|
1. |
Proceedings of the Chemical Society, Vol. 17, No. 240 |
|
Proceedings of the Chemical Society, London,
Volume 17,
Issue 240,
1901,
Page 161-184
Preview
|
PDF (1645KB)
|
|
摘要:
PROCEEDINGS CHEMICATJ SOCIE'I'Y. EDITED BY THE SECZIEI'ARIES. June 20th, 1901. Professor EMERSON Se,D,, F.R.S.,REYNOLDS, President, in the Chair. Messrs. Jerdan, Blake, Eyre and Shutt were formally admitted Fellows of the Society. The following Certificates were read for the first time :-Thomas Thorne Baker, 28, Church Road, Forest Hill, S.E. ; Edwin Hobson, 3, Oxford Road, Liscard, Cheshire ; Charles Harold Johnson, Beaumont, Northcote, Melbourne, Victoria, Australia ;Edward Hall Milier, Common Hall, Hadleigh, Essex ; Herbert Simpson Newbould Trinity Hall, Cambridge ;Allan Sandford, Market Place, Ulverton. The PRESIDENTannounced that Dr. Armstrong had undertaken to deliver the Frankland Memorial Lecture on Thursday, October 31st, 1901. ADDRESS TO GLASGOW UNIVERSITY.The following Address was presented to the University of Glasgow on the occasion of the four hundred and fiftieth anniversary of its foundation :-'( The Chemical Society, as representing Chemical Science in the United Kingdom, desires to congratulate the University of Glasgom on the celebration of the Four Hundred and Fiftieth Anniversary of its foundation. 6' The Chemical Society recalls with pride the fact that Members of the University of Glasgow have been most distinguished Fellows, and 162 have contributed by their labours, some of which are among the classics of 0111-Science, to the development of chemical learning. “Thomas Graham, one of the Founders of our Society and our first Presideut, was the most illustrious of the pupils of Thomas Thomaon, whose name is hononrably connected with Chemistry as head of one of t,hc first Schools of Practical Chemistry established in this Kingdom, a school which he inangnrated within your walls.‘‘ Thomtts Anderson, an honoured name with you as n teacher, who was among the earliest to cultivate with an energy and zeal eminently characteristic the newly developed domain of Organic Chemistry, was for many years one of the most active of our Fellows. ‘(We sincerely trust that your University may continue to flourish in the future as in the past, and that its efforts to foster and promote the Science which we represent may be as successful in the years to come 2s they hoe been since the days OF Black. J.EMERSON REYNOLDS, President. WILLIAM A. TILDEN, Treasurer. JVYNDHAM It. DUNSTAN, SLEXANDER SCOTT, Secretaries.” 1CAPHAEL MELDOLA, A ballot for the election of Fellows mas held, and the following were subsequently declared duly elected :-Orrnsby Gore Adams, Guy Ashwell, Thomas Aspinall, William George Aston, Hubert Haigh Barker, Ed win Sloper Benven, Fred Bedford, Joseph Samuel Bridges, B.Sc., Arthur Crabtree, George Dean, M.A., Thomas H. J. Eling, B.A., Edward K. Hanson, E.A., Frederick Thomas Harry, Edward Horton, Christopher G. Kiddell, B.A., Robert Tabor Lattey, B.A., Adolf L. F. Lehmann, B.Sc., Ph.D., William Lowson, B.Sc., F. G. Macdonald, Daniel McLaren, B.Sc., Frank Oram, John Powell, B.Sc., John Edward Purvis, M.A., James Bertram Russell, RSc., Thomas Sandford, Samuel Edward Sheppard, Gerald T.S. Sichel, Andrew Biggam Smith, John Davidson Spence, Arnold Rowsby Tankard, George William G. Tatam, William Arthur Whitton, James Whittle, and Duncan R. Wilson, B.A. Of the following papers, those marked * were read. *105. “The direct union of carbon and hydrogen. Part 11.” ByW. A. Bone nndD. S. Jerdan. Th0 authors have already shown (T~ans.,1897, 71, 41) that carbon and hydrogen combine at 1ZOOo, forming a saturated hydrocarbon ; and also that when the electric arc is passed bettween carbon terminals 163 in an atmosphere of hydrogen, a saturated hydrocarbon is produced in addition to acetylene, the formation of each continuing until a definite equilibrium between acetylene, the saturated hydrocarbon, hydrogen, and carbon vapour is established. It was then provisionally assumed that the saturated hydrocarbon produced both at 1200’ and in the arc is methane.Further experiments have been made in which the saturated hydrocarbons in question have been separated from the large excess of hydrogen (by means of palladium), and also, in the case of the arc gases, from the acetylene simultaneously produced. Analyses of the residual saturated hydrocarbons, mixed with whatever nitrogen was contained in the original hydrogen employed, have shown that whereas the gas obtained by the direct action of hydrogen upon solid carbon at 1200’ consists of methane only, the saturated hydrocarbons produced in the arc consist of methane with one of its homologues, which further investigation has shown to be ethane.The authors are able to show further that in the arc methane and ethane are produced simultaneously, and at rates which bear n con-stant ratio to one another throughout an experiment, until ;L definite equilibrium is reached. By calculation from the results of the previous experiments, interpreted in the light of later work, the proportions between the various hydrocarbons and hydrogen when this equilibrium is attained are shown to be : Hydrogen.......................... 90 to 91 per cent. Acetylene ....................... S to 9 ,, Methane ........................... 1.25 ,, Ethane ............................ 0.25 ,, “106.“Ammonium and other imidosulphites.” By E. Divers and lid. Ogawa. The authors have already called attention to the occurrence of ammonium imidosulphite amongst the products of the decomposition of ammonium amidosulphite, and have giveu some account of the salt (P~oc.,1900, 16,113). They now separate it by dissolving it out with warm 90 per cent. alcohol, after having used 95 per cent. alcohol to extract some other crystalline matter and the red substance. By working in this way, the imidosulphite is obtained at once almost pure, requiring only to be washed with alcohol. Tt forins minute, very thin, glistening prisms, somewhat deliquescent, neutral to litmus and of mild sulphurous taste. Heated in the dry state, most of it decomposes, but a little occurs in the sublimate along with pyro- 164 sulphite.The residue left on heating it up to 150’ consistsof sulphur, sulpliate, and imidosulijliate. The salt is very soluble in water, and slowly decomposes in solution. Boiled with hydrochloric acid, it yields sulphur, sulphur dioxide, and amidosulphuric acid, the sulphur and sulphur dioxide representing, no doubt, decomposed thiosulphate, ZNH(SO,NH,), + OH, = BNH,S0,NH4 + S,O,(NH,),. Ammonium iinidosulphite gives a barium precipitate soluble in hydrochloric acid. Potassium imidosulphite and barium ammonium imidosulphite have been prepared, and are crystalline soluble salts. +lor. LL Nitriloswlphates.” By E. Divers and T. Haga. Ammonium nitrilosulphate cannot be ob tnined by the sulphonation of ammonia, for the imidosulphate which is the product of the union of sulphur trioxide with ammonia is decomposed by heat only at a very high temperature, and then is radically broken up without giving any nitrilosulphate.The sulphonation of a nitrite first into hydroximido- sulphate and then into the nitrile is therefore the only way open. The ammonium and pot,assium salts were obtained by Fremy (1845), and a potassium sodium salt, S03Na*N(S0,K),, by Raschig (1887). The ammonium salt, as it has the composition of 4NH, + 3SO,, is a very interesting salt, the existence of which had been forgotten. Sodium nitrilosulphate is so very soluble that it has not been isolated before. It can be obtained by passing sulphur dioxide into the most concentrated solution possible, containing sodium nitrite and sodium carbonate in the ratio of two molecules of the former to three of the latter salt,, until the new salt begins to crystallise out.It occurs in small, sparkling, short, thick prisms containing 5H,O, and is exceed- ingly unstable. It is neutral to litmus. By dissolving the salt in concentrated, faintly alkaline solution of barium chloride, a precipi-tate is obtained, flocculent at first, but becoming crystalline and dense, of barium or barium sodium nitrilosulphate. *lo$. 