - H 2 0 . . 4-81 , 9 3 This substance is t,horefore the sulphate of a base of the formula This base is formed from berberine simply by substit'uting hydro-- -CI8H1,NO4 for which I propose the name berberoZine. gen for methyl in each of the two methoxy-groups ; thus :-C,sHiTO,(OCH,),- C18Hl,NO?(OH)*. Berberine. Berberoline. The snlphate of this base is stable and does not appear to undergo decomposition even on long standing.I n tlie presence of a trace of alkali decomposition sets in a t once owing 110 doubt t o oxidation-a dark blackish-violet solution being formed. An aqueous solution of the sulphate shows the following reactions :-Chlorine-water gives a dark-violet flocculent precipitate. N i t r i c acid gives a magnificent violet coloration which on standing-and particularly on warming-becomes a deep reddish-brown. Berber-dine solutions decompose solutions of platinic chloride auric chlo-ride and ammoniacal nitrate of silver wit,h sepayation of the metal. Fusion of Berberine with Potash. Hlasiwetz and Gilm (Juhresbericht 1864 407) who were the first to study the action of melted potash on berberine obtained by this decomposition two new substances that is berberinic acid C,H80a + H,O and an acid of the formula C9H805.With the object of deter-mining tlie constitution of these two acids I have again taken up the study of this important decomposition the experiment being con-ducted as follows :-100 grams of caustic potash and 5 C.C. of water were heated in a silver dish t o about 180' arid then 60 grains of berberine slowly added in small portions a t a time. The berberine on coming in contact with the melted potash was rapidly decomposed-little black balls being formed at first which swam about on the surface of the liquid but on stirring a s the temperature gradually rose (to 240°) these dissolved forming a dark-brown liquid. During the operation-which lasts about an liour-a quaiitit? of thick vapouis, smelliiig strongly of amrriouia a i d guaiacol wcre evolved.The pro W. H. PERKIN JUN. ON BERBERENE. 89 duct was dissolved in water acidified with dilute sulphuric acid, filtered from a quantiky of brownish flocks which separated evaporated t o a syrupy consistence and well agitated with about twice its volume of strong alcohol. The potassic sulphate thus precipitated was filtered off washed with a little alcohol the combined alcoholic solu-tions gently evaporated ou a water-bath and the residue dissolved in a little water was repeatedly extracted with ether. The ethereal extract after carefully drying over calcic chloride and evaporating deposited 5 grams of a dark-brownish crystalline mass consisting of impure berberinic acid. This was purified first by spreading it on a porous plate and then by repeated recrystallisation from water.The beautiful white crystals thus obtained gave on analysis the following numbers :-I. 0.1506 gram substance dried at 80" gave 0,0667 gram H,O and 11. 0.1683 gram substance dried at 80" gave 0-0735 gram H,O and 0.3160 gram C02. 0.3521 gram CO,. Found. Theory. r-7 cl3Ef*o4 - I. 11. C 57-15 p. C. 57.22 57.05 p. c. H 4.76 , 4.92 4-84 ,, 0 38.04 , 3i.86 38.11 ,, Berberinic acid a,ppears to crystallise with 1 mol. H20 which, however is gradually given off a t the ordinary temperatures if the crystals are placed over sulphuric acid in a vacuum. The melting point of this acid which is not given by Hlasiwetz and Gilm I found to be about 165". No accurate melting point can be given as when heated the substance softens at 145" and then melts with evolution of carbonic anhydride at about 165" ; this temperature may therefore be looked upon as its decomposing point rather than its melting point.The other properties of this acid agree in all respects with those given by Hlasiwetz and Gilm. If a drop of ferric chloride is added to an aqueous solution of berberinic acid a splendid dark-green coloration is produced which, on the addition of sodic carbonate solution becomes first violet then violet-red and at last deep-red coloured. This reaction and the fact that this acid reduces Fehling's solution and an ammoniacal so.1ution of silver nitrate and gives with acetate of lead a white precipitate soluble in acetic acid shows at once that berberinic acid must be very closely related to protocatechuic acid.As protocatechnic acid on distillation is split up into pyrocatechol and carbonic acid it was thought that under similar treatment, YOTI. LY 90 W. H. PERKIN JUN. ON BERBERINE. berbednic acid might give some decomposition-product which would afford some clue as to its constitution. In order to test this 2 grams of the pure dry acid were heated in a small retort until the evolu-tion of carbonic anhydride had ceased and the residue then rapidly distilled. In this way an almost colourless syrup was obtained which on analysis gave the following numbers :-0.1460 gram substance gave 0.0842 gram H,O and 0.3605 gram COz. Theory. C7H802. Found. C 67.74 per cent. 67.37 per cent. H 6.46 ) 6.41 ,, 0 25.80 , 26-22 ,) This substance has therefore the same formula as hornopyrocatechol, with which it agrees in all its reactions.It is readily soluble in water ; the solution reduces Fehling's solution and ammonincal nitrate of silver. Ferric chloride produces a deep-green coloration which on the addition of sodic carbonate becomes reddish-violet. There can, therefore be no doubt that berberinic acid on distillation is split up into homopyrocatechuic and carbonic acid thus :-0 = C,H,O + COz, but it is at present difficult to decide the positions of the carboxyl-group with reference to the OH and CH3-groups. I am at present engaged on the further investigakion of oxidising agents on berberine and on the alkyl addition-products of tetrahydro-berberine and also on a series of experiments on the constitution of berberonic acid. The completion of these experiments will be somewhat delayed owing to an unfortunate fire in the laboratories of the Heriot Watt College having consumed a number of new products which had already been prepared. For this reasonalso I have not been able to complete the examination of the substances described in this paper so thoroughly as I could have wished. I hope however at an early date to be able to communicate to the Society a further paper on this interesting alkalo'id. Heriot Watt College, Chemical Laboratory Edinburgh

ISSN:0368-1645    

DOI:10.1039/CT8895500063

出版商:RSC    

年代:1889

数据来源: RSC

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91 XII1.-On some Leadhills Minerals. By NORMAN COLLIE Ph.D. F.R.S.E. THE Leadhills in the south of Scotland has long been known as a locality from which many interesting minerals can be obtained. Some seemingly are peculiar to the Leadhills district viz. susanite a double sulphate and carbonate of lead ; and caledonite a basic sul-phate of lead cont.aining copper and carbonic acid ; whilst others, viz. leadhillite a mineral similar in composition to susanite ; lanark-ite a basic sulphate of lead ; vanadinite and plwmbo-calcite are met with only in one or two other localities. Most of the minerals the analyses of which are given in this paper, I obtained myself some years ago at Leadhills the remainder* were collected by Dr. Wilson of Wanlockhead Leadhills. These I have from time t o time analysed with results which I have now collected in the following paper.I have also incorporated several analyses made by Mr. Wheeler at the Queen’s College Belfast. Two minerals amoiigst those which I have analysed do not seem to have been pre-viously noticed. (1.) Plumbo-aragonite or aragonite containing lead carbonate. (2.) Calcium unnado-pyromorphite or pyromorphite containing calcium and vanadic acid with a small quantity of copper hydroxide. The investigation of these Leadhills minerals was undertaken for several reasons the chief being to ascertain whether in the large number of double carbonates sulphates phosphates &c. found there, the constituent salts were present in any simple molecular propor-tion; another being to determine which analyses amongst the con-flicting ones met with in mineralogical treatises are the most probably correct.Leadhillite. This substance is not often found a t Leadhills and for several years past few new specimens have been obtained. It occurs also as maxite in Sardinia. The earlier analyses given differ considerably from the later ones. At one time it was considered to be a mixture of sulphate and carbonate of lead in the proportions PbC03,3PbSOa. This however is obviously incorrect for not only does the substance contain from 1 to 2 per cent. of water but there is an insufficient * These minerals were first given to Professor Letts of Belfast who afterwards kindly handed them over to me for analysis. H 92 COLLIE ON SOME LEADHILLS MINERALS.amount of sulphuric and carbonic acids to combine with the whole of the oxide of lead. If the earlier analyses are omitted the carbonic acid is found to vary from 8.5-12.1 per cent. as the following analyses will show :-Calculated for I. IT. PPbS04,2PbCOs,Pb (0 a),. PbO 80-7 80.8 80.7 co, 12.1 9.2 9.1 SO3 7.1 8.2 8.3 HZO - 2.0 1.8 No. I is an analysis by 13ertrand (Bull. SOC. China. Paris 1873). No. I1 is by Hintze (Pogg. Ann. 152 356). Three separate specimens of leadhillite were ctnalysed and it was found that the amount of carbonic and sulphuric acids varied con-siderably. I. r-L- 7 (.) (6.) b) IT. 111. PbO 82.5 82.3 82.1 82.8 81.3 CO , 8.6 8.5 8.7 9.8 11.5 SO3 9.1 9.2 9-2 8.0 7.3 H,O 1.5 1.6 1.5 1.6 1.8 These results seem to point to the fact that leadhillite varies in com-position the ratio between the sulphate and carbonate of lead not remaining constant.Lanarkite. This mineral is stated by Brooke and Thomson to be a compound having the formula PbSO,,PbCO ; but subsequent analyses by Pisani and by Flight show that it does not contaiii carbonic acid aud this is corroborated by the following analyses III ( a ) and ( b ) . 111. I. 11. ( a ) . (b.) PbSO,,PbO. --T Calculated for PbSO 57.2 57 7 57.8 37.5 57.6 PbO 40.6 42.9 41.4 41.8 42.4 Loss on ignition 0.81 - 0.5 0.5 -No. 1 Pisani (Compt. reml. 1873). No. IT Flight (this Journal 1874 103). Lannrkite therefore unlike leadliillite seems to be of constant com-position. Caledonite. Caledonite is one of the rarest of the Leadhills minerals and is no COLLIE ON SOME LEADHILLS MINERALS.93 often met with. The few analyses given of i t differ very considerably, the earlier ones of Brooke and Thomson giving 31-9-32.8 per cent. of lead carbonate while Maskelyne and Flight (this Journal 1874, 191) find only traces of carbonic acid. Flight and Maskel~ne. 7 Found. Mean of f-- I. 11. PbSOa 60.2 59.5 59-1 PbO . 25.1 26-2 24.2 CUO 9.4 9.2 10.7 two analyses. CO 1.4 - 1.9 H,O - 3-7 3.5 These percentages do not agree with any simple formula and caledonite may be a hydrated form of lanarkite in which the hydrate OE lead has been replaced by a variable amount of copper hydrate. Linarite. This magnificent mineral is met with at Leadhills but fine specimens also occur in Cumberland and elsewhere.It does not Seem ever to contain carbonic acid and the analyses agree well with the formula P bS 04,Cu0,H20. Found. Mean of Calculated for 1. 11. two analyses. PbS04,Cu0,H20. PbSOd 75.4 74.8 75.3 75.6 CuO 18.0 19.7 7 9.6 19.8 H20 4.7 5.5 5.2 4.5 Pyromorphite. The specimens of this mineral which are found at Leadhills are remarkable for their great beauty of colour which varies from the richest orange to light or dark olive-green. The brilliant orange variety has been supposed to contain chromium and is sometimes called chromophosphate of lead but there are no analyses of any pyromorphite from Leadhills containing even a trace of that metal. Another variety of pyromorphite often found is light green in colour, and in botryoidal masses with a conchoidal fracture; this seems peculiar t o Leadhills and might possibly be mistaken for calamine.Various differently coloured pyromorphites were andysed :-Orange. Green. Yellow. 3Pb3(PO4).,,PbCl2. Ca.lculated for PbO 81-4 - 81.6 81.7 Pz06 15.7 15.9 15.9 15.6 CI . 2.6 2-6 2.8 2. 94 COLLIE ON SOME LEADELILLS MINERALS. Arsenic acid was only present in extremely small quantity. Several experiments were also made to determine whether the green colour was due to an appreciable amount of a ferrous salt but without success ; traces of iron were present but always seemed to be in the ferric state. From the above analyses the pyromorphites seem to differ but little in composition. Vanadhi t e. Although this mineral contains the rare element vanadium still it has been found in various other localities besides Leadhills.It is seldom found at Leadhills in the crystalline condition usually occurring as a deposit on calamine in the form of small granules. Two different specimens were analysed :-Calculated for I. 11. 3Pb3 (YO,) e,P b Clp PbO 80.0 79.6 78.2 VzO5 16.7 16.2 19.3 C1 2.5 2.4 2.5 H20 1.4 - 1.2 chromium but neither of these substances was present. Various specimens were tested for phosphoric acid and also for Calcium Yanado-pyromorphite. This new mineral occurs in black botrjoidd masses and is unlike either pyromorphite or vanadinite in appearance The frac-ture is uneven or conchoidal; i t fuses easily before the blowpipe, leaving a brown granule which when broken shows a crystalline structure.It dissolves readily in hydrochloric acid when warm and leaves a slight residue of a brown colour which consists chiefly of ail oxide of iron. Two analyses were made :-I. IT. Pbs(PO,) 52.0 -PbS(V04)z 19.2 Ca3(POA)z 15.8 -PbClz 11.4 10.7 Cu(OH) 1.6 1.4 Insoluble residue . . 0% 0.5 The specific gravity is 6.9-7.0. -Ratios between the phos-phates vanadates and the lead chloride in analysis No. I. 0.0224 3.3 0.0641 0.0510 0.0410 1.0 I The mineral is therefore a pyromorphite in which calcium replace COLLIE ON SOME LEADHILLS MINERALS. 95 lead and vanadic acid replaces phosphoric acid. The amount of water (0.4 per cent.) which the mineral loses wheE i t is heated is just enough to combine with the oxide of copper and as there is an insu6cient amount of acid to unite with all the bases present this is rendered probable.Unfortunately there was only a very small quantity of the mineral so no further analyses could be made. Pturnbo-calcite. Most of the calcite which is found at Leadhills contains some lead carbonate. The transparent crystals contain the least whilst the opaque and vitreous looking varieties contain sometimes as much as 9.5 per cent. The specific gravity does not vary much (2.7-2.8). Six different specimens were analysed two determinations of lead being made in each case:-I. 11. 111. 'Iv. v. VI. PbCO 1.4 1.2 1.4 3 9 5.2 3-9 CaC03 (by diff.). . 98.5 98.7 98.5 96.0 947 96.0 Lacroix (Jahrb. f. Min. 1887 Ref. i 238-239) also found that in five different specimens of phimbo-calcite from Leadhills the lead carbonate varied from 2.7 to 9.5 per cent.This mineral is evidently a varying mixture of the two carbonates. Plumbo-aragonit e. It is somewhat remarkable that corussite which is isomorphons with aragonite should be found combined with the calcspar in plumbo-calcite and that plumbo-aragonite should be seldom met with. That lead carbonate does however replace calcium carbonate in aragonite is shown by the following analyses of two undoubted specimens of aragonite from Leadhills -I. 11. PbCO,. . 0.8 1.3 CaC03 (by diff.). . 99.1 98.6 Professor Heddle (Mz'n. Mag. 5 1-31) has analgsed a specimen of CaC0 = The specitic gravity of plumbo-aragonite does not differ from that aragonite from Leadhills but did not find any lead in it.96.4 SrCO = 1.7 K20 = 0.6 NazO = 2.1 H,O = 0.3. of ordinary aragonite and is 2.9. Strontianite. S trontianite is found occasionally at Leadhills in solid crystalliu 96 COLLIE ON SOME LEADHILLS MINERALS. masses of a brown colonr. carbonate. It contains a certain quantity of calcium I. IT. Two analyses have been made :-S,O . 62-1 65.2 CaO 6.4 3.6 CO 31.2 30.8 I. This analysis was made by Mr. Wheeler. Dolomite. This dolomite is found often in very fine crystals and has a pink colonr due t o oxides of iron arid manganese :-I. IT. CaO 31.2 30.6 MgO 14.3 14.5 FeO 6.1 5.3 Fe& . 3.5 4.5 Mn,O 0.9 0-8 CO 43.3 42.6 SiOz 0.72 1.9 T. This analysis was made by Mr. Wheeler. Calamine. Calamine occurs in considerable quantit,y at Leadhills and can be obtained either crystalline or in botryoidal masses coloured by oxides of iron or copper :-Yellow. Blue. 7-7 7-7 I. IT. I. 11. ZnO 59.0 59.9 60.6 62.1 SiO,. . 31.5 32.1 24-2 24.3 1.5 2.7 1-9 PbO -Fe,03. 1.9 - 1.9 1.2 trace 0.9 cue S 2.6 trace E,O 4-9 5.2 10.17 9.3 - -- -The analyses marked I were made by Mr. Wheeler

