CHEMICAL NEWS,

Oct. 3, 1913

Experimental.

In one of the pieces of timber from northern New South Wales a small hollow in the wood had become filled with a solid crystalline mass, the greatest thickness of which was about one-eighth of an inch, but the usual mode of occurrence appears to be in thin veins more or less distinctly crystallised in rosettes. The substance was scraped off and boiled directly in water, filtered boiling hot, the stem of the funnel being lightly plugged with cotton-wool. As the water cooled, well-defined crystals formed, which, when of sufficient size, fell to the bottom of the vessel. This procedure was repeated three or four times, by which time the crystals had become colourless and appeared to be pure. The usual method of preparation was to saw the unsound timber into small pieces, divide along the "shakes," and trim the sides with a chisel. The shavings so obtained were then heated in alcohol to dissolve the substance, filtering the alcohol through cloth. Although it is somewhat soluble in hot alcohol, yet, if this was deficient in amount, a quantity of the substance soon separated on cooling. This separated portion was, however, identical in composition with that remaining in solution, as its identity was determined by separate purification. The alcohol was partly distilled off, and the remainder evaporated down to a small bulk which formed a crystalline mass on cooling. These impure crystals were then dissolved in boiling water, a portion at a time, filtering boiling hot, and this process repeated until the crystals were pure.

The crystals as thus obtained from water were rhombic prisms or plates, and they polarised very well in colours. They were of a glistening nature, and had altogether a brilliant appearance.

The crystals were insoluble in petroleum ether, slightly soluble in ether and in benzene, somewhat soluble in hot alcohol, but not very soluble in cold alcohol. They were exceedingly soluble in chloroform and carbon tetra chloride, but from these solvents a varnish remained at first, which slowly reverted to the crystalline form after several days.

The crystals dissolved in boiling water, but not very readily, separating out again on cooling. The pure crystals required 1470 parts of cold water at 22° C. to dissolve one part of substance, and the purest crude material in the wood was only soluble I part in 1315 parts of cold water at the same temperature, indicating the comparative absence of soluble impurities associated with the crystalline deposit when in the wood.

The aqueous solution of the pure crystals was quite neutral, and did not reduce Fehling's solution, either before or after boiling in acid. An ammoniacal solution of nitrate of silver was slightly reduced on long boiling. No coloration was obtained with ferric chloride, and the usual reagents gave no precipitate, except a very slight one with basic acetate of lead. The crystals were insoluble in potash and in the alkalis generally, even on boiling, except when the solution was sufficiently dilute to act

171 like water, in which case the crystals separated unchanged on cooling.

In glacial acetic acid the crystals dissolved readily and without colour. With nitric acid they dissolved with a yellow colour forming a dinitro compound. With sulphuric acid they dissolved forming a very deep ruby or reddish brown colour, and on adding water a purple-brown precipitate separated. When heated with hydrochloric acid a dark brown amorphous substance was produced. Analyses of the crystals gave the following results:0.1872 grm. gave o'4444 grm. CO2 and o*1066 grm. H2O; C 64'74 and H 6.327 per cent. 01574 grm. gave 03740 grm. CO2 and o'093 grm. H2O; C = 64 803 and H 6'565 per cent. C12H1404 contains C 64.865 and H = 6.307 per cent The molecular weight was taken in Beckmann's apparatus using alcohol as the solvent.

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04775 grm. in 16'4 grms. alcohol increased the boiling. point, o 16°. The molecular weight calculated from this is 209. By the freezing method with acetic acid as solvent, one determination gave 228 as molecular weight, but with other trials abnormal figures were obtained; this was also the case when boiling chloroform was used as solvent.

From the results in other directions it is necessary that four atoms of oxygen at least should be present in the molecule, so that C12H1404 may be assumed to be correct. Optical Rotation. The optical rotation was taken in chloroform as this appeared to be the best solvent for the purpose.

03 grm. crystals in 10 cc. CHCl3 rotated the ray 3.7° to the right in 100 mm. tube; the specific rotation from this [D + 123°33°.

