摘要:

96 ABSTRACTS O F CHEMICAL PAPERS. Mineralogical Chemistry. Jordanite from Upper Silesia. ARTHUR SACHS (Ceutr. X n . 1904 723-725).-A massive mineral which forms with galena and blende a vein in grey dolomite in the Blei-Scharley mine a t Beuthen,. is proved by the following analysis to be be jordanite ( l’b,As,S7) Pb. S. AS. Fed Total. 70.19 18.2 1 11.37 0.19 99.96 The bearing of the discovery of this arsenical mineral on the origin of the ore-deposits a t Beuthen is discussed. Minerals from Arizona. WALDEMAR LINDGREN and WILLIAM F. HILLEBRAND (Amel.. J. Sci 1904 [iv] 18 44S-460).-The minerals described are from the copper deposits a t Clifton and Morenci. The principal ore is massive chalcocite which has resulted from the replace- ment of pyrites by means of descending solutions of cupric sulphate.A partial analysis of the chalcocite gave 96 per cent. Cu,S and 2.4 per cent. FeS the latter probably mechanically admixed. Co~onadite.-A black metallic mineral not unlike psilomelane in general appearance and intimately intermixed with quartz is found in fairly large amount in the Coronado vein ; it is named coronadite. It has a finely fibrous structure ; hardness about 4 ; streak black with. a brownish tinge. Analysis gave MnO,. MnO. PbO. ZnO. CuO. MOO,. A1,0,. 56.13 6.56 26.48 0.10 0.05 0.34 0%3* Fe,O,. H,O. SiO,. Alk. &c. Total . Sp. gr. 1.01 1 *03 7.22 0.45 100~00 5.246 * With a little TiO P205 V,O,. L. J. S. Insol. and CaO MgO,MINERALOGICAL CHEMISTRY. 97 These results give the formula R0,3Mn02 or considered as a salt of a derivative of ortho-mmganous acid R(Mn,07)".Taking into account the water (only 0.14 per cent. of which is lost below 200°) the formula would be H,"H2(Mn1202,) ; the water is hovever probably due t o incipient alteration. Chrysocolla is of common occurrence in the oxidised part of the deposits and shows a s usual variations in composition. Microscopical examination shows that the different concentric layers have different microcrystalline structures. The term chrysocolla probably includes two mineral species. Copper-pitch-os.e.-This occurs in association with t h e chrysocolla. It is a dark brown t o black substance with sometimes a dull but generally a glassy t o resinous lustre. I n thin sections it is opaque or translucent the latter being optically isotropic.A partial ansljsis gave Insol. in HCL Loss on CuO. 2110. MnO. Fe203 A1203,P20,. (SiO,). ignition. Total. 38.6 8.4 21.2 4 4 32.8 135"i' 98.7 Copper-pitch-ore is usually considered t o be impiir e chrysocolla but the material now described contains no chrysocolln and i t does not appear to be a mixture. It is in some respects ielated to melanochal- cite (Abstr. 1903 ii 156). il.lorencite.-This name is given t o a mineral which occurs in cal- careous shale at Morenci as brown or green spreading masses. It is rendered impure by intermixed chlorite and pyrites but more pure material is present as brownish-yellow silky fibrous seams intersecting the mass. Under the microscope the minute fibres are brownish- yellow and slightly pleochroic and extinguish parallel to their length. -d Analysis gave SiO,.TiO,. A1,0,. Fe,O,. FeO. 45.74 trace 1.98 29.68 0.83 IJ,O II,O K,O. Na,O. (105"). (>105"). Cuo. 0.20 0.10 8.84 5.08 little MnO. CaO. trace 1.61 FeS,. P205. 0.66 0.18 Neglecting wxter a metasilicate formula R/R,"'(SiO,), whilst with t h e water as essential the ratio. is that of an orthosilicate. The SUbStiinCe is optically well individualised and is evidently an a1 teration product of some metasilica te contact-metamorphic mineral. Other minerals described from this district are millemite hemimor- phite dioptase libethenite and bronchantite all of which are found as distinct crystals ; also the rare minerals spangolite ( HI,Cu,A1C1S019) and gerhardtite ( H6Cu,N,01,). Microscopical examination of the green ores proves t h a t bronchantite is of extremely common occurrence mostly intergrown with malachite.L. J. S. nrgo . 3.99 Total. 98.89 is derived Emmonsite (3) from a New Locality. WILLIAM F. HILLEBRAND (Amer. J. Xci. 1904 [iv] 18 433-434).-A green rnammillary * Less 0 due t o conversion of MnO to Mn,04.98 ABSTRACTS OF CHEMICAL PAPERS. mineral occurring with gold and tellurite at Cripple Creek Colorado and resembling durdenite in appearance was found on analysis to approximate to ernmonsite in composition. The cleavage and optical characters are also in general agreement with those previously described for emmonsite. The following results (22.44 per cent. gangue mainly quartz deducted) give the ratios TeO Fe,O H20 = 3.16 1.00 1.77. TeO,. Se. Fe20,. H,O at 100". H,O above 100". '70.71 ni 1 22.76 0.21 4.54 P A A1203. Si02 &c. Total. $p. gr. 0.34 0.56 0.88 100-00 4-53 L. J. 5. The Sodalite Series. Z. WEYBERG (Centr. Min. 1904 727-729). -This is a continuation of the work of Lemberg Thugutt (Abstr. 1895 ii 358) and Morozewicz (Abstr. 1899 ii 764) on derivatives of the group Na,Al,Si,O,. A mixture of silica alumina and soda in the proportions Na,A-1,Si20 was fused with sodium chromate ; there was obtained a yellow crystalline powder of isotropic grains and cubes with the composition 7Si02,4A1,0,,5Na20,Cr0 ( = 7Na2A12Si,0,,Na,Al,0,,2Na,Cr0,). L. J. 8.

ISSN:0368-1769    

DOI:10.1039/CA9058805096

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

98 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Changes in the Viscosity of the Blood produced by Alcohol. RUSSELL BURTON-OPITZ (J. Physiol. 1904 32 8-1 ?).-The viscosity values were obtained by Hurthle’s method. The addition of 0.7 per cent;. solution of sodium chloride to blood causes an immediate and distinct decrease of viscosity whilst equal amounts of distilled water render the blood slightly more viscous. Alcob 01 intravenously in- jected or absorbed from the alimentary canal increases the viscosity of the blood ; the effect lasts from 30 to 45 minutes. The sp. gr. and viscosity vary in the same manner. Tho experiments were made on dogs. W. D. H. Nuclei of Birds’ Red Corpuscles. D. ACKERMANN (Zeit. physiol. Chem 1904 43 299-304).-A mass of nuclei of the birds’ red corpuscles was obtained by a method of washing with saline solution then with water to remove hzmoglobiu and centrifugalising.Leci- thin and cholesterol were removed by alcohol and phosphorus and nitrogen estimated in the residue ; from the numbers obtained it is calculated that the nuclei consist of 42 per cent. of nucleic acid and 58 per cent. of histon. W. D. II.PHYSIOLOGICAL CHEMISTRY. 99 Gaseous Metabolism of the Kidney. JOSEPH BARCROPT and THOMAS G. BRODIE (J. Physiol. 1904 32 18-27).-The experiments were made on dogs which had been subjected to evisceration a n operation they survive about eight hours. Diuresis usually produced by injection of ui'ea is accompanied by a large increase of oxygen absorption in the kidney but that increase is not in proportion to the diuresis produced.I n only one experiment was there any increase in the carbon dioxide given out. There is no definite relation between the oxygenabsorbedand the carbon dioxide given out at any one time. The volume of the latter is often in excess of the former especially at the commencement of an experiment before diuresis has been set up. The amount of the two gases exchanged during diuresis varies from 0.002 to 0.281 C.C. per gram of kidney substance per minute. There is no necessary accompaniment of increase of blood flow and this is never in proportion to the acceleration of the urine flow The blood gases were estimated by the pump and by the Barcroft-Haldane method. W. D. H. Nutritive Value of Proteid Decomposition Products. I. W.CRONHEIM (Pjuger's Archiv 1904 106 17-42).-The experiments were made on men and dogs and compare the work of the digestive tract during feeding on flesh and somatose. The latter can be given in large quantities (30 grams) to men without producing intestinal irritation ; this quantity necessitates a smaller digestive activity than flesh containing an equivalent amount of nitrogen. W. D. H. Sulphur and Phosphorus Metabolism on an Abundant Proteid Diet. KARL BORNSTEIN (Pjiiger's Archiv 1904 108 66-79).-The higher the percentage of neutral phosphorus and sulphur in the urine the smaller is the oxidative power of the organ- ism. The experiments recorded lend support to the doctrine that an abundant proteid diet improves the cellular activities of the organism. W. D.H. Peptic Digestion Products of Plasteins. JOSEPH GROSSMANN (Bezity. clzenz. Physiol. Path. 1905 6 191-205).-The addition of a peptic digest of plasteins to the finely subdivided mucous membrane OF stomach 01- intestine (obtained from fed or hungry dogs) leads a t 3s" to 40" to a disappearance of noii-coagulable and a corresponding appearance of coagulable proteid material. This is a proof that the mucous membrane contains not only proteolytic enzymes but agents which act in the opposite direction. W. D. H. Formation of Sugar from Proteid. HUGO LCnm (Pjiigw's Arc/& 1304 106 160-167).-The panc1~e.w was removed from a dog and the animal observed for about a month during which time it was kept on a proteid diet (mainly nutrose) ; the total sugar in the urine was far too large t o be accounted for by that in the food or present as glycogen in the body the remainder must therefore have been derived from proteid.W. D. H.100 ABSTRACTS OF CHEMICAL PAPERS. Pancreatic Diabetes. EDUARD PFL~GER (PJiiger’s Archiv 1904 106 168-1 72).-A commentary on Luthje’s work (see preceding abstract) i n which it is shown that a large amount of the excreted sugar cannot have had a carbohydrate origin; the figures work out rather differently from those calculated by Liithje but the main con- clusion is corroborated. The author holds t,hat the sugar excreted as the result of feeding on proteids (and the same is true for feeding on alanine glycine asparagine &c.) is due to a n indirect action analo- gous t o the way in which ammonium carbonate will cause an increase in the hepatic glycogen and further that the sugar attributed to proteid decomposition really originates from fat.I n many diabetics there is no increased nitrogen excretion. W. D. H Are Proteolytic and Rennetic Ferments Identical 3 IVAR BANG (Zeit. physiol. Chem. 1904 43 358-360).-Pawloff has advanced the view that the rennet action of gastric juice is a property of pepsin and holds similar views regarding other rennetic ferments. I n the present communication a number of weighty arguments are adduced to show that this cannot be the case. W. D. H. The Lymph-flow from the Pancreas. F. A. BA~NBRIDGE (Bvit. Ned. J. 1904 ii 1742-1’744 ; J. Phpiol. 1904 32 I-S).-The intravascular injection of secretin or extract of ileum in dogs causes an increased flow of lymph from the thoracic duct.This has also been shown to be the case by Falloise (Bull. Acad. Roy. BeZg. 1902 No. 3 2 p. 945). After ligature of the portal lymphatics secretin still causes a n increased flow of lymph whereas ileum extract has no effect. The increased flow of lymph is closely related to the secretion of pancreatic juice; it is derived entirely from the pancreas and is probably formed as a result of metabolic changes occurring in the pancreas during the secretion of the juice. It is produced by secretin and not by the depressor substance in the extract. W. D. H. Influence of Alkalis on the Growth of Bone. HANS ARON (f’JU9e~’s Amhiv 1904 106 91-92).-A preliminary account of ex- periments to show the importance of sodium and potassium salts in the food on the growth of bone. - W.D. H. Condition of Water in the Tissues. . R. DU Bors REYXIOND (Chem. Centr. 1904 ii 1661-1662 ; from Ye~h. Ges. Beut. iVfJ Arzte 1903 11 (2) 437-440).-The swelling which certain tissiies undergo with water is regarded not as due to mechanical forces but more probably to chemical union. This is supported by experiments with dried albumin. W. D. H. Universal Presence of Erepsin in Animal Tissues. HORACE M. VERNON (J. dPhysioZ. 1904 32 33-50).-Erepsin was obtained in glycerol extracts of a large number of tissues of both vertebrate and invertebrate animals ; least was obtained from invertebrates and most from mammals. The kidney is richest in the enzyme; then follow intestinal mucous membrane pancreas spleen and liver ; then after aPHYSIOLOGICAL CHEMISTRY.101 large drop heart muscle; whilst skeletal muscle and brain tissue are poorest. The relative amount in the tissues is constant and not a matter of chance and must be related to their function. The lower the animal in the scale of evolution the less are its tissue erepsins in- fluenced by the reaction of medium ; in mammals an alkaline medium is most and an acid medium least efficacious. To some extent the tissue erepsins are specific the intestinal extract for instance having relatively much more action on partially hydrolysed peptones than kidney and liver extracts. W. D. H. Chemical Changes produced in Flesh by Fungi. P. W. BUTJAGIN (Arch. Hggiene 1905 52 1-2l).-During the develop- ment of Pewicillium glazccztm and Aspergillus niger in flesh the amount of water increases the absolute amount of nitrogen diminishes and the nitrogenous compounds soluble in water increase ; the ethereal extract is lessened especially in early stages and the amount of extractives increases ; the alkalinity rises as also does the amount of volatile acids.The fungi appear to secrete enzymes which are proteolytic and lipolytic. Some quantitative differences between the actions of the two fungi are noted and on the whole P. gZnzcctcn2 destroys the constituents of flesh more rapidly. Tyrosinase in the Skins of some Pigmented Vertebrates. FLORENCE M. DURHAM (Proc. Ro?. Soc. 1904 74 310-313).-An aqueous extract of the skins of rabbits rats guinea-pigs and chickens acts on tyrosine and produces a pigmented substance.This suggests the presence of a tyrosinase in the skins of these animals. The action takes place most readily at 37' and is destroyed by boiling; the presence of an activating substance like ferrous sulphate is necessary to start it. Black substances are obtained when animals with black pigment in their skins are used and yellow substances when the skin contains the yellow pigment. These coloured substances are soluble in alkalis but insoluble in acids. W. D. H. W. D. H. Fat in Milk. WILHELM CASPARI (Chewt. C'entr. 1904 ii 1664-1665 ; from Zeit. Biol. 46 277-279).