ISSN:0368-1645    

DOI:10.1039/CT8895500091

出版商:RSC    

年代:1889

数据来源: RSC

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97 XTV.-CONTRIBUTIONS FROM THE LABORATORY OF THE UNIVERSlTY OF ZURICH. 11. Piazine-deriva.tives. By ARTHUR T. MASON Ph.D. F.I.C. Senior Demonstrator of Practical Chemistry. IN a paper pnblkhed in the Berichte (20 267) entitled “Ueber Condensations-derivate des Aethylendiamins,” I described amongst others two substances belonging to a class of nitrogenous compounds to which at the suggestion of Professor Merz I gave the name “ pyrazines ; ” this has since been changed t o “ piazines.”” The * In a paper which has just appeared in t,he Journal fiir pmktische Chemie (38, 185)) Professor Widman discusses the defective nomenclature a t present adopted in the aromatic and more especially in the alkalo‘id series. I n many caws the names have been chosen so as to indicate as far a~ possible the methods of preparation first discovered and then subsequent investigators seeing the inappropriateness of the terms thus given have adopted new ones so that in not a few cases we have one and the same compound referred to by different investigators under totally different names.A good illustration of this is offered in the many changes which the important nitrogenous compound above mentioned under the name of “ piazine,” hm under-gone. Its tetramethyl-derivative was discovered in 1879 by G utknecht in V. Meyer’s laboratory (Ber. 12 2290) and several other derivatives were imme-diutely afterwards studied by Treadwell and by Treadwell and Steiger (Ber. 14, 1461 ; 15 1059) and named a t the suggestion of Victor Meyer “ ketines.” At the suggestion of Professor Merz I afterwards proposed the name “ pyrazines” (Ber.20, 267) and in the same Journal Wolff adopted independently the same terni (Ber., 20,425) in both instances with the object of bringing out the analogy with the “ pyridines.” Victor Meyer finding the term “ ketines ’) inappropriate afterwards, and objecting to ‘‘ pyrazines )’ on the ground that Knorr (Annalen 238 144) had already used that term for pyrazole tetrahydride now proposed “ aldines ” (Ber., 21 20) but most of the investigators who have worked on this group still adopt the name “ pyrazines.” This single instance shows that a state of chaos exists and that some systematic nomenclature is an abRolute necessity. I n accordance with this Widman has propounded a systematic nomenclature for all compounds containing nitrogen in the ring.Every compound is an “azine” which contains a ring consisting of six atoms of carbon and nitrogen. He calls them respectively monuzines diazines triazines &c. according as they contain one or more atoms of nitrogen. To the “monazines” we should strictly have to reckon pyridine and quinoline but to alter existing names in these cases is impracticable and unnecessary. The I‘ diazines ” are divided into three great classes according as they contain the nitrogen-atoms in para- meta- or ortho-position relatively to each other. The first member of the para-class would thus be styled “ paradiazine,” but as this is rather long “ piazine ” can be used. In the meta-class we should have “ metadiazine,” which when shortened give 9s MASON PIAZINE-DERIVATIVES.simplest compounds and types of this class are the hypothetical ‘‘ piazine” and its hexahydride the latter of which has long been known as “ diethylenediamine.” H /N\ HC I CH Piazine (Pgrazine). /N\ HtC CH, I 1 \N/ HtC CH, Piazine hexahydride or diethylenediamine. The derivn tives described in the above-mentioned paper were “ phenanthrapiazine (xenylene-pyrazine) dihydride ” and ‘‘ diphenyl-piazine dihydride,” and they were prepared by the action of ethylene-diamine on phenanthraquinone and berizil respectively ; but in spite of their apparently similar modes of formation I found them to possess very different degrees of stability towards acids ; for whereas the phenanthra-derivative was not altered by concentrated hydro-chloric acid even at a temperature of 200” except that a salt was formed the diphenyl-derivative was split up into its constituents even by the dilutest mineral acids.These differences coupled with the fact (see p. 99) that diphenylpiazine dihydride gives by the loss of two atoms of hydrogen a very stable base have led me to the con-clusions on the one hand that the so-called phenanthrapiazine dihydride is in reality only phenanthrapiazine and on the other hand that the distribution of affinities is a radically different one to that holding in diphenylpiazine dihydride. That the first supposition was correct was easily proved by a new series of analytical data. For analysis the substance was recrystallised from glacial acetic acid and dried at 100”.The following results were obtained :-0.1432 gram gave 0.0579 gram water and 0.4385 gram carbon di-0.1540 gram gave 0.0645 gram water and 0.4694 gram carbon di-oxide. . - oxide. oxide. 0.1500 gram gave 0.0620 gram water and 0.4605 gram carbon di-(‘ miazine,” and in the ortho-aeries we should have ‘‘ arthodiazine,” or better, “ oiazine.” From these three parent substances we can have derivativee containing, besides the nitrogen-ring a benzeiie-ring to denote which the syllable “ phen ” is prefixed As will be seen I have adopted Widman’s nomenclature in this paper, Anding it most decidedly the simplest and best MASON PIAZINE-DERIVATTVES. 99 Calculated for 7--- -7 Phenanthrapiazine Phenanthra- Found. 7 dihydride. piazine. r-&-C16H12N2- C16H10N2- I.11. 111. C 82-76 83.47 83.51 83.12 83.72 H 5.17 4.37 4.49 4.65 4.59 These results point most deci-dedly to the fact that the compound is simply phenanthrapiazine and this agrees with recent experiments made by Strache in this laboratory ; he found that in the condensa-tion of a-propylenediamine with phenanthraquinone two atoms of hydrogen also disappear phenanthramethylpiazine being formed. The difference in the distribution of affinities in the two compounds is I think well expressed by the following formula :-Phenanthrapiazine. Diphenylpiazine dihydride. In corroboration of this view I have been able to prepare from the unstable diplienylpiazine dihydride by elimination of two atoms of hydrogen a base which is eminently stable towards acids./N\ HC I C The above-mentioned dihydride melts at 181" to a yellow liquid, and if heated for some time about 20" above this temperature the viscous mass thus obtained does not become solid and crystalline again on cooling; not until it had stood for several days were any signs of crystallisation visible. I€ however the product after two or three hours' heating at 200" be treated with tolerably concentrated hydrochloric acid the greater part will dissolve on warming and on filtering from undissolved resinous matter a solution of the hydro-chloride is obtained; on adding water to this until a permanent turbidity appears and allowing it to stand the new base is deposited as a crystalline precipitate the hydrochloride being decomposed by water. On recrystallisation from 50 per cent.alcohol the substance ia obtained in large colourless plates having the melting point 118-119". It distils with sligbt decomposition at about 340" small quantities of benzene and ammonia being liberated and a car 100 MASON PIAZINE-DERIVATIVES. bonaceons residue being left. The benzene wag recognised by conversion into aniline and testing with calcium hypochlorite. On finding that the compound was capable of distillation I imme-diately tried this method of preparation and found it decidedly the best. The dihydride is quickly distilled from a fractionating flask into a porcelain dish. It parts with two atoms of hydrogen and the base distils as a pale-yellow oil accompanied by a small quantity of benzene; this however soon evaporates and the whole on cooling solidifies to a mass of prismatic needles which are recrystallised from aniyl alcohol and washed with cold light petroleum.The mother-liquor is freed from light petroleum and amyl alcohol by distillation, and the residue is then redistilled when a second though small portion of base is obt,ained ; thiP however does not crystallise until it has stood several days and even then only part,ially owing to the presence of another compound in appreciable quantity in the form of a thick light brown syrup. The latter on oxidation with chromic acid in glacial acetic acid solution gave small quantities of benzoic acid but probably no piazinecarboxylic acid; it was not further investigated. Working according to this method and starting from 85 grams of benzil I got $0 grams of dihgdride and from this 55 grams of crude distillate which on recry stallisation yielded 40 grams of almost pure diphenylpiazine.It is insoluble in water, easily soluble in alcohol ether and benzene. From light petroleum, in which it is only sparingly soluble in the cold more easily on heating it crystallises in beautiful prismatic needles. The subst'alice dried at 130' gave the following results :-0.1833 gram gave 0-0908 P a m water and 0.5595 gram carbon di-0.1620 pram gave 0.0790 gra4m water and 0.4929 gram carbon di-oxide. oxide. Calculated for Found. r-- 7 7--7 C16H12N2' C16H14Nfl. I. 11. C 82.75 82-05 83.24 82.97 H 5-17 5-98 5.50 5-41 Diphenylpiazine has only feeble basic properties being precipi-tated by water from its solution in concentrated acids.It dissolves in concentrated sulphnric acid with a golden-yellow colonr which on addition of water becomes green ; if the solution in concentrated acid is heated it graduallg assumes a reddish tinge. If a crystal of potassium nitrate be added to the golden-yellow solution in concen-trated acid it immediately assumes a pale-green colour ; with potassium dichromate the colour is dirty green MASON P1AZINE-I)ERlVATIVES. 101 The pZatinochZoride ( Cl6H,,N,),,H2PtC1~ was prepared by adding hydrochloric acid to an alcoholic solution of the base and then alcoholic platinic chloride. The salt soon separates in the form of long yellow prismatic needles which as the following analpes show, are pure. The salt was dried a t 100".0.1008 gram salt gave 0.0225 gram platinum. 0.1923 , , 0.0426 , Y 9 Found. r-'-7 (C16H12N2)2,H2PtC16. I. 11. Calculated for Pt 22.25 22.32 22.15 No methyl iodide addition product could be obtained even on heating at 150° the base behaving in this respect like the previously described phenanthrapiazine. Dinitrodipheny ~ i u z i n e C1BH10N400 is prepared by warming a solu-tion of the base in concentrated nitric acid for some time on the water-bath. On precipitation with water an amorphous yellow powder is obtained having a very low and inconstant melting point ; hitherto I hare not been able to obtain this substance i n a crystalline form. It is easily soluble in hot alcohol only sparingly in ether and benzene insoluble in water and light petroleum.On rubbing the compound i n an agate mortar it becomes strongly electrical and it is only with the greatest difficulty that it can be brought together afterwards. For analysis it was dried in a vacuum over sulyhuric acid. 0.2058 gram gave 32.6 C.C. moist nitrogen a t 21" and 730 mm. Calculated for C16H10N404. Found. IT. 17.39 17-30 Reduction of Diphenylpiazixe. The method followed was that of Wischnegradski-Ladenburg, improved by Bamberger (Ber. 20 2915) which has yielded such excellent results of late. 15 grams of sodium were added quickly to about 50 C.C. of almost. boiling amyl alcohol contained in a litre flask connected with a reflux condenser and to this was added in a con-tinuous stream a boiling solution of diphenylpiazin2 in about 200 C.C.of amyl alcohol. The solution of the base is best added by means of a long funnel hanging in the condenser tube. Immediately the first drop comes in contact with the sodium the whole assumes a rich yellow colour and a rather violent reaction commences. The contents of the flask were kept boiling until the last particle o 102 MASON PIAZINE-DERIVATIVES sodium had disappeared and then poured while still hot into about half a litre of cold water the whole transferred to a separating funnel and well shaken in order to decompose the amyl alcoholate. The water was then drawn off and the residue after washing twice was distilled from a fractionating flask till the temperature had risen to about 1.50" when most of the amyl alcohol had passed over. The bases which on cooling solidify to a crystalline mass were dissolved in dilute hydrochloric acid filtered and the filtrate boiled with animal charcoal till colourless.On precipitation with sodium hydmte, the bases fall as an almost white crystalline precipitate composed of slender needles. By repeated recrystallisation from light petroleum, the mixture can be separated into two portions from which two dis-tinct hydrides can be isolated having the constant melting points 122-123" and 108-log" the latter being the more easily soluble. These compounds are apparently accompanied by a third having a much lower melting point. The properties of the bases are so similar that it was only by working on considerable quantities of rather expensive material that I was able to prepare enough of the two compounds to compare their properties and those of some of their derivatives.In the following part of the paper I describe merely the experimental results hitherto obtained reserving theo-retical considerations for a future communication when I hope to have isolated the third base. The two hydrides are referred to as a and 6 respectively as on analysis they both gave numbers closely agreeing with those demanded by diphenylpiaeine hexahydride. The simplest nomenclature to adopt for the substitution products of the " piazines " is probably the one made use of in this pamper ; it was suggested by Knorr's nomenclature for the (' pyrazoles." The following scheme will illustrate its use (Annalen 238 137) :-a (2 3) Diphenylpianine Hexahydride C,6H,,N2.This base crystallises from light petroleum in long slender white It is a strong Analysis of the substance 0,1279 gram gave 0.089 gram water and 0.3767 gram carbon needles having the constant melting point 122-123". base dissolving readily in dilute acids. dried at 100" gave the following numbers :-dioxide MASON PIAZINE-DERIVATIVES. 103 0.1482 gram gave 0,1056 gram water and 0.4372 gram carbon dioxide. Found. Calculated for 7- 7 C16H18N2. I. 11. C 80.66 80.32 80.66 H 7-57 7.73 7-91 The base is easily soluble in alcohol and benzene less readily in ether and light petroleum and insoluble in water. Hydrochloride C,6HlaN,,2HC1.-The base dissolves readily in dilute hydrochloric acid and on evaporation and standing in the cold the salt separates in long glistening white needles.For analysis the salt was dried at loo" a previous experiment having shown that there was no water of crystallisation in the air-dried salt. Melting point about 310". 0.137 gram gave 0.126 gram silver chloride. Calculated for C16H,,N2,2HC1. Found. C1 22.82 22.79 PZatinochZoride CISH18N2,H2PtC1 + $H20.-The hydrochloride in aqueous solution is treated with platinic chloride ; on standing the salt separates as a yellow crystalline powder. It is recrystallised from dilute hydrochloric acid and as thus prepared forms golden-yellow prismatic needles. The analysis gave the following num-bers :-0.2499 gram of air-dried salt gave 0.0035 gram water at 100". 0.2499 7 9 9 0.0737 , platinum. Calculated for C16H18N2,H2PtC16 + aH20.Found. HzO . 1.37 1.40 Pt 29.61 29-49 Nitroso-derivative CleH16N604.-The base was dissolved in dilute hydrogen chloride and to the cold solution an aqueous solution of potassium nitrite was added as lung a3 any precipitation took place. The white crystalline powder was collected washed well with water, and recrystallised from dilute alcohol. It separates after a short time in white prismatic needles which after a second recrystallisation melt sharply at 142-143' to a pale-yellow liquid. It is insoluble in water and light petroleum easily soluble in alcohol and benzene but only sparingly in ether. For the nitrogen determination the substance was dried at 100" ; the following results were obtained :-0.160 gram gave 33.4 C.C. moist nitrogen at 16" and 723 mm 104 MASON PIXZINE-DERIVATIVES.Calculated for C16H16N604* Found. N 23-31 23-13 The compound has therefore in all probability the following con-stitution :-N-NO N OH*~cACH*c6& NOH*=(! (bHaC6H5 ‘LNO The further study of this interesting substance is reserved. Action of Methyl Iodide on the a-Hydride C,,HIsN,. The base dissolves in methyl iodide to a clear colourless liquid, which on warming on the water-bath to expel excess of iodide and allowing it to remain in the cold crystallises t o an almost colourless mass the mother-liquor reacting strongly acid. Recrystallised from hot water it forms long colourless needles. It was dried at 100’ for the iodine estimation :-0.1515 gram gave 0.0889 gram silver iodide; 0.1525 gram gave 0.03077 gram silver iodide.Found. Calculated for 7-CH3H23N21* I. 11. I . 32-06 31.69 32.14 It is thus seen that the substance is a hydriodide of the (1 4) dimethyl (2,3) diphenylpiazine tetrahydride. I t is singular that only a monacid salt’ is formed the other molecule of hydriodic acid re-maining in the aqueous solution. (I 4) Dimethyl (2 3) Diphenylpiazine Tetrahydride, CH2.N ( CH3) *C H*C,H, ~H,~N(cH,)~H.c~H,’ is a strong base and is precipitated in slender white needles from an aqueous solution df the above salt on treatment with sodium carbonate. The substance thus obtained however is mixed with small quantities of a compound of a very low melting point and it is best t.0 extract several times with ether after adding the sodium carbonate in order to free the mixture from this product.The aqueous solution is then evaporated t o a small volume and on standing deposits the new base in long colourless needles having the melting point 263-264”. I MASON PIAZINE-DERIVATIVES. 105 is easily soluble in alcohol and water on warming but only very Rparingly in ether and benzene. For analysis the substance was dried at loo" and the following numbers were obtained :-0-1538 gram gave 0.1183 gram water and 0.4560 gram carbon Calculated for dioxide. Clt?H22N2. Found. C . 81-20 80-86 H. 8.27 8.54 Platinum Doub-ie SaZ.t ( Cl,H2,N,),,'2HCl,( PtCI,) + 8H,O. The base was dissolved in absolute alcohol concentrated hydro-chloric acid added and then an alcoholic solution of platinic chloride. The salt separates as a yellowish-brown crystalline powder which can be recrystallised from dilute hydrochloric acid.Thus prepared the salt forms yellow prismatic needles which on analysis give the following numbers :-gram air-dried salt gave 0.0127 gram water at 120". 9 , 0.01343 , platinum. 7 , 0.0130 , water at 120". {KE ,, (0.1620 ? 7 3 0.0372 , platinum. 0.1620 ,, Found. Calculated for +-7 (CIBHZ2N2)3,2HCl,(PtC14)2 + 8HZO. I. 11. H,O 8.53 8.48 8.02 Pt 23.03 32.92 22.96 The salt for analyses I and I1 were from different preparations. /3 (2 3) Diphenylpiazine Hexahydride CI6Hl8N2. This base is more easily soluble in light petroleum than the a-com-pound and remains in the filtrates together with small quantities of the base of low melting point above mentioned from which however, it is difficult to completely separate it.The most suitable solvent is 50 per cent. alcohol from which it separates in long silky white needles. By repeated recrystallisation the melting point ultimately becomes constant at 108-109". When freshly prepared and still moist the needles present a glistening silky appearance but on drying they become drill white the change being in all probability due to the 1058 of water or alcohol of crystallisation ; the distinction between the OC-and /?-compounds being very marked. Like the a-base it is easily soluble in alcohol and benzene less so in ether and insoluble in water ; i t has strong basic properties dissolving easily in dilute mineral YOL. LV. 106 MASON PIAZINE-DERIVATIVES. acids. For analysis the substance was dried in a vacuum over sulphuric acid ; the following results were obtained :-0.1527 gram gave 0.1103 gram water and 0.449 gram carbon dioxide.0.1409 , 0.099 , Y7 0.4416 , 9 7 9 , @163 9 19 C.C. moist nitrogen at 25" C. and 720 mm. 0-1863 , 20.3 , 10" C. , 723 , 9 9 Found. Calculated for +-7 1 6H18N2* I. 11. C . 80.66 80.19 80.25 H 7-57 8.02 7-80 I)u' 11.76 12.31 12.03 BytlrochZode C,,HI,N2,2HC1.-The base is dissolved in alcohol, concentrated hydrochloric acid added and the whole allowed to stand when the salt separates in colourless prismatic needles. The melting point is about 295". As the air-dried substance contains no water of crystallisation it was dried at 120" for analysis :-0.1520 gram gave 0.1384 gram silver chloride.Calculated for C16H,,N2,2HCJ Found. C1 22.82 22.57 PZatinochZoride C,,~,,N,,H,Pt~~ + 2H20.-The base is dissolved in 95 per cent. alcohol concentrated hydrochloric acid added and then an alcoholic solution of platinic chloride. On standing the solution deposits long pale-yellow needles which as the following analyses show are pure:-0.1201 gram air-dried salt gave at 120" C. 0.0064 gram water. 0.1201 , 7 ) 7 7 7 9 7 0.0067 ,, 0.1210 , 7 7 1 . , 0.0339 gram platinum. Found. Calculated for r- 7 C ~ ~ H ~ N ~ H Z P ~ C & + 2HzO. I. 11. H20 5.26 5.32 5.54 Pt . 28.44 - 28.01 On oxidation with chromic acid in glacial acetic acid solution, (2 3) diphenylpiazine gives a phenylpiazinecarboxylic acid which yields well-characterised salts. The melting point is about 202". This as well as other products shall be described in a future paper. In conjunction with Mr. L. A. Dryfoos to whom I am indebted for several of the analyses in the above paper I am studying the action of ethylenediamine on the recently discovered a-diketones of th MASON ACETAMIDE AND PHENANTHRAQUINONE. 107 fatty series and have already obtained interesting results which we hope to communicate to the Society a t no distant date. I cannot close t,his paper without expressing my thanks to Professor Victor Merz for his kindness and valuable advice during the whole of my student life at Zurich