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o'6 grm. crystals in 10 cc. CHCl3 gave rotation 7.4° to the right in the same tube, showing the specific rotation to be the same for both.

03 grm. crystals was just melted in a beaker, the glassy substance dissolved in chloroform and made up to ro cc., the optical rotation was again +3.7°, so that no alteration was observed between the crystalline and amorphous conditions of the substance.

The molecule thus contains one or more asymmetric carbon atoms, which, from the known constitution of the remainder of the molecule, must be in the side-chain.

Dinitro Compound. The crystals were dissolved in nitric acid, and gently heated to start the reaction. When this was completed the addition of water gave a lemon-yellow precipitate, which, when purified, was soluble in, and crystallised from, both ether and alcohol. It was readily purified from boiling water in which it readily dissolved, but separated out again in masses of yellow felted crystals on cooling. The melting point was sharp at 128-1290, although it agglutinated some degrees below that temperature.

0.1756 of the nitro compound gave 14 cc. of nitrogen at 17° C. and 755 nm. pressure, which equals 9.14 per cent nitrogen. C12H12(NO2)2O4 contains 8.98 per cent nitrogen. It is thus shown to be a dinitro compound.

Methoxy Groups.-The ready formation of insoluble halogen compounds when the crystals were boiled in a halogen acid made the results somewhat erratic. Figures more nearly correct were obtained when acetic anhydride was added, but even then the results were not too satis. factory. The greatest amount of silver iodide obtained in six determinations only represented about one and threequarter groups of OCH3, but this, together with the formation of veratric acid on oxidation, is sufficient confirmation for two OCH3 groups in the molecule.

Hydroxyl Group.-A portion of the crystals was boiled with acetic anhydride and sodium acetate in the usual way. On the addition of water a crystalline substance separated, which, when purified from acetic acid melted at 110° C. Analysis gave results in conformity with one OH group. When saponified by boiling with standardised alcoholic potash the following results were obtained :-0.3684 grm,

boiled two hours had used o'0756 grm. KOH. 0'41 grm. boiled one hour had used 0'084 grm. KOH. C12H13(OCCH3)O would require 00781 grm. KOH in the first instance, and o 087 grm. KOH in the second. One hydroxyl group is thus indicated, and as this is not phenolic it must be in the side-chain.

Bromide. The bromide was formed by the addition of bromine water in excess to the saturated aqueous solution of the pure crystals. It was light drab in colour, and was not distinctly crystalline. When well washed and purified from ether it melted at about 100°, darkening much at about 90°, but the melting point was not sharp.

Determination of the bromine gave the following results: -0.3435 grm. gave o 2114 grm. AgBr 26.2 per cent bromine. 01554 grm. gave o'0985 AgBr = 26.9 per cent bromine. C12H13BIO4 contains 26:58 per cent bromine. One bromine atom had thus been introduced into the molecule. When the bromide was boiled in alcoholic silver nitrate, a precipitate quickly formed; the metallic silver was boiled out from this with dilute nitric acid, the residue washed, dissolved in ammonia, and precipitated again by nitric acid. The bromine atom was thus shown to have been introduced into the side-chain.

Oxidation. The crystals were dissolved in glacial acetic acid and chromic acid in the same solvent slowly added until in excess. The oxidation commenced at once with the evolution of heat, the flask was then cooled under the tap. A chromium salt, which appeared to be insoluble in glacial acetic acid, continued to form until the reaction was complete. This salt was filtered off through cloth, squeezed, and the solid cake thus obtained dissolved in water, in which it was readily soluble. The solution was then acidified, extracted with ether, and after the removal of the acetic acid a solid acid remained. This was dissolved in dilute alkali, Altered, acidified, and the solution extracted with ether. The acid thus obtained was fairly soluble in boiling water but precipitated again on cooling, so that it could be easily purified. The acid sublimed unchanged. The melting point of the sublimed acid was the same as that of the acid obtained from water; this was 180° C. (cor.). It was found to melt at identically the same temperature as a sample of pure veratric acid, nor was the melting point different when equal parts of the new acid and veratric❘ acid were mixed together. The molecular value was determined by titration and agreed very well with that of veratric acid.