-Poleniica1. The quest'ion raised is the origin of the milk fat from the fat of the food. The casein used by some observers was not absolutely free from fat. Iodocasein and iodoalbumin freed from fat cause no trace of iodised fat in the milk.W. D. H. Functions of Thyroid and Parathyroid Glands. SWALE VINCENT and W. A. JOLLY (J. Physiol. 1904 32 65-86).-Removal of both thyroid and parathyroid does not necessarily cause death ; but fatal results when they do occur are due to the absence of these glands. Great variations obtain in the animal kingdom in this matter. Rats and guinea-pigs do not suffer at all. Monkeys show transient nervous symptoms. Dogs and cats suffer severely and usually die. In Zoxes the symptoms are of rapid onset and death occurs early. No symptoms of myxedema were ever observed ; this disease is therefore due t o causes more complex than thyroid insufficiency. I n young VOL. LXXXVIII. ii. 8102 ABSTRACTS OF CHEMICAL PAPERS.animals however thyroid extirpation causes temporary cessation of growth. When the thyroid is removed the parathyroids appear capable of replacing it to some extent and their histological structure changes accordingly. W. D. H. Elimination of Urea in Healthy Subjects. HENRI LABBB and E. MORCHOISNE (Compt. Tend. 1904 139 941-943).-That the amount of urea depends on the amount of proteid ingested is supported by the experiments recorded on a number of healthy people on the same diet. The amount in all was approximately identical. W. D. H. Organic Phosphorus in Urine. DOUGLAS SYNMERS (J. Pathol. Bacteriol. 1905 10 159-1 72).-The estimation of inorganic phos- phates is not a true index of phosphorus metabolism; in various pathological conditions the phosphoric acid in organic combination may be frequently 25-50 per cent.of the total. The excretion of organic phosphorus is to a certain extent rhythmical The amount is pronounced in lymphatic lenczemia and especially in degenerative nervous diseases. It may be due to an increase in endogenous phos- phorised katnbolites or may be an expression of lessened oxidation which normally would give inorganic phosphates as the end-products. The theory that it originates from bone is dismissed for in extensive disease of bone like osteomalacia the output of phosphoric acid is not increased. W. D. H. Substances Soluble in Ether in Human Faeces. FELIX OEFELE (Clmz. Centr. 1904 ii 1664; from Bey. Deut. phawn. Ges. 14 35 5-3 7 1 ),-Analytical numbers are given for preformed neutral fat fatty acids lecithin &c.in the faxes. A part is unsaponifiable. Great variations occur in health. W. D. H. Pernicious Anemia. G. LOVELL GULLAND and ALEXANDER GOODALL ( J . Pathol. Bacteriol. 1905 10 125-144).-This is a megaloblastic anzemia ; the blood cells are abnormally vulnerable ; a toxin is produced which does not always originate in the intestine. The large red corpuscles produced in the marrow fall a ready prey to endothelial cells and leucocytes. I n some cases this is congenital. The accumulation of iron in the liver is the usual result of excessive blood destruction and does not necessarily mean that the actual destruction occurs a1 together in that organ. W. D. H. Acid Dyscrasia. -4 LEXANDRE DESGREZ and J. ADLER (Compt. rend. 1904 139 944-945.Compare Abstr. 1904 ii 193).-An acid dyscrasia can be produced in guinea-pigs by repeated sub- cutaneous injections of hydrochloric acid. I n this condition there are (1) a preponderating disintegration of the proteids rich in sulphur (2) a lessening of the urine formed and (3) a considerable increase of nitrogenous metabolites in the tissues. Tho conditions are similar t o those noted in skin diseases. W. D. H.PHYSIOLOGICAL CHEMISTRY. 103 Influence of Fever on the Reducing Action of the Organism. C. A. HERTER (Amef-. J. Physiol. 1904 12 457-465).-The tempera- ture of rabbits was raised either by superheating or infection with hog-cholera. Elevation of temperature accelerates the reduction of methylene-blue by various types of cells. The differences of colour are especially striking in brain skeletal muscles heart spleen pancreas niid liver.A method for measuring the reaction-velocity of reduction was also devised. W. D. H. Production and Inhibition of Glycosuria in Rabbits by Salts. MARTIN H. FISCHER (PJiiger’s A r c h 1904 106 S0-83).- Intravenous injection of sodium chloride and other sodium salts in rabbits produces glycosuria which is inhibited by calcium chloride. This is most readily produced if the injection is made towards the brain ; the salt probably produces an osmotic change which affects the ‘‘ diabetes centre.” Cutting the splanchnic nerves prevents it. Lithium strontium and potassium salts also produce similar glycos- uria; ammonium salts do so also in large doses but here hzmo- globinuria also occurs.Calcium and magnesium salts kill the animal before any sugar can pass into the urine. Non-electrolytes such as urea alcohol and glycerol are inactive. W. D. H. Cystinuria. I. ADOLF LOEWY and CARL NEUBERG (Zeit. physiol. Chenz. 1904 43 338-354).-Friedmann and Neuberg have shown that the cystin of urinary calculi (calculus-cystein) is not identical but isomeric with that obtained from the decomposition of horn (protein- cystin). Protein-cystein is a-amino-P-thiolpropionic acid SH* CH,* CH(NH,) CO,H whereas calculus-cystein is P-amino-a-thiolpropionic acid NH,*CH,* CH( SH)*CO,H. The special-interest of this isomerism arises from the fact that this is one of the rare instances of a P-amino-acid arising during animal metabolism Tryptophan is another instance (indole-/3-aminopropionic acid Ellinger) and some of Levene’s amino-acids do not belong to the a-series.A patient ad. 18 excreting 0.5 gram of cystin daily came under the authors’ notice and contrary to expectation this was protein-cystin. Acting on the supposition that the case was not merely one of anomalous proteid metabolism but one in which there was a general breakdown of amino-acid metabolism the urine was searched for other aminc-acids but without swcess ; diamines were also absent. The anomalous nature of the metabolism was however shown when amino-acids were administered by the mouth. Tyrosine leucine and aspartic acid instead of being broken down in the body were excreted in the urine almost quantitatively ; the same was true for protein-cystin (given in 6-gram doses) whereas a normal man will burn 8 grams with the formation of sulphates and thiosulphates.On the other hand calculus- cystin was completely burnt with a correaponding increase in sulphates and neutral sulphur A fter feeding on lysine cadaverine (pentamethyl- enediamine) appeared in the urine and putrescine (tetramethylene- diamine) appeared after the administration of arginine. There is here a direct fermentative splitting off of carbon dioxide the first time 8-2104 ABSTRACTS OF CHEMICAL PAPERS. it has been shown to occur i n uivo. Whether this is brought about by enzymes or by intestinal bacteria it is impossible to say for the patient would not permit subcutaneous injections but the discovery of arginine by Kossel and Dakin would appear to point to an enzyme for ornithine by loss of carbon dioxide would yield tetramethylene- cliamine.The interest of the case is this if pyoteids are normally broken up in the alimentary canal into simple crystalline cleavage products why did not this pitient excrete thein unchanged as he did when they were given by the mouth? This tells against the theory of complete proteolytic breakdown in the intestine. It may be that cystin is specially loosely combined in the proteid molecule. Further experi- ments with polypeptides proteoses and peptones are in progress. W. D. H Oxaluria. FRIEDRICH KUTSCHER and MARTIN SCIIENK (Zeit. plqsiol. Chenz. 1904 43 337).-By oxidation of gelatin with calcium permanganate important amounts of oxamic acid are obtained. The mother substance of this must be glycine.Proteids poor in the glycine radicle such as casein and pseudomucin yield little or none. On the clinical side Lommel (Ueutsch. Arch. kZii2. Ned. 1899) showed that feeding with gelatin produced oxaluria. Oxidation in the body doubt- less caused the appearance of oxamic acid and this is broken down with the formation of oxalic acid and ammonia. W. D. H. Elimination of Sulphur and Phosphorus Demineralisation of the Organism and Size of the Molecule Elaborated in Skin Diseases. ALEXANDRE DESGREZ and J. AY RIGNAC (Conzpt. rend. 1904 139 900-901).-The examination of the urine in cases of skin disease shows that the disintegration is most marked in those proteids which are rich in sulphur. What is termed demineralisation of the organism was higher than normal in 56 per cent.of the cases. W. D. H. Tetanus and Quinine. E. VINCENT (dizn. Inst. Pasteur 1904 18 748-760). -Observers have not infrequently described tetanus as a sequel to injections of quinine given for malaria. I n these days of antiseptics this cannot be due to infection from dirty instruments. Quinine hydrochloride kills the tetanus bacillus and so cannot favour its development. The fatal dose of quinine varies a good deal in different animals; this had to be determined before the next experi- ments were performed ; these consisted in subcutaneously administer- ing quinine either with 01- subsequently to a subcutaneous dose of tetanus bacilli and the remarkable fact was elicited that these animals quickly died whereas those who received only one of the two substances injected recovered.With the injection of both the bacilli multiply more rapidly and pass more into other tissues. Quinine given by other channels does not act thus. I t s action is attributed to its harmful action on leucocytes. If quinine is given subcutaneously for malaria and the patient has cutaneous excoriations it is wise t o administer also antitetanic serum. W. D. H.PHYSJOLOGICAL CHEMISTRY. 105 Action of Chloroform on the Heart and Arteries. EDWARD A. SCHAFER and HERBERT J. J. SCHARLIEB (Trans. Roy. Soc. Edin. 1904 41 Part 11 (No. l a ) 311-341. Compare Abstr. 1903 ii 437).- By perfusing the vessels of a frog with blood or saline solution con- taining a high percentage of chloroform (1 to 5 grams per litre) the blood-vessels are directly constricted ; with more dilute mixtures the effect is less pronounced but dilatation is never obtained.In experiments on mammals the same main effect is produced even with dilute solutions except in the kidney where the vessels are dilated. The effect is one on muscular tissue not on vaso-motor nerve-endings for apocodeine does not abolish the effect as i t does that of adrenaline. The fall of blood pressure seen is of cardiac origin the depressant effect on the heart being more than sufficient to counterbalance con- striction of peripheral vessels. The effect on the heart resembles that of vagus excitation except that the arrest is more permanent. With the arrest of the circulation the respiratory centre also fails second- arily. During light anxsthesia vagus excitation easily causes arrest of the heart which however soon escapes from vagus control but in deep anaesthesia the effect is more pronounced.Quite small doses of atropine (0.00003 gram per kilo. of body weight in the dog given subcutaneously) prevent the effect of vagus excita- tion on the heart and this lasts for three hours. The precaution of administering a dose of atropine before chloroform anxsthesia in man should never be omitted even although it will not prevent death when an overdose of chloroform produces paralysis of respiration and complete ‘6 paralytic dilatation ” of the heart. The cardiac arrest sometimes noticed in the initial stage of ancesthesia is a reflex vagus effect ; this is prevented1 by atropine. The paralytic dilatation that occurs in later stages when too rnuch chloroform is given is due to action in the neuro-muscular inhibitory end-apparatus i-‘ather than in the muscle itself.The heart is then entirely inexcitable and respira- tion fails first This final effect on the heart is not antagonised by atropine nor is adrenaline of any avail as a rule. The addition of small quantities of ammonia vapour or ammoniated alcohol to the chloroform inhaled in cases where danger is signalled is strikingly beneficial and alcohol vapour itself without the ammonia is nearly as good. The post-mortem appearances after death from chloroform inhalation are very similar to those seen in asphyxia due to deprivation of air or by drowning even although there may be no true asphyxia and a free supply of air by artificial perflation.Action of Monatomic Alcohols on Simple Organs. PAUL GR~~TZNER and..H. BREYER (Chem. Centr. 1904 ii 1665 ; from Verh. Ges. Deut. ~Vtf. Arxte 1903 11 (2) 443).-These alcohols act harmfully on cilia the higher ones more intensely and rapidly. The alcohol in A.C.E. mixture is needlessly excessive. W. D. H. W. D. H. Relations between the Chemical Constitution and Physio- logical Action of some Ammonium Bases. ERNST SCHMIDT (Arch. PhCirna. 1904,242,705-714. Compare especially Abstr. 1892 905 and this vol. i 23 ; also for the preparation of the substances in106 ABSTRACTS OF CHEMICAL PAPERS. question Abstr. 1892 806 949 950; 1894 i 433; 1901 i 443; this vol. i 23).-A r8sunz8 of matter already published. ALOIS VELICH (Zeit.Zuckerind. Boha. 1904,29 14-25). -The author finds that pure betaine has no poisonous action the effects noticed by Waller and Lowton (,Qbstr. 1904 ii 65) being due to the insufficient neutralisation of the betaine hydrochloride employed. Even after very strong doses the author is unable to find any diminution of the blood pressure or retardation of the pulse. C. F. E. Betaine. T. H. P. Effect of Adrenaline on Excretion of Sugar and Nitrogen in Birds. DIARMID NOEL PATON (J. PhysioZ. 1904,32 59-64).