66 The decomposition of hydrocarbons at high temperatures. Preliminary note.” By W.A. Bone and D. S.Jerdan. .For some months past the authors have been studying the decorn- position of various hydrocarbons at a temperature of about 1150O.Since methane is tlie only hydrocarbon produced by the direct combina- tion of carbon and hydrogen at 120Oo, it seemed probable that any hydrocarbon would, at this temperature, be deconiposed, yielding illti- rnately carbon, hydrogen, and a small percentage of methane. So far tlie authors have only studied the decomposition of rnethnne and acetylene in detail, but the recent publication of a paper “Ueber pyrogen etische Reactionen organischer Substanzen ” by MT, Ipatiew (Bey., 1901, 34, 596), in which he announces his intention to investi- gate the decomposition of hydrocarbons at high temperatures, makes it desirable that they should publish this note. The method adopted by the authors, which will be described in det’ail in a future communication, consists in admitting tho pure hydrocarbon into a vacuous, glazed porcelain tube (length 60 cm., internal diameter 12 mm., capacity about 65 c.c.), nearly the whole length of which has been previously heated to about 1150’ in a specially designed Fletcber furnace.The experimental tube is properly jacketed so as to prevent any diffusion of furnace gases into it. The temperature, which can be maintained practically constant for several hours, was ascertained by means of a Roberts-Austen electrical pyrometer. After the gas under investigation has been subjected to the high temperature for a definite time, it is quickly pumped out into tubes over mercury. Acetytene is very rapidly decomposed at 1150’ ;after one minute not more than 10 per cent., and after five minutes only a mere trace of it remains.Considerable quantities of a saturated hydrocarbon, which subsequent examination has shown to be methane, are formed during the early stages of the decomposition, and afterwards this methane is slowly, though never completely, resolved into its elements. Neither benzene nor ethylene are formed at any stage of the decomposition, and, after the final disappearance of acetylene, the gaseous products contain hydrogen and methane only. Carbon is liberated during the early stages as ‘lamp-black,’ which doubtless arises from the rapid decomposition of the acetylene, but afterwards it is only deposited on the inner surface of the tube in a form much resembling ‘gas carbon.’ The following figures show the percentage composition of the gases obtained in a series of experiments in which the time of heating varied from 1 minute to 3 hours : Time .................. 1min.5 mins. 15 mins. la hours. 3 hours. Acetylene ............ 10.0 trace nil nil nil Methane ............ 16.0 21.5 16.0 7.75 3.0 Hydrogen ............ 74.0 88.5 S4.0 92.25 97.0 Methane is resolved into its elements at 1150’ more rapidly than would be generally supposed. The decomposition, however, only occurs at the surface of the containing tube, where the carbon is deposited in a form much resembling ‘gas carbon ’ in appearance. At no stage of the decomposition was it possible to detect the formation of acetylene, ethylene or any other unsaturated hydrocarbon.A careful examination of the gas left after 45 minutes’ heating has shown that it contains no other saturated hydrocarbon then methane. The following 166 figures indicate the percentage composition of the gas obtained at the end of 5, 15, and 30 minutes respectively, leaving out of the reckoning any small amount of nitrogen it contained : Time............... 5 15 30 minutes. Methane ......... 37.5 12.25 6.6 Hydrogen.. ....... 62.5 87-75 93.4 The authors are now completing a series of experiments on ethane, and then propose to extend the research to other typical h-ydrocarbons, and to temperatures other than 1150’. *lo9 lLMote on the sugars from cellulose.” By Henry J.H. Fenton. IDseveral previous communications (Fenton and Gostling, Trans., 1898, ’73,554; 1899, 75, 423; 1901, 79, 361, 807) it has been shown that various forms of ‘cellulose’ (such as filter paper and cotton) give considerable yields of the chloro-or bromo-derivatives of methylfurfural when they are heated with dry hydrogen chloride or bromide dissolved in an appropriate solvent. It was further shown than the formation of the bromo-derivative in any notable quantity is indicative of the presence of a ketohexose nucleus or grouping, and the existence of one or more such groupings in cellulose ’ was consequently inferred. Recent experiments indicate that the same observations apply also to the chloro-derivative.After treatment of cellulose in this manner with dry hydrogen chloride and complete removal of the methylfurfural derivative by washing repeatedly with ether, a dark brown residue is left which, in the case of filter-paper, still shows a fibrous structure and amounts to about 90 per cent. of the material taken. If this residue is digested with warm water, a solution is obtained which gives all the reactions of dexlrose. It is strongly dextrorotatory and with phenylhydraxine acetate, on heating, yields glucosacxone (m. p. 204-206’. N = 15.83, theory requiring 15.64 per cent.). On evaporating the solution to small bulk in a vacuum and adding alcohol, a syrup is at once pre- cipitated, which solidifies on standing, and the solution continues to deposit crystalline crusts after a time.Mannose appears to be excluded from the fact that phenylhydrazine gives no precipitate in the cold even after standing for several hours, Fifty grams of Swedish filter-paper mere treated in the manner above described, the solvent used being carbon tetrachloride, and the resulting chloromethylfurfural estimated by weighing the crystals. The residue was then extracted with water and the dextrose estimated by means of Fehling’s solution. The results gave chloromethylfurfural 3.1 grams, and dextrose 1.57 grams. At first sight therefore it would 167 appear that the methylfurfural derivative is produced in excess, But it is found that when dextrose is treated in the same manner, a con-siderable portion is destroyed, leaving a black residue. A blank experiment was made with 5 grams of dextrose under exactly similar conditions, with the result that the carbon tetrachloride extract weighed only 0.01 gram, and the residual sugar 2.2 grams.If it be assumed that the dextrose resulting from the action on cellulose is destroyed to a similar extent, the calculated amount of this sugar pro-duced in the first experiment mentioned would be 3.54 grams. This, it will be seen, is approximately the quantity required (3-86 grams) on the