When a very dilute alkaline solution of potassium permanganate was added to a large quantity of a saturated aqueous solution of the crystals the colour remained persistent for a long time; it then slowly faded with the formation of the oxide of manganese; oxidation had thus taken place. The acid formed in this way was collected, purified by sublimation, and found to melt at the same temperature and to be identical with the acid formed by oxidation with chromic acid. It was thus veratric acid.

It is apparent that oxidation of the side-chain had taken place in both instances, with the formation of dimethylprotocatechuic acid.

When oxidised with bichromate of potassium and sul phuric acid with the aid of heat, the action was too energetic, and most of the substance was destroyed by this method.

Potash Fusion.-When the crystals were heated with potash at a temperature not exceeding 200° C. for one-half hour, the colour of the melted substance had become very dark, and phenolic bodies were largely formed. The odour of creosote was most marked. The melt was dissolved in water, and the solution repeatedly agitated with ether to remove the unaltered substance. The remainder was acidified, extracted with ether, and the ether evaporated. The residue was treated with a solution of sodium carbonate, to fixed the small amount of acid formed at the same time, and this solution again extracted with ether. The phenol thus obtained had a marked creosote odour, was but little coloured, was semi-solid, and practically insoluble in water. The alcoholic solution was coloured a bluish

green to dark green with ferric chloride, indicating its relation to the catechol group.

A fresh portion of material was fused with potash between 210° and 225° C. for one hour. The action was more energetic at this temperature, with frothing and evolution of hydrogen. The melt was dissolved in water, when the creosote odour was again observed. The solution was acidified, and three-fourths distilled over, and although acid, yet the amount of free acid formed was very small indeed. The remainder was agitated with ether, the ether evaporated to dryness, the crystalline residue dissolved in sodium carbonate, and agitated with ether to remove the small amount of phenol. The alkaline solution was acidified, extracted with ether, the ether evaporated, the residue dissolved in water, and decolorised by boiling with animal charcoal. The crystals finally obtained were very soluble in water, melted at 198°, and gave all the reactions for protocatechuic acid. The yield of acid formed in this way was very good.

In am indebted to my colleague, Mr. R. T. Baker, F.L.S., the Curator, for botanical information, and to Mr. Roughley for photographs.

THE SCIENTIFIC WEEK. (From Our Own Paris Correspondent).

FLEAS CAN TRANSMIT INFECTIOUS DISEASES. The flea has already been the object not only of male. dictions but also of serious allegations. Like many other insects, it is not content with victimising human beings, but it must also inoculate them with infectious germsIn a note presented to the Academy of Sciences of Paris, M. Laveran has indicated that all kinds of fleas do not offer the same dangers. The eminent hygienist has, however, signalled most particularly the flagellant flea, which secretes in its intestine a very dangerous parasite. The flagellants also are sometimes to be met with in the dog. It results, from certain experiments made at the Pasteur Institute, by MM. Laveran and Francini, that mice have been infected by injecting into their peritoneum the con tents of these parasites diluted in a little physiological water. This had already been remarked in 1912 by Lafont, who had operated with a flagellum from the digestive tube of a bug. M. Laveran has not stated whether men or dogs could be infected by the contact of these fleas, but the effect produced upon the mouse is sufficient to make us uneasy. So let us continue to fight against this troublesome insect and to destroy it everywhere by all the means in our power.

THE CONSUMPTION OF PAPER.