-When adrenaline is administered subcutaneously it produces glycosuria in birds as in mammals. I t causes a decrease in the proportiou of nitrogen elaborated into uric acid an increase of the nitrogen present as ammonia and probably in that in urea also It does not act through the pancreas.W. D. H. Selective Action of Cocaine on Nerve-fibres. WALTER E. DIXON (J. Plqsiol. 1904 32 87-94).-Cocaine locally applied to nerve-fibres picks out and paralyses some before others sensory beiore motor afferent before efferent vagal fibres vaso-constrictors before vaso-dilators and broncho-constrictors before broncho-dilators. It is suggested that the local application of cocaine to the vagi may be a means of combating death during early chloroform narcosis. Drugs which attack the central nervous system almost invariably attack the sensory cells and fibres before the motor. There is no reason to suppose that cocaine has a specific action on sensory nerve- endings. W. D. H. Physiological Action of Azoimide. LETCHWORTH SM~TH and C. (3. L. WOLF (J.Medical Research 1904 12 451-474).-Azoimide is a very powerful protoplasmic poison; the effect of small dosea is almost instantaneous death. It is almost impossible to determine the details of its action unless very small doses are employed and the use of the sodium compound minimises to some extent the danger and unpleasant symptoms which the observers experience The experi- ments made on frogs and mammals show that the action in the main resembles that of hydrocyanic acid. Muscle and nerve are simul- tmeously paralysed after a preliminary stage of increased excitability. The respiratory centre is similarly first excited and then paralysed. The fall of blood pressure seen is primarily due to vascular dilatation especially in viscera other than intestine and kidney It forms a compound with methzemoglobin resembling that formed by hydrocyanic acid but the existence of a compound with hwnatin or hzmoglobin was not made out.Introduction of a phenyl radicle lessens its action. W. D. H. The Toxic and Anti-toxic Action of Salts. ALBERT P. MATHEWS (dnzer. J. PhpioZ. 1904 12 419-443).-The valence of anVEGETABLE PHYSIOLOGY AND AGRICULTURE. 107 ion is of little or no importance in determining its anti-toxic action. Attention should therefore be directed to its other properties potential weight velocity and volume. W. D. H. Action of Calcium Permanganate on Alkaloids. G. BAUDRAN (Compt. rend. 1904 139 1000-1002).-1f strychnine sulphate or hydrochloride is treated a t 37" with a 5 per cent. solution of calcium permanganate a product is obtained which when mixed with strychnine annihilates its poisonous effects.Similar results were obtained with morphine and aconitine. The products all contain manganese. W. JI. H. Chemical Combination and Toxic Action as Exemplified in Hamolytic Sera. ROBERT MUIR and CARL H. BROWNING (PYOC. Boy. Xoc. 1904 74 298-309).-1n the action of a complement there are two distinct factors (1) the power of chemical combination and (2) toxic action which correspond to Ehrlich's haptophore and zymotoxic groups. Deficiency in action does not necessarily imply absence of the first factor but may be clue to the non-sensitiveness of the tissue molecule to the second group. In testing the corpuscles of an animal it is found that very large doses of both complement and immune substance are necessary if serum from the same species of animal is used and want of sensitiveness is especially noticeable in connection with the zymotoxic group. In some cases there is also deficiency in the com- bining power of the complement with the receptors of red corpuscles. The diflerences of dosage of the immune-substance with different comple- ments and also of various complements do not appear t o be clue to multiplicity of immune-substances. W. D. H. Plurality of Cytolysins in Snake Venom. SIMON FLEXNER and HIDEYO NOGUCHI (J. PathoE. Bacterial. 1905 10 11 1-124).-Snake venoms from different sources contain solvents for numerous cells other than blood corpuscles. This is due to a number of distinct solvents and depends on the interaction of amboceptors and complements The latter are contained within the affected cell. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9058805098

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 107 Chemistry of Vegetable Physiology and Agriculture. New Method for the Purification of Water Supplies. GEORQE T. MOORE (Amer. J. Phccmn. 1904 76 553-564).-The treatment consists in adding copper sulphate t o the water in the proportion of 1 t o 5,000,000. By this means the growth of a l p is prevented sewage bacteria are destroyed and the total number of bacteria is reduced by a t least 95 per cent. Over 50 public water supplies in the United States are cow being treated with copper sulphate the reservoirs concerned holding from a few to hundreds of108 ABSTRACTS OF CHEMICAL PAPERS millions of gallons. The quantity of copper added to the water is con- sidered to be too small t o have the slightest effect on the health of the consumers even if copper itself be injurious which is doubtful.w. P. s. The Copper Treatment of Water. HENRY KRAEMER (Amer. J. Pharm. 1904 76 574-579).-The results are given of experimentE carried out for the purpose of testing the efficiency of copper in re- ducing the number of micro-organisms in drinking-water. The con- clusions arrived a t are (1) that intestinal bacteria such as Bacillus coli and B. typftosus are completely des troyed by placing clean copper-foil in the water containing them ; (2) that the etfects of colloidal copper and copper sulphate in the purification of drinking-water art? in a quantitative sense much like filtration only the organisms arc com- pletely destroyed ; (3) that pending the introduction of the copper treatment on a large scale drinking-water may be purified by the use of strips of copper foil 3.5 inches square t o each quart of water ; after being allowed to act for S hours a t the ordinary tem- perature the water is then drawn off or the strips are removed. w.P. s. Hydrogen Sulphide Microbes in Mineral Waters. N. GOSLINGS (Centr. Bakt. Par. 1904 ii 13 385-394).-Passugger water was found to contain sulphate-reducing bacteria perhaps Reijerinck’a Microspira desulfuricans ; but attempts to obtain pure cultures of the hydrogen sulphide microbe mere unsuccessful. N. H. J. M. Is Hydrogen Peroxide suitable for Sterilising Milk? P. GORDAN (Centr. Bakt. Par. 1904 ii 13 716-728).-8mall amounts of hydrogen peroxide as employed by Budde (Afilc?~-Zeit. 1903 No. 44) have practically no sterilising action on milk.Larger quantities which impart an unpleasant taste to the milk have a temporarily retarding effect on the growth of the bacteria. Complete sterilisation is only effected by amounts three times as great as those employed by Budde and the milk is then useless for human consumption. The process ip besides troublesome and rather expensive. N. H. J. M. Production of Fat from Proteid by Bacillus pyocpneus. S. P. BEEBE and B. H. BUXTON (Anzer. J. P?qsiol. 1904 12 466-270).-1n growths of Bncillus pyocynneus in proteid media a pellicle of fat is formed ; this is partly crystalline and various constants were determined. It is probable that the fat is formed in part by oxidation of albumoses apart from any carbohydrate nucleus they may contain. W. D.H. Respiration and Ferrnsntation of Mould Fungi in Rose Cultures. T. KRASNOSSELSKY (Centla. Hnkt. Par 1904 ii 13 673-687).-iWucor spinosus and Aspergillus niger give in air on substrata capable or incapable of fermentation similar curves of elimination of carbon dioxide. In absence of oxygen they behaveVEGETABLE PHYSIOLOGY AND AGRICULTURE. 109 differently on fermentable substrata the carbon dioxide curve showing that fermentation takes place with Mucor spinosus but not with Asperg illus. Jfucor spinosus on non-fermen ting snbstrata and Aspergillus on both substrata give off less carbon dioxide in hydrogen than in air. Sometimes only traces of carbon dioxide are produced. Under these conditions they can live a long time (67 and 141 hours respectively) and become capable of further det-elopment when air is admitted.The amount of carbon dioxide then rapidly increases and may often exceed the amount produced under normal conditions of aEration. This vigorous production of carbon dioxide does not however last long. The results are similar t o those observed by Palladin with Chloro- the c iunz SCL ccltai-opld urn. N. H. J. M. Comparative Production of Alcohol and Carbon Dioxide during Fermentation. LEON LINDET and P. MARSAIS (Conzpt. rend. 1904 139 1223-1225).-1t has been established by Pasteur by Gay- Lussac,and by Buchner and Hahn that the ratio between the alcohol and carbon dioxide in the final products of fermentation is sensibly equal t o unity ; the authors find however that if the alcohol and carbon dioxide are estimated during the process of fermentation the ratio which is greater than unity a t the early stages of the process diminishes towards unity as the reaction proceeds.Tho experiments mere con- ducted on three equal quantities of sterilised grape extract containing the same quantities of the same yeast and the alcohol and carbon dioxide estimated at three different stages of the reaction. Further experiments showed that the ratio between t h e alcohol and carbon dioxide is not appreciably influenced by changes i n t h e temperature or in the acidity of the sucrose extract. The initial preponderance of the alcohol over the carbon dioxide is connected with the growth of the yeast which is more rapid at the early stages of the ferGentation. M. A. W. The Alcoholic Ferment of Yeast Juice.ARTHUR HARDEN and WILI;IA>I J. YOUNG (Proc. Yl~ysiol. Soc Nov. 1904,1-2 ; J. Pl~ysiol.,32). -The alcoholic fermentation of dextrose by yeast juice is greatly increased (doubled) by the addition of boiled and filtered yeast juice although the latter fluid is itself incapable of causing the fermentation. This may be due to a n increase in the activity of the alcoholic ferment or to a decrease in that of the proteolytic enzyme (endotryptase) ; the former however is the more important action of the two. The substance in the boiled juice responsible for this action or ‘( CO-ferment,” is not affected by boiling ; it is dialyeable and precipitated by 75 per cent. alcohol. By filtration through a gelatin filter the enzyme and its co-ferment can be separated ; neither by itself produces fermentation ; a mixture of the two is equal in power t o the original juice.No co-ferment of endotryytase was discovered. F. L~HNIS (Centr. Rnkt. Par. 1904 ii 13 706-715).-Denitrification in soils can only be inconsiderable owing to the amount of air present. Pro- W. Y. H. Nitrification and Denitrification in Arable Soil.110 ABSTRACTS OF CHEMICAL PAPERS. duction of proteids is also inconsiderable owing to the absence as a rule of sufficient readily assimilable organic matter. Niixification generally greatly exceeds the antagonistic processes because the conditions usually present in soils are more favourable to nitrifying organisms than to the others. All three processes may honever under certain conditions be going on simultaneously.N. H. J. M. Assimilation of Free Nitrogen by Bacteria. GEORGE S. FRAPS (Bep. of Chemist Agric. Exper. Stat. N.C. 1902-1 903 40-44).-The results of preliminary experiments on soil bacteria which assimilate free nitrogen without symbiosis indicated that the greatest activity is in alkaline solutions containing glucose (a) potassium phosphate (0.2) sodium chloride (0*2) magnesium sulphate (0*2) and ferric chloride (0.01 per cent.) calcium carbonate (0.5 per cent.) being present. Less activity was observed when magnesium sulphate was omitted and much less in neutral solutions containing mannitol potassium sulphate ferric chloride and soil. Bacteria may possibly exist which are more active in a neutral medium. Substitution of glucose by starch did not increase the assimilation of nitrogen.Nearly all the nitrogen was fixed in the first week of the experiment a small amount being fixed in the second week. N. H. J. M. Nitriflcation of Different Fertilisers. W. A. WITHERS and GEORGE S. FEAPS (Rep. of Chemist Agric. Exper. Stat. Z.C. 1902-1903 3-8).-Four soils a poor sandy soil a rich loamy soil a rich clay soil and a poor clay soil (500 grams of each) in jars received calcium carbonate (3.1 grams) and 0.3 gram of nitrogen in the form to be tested. The jars mere kept a t a temperature of about 35' and water was added twice a week so as to maintain an amount equal to about one-third of the saturation capacity. After four weeks the amount of nitrogen as nitrates was determined. Taking the amount of cotton-seed nitrified as 100 in each case the variations were as follows ammonium sulphate 13 to 127 ; dried blood 70 to 120 ; fish 85 to 100; bone 22 to 43. In the case of farm-yard manure (16.1 grams to 500 grams of soil) there mas less nitrification in three of the soils than occurred without manure whilst in the fourth soil (the poor clay) 0.5 per cent.of the nitrogen was nitrified. Nitrification varied somewhat in the different s o h . N. H. J. M. Studies on Nitrification. GEORGE 5. ERAPS (Rep. of Chemist Agric. Exper. Stat. N.C. 1902-1903 9-30).-The number of nitrify- ing organisms in a soil varies according to conditions of moisture and temperature &c. and their activity is periodic rapid nitrification being preceded and followed by periods of less activity. Soils contain two groups of nitrifying organisms one which nitrifies cotton-seed meal the other ammonium sulphate.!Che relative numbers of one group may be increased by growing in a soil containing the corresponding manure.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 111 There are probably four groups of organisms three which successively convert organic nitrogen into ammonium salts nitrites and nitrates and one which directly produces nitrites or nitrates from organic nitrogen. Ammonium sulphate is nitrified more quickly than the phosphate chloride or citrate. N. H. J. M. Nitrification of Ammonia fixed by Chabazite. W. A. WITHERS and GEORGE S. FRAPS (Rep. of Chemist Ayic. Exper. Stut. N.C. 1902-1903 31-32).