assumption that the chloromethylfurfural and dextrose are pro- duced in equal rnoleculccr proportions (144.5 :1SO). These facts appear to be of especial interest in relation to the recent work of Skraup and Kijnig (Ber., 1901, 34,1115), in which it is stated that the cellulose acetate obtained by the action of acetic anhydride and concentrated sulphuric acid on filter paper is an octoacetyl biose and that this on hydrolysis yields 'cellose,' C,,H,,O,,.A simple explanation of the results above mentioned would be afforded if it be assumed that this 'cellose '(and its antecedent) con. tains both ketohexose and aldohexose residues, so that the action of hydrogen chloride could be represented by one of the following equations : Cl,H,~O,, +HCl =C6H502C1+C6H1206+2H,O C,,H,,O,, +HCI =C6H,02C1+C6H,,0, +3H20. If the brown residue which-remains after extracting the chloromethylfurfural and sugar be dried and again treated with dry hydrogen chloride as before, a further yield of both products is obtained and experiments are being made to ascertain to what extent this treatment may be repeated, and what is the nature of the filial residue.*110. "Studies in the camphane series. Part IV." By M. 0. Forster. I1-13enxoxy-2-beitxo ylcamphene, C,H,,<I C*C0*C6H5 ,prepared by the C*0.CO*C,H, action of benzoyl chloride on the sodium derivative of camphor dis- solved in toluene, crystallises from alcohol in colourless, highly refrac- tive prisms and melts at 144'; a 4 per cent. solution in chloroform has the specific rotation [ajD= +189.7'. 1-fIyclroxy -2 -benxoylcccnzphene (enolic a -benzoy!ccinaphor), C.CO*C H C!fFI*<&()H 5, obtained by hydrolysing the foregoing substance with alcoholic potash, crystallises from alcohol in flattened octahedra and melts at S9O ;a 2 per cent.solution in chloroform gave [a],= +281*1". It dissolves in sodium carbonate, and an alcoholic solution developes immediately an intense purple coloration with ferric 1GS chloride ; cold concentrated sulphuric acid and boiling formic acid convert it into the ketonic modification, a change which also proceeds spontaneously when the substance is dissolved in organic media, the transformation into the ketone being accelerated by addition of piper-idine or by exposure to sunlight. The sodium, coppel', andferric derivn- tives are crystalline, and are freely soluble in organic liquids ; the phen~/Zu~ethanederivative melts at 117") and the acetyl derivative, which crystallises from alcohol in lustrous, rectangular plates, melts at 107".CH*CO*C'Ha-Bemoylcamphor, C8HI4< I ', produced on boiling a solu- co tion of the isomeride in formic acid, crystallises from alcohol in colour- less, transparent prisms melting at 87--8S0; a 2 per cent. solution in chloroform gave [a],= +125.0". The alcoholic solution remains in- different to ferric chloride at first, but a green colour is rapidly de- veloped, and changes ultimately to bluish-violet. Fusion converts the ketone into the enolic isomeride, and the specific rotation of a solutioii in chloroform gradually increases until [a],,= + 216O, the value to which the optical activity of the enol diminishes. *111. On the decomposition of carbon dioxide, when submitted to electric discharge at low pressures.'' By J.N. Collie, Ph.D. During some experiments that were being made on the relative resistance of carbon dioxide in a vacuum tube to the electric spark from an induction coil, it was noticed that the resistance varied con-siderably. At the same time, the colour of the incandescent gases at the negative electrode was seen to change. In order to ascertain what changes had taken place in the composition of the gas after sparking, the contents of the vacuum tube were pumped out and analysed. It was found that considerable decomposition had occurred into carbon monoxide and oxygen, 2C0, = 2CO + 0,. A series of experiments gave the following results. When carbon dioxide at 5 mm. pressure is sparked in an ordinary vacuum tube for 10 minutes, 63 per cent.of the gas is decomposed, and when sparked for 5, 3, 24, 1, and even 8 a minute as much as 55-60 per cent. decomposition occurs. In 15 seconds one experiment showed that 48 per cent, was decomposed, whilst in some others when the gas was sparked for 10 seconds at 10, 3, and 1 mm. pressure, 32, 55, and 65 per cent. respec- tively was decomposed. Most of these experiments were made with platinum electrodes. Aluminium electrodes gave a rather higher amount of decomposition, whilst with an electrodeless tube only 50 per cent. suffered decomposition after 1 minute sparking. Another interesting observation was that if the platinum electrodes 169 are allowed to become red-hot, recombination at once occurs between the carbon monoxide and oxygen till the gas which remains, instead of containing the products of decomposition of 60 to 70 per cent.of the carbon dioxide, is almost pure carbon dioxide. Under electrical strain, therefore, at low pressures, carbon dioxide is a very unstable gas, but when the products of decomposition come in contact with red-hot platinum wire recombination occurs. Carbon monoxide, even after 20 minutes’ sparking, seemed almost unchanged, and gave only a faint turbidity with baryta water. When a mixture of carbon dioxide and hydrogen is sparked at reduced pressures small quantities of a gas which seems to be methane are formed, but under no conditions could formaldehyde be detected.It is probable that the methane is formed by the action of hydrogen on carbon monoxide. *112. ‘‘Halogen derivatives of p-cymene from substituted nitro- camphanes.” By M.0. Forster and W.Robertson. The oil which accompanies the conversion of 1: l-brornonitrocam-phane into the anhydride has been identified as bromo-p-cymene [CH, :Br :C,H,P = 1:2 :41. The anhydride of 1 :1-chloronitrocamphane, prepared by dissolving that substance in cold concentrated sulphuric acid, crystallises from alcohol in colourless opaque prisms, and melts at about 230’ ; chloro-p-cymene is formed during the production of this compound. The isomeride, C,,H,,ONCi, obtained by the action of an alcoholic solution of hydrochloric acid, crystallises in transparent, six-sided plates and melts at 248’ ;it forms a benxoyl derivative which melts at 166’.The hydroxylanzino-derivative,C,,H170,N,C1, prepared from either compound by the action of alcoholic hydroxylamine, melts at 187’ ;the benxoyl compound melts at 164’. The nitro-derivative of the anhydride melting at 248O crystallises in flat prisms, which melt at 71-72”; reduction with zinc and acetic acid regenerates the anhydride. 