Paper may be divided into three great classes-fine, high-class, ordinary paper for current uses, and paper for folding. It is certain that the consumption of the higher classes of paper is increasing, but very slowly, and this industry will always find sufficient raw material for its requirements, more especially as the scale of its prices is very elastic. The same cannot be said for the second class, that of paper for ordinary use; that is to say, paper intended for daily uses, such as newspaper editions, prospectuses, and generally speaking for all printed and written matter. It is this consumption that is continually increasing, and whose needs and demands of paper are ever becoming more and more imperious. It is in order to fulfil these requirements, considerably increased by the use of rotary printing machines, with a large output, that the stationery industry has also been obliged to create paper machines of great width and great speed, which can turn out as much as forty or fifty tons of paper in twenty four hours; it is also for this kind of paper the forests are pillaged. When there is no longer a sufficient quantity of wood to be had, with what will these papermills be fed? At that moment the only wood remaining

will be that obtainable from the annual growth of forests reserved and arranged for periodical cuttings, and the stationery industry will have to share them with other industries. M. Henry Montessus de Ballore, in his interesting technical work, tries to solve the question concerning the future resources in raw material of paper He has drawn up a list of those materials of which the cellulose could be used for the manufacture of paper.

manufacture.

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VARIABILITY OF NEBULE.

The question of the variability of the brillancy is now discussed after having been considered as certain. Astronomers are to-day apt to look upon it as doubtful, and that on account of the difficulty of conceiving the mechanism of such a variation, as much in the case of resolvable nebulæ or masses of stars as in the case of nonresolvable or purely gaseous neublæ. A nebula discovered by Hind in 1845, in the constellation of the Eagle, was considered as variable; quite recently, M. Borelly announced that at present it appears to be attaining a maximum state of brilliancy. M. Bigourdan shows that former observations do not confirm the variability. He insists on the interest of the fact noticed by M. Borelly, and on the importance just at present of the observation of the Hind Nebula, as this is just now very distinctly visible in instruments of average opening.

THE AERIAL GULF STREAM.

The Gulf Stream, when it leaves the Gulf of Mexico, enters the Atlantic with a speed of 8 kilometres an hour. It is 60 kilometres wide and 400 metres deep, and daily transports about 40 millions of milliards of calories. This enormous quantity of heat, of which it is almost impossible to obtain an exact idea, plays a fundamental rôle in the general climatology of the earth. Strangely enough it is this stream of hot water, exercising its temperate action on the coasts it waters, which is the direct cause of the existence of deserts. And this is how. Water is one of the bodies in which heat is the most easily preserved, and consequently the Gulf Stream even in high latitudes still keeps an enormous quantity of heat. The masses of air that rest on these hot waters are kept at a temperature higher than the surrounding temperature and form a veritable aërial gulf stream superposed over the marine

current. But the aërial current is not like the marine one arrested by the mass of the continents. It continues its route above Europe, abandoning, in the form of rain, the enormous masses of water it contains; it is these abundant precipitations which feed the numerous lakes of Sweden, Finland, and Northern Russia. But, on account of the rotation of the earth, the aërial current turns first to the east, then inclines towards the south. It thus constitutes masses of dry cold air which give to the plains of Russia their principal meteorological character. As it draws nearer to the Equator the current is again warmed, but remains at the same time dry and without vapour; its direction is then north-east, and it is in the state of a drying wind that it blows over the regions it crosses. It is the origin of the band of deserts of Turkestan, Arabia, Sahara, which are to be found on its return route. After having left the Continent, the aërial current, thanks to the trade-winds, links itself on again to its starting point, the Gulf Stream, thus looping its circuit after having, like everything else, done much good and much evil.

ELECTROMAGNETIC WAVES.

173

signals in the atmosphere during the day and during the The laws governing the propagation of radio-telegraphic night are still but imperfectly known, and the development of aëronautics has enabled us interesting information on this subject. The signals grow to gather some weaker as the distance increases, but one of the points to be examined is to know how the height above the ground influences this problem; in other words, are the signals the intense ionisation of the high regions of the atmosaffected by a weaker density, a lower temperature, and by phere. M. G. Lutz has given several results obtained in utilising a balloon of 1680 cubic metres, with a circumference of 45 metres. metallic wire of 100 The autenna was formed by a metres long hanging under the balloon covered a distance of 120 kilometres at an average basket. During the experiments made in the night, the altitude of 1277 metres. of the signals received decreased when the distance inIt was found that the intensity creased, but that this weakening is not proportional to the square of the distance; it varies as the power 1.96 of the distance and when far from the starting station, as the power o'88. At an equal distance it is remarked also that the signal is so much the weaker as the balloon is higher. To be more precise on this point, a second ascension was made, the balloon then rising to a height of 6500 metres. At this height, the intensity of the signals equalled what they would have had on the earth at the same distance from the station. These results are worth being confirmed and completed, for the question is still but very incompletely known, and up till now the experiments have been insufficient.

