NOTICES OF PAPERS CONTAINED IN THE FOREIGN JOURNALS. BY HENRYWATTS,B.A. F.C.S. On the presence of Lead Copper and Silver in Sea-Water and on the existence of the latter in Plants and Animals. By MM. Malaguti Durocher and Sarzeaud.* The existence of silver in sea-water was suspected by the authors from the following considerations ;it is extensively diffused in the mineral kingdom it is easiIy converted into chloride by the action of salt-water ;its chloride is soluble in other chlorides especially in chloride of sodium; and its sulphide is readily acted upon by sea- water and converted in to chloride. Further as silver frequently accom- panies galena and that mineral always contains small quantities more or less appreciable of iron zinc and copper it seemed probable that these metals might also be found in sea-water.The authors’ re-searches were limited to the detection of silver lead and copper- the presence of iron being already known and the detection of zinc in very minute quantities being almost impossible for want of a test of sufficient delicacy. As the quantity of the above metals in sea-water is extremely small the utmost care was necessary to ensure that they were not introduced by the reagents employed in the analyses. The silver after precipitation by sulphuretted hydrogen or otherwise was alloyed with lead by fusing the precipitate with litharge and reducing agents as free from silver as they could be obtained and the metallic button thus produced was cupelled to separate the silver-a comparative experiment being made in every instance with the same materials but without the silver-precipitate in order that any error arising from the presence of traces of silver in the reagents might be detected and allowed for.The water used for solution washing Stc. was spring-water containing but a very small quantity of solld matter and ascertained by careful examination to be quite free from silver. This was considered preferable to distilled water inasmuch * Ann. Ch. Phys. [S] XXVIII 129. NOTICES OF FOREIGN PAPERS. as the latter might have taken up traces of silver by being kept in vessels of tinned copper or by contact with the solder at the joints of the tin tubes in the distilling apparatus since copper tin and lead frequently contain minute quantities of silver.Silver in sea-satt.-400 grms. of sea-salt fused with 25 grms. litharge and 1grm. lamp-black yielded a button of lead which left a very small button of silver on the cupel whereas the same quantity of lead extracted from the same litharge left nothing upon the cupel. This preliminary trial was checked by precipitation with sulphuretted hydrogen.-3 kilogrammes of crude-salt (obtained from salt-marshes and not subjected to any purifying process whatever) were dissolved in 24 litres of the spring-water above-mentioned and the solution saturated by sulphuretted hydrogen purified by two washings. The liquid became opalescent but after standing for two months it regained its transparency and deposited a greyish-white precipitate.This deposit was cupelled with 3 grms. of pure lead and a button of silver obtained but not much larger than that produced by the former method from a much smaller quantity of salt. From this it would appear that sulphuretted hydrogen does not precipitate the whole of the silver contained in a solution of sea-salt ; and in fact if such a solution be precipitated as completely as possible by sul- phuretted hydrogen and afterwards evaporated to dryness the residue if treated with lead and cupelled as above will yield a button of silver. Estimation of silver in sea-water.-A considerable quantity of sea- water was taken from off the coast of St. Malo a few leagues from land and preserved during the course of the experiments in a wooden cistern from which it was taken out as occasion required in glass vessels.The presence of silver in this water was first demonstrated by the sulphuretted hydrogen process above described ;but in order to obtain a more exact estimation of the quantity 50 litres of the water were evaporated to dryness and the crude-salt thence obtained weighing 1300 gramrnes was divided into 13 equal portions and each portion fused with 30 grms. of pure litharge and 1 13 grms. of lamp-black. This mixture which was made very intimate by long trituration in a porcelain mortar was gradually heated to dull red- ness in a cixcible and maintained at that temperature for fifteen or twenty minutes; the heat was then gradually raised till the mixture fused and afterwards increased to whiteness as soon as that tem- perature was attained the crucible was withdrawn from the fire.Thirteen operations of this kind yielded 12-4 grrns. of lead and the silver contained in this was found by cupellation (deducting that which was yielded by the lead alone in a test experiinent) to amount to 0.0005 grm. Now as this demi-milligramme of silver was ex-tracted from 50 litres of sea-water it follows that 100 litres-or for simplicity say 100kilogrammes of sea-water-contain 1milligramme ; hence the proportion of salt in sea-water is approximately 1 part in 70 NOTICES 100,000,000 80 that a cubic myriametre of sea-water contains 1000 kilogrammes or a cubic mile (English) contains about 2g1b. avoir- dupois. This estimation must be regarded as a minimum; for all the preceding operations are attended with slight loss.Silver in Fuci.-The well-known faculty which plants possess of condensing within their substance certain of the principles which form the medium in which they grow induced the authors to search for silver in sea-weed with the full expectation that these plants would be found to contain it in larger proportion than the sea-water itself. The species examined were Fucus canalimlatus F. vesiculosus F. serratus F. ceramoydes F. !?aodosus; Ulva cmpressa. These plants were incinerated by burning them on an iron grating supported on four feet resting on plates of porcelain the whole apparatus having never been used for any other operation. The ashes of all these species yielded buttons of silver by cupellation.100 grms. of the ashes of Fucus serratus yielded 0.001 grm. silver ; the same proportion was found in the ashes of Fucus ceramoi'des; the other species yielded buttons too small to be weighed. The proportion of silver contained in the ashes of Fucus serratus and ceramoi'des is From this it is calculated that the fuci are about 26 times 10000* as rich in silver as the water itself. By similar methods the authors have demonstrated the existence of silver in various chemical products in the preparation of which sea- salt is employed e. y, in carbonate of soda and hydrochloric acid. The quantity of silver in carbonate of soda was found to be greater than that in the sea-salt itself. The excess arises from the use of sulphuric acid in the preparation that acid always containing lead and therefore also silver.The wood of various trees e. g. the oak birch beech hornbeam aspen apple and ash grown at a considerable distance from the sea and on laud which had never been manured with salt or sea-weed likewise yielded ashes in which silver was detected. The presence of silver in these plants appears therefore to be connected with the general distribution of silver in the mineral kingdom-a fact pre- viously established by the experiments of two of the authors of this memoir. The blood of an ox was likewise found to contain silver derived oi course from the vegetable substances on which the animal ha$ f cd These experiments are sufficient to show that the occur-rence ot silver in organic substances is by no means uncommon although they cannot safely be regarded as a proof of the constancy of its occurrence.With regard to the question whether the silver in the waters of the ocean has been carried thither by rivers in recent times and derived from the waste of that which is used by man or whether its existence therein is of more ancieut date-the authors observe in the first OF FOREIGN PAPERS. place that supposing the proportion of silver in all parts of the ocean to be the same as that which was found in the particular portion examined the total quantity contained in the ocean would amount to about 2,000,000 tons a quantity which is probably greater than that which has even been extracted from the earth by artificial means.The question however is more completely decided by the examina- tion of marine deposits anterior to the existence of man upon the earth. For this purpose the authors searched for silver in rock-salt occurring in sedimentary strata and deposited from ancient salt lakes or marine basins and likewise in coal. In the rock-salt the presence of silver was demonstrated beyond all doubt; the ashes of the coal likewise yielded a button of silver but the authors consider that the result of the experiment is rendered somewhat doubtful partly by the possible occurrence of iron pyrites in the coal (though the most careful examination failed in detecting any) and partly in consequence of the large quantity of the reagents which it was found necessary to use.The occurrence of silver in the rock- salt is however quite sufficient to show that the presence of that metal in sea-water is of ancient date. Lead and copper in Fuci.