113. (‘On a theory of chemical combination.” By G. Martin. Atoms are complex structures analogous to a benzene nucleus which in their ordinary state are incapable of acting on each other, but if by some cause the atomic ring is broken, the atoms become capable of acting together. In this state they are said to be ‘I ionised.” Chemi-cal action will only take place of its own accord when the rate of variation of ether strain experienced by a molecule, produced by the approach and recedence of neighbouring molecules, is of such a rate as to coincide with an internal rate of vibration of an atom or molecule.170 The atoms thus become ionised. The dissociation of gaseous molecules is controlled by two circumstances : (a) The gradual increase of temperature, by increasing the velocity of the atoms in the molecule, may cause it to decompose of its own accord; (6) if the rate of vibration of ether strain happens to coincide with the rate of vibration of the molecule, the dissociation mill occur long before cause ((6) of itself would cause decomposition. In dissociation the atoms need not necessarily be ionised.The rapid increase of velocity of reaction with the temperature is due to the coincidence of t’he time rates of atomic vibration and the rate of variation of ether strain. If two gaseous molecules, A and B, act on each other at (say) to, then the same reaction will also take place at higher temperatures- t” and t”’-the condition being that at t3 the rate of variation of ether strain is approximately equal in value to the rate of vibration of the atoms of the molecule. But at t” and t” the rate of variation of ether strain is respectively double or treble the rateof atomic vibration, It may happen, however, that the products of the change are incapable of existing at these temperatures. The atoms mill, however, be ionised at each of the ranges to, t”, and t”’, no matter whether any reaction takes place or not. At intermediate temperatures no reaction mill take place.In certain cases we have experimental evidence of such ranges of temperature, silicon heuachloride, Si,Cl,, for example, is stable enough at the ordinary temperature, but above 300’ its vapour begins to dissociate, and at 800’ it is entirely decomposed. If, however, ths temperature be raised rapidly above 1000’ no decomposition of the substance occurs, The substance, therefore, is stable above lOOG’ and below 350°, but will not exist at intermediate temperatures. The occurrence of these temperature ranges may be obscured by the fact that the products of the reaction may exist continuously from one range to the other. A reaction will only proceed to completion when the rate of varia-tion of ether strain necessary to cause the molecules to react together does not also induce the products of the change to decompose.Com-plete reactions occur only very seldom, as a complex molecule has so many modes of vibration that it is not difficult for it to be affected at almost any temperature. 114. ‘‘ On the occurrence of paraffins in the leaf of tobacco.” By T. E. Thorpe, C.B., F.R.S.,and J. Holmes. In connection with the workidg of the Revenue Act, which imposes a limit upon the amount of oil which may be present in manufactured tobacco, the authors have had occasion to study the nature of the material which is extracted from tobacco by ‘petroleum-ether.’ In the extract thus obtained, they have discovered the presence of two paraffins, hentriucontane, C31H64,melting at 67.8-68.5”, and heptaco-sane, C243&, melting at 59*3-59*8”, which are present in the leaf in about equal amounts to the extent, in the aggregate, of rather more than 1 part per 1000. In Kentucky and Virginia leaf, the mixed hydrocarbons, in three separate preparations, had the following melting points :western leaf, 63.0-63*S0 ; ‘‘wrappers,” 63-5-64*0° ; ‘(fillers,” 63*7-65*0°.The authors are of opinion that the snow-white substance of satiny lustre extracted from Kentucky tobacco by Kissling (Ber,..,1883, 16,2432), which he found to melt at 63.0° and which he regarded as probably an impure mellissyl mellisate, and the substance of similar appearance found by him among the constituents of tobacco-smoke, melting at 64*5O, but which he regarded as a hydrocarbon, are in reality the same products, and identical with the mixture of the two paraffins, the and hentriacontane, C31H64,heptacosane, C27HS6, of Krafft, which the authors have found to be present in all the American tobaccos ex-amined by them. 115.61Twonew substances in lemon oil.” By H.E.Burgess. If 3 or 4 litres of the terpenes obtained during the distillation of the lemon oil are well shaken with a cold solution of sodium metabisul- phite, a small quantity of a crystalline compound is formed which can be separated and washed with alcohol and ether.This on being de- composed in the usual way gives an aldehyde of which the constants are very different from those of citral :-boiling point, 80-85O at 15 mm. ;optical rotation, +Oo.30’; refractive index, 1.4314 at 20’. It has an odour resembling cocoanut oil. On shaking the aldehyde with hydrogen peroxide and caustic soda solution it is at once poly-merised into a solid form which can be recrystallised from alcohol. It forms an oxime melting at 35”, and on oxidation with potassium permanganate it gives an oily acid; from the ammonium salt the silver, copper, and magnesium salts have been prepared and analysed. Apparently the same aldehyde exists in orange oil, but was not found in the terpenes as in the case of lemon oil. A crystalline substance was obtained by shaking together one litre each of acetone and lemon oil and then adding about 200 C.C.of water, when it separates into two layers ;the lower portion was separated and allowed to stand for 24 hours, when small crystals were formed in the globules of oil floating on the surface; these were filtered off and recrgstallised from ,zlcohol and ether. Several such separations may be made from each quantity of oil, 172 but the total yield from one litre was extremely small, The crystals so obtained melted at 145'. They are sparingly soluble in alcohol, the solution having a marked blue fluorescence. Several combustions have been made of the recrystallised substance which forms a crystalline dibroniide and is oxidised to oxalic acid and .carbonic acid. 116. '' Preparation and properties of 2 : 6-diketo-44sopropylhexa-methylene (2 :6-dihydroxy-4-isopropyldihydroresorcinol)." By A. W.Crossley. Ethyl 3 : 6-diketo-4-isop~opyZhexanaetl~yZene-3-cnrboxyZ~te,obtained by the condensation of isobutylideneacetone and ethyl malonate, separates from a mixture of benzene and light petroleum in small needles melt- ing at 101'. When boiled with sodium carbonate or potassium hydroxide solution it yields : 2 :6-Diketo-4-iso~o~yIhexc~methylene, CH *COc3g7C<CHz. CO>CH,, which crystallises from dilute alcohol, with 1H,O, in well formed needles melting at 67.5'. Its constitution is proved by its method of formation and because on oxidation with sodium hypobromite it yields p-iso-propylgiutaric acid.The silver salt is an insoluble white precipitate and the dioxinze separates from dilute methyl alcohol in clusters of stumpy needles melting somewhat indefinitely about 145'. When hydrolysed with barium hydroxide diketoisopropylhexa- methylene is converted quantitatively into /3-isopo~~yZ-y-acetyZbutyric acid, "3H7C<",2:~4~H; which is an almost colourless oil boiling at 195' (39 mm.). 117.(' Action of bromine on the three toluene azophenols." By J. T. Hewitt and J. N.Tervet. In continuation of the work of one of the authors and his pupils on the substitution of oxyazo-compounds, the bromination of the three tolueneazophenols has now been studied. In glacial acetic acid solution, sodium acetate being present, toluene azodibromophenols result in all these cases, the reactions being quite analogous to those observed with phenol itself.Metatolueneazophenol brominates smoothly only if the solution in acetic acid is well cooled whilst the bromine is added. The following substances have been prepared : o-toluenec6xodi-bromoplienol, m. p. 121' ; ethyl ether, m. p. 95' ; ncetgZ derivative, m. p. 153' ; benzoyl derivative, m. p. 169' ; m-toluenecczocEibronao~~~noZ, m.p. 129'; ethyl ether, in. p. 8s'; met$ derivative, m, p. 11s'; benzoyl 173 derivative, m. p. 141' ; p-tolueneaxopl~enol, m. p. 137'; ethyl ether, m. p. 95' ; acetyl derivative, m. p. 14s' ;benxoyl derivative, m. p. 114'. 