ISSN:0368-1645    

DOI:10.1039/CT8895500097

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

MASON ACETAMIDE AND PHENANTHRAQUINONE. 107 XP.-CONTRIBUTIONS FROM THE LABORATORY O F THE UNIVERSITY OF ZURICH. No. 111. Acetamide and Phenanthrapuimne. By ARTHUR T. MASON Ph.D. F.I.C. DURING experiments undertaken some time ago with the view of ascer-taining whether the amido-groups in oxamide were available f o r condensation purposes I had occasion to heat that substance in closed tubes with phenanthraquinone and glacial acetic acid for some hours at 220-230". The tubes were then found to contain consider-able quantities of a dark-red crystalline substance and on opening them a great deal of carbon-monoxide and dioxide escaped. This led me to the conclusion that the oxamide at least to a great extent had undei*gone decomposition with formation of these gases and that pro-bably the amido-groups had reacted with the quinone.Some tubes were now filled with oxamide and glacial acetic acid alone and heated as before for four hours to 220-230" in order to see if at this tem-perature any reaction took place in the absence of phenanthra-quin0ne.x The whole of the oxamide had now disappeared leaving a perfectly clear and colourless solution and there was a great pressure on the tubes the same gases escaping on opening as in the previous experiments. The whole was submitted to distillation from a frac-tionating flask. After the excess of acetic acid had gone over the thermometer rose rapidly to about 210° and between that temperature and 215" almost the whole distilled as a colourless liquid solidifying in the receiver to long needles and having a slight odour of acetamide.By recrystallisation from ether or benzene the substance cntirely lost * The action of formic acid and acetic anhydride on oxamide was studied by Scheitz Marsh and Geuther in 1868 (Zeitschrift 1868 301). They state that acetic anhydride is without action on oxamide a t 140-160". This is also my experience at that temperature but at 220-230" the reaction is complete a0 shown above even with glacial acetic acid. I 108 MASON ACETAMIDE AND PHENANTHRAQUINONE. the acetamide smell and was then considered to be free from that substance. On combustion of the compound dried in a vacuum over snlphuric acid the following results were obtained :-0.1935 gram gave 0.1528 gram water and 0.2890 gram carbon 0.1248 gram gave 27.5 C.C.nitrogen at 21" C. and 730 mm. dioxide. Calculated for C,H,NO. Found. C . . 40.67 40.73 H . 8.47 8.77 N . 23.72 24.07 These numbers as will be seen are the ones required by acetamide, and taking into consideration the other properties of the substance I was forced to the conclusion that I had in reality acetamide in my hands but freed from the smell which had hitherto been supposed to be its principal characteristic. To finally decide the point pure acetamide obtained from Kahlbaum was redistilled and then recrys-tallised several times from absolute ether whereby a perfectly odonrless product was obtained crystallising exactly like and in all respects identical with the one I had prepared from oxamide. It even suffices to rectify twice rejecting the first 'portions of the distillate, which seem to contain the bulk of the odoriferous principle in order to obtain a practically pure preparation.Quantities of 20 grams of perfectly pure acetamide distilled com-pletely at 213*5-214" (corr. 216.5-217" C.) with the barometer at 728 mm. and Kahlhaum's preparation twice rectified as above dis-tilled at exactly the same temperature. I have since heard that results similar to those here described in connection with acetamide have been obtained in another laboratory. That my observations are the older ones however is clear from the fact that mention thereof was made by Professor Merz in his lectures over two years ago. After the fact had thus been established that acetnmide is one of the products of the action of acetic acid on oxamide i t was thought that this substance might also be a principal factor in the formation of the crystalline red compound mentioned above, Phenanthraqiiinone was therefore heated in sealed tubes with acet-amide and glacial acetic acid and as expected large quantities of the red crystalline compound were obtained It proved on investigation to he a very indifferent substance the only solvents found being aniline nitrobenzene and phenol.It was repeatedly re-crystallised from nitrobenzene and ultimately obtained in the form of yellowish-brown flat needles having a melting point about 400" MASON ACETAMIDE AND PHENANTHRAQUINONE. 109 Great inconvenience was at first caused during its combustion the carbon being deposited in a graphitic form on the sides of the tube and in the boat and rendering it necessary to heat for several hours in a current of pure oxygen before complete oxidation was effected.Working according to this method the following results were obtained on analysis. The substance for I was recrystallised from nitrobenzene five times then washed with ether till odourless and dried at 120". For 11 a sublimed sample was used :-0.1692 gram gave 0.0704 gram H20 and 0.5440 gram CO,. 0.1330 , 0.0566 , , 0,4335 ,, 0.2045 , 13.4 C.C. moist nitrogen at 18.5" C. and 728 mm. 0.2145 , 14.5 C.C. , 9 9 21" , 726 ,, Found. Calculated for r-h-- 7 CJSHIIjN2. I. 11. C 88.42 67-68 88.88 H 4-21 4.62 4.72 N 7.36 7-21 7-33 The substance possesses therefore in all probability the empirical formula (C14H8)3, which is also that of a compound isolated by Sommaruga (Juhresbericht 1880,735) from the products of the action of alcoholic ammonia on phenmthraquinone and by Japp and Burton by the distillation of ditolane-azotide over heated soda-lime. The latter authoi-s proved that i t was an azine and gave it the name tetraphenylene-azine (Japp and Wilson Trans. 1886 830, footnote and Japp and Burton ibid. 1887 101). This according to Widman's nomenclature (see previous paper) would become diphe nanthrapiazine. The compounds obtained by these different methods agree in their properties and there can be little doubt that we have to do with one and the same substance. The yield by the above method is almost theoretical

ISSN:0368-1645    

DOI:10.1039/CT8895500107

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

110 XVL-Note on Fluoride of Methyl. By NORMAN COLLIE Ph.D. F.R.S.E. IN a paper published in the Comptes rendus (1888 107 1155) a new method is described by Moissan and Meslans for the preparation of fluoride of methyl. But as they do not seem to be aware that Dr. Lawson and myself prepared this substance by the action of heat on the fluoyide of tetramethylammonium I now take the opportunity of bringing before this Society the results of some further experiments made with this gas although they are n o t yet completed. Determina,-tions have been made of the vapour-pressures of methyl fluoride at, various temperatures; the sp. gr. and critical point have also been ascertained ; and the combined action of chlorine and sunlight on this gas has been studied. The method given by Moissan for the production of methyl fluoride, namely the action of methyl iodide on silver fluoride is by no means so easily carried out as the one employed by Lawson and myself for the products of the reaction have to be passed through a lead spiral cooled to -50° and then ovcr silver fluoride heated to go", in order to free the gas from traces of iodine and methyl iodide.the action of heat on fluoride of tetramethylammonium a mixture of pure trimethylamine and methyl fluoride is produced and the former can be completely absorbed by passing the vaponr through a U-tube filled with pumice stone moistened with strong sulphuric acid leaving the methyl fluoride perfectly pure. A determination of the sp. gr. of the gas gave 17.38 as compared with hydrogen the theoretical sp.gr. being 17.05. The following measure-ments of some of the physical constants of methyl fluoride were made in conjunction with Professor Ramsay. A modified Andrews ap-paratus of which a drawing and description is to be found in the Philosophical Transactiorts (1887 A p. 59) was employed. I t s volume tube was filled with methyl fluoride by repeatedly exhausting and admitting the gas. The gas was thencompressed and liquefied. The following table shows the vapour pressures of methyl fluoride. The pressures it should be remarked are absolute the actually read pressures in the air gauges being converted by means of Amagat's measurements of the compressibility of air. The lower temperatures were secured by jacketing with water ; the higher temperatures which are more accurate by means of alcohol vapour boiling under reduced pressures.(See Trans. 1885 47,640.) B COLLIE ON FLUORIDE OF METHYL. 111 Temp. Press. 35" c. 40 45 -I I I --mm. 36204 40496 46010 -_ Temp. 1 Press. I Temp. I Press. - 5" c. 0 5 10 15" C. 20 25 30 mm. 11385 14696 17740 20091 mm. 23003 25621 28840 32756 mm. (u.) All liquid . . . 42962 (b.) Half gas . 41584 ( c . ) Liquid gone . . 36868 min. (d.) Trace of liquid . 41951 (e.) Smaller trace 41052 (f.) Minute trace . 40622 A second series was obtained with gas presumably not so pure, inasmuch as the numbers are somewhat higher. Still the methyl fluoride must have been even then very nearly pure as the following.results at 40" show :-It will be observed that the last observation is nearly coincident with that of the former series a t 40". In each series the small bubble of air was absorbed by the liquid without much rise of pressnre. The critical temperature and pressure were determined by direct observation. I t need hardly be remarked that a laborious series of researches is necessary to determine the point accurately ; for i t can only be ascertained by constructing sets of isothermals and deducing from them the true temperature pressure and volume. Still the numbers may be regarded as far more accurate than many similar determinations. The substance assumed the critical state a t 44.9", and a t a pressure of 47123 mm. ; here again the pressure is probably R little too high owing to the presence of a trace of a i r ; and the tem-perature too low.The error in pressure probably does not exceed lfi00 mm. and the temperature 0.2". Action of Chlorine o n Methyl Fluoride. When chlorine and methyl fluoride are mixed in equal volumes and exposed to sunlight substitution of the hydrogen in the methyl fluoride takes place at once and in a few hours the mixture becomes quite colourless. Several experiments were made and always with the same result a chlorofluoride of methylene and hydrogen chloride was produced and no diminution occurred in the volume of the gas ; equal volumes of the two gases were formed. In one experiment the amount of hydrogen chloride produced was titrated with decinormal ammonia solution. 128.5 C.C.of methyl fluoride were mixed with 128.5 C.C. of pure chlorine and exposed in the sunlight for thre 112 COLLIE ON FLUORIDE OF METHYL. hours ; the amount of hydrogen chloride obbained mas 0.207 gram, while the amount required by theory is 0.209 gram supposing the reaction to take place as follows :-CHSF + Clz = CHzClB’ + HCl. The methylene chlorofluoride seems to be more soluble in water than flucjride of methyl but is easily expelled again when the aqueous solution is warmed. This property can be made use of in purifying the gas from traces of air. The sp. gr. of the gas was found to be 34.18 while the theoretical sp. gr. is 34-25 The gas is hardly infhmmable and considerable difficulty was experienced in exploding it with oxygen alone the combustion only taking place when a powerful electric spark was passed through the mixture ; when mixed however with hydrogen and oxygen it explodes easily with an ordinary electric spark.Several analyses were made with the following results :-I. I. 111. Taken of gas 4.1 C.C. 8.5 C.C. 8.5 C.C. Carbon dioxide produced . . 4.0 , 7.5 , 8.0 9 , Thus showing that the gas produced its own volume of carbon dioxide after combustion. An estimation of the chlorine was also made; 0.03526 gram gas gave 0.072 gram AgCl = 50.6 per cent. C1. Calculated for Po \ma. CH&lF. C1 50.5 51-8 An attempt was made to estimate the fluorine but the results were 3 per cent. too low. Methylene chlorofluoride seems to be much more easily decom-posed by water than methyl fluoride for if an aqueous solution of this gas be allowed to stand f o r two or three days both hydrochloric and hpdrofluoric acids can be detected in the water.Methylene chlorofluoride does not seem to react easily with chlo-rine and the two gases when mixed i n equal volumes and exposed to sunlight for many days remain partly uncombined. I hope however, to be able to continue the investigation. I may mention that experiments made to obtain tetrafluoride of carbon by passing a mixture of fluoride of silicon and carbon dioxide through a platinum tube heated to bright redness were not successful. Silica was certainly formed in the platinum tube and traces of a liquid were obtained which might possibly have been tetrafluoride of carbon but unfortunately only in such small quanti-ties that no analysis could be made COLLIE ON FLUORIDE OF METHYL.113 During these experiments when t,he mixture of carbon dioxide and silicon tetrafluoride was passed hhrough a red-hot platinum tube, the following piece of apparatus was found t o be extremely useful, and might doubtless be also used in many other experiments where the same result is desired. The object was to enable a continuous stream of the same gas to be slowly passed again and again through the red-hot platinum tube. A was connected with the platinum tube beyond which was a balloon (with two stopcocks) containing the mixed gases. B was connected directly with the balloon. The tube C was made of the ordinary glass tubing such as is used for the Sprengel pump. When the receiver D was filled with mercury and raised just high enough t o allow the mercury to flow down the tube C gas was carried down with the falling meycury into the wider tube E ; here the mercury escaped into the basin F while the gas was forced through B back again into the balloon and was then ready to be used again