-Chabazite (250 grams) was kept for two days in a solution of ammonium chloride (40 grams in 1 litre).After being washed it contained 1.86 per cent. of nitrogen. An aniount containing 0.3 gram of nitrogen mas added with calcium carbonate (5.1 grams) t o 500 grams of soil which were kept for 3 weeks a t 35’. It was found that the ammonia absorbed by the chabazite was much more readily nitrified than ammonium sulphate or cotton-seed meal added directly to the soil It is possible therefore that zeolitic silicates in soils may assist the nitrification of ammonium sulphate by fixing a portion of the salt. N. H. J. M. Nitrifying Power of Typical North Carolina Soils. W. A. WITHERS and GEORGE S. FRAPS (Rep. of Clmmist Agric. Exper. Stut. N. C. 1902-1 903 33-39).-The nitrifying power of fifteen soils varied from 11 to 106 the lowest being sands with low water capacity low humus low absorptive power for ammonia low acidity and those con- taining a moderate amount of humus.Acidity of the soil did not prevent the growth of nitrifying organ- isma and low water capacity and atmospheric power are not necessarily coincident with low nitrifying power. N . H. J. M. Fixation of Atmospheric Nitrogen by Dead Leaves. ED. HENRY (Biecl. Cent?.. 1904 33 795-798 ; from Ann. Sci. Agron. 1903 8 313).-Dead leaves of various trees were found to fix con- siderable amounts of atmospheric nitrogen. No fixation or very little was observed when leaves were kept on very dry sand ; at the same time there was no loss of nitrogen. N. H. J. M. Changes in the Dimensions and Volume of Vegetable Organs and Tissues under the Influence of Desiccation.MARCELLIN BERTHELOT (Conzpt. rend. 1904 139 825-S34).-The results of experiments with stems of J’eestucu wheat and maize and leaves of Gynerizcm argenteunz showed that whilst the length was hardly altered by variations in the amount of water present the diameter changed a good deal. Filter paper free from ash did not vary in length and very slightly in width and thickness. Ordinary filter paper varied slightly in width more in length whilst the thic kness remained con st ant. N. H. J. &I. Vegetation in Atmospheres rich in Carbon Dioxide. EM. DEMOUSSY (Compt. re?&d. 1904 139 883-885).-Sixteen different plants were grown in normal air and in air containing 0.15 per cent.112 ABSTRSCTS OF CHEMICAL PAPERS. of carbon dioxide.Fifteen of the plants gave much more dry matter in presence of the larger amount of carbon dioxide than in ordinary air the amounts being as 122 to 262 100. The sixteenth plant Eicchsia produced 97 of dry matter with carbon dioxide against 100 in normal air and this may have been due to other conditions of the experiments. N. H. J. M. Assimilation of Certain Ternary Substances by Vegetables. PIERRE MAZ& and A. PERRIER (Ann. Inst. Yasteur 1904 18 72 1-747).-Sugars7 glycerol and methyl and ethyl alcohols retard for some days the germination of grains of maize but do not inhibit the growth of the small plants. Sugars are assimilated in the dark but light is essential for sugar synthesis. These substances added to a mineral solution are actively assimilated in the light concurrently with those which result in chlorophyllic function.The plants grow more quickly than control specimens. These organic materials there- fore contribute to plant anabolism. Glycerol is also absorbed in the light but it hinders development. Ethyl alcohol is harmful and leads to the production of aldehyde. Methyl alcohol activates vegetation and is presumably absorbed. The tolerance of plants to alcohols varies a good deal. Dextrin sometimes causes chlorosis; in this condition produced by want of iron the result is partly due to excess of bases which fix the iron. W. D. H. Decompositioii of Fallen Leaves. ED. HEKRY (Bied. Centy. 1904 33 793-7'94; from Ann. Sci. Agron. 1902-1903 8 328).- Leaves of aspen when kept over sand in wooden boxes lost in eleven iiionths 52 per cent.and when chalk was employed instead of sand 45 per cent. The much lower results obtained in earlier experi- ments are now shown t o be due to zinc boxes having been employed. Leaves of Curpinus betulus which are much less leathery and contain less tannin than oak leaves do not decompose more quickly than the latter. N. H. J. M. Formation and Distribution of tho Eesential Oil of an Annual Plant. EUG~NE CIrARABoT and G. LALOUE (Compt. rend. 1904 139 928-929).-The essential oil migrates from the leaves to the flower along with carbohydrates. After fructification the migration of nutritive matters to the flower ceases and the essential oil seems to return to the leaves. I n the plant examined (basil) i t was found that most of the essential oil is in the leaves and flowers The stems only contain a little and the roots none at all.N. H. J. M. Occurrence of Ricinine in Young Ricinus Plants. ERNST SCHULZE and ERNST WINTERSTEIN (Zeit. physiol. Chern. 1904 43 2 ll-221).-The compound described as ricidine (Abstr. 1898 i 42) is now shown to be identical with ricinine C,'H,O,N (Maquenne and Philippe Abstr. 1904 i 339). It gives a characteristic reaction very similar to the murexide reaction and also gives the Weidel reaction. The amounts present in young etiolated or even green plants are someVEGETABLE PHPSIOLOGY AND AGRICULTURE. 113 12-15-fold that contained in the same number of seeds. So far tyrosine and lycine have notl been obtained from these plants. J. J. S. A Substance which Inhibits the Fat-splitting Action of the Seed of Abrus Precatorjus. KARL BRAUN (C‘hem.Zeit. 1905 29 34. Compare Abstr. 1903 ii 74S).-An aqueous extract of the seeds of Abrus precatorius was injected subcutaneously into rabbits the serum from which was then used in the experiments described. The aqueous extract itseli was added t o castor oil and the slight amount of hydrolysis of the latter estimated. The addition of the serum lessened the extent of this hydrolysis when the latter was conducted a t low temperatures. A. McK Presence of Trahalase in Fungi. EMILE BOURQUELOT and HEXRI HERISSEY (Con@. rend. 1904 139 874-S76).-Trehalase was found in the tops of Boletus edzilis B. nurantiacus and Coytinarius elcttior but not in the tubes and lower parts. It also occurs in Paxillus involutus and I-lusszcla deliccc and in smaller quantity in Boletus badiits and A nta?zita muscaria.N. H. J. M. Medicinal and Useful Plants of Brazil. THEODOR PECKOLT (Chem. Cenli*. 1904 ii 1618-1619 ; from Re?*. Beut. Pharnz. Ges. 14 372-388. Compare Abstr 1904 ii ‘764).-RIost of the following Labia+,= :-Ocimun-L busilicum 0. carnosurn 0. micrantlmna. Aeolanthzts suuvis Peltodon mdicans lfepptis spicccta I[yptis Sulxmccnni Ifeptis fasciculutn C‘unilm gnlioides Salvia splendens Leonuvus sibiricus Leonit i s qiepetn f oliu and Scutellccria uliginosu-contain con siderabl t? quantities of ethereal oils and resins often together with an amorphous bitter principle ; glucosides and alkaloids are however seldom present in these plants. The abstract contains some account of these substances which are prepared in most cases from the leaves ; the yields and the quantitative composition of various parts of the plants are also given.E. W. W. Proteids of Wheat Gluten and its Relations to the Baking Properties of Wheat Flour. JOSEF KONIG and P. RINTELEN (Zeit. Nnhr. Genussm 1904 8 721-728. Compare Abstr. 1904 i 1066).-The amounts of water ash total nitrogen,nitrogeninsubstances soluble in 65-70percent. alcohol nitrogen as gluten and the total gluten were determined in seven samples of wheat flour and in three samples of spelt wheat flour. The quality of the flour was also ascertained by making loaves the actual volume of the loaves being determined by Kreusler’s and Maurizio’s method. The results showed that one of the spelt loaves was of bad quality although the meal as regards gluten proteid soluble in alcohol did not differ from ordinary wheat-meal.The quality therefore depends as little on the gluten alone as on the relation of total gluten or of the insoluble portion t o the portion soluble in alcohol. N. H. J. M.114 ABSTRACTS OF CHEMICAL PAPERS. Composition of Rice Refuse. GEORGE 8. FRAPS (Chem. Cerztr. 1904 ii 1430; from BUZZ. Texus Agr. Exper. Stat. 73 3).-The composition of rice hulls is similar to that of wheat straw. The bran consisting mainly of the seed-skin without much of the hulls should contain a t least 10 per cent. of proteids and not more than 20 per cent. of crude fibre. Addition of hulls lowers the value. The mixture of bran meal and hulls in the proportions present in the whole seed contains about 7.5 per cent.of proteids and 28 per cent. of crude fibre ; its value is about half that of the pure bran. N. H. J. &I Volatile Fatty Acids in Cheese. Biology of the Cheese Ferment. ORLA JENSEN (Centr. Bakt. Par. 1904 ii 13 161-170 291-306 428-439 514-527 604-615 687-7’05 and 753-765). -Acetic and formic acids were always found to be present the latter however frequently only in traces. Cheeses the ripening of which depends chiefly on mould fungi contain only small amounts of acetic and formic acids. All other cheeses contain some and often con- siderable amounts of propionic acid. Valerie acid was only found in Eackstein cheese made by the Limburg method but traces probably occur in all kinds of cheese. Rennet cheeses do not contain appreciable amounts of butyric acid owing probably to the low temperature of cheese ripening and the Gonsequent luxuriance of the lactic ferment Schabzeiger cheese in which the lactic ferments are killed contains considerable amounts (0.45 per cent.) of butyric acid.Cheeses in which a considerable decomposition of fat has taken place generally contain a good deal of ammonia but in no case was sufficient ammonia found to show an alkaline reaction with phenol- phthalein. Alkalinity as indicated by litmus often occurs with soft cheeses. As regards the aromas of different cheeses amino-acids are promi- nent in Emmenthaler cheese butyric esters in Roquefort and products of putrefaction in Limburger cheese. Bacillus casei linzburgensis alone produces only primary albumoses. Micrococcus casei Ziquefaciens Paraplectrum fatidurn and B.nobilis produce chiefly peptones amino-acids and ammonia. N. H. J. M. Lime Requirements of Hessian Soils. TH. DIETRTCH (Bied. Centr. 1904 33 814-818 ; from Ber. kandzu. Versuchs-Stat. Mar6urg 1903).-Application of lime (as burnt lime lime marl and dolomite marl) was beneficial in the case of the lighter soils from sand to sandy loam Well cultivated soils which contain little lime can do without liming better than badly cultivated soils possibly because of the presence of calcium compounds other than carbonnte such as humate and sulphate. Calcium silicate which occurs in less cultivated soils is probably unable to take the place of calcium carbonate. N. 13. J. M. Manurial Value of Human Excrement. JOHN SEBELIEN (Nied. Centr. 1904 33 805-808 ; from Tidsskr. Norsk. Lccndbr. 1904 45-55 and J. Landw. 1904)-The results of experiments with oatsANALYTICAL CHEMISTRY. 115 showed the value of fzeces as a nitrogenous manure to be 75 as com- pared with sodium nitrate = 100. The value however when compared with a mixture of sodium nitrate with phosphatic and potassium manure was 63 per cent. The nitrogen of urine is shown t o be about equal in value to that of sodium nitrate. Notwithstanding the considerable manurial value of faxes the conclusion is drawn that as regards the total excreta the feces are only one-ninth the value of the urine as the latter is produced in so much larger quantity. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9058805107

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

109 Organic Chemistry. Fundamental Conceptions underlying the Chemistry of the Element Carbon. JOHN U NEF (J. Arne?-. Chem. Xoc. 1904 26 1549-1577).-The fundamental conceptions on which the present system of organic chemistry is based are the constant quadrivalence of carbon and the process of substitution. These conceptions are discussed in the light of recent work and i t is pointed out that they are inadequate and must be replaced by the conceptions of a variable carbon valency and of dissociation in its broadest sense The importance of the so-called methylene chemistry is insisted on. It is suggested that at certain temperatures which vary according to the nature of the groups or atoms united to it the qnadrivalent carbon atom spontaneously becomes bivalent whilst a t lower temperatures the bivalent and quadrivalent carbon atoms are in dynamic equilibrium.The mechanism of substitution must be regarded as the union of an unsaturated molecule with a second molecule to form an additive compound which in many cases subsequently dissociates spontaneously with formation of two new molecules. E. G. isoHexanes in Roumanian Petroleum. PETRUS PONI and N. COSTACHESCO (Ann. Sci. Univ Jassy 1904,3 95-102. Compare Abstr. 1903 i 593).--The nature of the hexanes in the fraction of petroleum from Colibasi distilling between 58' and 66' has been investigated. This fraction was twice refractionated and the fraction obtained at 61.5-62.5" mas treated with nitric acid of sp. gr. 1.4 in a sealed tube at a temperature of 60". The nitrated product was dried and fractionated under a pressure of 35 mm.From the sp. gr. (0.9681 at O'/O") and the boiling point (168-1'70' under 750 mm.) this appears to be y-nitro-y-methglpentane. The fraction of highest boiling point ( l50-158')isadinitro-compound but it was only obtained in very small quantity A t intermediate temperatures mixtures of mono- and di-nitro-derivatives were obtained. The hydrocarbon unattacked by the nitric acid is P-methylpentane. The same products were obtained by treating the fractions collected a t 59.5-61.5' and 63.5-64.5O in the same manner and the results indicate that the petroleum fraction examined consists essentially of a mixture of &me th y lpen tane and y-me th ylpen tane. When treated with fuming nitric acid of sp. gr. 1.525 two crystalline products are obtained.One of these i a identical with /3yy-trinitro-/3-methylpentane. The other forms acicular crystals melting at 85' and appears to be PPy-trinitro-y-methylpentane (compare Youug Trans. 