118. "Reduction of ay-dibenzoylpropane and dibenzoyldiphenyl-butadiene." By F.R.Japp, F.R.S., and A.C. Michie, B.Sc. By the action of sodium on an ethereal solution of ay-dibenzoyl-propane, C,H, -CO*CH,*CH,* CH,*CO* CGH,, floating on water, J. IVislicenus and Kuhn (Annalen, lS98, 302, 221) obtained a "pale yellow oil " which they regard as the cyclic pinacone, 1 :2-tliphelnyl-1 : 2 CGHs*$J(OH) *CH, >CH,.dihydyoxyc yclopentane, C,H5 C(OH)*CH2 The present authors show that this oil is, in reality, a very complex mixture. The pina- cone, which when pure forms colourless needles showing oblique extinction and melting at 103-104.5°, is contained in it to the extent of about 50 per cent. From glacial acetic acid the pinacone is deposited in large, sparingly soluble crystals of the formula C,7H,,0,,C,H40,, in which form it %may be separated from the other substances present.A quantitative yield of it may be obtained by the reduction of dibenzoylpropane in hot aqueous alcoholic solution with aluminium amalgam. Oxidised with chromium trioxide, it regenerates dibenzoylpropane. In addition to the pinacone, the "pale yellow oil " contains, along with other substances, a small quantity of a€-diphenyl-sedihgdroxypentane, C,H,*CH(OH)*CH,-CH,.CH,*CH(OH).C,H,, lustrous, slender, six-sided prisms showing straight extir-ction and melting at 84-88' to a turbid liquid which clears at 92'. A better although still unsatisfactory yield of the latter substance is obtained by reducing dibenzoylpropane in boiling alcoholic solution with sodium.By reducing the "pale yellow oil" with hydriodic acid, Wisli- cenus and Kuhn prepared a hydrocarbon melting at 108' to which they assign the constitution of a 1:2-diphenylcyclopewtane. The authors find that this supposed 1:2-diphenylcyclopentane is a highly polymerised substance which does not boil even at 340' under a pressure of 12 mm., whereas the known 1:2-diphenylcyclopentane (m, p. 47") obtained from anhydracetonebenzil (Japp and Burton, Frccns., 1887, 51, 423; Japp and Lander, ibid., 1897, 71, 128 and 131)) the existence of which has been overlooked by Wislicenus and Kuhn, boils at 189' under a pressure OF 13 mm. The authors give a further proof of the constitution of the latter 1 : 2-diphenylcyclo-pentane by oxidising it to ay-dibenzoylpropane.J. \Vislicer,us and Lehmnnn (Annaleiz, 1898, 302, 214)) by reducing dibenzoyldiphenylbutadiene with hydriodic acid, obtain, along with other products, a substance melting at 92-94' to which they assign the formula C,,H,,O. The authors find that this compound has in reality the formula C,,HIBO, and is 2 : 3 :~-tri~~l~enylfiL?~ui.c~n(Japp and Klingemann, Trans., 1890, 67, 663), and that ncetophenone is simultaneously formed, the reaction taking place as follows : a@.Diben zoylph enylcthylene. 0 For the sake of simplicity, the symmetrical formula for dibenzojl-diphenylbutadiene has been employed; but the validity of the ex-planation is quite independent of this. The various papers on the condensations of benzil with ketones published by one of the authors, conjointly with others, have, with one exception, been overlooked by J. Wislicenus and his pupils, and the errors into which they have fallen are in part attributable to this cause.119. ''Hornologues of anhydracetonebenzil." By F. R. Japp, F.R.S., and A. N.Meldrum, B.Sc. The authors find that under the influence of potassium hydroxide benzil condenses with homologues of acetone of the general formulz CH2R*CO*CH,, CHR2*CO*CH,, C€€,R*CO*CH,R,and CHR,*CO*CH,R, t.0 form homologues of anhy dracetonebenzil (di~l~enyZcyclopentenoZo?~e), a C6H5*y= CH>CO. In naming t'hese compounds the CH groupC,H,*C(OH)*CH, B in the pentacarbon ring is distinguished as the a-and the CH2 group tts the P-position.Thus benzil and methjl ethyl ketone yield a-methyl-c6nhyd~acotonebenziZ, C0H5*9=C(CH3)>C0 (large, flat, lozenge-C,H,-C(OH)*CH, shaped crystals melting at 11So), and P-methylanhydracetoneben;;il, c,H 7-----CH>CO (prisms, melting at 180°)-the latterC,H,* C(OH)*CH(CH,) ttlready prepared by Japp and Burton (5!'~ans.,1SS7,51, 431)-whiist at the same time an open-chain compound, clesylene-methyl ethyl Letoi~e, U,H,-$:: CH*COOC2H, (m. \pa 157"), is formed. The latter SubStailce C,H,* CO is more readily obtained by boiling P-niethylnnhydracetonebenzilwith I75 glacial acetic acid, and, on the other hand, is reconverted into the P-compound by heating at 300-320°. The authors show that the sparingly soluble monalkyl homologues of anhydracetonebenzil prepared by Japp and Burton by heating a mixture of benzil and homologues of acetone with aqueous potassium hydroxide, belong to the @-series, and that readily soluble a-isomerides, overlooked by these authors, are formed in small quantity at the same time. By using cold alcoholic potassium hydroxide as a condensing agent, the a-compounds may be obtained in larger quantity.All the a-compounds are distinguished by forming benzylidene derivatives when treated wit'h benzaldehyde and alcoholic potassium hydroxide. With benzil and alcoholic potassium hydroxide, a-methylanhydr- acetonebenzil yields a-methylanhydracetonedibenxil, C,,H,,O, (dimorph-ous : silky needles, m. p. 185O ; and warty crystals, m. p.194O), which is obtained in the form of a complex potassium salt, The sodium salt may be obtainedC,,H250,K,C,2H2,0,,4C2H5*OH. directly from benzil and methyl ethyl ketone by condensation with alcoholic sodium ethoxide. a-Methylanhydracetonedibenzil is ethylated by boiling it with alcohol and sulphuric acid, yielding the compound C',,H,,(OC',H,)O, (short needles, melting at 250'). Both a- and P-methylanhydracetonebenzil are transformed, by brief boiling with hydriodic acid, into the same methyldipheiaylcyclopentenone, C,H,*E*CH(CH,) >CO (faint yellow, oblique, flat prisms or plates,C,H,*C--CH, rn: p. 77-'7S0), which yields a phenylhydi*azone, C,,H,,N,, melting at 145-152'. By boiling a-methylanhydracetonebenzil for 5 hours with hydriodic acid and red phosphorus, the methyldiphenylcyclo- pentenone, which is first formed, is in its turn reduced to 1-methyl-2 :3-C,H,*$23 CHICH,)diphenylcyclopentane, C,H,* CH-C H,>CH, (EL p.62-63')? already obtained by Japp and Murray (T~ans., 1897, 71, 153) by the reduction of a-anhydrobenzillmwlic acid, the carboxyl group being eliminated in the latter case. By boiling with slightly diluted sulphuric acid, or with glacial acetic acid, a-m e thy].an hy drace t'one ben zil yields a dehydration product, C,,H2,0, (m. p. 230°, with evolution of gas). P-Methylanhydracetone-benzil, when heated with formic acid, gives the same product. In addition to the foregoing, the following compoands have been prepared : Benxyliclene-a -methyZanI~ydracetonebe?zxil, m.p. 2.25' ; a-desylene-ethyl ethyl keione, CGH5*C):C(CH3)*C0*C2H5, m. p. 128",C,H;CO converted, on heating, into ap-dirnethylanhydracetonebenzil,m. p. 150"; PP-dimethyl~nl~ydTacetonebe~a~~l,m. p. 18l0; a-ethylnnhpdr-acetonebenxil, m. p. 114O, and its benxylidene derivative, m. p. 17S0 a~P-trinzethy2c~r~~~yclrciceto?ze6enxiZ7p. 131’ ; a-~)g’o~’ylu?zh?