ISSN:0368-1645    

DOI:10.1039/CT8895500110

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

114 XVI1.-Researches on the Constitution of Azo- and Diazo-derivatives. V. Compounds of the Naphthalene P-Xeries-continued. By RAPHAEL MELDOLA F.R.S. and GILBERT T. MORGAN. IN the last paper referring t o the present branch of investigation (Trans. 1888 460; Meldola and East) it was shown that the azo-derivatives of &naphthol contain an atom of hydrogen capable of beiiig displaced by acid radicles a property which they share in common with their a-analogues (Zincke and Bindewald Ber. 1884,3030). Of the alkyl-derivatives of the azo-P-naphthol compounds the only re-presentative at present known is the benzeneazo-P-naphthyl ether of Weinberg (Ber. 1887 3171). The importance from a theoretical point of view of ascertaining whether this displaceable hydrogen-atom of the azo-@-naphthol compounds is attached to the oxygen o r to the nitrogen of the azo-group has from time to time been pointed out in the course of the present series of researches and has recently been emphasized in a paper read by one of the authors at the Bath meeting of the British Association (Phil.Nag. 1888 403). The present paper contains the results of experiments undertaken w itli the object of throwing further light on this question. I. Benzoyl-derivatives of Azo-/I-Naphthol Compounds. Acetyl-derivatives of azo-P-napht,hol compounds can be prepared, as pointed out in the last paper by two distinct methods. If the radicle attached to the azo-group is more o r less of an acid character, such as nitrophenyl CsH4.N02 ( p or rn) the corresponding fi-naph-thylamine azo-compound is attacked by nitrous acid in the presence of glacial acetic acid with the formation of the azo-naphthyl acetate (Zoc.cit. p. 465).* This method does not appear t o be applicable * The formation of phenylic acetates from the corresponding amines by means of the diazo-reactinn in the presence of glacial acetic acid was made known in it paper communicated to the Chemical Society of Germany on January 24th 1888 (Be?, 1888 Sol) and in a subsequent paper read to this Society (Trans. Nay 1888, 465) i t was stated that " as the reaction promises to be widely applicable for the synthesis of phenylic acetates and other et,hereal salts it is proposed to extend the investigation in this direction and to make B special study of the conditions which determine the displacement of amidogen by the C2H30.0-group by means of the diazo-reaction." Notwit.hstanding the publicity thus given to the method and the explicit claim to continue its further investigation a paper appeared in the Amer.Chem. Jour. of last September (10 368) by W. R. Orndorff containing the results of the application of this reaction for the formation of phenyl cresyl an THE CONSTITUTION OF AZO- AND DIAZO-DERIVATNES. 11 5 when the radicle attached to the azo-group is not acid such as phenyl or naphthyl C6H5 CloH7 &c. in the azo-P-naphthylamine com-pounds. I n such cases however azo-p-naphthyl acetates can be prepared by the direct acetylation of the azo-/I-naphthol compounds by means of sodium acetate and acetic anhydride and the same method is generally applicable whatever may be the nature of the radicle associated with the azo-group.The same remarks apply t o the benzoyl-derivatives of azo-/I-naphthol compounds some of which have been prepared by both methods in the manner described below. Berzzeneaxo-p-Na~hthyz Benzoate C6H,*N,*CI~H~-OC7H50 (p). This compound cannot be prepared by fusing benzeneazo-6-naph-thylamine with excess of benzoic acid and adding the calculated quantity of sodium nitrite to the mixture complete decomposition takes place under these circumstances with the formation of tarry products. A mixture of benzeneazo-p-naphthol with dry sodium benzoate and henzoic anhydride if heated for some hours to the fusing point of the anhydride gives only a small yield of the azo-p-naphthyl benzoate owing to the difficulty of keeping the mixture in a homo-geneous fluid condition and to the continuous loss of anhydride by sublimation.After many partially successful attempts with benzoyl chloride the following method was found to give perfectly satisfactory results :-Benzeneazo-&naphthol is mixed with about an equal weight of dry and finely powdered sodium benzoate and the mixture is then made just pasty with benzoyl chloride. The flask containing the mixture is fitted with a cork perforated for the reception of a tube drawn out to a fine point and heat is applied by immersing the flask in boiling water.* The reaction commences immediately on the application of heat and is complete in about an hour when the product is repeatedly extracted with hot water as long as benzoic acid is dissolved out.The contents of the flask fuse to a dark reddish oil under boiling water a property which facilitates the washing operations as the oil and hot water can be thoroughly mixed by agitation and the former rapidly subsides t o the bottom of the flask on allowing the contents to remain a t rest f o r a few minutes. The benzoyl-derivative is easily decomposed by other acetates from aniline toluidine &c. The investigation of the method has been going on in my laboratory since the beginning of last year and these and other acetates and benzoates had been prepared from the diazo-salts of the corre-sponding amines before the appeai'ance of the paper by the author refevred to. * At higher temperatures the reaction takes a ditferent course ; tarry products -R.M. are formed which have not been further investigated 116 MELDOLA AND MORGAN RESEARCHES ON THE ammonia even when the latter is very dilute so that it is unsafe to attempt to shorten the washing by the use of ammonia. In some of our first preparations unaltered heuzenenzo-@naphthol was always found, and this was afterwards traced to the use of ammonia in the washing waters. Sodium or ammonium carbonate also readily hydrolyse the bekzoyl-derivative and it is evident that the benzoyl-group is much more readily removed from this compound than is the acetyl from benzeneazo-p-naphthyl acetate. When completely washed the sub-stance is cry st.allised from boiling alcohol in which it dissolves readily. A specimen was further purified for analysis by dissolving in chloro-form in which it freely dissolves in the cold and allowing the solvent t o evaporate spontaneously in an open dish.The substance forms dense orange-red crystals melting at 125". 0.1025 gram gave 0.2951 gram COz and 0*0438 gram H,O. 0.0894 gram burnt in a vacuum with CuO gave 5.9 C.C. moist N at Calculated for HBH,,N202. Found. 13" C. and 770.1 mm. bar. C . 78.41 78-52 H . 4.55 4.74 N . 7.95 7.90 Metanitrobenzeneazo-P- Napht hy 1 Benzoate, (m)NOZ*CBH**Nz*C10H6*0 C,HbO (p) . Mehnitrobenzeneazo-/bnaphthylamine (m. p. 182') is fused with excess of benzoic acid and the calculated quantity of dry sodium nitrite added in small portions to the fused mixture. Nitrogen is freely given off and when all the nitrite has been added the product is washed with hot water till free from benzoic acid.The washing may in this case be accelerated by the use of dilute ammonia without fear of decomposition. The washed product is crystallised from hot glacial acetic acid in which it is not very soluble and finally from boiliiig alcohol in which it dissolves only very sparingly separating on cooling in the form of dull reddish-orange silky needles. The melting point is 171". The following results were obtained on analysis :-0.16'76 gram gave 0.4280 gram GO2 and 0.0612 gram HzO 0.2196 gram burnt in a vacuum with CuO gave 19.8 C.C. moist N Calculated for at 17" C. and 761.7 mm. bar. C23H,,N304. Found. C . 69.52 69.64 H . 3-77 4.05 K 10.57 10.4 CONSTITUTION OF AZO- AND DIAZO-DERIVATIVES.11 7 The substance is formed in this process according to an action perfectly similar to that which gives rise to the production of the acetate. C,0H,<~&~"H"N02 + NaNO + 2C7H50*OH = CIOH6<N2'C6H4"02 + C7H50*ONa + N2 + 2H,O. 0.C7H,0 The benzoate may also be prepared by direct benzoylation and this method is much more convenient when the compound is required in quantity. For this purpose metanitrobenzeneazo- - naphthol (m. p. 194") is mixed with about its own weight of dry powdered sodium benzoate and enough benzoyl chloride added to make the mixture int,o a paste. The contents of the flask are then kept just at the boil-ing point of the benzoyl chloride for 4-5 hours. The product is washed with dilute ammonia and purified by crystallisation in the manner already described.11. Reduction of Axo-P-Naphthol-derivatives containing Acid Radicles. I n order to see whether any information concerning the position of the displaceable hydrogen-atom could be derived from a study of the products of reduction of the acetyl and benzoyl-derivatives these compounds were reduced with tin and hydrochloric acid and with stannous chloride under various conditions. Reduction of Benxenenzo-P-Na~hth~l Acetate. An alcoholic solution of the above compound is soon decolorised if boiled with tin and hydrochloric acid. On distilling off the alcohol and filtering t o remove tarry impurities the filtrate on standing gradually deposits a white curdy substance which under the microscope is seen to consist of agglomerations of white needles.The addition of strong hydrochloric acid to the solution promotes the deposition of the white compound. The latter was therefore purified by being collected dissolved in hot water filtered and 1-eprecipitated by the addition of strong hydrochloric acid this treatment being repeated till the substance dissolved without leaving any residue. The white substance thus obtained proved to be the hydrochloride of a mixture of bases. Many specimens mere prepared and analped without any concordant results being obtained ; all attempts t o separate the mixture into its constituents by fractional crystallisation or by con-version into other salts were unsuccessful. The free bases could not be isolated owing to their extremely oxidisable character.This pro-duct or -3uction contains a considerable quantity of x-amido-p-xiaph 118 MELDOLA AND MORGAN RESEARCHES ON THE fhol the presence of the latter compound being shown by the formation of P-naphthaquinone on oxidation by ferric chloride. I n spite of the unfavourable results obtained in our first experiments, the reduction was repeated an alcoholic solution containing the theoretical qiiantity of stannous chloride being gradually mixed with a slightly warm alcoholic solution of the substance After the mixture had stood for some hours the alcohol was distilled off and t,he product treated as above. The same white hydrochlorides were obtained but the siibstance was evidently a mixture and a-amido-p-naphthol was identified as one of its constituents as before.The analyses showed that in this case the mixture contained different proportions of the bases from those present in the product formed by violent reduction with tin and hydrochloric acid. 'In both series of experiments the filtrate after the removal of the white hrdrochl orides first deposited, was treated with sulphurettcd hydrogen in order to remove tin and after the removal of the stannous sulphide the filtrate was evaporated to a small bulk made alkaline with caustic soda and submitted to steam distillation when a considerable quantity of aniline was obtained, showing that this base is one of the products of reduction. According to the current hypotheses of the constitution of the azo-p-naphthol compounds the acetyl-derivative of benzeneazo-&naphthol may have one of the following formula :-I.11. 111. The first of these is what may be called the old formula the second is that proposed by Liebermann and the third is Zincke's that is the hydrazone formula. Supposing the compound to be capable of complete reduction without the elimination of acetyl these three compounds might be expected to yield the following products :-I. Aniline and a-amido-p-naphthyl acetate. IT. Aniline and a-acetamido-p-naphthol. 111. Acetanilide and a-amido-p-naphthol. We may state a t once that a most careful search for acetanilide in the product of reduction has led to negative results. If the acetyl were attached to tlie nitrogen-atom it is improbable that t h i s group would be removed under the conditions of reduction since acetanilide is well known to be a stable compound nnder such circumstances.The third formula appears therefore to be inadmissible and th CONSTITUTION OF AZO- AND DIAZO-DERIVATIVES. 119 decision rests between Nos. I and II.* A complication of the question however here arises from the possibility of intramolecular migration of the acetyl. Thus according to the formule the naphthalene portion of the molecule ought to give on complete reduction-I. 11. The investigations of Bottcher (Bey. 1883 1933) have shown that such a compound as No. I is incapable of existence as it immediately becomes transformed into No. 11. This was proved by preparing the acetyl-derivative of a-nitro-P-naphthol and reducing the latter when a phenolic substance viz.acetamido-P-naphthol was obtained instead of the ba.sic amido-P-naphthyl acetate. The acetyl-group accordingly becomes transferred from the oxygen to the nitrogen probably through the intermediate formation of the anhydro-base and hydra-tion of the latter :-Whichever of the formula (I or 11) be the correct one it might therefore be expected that extreme reduction would give rise to the same acetamido-&naphthol. The latter is a perfectly stable phenolic substance melting according to Bottcher at 225". It does not appear to be present however aniong the products of reduction of benzene-azo-6-naphthyl acetate obtained by us in accordance with the method previously described. Caust.ic soda does not dissolve any stable sub-stance out of the mixed hydrochlorides but simply gives a mixture of highly oxidisable bases the chief constituent of which is undoubtedly a-amido-/%naphthol.The extreme reduction of the acetate therefore gives rise to the formation of aniline and a-amido-@-naphthol as chief products a fact which is in itself of considerable importance in connection with the present line of investigation since it shows that t,he acetyl-group is split off during reduction arid this lends support to the view that the said radicle is attached to oxygen and not to nitrogen in the original compound. * The formula proposed by one of the authors (Meldola Phil. Jfug. Nor. 1889, p. 4.11) is for the present left out of consideration because i t indicates the formation of products of reduhon identical with those indicated by KO.I 120 MELDOLA AND MORGAN RESEARCHES ON THE IdentiJcation of a- Amid+ Naphthol. At this stage of the work seeing that the products of reduction of the acetyl-derivative contained some other base in addition to amido-p-naphthol it became necessary to discover a method by which the mixed bases could be converted into stable derivatives capable of being separated and characterised. The identification of the amido-naphthol itself