-Ten kilogrammes of a mixture of several species of fucus chiefly F. serratus nodoszcs and ceramoiiles gathered on the coast of St. Malo were incinerated and yielded 1.7 kilograrnmes of ashes. These ashes were washed with a large quantity of water to free them from soluble salts especially sulphate of lime which they contain in large quantity. The residue was then digested in hot nitric acid not in excess the liquid left to stand for several days and then mixed with a large quantity of spring-water all these operations being conducted in porcelain basins.After filtration the liquid was introduced into a glass vessel and saturated with sulphuretted hydrogen previously washed ;a very light floc-culent greyish precipitate was soon formed consisting chiefly of sulphate of lime. The whole was then left at rest for several weeks ; the liquid filtered; and when the filter was dry the sulphate of lime was easily removed by a feather. There was then left on the filter 8 very thin film of a brownish colour. As this could not be detached the filter was burnt over a porcelain capsule; the ashes dissolved in nitric acid; the liquid diluted with water and filtered and then strongly acidulated with sulphuric acid. It immediately became turbid and after a few hours a white heavy precipitate settled down which when washed and dried weighed 0.047 grin.From this precipitate a button of lead was easily obtained by the blow-pipe. Now as the quantity of ashes operated upon was 1700 grins. and as 32 parts of lead correspond to 4.7 of sulphate it follows that the l2 ashes contain at least 1,000,000of their weight of lead. The nitric acid the sulphuric acid the filter-paper and the glass used in thc 72 NOTICES experiments were examined for lead with the utmost care and were found to be quite free from it. The experiments were repeated three times and always with the same result. The presence of coppw in the sea-weed was demonstrated by two distinct processes.-l The acid liquid separated by filtration from the sulphate of lead in the operation above described was super-saturated with ammonia and then filtered the clear solution had a blue tint.It was again saturated with acid and a bright iron wire im- mersed in it; the wire soon became coated with metallic copper.- 2. 12’15grms. of sea-weed (undried) were introduced into a large glass vessel previously washed out with aqua-regia and a su%cient quantity of spring-water added to immerse them completely. The liquid was then saturated with chlorine gas previously well washed the vessel closed and the whole left at rest for twenty-four hours. This operation was repeated every day till the fuci were completely bleached and no further action took place. After this the liquid was concentrated by evaporation in a porcelain basin then saturated with ammonia filtered and neutralized with pale acetic acid.The neutral solution treated with a few drops of ferrocyanide of potassium gave the characteristic red-brown colour indicative of the presence of copper. These experiments sufficiently establish the presence of lead and copper in fuci and therefore also in sea-water. The fuci were chosen in preference to other marine plants because having no real roots they do not insert themselves into the rocks but merely rest upon them and must therefore derive all their mineral constituents from the water. In conclusion the authors observe that the presence of silver copper and lead in sea-water though it may appear singular on first consideration will be easily understood if it be remembered that the sulphides of lead and copper are very widely diffused in nature as likewise is the sulphide of silver either alone or associated with other metals.Now salt-water attacks all these sulphides and converts them into chlorides which it dissolves. The waters which circulate through the upper parts of the earth’s crust and which almost always contain chlorides and other salts of the alkalis react in the same manner on these natural sulphides dissolving out small quan- tities of metal which they carry away and transfer to the tissues of plants ;lastly the same waters contribute together with the solid food to introduce these metals into the bodies of animals. OF FOEETGN PAPERS. On a Chromate of Copper and Potash. By A. Knoy.* When bichromate of potash is poured upon recently precipitated hydrated oxide of copper a light brown crystalline compound is formed composed of small hexagonal tables.This salt is insoluble in water. Carbonate of ammonia and caustic ammonia dissolve it producing a deep green solution. This solution if saturated while hot and then left to cool deposits brilliant green prisms having a golden lustre by reflected light; these crystals appear to be the chromate of copper and ammonia described by Malagu t i. The same chromate of copper and potash is obtained by mixing a solution of sulphate of copper with excess of bichroinate of potash arid gradually adding caustic potash. It contains KO. Cr 0 + 3Ca 0. CrO + 3HO. On a native Borate. By 6. L.U1ex.t Beneath the nitre beds of Southern Peru there are found white tuberculous masses which in that country are called Tiza.In size they vary from a hazel-nut to a middling sized potato and have exactly the external appearance of the Aluminite described by Halle; but the fractured surfaces show that the mass is composed of soft white silky fibres interlacing each other; they absorb water rapidly and have a slightly saline taste. Embedded in the tuberculous masses are sometimes found sharp-edged fragmepts of Andesite and of quartzose and argillaceous minerals and invariably large rhombic prisms of Brogniartin. The density of the crystalline fibres is 1.8; their form appears to be that of a hexagonal prism or perhaps a rhombic prism with the acute lateral edges truncated.Their composition is as follows Boracic acid . 49.5 49.5 Lime . . 15.7 15.9 Soda . 8.8 8.8 Water . . 26.0 25.8 100.0 100.0 Assuming that the relation of the boracic acid to the soda is the same as in borax these numbers give the formula NaO. 2B0 + 2 CaO. 3 BO + 10 aq. The author is of opinion that this mineral is identical with the Hydro-borocalcite described by Hayes. The brogniartin with which this borate is mixed consists of sulphate of soda and lime NaO. SO + CaO. SO,. * Ann. Ch. Pharm. LXX,52. -f Ibid. LXX 49 74 NOTICES On the Preparation of Hydrobromic and Hydriodlc Acids. By Ch. Mene.* bf. Mene recommends for the preparation of these gases the use of crystallized hypophosphite of lime resulting from the preparation of phosphuretted hydrogen by means of phosphuret of lime or else sulphate of soda in the state in which it is found in commerce.The proportions are as follows Water . 1pt. or Water . 1 pt. Iodine or bromine . 5 , , Iodine or bromine . 3 , Hypophosphite (cryst) 4 , , Sulphite (cryst) . 6 , The hypophosphite of lime is introduced into a flask or a retort together with a small quantity of water and liquid bromine poured in by means of a funnel. The reaction takes place in the cold; but it is indispensable to put into the iieck of the retort or flask a few pieces of cotton or asbestus in order to retain the vapour of bromine which would otherwise be volatilized by the heat evolved. The operation is the same with iodine excepting that it is necessary to apply a gentle heat.The use of crystallized sulphite of soda is more economical because it is a commercial product. The crystals are simply moistened with water then iodine or bromine added and a gentle heat applied. These two processes are not attended with the dangerous explosions to which the old method is liable. On Anisol and PhenetoI. By A. Cah0urs.t In a former memoirJ M. Cahours has shown that when anisic acid or its analogue,- the salicylate of methyl is distilled in contact with an excess of baryta the baryta is transformed into carbonate and a limpid colourless liquid distils over having the compo-sition C, H 0 C, H 0 = 2 CO + C14H 0,. To this liquid Cahours gives the name of Anisoh By the action of fuming nitric acid upon anisol three distinct products are formed according to the proportions used and the rapidity of the action.If the acid is added in small portions at a time and the containing vessel is surrounded with pounded ice to prevent rise of temperature a liquid product is formed which differs from anisol merely by the substitution of 1 eq. hyponitric acid for 1 eq. hydrogen. This compound is called Mononitranisol C, H NO,. It is a limpid amber-coloured liquid heavier than water boiling between 26%’ and 264O C. and having an aromatic oclour somewhat like that of bitter almonds. Caustic potash in * Compt Rend. XXVIII 478. .f. Ann. Ch. Phys. [3] 27 439. Ann. Ch. Phys. [3] 10 327. OF FOREIGN PAPERS.solution has no action upon it; strong sulphuric dissolves it with the aid of a gentle heat; water added to the liquid separates the anisol unaltered. When heated with fuming nitric acid it is converted into binitranisol and subsequently into trinitranisol. When anisol is treated with fuming nitric acid in excess the liquid boiled for a few minutes and then water added a yellow liquid separates which quickly aggregates into an amber-coloured mass easily soluble in boiling alcohol and separating from the solution on cooling in the form of long yellowish needles. This compound is Binitranisol C, H N O,o formed from anisol by the substitution of 2 eq. hyponitric acid for 2 eq. hydrogen.