NOTICES OF BOOKS.

Studies in Valency. By F. H. LORING. London : Simpkin, Marshall, Hamilton, Kent, and Co., Ltd.

In this little book certain relations between the combining powers of the elements are shortly discussed, and some new lines of experimental work are suggested. The valencies of some of the elements which are specially interesting, such as vanadium and bismuth, are treated in detail, and a chapter is devoted to the consideration of electricity as a conditioning agent in chemical changes, and another to modern theories of atomic structure based upon experiments in molecular physics. The author has evidently carefully studied the literature of theories of valency, and he shows much skill in stating briefly the gist of an argument and ingenuity in pointing out the directions in which fruitful research may possibly be undertaken. Laboratory Methods in Agricultural Bacteriology. By F. LÖHNIS, Ph.D. Translated by WILLIAM STEVENSON, B.Sc., N.D.A., N.D.D., and J. HUNTER SMITH, B.Sc., N.D.A., N.D.D. London: Charles Griffin and Co., Ltd. 1913.

THE need of such a work as this in the English language has long been felt by agricultural teachers and students, who have found considerable difficulty in devising and satisfactorily carrying out the practical work in bacteriology which is an essential complement of the study of the theory of the subject. The technique of bacteriology is first described, and clear directions are given for preparing culture media and isolating and examining bacteria. The use of only comparatively simple apparatus is recommended, and sources of error to be avoided, and the precaution which must be adopted to ensure successful work are repeated pointed out and emphasised. The application of general methods to dairy, manure, and soil bacteriology is then described in detail. Tables are given for the identification of bacteria, and the question of laboratory equipment is shortly discussed. The book is sure to

Simplex Atomic Models. Designed by E. G. LESTER, B.Sc. Birmingham: Philip Harris and Co., Ltd. TEACHERS of chemistry will undoubtedly find that these models greatly diminish the difficulties of theoretical chemistry for the young beginner. They have the advantages of being simple and cheap, and by means of them the boys can themselves build up structural formulæ, work out equations, and illustrate the laws of chemical combination, while they should be simultaneously acquiring clear ideas of valencies, variable valencies, &c. The boxes of models contain a little stand, a number of wire links, and detachable cardboard discs (pink in the case of nonmetals, white for metals) with the symbol, valency, and atomic weight of the elements printed on them. Some blank discs are also included for use as compound radicles. With the necessary links and discs the pupil can build up Na-O. such formulæ as S &c., and it will un Na-O O' doubtedly mean much more to him than the same formula written on a blackboard. It may of course be objected that he will form some very concrete and erroneous conceptions as to valencies, but that is perhaps unavoidable, at any rate in an elementary exposition of the subject, and in the hands of a good teacher the models should be a valuable educational aid. By bending the wire links the models can be used to illustrate the arrangement in space of carbon compounds. Metropolitan Water Board.

Dr. A. C. HOUSTON.

Ninth Research Report.

By

THE ninth research report of the Metropolitan Water Board contains accounts, with tables and diagrams, of the search for pathogenic microbes in raw river water and for the typhoid bacillus in sewage. The results of the investigations show that the purification processes practised by the Board amply safeguard the health of the metropolis. The consideration of the question, "Where is the typhoid bacillus ?" appears to lead to the conclusion that its home is not so much in impure water, nor even in crude sewage, as in the "factories" of disease, as exemplified by the

"carrier" case.

OBITUARY.

DR. LOUIS MERCK.

DR. LOUIS MERCK, the head of the famous firm of E. Merck, of Darmstadt, died on September 15th after a short illness. He had been connected with the firm for over thirty years, and for twenty-five years had been its senior partner. The growth and wonderful success of the house were largely due to his foresight, energy, and enterprise, and his loss will be very severely felt.