presents but little di%culty since it gives /3-nayhtha-quinone on oxidation with ferric chloride. It is well known how-ever that the formation of this quinone is somewhat capricious and when formed it is not easy to identify unless in a condition of tolerable purity. The quinone could not be obtained pure from our mixed hydrochlorides became the oxidising agent also attacked the other base with which the amidonaphthol was mixed and so gave rise to the formation of impurities of a resinous character.The method of oxidation being thus dest,ructive to the other base had to be abandoned. It was then found that the purified hydrochlorides when dissolved in water and treated in the cold with dilute hydro-chloric acid and sodium nitrite gave a crystalline yellow substance which after being collected and washed was identified as nitroso-p-naphthol (melting point about 1 1 0 O ) . This last substance is formed by the action of nitrous acid on a-amido-&naphthol according to a process of decomposition which has not hitherto been studied but which has also been observed by Dr. H. E. Armstrong." The action of nitrous acid thus confirms the presence of a-amido-@-naphthol but as this reagent did not appear t o give a satisfactory product with the other base its use was also abandoned.Benzoyl and acetyl-deriva-tives of the mixed bases were next prepared and these promised to answer our requirements so that in the first place the benzoyl and acetyl-derivatives of pure a-amido-&naphthol were prepared aud studied in order that we might familiarise ourselves with their properties. As these derivatives have not hitherto been described, we think it may be of use to give further particulars as they are well characterised and stable crystalline substances very easy of prepma-tion and thus offering many advantages over the quinone method foy the identification of a-amido-@-naphthol when the latter is mixed with other oxidisabIe bases.Benzeneazo-/l-naphthol was reduced in alcoholic solution with tin and hydrochloric acid the alcohol distilled off and the amid+ naphthol hydrochloride allowed t o crystallise out of the solution in the usual way. This salt was collected dissolved in water and again crystallised with the addition of strong hjdrochloric acid this process * Private communication to one of the authors COSSTITUTIOS OF AZO- ASD DIAZO-DERIVATIVES. 1 ',I being repeated till the substance dissolved completely in water. The aniline arid tin salts are thus got rid of aud the pure amidonaphthol hydrochloride is left as a white crystalline compound. The latter was collected drained completely from adhering mother-liquor and dried iii the water-oven.The dry salt was then just covered with glacial acetic acid and powdered anhydrous sodium acetate and acetic anhydride added. The mixture was boiled for 2-3 hours and the acetyl-derivative thrown o u t by dilution with water. The substance was collected washed and purified by crystallisation from alcohol in which it readily dissolves when hot and separates very slowly on cooling in the form of dense colonrless transparent rhombic prisms, melting sharply a t 206". hnaljsis showed thnt the compound was a d iacetyl-derivative :-0.1081 gram gave 0.2742 gram GO and 0.0502 gram H,O. 0.1460 , , 7.6 C.C. moist N at 17' C. and 738.4 mm. bar. 0.3458 , , . 18.2 , , 14.5" C. and 731.5 ,, Calculated for Found. NI1.C H 0 +-.-) c~oH6<*.~,~32,03 * I.11. - c 69.13 69.18 H 5.35 5.16 N 5-76 5.84 5.94 -The substance is accordingly acetamido-p-nnphthyl acetate. It is of interest to note that t.he acetylation in this case leads to the forma-tion of a diacetyl-derivative and not of an anhydro-base although the amidonayhthol is an ortho-derivative. As a parallel instance we may mention a-p-naphthylenediamine which although an ortho-compound also gives a diacetyl-derivative and nut an anhydro-base, on acetylation (Lawson Iuuug. Diss. 1885 p. 26). By heating dry amido-B-naph tho1 hydrochloride with anhydrous sodium benzoate and benzoyl chloride to the boiling point of the latter for about two hours a dibenzoyl-derivative is formed. The product of the reaction is washed repeatedly with hot water and dilute ammonia and finally pnrified by two or three crystallisations from boiling alcohol in which the substance dissolves somewhat sparingly.The pure compound forms whitish needles melting at 226.5". 0.1186 gram gave 0.3420 gram GO and 0.0544 gram H,O. 0.1508 gram burnt in a vacuum with CuO gave 5 C.C. moist N at 24.5" and 765.3 mm. bar. VOTI. LV. 122 MELDOLA AND JIORGAN RESEARCHES ON THE Calculated for NH*C H 0 Cl0%<O.C7&(j Found. C . 78-47 78.66 H . 4-63 5.09 N . 3.81 3.73 These results show that the compound is benzamido-5-naphthyl benzoate and t,hat as in the case of acetylat,ion both the hydroxyl and nniidogen of the amidonaph thol are simultaneously a t tacked. 2lfild RelEzmSon of Benzeneazo-p-Naphtliol nnd its Acetgl-derivative, 111 accordance with the well-known fact that aromatic azo-corn-pounds by mild reduction yield hydrazo-compounds which nrider tbe influence of acids become transformed into bases of the diphenyf or riapht,hylphenyl series it became of interest to investigate the action of mild reducing agents on the azo-compounds of p-naphthol.Corn-mencing with the simplest case benzeneazo-/3-nnph thol was dissolved in a sufficient quantity of alcohol to retain the whole of the substance in solution when cold and stannous chloride mixed with alcohol was added t o the solution till reduction had been effected. The alcohol Was distilled off nnd the residual solution after filtration to remove a small quantity of tarry matter was mixed with dilute sulphuric acid and allowed to stand for 24 hours.A small qnantity of a crystaJline substance consisting of slender white needles had sepa-rnted but the yield was too small to enable analyses to be made. The presence of sulphuric acid was proved qualitatively in the compound after the latter had been purified by crystallisation from boiling water in which it dissolves with areat difficulty. The sub-stance is in all probability the sulphate of dinmido-oxynaphtliylphengl, aud we hope to return to its investigation on a future occasion but the small yield has deterred us from making further experiments in this direction as the preparation of this compound has only an indirect bearing on the present line of work. The free base is very unstable forming dark products of oxidation with extreme rapidity on exposure to the air.During the boiling of the solution of the sulphate for the purpose of purifying this salt a conside~able loss was incurred by the formation of a resinous product. If the sulphate is basified by ammonia a greenish colouring matter is produced by the action of atmospheric oxygen. A small quantity of the sulpliate heated with dry sodium acetate and acetic anhydride gave an acetJ1-derivative which after crystallisation from alcohol formed small, white needles melting at 130-131". Benzeneazo-P-naphthyl acetate when reduced in a similar manne COXSTITUT[OY OF AZO- AND DI.\ZO-DERIVATIVES. 123 with stannous chloride in cold alcoholic solution gives a mixtupe of bases from which nothing definite could be isolated. Amido-/j-naphthol is undoubtedly present but not in sufficient quantity to separate out as a hydrochloride in the presence of excess of acid.The presence of amido-@-naphthol was proved by the formation of nitroso-/%naphthol by the action of sodium nitrite on the acid solu-tion. The other base which is present is so rea lily decomposable that a dark resinous scum is continually formed during the evaporation of the solution. The addition of sulphuric acid to the solution of the hydro-chlorides does nof cause the sepiiration of an insoluble sulphate. Nevertheless the absence of a naphthylphenyl base cannot be inferred from this circumstance because it is highly probable that such a base, if formed would contain the acetyl-group in one of the amidogens and would thus lose the pyoperty of fonning an insoluble sulphate.We have proved that such a naphthylphenyl-derivative is formed by a method which is described further on so that the uiistable base pre-sent in solution with t'he amidonaphthol is in all probability the ncetyl-derivative of diarnidoh,ydroxynaphtliylphenyl with the acetyl in one of the amidogen-groups by intramolecular transference i.~., The proof that such a base is formed is furnished by the isolation of the diacetyl-derivative. The mixtiire of dry hydrochlorides. obtained by the reduction of benzeneazo-p-naphthyl acetate in sZigh/l.i/ wurm alcoholic solution with Ftannous chloride was boiled for aboiit two hours with glacial acetic acid dry sodium acetate and acet.ic+ anhydride. The product was diluted with water collected washed, and crjstallised two or three times from hot alcohol.Microscopic needles were obtained melting sharply a t 252". From the first mother-liquor there slowly separated the familiar rhombic prisms of' acetamido-p-naphthyl acetate (m. p. 206"). The substance meltiu:.; a t 252" was analysed with the following results :-I. 0.1513 gram gave 0.3892 gram GO and 0.0724 gram H,O. 11. 0-1310 , 0.3368 ,, 111. 0.1194 , 0.3076 , , 0-0581 ,, IV. 0,2154 , 13.1 C.C. N at 15" C. and 745 mm. bar, Found. Calculated for -7 C22H20N204. I. 11. 111. IV. C 70.21 70.15 '70.12 70.26 -H 5-31 5.31 - 5.40 -N . . - 7.44 - - 6-9s K 124 MELDOLA AND MORGAN RESEARCHES ON THE These numbers indicate that. the compoiind is the triacetyl-derira-tive of diamido-hydroxynaphthylphenyl the constitutional formula being-\-/ The other base mixed with the amido-&naphthol is accordingly, the monacetyl-derivative of diamido-hydroxynaphthylphenyl the acetyl being most probably present in the a-amidogen-group throngh intramolecular migration in the manner explained.The absence of two arnidogen-groups in the monacety 1-derivative appears as we have already stated from the fact that it does not form an insoluble sul-phate a property which is so eminently characteristic of all the bases of the benzidine series and which as we have previously shown, pertains t o diamido-hydroxynaphthylphenyl itself. Summing up the results given by the present investigation of the products of reduction of benzeneazo-p-nnphthyl acetate the following conclusions have been ai-rived at :-1.By violent reduction with tin and hydrochloric acid the chief product is a-amido-/I-naphthol a small quantity of the monacctyl-derivative of diamidohjdroxynaphthylphenyl being a t the same time produced. The splitting off of acetyl f:bvours the view that this radicle is attached t o the oxygen atom and not to the nitrogen atom. 2. Reduction in cold alcoholic solution with stannous chloride gives monacetyldiamido- h ydroxyna p ht h yl phenyl as the chief product, a-amido-p-naphthol being a t the kame time formed in smaller quantity. 3. Moderate reduction with stannous chloride in warm alcoholic solution gives a mixture of the two bases from which the triacetjl-derivative of the hydroxynaphthylpheiiy 1 base can be isolated by acetylation and crystallisation of the product.I n all three cases a,niline is also one of the products of reduction. Reduction of Benzeizeaxo-p-Naphthy 1 Benzoate, When this compound is reduced by boiling its alcoholic solution with ttin arid hydrochloric acid the proclucts are aniline and a-amido-&naphthol the benzoyl-group being split off as in the case of the acetate when it is submitted to violent retluction. A cold alcoholic solution of the benzoate when mixed with a solution of st,annous chloride also gives a considerable quantity of amido-/3-napht hol together with a benzoj 1-derivative of a naph1hJllphenyl base. Th COXSTITUTION OF AZO - AND DIAZO-DERIVATIVES. 1 S 5 separation of the two products in this case offers no difficulty as the hasic properties of the latter are neutralised by the benzoyl-group and the substance is insoluble in dilute acids.After the reduction is complete the alcohol is distilled off the residue diluted with water and filtered. The filtrate contains the amido-P-napht<hol hydrochlo-ride which can be identified in the usual manner. The dark tarry, insoluble residue left after this treatment is extracted two or three times with hot dilute hydrochloric acid then washed with water and finally extracted with cold alcohol which dissolves o u t a tarry impurity and leaves the crude naphthylphenyl-derivative in the form of a whitish crystalline powder. The latter af'ter being twice crystallised from boiling alcohol in which it is rather sparingly soluble forms white silky needles melting a t 172-173" :-0*10@4 gram gave 0.2860 gram C02 and 0.0416 gram H,O.0.0813 gram burnt in a vacuum with CuO gave 3.5 C.U. moist N a t 14" C and 750.9 mm. bar. Calculated for C& 0 2 . Found c . 77.96 7 7-69 H . 5.08 4-60 N . 7-91 7-86 The formula deducible from these analyses indicates that the com-pound is a monobenzoyl-derivative of diamidohydroxynaphthlyphenyl. The yield is n u t very great as tshe chief products of reductioii are, even under the described conditions of working chiefly amido-p-naphthol and aniline. The fact that the substance is not basic tells against the view that two amido-groups are present and points LO the tyansference of the benzoyl from the oxygen to the nitrogen i n the naphthalene nucleus by the same process as that which takes place with ihe corresponding acetate.We are therefore led to the view that the constitutional formula of the compound is-The proposed LJ formula certainly indicates a phenolic substance, whereas our compoiind is insoluble i n aqueous alkali. The disguisiug of the phenolic character of the molecule by the proximity of the C,H,O*NH-gronp seems however more probable than that two free nmido-groups should be present when the distinctly non-basic character of the substance is borne in mind. For t h i s reason we attach the greater weight to the above f.mniilit 126 MASSON AND KIRKLAKD ACTION OF BROJlINE AND The general conclusion to which these experiments point is that tho acid radicle acetyl or benzoyl introduced into benzeneazo-B-naphthol or its derivatives displaces an atom of hydrogen which is attached to oxygen and not to nitrogen. This is shown by the facility with which flie radicle is split off during reduction and by the absence of acetanilide or benzanilide among the products of reduction. The transference of the radicle from the oxygen to the nitrogen in the naphthylphenyl base is effected by intramoiecular change in the ortho-position through the intermediate formation of an nnhydro-base. An investigation of the products of reduction of the alkyl-derivatives of azo-/?-naphthol compounds has been carried on concurrently with the foregoing experiments and the results w-ill be made known in a subsequent, communication. In the early part of tbe present research we received much assistance from Mr. E. H. R. Salmon and more recently we have had the beiiefit of the co-operation of Mr. J . H. Coste. It gives us mnch pleasure to acknowledge the services rendered by these gentlemen. Finsbury Tech n ical Co 1 leg e