-By treating anisol with a mixture of equal parts of sulphuric acid and fuming nitric acid a third compound is formed in which 3 ey.of hydrogen are replaced by hyponitric acid this is Trinitranisol. When first formed it is a heavy oily liquid but soon aggregates into a hard mass of a clear yellow colour it is perfectly insoluble in water. Action of Hydrosulphate of Ainrnoniu on the preceding Compounds. 1. Anisidine.-C! H N O,.-When an alcoholic solution of hydro-sulphate of ammonia is brought in contact with mononitranisol an energetic reaction takes place sulphur being deposited and a basic sub- stance formed by the substitution of 1 eq NH for 1 eq. NO,. This base is Anisidine. To obtain it in a state of purity the alcoholic solution is evaporated at a gentle heat till it is reduced to a third or a fourth of its original bulk then mixed with a slight excess of hydrochloric acid and filtered after the addition of a small quantity of water in order to separate sulphur.The filtered liquid evaporated at a gentle heat deposits crystals of the hydrochlorate of the new base; and these crystals when distilled with a concentrated solution of potash yield the anisidine in the form of an oily liquid which solidifies in crystals on cooling. Hydrochlorate oJ' anisidine crystallizes in fine colourless needles. When a hot concentrated solution of this salt is mixed with a concentrated solution of bichloride of platinum yellow needles of a double salt are deposited on cooling. Anisidine likewise forms crystalline compounds with oxalic nitric and sul- phuric acid.2. Nitranisidine.-C, H N O,.-Formed by mixing an alcoholic solution of binitranisol with hydrosulphate of ammonia. The solution is then evaporated to a third of its bulk mixed with a slight excess of hydrochloric acid filtered and the filtered solution treated with ammonia. A red crystalline precipitate is then thrown down which is washed with distilled water and dissolved in boiling alcohol. The solution left to cool slowly deposits the base in long needles having the colour of garnet and considerable lustre. It is insoluble in cold water but dissolves with tolerable facility in boiling water and the solution solidifies in a mass on cooliag. Boiling alcohol dissolves it ivith facility. Ether likcwisc dissolves it rcadily especially when 76 NOTICES warmed.The solution if left to spontaneous evaporation deposits the base in long orange-coloured needles. With nitric sulphuric hydrochloric and hydro bromic acid nitranisidine forms salts which crystallize very distinctly. The sulphate when pure is perfectly colourless. The hydrochlorate forms with bichloride of platinum a double salt which crystallizes in orange-brown needles. Nitro-benzanisidide.-C, Hi N 0,. When crystals of nitranisidine are dropt into chloride of benzoyl no action takes place in the cold; but on gradually raising the temperature a brisk action soon com- mences ;hydrochloric acid is given off; and a coixipound is formed analogous to benzamide and benzanilide. The solid mass thus pro- duced is then treated successively with water hydrochloric acid and an alkaline solution to free it from benzoic acid and nitranisidine.It is then washed several times with distilled water and dissolved in a quantity of alcohol just sufficient to take it up at a boiling heat it then separates in a state of purity on cooling. This substance crystallizes in small needles of a blonde colour. It is insoluble in water both hot and cold and scarcely soluble in alcohol at ordinary temperatures. Fuses when gently heated and volatilizes at a higher temperature. Dissolves in strong sulphuric acid when gently heated imparting a deep red-brown colour to the liquid. Nitl.o-cinnanisidid~.-C, H, N 0,.-Obtained in the same manner as the preceding compound by the use of chloride of cin-namyl instead of chloride of benzoyl.Dissolves sparingly in cold alcohol and with tolerable facility in boiling alcohol from which on cooling it separates in small yellowish needles. Similar products are likewise obtained by the action of chloride of cumyl and chloride of anisyl on nitranisidine. 3. Rinitranisidine.-C, H N O,,.-Formed by digesting trini- tranisol at a gentle heat with an alcoholic solution of hydrosulphate of ammonia. Separated by converting into a hydrochlorate and treating the solution with excess of ammonia. It is then gradually deposited in the form of red flakes which after being repeatedly washed with distilled water and then dried either in vacuo or over the water-bath are converted into a powder which exhibits a bright red or a violet-red colour according to the strength of the solution from which it was precipitated; it is quite destitute of crystalline character.Cold water dissolves but a mere trace of this compound; boiling water dissolves it in small quantities. Cold alcohol dissolves but little of it ;boiling alcohol takes it up pretty readily and if slowly cooled deposits it in the form of blackish violet-coloured needles resembling crystals of cinnabar. Slightly soluble in warm ether from which it separates in needles of a very deep violet colour. Fuses at a moderate heat and solidifies on cooling in a radiated crystalline mass having a blackish-violet colour and resembling cinnabar. With hydrochloric nitric and sulphuric acid binitra-nisidine forms salts which are soluble and crystallizable if the acid be OF FOREIGN PAPERS.added in excess; but water decomposes them setting the base at liberty. Fuming nitric acid attacks it strongly at a boiling heat producing a substance of a brownish-yellow colour like resin which dissolves in potash and then assumes a very deep brown colour. Binitranisidine may be considered as anisidine with 2equivalents of hyponitric acid substituted for 2equivalents of hydrogen Cl,H7N3010=C14HsN02+2N04-~HH. Chrysunisic ucid.-Cl4. H N O14.-When anisic or nitranisic acid is treated with fuming nitric acid binitranisol and trinitranisol are formed and likewise an acid product which is soluble in hot alcohol and crystallizes on cooling in the form of rhomboidal scales of a magnificent golden-yello w colour.This compound is chrysunisic acid; it is isomomeric with trinitranisol and therefore a homologue of picric acid (trinitrophenol). It may in fact be regarded as picric acid plus 1 eq. methylene (C2 Hg). '14 H5 N3 Ol4 = 'l2 H3 N3 '14 + '2 H2* U L-+ Chrysanisic acid. -,?T-IJ Methy!ene. Picric acid. This acid is not sensibly soluble in cold water; boiling water dissolves it in small quantities and deposits it in crystals on cooling. Alcohol at ordinary temperatures dissolves but a mere trace of it; boiliug alcohol dissolves it abundantly so that a saturated solution solidifies in a mass on cooling. Ether dissolves it especially when warm and on evaporation deposits it in very brilliant yellow lamina Fuses when carefully heated and on cooling solidifies in a crystalline mass when more strongly heated it gives off a yellow vapour which condenses on the sides of the retort in small very brilliant scales.When boiled with strong nitric acid it is converted into picric acid. By distillation with chloride of lime it yields a large quantity of chloropicrine. When mixed with a quantity of potash just sufficient to saturate it it forms a very soluble salt; an excess of potash decomposes it converting it into a brown substance. Chrysanisute of amtnoniu C, H N 01, crystallizes in small needles. Its solution precipitates a great number of metallic salts- forming with salts of protoxide of copper a yellowish-green gela- tinous precipitate; with salts of sesquioxide of iron light yellow ; with zinc-salts a precipitate similar to the last but lighter ; with pro-tochloride of mercury no immediate precipitate if the solutions are dilute ; yellowish-red flakes if they are concentrated ; with nitrate of lead a copious flocculent precipitate of a fine chrome-yellow colour ; with nitrate of silver a fine yellow flocculent precipitate ; and with nitrate of cobalt a gelatinous precipitate of a yellow colour slightly tinged with green.-Cbysan,isate of silver C, (H Ag) N OI4 is precipitated in fine yellow flakes on mixing solutions of nitrate of silver and chrysanisate of ammonia.78 NOTICES Chrysnnislc ether C, H N 0, is obtained by passing dry hydro- chloric acid gas into a solution of chrysanisic acid in strong alcohol till it is no longer absorbed; then boiling the liquid gently for a short time and adding water.A voluminous precipitate is then produced which must be thrown on a filter and washed with water containing ammonia to remove any chrysanisic acid that niay remain unaltered. It is afterwards washed with pure water and then dis- solved in boiling alcohol which on cooling deposits it in trans- parent scales of a very rich golden-yellow colour. Dissolves in warin ether ;fuses at about looo. &dphanisolide.-c, H S O,.