/dracetone-m. benxil, m. p. 89O, and its beneylidene derivative, m. p. 166’; p-propyl-ccnhydracetonebenzil, m. p. 152O ;a~-diethylanhpdw~cetonebenzil,m. p. 113-1 14’ ;a-amyZc~al~~drtl.cetonebenxi1,m. p. 57”, and its benzylidene derivative, m. p. 156’. A11 P-monalkylanhydracetonebenzils corresponding with these a-coin- pounds, but not included in the foregoing list, have been already described by Japp and Burton (loc.cit.). The oxidation products of the various methylanbydracetonebenzils are at present under investigation. 120. ‘‘Formation of carbazoles : a preliminary note.” By FTR. Japp, F.R.S., and W. Maitland, B.Sc. The fact that; P-phenanthrol (phenccnthrone), yBH4’pC,H,*C.OH ’ interacts, apparently in the keto-form, YGH4*yH’ with phenylhydrazine,C,H,*CO ’ eliminating simulta,neously water and ammonia, and yielding 2’ :3’-di-CFH4*C--/\ phenyleneindole (phenyl-p-~)he?znnths.~lcai.baxole),6H .8\/\/’1 I as NH in E. Fischer’s synthesis of indoles (compare Japp and Findlay, Trans., 1597, 71,1117), led the authors to try whether P-naphthol, which P-phenanthrol in many respects resembles, would behave in an analogous manner.On heating /3-naphthol with excess of phenyl-hydrazine there was no reaction, but on adding to the mixture some phenylhydrazine hydrochloride and continuing the heating, water and ammonia were evolved, and a fair yield of a pl~enyZ-P-nc~phthylcccrbaxole, FGH4->NH (needles melting at 134-1 35O), was obtained. The CWH6 reaction does not take place when ,%naphthol is heated with phenyl- hydrazine hydrochloride alone. The following derivatives of this carbazole were prepared and anaIysed : nitroso-derivative, yellow flat needles, m. p. 144-145O (with decomposition) ; cccetyl derivative, small pearly laminae, m. p. 149O ;benxoyl derivative, slender needles, m. p. 1S9.5’. Two pheny I-P-naplithylcarbazoles-the number predicted by theory-are already known : one melting at 330’, isolated by Graebe and Knecht from coal-tar and afterwards synthesised by them by passing the vaponr of phenyl-P-naphthylamine through a red-hot tube (Annnlen, 1880, 202,l) ;and a second obtained by Schijpff (Ber., 1896,29,269) by elimination of carbon dioxide from phen yl-P-naphthylcarbazolecarboxylic 1'77 acid, and asserted by him to melt at 120".The melting points of the derivatives are given by Schopff as follows : ?zitroso-derivative, 132' ; acetyl derivative, 142' ; benaoyl derivative, 170'. With the exception, however, of these very considerable differences in the melting points, the descriptions given by Schopff of his compounds would apply to those prepared by the authors ; moreover, various colour reactions which he mentions are the same in both cases.The authors, therefore, prepared Schopff's phenyl-P-naph thylcarbazole by his method, and found that it melted at 154-135' (instead of at 120°, as stated by him) and was absolutely indistinguishable from their compound. As the yield by Schiipff's method is very poor, they did not trouble to pre- pare the derivatives over again from substances obtained in this way; but they have no doubt that similar errors in the determination of the melting points have been committed by the German investigator in the case of these also. Schopff obtained his phenyl-P-naphthylcarbazolecarboxylic acid by heating 3-hydroxy-P-naphthoic acid (m. p. 2 16") with phenylhydrazine, a reaction which would correspond with that described ,by the authors, except that this so-called hydroxynaphthoic acid is the keto-form CHrJ dihydro-2-keto-3-naphthoicacid, /\/\CO , and that the1 \/\/ICO,H1 dition of phenylhydrazine hydrochloride is unnecessary.a-Naphthol, when heated with the mixture of phenylhydrazine and its hydrochloride, yielded phenyZ~-a-nap?~thyZcarbaxoZe(m. p. 225.5'), already obtained by Kym (Bey., 1890, 23,2465) by desulphurising thiophenyl-a-nsphthylamine with finely divided copper. The present reaction does not take place so readily as with P-naphthol, and the yield is small. The authors are engaged in extending this reaction to other phenols and to other arylhydrazines in presence of their hydrochlorides.121. L6 Metal-ammonia compounds in aqueous solution. Part 111, Solutions of salts of the alkaline earth metals." By H. M. Dawson and J. HcCrae. The distribution of ammonia between solutions of salts of the alkaline earth metals and chloroform has been determined at 20°, and the results obtained indicate that the calcium ions form complex ammonia ions to a slight extent in solution, whilst the strontium ion possesses the power of fixing ammonia in a less degree, and the barium ion has the lowest power, 178 122. ‘(Metal-ammonia compounds in aqueous solution. Part IV. The influence of temperature on the dissociation of cupri-ammonia sulphate.” By H. N.Dawson and J. McCrae. The distribution of ammonia between water and chloroform and between aqueous copper sulphate and chloroform has been determined at 10’ and 30’.The results indicate that the copper sulphate fixes more ammonia at the lower than at the higher temperature ; but no exact quantitative statement can be made as to the influence of tem-perature on the dissociation of the compound Cu4NH3*S0,,since within the limits of temperature at which the experiments were made this influence is very small. The same relat,ionship between ammonia concentration and dis- tribution coefficient has been found at 10’ and 30’ as that previously observed at 20’ (Tmns., 1901, 79, 496). 123. LL On the combined action of diastase and yeast on starch-granules.” By G. H. Morris, Ph.D. When yeast is allowed to act on a solution of starch-conversion products in the presence of active diastase, the quantity of matter fermented is greatly in excess of that which can be fermented by the yeast alone; and when active diastase and yeast are allowed to act conjointly on the so-called stable-dextrin, which under ordinary con- ditions is neither degradable by diastase nor fermentable by yeast it is entirely fermented.It is now shown that a similar action takes place when certain ungelatinised starch-granules are submitted to the joint action of malt-extract and yeast, the quantity of starch decomposed by the joint action being about three times that dissolved by malt-extract alone. The increased action in the presence of yeast is not due to the removal of the soluble product, maltose, from the field of action, and the consequent greater activity of the diastase.No increased diastatic action takes place in the presence of yeast if the fermentative power of the latter is checked by chloroform, neither does any increase of action take place when the malt-extract is submitted to fermentation, and the yeast-cells removed, before the addition of the starch-granules. Precipitated diastase behaves in the same way as cold water malt- extract, but to a lesser extent. The combined action of diastase and yeast only occurs with those starches which are attacked in the ungelatinised form by diastase, such as barley or malt starch. The granules of potato starch are not acted on by diastase even in the presence of yeast.124. ‘‘A calibrating mercury pipette.’’ By C. A.Bell, M.B. The little device figured in the diagram will be found very useful in calibrabions of all kinds. It is easily constructed on any scale; t,he volume of mercury delivered by it is for all practical purposes constant, and the time saved by its use is considerable. The mercury reservoir, A, is made from a piece of soft German or soft Jena tubing, of moderate wall thickness and free from internal flaws. At the lower end it is drawn out to a narrow tube terminating in an orifice about 0.4 mm. in diameter. The edge of this orifice may be slightly fused, but not so as to invert it. At its upper end, A is drawn out to a very fine capillary tube, which should be of such diameter at its riarrowest section that a pressure of cct Zeccst 15 cm.of mercury is re- quired to drive the metal through it. A short tube of such narrow bore is not easily prepared in an ordinary blow-pipe or Bunsen flame; the final drawing may, however, be easily effected in the outer mantle of a candle-flame, as in preparing a Lippmann’s capillary electrometer. The little tube so formed should be cut at such a point that the diameter of tho portion left on A (from 1 to 1.5 cm. in length) diminishes continuously from A to the end. A constantly increasing pressure is then required to drive mercury nearer and nearer to the orifice. The reservoir A thus prepared is cemented, as shown, air- tight into a somewhat wider tube, B, which is drawn out at its upper end so that an india-rubber tube may be attached to it.The cement used may be sealing-wax; but if B is just, wide enough to receive A, a much neater joint may be made with fused silver chloride. A little of the chloride is melted in a porcelain crucible and the well heated end of B dipped into it repeatedly until a sufficient quantity of the chloride has been collected. That which adheres to the inner surface of B is removed with a penknife ; the previously warmed end of A is then passed into B,and the two tubes heated together high above a Bunsen flame, to avoid reduction of the silver, until the chloride melts. When prepared in this way, the pipette may be heated and dried by a current of air, if necessary, without disconnecting A nncl B.To use the pipette, an india-rubber tube of some length is slipped over the narrow end of B,and secured air-tight Toy a few turns of soft copper wire, the ends of the wire being left loose. The point of the pipette is then plunged well below the surface of mercury contained in a bottle or basin, and suction applied uut’il the metal rises to within n couple of millimetres of the capillary orifice. If the capillary tube has been properly formed, it can, without the slightest difficulty, 180 be brought to any desired level which may be maiked on the outside of R;but generally it is sufficient to bring it within a short distance of the orifice. A rather coarse capillary measured by a microscope micrometer was found to have, at the orifice, a diameter of 0.008 cm.The capacity of a tube of this diameter is only 0*00005C.C. per centi- metre of length, so that a variation in the level of a milliwetre either way is of small importance. The filling having been accomplished, the rubber tube is pinched ; the pipette may then be lifted and carried about without the loss of a particle of mercury, so long as it is held in a nearly vertical position. Inclining it, however, by increasing the effective pressure on the cap- illary, may cause mercury to pass from A to B. This is much less likely to happen when in the process of filling the mercury has not been drawn right up to the orifice ; the pressure may then increase or diminish considerably without causing the escape of mercury from either end of A.In discharging the pipette, the pressure of the fingers on the rubber tube having been released, the mercury is allowed to trickle gently down the side of the tube or vessel to be calibrated. Usually a short thread of met.al remains in the lower prolongation of A ; this is best removed by pinching the rubber tube near its open end with the fingers of the hand holding the pipette, and compressing it about its centre with the other hand. It is not advisable to blow into B, as in the course of a calibration moisture from the breath may find its way into A, causing the formation of air bubbles within it. As air bubbles never form in A when the mercury entering it is dry and free from surface impurities, any sensible variation in the volume delivered at constant temperature can be due only to vari- ations in the point at which disruption occurs in the mercury when the pipette is raised.These, however, are exceedingly small. In a series of tests with a pipette holding about 17 grams of mercury, and having an outflow orifice 0.05 cm. in diameter, the weight of mercury delivered was constant within 0.0005 gram, or in volume 0*00004C.C. By making the outflow orifice very small, still greater constancy can be secured ;but the time occupied in charging and emptying is then greatly increaeed. In conducting a test of this kind, of course, the temperature of the mercury must be carefully observed. Mercury contained in a bottle or jar can never be assumed to be at room temperature, and +lien poured into a basin its temperature may alter rapidly from a variety of causes.Sometimes a small globule of metal sticks very persistently in the lower constricted part of A. Such a globule can usually be rinsed out by sucking back a little of the metal already delivered, especially if the part of the tube containing it has been previously warmed. 181 The advantages of this pipette over Bunsen's well-known cnlibra- ting device are obvious, The quantity of mercury required for any calibration is a minimum; the metal need never be touched by the fingers ; and as surface impurities are excluded by the pipette, which acts as a filter, the mercury delivered by it is always bright and clean, and lies in perfect contact with the mall of the receiving vessel.125. L'a-Amido-p-methylhydrindene." By F. S. Kipping and G. Clarke. The authors have prepared a -amido -p-methylhydrindene, C6H4<:E$E7F>, in order to study the salts obtained by com- - . bining it with various optically active acids, and thus perhaps to elucidate the curious behaviour of its lower homologue hydrindamine (Kipping, Trans., 1900, 77,S61 ; and Kipping and HiLli, Trcms., 1901, 79,442). /3-Methylhydrindone, C,H,<:E?>CH*Me, is easily obtained by the action of aluminium chloride on a-methylhydrocinnamic chloride, ring formation taking place with the elimination of hydrogen chloride (compare Kipping, Tmns., 1894, 65, 6SO; Kipping and Hill, Trans., 1899, 35, 144 ; and Kipping and Hunter, Tkans., 1901, 79, 604).This niethocl gives much better results than the treatment of the acid with concentrated sulphuric acid (von Miller and Rhode, Ber., 1890, 23, ISSS), the yield being from 70 to 80 per cent. of the theoretical. P-MetTuJ-a-h ydrindoxinze crys tallises in well-de6 ned octahedra me1 t-ing atabout 103". The base, of which the formula is given above, is obtained by reducing the oxime with sodium amalgam in dilute acetic acid solution. It resembles hydrindamine in general properties. Since a-amido-P-methylhydrindenecontains two asymmetric carbon groups, it should consist of four optically different forms, and when combined with optically inactive acids it might be expected to give rise to two series of salts.As a matter of fact, on fractionally crystallising the Iqdrochloride of the original base from water, it is resolved into a sparingly soIuble salt which forme long, silky needles decomposing at about 252O, and a readily soluble salt which is obtained in small, ill-defined nodular masses decomposing at about 325". The two hydrochlorides are probably the salts OF the two externally compensated ( If Iand -I--) bases, but the more readily soluble one --t may not be quite free from its isomeride. The sparingly soluble salt gives a pkatinichloride, (C,,H,,N),,H,PtCI, + 2H,O, which crystallises 182 from water in IUS~~OUB,yellow plates decomposing at about 192O, whilst the readily soluble isomeride gives a platinicido~ide, (C,, H,,N),,H,PtCI,, wliich is anhydrous, and decomposes at about 202O.The benxoyl derivative prepared from the sparingly soluble hydro- chloride crystallises in silky needles melting at 169", whereas the corresponding compound, obtained from the readily soluble bydro- chloride, melts at about 138". The suZphate of the original base crystallises iii large transparent prisms, and does not seem to be resolved into different products when fractionally c&stallised from water. The investigation of these bases is being continued. 