ISSN:0368-1645    

DOI:10.1039/CT8895500114

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

126 MASSON AND KIRKLAKD ACTION OF BROJlINE AND XVII1.-Action of Bromine and Chlorine on the Salts of Tetrethyl-phosphonium,. By ORME MASSON M.A. D.Sc. (Edin.) and J. B. KIRKLAND. University of Melbourne. THE action of the halogens on trimethylsulphine salts formed the subject of a paper communicated to the Society by Dobbin and one of us (Trans. 1885 56) and in a subsequent commcnication the action of the halogens on tetrnmethylammonium salts was described by the same authors (Trans. 1886 846). In these papers it was shown that the halo'id salts of these bases can combine directly with iodine bromine chlorine or iodine monochloride to form compounds of the general formula RXs (where R is the basic radicle and X is I Br or Cl) ; that those members of the series which contain not less that one atom of iodine in the molecule are fairly stable crystalline solids of a characteristic black red or yellow colour ; that the other members containing only bromine or chlorine or both are red or yellow liquids stable only i n an atmosphere of the halogen from which they have been formed; that some of these unstable com-pounds have a sufficiently definite composition (corresponding t o the general formula RX,) as proved by synthetic experiments ; but tha CHLORINE ON SALTS OF TETRETHYLPHOSPHONIUN.127 P. C. Found (per cent.) . . . . . . . . . . . - 34 -79 ---others have a tendency t o absorb a large excess of halogeii without very great alteration of properties particularly where bromine is the halogen added. It was also shown that this formation of perhnlo’id compounds is an action of wider application than at first would seem probable ; for not only may the nature of the organic basic radicles be varied very considerably but qualitative experiments with the sulphates of trimethylsulphine and tetramethylsmmoniurn showed that these as well as the halo’id salts can combiuc? directly with bromine and chlorine.The striking resemblance between the behaviour in this respect of the sulphates and the chlorides led the authors to reject that view of the constitution of the perhalo‘id compounds which is represented by the formula R’*X<X; and the option was left of regarding them all as molecular compounds of the formula R’.X,X., or of regarding the central atom of the basic radicle (S o r N) as capable of directly attaching to itself the additional halogen atoms (R’”X3).Quantitative data however were required to fully prove the similarity of the action of the sulphates and chlorides or bro-mides. It was thought that more stable compounds might be obtained from the salts of a phospllorus base and a preliminary experi-meiit with tetrethylphospboniuu iodide showed that a t any rate this salt is capable of yielding perhaloid compounds resembling those already studied. The investigation was then interrupted and has only lately been resumed by the present authors. ‘l’etrethylphos-plionium salts have been used on account of the greater ease with whicti they may be prepared as compared with the methyl compounds. The iodide was prepared by HoEmann’s method from phosphonium iodide and absolute alcohol and was proved by analysis to be of suffi-cient purity.x H. I. --7 *39 45-68 ---_-Calculated (per cent.) . . . . . . . In any future experiments however we should prefer the method of preparation described by us in the next paper (p. 138) on account of its greater simplicity and economy. 11 -31 35.03 7-29 46 ’35 A c t i o n of Bromirhe on TetrethlJ1phosphoniunz Iodide. When bromine is added to this salt cotiibin a t,’ ion oc(’urs accpm-paiiied by tlre development of much Lent the wliole pheuouien 128 MASSON AND KIRKLAND ACTION OF BROXINE AND bejng similar to those observed in the cases of the iodides of trimethyl-mlphine and tetramethylammonium. When the resulting heavy red liquid is freed from excew of bromine by evaporation and by washing with anhydrous ether it bright red solid remains which dissolves in warm alcohol and on evaporation may be obtained in orange-red crystals.The appearance and properties of these leave no room for doubting that they are tetrethy lphosphonium dibrorniodide, this was confirmed by analysis. P (C,H,),I Br ; *I. 0.1899 gram gave 0.1450 gram CO and 0-0880 gram H,O; or 0.03955 gram C and 0.00798 gram H. 11. 0.1970 gram gave after redaction with sulphurous acid, 0,2t?OO gram of the mixed silver salts AgBr and AgI Assuming this mixture to be in the proportion 2AgBr AgI, it contains 0.07332 gram 13r and 0-05820 gram I. Found. -7 Calculated for P(CZH5)41Br2. I. - - P 7-18 H 4-61 5-40 1 . 29.26 - 29.54 Br 36.87 - 37-22 c 22.12 21.86 -This dibromiodide like those previously described yields a black explosive substance when treated with aqueous ammonia ; and forms an additive compound of the formula P(C,H,),IBr + 2NH3 whelk subjected to the action of a current of dry ammonia.This com-pound is black in colour. When left exposed to the air it loses ammonia and leaves the dibromiodide as a red powder. 0.1470 gram of the dibromiodide yielded 0.1582 gram of the black ammonia compound. * This dibromiodide the corresponding dichloriodide and the tribromide were found to present unusual difficulties when submitted to combustion-difficullies not met with in the case of tetrethglphosphonium iodide on the one hand or of the perhalo'id compounds of trimethy1sulr)hine and tetmmethplammonium on the other.An open tube was employed with oxide of copper and chromate of lead with silver a t the exit end. The combustions had to be conducted with extreme slowness to avoid loss of phosphine-smelling volatile matter (which spoilt the first experiments), and in every case a refractory black residue remained which yielded only to prolonged heating in the oxygen current. This may account for the high percentages of hjdrogen found though all the usual precautions were employcd for drying the gas CHLORIXE ON SALTS OF TETRETHTLPHOSPHONlUM. 1-29 Increase per cent. Percentage increase of weight. 7-26 7.47 Calculated for P(C2H5),IBr2 + 2NH3. . . . Found . . A synthetic experiment was made in order to ascertain whether, by bromination of the iodide any compound could be obtained con-taining more bromine than the dibromiodide.0.3087 gram of the dry iodide was exposed for three-quarters of an hour at the ordinary tem-perature to a current of dry air laden with bromine vnpour. The iodide was contained in a porcelain boat placed in a glass tube and the boat and tube together with the glass stopper were tared at the commencement. After clearing out the tube with a rapid current of dry air i t was found that there was an increase of weight equivaleiit to a gain of 3.4 atoms of Br by each molecule of Y(C2H5)J. Tlie product was a dark-red liquid. The tube was now placed in a n air-bath and kept a t 110" for two hours whilst the bromine current was kept up and the increase of weight was again ascertained and forind to be equivalent to a gain of 5.2 atoms of bromine by each molecule of P(C,H,),I though there was not much change in the appcbarance of the liquid product.This was then subjected to a current of pure dry air at the ordinarF tempeiature and weighed from time to time. It was soon converted into a bright-red solid substance and this con-tinued to lose bromine slowly but after three hours still retained what was equivalent to 3.6 atoms for each molecule of the iodide. Atoms of Br per mol. Bromine passed. 4 how cold. 1 -Dry air passed. 2 hours a t 11Q '}I - -- - I 3 hours Weight found. -0 '6172 0 * 7827 --0 * 6320 I- -99.8 I 3.4 Nature of product. Liquid. Liquid. Solid. --Weight of iodide used 0.3087 gram.There is t.hen a marked tendency for P(C,H5)J t o take up more than Br2 but if a definite higher compound exists i t is of an unstable nature. It will be seen that the behaviuur of the iodide towards chlorine favours by analogy the supposition that an unstable tetra-brorniodide P(C,H,),IBr, may exist. Action of Chlorine o n Tetrathylp23hosphoniu.m Iodide. The absorption of chlorine by the dry RRlf is atiended by develop-ment of heat and the formation of st substance which a t first brown 130 MASSON AND KIRKLAND ACTION OF BROMINE AND becomes yellow as the action proceeds ; it is facilitated by keeping the salt a t a temperature of about 70° in which case a red liquid is obtained that solidifies to a darkish yellow crjstalline mass on cooling in an atmosphse of chlorine.Its composition was ascertained by the following synthetic experiment which was conducted in a manner similar to that already described :-Weight of iodide taken . 1.011 gram. Chlorine passed at 70” 1 hour. Weight of product (solid) . 1.520 gram. Percentage increase of weight 50.3 per cent. Percentage increase calculated for forma-tion of P(C2H5)JC14 51.8 per cent. This tetrachloriodide very slowly loses chlorine in dry air. but decomposes with loss of chlcrine when treated with water or alcohol. Its alcoholic solution on evaporation yields yellow crystals of the dicliloriodide P(C2H5)JC12 a substance closely resembling the dichlor-iodides previously described both in appearance and in its reactions with ammonia &c. I. 0.1233 gram gave 0.1255 gram CO and 0-075 gram H,O, equivalent to 0.03423 gram C and 0.00833 gram H.11. 0.1586 gram after reduction with sulphuric acid gave O*%W gram of mixed silver salts. On the assumption that this con-tains iodide arid chloride in the proportions of AgI SAgCI, it is equivalent to 0.0576 gram T and 0.0:422 gram C1. On analysis it gave the following results :-Found. Calculated for +-7 Y (CpHb)dIC12. I. 11. - - P . H.98 C . 27.83 27-75 H 5-80 6. i 4 I 36-81 - 36.32 20.30 C1 20.58 ---Action of Bromine om Tetrethy~hos~hoikiunz Bromide. The bromide employed was made from the iodide. by shaking its An estimation of solution with recently precipitated silver bromide. the bromine showed it to be of sufficient purity. Br per cent. Found 54-79 Calculated f o r .. . . . . . . . . . . . . 35.2 CHLORIXE ON SALTS OF TETRETHTLPHOSPHONIUM. 131 A synthetic experiment with this sait showed that when subjected to the action of bromine-vapour a t 110" it absorbs it to form a dark-red liquid which a t the ordinary temperature is converted in to a scarlet, crystalline solid having the composition indicated by the formula P(C2H5j4Hr, that is the bromide is converted into the hoptabromide by addition of six atoms of bromine. The details of the experiment are given in the following table :-Weight of bromide taken Bromine current a t 110". . Weight of product (solid) 0.4554 gram. Increase of weight 209.4 per cent. Increase calculated for P(CzHg)4Br,33i.6. 211.4 per cent. 0.1472 gram. 1 hour.This heptabromide like thg higher compounds derived from the iodide is not stable in air a i d also loses part of its bromine when treated with absolute alcohol. The alcoholic solution yields red crystals of the tribromide P( C2H5),Br3. This compound. closely resembles the dibromiodido but does not form an addition product with ammonia and is dissolved by ammonia solution. No solid tribromides were obtained from trimethylsulphine or tetramethylam-rnoniuru but only unstable red liquids. The difference in behaviour in the present instance may be wholly attributable to the presence of ethyl in place of methyl radicles rather than to the presence of phosphorus in place of sulphur or nitrogen; for Marquardt ( J . pr. Chem. 1 429) obtained a solid tribromide of tetrethylammonium.The following were the results obtained by analysis :-I. 0.2046 gram gave 0.1860 gram COz and 0.1022 gram H20, 11. 0.2645 gram gave 0*2380 gram CO? and 0.1362 gram H,O, 111. 0.18~8 gram after reduction with sulphuric acid gave 0.26'40 equivalent to 0.05073 gram C and 0.01135 gram H. equivalent t o 0.013491 gram C and 0.01513 gram H. gram AgBr equivalent to 0.11234 gram Br. Found. A Calculated for r- I P( C-H,) .&r3. 1. 11. 111. - - - P 8.01 C 24.80 24-79 24-54 H 5.18 5-54 5-72 Br - . 62.01 --- 62-14 100.0 132 RlA4FSON AKD KIRKLASD ACTION OF BROMTNE AND Action of Chlorine o n Tet ret hy 7phosp honium Chloride. The chloride employed was prepared by shaking a solution of the iodide with recently precipitated silver chloride and was thoroughry dried by heating in a current of dry air a t 110".The salt absorbs chlorine and turns yellow ak the ordinary temperature but the action goes better at 105-110". Under these conditions a yellow liquid is obtained which on cooling solidifies to a yellow crystalline mass. A quantitative experiment showed this to consist of the trichloride, P(C2H,),CL Weight of chloride taken Chlorine passed in the cold Chlorine passed a t 105-110" 14 ,, Weight of product (solid). . Calculated increase for P(C2Ha)aCl*C12 0.1172 gram. 2 i hours. 0.1608 gram. 38.9 per cent. Increase of weight 37.2 per cent. The trichloride is a yellow cryst,alline substance which deliquesces in t,he air and is decomposed by water and alcohol with reformation of the chloride.Like other perhaloid compounds it is insoluble in anhydrous ether. There appears to be no tendency to form a. higher addition product than the trichloride. Action of Bromine on Tet,.ethylphos~hon.iuwc Xulphate. The sulphate was prepared from the iodide by means of silver sulphate. In order to thoroughly dry the salt obtained by evapora-tion of the solution i t was found necessary t o heat it for some hours at a temperature ranging from 100" to li0" in a Sprengel vacuum. It was then submitted to the action of bromine vapour in the same manner as the bromide the increase of weight being observed first after bromination at UO" and subsequently after further bromination at the ordinary temperature. It was found that the sulphate has the power of iaking up a large quantity of bromine but that the amount absorbed and the character of the product vary considerably accord-i n g to the temperature.The product formed at 110" is when cold, a red solid ; and the increase of weight in this case corresponds to the formation of [P(C,H,)4]2S04,Br12 ; and this it may be remarked, is analogous to the highest brominated derivative of the bromide, P(C2H5)4Br,Br6 which it closely resembles in its general properties-appearance instabilit,y in air decomposition by alcohol &c. The product formed ar t h e ordinary temperature differs from this being a dark red liquid and containing a still larger amount of bromine. In the two experiments made details of which are given below th CHLORIXE ON SALTS OF TETRETHYLPHOSPHOSIUN.133 increase of weight at the ordinary temperature corresponded closely with that required for the formation of [P(C2H,),),SOa,BrT. ; but it is doubtful whether this really marks the formation of a distinct corn-pound or the extreme limit of bromine absorption. When this highly brominated liquid is left in a desiccator over solid potash or when i t is treated with a current of dry air i t quickly loses bromine and assiimes the solid state; but the decomposition does not stop here, and we have not succeeded in obtaining any brominated sulphate of stability equal to that of the tribromide or the dibromiodide. Experiiri ent. I. 11. Weight of sulphhte used in grams . . 0.2678 0.2192 Bromine passed a t 110" . 1 hour 1 hour Percentage gain of weight .243.8 244.5 Bromine subsequently passed in cold 2 hoiirs 1 hour Weight of product (liquid) 1.4848 1.2207 Percentage gain calculated for [P(C2H5)J]2S04,Br22 451.3 Percentage gain calculated for [ I'(C,H,),]2SOd,Br12 246.2 Weight of product (solid) . 0.9206 0.7.552 Percentage gain of weight . 454.4 4563.9 The solid brominated sulphate dissolves in alcohol and red crystals are formed in quantity when the solution is partly evaporated ; but a study of these and estimations of the bromine proved them to consist of tetrethylphosphonium tribromide. It was proved that the crystals contained no sulphuric acid but the mother-liquor was found to be strongly acid. The alcohol therefore produces deoompositioil and it is interesting to uote that the phosphorus radicle retains the bromine in preference to the sulphuric acid group.I. 0.1196 gram after reduction with sulphurous acid gave 0.176 11. O*U492 gram gave 0.072 gram AgBr equivalent to 0.03064 gram AgBr equivalent to 0.07489 gram Br. gram Br. Found. 7 Calculated for r-L for P(C2H,),Br3. I. 11. Br per cent . 62.01 62.62 62.27 Action of Chlorine on Tetrethylphosphoniuin Xulpphate. The thoroughly dried sulphate combines with chlorine but less readily and (as in other cases) to a less extent than wit,h bromine. The salt turns yellow and if the temperature be raised to 130" while the chlorine is passing. fuses to a yellow liquid which solidifies on cooling in the clilorine atmosphere. In the two experiments made i 134 S-4LTS OF TETRETH VLPHOSPHONIUM. Chlorine on iodide.Alcohol on 3 Bromine on bromide was found that the increase of weioht corresponded to the formation of the compound [P(C2H5)4]2SO~,C14; and this it may be noted is analogous to the formation of the chlorinated chloride P(C2H5),C1,C1,, already described. The sulphate therefore appears to resemble the bromide in its action towards bromine and the chloride in its action towards chlorine both as to the composition and as to the appearance and properties of the products formed. This is in accordance with the previously recorded qualitative observations on the sulphates of trimethylsulphine and tetr:tmethylamnionium. Experiment. I. 11. Weight of sulphate used in grams 0.2172 0.2018 Chlorine passed a t 130". . 14 hours I$ hours Weight of product 0.2964 0.2790 Percentage gain calculated for [ P( C,H5),],S0,,Cl, Percentage gain of weight .36.4 38.2 36.4 This chlorinated sulphate dissolves in water with effervescence due to escape of chlorine deliquesces when exposed to the atmosphere and slowly evolves chlorine when subjected to a current of dry air. Tlie following table contains a list of the polyhaloi'd-derivatives described in this paper together with a summary of the methods of forming them and of their properties. In some cases the fornlulae given are doubtfully indicative of definite compounds. 70" -110" 1 2 . . 3 4 5 . . 6 . 7 8 . . 9 . . 10 Compoiind formed. P(C2H5)41Br4 (3) P(C2H5)JBr2 P(CZH5)4IC14 . P(CZH,),IC12 . P (C2H5),Br,. . P(C2H5)4Br3 P(CzH,),ClS P(CZH6)412S04Br22 (?) . (C2H6)ihS04Br12 - * -P(CzH5),]2SO4C14 Method of forma-tion. tion. -.- -_-Bromine on iodide. 1 cold Alcohol on 1 Bromine on sul-Bromine on sul-Chlorine on sul-phate phtLte phate cold 110" 130 Characters of the compound. Bright red crpst. solid unstable in air. Orange crystals : stable. Dark yellow cryst. mags unstable. Yellow cryst,als, stable. Scarlet cryst. mass : unstable. Red crystals stable. Yellow cryst. mass: Red liquid un-Red solid unstable. unstnble. stable. Yellow solid un-stable