-When vapour of anhydrous sul- phuric acid is passed into anisol artificially cooled the vapour is gradually absorbed and the liquid thickens. If water be then added three products are formed viz anisol unaltered sulphanisolic acid and sulphanisolide which is a solid substance analogous to sulpha- benzide ; it forms delicate needles having a silvery lustre and easily soluble in alcohol and ether.DERIVATIVES OF SALICYLIC ETHER. When chlorine gas is passed in excess through salicylic ether (salicylate of ethyl) heated over a water-bath a solid substance is formed which is soluble in hot alcohol and crystallizes on cooling in beautiful colourless tables. This compound is bichh-ruretfed salicylic ether formed from salicylic ether (Cis H, 0,) by the substitution of 2 eq. chlorine for 2ey. hydrogen its com- position is therefore C, H Ci2 0,. The corresponding bromine compound which forms magnificent crystals is obtained in a similar manner When salicylic ether is acted upon by a mixture of sulphuric and fuming nitric acid a product is obtained which dissolves in boil- ing alcohol and crystallizes on cooling in beautiful white scales with a faint tinge of yellow.This compound is Binitro-salicylic ether formed by the substitution of 2 eq. N 0,for 2 eq hydrogen hence its composition is C, H (N oJ20 = C, H N2 Ol4. Phenetol.-C, H, 02,-Salicylic ether forms definite compounds with caustic alkalies. On distilling the baryta compound the salicylic ether is resolved into 2 eq. carbonic acid and 1 eq. phenetol, which distils over '18 '10 '6 = O2.+ cl6 '2 Phenetol is a colourless very mobile liquid lighter than water ; and having an agreeable aromatic odour; it is insoluble in water but dissolves readily in alcohol and ether.Solution of caustic potash has no effect upon it. Sulphuric acid converts it into a copulated acid. Chlorine and bromine convert it into crystallizable products. BinitrophenetoZ.-C16 H N O,,.-Formed by the action of fuming nitric acid at a boiling heat on phenetol. Crystallizes in yellow needles much like those of binitranisol of which this compound is the homologue. OF FOREIGN PAPERS. Nitr0phenitidine.-C, Hlp N O,.-Formed by passing sulphu- retted hydrogen and ammoniacal gas through an alcoholic solution of binitrophenetol. Crystallizes in brown needles. This compouhd is a base analogous to nitranisine and forms crystallizable com- pounds with sulphuric nitric and hydrochloric acid. The other homologues of the anisol series M.Cahours has not yet formed but there can be no doubt of their existence. The following table contains all the derivatives of salicylate of methyl and salicylate of ethyl described by M. Cahours in this and in former memoirs the bodies of the second group differing from the first only by the additior If C2 H2. FIRST GROUP. SECOND GROUP. c) H O6 Salicylate of methyl. C, H 0,.C H2 Salicylic ether. Monochloruretted Monochlor. sa-'I6{ O6{ salicylate ofmethyl clG{ 06Dc'2H2( licylic ether. 3 } 3} Bichloruretted sali- Bichlor. sali-'16{ 3 } { cylate of methyl. clG{ c"16 } 06'c2H2{ cylic ether. Fi } Monobromuretted Monobrom. sa-? Fi } salicylate of methyl c16{ 06*c2H2{ licylic ether. { '16{ Bibromuretted sali- Bihroniuretted :,%{ } O6{ cylateof methyl.O,.C,H,[ salicyl. ether. '16{ Mononitro -sa- $d4 } 06*c2H2{ licylic ether. '16{ Binitro-salicylate of methyl. '6' '2 Hf{ Binitro-salicyl. ether. 0,.C2 H -2 CO2 = (34)2] H (a4),} O6{ '16{ '16{ C, a C,4{ a4} 02{ Nitranisol. C14{ ;A4 } 0,.C2 H C14H802 * %HZPhenetol. Nitrophenetol. CI4{ } 0 { Binitranisol. C, { 0,{ Trinitranisol. C, H N 0 Anisidine. C14 H N 0,. C H Phenetidine. Nitropheniti-{NO,} :$4{C, H2{ dine. C1 { (adl2} NO,{ Binitranisidhe. Binitrophene-On the Characteristic Properties of the two Acids which compose Racemic Acid. By M. L. Pasteur.* Pasteur has shown that racemic or paratartaric acid is a corn-pound of two acids one of which turns the plane of polarization of luminous rays to the right the other to the left hence called Dextro-racemic acid and Levo-rucemic acid.These two acids enter into racemic acid in equal quantities; and their crystalline forms which are identical in all their individual parts are symme-* Ann. Ch. Phys. [3] XXVIII 56. Nitranisidine. '14{ :64 '2 * 80 NOTICES tricaZ* yolyhedrims iiicapable of coinciding by superposition. The corresponding salts of these acids likewise exhibit the most striking analogies in their physical and chemical properties; the only diffe- rence between them consisting in the opposite directions in which they turn the plane of polarization of luminous rays and in the sym-metry of their crystalline forms. Dextroraeemic acid is identical with tartaric acid.Racewate of Soda and Ammonia.-This is the salt by which the separation of the two acids is effected. When equal weights of racemic acid are saturated the one with soda and the other with ammonia and the neutral solutions mixed the liquid by cooling or by spontanews evaporation deposits a double salt in remarkably fine crystals which if the liquid be left to itself for three or four days often attain the length of several centimetres. These crystals are rectangular prisms having their lateral edges replaced by planes ; and the intersection of ti00 only of these planes with the terminal faces of the prism are replaced by facets; hence the crystals are hemihedral. Further on minutely examining these crystals one by one it is found that they may be divided into two groups the crystals in the one having the hemihedral facets symmetrically situated to those in the other.The crystals of one of these groups turn the plane of polarization to the right; those of the other to the left. In other respects the crystals of the two groups are absolutely identical. It is impossible to obtain a complete separation of the two kinds of crystals by merely picking them out; but after separating them in this way as well as possible and drying them on bibulous paper to remove the adhering mother-liquid complete purification may be effected by dissolving the crystals of the dextroracemate and levoracemate in separate portions of water and crystallizing again.-That these crystals are really of different kinds and that neither of them taken alone con- tains racemic acid may be shown by dissolving one of them in water and treating the solution with a lime-salt.If the solution be some- what dilute no precipitate will be formed at first ; but after a while brilliant isolated crystals will be formed consisting of right rhombic prisms passing into the octohedral form at the angles of the base ; in short the lime-salt is precipitated with all the characters of tartrate of lime. The solutions of both kinds of crystals behave in the same manner. But if instead of taking separate crystals two crystals belonging to different groups be dissolved together the precipitate with the lime-salt even in very dilute solutions will form imrne- diately or after a few seconds in the state of an amorphous powder or of small thin lamin= either isolated or arranged in stellated groups according to the slowness of the precipitation,-in short presenting all the characters of racemate of lime.-Eacemic acid is * The term symmetrical must be understood throughout this Paper in the strict technical sense in which it is used in geometry. OP FOREIGN P;\f-'ERS. not however a mere mixture of dextroracemic and levoracemic acid; every crystal of racemic acid however small gives with a salt of lime the distinguishing character of racemate of lime. In fact the two acids cannot exist together in a solution without combining and forming racemic acid. The same is the case with all the salts of these acids excepting the double racemate of soda and ammonia already described and the double racemate of soda and potash which is isomorphous with it.Dextroracemic and Leuoracemic Acids.-Dextroracemic acid is prepared by mixing a solution of dextroraceniate of soda and ammonia with nitrate of lead and treating the precipitate with sulphuric acid. The acid then separates and may be obtained in crystals the crys- tallization being facilitated by the presence of a slight excess of sulphuric acid. By slow evaporation large clear crystals of great beauty are obtained. These crystals are oblique rectangular prisms with hernihedral modifications. The crystalline form is absolutely iden- tical with that of tartaric acid obtained from ordinary cream of tartar ; the acid has likewise the same composition density and solubility and in short is nothing but tartaric acid.It is convenient how- ever to retain the name of Dextrorucewic acid when we wish to refer to the acid as one of the constituents of racemic acid or to con-trast its propertics with those of levoracemic acid. The preparation of levoracemic acid is precisely similar to that of the dextroracemic ; it has likewise the same composition density and solubility. The crystalline forms of the two acids however are not si~rcilarbut symmetrical,-so that although their faces are pre- cisely the same in form number and magnitude they cannot be made to coincide by superposition. Moreover tartaric or dextro-racemic acid turns the plane of polarization of a luminous ray to the right; levoracemic acid turns it by exactly the same quantity to the left.For these reasons levoracemic acid might also be called Leuotartaiic acid. The crystals of both these acids are strongly pym-electric ;each crystal when heated or cooled becoming charged with opposite electricities at its two ends; but in either case the hrection of the positive and negative poles in a crystal of dextroracemic acid is precisely opposite to that which obtains in a crystal of levoracemic acid. Levoracemates and Dextroracernates.