1898 '73,930). Oxalic acid and carbon dioxide were the only oxidation products observed in the action of the nitric acid of sp. gr. 1.4; carbon dioxide alone being formed in the action of the fuming acid. IX. M. D. More than half distilled a t 75-76". VOL. LxxxvIII. i. i110 ABSTRACTS OF CHEXlCXL PAPERS. Preparation of Acetylene Tetrachloride. CONSORTIUM FUR ELEKTROCHEMISCHE INDUSTRTE (D.R.-P. 154657. Compare Berthelot and Jungfleisch 1870).-Acetylene tetrachloride is best prepared by passing acetylene and chlorine alternately into antimony pentachloride and fractionally distilling the product.The gases may also be passed in simultaneously if precautions are taken to prevent contact between the two gases and to prevent supersaturation at any point. C. H. D. Trichloroisopropyl Alcohol. EDOUARD VITORIA (Bull. Acud. Roy. Relg. 1904 1087-1123. Compare Abstr. 1904 i 279 and 794).-yyy-Trichloroisopropyl alcohol CCl,-CHMe*OH prepared as already described (Zoc. cit.) forms monoclinic crystals similar to those of potassium tetrathionate (the crystallographic measurements are given in the original). It exerts vapour pressures equivalent to 3 18 and 115 mm of mercury at 19" 56' and 100' respectively. The alcohol could not be deracemised. yyy-Tricl~Zo~oiso~i.o~?jl acetate is a colourless liquid with an odour recalling that of ethyl acetate ; it melts at 8' boils at 180-18 1' under $66 mm.pressure has a sp. gr. 1 *353 a t 15'/15" and nD 1.46017. The nitrate is a colourless or slightly yellow liqiiid having a sp. gr. 1.499 a t 13" and n 1.47953. Attempts to prepare the benzoate chloride and bromide by the usual methods were unsuccessful. When treated with phosphoric oxide trichloroisopropyl alcohol furnishes the corresponding. yyy:t?.ic~~Zo.,-o),rop?jZene CCl,*CH:CH which is a colourless mobile liquid with an odour like that of aldehyde; it melts a t - 30° boils a t 114-115' under 757 mm. pressure has a sp. gr. 1.359 a t 13" and readily coiribiiies with chlorine to form perztachZorop~~opc~ne COI,*CH Cl-CH,Cl; this crystallises from warm alcohol in colourless needles has a caiiiphoraceous odour and melts a t 179-180".yyy-T,.icl~Zoro-ap-dib.r.o?izopro;uane CCl,*CHBr*CH,Br similarly prepared melts and decomposes slightly a t 210° but in other respects resembles the pentachloropropane. On oxidation with chromic acid trichloroisopropyl alcohol gave negative results but with nitric acid some trichloroacetic acid was produced. These results indicate that the alcoholic character of the substance and the reactivity of the H atom in the group - CH-OH are enfeebled by the presence of the three chlorine atoms. In attempting to prepare various ethers from yyy-trichloroiso- propyl alcohol by the application of the Grignard reaction to tetra- chloro-ethers of the type CCl,*CHCl*OR a series of alkoxydichloro- propylenes was obtained. p- Methozy-aa-dich Zovopropylene CC1,:CMe- OMe is a colourless liquid which melts at - 71" or - 72' boils at 126-127° under 750 mm.pressure has a sp. gr. 1.239 a t 20' and nD 1.469. P-Ethoxy-aa-ciichZoropropyZene melts at - 80' to - 8 5 O boils at 144-146' under 763 mm. pressure has a sp. gr. 1.179 a t 20' and nD 1 *46434. P-Propoxg-aa-dichZoropropyZenf3 melts at - 90° boils a t 163-164' under 764 mm. pressure has a sp. gr 1.134 at 20" and nD 1.45939. All these derivatives readily combine with halogens. Chloral propgZ alcoholate CCI,*CH(OH)*OPra is liquid and with0 RG AN IC CH E?tIlS'I'RY. 111 phosphorus pentachloride yields the telracl~?o)go-etfier CCl,*C HCl*OPra which boils a t 199-300' under 764 mm. pressure. Action of Organqrnagnesium Compounds on P-H ydroxy- aldehydes and on Reto-alcohols.ADOLF FRANKE and MORITZ KOHN (Her. 1904 37 4730-4731. Compare Ahsty. 1904 i 845).- A good yield of pe)ttane-/38-clioZ OH*CHMe-CH,*C HMe-OH niny be obtained by the action of magnesium methyl iodide (2 mols.) on aldol ; it is a viscid colourless liquid distils at 98' under 1 2 mrn. pressure 01- a t 198-199' under 748 mm. The dicccetate distils a t 88' under 10.5 mm. or a t 200-202' under the ordinary pressore. Diacetonealcohol and magnesium methyl iodide yield /3&-dinzethyZ- pentane-P8-dioZ OH*CMe,*CH,*CMe,*OH which is also a viscid liquid with a faint odour of peppermint. It distils a t 98" under 13 mm. pressure. Formylisobutyrylaldol and magnesium ethyl iodide yield in addition t o the hydroxypivalic ester already described (Zoc.cit.) a ylycol probably PP-clinzethyZpen tane-ay-cl ioZ OH* CH *CMe,*CH(OH)*CH,Re which melts a t 55' and distils a t 21 1-2 14". T. 8. H. J. J. S. Quadrivalent Oxygen. EDNOND E. BLATSE (Compt. ?*end. 1904 139 1211-1213).-The crystalline compound melting a t 52 - - 5 3 O obtained by the action of magnesium on iodine in the presence of ether probably has the constitution OEt,<31g>OEt (compare Abstr. 1901 i 317 and Zelinsky Abstr. 1903 i 802) and similw com- pounds are obtained when the ethyl ether in tbe above reaction is replaced by methyl ainyl ether or by phenyl amyl ether but the products are not crystalline whilst diethyl methylene ether or ethyl acetate yield the solid compounds Mg(OEtI*CH,*OEt) and MgI,,GMeCO,Et respectively. The basic character of the quadrivalent oxygen in these compounds increases with the complexity of the alkyl groups associated with them; thus the ethyl ether in the compound of magnesium iodide and ethyl ether is readily replaced by amyl ether diethyl methylene ether 01- by ethyl acetate and less readily by methyl amyl ether whilst ethyl ether readily replaces the more acidic phenyl ethyl ether in the compound i t forms with magnesium iodide.Direct evidence in favour of the constitution suggested for the compound of magnesium iodide and ether is afforded by the action of benzoyl chloride at the temperature of boiling water; the products are ethyl iodide ethyl benzoate and magnesium chloride and the following I 1 V / I I\/Et Et/\Mg/\ Et equation represents the reaction 0 0 +2PhUOC1= 2EtI + 2PhC0,Et + MgCl,.FRITZ FOERSTER and A. PIGUET (Zeit. Elektyochenz. 1904 10 924-925).-Tn reply to the criticisms of Hofer and Moest (this vol. i 8) of the authors' previous paper on this subject (Abstr. 1904 i 965) they point ont that the fact 31. A. W. Electrolysis of Potassium Acetate. i 2112 ABSTRACTS OF CHEMICAL PAPERS. that they mistook the nature of the reaction brought about by that portion of the current which does not produce ethane does not affect the accuracy of their determinations of the division of the current between ethane-forming and non-ethane-forming reactions. T. E. Constitution of Sodium Salts of Certain Acids containing a Methylene or Methinene Grouping. Alkyl Cyanoacetatee Acylcyanoacetates Malonates and Cyanomalonates ; Malono- nitrile and Cyanocamphor.ALBIN HALLER and PAUL T. MULLER (Conyt.rend.,1904 139 1180-1185. Compare Abstr. 1904 ii,221).- It has already been showii by one of the anthors (Muller 1902 i 354 ; Muller and Bnuer 1903 ii 705) that the difference between the molecular refraction for the D ray of a normal acid and its sodium salt is less than 2 (1.4 to 1*9) whilst the corresponding value in the case of a pseuclo-acid is greater than 2. I n the present paper the densities ancl specific refractions for the a y and D rays of solutions of approximately equal concentration in absolute alcohol of acids con- taining a methylene or methinene grouping and their sodium salts are given ; the difference between the molecular refraction for the B ray of the acid and its salt is in a11 cases greater than 2 and the following table comprises the results br & Acid.Salt. A d . Diff. Nthyl cyanoacetate .................. 33.03 26.S4 6-19 Ethyl cyanomalonate ............... 49.48 44.23 5.25 Ethyl cyanopropionylacetate ...... 46.73 44.00 2.73 Ethyl rnalonate ..................... 42.00 38.10 3-90 Malononitrile ........................ 21.21 15.67 5.54 Cyanocamphor ........................ 54.93 49.18 5.75 Whence it follows that the acids are pseuclo-acids that is the acid and its salts have different chemical constitutions. M. A. W. Action of Ethyl Sodioacetoacetate on Dibromo-hydro- carbons. ANDREI A. SOLONINA (J. Russ. Phgs. Chern. Soc. 1904 36 947-988 and 1209-1244).-Af ter discussing the results obtained by other investigators in this direction the author gives his own results which are briefly as follows.With ay-dibromobutane ethyl sodioacetoacetate gives together with sinnll quantities of acetic and dehydracetic acids mainly the estei* C H X e < ~ ~ ~ ~ f ~ > C H * C O E t which separates in very large prisms meltiiig at 34' and boiling a t 116-11So under 16 mm. pressure ; i t is readily soluble in alcohol ether light petroleum benzene or chloroform and it does not decolorise cold 2 per cent. potassium permanganate solution ; sulphuric acid is not coloured by it in the cold but nitric acid rapidly turns it green; with vanillin and concentrated hydro- chloric acid i t gives after some time a red coloration which is rapidly cliangecl to eruerald-green by heating ; it gives a liquid compouiid with phonylhydrazine and only combines with semicarbazide on heating.ORGANIC CHEMISTRY. 113 Under the action of barium hydroxide it yields the acid melting a t 125-126" (compar'e Euchner Abstr.1898 i 639) ; the sileer salt of this acid was prepared and analysecl. With ap-dibromo-P-meth ylpgopane ethyl soclioace t oacet a t e gives mainly a-bromo-P-methylpropyleiie and isobuty leiie. With $-butylene bromide (6-butylene hroniicle) i t jields the two stereoisomeric /3-bromo-AP-butylenes. With PG-di bromo-P-met h yl but an e e t h y 1 sod iosce t oace t at e yields ( 1 ) a small proportion of ethyl dimethylallyl ether CMe,:CH*CH,*OEt but mainly the two following compounds. (2) Ethyl 88-dimethylallyl- acetoacetate (compare Ipatieff Abstr. 1901 i 256) which refracto- metric and niagnetic polarisation measurements show to have the enolic structure CAle, CH* CH,*C( C0,Et) CMe OH.Heating the ester with barium hydroxide solutioii gives principally the methyl- heptenone CMe,:CH*CH,*C'H,*COMe together with a small quantity of the methylhexenoic acid prepared by Barbier (Bull. Soc. chin^. 1887 [ii] 47 '701) and by L@ser (Abstr.. 1899 i 414) and already studied by the author (Abstr. 1902 i 256). (3) The estey COMe*C(CH,*CH:CMe,),*CO,Et which boils at 140-149° under 13 mm. pressure and a t 280-290' under the ordinary pressure ; on heating with barium hydroxide solution it gives the ketone COMe*CH(CH,*CH:CMe,) which boils a t 230° and the acid CH(CH,*CH:CMe2)2*C0,H boiling a t 121-131° under 13 mm. pressure the silver salt of which was prepared.With py-dibronio-P-methylbutane ethyl sodioacetoacetate gives principally a-bromo-a-methyl-4~-butylene. With pa-dibromopentane ethyl sodioacetoacetate yields mainly the ester CMe,:CH*CHMe*CHAc.CO,Et which boils at 120-1 25' under 18 mm. pressure and a t 334-238" under ordinary pressure and has the sp. gr. 0.99395 at Oo/Oo and 0.97713 at 19'/O0 ; the enolic formula is indicated by refractometric and magnetic rotation measurements. When boiled with barium hydroxide solution i t undergoes principally the ketonic decomposition yielding the ketone CMe,.CH*CHMe*CH,*COMe which boils at lSS-lS9' has the sp. gr. 0.87030 a t Oo/Oo and 0.85404 a t 1 9*4'/O0 and foxms a senzicus.buxo?ze ClOHIRON3 melting at 140'; the ketone is accompanied by a small quantity of the acid CMe,:CH*CHMe*CH,*CO,H the silver salt of which mas prepared and analy sed.With BE-dibromohexane ethyl sodioacetoacetate gives ( 1 ) the ester - . . ~H2'CHAfe>CAc*C0,Et which boils at 125-1 30" and has the CH; CHMe sp. 'gr. 1.0617 at Oo/Oo and 1.0457 a t 19*2'/0'; (2) the este7- C,H,(C€€Me*CHAc*C0,Et)2 boiling at 120-125'. With ay-dibromo-y-ethylpentane ethyl sodioacetoacetate yields mainly the unsaturated esterr. CEt,:CH.CH,*CHAc*CO,Et which boils at 142-147° under 14 mm. pressure and has the sp. gr. 0.9854 at O0/Oo and 09713 a t 16*8'/0". When heated with barium hydroxide the ester gives mainly ketone with a small proportion of acid.114 ABSTRACTS OF CHEbIICAT PAPERS. With pxy lylene di bro mide e thy1 sodioacetoacetat e gives exclusively the ester C,H?(CH,*CHAc*CO,Et) which is deposited from alcohol in crystals melting at 62.5'.When heated with barium hydroxide or dilute potassium hydroxide solution this yields (1) the compound C,H4(CH,*CH,Ac) which crystallises from alcohol in shining plates melting at 53- 54' and is readily soluble in benzene or ether ; (2) the acid CH2Ac*CH2*C~,H,.CH,.CHAc*C0,H separating from water in crjstals melting at 206' ; the silver salt was prepared and analysed ; (3) small quantities of acetic dehydracetic and a n unknown acid. With o-xylylene dibromide ethyl sodioacetoacetate gives (1) the ester C,H,<~~~>O.Ac*CO,Et which boils a t 185-190" under 21 mm. pressure and lias the sp. gr. 1,122666 at O'/Oo and 1.106205 at 19*Zo/O0 and n 1.51 144 a t 19.2'. When heated with barium hydroxide solution it yields ( a ) the conipoti?~d C,H,:(CH,),:CHAc which boils at 164-168' under 47 inm.pressure has the sp. gr. 2.0685 at O'/O' and 1.0546 at 17*5°/00 and n 1.53320 at 22'; the senzicnrbaxone C,,H,,ON of this methyl hydrindeneketone separates from alcohol in white silky needles melting at about 178' ; ( b ) o-hydrindonaphthene- carboxylic acid (Yerkin and ItQvay Trans. 1894 65 228); (2) the ester C,H4(CH2-CHAc.C0,Et) which boils a t 222-256' under 20-23 mm. pressure. With m-xylylene dibromide ethyl sodioacetoacetate yields the ester C,H4(CH2*CHAc*C02Et) which boils at 251-255" under 58-60 mm. pressure has the sp. gr. 1.107871 atl Oo/Oo and 1.09385 at 16*So/O0 and n 1.495256 a t 19.7'. With semicarbazide i t gives the seniicwbazone which separates from water in crystals melting and decomposing at 230' and is soluble in ethyl or aniyl alcohol ether ethyl acetate or 912-xylene.When heated with barium hydroxide solution the ester yields (1) the ketone C6H,(CH;CHAc) melting a t 202-207" under 23 mm. pressuie and giving a selrLicarbaxone ClpHzr02N melting and decomp'osing a t 184' ; (2) m-phenylenedipropionic acid. Concerning the action of ethyl sodioacetoacetate on dibromo- derivatives of hydrocarbons the following conclusions are drawn (1) if the atoms of bromide in a dibromide with an open chain are not attached t o neighbouring carbon atoms products of combination of ethyl acetoacetate are always formed; if one bromine atom is tertiary and the other primary or secondary unsaturated compounds with one or two double linkings are obtained; in the absence of a tertiary bromine atom unsaturated acetoacetic esters are not formed but esters of keto-acids with a polymethylene ring or else diaceto- acetic esters ; finally condensation may occur and give rise t o esters of keto-acids with a keto-polymethylene ring.