ISSN:0368-1645    

DOI:10.1039/CT8895500126

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

135 XTX. -Preparation of the Salts qf Tyieth ybulphine Tetrethylphos-phonium aiid Analogous Bases. By ORME MASSON M.A. D.Sc. (Edin.) and J. B. KIRKLAND. University of Melbourne. THE preparation of such a salt as triethylsulphine iodide in any quantity by the ordinary method though easy in theory is practically a most disagreeable opei-ation since it necessarily involves the making and manipulating a large amount of ethyl sulphide or some equally objectionable substance. The preparation of analogous selenine salts by the ordinary method is open to a siniilar objection which is more-over of greater weight on account of the still more noxious character of volatile selenium compounds; and there is also an additional disadvantage i n that a loss of the somewhat costly selenium in the preliminary operations is unavoidable.It is obvious that any method by which sulphur (or selenium) may bn converted directly into sul-phine (or selenine) salts affording a good yield and avoiding the manipulation of noxious volatile substances should he of value to chemists engaged in the study of such compounds. Klinger 12 years ago mentioned the factj (Rer. 10 ISSO) that trimethylsulphine iodide could be obtained by heating sulphur in sealed tubes with methyl iodide and extracting the product with water. He did not however enter into details of the procpss which has so far as we are aware not been made use of since then ; nor was the method adopted by him sufficiently practical to replace that of von Oeffele. We have found that the following method gives good results.(1.) Powdered roll sulphur is heated with ethyl iodide in sealed tubes a t 180" for about 24 hours the two substances being taken in the proportion of S SC2H51 with a slight excess of the latter. Soft glass tubing may be empioyed as there is only a little pressnre when the tubes are opened (due to the formation of a combustible gas by a secondary reaction) we have adopted no special precautions to avoid the bursting of the tubes and have not lost any. The sulphur entirely disappears and the tubes when cold are seen to contain a large amount of a black tarry liquid a t once recognisable as a poly-iodide by any one acquainted with such compounds. The reaztion in fact may be correctly represented by the equation-It may be divided into three stages :-S + 3C,H,I = S(CJIS)dI3.(2.) Klinger's method of extracting this substance with water could certainly not be worked satisfactorily for such polyiodides are onl 136 MASSOX AN3 KIRKLAND PREPARlTIOS OF decomposed with difficulty by water even on prolonged boiling. It is best to proceed as follows :-The contents of the tubcs are washed into a tall glass cylinder covered wit,h water to a depth of some inches and a current of hydrogen sulphide is then passed in through a tube which dips under the liquid polyiodide hy this means the latter is decomposed in the course of an hour o r two. The action resembles that which occurs when hydrogen sulphide is led ander the surface of bromine covered with water except that no sulphuric acid is formed as always happens in the latter case.When the polyiodide has disappeared the vessel contains a clear acid solution of triehhyl-sulphine iodide and hydrogen iodide and a flocculent deposit of sulphur. The reaction is represented by the equat,ion-(3.) The solution decanted from the sulphur precipitate cannot be advantageously evaporated for the recovery of the sulphine salt as this is attacked by the hydrogen iodide present. It is therefore, mixed with excess of moist silver hydroxide by which means a pure solution of triethylsulphine hydroxide is obt'ained ; and this may then be converted into any desired salt by exactly neutralising it with the appropriate acid. In our first cxperiment we thought to simplify matters and save silver by adding the silver hydroxide gradually to the acid solution until its reaction was neutral so as to obtain the sulphine iodide a t Once by filtering and evaporating.It was found however that only a small quantity of the salt could be recovered in this way. As the fiilver iodide precipitate had been washed with boiling water until the washings were practically free from soluble iodide the missing salt bad to be looked for in the insoluble residue on the filter. Experiment showed that this when treated with more moist silver hydroxide yielded a quantity of the soluble alkaline sulphine llydroxide ; so that it is evident that silver iodide and the sulphine iotiide unite to form an insoluble double salt. This was further proved hy mixing fresh moist silver iodide with a little solution of tile sulphine iodide ; the solution after a sliort time was found to give the iodine reaction only faintly.The silver iodide simultaneously changed in colou~ from yellow to white. The fact that the precipitate f i d formed when silver nitrate is added to a solution of an iodide is white and become yellow only as the reagent is added in excess is probably attributable to the same cause. If the sulphine hydr\)xide solution is converted into the iodide by neutralisation with hydriodic acid and this solution is evaporated to (jpyness ;t yield is obtained which falls only a very little short of th:tt calculated from the weight of sulphur employed according to th THE SALTS OF TRIETHYLSULPHINE ETC. 137 ’ grams. 3 -2 48-0 3.5 equations we have given. In one such experiment we obtained more than five-sixths of the theoretical yield.The following are the details of the experiment. 3.2 grams of powdered roll sulphur and 48 grams of ethyl iodide were heated in a sealed tube for 22 hours at 180-185”. Some com-bustible gas escaped when the tube was opened. The tarry polgiodide was washed out with water and treated with R current cjf hydrogen sulphids €or four hours in the manner described above. The solution was decanted from the precipitated sulphur ; the latter was washed, and the washings added to the solution which was then made up to a definite volume. The sulphur after drying weighed 3.5 grams. One-fourth of the solution was then treated with excess of moist silver hydroxide (from a weighed quantity of silver nitrate) in the cold until a drsp of it give no iodine reaction ; the mixture was then filtered the silver iodide washed tharoughly with hot water the washings being added to the filtrate.The filtrate and washings were then made up to a definite volume and a small portion of it was titrated with qtandard hydrochloric acid. By this means it was found that supposirg the whole solution to have been treated with silver hydroxide the sul phine hydroxide produced would have required 94 C.C. of normal hydrochloric acid for neutralisation or would have weighed 12.8 grams. This result was checked by neutralising the remainder of the solution with hydriodic acid evaporating to dryness, and weighing the sulphine iodide obtained. The weight was found to be 5.56 grams which was equivalent to 22.68 grams if the whole of the originnl solution had been treated in like manner.Finally, the iodide was recrystxllised from alcohol (the equivalent of a total yield of 20 grams of pure salt was obtained) and its identity was estsblished by an iodine estimation although its properties left no doubt as to its true nature :-Calculated for S(CaH5)J 51.62 per cent. of I. Found. 51.60 I The details of the experiment may be tabulated side by side with the figures calculated from the equations given above. S taken (and used up) . S precipitated by the H2S action Normal HC1 required by the whole of the S(CzH5)3*OH after AgzO action . S(C2HJ3*OH calculated from above. . S(C2H5),I obtained (crude). C2HQI taken 94 C.C. 12.8 22 -7 grams.3 -2 46 -8 3 ‘2 100 C.C. 13.6 24 -6 VOL. LV. 135 MASSON AND KIRKLAND PREPARATION OF We have also ascertained by experiment that triethylseleniiie salts may he prepared by this method if selenium is used in place of siilphur. We have not made quantitative experiments however and so cannot state the yield obtainable. The preparation of tetrethylphosphonium salts and their homo-l o p e s is notoriously a troublesome matter in spite of the classical researches of Hofmann Cahonrs and others. That this is so was shown in 1880 by Letts (Trans. Roy. SOC. Edin. 30,185) who discussed a t length the various processes then known and rejected them all as uncertain trouhlesome and expensive. The well-known method of Hofmann which consists in heating phosphonium iodide with absolute alcohol in sealed tubes a t 18Go and acting on the resulting mixture of iodides with potash so as to precipitate the tetrethylphosphonium iodide &c.is generally considered the best process ; but this was rejected by Letts because he found it impossible to avoid the loss bg explosion of the great majority of his tubes. We have not found this t o be the case when the precautions mentioned by Hofmann are carefully attended t)o ; but still we agree with Letts that the process is a t best a very troublesome one; and i t may be added that the preliminary preparation and preservation of large quantities of phos-phonium iodide PHJ constitute an undesirable factor. The method which we have adopted avoids all these disadvantages by making use of phosphorus itself and ethyl iodide as the raw materials which are converted directly into a tetrethylphosphonium-derivative without risk of loss by explosions.The practical details of the method are similar to those already described f o r the preparation of sulphine salts. Either ordinary phosphorus or red phosphorus may be used. Ethyl iodide is taken in excess of the proportion indicated by the formula 7C2H51 + 2P ; we have found no harm result from using as much as 6C2H51 P ; tho mixture is heated in sealed tubes a t 180" for about 24 hours. When cold the tubes are seen t o contain a black tarry liquid or a semi-solid black crystalline mass of polyiodide but no phosphorus. Combus-tible gas escapes on opening the tubes but there is never enough pressure developed to cause explosions.The greater part of the excess of ethyl iodide may be recovered by distillation on a water-bath. The contents of the tubes are then reduced with hydrogen sulphide under water ; and the clear acid solution decanted from the precipitated sulphur is treated with moist silver hydroxide in excess, BO as to give a solution of the tetrethylphosphonium hydroxide. An alternative method of procedure in this case however may be em-ployed with advantage ; after the reduction with hydrogen sulphide, the excess of that gas is got rid of by zt current of carbon dioxide, and the solution (containing the tetrethylphosphoniurn iodide an THE SALTS OF TRIETHPLSULPHINE ETC. 139 hydriodic acid) is saturated with potash and warmed. The result, as in Hof mann’s method is the separation of the phosphonium iodide, which floats as an oily layer on the potash; and it may be readily purified by crystallisation from alcohol.This method is indeed pre-ferable to the other as it does not involve the use of silver. I t may also be stated that this potash method has been successfully applicd to the preparation of triethylsulphine iodille; but it is doubtful whether in this case the yield obtained is as good as by the silver hydroxide process. It is evident that the equation for the action of phosphorus on ethyl iodide cannot be so simple as that which we have shown to be true in the case of sulphur for there is no polyiodide possible of tlie formula P(C,H,),T,. It was thought that a mixture of the two poly-iodides P( C2H5)J3 and P( C2H5)J5 might be produced in which case the whole of the phosphorus worild be eventually recoverable in the form of tetrethylphosphonium iodide.But experiments have proved that only half of this quantity can be actually obtained while tlie other half of the phosphorus assumes a form which is converted during the treatment with hydrogen sulphide and water into tricthyl-phosphine oxide. As this is a neutral substance extremely soluble in water and volatile in the steam produced by the evaporation of the solution its formation is at first liable to be overlooked. Any theory of the reaction then to be tenable must among other condi-tions be such as to account for the conversion of one half of the phosphorus into a polyiodide of tetrethylphosphonium and the other half into some substance of similar appearance but convertible by water or hydrogen sulphide (or both acting together) into triethyl-phosphine oxide.These conditions are fulfilled by the following theory; and i t will be further shown that most of the observed. details of a quantitative experiment distinctly favour it whilst they are not capable of equally satisfactory explanation in any other way. (1.) The tarry product in the sealed tube consists of a mixture of the polyiodides of tetrethylphosphonium and tziethylphosphine produced according the equation-2P + 7CZH5I = P(C2H5)JIs + P(C2H5)314. (2.) When this mixture is treated with water and hydrogen sulphide the following changes occur simultaneously :-P(CZH5)Js + HZS = P(CzK)J + 2HI + S , P(C2H,),I + HZS + HZO = P(C,H,),O + 4HI + S.A solution is thus obtained containing hydrogen iodide tetrethpl-phosphonium iodide and triethylphosphine oxide ; whilst sulphur is precipitated. L 140 MASSON AND KIRKLAXD PREPARATIOX O F The following are the details of the experiment which suggested this theory :-3.1 grams of phosphorus (in this case ordinary phosphorus was used; but it was afterwards found that red phosphorus would also answer) and 93% grams of ethyl iodide (equal to onertenth of the weight in grams indicated by the formula F + GC2H51) were heated for 22 houra a t 180-185" in a sealed tube. All the phosphorus dis-appeared and 30 grams of ethyl iodide was recovered by distillation of the contents of the tube. The black tarry product was completely decomposed in two hours by the hydrogen sulphide treatment giving 3.4 grams of sulphur.One small portion of the solution (which was made up to a known volume) was titrated with standard alkali and the total quantity of hydrogen iodide in solution was calculated from tbe result and was found to be 33.6 grams. Another small portion WRS used for an estimation of the total iodine ; and this calculated for the whole quantity was found to be 41.0 grams. The rest of the solution was treated with excess of moist silver hydroxide; and a portion of the filtrate and washings (made up to a known volume) was titrated with standard acid and the total available hydroxide calculated from the result and found to be 8.2 grams. The whole of the remainder of this alkaline solution was then neutralised with hydriodic acid and evaporahed on the water-bath; and the salt thus obtained was dried and weighed.From this the total available iodide was calculated (allowance being made for those portions of the solution used for titration) and was found to amount to 13.45 grams. Finally this salt which possessed all the properties of tetrethyl-phosphonium iodide was crystallised from alcohol ; and iodine estimations were made with crystals of two distinct crops for the purpose of complete identification :-Found. Calculated for e - 3 P(C,H,),I. I. 11. Iodine per cent. . . . . . . 46.35 45.98 45.90 The triethylphosphine oxide was not saved or estimated in this experiment as indeed its formation was not suspected until the results were calculated ; but in a subsequent experiment the solution from the hydrogen sulphide action was distilled in such a manner as to permit of the oxide being collect,ed and identified.The details of the above experiment are tabulated for the sake of comparison with the figures calculated from the theory which we have enunci-ated THE SALTS OF TRIETHTLSULPHISE ETC. 141 P taken and used up in the reaction C2H,I taken C,HJ recovered by distillation. . C,HJ used up (or lost). . S precipitated by the H,S action Normal NaOH required for free HI . Total free HI deduced from above. Total iodine as Hl and P(C2H5),I. Normal HC1 required by the P(C2H,),-OH Total P(C,H,),-OH formed deduced from above Total P(C2HS),I prodbeed (crude) P not thus accounted fbr [lost a8 €'(CzH5)aO] grams.3.1 95.6 30 -0 63 *6 3 -4 262 *5 dc 33 *6 50 C.C. 8 . 2 13.45 1' '58 4s '0 grame. 3 -1 --54 *6 3 *2 so0 C.C. 38 '4 44 -4 50 C.C. 8 *2 13 -7 1 *55 This is not the first time that the action of phosphorus on ethyl iodide has been investigated and a theopy of €he action advanced, although i t is the first time so far as we are aware thdt it has been made use of fop preparing the sales of tetrethylphosphonium. Carius (Annnlen 137 117) adopted the Peaction as a means af preparing triethylphosphine oxide and his method was further worked out by Crafts and Silva (this Journal 1871 24 629). Their procedure differed essentially from that described' by US in the following particulars The phosphorus and ethyl iodide'were mixed in a very different proportion viz.2 P 5C2H51. The ph&phdrus was not all consumed some remaining in the amorphous form even aftel( beating for 24 hours at 175-180". The iodine-coloured product was ground up with the residual phosphorus and the whole distilled with alcohol till colourless. Ethyl iodide was produced in t h i s reaction. The residue from the solution was found to contain phosphorous acid. The whole was then distilled in a copper retort with solid potash ; when ethane triethyl-phosphins phosphine and a large amount of triethylphosphine oxide were obtained. Carius proposed the following equations to represent (2) the action which occurs in the sealed tubes (2) that which occurs when the product is treated with alcohol:-(1.) 2P + 4CzHJ = P(CzH,),T + PI,.P(CzH5)J + CzJ&O = P(CzH,),O + CzHJ + CJLj PI3 + 3C,H60 = P(oH)3 + 3CzHsT. (2.) { Crafts and Silva rightly rejected these equations but they retained the hypothesis of the formation of phosphorus triiodide. They proposed tlie following : 3 48 PREPARATION OF SALTS OF TRIETHYLSULPHINE. As these equations have found their way into many text-books and as we are convinced by our own experiments that they are erroneous, we venture to reproduce them here for the purpose of criticising them. The first four equations haw never been supported by any experimental facts. The formation of phosphorus triiodide in particular is an assumption which the facts do not justify. The obvious polyiodide character of the product found in the reaction is entirely overlooked.The decolorisation by the subsequent distillation with alcohol was certainly due to the presence of the uncombined red phosphorus as was the production of ethyl iodide and phosphorous acid ; for polyiodides would act towards phosphorus and alcohol in the same manner as free iodine does ; but no account is taken of this in the equations given. Had Crafts and Silva used a larger propor-tion of ethyl iodide they would have got no residue of phosphorus ; and the distillation with alcohol would have been ineffective. We feel convinced moreover that they would not have proposed the first set of equations had they been sufficiently acquainted with the appearance of organic polyiodides to recognise the real nature of the contents of the t,ubes. Our experiments with both sulphur and phosphorus show that there is no reason for representing their reactions with ethyl iodide by more complicated equations than those we have given, VIZ. :