-The relations of form rotatory power and chemical properties already noticed in the dex- troracemic and levoracemic acids are likewise found to the fullest extent in salts of these acids. All the chemical properties of the tartrates or dextroracemates are reproduced even in the minutest details in the corresponding levoracemates.To each tartrate there corresponds a levoracemate differing from the former in nothing but in the position of the hemihedral facets and the direction of the VOL. 111.-NO IX. G 82 NOTICES rotatory power. With regard to the angles of the faces the absolute value of the rotatory power the specific gravity chemical compo- sition solubility optical properties of double refraction &c. the corresponding salts of the two groups are absolutely identical. Racemic acid and Racemates.-It is well known that this acid was originally produced by an accidental alteration of tartaric acid in the manufactory of M.Kestner at Thann. Its production on that occasion appears to have been due either to some particular and unobserved circumstance in the process of fabrication or to some discase in the grapes from which it was formed; at all events it has never been produced again notwithstanding all the attempts which M.Kestner has made for t,hat purpose. Its production is evidently due to some molecular alteration in tartaric or dextroracemic acid by which a portion of that substance is converted into levoracemic acid Now as Biot has shewn that the rotatory action of tartaric acid on polarized light is diminished by reduction of temperature it seemed possible that by the action of intense cold the direction of the rotatory power might be reversed and thus the transformation into levoracemic acid effected.M. I’asteur has tried the experiment but without any satisfactory result. For the present then the direct formation of racemic acid from tartaric is an unsolved pro- blem ;but this much is certain that when equal weights of dextro-racemic and levo-racernic acids are dissolved in water and the solu- tion left to crystallize ; the crystals obtained are perfectly homohedral and present all the characters of raceniic acid.-M. Pasteur has also carefully examined the crystalline forms of several salts of racemic acid,-particularly the neutral and acid racemates of soda and the racemate of antimony and potash-and finds them all perfectly homohedral. On the Separation of some of the Acids of the Series (C H)n 0,.By Justus Liebig. For detecting small quantities of butyric or valerianic acid in a mixture of the two acids and for separating one of them in a pure state fit for analysis the following method may be advantageously pursued. A portion of the acid mixture is first saturated with potash or soda the remainder is then added to the neutral solution and the whole distilled. One of two results will then follow 1. If the valerianic acid is present in quantity more than sufficient to saturate the whole of the alkali the residue in the retort will con-tain no butyric acid but onlypure valerianic acid. 2. When the quantity of the valerianic acid is less a proportional quantity of butyric acid remains behind in the retort together with the whole of the valerianic acid; but the distillate is then free from the latter and consists ofpure butyric acid.OF FOREIGN PAPERS. The quantity of the acid mixture to be neutralized with the alkali must be regulated by the supposed quaiitity of valerianic acid present. For instance if the proportion is calculated at 10 per cent of the mixture must be neutralized ;and in a solution of valerianic acid containing 10 per cent of butyric acid which it is required to separate -+$ of the acid mixture must be neutralized. It is at once evident that by a single distillation one of the acids will always be obtained pure. Thus either the distillate will con- sist of pure lizctyric acid and the residue in the retort of a mixture of valerianic and butyric acids ; or the distillate will contain both valerianic and butyric acid and the residue will consist of pure valwianic acid.By repeating this process of partial saturation and distillation either with the mixed residues or the mixed distillates as the case may be a fresh portion of one or the other acid may again be obtained pure till at last a complete separation is effected such as can scarcely be accomplished by ordinary distillation. Since butyric and valerianic acids have different boiling points it may be supposed that the soda inasmuch as it combines with one only of the acids and that the least volatile-in this case the valerianic- will arrest the volatility of the latter at the temperature at which the former boils ; and in a mixture of the two acids if the valerianic acid is rendered permanent at the boiling point of the butyric it is evident that the butyric acid may be distilled off in the pure state.A mixture of valerianic acid with acetic acid or of butyric acid with acetic acid behaves under these circumstances in a totally different manner. Thus if a mixture of this kind is partially neu-tralized with potash and then distilled the acid which passes over consists not of acetic acid as might be expected but of the two other acids although the boiling point of the acetic acid is upwards of 50° C. lower than the boiling point of butyric acid and upwards of 709 lower than that of valerianic acid. This effect is due to the formation of an acid acetate which does not appear to be decom- posible by either of the other acids.Valerianic acid added to a solution of neutral acetate of potash dissolves immediately and in considerable quantity ; but with acid acetate of potash the valerianic acid remains swimming in oily drops on the surface and does not appear to be more soluble therein than in pure water. On distilling a solution of neutral acetate of potash to which valerianic acid has been added in excess valeriaiiic acid passes over and the residue in the retort contains acid acetate together with valerianate of potash. But if valerianic acid is added to acid acetate of potash and the mixture distilled valerianic acid passes over and the acid salt remains behind free from valerianic acid. Butyric acid behaves in a precisely similar manner to valerianic acid.G2 84 NOTICES Hence when a mixture of butlyric or valerianic acid with acetic acid is partially saturated with potash and distilled either the whole of the acetic acid remains behind in the form of' an acid salt together with butyric acid the distillate in this case being pure and free from acetic acid ; or acetic acid alone remains in the retort and the distil- late still contains a portion of acetic acid which may be separated from the butyric or valerianic acid by repeating the process. On the Derivatives of Xanthic Acid. By H,Debus.* Dessainst has shown that when iodine acts upon xanthate of potash the potassium is removed in the form of iodide and a com-pound formed containing C H S 0,; thus C H K S 0 + I = K I + C H5 S 0,.This product has been further examined by Debus; he however finds that it can be more conveniently formed from xanthate of lead. This salt is obtained by dissolving potash in common alcohol ;adding to the solution a quantity of bisulphide of carbon and hydrated oxide of lead cprresponding to the quantity of potash used; and leaviug the mixture at rest for 6 or 8 hours. At the end of that time part of the oxide of lead is found to be transformed into sulphide mixed with crystals of xanthate of lead while another portion is dissolved by the potash. The black precipitate is separated by filtration and water added to the filtered liquid till a milkiness is produced. After a while the liquid becomes clear and deposits xanthate of lead in long silky crystals containinf; C H 0 '3 Pb 0.This salt is diffused through alcohol and iodine added in small portions at a time till the liquid acquires a permanent brown colour. The iodide of lead is separated by filtration the liquid diluted with its own volume of water and then left at rest for some hours at a temperature of la0C. The compound above-mentioned C H S O, is then deposited in small colourless prisms. This substance is regarded by De b us as BiGxysu&hocarbonaie of ethyl C H S 0 = C H 0 C {3 This substance is very soluble in absolute alcohol and in ether ; its solution gives no precipitate with acetate of lead and with several other metallic solutions. When it is boiled with nitrate of silver a precipitate of sulphur is formed.Chloride of mercury produces with it a white precipitate which blackens at 40°C.; and bichloride of platinum gives after a while a brown pulverulent precipitate. When dry ammoniacal gas is passed into an