(2) If the two atoms of bromine in a dibromide having an open chain are attached to two neighbouring carbon atoms the compound does not combine with ethyl acetoacetate unless i t contains one primary bromine atom. (3) When the bromine atoms are situated in a benzene or anthracene ring no combination takes place with ethyl acetoacetate. (4) WhenORGANIC CHEMISTRY. l l * 5 the bromine atoms are in side-chains of aromatic compounds the reaction proceeds just as with aliphatic dibromo-compounds and if the bromine atoms are in side-chains having the o-position to one another the ring is simply closed whilst where the side-chains are in the meta- or para-positions products are always obtained containing two aceto- acetic residues.(6) All the products of combination of ethyl aceto- acetate obtained by the action of ethyl sodioacetoacetate on di- bromides may be ranged in the three following classes (I) esters of P-keto-acids containing a poly methylene ring forived by the replacement of two atoms of bromine by an ethyl acetoacetate residue such as -(?H2'CHMe>CAc*C0,Et. CH-; CHMe (11) Unsaturated esters oi /I-keto-acids divisible into two groups (a) those containing one double bond in the radicle formed after the action of ethyl sodioacetoaceta-te for instance CNe,:CH*CHMe*CHAc*CO,Et ; ( b ) those containing two double bonds in the radicle formed after the action of ethyl sodioacetoacetate for instance COMe*C( CH,* CH CMe2)2 *CO,Et.(111) Esters of keto-acids containing two ethyl acetoacetate residues and divisible into two classes ((6) diacetoacetic esters such as C,H,(CH2CHAc*C02Et)2 ; ( b ) ketb-polymethylene ester; of keto- $JHMe*CH,*$X€ T. H. P. acids such as CHAC CO-CH- CO,E~' The Reduction of the Anhydrides of Dibasic Acids. GUSTAVE BLANC (Compt. rend. 1904,139,12 13-1214).-When theanhydride of an unsymmetrical dibasicacid of the type CH,<CH,-CO CRR*Co>O was reduced by sodium and absolute alcohol (compare Bouveault and Blanc Abstr. 1903 i 597 673 730 ; 1904 i 213) a yield of 20-50 per cent.of the lactone CH,<EEYb%:>O was obtained and normal results were obtained with the anhydrides of pyrotartaric aa-dimethylsuccinic aa-dimethylglutaric ,8/l-dimethylglutaric and camphoric acids. is0 . Propylsuccinic anhydride yielded a lactone which on treatment with potassium cyanide and subsequent hydrolysis gave a mixture of a- and P-isopropylglutaric acids in which the latter preponderated. M. A. W. Solubility of Metallic Succinates in Water. H. CANTON and D. DIOTALEVI (Bull. Xoc. chim. 1905 [iii] 33,27-36).-The solubilities of barium strontium calcium copper and lead succinates in water at temperatures ranging from 0-50" have been determined and in the cases of the alkaline earth metals compared with those of the malonates and oxalates.The results which are given in tabular form in the original show that the solubility of barium succinate slowly increases between 0' and 20' and then diminishes; that of strontium increases from 0-30° then diminishes between 30' and 40° and beyond this temperature again increases. Those of the calcium and lead saltsincrease116 ABSTRACTS OF CHEMICAL PAPERS. steadily with rise of temperature whilst that of copper succinate increases until the temperature reaches 39' and then diminishes. It is suggested that the alternating changes in the case of the strontium salt are due to changes in the state of hydration and in that of the barium salt to polymorphism At 20° the solubility of the three alkaline earth succinates decreases in the order strontium barium calcium and a t 40' in the order barium strontium calcium.Modes of Formation and Preparation of Aliphatic Aldehydes and a General Synthetical Method for the Preparation of Aldehydes. LOUIS BOUVEAULT (Bull. Xoc. china. 1904 [iii] 31 1306-1322 1322-1327).-The first paper is a rbsum6 of methods which have been devised from time to time for the preparation of aldehydes The second paper deals in greater detail with the process already described by the author (Abstr. 1904 i 13) which consists in gradually adding disnbstituted formamides dissolved i n dry ether to magnesium alkyl haloids (compare Beis Abstr. 1904 i 15 and Bodroux ibid. i 421). The best yields are obtained when diethyl- formamide is employed. In addition to the aldehydes other secondary products are formed in the reaction in particular paraffins produced by combination of twoalkglgroups of the magnesium alkyl haloid employed.When dimethylformamide reacts with magnesium isoamyl chloride there is formed as a by-product dimethylamir~odiamylmetha~~~ [l-di- metl~ylnnzinoundeca~ze] CH(C,H ),*NMe a liquid having a character- istic amine-like odour a i d boiling a t 110" under 15 mm. pressure and giving a picrate which is crystalline and melts a t 103'. The primary and secondary alkyl haloids react normally both in the Grignard reaction and in the subsequent interaction with formaniides but the magnesium derivatives of the tertiary haloids behave differently. The base formed together with amylene by the inter- action of magnesium tert.-amyl chloiide and diet hylformamide (Abstr. 1904 i 546) is probably produced in the manner indicated by the following scheme 2CMe2Et*MgC1 + H*CO*NEt = MgO .t MgC1 + NEt,*CH(CMe,Et) = CMe,Et.CH,.NEt + CISle,:CHMe. A number of aldehydes prepared by this process are referred to in the original. T. A. H. T. A. H. General Method of Synthesising Aldehydes by means of the Substituted Glycidic Acids. GEOEGES DARZENS (Compt. rend. 1904 139 1214-1217).-The ethyl esters of the disubstituted glycidic acids readily prepared by the condeiisation of the correspond- ing ketone and ethyl chloroacetate in the presence of sodium ethoxide ,CRR' according to the equation CORR' + CH,Cl*CO,Et = OK I CH* C0,Et 4- HCI are colourless odourless liquids boiling 60-703 iigher than the corresponding ketones and not reacking with bromine hydroxylamine phenylhydrazine or phenylurethane.The disub- stituted glycidic acids obtained by hydrolysing the esters are unstable and readily break down into carbon dioxide and the cor- CRR O<(!JH.CO,H = responding aldehyde according to the equationCHRR'*COH + CO,. The boiling points of the ethyl disubstituted glycidates and the aldehydes thus prepared and the melting points of the semicarbazide of the latter are given in the following table Melting corresponding Boiling point of of semi- Ketone. ctliyl glycidate. nlclchy de. cnrbazide. Boiling point of point pressure. pressnre. - - Acetone .................. 163-1 68" nnder 760 nim. Methylisohexyl ketone 151-152 30 90" uiider 40 imi. 60" Methyl heptylketoiie.155-156 19 105-106 20 66-67 Methyl nonyl ketone ... 165-170 16 119-122 .. 16 85 Acetoplienone.. .......... 153-159 . 20 ) 95-97 19 ) 153-154 Tolyl methyl ketone ... 160-164 16 107-108 19 . 159-160 p-Ethyl acetophenone.. 210-215 19 118-120 . 20 . - Renzglacetone ........ 175-180 . 16 129-130 19 70-72 Phenyl propyl ketone.. 155-158 18 128-123 28 116-116 i,4oButylacetoplienone . 175-180 16 ,. 153 . SO . 183-156 Methylcycloh~xano~ie . 131-132 15 66-67 16 138-139 M. A. W. Ghloromalonaldehyde [p-Chloro-Afl-propene-y-ol-a-all. WALTER DIECKMANN and LUDWIG PLATZ (Ber. 1904,37,4638-4646)-/3-ChZoro- y- an ilino- a-phe H y linz in0 - As -propylene h ydrocldoritle NHPh*CH:CCl*CH:NPh ,HC1 obtained by heating mucochloric acid (Simonis Abstr. 1901 i 268) with alcoholic aniline crystallises from alcohol with lEtOH in golden- yellow needles and melts and decomposes at 228'; on adding it to an excess of boiling water /3-chloro-y-aniZino-A~-propene-a-al (nzono- niailide of chZoroil?zaZonaZdel~yde) NHPh*CH:CCl*CHO is obtained in long nearly colourless needles ; it inelts and decomposes at 193' and is hydrolysed by 30 per cent.aqueous potassium hydroxide giving cldo~~omalonaZdelyde OH- CH CC1* CHO which crys tallises from chloroform in slender colourless needles melts and decomposes at 144' readily reduces Fehling's solution and gives on dissolution in the aqueous alkali hydroxides crystalline sodium and potassium derivatives. Aniline converts the aldehyde into the mono- and di-anilides iust described and with phenylliidrazine 4-clJoro- 1 -phenylpyraxole CH $221 NP1l<&f=CH 7 is obtained ; it crystallises from dilute alcohol in colourless needles and melts a t 75 '.NMePh*CH CC1* CHO prepared by the action of methylaniline on chloromalonaldehyde in alcoholic solution forms colourless crystals and melts a t 76'. The benzoate CHO*CCl CH*OBz of chloromalonaldehyde forms colourless needles and melts a t 1 0 5 O . /3- Ctdoro- y -meth ykaniZino-A~-~~ro2~eiae-a-aZ /3-Bromo-y-ccnilino-a-phenyZimino- A fl-popylene hyds.obromide NHPh*CH CBr * CH:NPh,HBr,EtOH obtained from mucobromic acid and aniline crystallises from alcohol in golden needles and melts and decomposes at 2 17'. P-Bromo-y-anilino- AS-popene-a-al crystallises from alcohol in colourless needles,118 ABSTRACTS OF CHEMICAL PAPEIIS.melts and decomposes a t 184O and is easily convertible into bromo- malonaldehyde which has already been described by Lespieau (Abstr. 1902 i 13). 4-Bronzo-l-pheia~lp~?~a~ole crystallises from alcohol in colourless needles and melts and decomposes a t 81". Incidentally the following substances are described. Xod,ium aP-dibl.onzo-E-phei~y1- Aar-lve.l.Ltccdieize-€-one-a- carboxylate COPh*CH:CH*CBr CBr-CO,Na obtained by the condensation of acetophenone and mucobromic acid forms colourless crystals and decomposes a t 154". The lactone CBr.CH*CH,Bz II >o A of u~-cEibron~o-~-;uhen~l-Aa-~e~tei~e-y-ol-~-oi~e-a-CBr*CO oxylic acid crystallises from alcohol in colourless leaflets and melts at 168'. The analogous Zuctone 11 >O is similar and melts a t 121-122O.CC1* CH* CH,Bz CCl-CO W. A. D. Migration of the Ethylenic Linking in Alkyl Ally1 Ketones. EDMOXD E. BLAISE (Bull. Xoc. china. 1905 [iii] 33 43-49. Compare Abstr. 1904 i 290).-When alkyl allyl ketones are treated with hydrogen bromide even a t -80° they are converted into saturated bromo-ketones which on treatment with potassium hydrogen carbonate furnish alkyl propenyl ketones isomeric with the original alkyl allyl ketones indicating that in these circumstances the ethylenic link- ing migrates from the up- to the py-position. A similar change is brought about directly by boiling the ketones with dilute sulphuric acid (20 per cent.); the yield of the isomeride in this case is from 60-70 per cent. the loss being due partly to hydration of the ketone and partly t o polymerisation.With sodium ethouide the alkyl allyl ketones furnish the corresponding ethoxy- ketones thus ethyl allyl ketone under these conditions yields ethyl P-ethoxypropyl ketone. Further when propyl allyl ketone (2 mols.) is boiled with formaldehyde (1 mol.) in presence of piperidine no con- densation occurs but propyl propenyl ketone is formed. The brornides of the alkyl allyl ketones are readily distinguished from their isomerides by ebullition with an aqueous solution of an alkali carbonate the former yielding a colourless distillate whereas the latter furnish a-diketones which are yellowish-green thus R*CO*CHBr*CHBrMe -3 R*CO.CBr:CHMe -+ R.CO*C(OH) :CHMe -+ R*CO* COEt. The interaction with semicarbazide also serves to distinguish these two classes of unsaturated ketones the alkyl allyl ketones furnishing under all conditions semicarbazones whereas their isomerides furnish with 1 mol.of semicarbazide semicarbazones and with 2 mols. of the reagent semicarbazide-semicarbazones ; the propenyl ketones also behave in the same may with hydroxylamine. The semicarbaxones of methyl- ethyl- and propyl-propenyl ketones melt a t 1 1 4 O 157O and 147" respectively. A specimen of etlqi! semicarbanqwopyl ketone semica,rbazone CHMe(NH.CO*NH*NH,)*CH2*CEt:N-NH*CO*NH which could not be obtained pure melted at 157'' The hydroxylamino-ORGANIC CHEMISTRY. 119 oxime derived from the same ketone is liauid. as is also its benzoyl derivative (compare Rupe and Schlochoff i b s t r . 1904 i 144). T. A. H. Constitution of Cellulose. CHARLES F.CROSS and EDWARD J. BEVAN (Zeit. Fcmb. Text. Ind. 1904 3 441-442).-A reply to Green (this vol. i 82). W. A. D. Humic Acid. PH. MALKohiEsIus and ROBERT ALBERT (J pr Chem. 1904 [ii] 70 509-515).-Cassell brown sold as an artist's colour contains 90 per cent of humus substances from which humic acid containing only 0.87 per cent. of ash is obtained by extraction with lithium carbonate and water and addition of hydrochloric acid t o the filtrate. Humic acid so obtained gives C=60.03 H=4.40 N = 1.09 per cent. ; when treated with concentrated nitric acid it forms a reddish-brown nit?-o-derivative which has the composition C = 55.52 H = 4-51 N = 3%0 S = 0.92 ash = 0.82 per cent. is easily soluble in methyl or ethyl alcohol glacial acetic acid or acetone and when heated with bromine or glacial acetic acid in a sealed tube at looo yields a bromo-derivative containing 41-43 per cent.of bromine. G. Y. Aminoethyl Ether. LOUIS HENRY (Bull. Acccd. Roy. Belg. 1904 984-994. Compare Knorr Abstr. 1904 i 854).-The author has shown (Abstr. 