ISSN:0368-1645    

DOI:10.1039/CT8895500135

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

143 XX.-CONTRIBUTIONS FROM THE LABORATORY OF GONVILLE AND CAIUS COLLEGE CAMBRIDGE. No. XIII. On a C,ubical Form of Bismuthous Oxide. By M. M. PATTISON MUIR M.A. Fellow of Caius College and ARTHUR HUTCHINSON B. A, Scholar of Christ's College Cambridge. 1. WHEN 2$ to 3 parts of potassium cyanide in concentrated aqneous solution are added to 1 part of bismuth nitrate dissolved in the smallest possible quantity of cold dilute nitric acid a white precipi-tate of hydrated bismuthous oxide is obtained. About nine-tenths of the bismuth present as nitrate a t the beginning of the reaction is precipitated as hydrated oxide ; the addition of a very large excess of potassium cyanide fails to precipitate all the bismuth. If this pre-cipitate is thoroughly washed and then boiled with concentrated potassium cyanide solution it remains unchanged.2. When 2+ to 3 parts of potassium cyanide are added to a hot solution of 1 part of bismuth nitrate in the minimum quantity of nitric acid a brownish-red precipitate is obtained; and in this case also about niue-tenths of the total bismuth is precipitated. The composi-tion of this precipitate is represented by Baedeker to be Bi,0,,2Hz0 (Annalen 123,61) ; one of the present authors has described the pre-cipitate as an oxycyanide of bismuth (Proc. Roy. SOC. Edin. 11 557) ; and C. Hoffmann asserts that the substance is bismuth sulphide (Annulen 223 110). When this puce-coloured precipitate is re-peatedly treated with concentrated Iioiling potash solution a deep-red liquid is produced and a heavy greyish-black solid remains.3. Numerous specimens of this greyish-black solid have been prepared by us. In each case from 2-2$ parts of potassium cyanide were used for 1 part of bismuth nitrate ; the liquids containing the precipitates were boiled for 10-15 minutes and the precipitates allowed to settle ; the supernatant liquids were poured off and the precipitates were then heated with boiling potash (1 part of potash to 6 01' 7 of water) ; as soon as the potash became coloured brownish-red it was poured off and treatment with fresh quantities of boiling potash was continued till the liquid ceased to be coloured; the residues were then washed with boiling water until perfectly free from potash that is until the colour of slips of red litmus-paper was unaffected after the paper had remained in the liquid for about 12 hours ; they were then dried at 150-1 70".4. The substance thus prepared is a dark-grey crystalline powder 144 MUIR AND EUTClhNSOS ON A which is seen under the microscope to codsist of sniall tetrahedra belonging to the cubic system ; it is soluble with diaculty in acids ; on heating in air it turns yellow. Qualitative examination of the different specimens shewed- (I.) Absence of chlorine compounds. (2.) Absence of sulphur compounds. (3.) Presence of small traces of potassium but absence of all other metals except bismuth. (4.) Presence of very small quantities of nitrogen and carbon. (5.j Presence of a little silica. And (6.) Presence of a little water. Numerous quantitative analyses of the substance have bseb made.Bismuth was estimated (1.) By heating the specirneti in air then dissolving i a nitric acid precipitating as carbonate and weighing as Bi,O,. (2.) By fusing with potassium cyanide and weighing as Bi. (3.) By heating in air dissolving in hydrochloric acid precipitating as oxychloride and weighing as BiOCl. O q g e n was estiinated by heating in pure hydrogen ahd weighing (1) the water formed and (2) the residue left. SiEica was separated in the ordinary way during the course of the determination of bismuth by methods (1) and (3) above. Carbon was estimated (1.) By heatiag in pure air and leading thr caisbon dioxide (a) into tt potash tube weighed before add after the experiment j ( b ) into baryta-water. and determining the BaCO, formed.(Duprk and Hake Jodr; Chew 8oc. Trans. 1879 159.) (2.) By heating in connection with a Sprengel primp arld measuring the carbon dioxide evolved. The percentage of carbon found ranged from 0.03 to 0.23. Nitrogen was not estimated as the qualitative examination showed it to be present in very Minute quantities. Determination of Wuter.-On heatirig in air the substahce turned yellow and was converted intb Bi2O8 this change being accompanied by slight losx of weight which varied from 0.13 tb 0.75 per cent. the mean being about 0.3 per cent. When heated in a stream of dry nitrogen quite free ft-om oxygen and oxides of nitrogen the substance does not turn yellow but a loss of 0.5 per cent. (mean of several closely agreeing experiments) takes place; as this loss of weight was almost equal to the gain in the weight of a calcium chloride tube attached the loss was shown to be due to the removal of a little water; st the same time minute fragments of metallic bismuth were prodtlced due to the reducing action of traces of carbon present in the original substance.We do not give details of our estimations as the experiments were so numeroua ; we rather present a condensed statement of the results. I. The most trustworthy results for bismuth were obtained from a specimen prepared with great cape and which was specialIy well crystallised j several complete analyses of this were made the sub CUBIO-PL FORM OF BISMUTHOUS OXIDE. 145 stance being first heated in dry air silica and potassium being determined in the residue. BizO found varied from 97.45 to 98.10 ; mean = 97.81 per cent., which is equal to 87-67 per cent.Bi. 11. SiO varied from 1-1-1.2 Mean value = 1.13 per cent. 111. The amount of potassium found was equal to 0.45 per cent. IT. Mean peTcentnge of oxygen found by rediking in hydrogen and deducting weight of residue from that of o&ginnl: Twd different specimens were used ; the results varied from 10.58 t o 11.34. V. Mean percentage of oxygen found by redacing in hydrogen a d weighing water formed. Two different specimens were used ; the results varied from 992 t o 12.8. Some small part of the loss of weight observed when the substauce was heated in hydrogen was doubtless due to removal of water associated with the silica and potassium compounds present and a small part of the water obtained almost certainly came from this Rource; but the magnitude of t'he coi*rect,ion to he applied to the oxygen estimation on thiR account could not be accurately determined ; it certainly did not exceed 0.3 per cent.The results of the complete analysis of the greyish-black solid may then be stated as follows :-KZO. Mean = 10.84 per cent. Mean = 10.87 per cent. Oxygen . . . . . . . . . . . Bismuth . . . . . . . . . . Silica . . . . . . . . . . . . Potash (&O) . . . . . . Water (approx.) . . . . C and N (approx.) . . . 10.85 (mean of many determinations made with different specimens). 87.51 (mean of 6 determinations made with t'he same specimen). 1'13 (mean of 6 determinations made with the same specimen). 0.45 (mean of 3 determinations made with the same specimen).0.30 (mean af many determinations made with different specimens). 0.20 (N not determined ; mean per cent. of C from diflerent specimens - = 0.125). 1 0 0 9 ~ I€ a correction is made on the bismuth for the quantities of silica, potash water carbon and nitrogen we have I 146 MUIR AXl) HUTCHINSON ON A Calculated for Bi20,. Bismuth . 89.46 Bismuth. . 89.65 Oxygen. 10.85 Oxygen 10.35 100.31 100~00 5. When the greyish-black substance which we have proved to consist almost entirely of bismuthous oxide was heated to redness in air or in a stream of oxygen i t rapidly changed to the colour and appearance of ordinary bismuthous oxide. This colour change was accompanied bya loss of weight amounting to about 0.3 per cent.(see paragraph 4). Microscopical examination showed that the greyish-black compound and the yellow substance remaining on heating in air were identical in crystalline form and consisted of minute regular tetrahedra. The sharpness of the outlines and the brightness of the faces of the tetrahedrons remained unaffected by heating the only change visible t o the eye being that of colour. The change produced on heating in air or oxygen almost certainly consists in the oxidation of a minute quantity of the puce-coloured compound formed by the reaction of potassium cyanide with bismuth nitiate. This small quantity of the compound in question adheres most persistently to the tetrahedral crystals of the bismuthous oxide. When the greyish-black crystals are heated i n nitrogen the colour does not chauge but a very little bismuthous oxide is reduced to bismuth (see paragraph 4) ; in this case the adhering film of the com-pound containing carbon and nitrogen is not burnt away but some of it reacts with the bismuthous oxide which it reduces to metal.We found that i t is possible to remove the whole of the puce-coloured compound containing carbon and nitrogen by prolonged treatment wir;h boiling potash solution so concentrated that it solidifies on cooling; the residual product is the pale yellow bismuthous oxide. Specimens thus prepared and dried a t 160" did not undergo any change in weight when heated to full redness in air. 'l'he long-continued boiling with very concentrated potash tends to corrode the cubical crystals and produce needles apparently rhombic, which are contaminated with much silica.6 . We find that the best method of obt'aining cubical bismuthous oxide is to prepare the gray substance as described in paragraph 3, and then to heat this in air till it turns yellow. The oxide thus prepared is pale buff-yellow; it consists of minute but well-developed regular tetrahedra the faces of these are very smooth and bright and their edges are in some cases modified by the cube planes or in crystallographic notation the crystals exhibit the form k ( l l 1 ) and (100) of the cubic system CUBICAL FORM OF BISMUTHOUS OXIDE. 147 According to Nordenskjold ( P o g g . Ann. 114 512) bismuthous oxide crystallises in rhombic prisms; the ratio of the axes given by him is not identical with tthe ratio for either arsenious or antimonious oxide but the three oxides are probably isomorphous in the usual acceptation of this term.It is moreover well known that antiinonious and arsenious oxides are also dimorphous crystallising i n the cubic as well as in the rhombic system (Malard is however of opinion that the apparently cubic crystals of antimonious oxide are in reality built up of indi-viduals belonging to the oblique system). The cubic crystals of t'hese two oxides are usually octahedra but arsenious oxide sometimes crystallises in tetrahedra also and we may therefore consider that t,he preparation by us of tetrahedral bismuthous oxide establishes in a broad sense the isodimorphism of this group of oxides as is seen in the following table :-rhombic; prisms 0.3758 1 0.35; sp.gr. 4.2; cubic ; octahedra and tetrahedra ; sp. gr. 3.689. Arsenious oxide Antimonious oxide rhombic; prisms 0.394 1 1,414; sp. gr. 5.5 ; { cubic ; (2) octahedra ; sp. gr. 5.1. cubic ; tetrahedra ; sp. gr. 8.828. rhombic ; prisms 0.8165 1 1.064; sp. gr. 8.3 ; oxide Cubical bismuthous oxide is specifically heavier than the rhombic form. The sp. gr. of the specimen prepared by us was found to be 8.868 a t 25" referred to water a t the same temperature (mean of several closely agreeing determinations made with different speci-mens). Herapath (Phil. Mug. 64 321 [18%4]) gave the value 8.21 ; Karsten (Schweigyer's Journ. 65 320 394 [ 18321) gave 8.173 ; Playfair and Joule (Chenz. SOC. iWem.3 57 [l848]) gave 8.079 ; and Le Royer and Dumas gave 8.45 (see Playfair and Joule). The mean of these values is 8.304. 7. We have endeavoured to trace the reactions by which the cubical form of bismuthous oxide is produced but we have not yet succeeded in fully elucidating the stages of the process. Our experi-ments have shown (1.) That the tetrahedral crystals are formed in the largest quantity under the conditions described in paragraph 3. (2.) That if the precipitate is thoroughly wmhed before it is heat'ed with potash very few tetrahedra are formed. ( 3 . ) That if this precipitate is not washed but is kept in contact with very concen-trated potash solution for several weeks in the cold a few tetrahedra axe formed. We have also found that the puce-coloured precipitate produced by potassium cyanide is amorphous 148 KISIMINS PERIODATES.Repeated experiments have convinced us that the action of hot potash on this amorphous precipitate frequently results in the forma-tion not onlF of tetrahedra but also of needles which are perhap rhornbic prisms and ako of more or fewer twin-crystals somewhat of this form-In some cases the product consisted mainly of these twins in some the twins were mixed with needles and in some the product was mostly composed of tetrahedra. Analyses detailed by one of us (Proc. Roy. SOC. Edin, 11 557) led to the conclusion that the puce-coloured precipitate is an! olxycyanide of bismuth. More recent analyses and an examination of tbe action of acids on t h i s precipitate lead us to say rather that it is a compound of bismuth oxygen carbon and nitrogen. When this precipitate is boiled with concentrated potash solution 2-3 per cent. of the bismuth iri the snbstance goes into soIution along with practically all the carbon and nitrogen. Neutralisation of the deep red liquid thus obtained produces a red-brown solid which contains bismuth carbon, nitrogen and water. Analyses of this solid have led to conflicting results ; i t does not give the reactions of a cyanide and the nitrogen and carbon are present in approximately the ratio 1 1.4 whereas in cynnogen they are present in the mticr 1 0,857. We reserve m account of the puce-coloared precipitate and of the red-brown solid until we have exsmked them more fully

ISSN:0368-1645    

DOI:10.1039/CT8895500143

出版商:RSC    

年代:1889

数据来源: RSC