alcoholic solution of bioxysulphocarbonate of ethyl the liquid gradually becomes turbid * Ann. Ch. Pharm. LXXII 1. f-Ann. Ch. Phys. [S] XX 496. OF FOREIGN PAPERS. and deposits long needles of sulphur. If the filtered liquid be then evaporated in vacuo a saline residue is obtained containing a mixture of xanthate of ammonia and a new substance to which Debus gives the name of Xanthogenamide. These substances are separated by digestion in ether which dissolves the latter only. The xanthogenamide remains after the evaporation of the ether in the form of a yellow oil which ultimately solidifies in a crystalline mass.It is purified by solution in a small quantity of alcohol from which it crystallizes on evaporation in splendid rhomboidal prisms often of considerable size. These crystals fuse at about 30'; they are slightly soluble in water but dissolve in all proportions in alcohol and ether. The solution is neutral and gives DO precipitate with nitrate of silver acetate of lead sulphate of copper or baryta-salts ;but it precipitates bichloride of platinum and corrosive sublimate. The oxides of mercury silver and lead and likewise carbonate of silver decompose this substance producing a sulphide of the metal and a substance which attacks the eyes powerfully and has an odour like that of acrolein.Concentrated sulphuric acid readily dissolves xanthogenamide ; water precipitates it again without alteration. Nitric acid attacks it strongly forming a peculiar acid. Potash and baryta-water at a boiling heat resolve it into alcohol and hydro- sulphocpanic acid. Ammonia at 1509C. produces carbonic acid hydrosulphocyanic acid and a numbey of fetid ppoducts. The composition of xanthogenarnide is C,H,O S,N. In its formation 2 eq. bioxysulphocarbonate of ethyl and 2 eq. ammonia are resolved into1 eq. xanthate of ammonia 2 eq. sulphur and1 eq. xanthogenamide When an alcoholic solution of xanthogenamide is mixed with bichloride of platinum a yellow crystalline precipitate separates, after a few minutes and the filtered liquid continues for some days to deposit crystalline scales.By analysis these crystals gave the following results Calculated. Found. r--7 7-A- 1 Carbon. Eq. . 12 72 1401 13.97 1. 13.39 11. -111. Hydrogen . 14 Oxygen. . 4 Sulphur. . 4 Nitrogen . 2 Platinum . 2 Chlorine . 3 14 2.72 32 6.2464 12.46 28 5*45 197.4 38.43106.2 20.69 2.69 -38.0419.08 -I 2.72 13.35 38.2623.30 -c -37% -I 513.6 100*00 86 NOTICES Hence may be deduced the formula Pt CI, c H 0;c,{;I+ Yt c1 c €3 0; c {i}. The mother-liquid separated from these precipitates is very dark-coloured and when evaporated gives off' vapours of hydro-chloric acid and yields a brown oil which gradually volatilizes together with the water and alcohol vapours; there then remains a brown substance possessing the properties of sulphide of platinum together with a white crystalline body which was recognized as sal-ammoniac.The above-mentioned platinum compound is insoluble in alcohol ether and water. Strong sulphuric acid has no action upon it in the cold and but a slight action when heated. Potash nitric acid and hydrochloric acid produce no alteration in it; bnt qua regia dissolves it with facility At 120°C. it begins to decompose evolving a fdd oil. Potash and baryta transform xanthogenamide into alcohol and a sulphocyanide of the metal the reaction consists in simple decom- position. c6 117 02 s2 3 = c 11 02 $-c2 H Ns2. When xaiithogenainide is submitted to dry distillation mercaptan and vapours of cyanic acid are given off'.If the distillation is performed at 152O C. the residue contains pure cyanuric acid C H7 02 S N = C €16 $2 +-C H NO,. The distillate smells powerfully of mercaptan and cyanic acid ; becomes gradually darker in colour by exposure to light is insoluble in water but miscible in all proportions with alcohol and ether. When it was rectified several times after drying over chloridc of calciuIIi the boiling point did not become fixed but gradually rose from SO0 to 230°C. The portions which first went over were colourless; the last had a strong yellow colour. Both portions had a very feeble alkaline reaction and when dissolved in alcohol gave scanty white precipitates with silver copper and lead salts ;but with corrosive sublimate a copious bulky precipitate which when left for some time in contact with the mother-liquid was converted into crystalline lamin=.By analysis it was found to be a compound of mercaptide and chloride of mercury Ae S . Hg S +-Hg C1. As a check on the preceding results the cyanuric acid produced by the distillation of the xanthogenamide was mixed in the state of a hot dilute solution with nitrate of silver and dilute ammonia was added as long as a precipitate continued to form. The salt thus obtained evolved ammonia when heated and acquired a violet colour. Potash in the cold had no action upon it. Analysis gave the follow- ing results OF FOREIGN PAPERS. -87 Calculated. Found. 7- Eq. 1. 11. Carbon . . 6 36 7.85 7.6 7.4 HydrogenOxygen .. . . 1 7 1 56 0.21 12.27 0.3 - 0.3 _I Nitrogen. Silver . . . . 3 3 42 324- 9.10 70-57 8.98 70.25 -70.41 -___I 459 100~00 Hence the salt is a tricyanurate of silver with 1 eq. water 3 Ag 0. C N3 0 + HO. Liebig and Wohler found in the same salt dried at 300° C. Liebig. Wiihler. Carbon . 8.13 7.82 ' 8.4 Hydrogen. 0.13 0.18 0.12 Silver . . 70.00 71.10 70.52 On Caffeine. By Fr. Roch1eder.r When chlorine gas is passed into a thick magma of crystals of caffeine the liquid becomes heated and a solution is obtained contain- ing four substances hydrochloric acid the hydrochlorate of an alkaloid a weak acid and a very volatile product which could not be procured in sufficient quantity or sufficiently pure for analysis. On heating the solution in the water-bath the excess of chloride is driven off together with the hydrochloric acid and the volatile product which is remarkable for its offensive odour; it irritates the eyes and produces an intolerable pain in the head.As soon as the liquid is evaporated to a third of its original bulk it begins to deposit crystals the quantity of which gradually increases. When the crystals no longer appear to form the liquid is left to cool and the crystals are taken out. They are then washed with cold water in which they are nearly insoluble and then exhausted in boiling absolute alcohol which does not dissolve them at all. They may also be recrystallized from boiling water. They are colourless and transparent contain no water that can be driven off at looo redden litmus slightly and at the same time acquire a slight rose-colour by the action of the ammonia contained in the blue litmus-paper.With baryta potash and soda this substance forms compounds of a dark violet colour. When a solution of either of these bases is brought in contact with the above crystals the latter immediately assume a violet colour while the liquid remains colourless. This eolouring is but transient if the base is in excess but tolerably per- sistent in the case of an excess of acid. * Ann. Ch. Pharm. LXXI 1. 88 NOTICES To this acid ltochleder gives thc name of ainalic acid (from apahos weak) to denote its feebly acid nature and likewise the slight affinity by which its elcments are held together and the consequent facility with which it is decomposed.Ammoniacal vapours impart to amalic acid a red colour faint at first but gradually changing to deep violet. The resulting compound dissolves in water forming a solution of the colour of murexide. This solution however does not yield crystals of murexide; but Roc h le d e r has succeeded in obtaining a crystalline substance from it the description and analysis of which will be given in a future memoir. With ferrous salts and ainxnonia amalic acid forms an indieo-coloured solution. Amalic acid fuses when heated becoming first yellow then red afterwards brown and volatilizes leaving scarcely a trace of carbon but giving off ammonia and forming an oil and a crystallized compound. The solution of amalic acid placed upon the skin produces red stains having a disagreeable odour like those produced by alloxan.It reduces silver salts throwing down black fiakes of metallic silver just as alloxantine does When boiled with nitrate of silver and nitric acid it is decomposed without the formation of even a trace of chloride of silver ;hence amalic acid contains no chlorine. When heated with nitric acid it evolves red vapours and is converted into a new ciystalline body. The composition of amalic acid is C, H N O, as appears from the following analysis Calculation. Experiment. Carbon .. 12Eq. 72 r-7 42.10 41.83 r 42.04 A- 42.04 -7 Hydrogen Nitrogen Oxygen . 7 . 2 . 