1901 i 16) that in two carbon compounds the substitution of the OH group by NH leads to an abnormal rise in boiling point when an amino-alcohol is the product of the reaction and has ascribed this to the mutual influence of the OH and NH groups. H e now points out that the substitution of an OEt group by NH in such cases with the formation of an amino-ether gives rise to a normal increase in boiling point affording evidence of the validity of his explanation. Thus the difference between the boiling points of ethyl ether and ethylamine is 1 6 O and that between those of the diethyl ether of gljcol and aminoethyl ether is 14' or 15".Further evidence of the mutual influence of the OH and NH groups in the amino-alcohols is afforded by a comparison of their densities in the liquid state with those of the corresponding alcohols and amines. The substitution of OH by OEt in compounds of the type XCH,*CH,*OH leads t o a fall in the boiling point and the amount of this depends on both the mass and the nature of the group X. These statements are illustrated by examples in the original. T. A. H. Synthesis of Serin and Cystin. EMIL ERLENMEYER jun. and F. STOOP (Arznalen 1904 33'7 236-263. Compare Abstr. 1903 i 29 791).-The synthesis of serin (a-amino-P-hydroxypro- pionic acid) has been achieved by a method differing materially from that of Fischer and Leuchs (Abstr.1903 i 12). Ethyl hippurate condenses with ethyl formate forming the oxy-rnethylene compound OH*CH:C(NHBz)*C'O,Et which on reduction gives the ester of benzoylserin OH*CH,*CH(NHBz)*COBEt ; the latter can be hydrolysed either to benzoylserin or to serin. Ethyl hippurate is best prepared by passing hydrogen chloride into a boiling solution of hippuric acid in ;tlcoliol and crystallising the product from benzene or ether. When treated with sodium ethoxide the ester yields a sodium derivative ONa*CPli:N*CH2.C'0,Et as a white crystalline precipitate. Ethpl foi.?i~ylhiiii~wrute was prepared by adding ethyl formate t o a solution of sodium ethoxide when the sodium derivative separates; unless both the alcoliol and the sodium are quite pure decomposition takes place with the evoliition of carbon monoxide.Ethyl hippurate is now added when the mixture sets to a crystalline mass and is kept for ten days when the sodium derivative C1,H120,NNa is collected ; the e s t e ~ is difficult to obtain from the sodium derivative in a solid state but when pure crystallises in needles melting a t 1 2 8 O . The ethyl ester of henxoylserilh is prepared by reducing the ethyl formyl- hippurate with aluminium amalgam in moist ether and crystallises from benzene in needles melting at 80". OH*CH,-CH(NHBz)* CO,H is prepared by hydrolysis of the ester by alcoholic sodium hydroxide and forms crystals melting at 159'. The ester of benzoylserin can be converted into serin by prolonged boiling with sulphuric acid (1 in 15) the use of sulphuric acid of any other strength either not effecting the hydrolysis or causing decomposition ; the serin was characterised by conversion into its copper salt and by measurement of the crystals.Baumann's formula for cystein SH*CMe(NH,)*CO,H which was long accepted as correct represents this substance as a derivative of thiopyruvic acid. There is no strong evidence however in favour of this formula tho known facts rather support one of the expressions SH*CH,*CH(NH2)*C0,H or NH,*CH,*CH(SH).CO,H ; since the former represents it as a thioserin it is the more probable. The work of Neuberg (Abstr. 1902 i 743) and Friedmann (Abstr. 1902 i 731; 1903 i 75 301) has shown this view to be correct.The synthesis of serin therefore rendered possible a synthesis of cystine and it was found that the oxygen of the hydroxy-group in the ethyl ester of benzoylserin could be replaced by sulphur by the action of phosphorus pentasulphide the ethyl ester of benzoy lcystein SH*CH,* CH(NHBz)* CO,Et being produced. The ester is molten with twice the theoretical quantity of phosphorus pentasulphide being heated finally for 8 hours a t 120" ; the product is extracted with alcohol and recrystallisecl from ether; it forms colourless needles melting a t 158'. On boiling the ester with hydrochloric acid it is hydrolysed to cystein which was recognised by means of the additive compound with mercuric chloride. Cystein is very readily oxidised to cystin the process being best carried out by drawing air through the warmed solution in ammonia.The cystin thus obtained was identical in all respects with the natural cystin prepared from urine with the exception that i t was inactive towards polarised light. Bewoylserin K. J. P. 0.ORGANIC CHEMISTRY. 121 Polypeptides of the Diamino-acids. EMIL EISCHER and UMETARO SUZUKI (Sitzungsber. K. Akad. Wiss. Berlin 1904 1333-1341. Compare Abstr. 1903 i 645 799,800 ; 1904 i 771 ; this vol. i 30)- The diamino-acids so important biologically are converted on heating their methyl esters into dipeptide and diketopiperazine derivatives. JIethg1 diaminopropionate hpdrochlor ide C,H loO,N 2 HCl con- veniently prepared by the action of dry methyl alcohol and hydrogen chloride on the hydrochloride of diaminopropionic acid melts and decomposes a t 166" (corr.) ; the free ester is obtained from this by the action of sodium and methyl alcohol as a colourless strongly alkaline syrup.Nethyl diaminopropionate dipeptide NH,*CH,*CH(NH,)*CO*NH*CH,*CH(NH,)*CO,Me (?) is prepared by heating the foregoing ester at 100" for an hour and purified by conversion into the picrate or hydrochloride. The picrute forms yellow crystals sparingly soluble in water which on heating darken at 170-180' and melt and decompose between 200" and 210' ; the hydrochloride is an almost colourless dense powder sintering a t 90" and decomposing at 135'. Methyl lysine hydrochloride prepared by the action of methyl alcohol and hydrogen chloride on r-ly sine hydrochloride crystallises in colourless oblique prisms melting and decomposing at 2 18'. Lysiwe ccnl~ydride is obtained on heat'ing methyl lysine at loo" as a slightly brown limpid mass ; the picrate C,,H,,O,N,?20,H,O,N crystallises from water in small yellow prisms or plates which when heated darken a t 210" and melt and decompose a t 230" (corr.); the hydrochloride forms microscopic colourless needles melting and decomposing a t 270" (corr.).Histidine anhydride C,,H,,O,N prepared from the methyl histidine hydrochloride described by Pauly (hbstr. 1904 i 1068) crystallises in colourless glistening prisms darkening about 260" and melting to a brown liquid at about 340". Methyl arginine hydrochloride prepared from the double salt of arginine and copper nitrate crystallises in long colourless needles or prisms melting and decomposing a t 195' (corr.).E. I?. A. Action of Potassium Thiocyanate on Metallic Oxides at High Temperatures. JAR. MILBAUER (Zeit. ar,org. Chem. 1904 42 433-449).-Potassium thiocyanate melts a t 171 -172" becomes brown at 300' and assumes a blue tint at 405". It was heated with various metallic oxides in vessels of porcelain or of glass and at temperatures ranging from 200" to 1200'. At 300° lead monoxide reach with potassium thiocyanate according to the equation PbO + KCNS=PbS+KCNO. The action of zinc oxide and of cadmium oxide is similar. The action with stannic oxide proceeds in two stages namely (1) 2KSCK + SnO = SnS + K,S + 2CO + N and (2) KCNS + K,S + SnS = K,SnS + HCN the latter action proceeding at a temperature higher than that at which the first action takes place.When manganous oxide was used manganese sulphide was generally produced ; in one case manganese potassium sulphide was isolated. With cupric oxide cuprous sulphide was produced whilst122 ABSTRAC'TS OF CHEiClICBli PAPERS. the double sulphicle K,Cu,S was formed a t more elevated tempera- tures thus 2CuO + 2KSCN = Cu,S + K,S + 2CO + N and 4Cu,S + K,S + KSCN = K2Cu,S + KCN. With molybdenum oxide the sul- phides MoS and MoS were isolated. Bismuth oxide yielded bismuth sulphide mixed with the double sulphide Bi,K,S when higher temperatures were employed. Chromium oxide yielded the compound K,Cr,S which forins glistening metallic greenish-grey crystals insoluble in warm hydrochloric acid and which at a red heat decom- pose to form sulphur dioxide and chromium oxide.Its formation is represented by the equations (1) Cr,O + SKSCN = Cr,S + 3KCN0 (2) ZKCNO + KSCN = K,S + KCN + 2CO + N (3) Cr,S + K,S = K2Cr,S,. With ferric oxide at 400° the sulphide K,FezSp was produced. Cobalt oxide formed the sulphide K,CO~,S,~ the action of nickel oxide being analogous. From the mixture of oxides obtained by heating uranyl acetate the sulphide U0,S was isolated. A. McK. Compound Thiocyanates of Palladium. ITALO BELLUCCI (A t l i R. Accnd. Lincei 1904 [ v] 13 ii 386-393).-Palladium resembles platinum in forming double thiocyanates of the form Pd(SCN),X but the corresponding compounds derived from quadrivalent palladium either do not exist or are unstable and when attempts are made to pre- pare them the bivalent palladiam compounds are always obtained.Pcdladous thiocyanate Pd(SCN) forms a reddish flocculent precipi- tate which dissolves readily in potassium thiocyanate solution yielding potassium pallaclothiocyanate Pd(SCN),K separating from water in ruby-red acicular crystals. This double salt which is best obtained from potashium palladochloride (1 mol.) and potassium thiocyanate (4 mols.) is a true complex salt as is seen from a comparison of the electrical conductivity of its solutions with that of the corresponding platinum compound. Silver iualladothiocyanr~e Pd(SCN) Ag is an insoluble amorphous red salt whilst the barium salt is crystalline and very readily soluble in water The free acid is unstable and could not be prepared.T. H. P. 5Methylbarbituric Acid. EMIL FISCHER (AnnaZen 1904 336 345. Compare this vol. i 37).-5-Methylbarbituric acid has been previously described as isosuccinic-ureide by Franchimont and Klobbie (Abstr. 1888 1181). Q. Y. At tempts to Synthesise Nitroacetonitrile. WILHELM STEIN- KOPF (Bey. 1904 3'7 4623-4627. Compare Ratz Abstr. 1904 i 857). -An attempt was made to prepare ethyl nitroacetate by distilling potassium ethyl malonate CO,Et.CHCl*CO,K with aqueous potassium nitrite but the principal product was simply ethyl chloroacetate formed by the decomposition of the malonate by water. Nitro- acetamide (R,atz Zoc. cit.) was obtained by heating Bouveault and Wahl's nitroacetic acid (Abstr. 1904 i 795) in the form of its ammonium salt with concentrated alcoholic ammonia for 2 hours at 100" ; the immediate product is ammonium nitroacetamide C2H703N3,ORGASIC CHEMISTRY.I23 which crystallises in long yellow needles melts a t 152" and on treatment with dilute sulphuric acid liberates nitroacetamide melting at 101-102°; Ratz gives the melting points for these two substances as 148O and 98" but the author by using Ratz's method obtained products identical in melting point with his own. Monomethyl-tin Derivatives. 111. PAUL PFEIFFER [with IDA HELLER] (Ber. 1904 37 4618-4620. compare Abstr. 1903 i 470 802 and Pope and Peachey ibid. 74 1).-Methylstanniodoform (tinmethyl iodide) SnMeI is readily obtained by heating stannous iodide with methyl iodide for 4 hours a t 160'; the best method of preparing it however consists in boiling an ethereal solution of magnesium methyl iodide with stannic iodide.Preparation of Cyanides from Ferrocyanides. GROSSMAN'S CYANIDE PATENTS SYNDICATE (D.R.-P. 156397. Compare Abstr.? 1904 568 86O).-The iron alkali ferrocyanide (" Everitt's salt ") obtained in the preparation of hydrogen cyanide from ferrocyanides may be oxidised to Prussian blue and then decomposed by an alkali in order to recover the ferrocyanide. The oxidation however proceeds with dificulty with the usual osidising agents. When air is blown into the solution oxidation takes place rapidly. The reaction is best carried out by adding a ferrous salt and passing a current of air through the boiling solution. The oxidation takes place quantitatively and the ferrous salt is continually regenerated 3Na,Fe2Cy + 2Fe2C1 = Fe,Cy + 3FeC1 + 6NaC1.Preparation of Sodium Ferrocyanide from Calcium Ferro- cyanide. ADMINISTRATION DER MINEN VON BUCHSWEILER (D.R.-P. 155$06).-1n the preparation of potassium ferrocyanide from a solu- tion of calcium ferrocyanide one-half of the calcium may be replaced by the addition of potassium chloride the sparingly soluble double salt K,CaFe(CN) being precipitated. Sodium does not form a similar salt and the addition of sodium hydroxide or carbonate has therefore been necessary t o remove the calcium. I t is however possible to separate the sodium ferrocyanide and calcium chloride formed according to the equation Ca2Fe(CN) + 4NaC1= Na,Fe( CN) + BCaCl by crystallisation the calcium chloride remain- ing in solution. The sodium ferrocyanide is not decomposed during evaporation.C. H. D. New Additive Compounds of Tetrahydrobenzene. L&ON BRUNEL (Compt. rend. 1904 139 1029-103 1. Compare Abstr. 1903 i 157 338).-o-lodocyclohexyZ acetate C,H,,I*OAc obtained by the action of mercuric oxide iodine and acetic anhydride on cgclo- hexene in ethereal solution is a yellow oil with an aromatic odour soluble in the ordinary organic solvents has a sp. gr. 1.61 at Oo and decomposes when distilled under reduced pressure. o-Iodocyclohexyl propionate C,H,,I*CO,Et similarly prepared is a yellow oil having a sp. gr. 1-64 a t Oo. The mercuric oxide and acid anhydride in the above reactions can be W. A. D. TV. A. D. C. H. D. replaced by the mercuric salt of thb corresponding acid. M. a. w.124 ABSTRACTS OF CHEMICAL PAPERS.Preparation of Benzene free from Sulphur. CARL SCHWALBE (geit. Farb. Text. Ind. 1904 3 461-464).-The carbon disulphide present in commercially purified benzene is best removed by passing moist gaseous ammonia through the hydrocarbon and subsequently washing it with dilute sulphuric acid. The thiophen is most completely eliminated by passing nitrous fumes from sodium nitrite and sulphuric acid through the liquid and subsequently shaking it two or three times with concentrated sulphuric acid. Shaking the oil with sulphuric acid containing nitrous fumes is not so advantageous. W. A. D. o-Chloro-nmitrotoluene-a-sulphonic Acid. FARBWERKE VORM. MEISTER LUCIUS Bs BRUNING (D.R.-P. 154493).-Sodium hydrogen sulphite converts o-chlorobenzyl chloride into o-chlorotoluene-o- sulphonic acid the sodium salt of which crystallises in glistening leaflets.On nitrating in sulphuric acid solution o-c~loro-m-mitrotolu- ene-w-sulphonic acid is obtained. The sodium salt crystallises from hot water in yellow needles. The chlorine atom is readily displaced by ammonia or amines. Permanganates oxidise the acid to 2-chloro-5-nitrobenzoic acid. C. H. D. Separation of Toluene-o- and -p-sulphonamides. RUDOLF BARGE & LEON GIVANDAN (D.R.