CHEMICAL NOTICES FROM FOREIGN SOURCES.

Bulletin de la Société Chimique de France.
Vol. xiii.-xiv., No. 13, 1913.

Cryoscopy in Fused Hydrated Salts.-Ch. Lenhardt and A. Boutaric.-The melting point of a hydrated salt is lowered by the presence of a dissolved substance, and it is the same with the equilibrium temperature which is established between two solid hydrates and an excess of solution. The authors have investigated whether the cryoscopic formula of van't Hoff, K=001985 T/L, is applicable to these phenomena, and, using sodium hyposul

with 10H2O, they have found that the formula holds good. New Physico-chemical Volumetric Method. - René Dubrisay. The author has devised an acidimetric method, based upon capilliary phenomena, which is both simple and accurate. He makes use of the fact that when an oil is shaken with water centaining alkali, the drops formed remain in suspension and an emulsion is obtained. When the water is neutral or acid no emulsion is formed, but after a few moments the liquid divides into two layers. According to Tate's law, the weight of a drop of liquid which detaches itself from the extremity of a pipette is proportional to the superficial tension of the liquid. Thus if N is the number of drops corresponding to the flow of an invariable volume N=A/d, where d is the superficial tension and A is a constant. If the drops are counted when oil of vaseline flows into a solution of acid to which increasing quantities of alkali are added, and the results are expressed graphically, it will be seen that the curve has an abrupt turning point at the point of neutralisation.

Catalytic Preparation of Ketones.—A. Mailhe,— The author has repeated his experiments on the catalytic preparation of ketones, using zinc or cadmium oxides as catalysts, since his results were questioned by M. Senderens. He finds that both oxides, either alone or mixed with the metals, are good catalysts, except in the case of isobutyric and isovaleric acids, which give either very poor yields of ketone or none at all. Calcium carbonate is also a good catalyst for acids.

Nitro Derivatives of p- Phenetidine. - Frédéric nitro derivatives of p-phenetidine three only have hitherto Reverdin and Ludwik Fürstenberg.-Of the nine possible been described. By the nitration of the acyl derivatives of the base the authors have now succeeded in preparing three new compounds, viz., the 3.5-dinitro derivative, the 2.6-dinitro derivative, and the 2.3.5-trinitro derivative.

Atti della Reale Accademia dei Lincei.
Vol. xxii. [i.], No. 10, 1913.

Compounds of Monovalent Nickel.-J. Bellucci and R. Corelli.-Red solutions of nickel cyanide evolve hydrogen at the ordinary temperature, and measurements of the amount evolved show that it corresponds with that which would be generated in the change from NIX to NiX2. Iodometric determinations also show that the red solution also contains a compound of monovalent nickel.

Action of Hydroxylamine on Ketones of the Type R.CH:CH.CH:CH.COR. - R. Ciusa and G. B. Bernardis. -When hydroxylamine hydrochloride acts on the ethyl ether of cinnamilidenepyruvic acid a substance of formula C26H34O9N4, fusing at 213°, is obtained. It contains a molecule of alcohol of crystallisation, and is formed by the union of two molecules of the hydroxylamine oxime of cinnamilidenepyruvic acid, combined in such a way as to mutually saturate the double bonds. The substance C24H28Ó8N4.C2H5OH immediately gives an insoluble sodium salt when treated with sodium carbonate. It is decomposed by boiling with dilute sulphuric acid. In the original reaction a small amount of a substance of formula C26H31O8N4NO is also obtained.

NOTES AND QUERIES.

Aluminium Sulphate-A correspondent asks for a reference to a process for manufacturing al iminium sulphate from bauxite by the use of gypsum instead of sulphuric acid.

MEETINGS FOR THE WEEK.

FR DAY, 10th.-Biochemical Society, 8.30. (In the Department of
Chemical Pathology, St. Thomas's Hospital,
London).
Alchemical Society, 8.15. (At International Club,
Regent Street). Address by the Hon. President,
Prof. John Ferguson, M.A., LL.D., &c.