8 7 28 64 4.09 16-37 37.44 4.35 4-17 4.27 -16.63 16.30 -37.16 37.39 4.18 - -__I_ 171 10000 100*00 100*00 When the mother-liquid decanted from the crystals of amah acid is evaporated to a fourth of its original volume to expel the greater part of the hydrochloric acid it solidifies on cooling in a thick crystalline mass which may be separated from the adhering liquid by pressure between linen and afterwards crystallized from boiling water or alcohol.In this manner a crystalline mass is obtained greasy to the touch and consisting of large laminated crystals. The solution of this substance gives with chloride of platinum a copious yellow precipitate and with nitrate of silver an abundant precipitate of chloride of silver. The crystals consist of the hydrochlorate of a new base. To analyze this base Rochleder converted it into a platinum salt by mixing the mother-liquid above-mentioned with bichloride of platinum collecting the yellow precipitate on a filter and dissolving it in boiling water :the solution on cooling yielded OF FOREIGN PAPERS.very brilliant yellow granular crystals of the double salt. This salt was found by analysis to contain _. Carbon . 4.87 4.86 -Hydrogen . 2-49 2-49 2.42 -Platinum. . 41-42? 41.43 41.61 41.06 agreeing with the formula C H N. C1 H + Pt C1 ; whence the formula of the new base is C H N. To this base Rochleder* gave the name Formyline. Subsequently however on repeating the analysis he found the per centage of carbon to be 5.2 and of hydrogen 2.62. These numbers agree better with the formula C H N.which is that of Methamyline discovered by Wurtz. RIoreover the properties of the so-called formyline are identical with those of methamyline ; whence Rochleder concludes that methamy- line is one of the products of the action of chlorine on caffeine. The composition of caffeine may be thus expressed Cyanogen. Methamyline. By the action of chlorine in presence of water the cyanogen is decomposed; the methamyline is obtained in the form of a hydro-chlorate; and the group C, H N 0 takes up 2 eq. oxygen and 2 eq. water and forms amalic acid C, H N 0 + 2 0 + 2 HO = C, H N 0,. That cyanogen is really contained in caffeine is shown according to Rochleder by its behaviour with alkalis. Caffeine treated with strong potash-ley or soda-lime yields cyanide of potassium or sodium whereas quinine cinchonine morphia and piperine when sirnilarly treated yield not a trace of cyanogen.The volatile tear-exciting substance above-mentioned is considered by Rochleder to be produced by the action of chlorine on the cyanogen of the caffeine at the moment when the cyanogen is separated from the other elements of that substance. M. Gerhardt,? however remarks that it is highly improbable that cyanogea should be actually set free by the action of chlorine on a liquid containing a cyanide or indeed on any cyanogen compound whatever accordingly he is of opinion that the volatile substance just mentioned is chloride of cyanogen. Ac-cording to this view the action of chlorine on caffeine will be repre- sented as follows C16 H, N 0 + 3 C1+ 4 HO = C H N + C, II,N 0, + C N.C1+ 2 C1 H. If the action of the chlorine be continued further a product is obtained from the amalic acid closely resembling cholesterine. This is the substance which Stenhouse obtained by the action of nitric * Ann. Ch. Pharm LXXIII 56. t. Compt. Rend. des Trav. en Chim. Jawvier,1850 25. 90 NOTICES acid on caffeine or theine and to which he gave the name Nitrotheine. This name however is inadmissible inasmuch as the substance in question contains no nitrogen and is formed by the action of chlorine as well as by nitric acid. R o chl e der calls it Cholestrophane. It contains carbon 42.15 hydrogen 4*28 nitrogen 19.56 and is expressed by the formula C, H N 0,.When boiled with potash it evolves a volatile alkali probably methamyline and forms carbonate and oxalate of potash. On the Compounds of Cyanuric and Cyanic Acid with the Oxides of Ethyl Methyl and Amyl and on the products resulting therefrom viz. :Acetyl- and Metacetyl-Urea and Methylamine Ethylamine and Valeramine. By Adolph Wurtz.* 1 Cyanurates of ethy2 and methyl.-Cyanurate of ethyl is obtained by distilling alkaline cyanurate of potash with sulphovinate of potash over an oil-bath. The product condenses in the neck of the retort and in the receiver in the form of a crystalline mass; it may be purified by repeated solution in alcohol from which it separates on cooling in very brilliant prismatic crystals. Cyanuric ether fuses at 85" C. forming a colourless liquid which is heavier than water.Boils at 276q distilling over completely and without the least de- composition. Vapour-density = 7.4 by experiment 7.37 (4 vol.) bp calculation. Formula C N 0,.3 C H 0. Sparingly soluble in water but easily dissolved by alcohol and common ether. This compound is likewise formed together with cyanate of ether (which boils at 60° C.) on distilling cyanate of potash with the sulphovinate. The two ethers inay be easily sepa- rated by distillation; and the cyanuric ether which remains in the retort forms after purification even finer and more regular crystals * than those obtained by the first described process. Cyanurate of methyl.-Obtained by distilling cyanurate or cyanate of potash with sulphomethylate of potash.When purified by repeated crystallization from alcohol it forms small colourless prismatic crystals which fuse at 140' C. and volatilize at 295'. Vapour-density = 5.98 by experiment 5-94 (4 vol.) by calculation. Formula C N 0,. 3 C H 0. The composition of these ethers verifies Liebig's statement that cyanuric acid is terbasic. Cyanate of ethyl.-Obtained by distilling cyanate of potash with the sulphovinate ;separated by distillation as above described from the cyanurate formed at the same time. When purified by repeated distillation over chloride of calcium it forms a light highly refrac- tive liquid of extremely penetrating odour and exciting a copious flow of tears. Lighter than water Vapour-density = 2.4 (4 vol.). * Ann.Ch. Pharm. LXXI 326 ; Compt. Rend. XXVI 368 ; XXVII 241 (1848) ; XXVIII 322 and 323 ;XIX 169 I86 and 203 (1849). OF FOREIQN PAPERS. Formula c6 H NO = c NO. c H 0. When cyanic ether is mixed with liquid ammonia it dissolves with evolution of heat ; and on evaporation beautiful prismatic crystals are obtained consisting of c6 H N O, thst is to say cyanic ether pZus ammonia. They fuse easily and dissolve with facility in water and alcohol. In contact with water cyanic ether gives off carbonic acid and forms a crystalline mass containing C, H, N 0 2 (C H NO,) + 2 HO = 2 CO + C, Hi N 0,. Cyannte of methyl is prepared and purified by methods precisely similar to those just described for cyanic ether. It is a volatile liquid which with ammonia forms a crystalline compound = C H6 N O, and in contact with water is resolved into carbonic acid and a crys- talline compound isomeric with the ammonia-compound of cyanate of ethyl.2 (6= H NO,) + 2 HO = 2 CO + c6 H N 0,. The compounds thus formed are to a certain degree analogous in composition to urea. For urea with 1 eq. methylene C H, or its ele- ments gives C H N O, which is the body corresponding to urea in the acetic acid series. This is the substance formed by the action of ammonia on cyanate of methyl. Further if to this formula we again add the elements of methylene C N we obtain C6 H N 0 the urea of the metacetyl series. This compound may be formed in either of the two ways mentioned above. By treating cyanic ether with water we obtain the analope of urea in the valerianic acid series.Two other bodies of this series might be formed from cyanate of amyl. The compound formed by the union of cyanic ether with ammonia and that which is produced by the action of water on cyanate of methyl are not however identical but merely isomeric. The former appears to be analogous to urea; while the latter appears rather to belong to the class of Amethanes that is to say compounds of ethers with amidogen. The formula C H N 0 may be decomposed in two ways; viz. C NO. C H 0. NH or C NO. C H 0. C H (NH,). The first of these formuh is that of urea with 1eq. water replaced by 1eq. ether; the second is that of a compound of cyanate of methyl with methylamine (vide infra) . Similarly the compound Cl0 H, N 0 may be regarded as cyanate of ethyl with ethylamine.C, H, N 0 = C NO. C H 0. C H (NH,). Urea = C H N 0 = C NO. HO. NH Cyanate of methyl-oxide and ammonia = C NO. C H 0. NH I-v-Acetyl-urea. Cyanate of ethyl-oxide and ammonia = C NO. C H 0.NH Metacetyl-urea. 92 NOTICES Methyl-cyamethane = C H NO + C H (NH,) Ethyl-cyamethane = C €I NO + C H (NH,). ETHYLAMINE AND METHYLAMINE. Formation.-The ammonia-compounds form a sort of connecting link between organic and inorganic compounds. Indeed ammonia would no doubt be regarded as an organic base and the simplest and strongest of the whole class were it not that it contains no carbon. Possibly however this difference may not be of so much importance as it has hitherto been thought ;for Wurtz has succeeded in form-ing organic compounds from this alkali by adding to it the elements of methylene C H, or etherine C H, without depriving it of its strong basic properties or even of its smell.If to the elements of ammonia NH, there be added the elements of 1 eq. C H, there is formed a compound C H N which may be called Methyl-ammonia MetWy Eamide or Methylarnine. On adding to the elements of ammonia the elements of 1 eq. C H, there results the compound C H N which may be called Ethyl-ammonia, Eth,ylamide or Ethylamine. The compounds C H5 N and C H N may be regarded either as methyl-ether C H 0 and common ether C H 0 in whi:h 1eq. oxygen is replaced by 1 eq. amidogen NH, or as ammonia in which 1 eq.hydrogen is replaced by methyl C H, or ethyl C H,. The relations between these bodies and ammonia may be exhibited as follows H N Ammonia. NH H Hydramide. C H N Methyl-ammonia. NH, C H Methylamide. C H N Ethyl-ammonia. NH, C H Ethylamide. These bases may be formed in three ways 1. By the action of potash on the Cyanic ethers. 