126. ''Stereoisomeric a-and a'-sulphonic derivatives of camphor." By H. E. Armstrong and T. M.Lowry. The authors have further examined Reychler's camphorsulphonic acid, prepared by sulphonating camphor by means of a mixture of sulphuric acid and acetic anhydride ;they have also prepared corresponding acids from chloro- and bromo-camphor which are reducible to Reychler's acid.They confirm Iteychler's observation that two cnmphorsulphon- amides arc formed by the action of ammonia on the sulpliochloride, and shorn that this is not due to any want of homogeneity in the latter, but to the occurrence of isomeric change during the interaction. Reychler's camphorsulphonic acid is probably an a-acid, the sulpho- group occupying the same position as the bromine atom in a-bromo- camphor. When the sulphochloride or sulphobromide is acted on with dilute ammonia the action proceeds normally, only the a-sulphonamide, m.p. 223O, being produced; the isomeric a'-sulphonamide, m. p. 132O, is formed when strong arnmonia is used and the action is allowed to proceed violently; it is a labile substance, and is readily converted into the stable a-sulphonamide by the action of bromine or of mineral acids. Cc~~~~~~i~o~~-cC-Sulpi~obi.o~~ide,m. p. 93", [a], +26'. Cnmplm-a sulpho-p-b~omoccnilide,m. p. 165'' [.ID +56". C~cLnL~)1~o,.suZi/~o~iperidide,rn. p. 140", [..IL, +32.2", is the chief product of the action of piperidine on the sulphochloride, but a more soluble pipei*icZide, m. p. 55", [a], +33*6O,is also produced. a-BroniocciPiz~~hor-a'-suZl,honicacid is readily isolated in the form of the cdcizcvz salt, (C,,H,,SO,),Cn +6H,O ; this crystallises from hot water in pearly scales. The sul$,ochZoride, m.p. 65", [ajD +104O, yields a single szdpl~o~zr~niicle,m. p. 15G", [a],) +10Go,wliich is reduced by zinc dust and acetic acid to cai33pho~-a'-sulyhonamide. The suZphoanilicZe, ni. p. 106O, [a], +lr'i", is reduced to camphor-a-sulphoanilide. The 183 sulphopiperidide, m. p. 123O, [.ID +11l0,is reduced to the camphor- sulphopiperidide melting at 140". has m.a-C?~lol.ocnmp~~or-a'-su~~J~ochloride p. 60°, [.ID + 81". The sulphonumide, m. p. 141") [a],+ S3O, is reduced to camphor-a-sulphon- amide. When a-bromocamphor-a'-sulphonamide is boiled with acetic anhydride it is converted into an anI&Z&Ze,C11,Hl,BrS02N, m. p. 186", [.ID + 98", CBr-70,to which the formula C,H,,<&=IN , may perhaps be assigned ; it is reduced by zinc dust and acetic acid to camphor-a-sulphon-amide. By the action of bromine on camphor-sulphonamide or of bromhydric acid on a-bromocamphor-a'-sulphonamide,the stweoisorneric anhydride of a'-bromocamphor-a-sulphonamide, m.p. 166O, LaID + 41°, is also produced. By the further action of bromine these are converted into the anhydride, C,,H, 3Br2S0,N, of a dibromocccmpho~sulp~~on~mide, m. p. 195') [a], -7", which on reduction yields camphor-a-sulphon- amide. m.The anhydride of a-chlo~~ocam~l~or-a'-suIp?~onammidep. 167", [a], + 60°, yields camphor-a-snlphonamide on reduction. An anJLydds, C,,H,,Cl,SO,N, of a dichlorocccnaiviio1'su~Jio9Lnnaid6may be prepared by the action of chlorine on camphorsulphonarnide, chloro- camphorsulphonamide, or its anhydride ; m.p. 172", [aID + 4", on reduction this yields camphor-a-sulphonamide. 127. (6 Displacement of alkyls from phenols by nitration. I. Thymol." By A. T. Larter. Maldotti, in a recent note (Gaxxetta, 1900, 30, ii, 365), states that trinitrothymol is formed on nitrating dinitrothymol ; he was unable to analyse the product, and bases his statement solely on molecular weight determinations made by the cryoscopic method. This conclu-sion is in opposition to the result arrived at by Armstrong and Rennie (Chenz. News,1883, 47, 115)) who found that the socalled trinitro- thyniol was in reality trinitrometacresol. The author has repeated the experiments at Dr. Armstrong's re-quest, and his results confirm the conclusion arrived at by Armstrong and Rennie.The melting point of the product from thymol is the same as that of trinitrometacresol, and is unaffected when the substance is mixed with the trinitro-compound prepared from metacresol. On methyla-tion, the product affords an ether identical with that prepared from trinitrometacresol, the two substances melting at 91", whether singly or in admixture, and giving the same trinitrometatoluidine (m, p. 136') when subjected to the action of ammonia. 184 When dinitrothymol ethyl ether is subjected to nitration, it is con-verted into trinitrometacresol ethyl ether-an observation of import- ance as proving that the displacement of the alkyl does not involve the formation at an intermediate stage of a keto-compound. 128.‘(Taka-diastase and reversed ferment action.” By A. C. Hill, The hydrolysis of dilute starch solutions by taka-diastase ends in an almost complete transformation to glucose, as shown by the combined polarimetric and copper reduction methods of estimation ; no dextrin which resists further hydrolysis is formed, and there is sufficient maltase in commercial taka-diastase to convert all the maltose to glucose. A solution containing 35 per cent. of glucose and 6 per cent. of maltose hydrate, that is, 41 per cent. of total sugar, on treatment by taka- diastase containing maltase, was further hydrolysed until the measure- ments indicated nearly 39 per cent. of glucose and about 2 per cent. of maltose hydrate.A 60 per cent. solution OF glucose, however, similarly treated, showed a reversed ferment action until its optical and reduc- ing properties corresponded with those of a solution containing 58 per cent. of glucose and 2 per cent. of maltose hydrate. On diluting the solution without boiling, hydrolysis again took place. The difference in equilibrium point in this case from that found by the author when acting on concentrated glucose solutions with yeast extract (Tyans., 1898, 73, 631) (in the latter case the rneasiirements at equilibrium corresponded to a mixture of 34 per cent. of glucose and 6 per cent. of maltose hydrate) is probably to be explained by the presence in the yeast extract of enzymes other than maltase and diastase, whereby other polysaccharides are formed either from glucose or maltose, such ferment actions being quite distinct from a possible formation of higher polysaccharides from maltose, which may occur also in the case of taka-diastase. LIBRARY. The Library will be closed for stock-taking during the first fortnight of August. Fellows are pnrticularly requested to return all Library books in their possession not later than July 27th.
ISSN:0369-8718
DOI:10.1039/PL9011700161
出版商:RSC
年代:1901
数据来源: RSC
|
|