2. By the action of potash on the Cyanuric efhers. 3. By the action of potash on the Ureas. These reactions may be exhibited as follows C NO. HO + 2 (KO. HO) = 2 (GO,. KO) + H3 N -+ Cyanie acid. Ammonia. C NO. C H 0 + 2 (KO. HO) =2 ((30,. KO) + C2 H N -w Cyanate of methyl. Methylamine. Cyanate bf ethyl. Ethylamine. If all these formu18 be multiplied by 3 they will exhibit the formation of these compounds from the cyanuric ethers.From the ureas they are formed as follows OF FOREIGN F4PERP. C H4 N 0 t 2 (KO.HO) = 2 (GO,. KO) + H N + H N \+ Urea. C H N2 0 + 2 (KO. HO) = 2 (CO,. KO) + H N+ C H N Acetyl-urea. Met ace$-urea. Methylamine.-When cyanurate of methyl is boiled with excess of caustic potash and the evolved vapours are passed through a condensing tube into water a highly caustic liquid is obtained which smells strongly of ammonia but does not contain a trace of that alkali; it is an aqueous solution of methylamine. On saturating this solution with hydrochloric acid and evaporating to dryness a residue is obtained which dissolves readily in warm absolute alcohol. On cooling the hydrochlorate of methylamine crystallizes out in splendid lamin= which are iridescent as long as they remain in the liquid and assume a mother-of-pearl aspect when dry.From the hydrochlorat,e the base may be obtained in the free state by a process exactly similar to that adopted for the preparation of am-monia viz. by heating the dry salt with quick lime in a flask provided with a gas-delivery tube. The methylamine is then evolved in the gaseous form and may be collected over mercury. Methylamine is gaseous at ordinary temperatures; at Oo C. it con-denses to a very mobile liquid. Specific gravity of the gas 1.13 by experiment 1.075 by calculation. Water at lZO,absorbs 1040 times its volume of gaseous methylamine a larger quantity than of any other known gas; at 25O the volume absorbed is 950 times that of the water.The gas resembles ammonia in the following respects. It is rapidly absorbed by charcoal ; turns reddened litmus paper blue; forms dense white fumes with hydrochloric acid; absorbs an equal volume of hydrochloric acid gas and half its volume of carbonic acid It is distinguished from ammonia by taking fire when brought in contact with the flame of a candle and burning with a yellowish flame. It is decomposed when heated with potassium cyanide of potas-sium being formed and hydrogen set free. This furnishes a good method of analysis. The solution has the strong smell of the gas itself; its taste is caustic and burning. Iodine introduced into this solution is con-verted into a garnet-coloured powder and the liquid which scarcely becomes coloured holds in solution hydriodate of methylamine, I H.C H N. The redinsoluble substance is the compound analo- gous to iodide of nitrqen. The salts of magnesia alumina manganese iron bismuth uranium 94 NOTICES tin lead and mercury are precipitated by methylamine just as by ammonia. Zinc-salts give a white precipitate soluble in a large excess of the alkali.-Copper-salts are precipitated bluish-white ; an excess of methylamine dissolves the precipitate forming a deep blue solution. Cadmium cobalt and nickel salts give precipitates not soluble in excess.-Nitrate of silver is completely precipitated by methylamine the precipitated oxide being easily soluble in excess. Chloride of silver is also dissolved by aqueous methylamine.The solution when left to spontaneous evaporation deposits a black powder analogous to fulminating silver but not exploding either by heat or by percussion.-Chloride of gold gives a brownish-yellow precipitate easily soluble and forming an orange-yellow solution.- Chloride of platinurn gives a yellow crystalline precipitate composed of C1 H. C H N. Pt Cl,. Rydrochlorate of Methylamine gave by analysis the following numbers agreeing with the formula C1 H. C N,N. Eq. Calculated. Experiment. Carbon . .a 12 I-- 17.7 17.4 Chlorine . Hydrogen . .1 .6 35.5 6 52.5 8.8 52.2 8.7 Nitrogen . .1 14 - 21.0 21*7 67.5 100.0 100.0 Chloroplatiiaate of Methylamine which crystallizes in beautiful golden-yellow scales was also analysed and gave carbon 5.3,hydro-gen 2.8 chlorine 444 platinum 41.4 (nitrogen not determined) agreeing with the formula C1 H.C H N. Pt C1,. EthyZamine.-The hydrochlorate of this base is prepared and puri- fied by processes precisely similar to those described for methylamine ; and the base itself is likewise obtained by dry distillation of the hydrochlorate with quick-lime. But as ethylamine is easily con- densed and is liquid at ordinary temperatures the gas-delivery tube is made to pass into a receiver surrounded with a freezing mixture. Light very mobile and perfectly transparent liquid. Begins to boil at 18O C. If poured upon the hand it volatilizes immediately producing a sensation of intense cold. It diffuses a highly penetrat- ing ammoniacal odour.Its causticity may be compared with that of potash. Blues reddened litmus-paper strongly. Forms dense white fumes with hydrochloric acid Each drop of the acid poured into it produces a hissing noise. Caustic potash or baryta may be left in contact with the base at ordinary temperatures without producing any change. In contact with a burning body ethylamine takes fire and burns with a bluish flame. Ethylamine is miscible with water in all proportions and the solu- OF FOREIGN PAPERS. tion possesses exactly the same properties as that of methylamine excepting that it dissolves hydrated oxide of copper less readily and does not precipitate bichloride of platinum. When a solution of ethylamine is mixed with oxalic ether the mixture soon becomes turbid alcohol being formed and delicate crystals being deposited which consist of a compound bearing the same relation to oxamide that methylamine bears to ammonia.This compound is EthyFoxumide C H N 0,. The composition of anhydrous ethylamine is expressed by the forinula C H N as appears from the following analysis Eq* Calculated. Experiment. r--7-7 Carbon . -4 24 53-3 53.4 Hydrogen . *7 7 15.5 15.9 I Nitrogen . .4 14 31.2 30.9 31.3 -45 100.0 100*2 Hydrochtorate of Ethylamine crystallizes in laminz ; fuses at looo and solidifies in a crystalline mass on cooling; its composition is C1 H. C; H N. Eq. Calculated. *Experiment. Carbon . .4 r-24 7 29.4 28.9 29.4 Hydrogen . Nitrogen . Chlorine . .8 .I .l 8 14 35.5- 9.8 17.2 43.6 9.917.5 43.7 9.9-CI 81.5 loo'o lOO*O ChZoropZutinate of EkhyZamine.-Golden-yellow scales soluble in The analysis of this salt gave in 100 parts carbon 9.5, water.hydrogen 3.2,chlorine 42.4and 42 platinum 39.2 and 39 agreeing with the formula C1 H. C H N. Pt Cl,. Valerumine C, HI N.-Formed from ammonia by the addition of C, Hl0 or by the substitution of 1 eq. of amyl C, Hll for 1 eq. of hydrogen. Cyanate of amyl prepared by distilling cyanate of potash with sulphamylate of potash yields this base when decomposed by caustic potash C NO. C, H, 0 + 2 (KO. HO) = 2 (GO KO) + C, H, N \-Cyanate of amyl. -The valeramine distils over and may be condensed in a receiver con- taining water. The alkaline solution neutralized with hydrochloric acid yields the hydrochlorate; and this when purified dried and distilled with caustic lime yields anhydrous valeramine.Valeramine is liquid at ordinary temperatures has a burning 96 NOTICES OF rORElGN PAPERS. bitter taste and a stroiig ammoniacal odour. It is soluble in water. The solution precipitates copper-salts and an excess redissolves the preci- pitate forming a deep blue solution less readily however thaii ethylamine methylamine or ammonia. With nitrate of silver it gives a brownish precipitate soluble in excess. Valeraniine dissolves chloride of silver but less easily than ammonia. Hydrochtolrate of Valeramine C1 H C, fI, N crystallizes in scales unctuous to the touch and soluble in water and alcohol.Carbon . Eq. . 10 60 48.5 Calculated. r-7 48.2 Expenment. Hydrogen Chlorine Nitrogen . . 14 *I.1 14 35.5 14 - 11.3 28.7 11.5 11.4 28.3 - 123 100.0 C~~oro~ta~~na€~ of VaZeramine.-Golden- yellow scales soluble in water. Analysis gave 32.4 platinum 36 chlorine 20.4 carbon 4.8 hydrogen agreeing with the formula C1 H. C, H, N. Pt Cl,. Dr. Hofmann* has lately shown that €zoo and even all three of the hydrogen-atoms in ammonia may be replaced by organic radicals ethyl methyl &e. and has thus obtained new volatile compounds resembling ammonia and possessing very strong basic properties. The following table exhibits the composition of these bases C H = Ae = Ethyl C, H, = Ayl = Amy1 C1 €1 = Pyl = Phenyl ''IN Aniline H Ae Ethylo-phenamine PYl Ae The first of these series contains bodies previously known viz.aniline and Wur t z's ethylamine ;these are Amidogen-bases. The second and third series which may be called Imidogen-bases and Nitrile-bases are new. * Ann. Ch. Pharm. LXXIII 91. ('1