-P. 154655).-Ammonium salts may be employed in place of acids or acid salts to precipitate toluene-o- and y-sulphonamides from the solutions of their alkali salts C,H,Me-SO,*NHNa + NH,Cl= C,H,Me*S02*NH + NH + NaC1. A better fractional separation is obtained than when acids are used. The ammonium chloride solution obtained in the preparation of the sulphonnmides from the sulphonic chlorides may be employed and the ammonia produced may be recovered.C. H. D. Dibromoanthracene Tetrabromide. FELIX KAUFLER and M. IMHOFF (Bey. 1904 37 4706-4709).-The difference in melting point between the bromoanthraquinone prepared by Graebe and Liebermann from tr i bromoanthracene and the P-bromoanthraquinone prepared from P-arninoanthmquinone (Abstr. 1904 i 256) is due to the presence of 2 6 9 10-tetrabromoanthracene in the former product. 17etrabromoanth?*ace?2e prepared by heating dibromoanthracene tetra- bromide at 200' until the evolution of bromine and hydrogen bromide ceased melts at 298-300' and when oxidised in glacial acetic acid solution by chromic acid forms dibromoanthrapuinone which melts a t 289-290'.During the preparation of tetrabromoanthracene tri- bromoanthracene was also formed. The bromoanthraquinone prepared by oxidising the latter melted at 201-202' and was identical with the P-compound obtained from /3-aminoanthraquinone by the diazo- reaction. 2 6-Ditti~iinoanthl.ayliinone was converted into 2 G-nnthrquinone-ORGANIC CHEMISTRY. 125 tetrazonium perbromide which when heated at 1 70° formed 2 6-dibromoanthraquinone identical with the product obtained from dibromoanthracene tetrabromide. The bromine atoms in the tetra- bromoanthracene described are accordingly in the 2 6 9 10-position. A. McK. Separation of the Three Dimethylanthracenes obtained in the Action of Methylene Chloride and Aluminium Chloride on Toluene. JAMES LAVAUX (Compt.Tend. 1905 140 44-45. Compare this vol. i 43).-Experimental details connected with the working up of the products of the reaction are communicated for which the original must be consulted. The three dimethylanthr- acenes which are simply referred to as A B and C melt respectively at 240° 244*5' and 86'. H. M. D. Ullmann and Borsum's '' Hexaphenylethane " ; Terva- lency of Carbon. ALEXEI E. TSCHITSCHIBABTN (Ber. 1904 37 4709-471 5).-The constitution of the hydrocarbon described by Ullmann and Borsum as hexaphenylethane (Abstr. 1902 i 755) is discussed. If this hydrocarbon were hexaphenylethane i t should undergo oxidation to triphenylcarbinol which it does not do. Further its formation takes place under abnormal con- ditions where the presence of condensing agents is necessary.The author supposes that the hydrocarbon in question is not hexaphenyl- ethane but diphenylmethyl-tetraphenylmethane formed in accordance with the equation CPh,*OH + CGH,*CHPh = CPh3*C,H;C!HPh + H20. Evidence for this view is afforded by the action of bromine-on the hydrocarbon which is proved .to contain one hydrogen atom com- bined like the hydrogen atom of the (CH) group in triphenylmethane. This result makes it more probable than before that Gomberg's tri- phenylmethyl is in reality hexaphenylethnne especially since Gomberg himself has shown that his hydrocarbon has a molecular weight double that corresponding with triphenylmethyl. Bromine was gradually added in direct sunlight to a solution of Ullmann and Borsum's hydrocarbon in carbon disulphide.Only one molecular proportion of bromine interacted and the monobromide was produced in almost quantitative yield as faintly yellowish-red crystals melting a t 240-242'. This compound rese'mbles triphenylbromo- methane and reacts readily with water alcohol and acetic acid re- spectively its action with water being represented as follows CPh;C,,H,*CPh,Br + H20 = CPh,*C6H,*CPh2*OH + HBr. The latter reaction proceeds quantitatively when the solution of the bromide in pyridine is decomposed by hot water the carbinol CPh3*C,H,*CPh2*OH separating as a white powder which crystallises from a mixture of benzene and light petroleum in glistening balls and melt,s a t 220-220.5". It forms n brownish-red solution with concentrated sulphuric acid differing in this respect Erom the original hydrocarbon A.McK. Nitrophenylcyanamides. PAUL PIERRON ( BUZZ. SOC. chim. 1905 f iii] 33 69-74)- 0- Nitr~~~en?/lc~ccnnm?:da KO,* C,H; NH*C N ob- vor.4. LXXXVIII. i k126 ABSTRACTS OF CHEMICAL PAPERS. tained by heating in dosed vessels cyanogen bromide dissolved in water with o-nitroaniline in alcohol crystallises in bright yellow needles melts a t 146" is readily soluble in alcohol and fairly so in ether. The benxoyl derivative crystallises in almost colourless needles from alcohol and melts at 105". m-NitropiLenylcyunamide prepared by boiling together cyanogen bromide and m-nitroaniline dissolved in a mixture of water and alcohol crystallises in short pale Sellow needles melts a t 130° and is soluble in alcohol less so in ether or benzene.The benxoyl derivative crystallises in pale yellow lamellz melts a t logo and is soluble in alcohol or ether and less so in benzene p-hTitrophen ylcyunamide similarly prepared c rystnllises in bright yellow needles,melts a t 180° and probably polpmerises a t the same time. It is very soluble in alcohol less so in ether and slightly so in benzene. The 6enxoyZ derivative crysttallises in almost colourless lamell~e melts a t 131" and is less soluble in alcohol than its isomerides. p-L~ilrophenylcnrbamide obtained by heating the cyanamide dis- solved in alcohol with hydrochloric acid forms short prisms when crystallised by cooling a concentrated solution in alcohol and separates in needles from alcohol a t 40'; i t melts a t 238O is soluble in alcohol and slightly so in benzene or ether.On reduction with tin and hydro- chloric acid it yields p-aminophenylcarbamide (m. p. lag0) and when heated with hydrochloric acid for from 10 to 12 hours furnishes p-nit roa niline. T. A. H. Preparation of o-Chlorophenol. WILHELM LOSSEN (D.R.-P. 155631. Compare Hazard-Flamand Abstr. 1903 i 622).-Phenol may be directly chlorinated a t a low temperature in an indifferent solvent such as carbon tetrachloride chloroform or a liquid hydrocarbon. Solutions of phenol and chlorine may be mixed or a current of gaseous chlorine may be employed. The pure o-chlorophenol is isolated from the product in the usual manner. C. H. D. Picrolonates derived from Substances [Amines] of Physiologi- cal Importance. J. OTORI (Zeit.physiol. Chew. lY04,43 305-315. Compare Know and Mathes Abstr. 1899 i 462 ; Steudel ibid. 1903 i 43 1 >. -Penta??aethylenediantine picrolonate C,H,(NH,) 2CIOH8O5N4 obtained by mixing alcoholic solutions of the acid and of the hydro- chloride of the base crystallises in slender orange-yellow needles or plates begins to turn brown a t 220° and decomposes sharply at 250". One part dissolves in 7575 of water a t 16' or 357 at looo and in 5952 parts of cold or 475 of boiling alcohol. When prepared from the carbonate of the base it decomposes a t the same temperature 250° but differs as regards its solubility. Tetrccrneth~lenediccmine picrolonate crystallises in yellow needles decomposes at 263" when slowly heated and is very sparingly soluble One part dissolves in 13,157 parts of cold or in 653 parts of hot water ; also in 17,857 parts of cold or 954 of hot alcohol.ORGANIC CHEMISTRY.127 Picrolonate of Methylniiiiiie ........... Diriiethylaiiiiiie ........ Trimcthy1;t mine ........ E thylamine ............. Diethjlaniine from hy clrochloride . . . . . . . . Diethylaniine froin cai b- onate .................... TricAthylainiiie .......... Bet aiiie ................... Cholin e ..................... Nenrine .................. Lysine .................... No. of inoleculcs of acid conibiiied with one of base. 2 1 1 I 1 1 1 1 t 1 H20 1 1 Deconiposes a t 244" 222 250 -25'2 2-14 260 260 160 200 (or fro11i carbonate at 192") iielts at 158" clecomposes a t 241-245" 233 246- 252 One part dissolves in Water. Cold. 107:s 764 1121 3846 3788 1984 536 - I i- - - - Boiling.AIcohol. Cold. $717 853 i 9 4 1 i O O 2941 21 93 494 - - - 01 uble - I J. J S. Alkyl Ethers of p-Allylphenol. QLBERT VERLEY (D.R.-P. 154654).-p-Bromoanisole and its homologues react with magnesium in ethereal solution t o form compounds having the constitution OMe*C,H,*MgBr which then react with ally1 haloids forming p-allyl- anisole and its homologues. p-Allylanisole OMe*C6H,*C3H5 boils at 108-1 14' under 25 mm. pressure and is converted into the propenyl compound anethole by boiling with alcoholic potassium hydroxide. p-Allplphenetole boils at 113-114" under 20 mm. and a t 224' under 750 inm. pressure; p-propenylphenetole boils a t 241' under 750 mm. pressure and melts a t 61". C! H. D. ~4-Phenoxy-2-arninobenzenesulphonic Acid.] BADISCHE ANILIK- (e; SODA-FABRIK (D.R.-P.156156).-On heating a solution of sodium 4-chloro-3-nitrobenzenesulphonate and sodium phenoxide sodium 4-phenoxy- Z-nitrobe.lazeneszcZ~~o~~€e OYh*C,H,( NO,).SO,Naj is produced. It yields on reduction 4-phenoxy-2-arninobenxenesuZphonic acid crystallising from water in glistening white leaflets. The diuxo-com- pound is stable and dissolves sparingly in water ; it yields a red azo- dye with @naphthol. C. H. D. Aminoacetylcatechol. FARBWERKE VORM. MEISTER LUCIUS Cpr; BRUNINU (D.R.-P. 155632).-Aminoacetylcatechol may be prepared by k 2'1% ABSTRACTS OF CHEMICAL PAPERS. the method employed for the preparation of its alkyl derivatives (Abstr. 1904 i 873) ammonia being used in place of alkylamines. Chloroacetylcatechol at first combines with ammonia to form the sparingly soluble ammonium salt which then passes spontaneously into the amino-compound which is isolated in the form of its hydro- chloride.AminocccetyZcatecho7 C,H,(OH),*CO~CH,*NH forms a crystalline powder dissolving sparingly in water alcohol or ether. The hydyo- chloyicle crystallises froin alcohol in colourless leaflets decomposing a t 260° and dissolves readily in water. C. H. D. [Alkyl Ethers of o-Tolylcarbinol.] FARBENFABRIKEN VORM. I'RIEDR. BAYER & Co. (D.R -P. 154658).-Chloromethyl alkyl ethers react with the double compounds of magnesium benzyl haloids and benzyl ether forming alkyl ethers of o-tolylcarbinol CH,Cl*OR + Cl*Mg*CH,Ph = MgC1 + C,H,Me*CH,*OR. o-Y'oZyZcarbinyl methyl ether C,H,Me*CH,*OMe is a colourless oil The ethyl ether boils at with aromatic odour and boils a t 187-188°. 202 -203O ; the amyl ether boils a t 124' under 15 mm.pressure. C. H. D. [ Colourless Salts of Triphenylcarbinol and Diphenylcarbinol.] RUDOLF LAMBRLCHT and HUGO WEIL (Ber. 1904 37 4647).-An historical correction (compare Bey. 1904 37 3058). W. A. D. Action of Light on Cholesterol. ERKST SCHULZE and ERNST WIITTERSTEIN (Zeit. plysiol. Chem. 1904 43 316-319).-When cholesterol is exposed to bright sunlight for some time it turns yellow its melting point is considerably lowered and i t ceases to give the characteristic reactions with acetic anhydride and sulphuric acid or with vanillin and hydrochloric acid. A11 these changes are due to the formation of a small amount of brownish-yellow substance which remains in the mother liquor when the cholesterol is crystallised from alcohol.Cholesterol is not affected when sealed in a glass tube containing carbon dioxide and then exposed to light. J. J. S. Cholesterol. IV. ADOLF WINDAUS (Ber. 1904 3'7 4'753-4756. Compare Abstr. 1904 i 49 667 and 1010. Compare Diels and Abderhalden ibid. 88C)).-I3romocholestanonic acid (Abstr 1904 i 667) when heated with glacial acetic acid containing hydrochloric acid is converted into the lactone C27H4005 of a hydroxycholestanonic acid ; the lactone crystallises from alcohol in long needles melts after sintering at 192-193O and behaves on titration with cold aqueous sodium hydroxide as a monobasic acid but with the hot alkali as a dibasic acid. On heating the lactone-acid with 10 per cent.aqueous pobassium hydroxicle for two hours it is transformed into a hydroxy- ketodicarboxylic acid C21H4206 which crystallises from diluted acetic acid melts at 174-175O -and as it does not give a lactone is isomeric with the acid corresponding to the lactone just described. This acidORGANlC CHEMISTRY 129 can be readily obtained by heating bromocholestanonic acid directly with aqueous potassium hydroxide; I s it is very resistant to chromic acid it probably contains a tertiary hydroxyl radicle Dehydration of a-isoDypnopinacolin. I. &GIDE TERLINOK (BulZ. Acad. Roy. Bely. 1904 1049-1086. Compare Delacre and Geschd Abstr. 1904 i 32).-The first part of the paper gives detailed descriptions of methods for the preparation and isolation of a-iso- dy pnopinacolin homod ypnopinacolin and the hydrocarbon C25H22 from dypnone or acetophenone (compare Delacre Abstr.1896 i 591 ; 1900 i 603 and Geschd 1900 i 604; 1903 i 484). By the dehydration of a-isodypnopinacolin the a- and P-isodypno- pinacolenes C,,H, are formed (compare Delacre Abstr. 1896 i 591). The dehydration may be brought about by mixtures of acetic acid with sulphuric hydrochloric or hydro bromic acid or by acetyl chloride. The relative amounts of the two isomerides formed varies with the nature of the dehydrating agent employed a '' strong " acid favouring the production of P-isodypnopinacolene (m. p. 171") and a feeble one the formation of the isomeride. No evidence of the conversion of one isomeride into the other by the action of these dehydrating agents was obtained. a-isoDypnopinacolene crystallises from acetic acid or alcohol in lamellze melts a t 175.5' and distils under atmospheric pressure with the formation of a small quantity of the pisomeride.When heated with potassium hydroxide a t 320° it is converted into a pyoduct C,,H200 which crystallises from chloroform on addition of ether in needles or parallelopipeds and melts at 173". With sulphuric acid there is formed a derivative (sulphonic 1) which crystallises in white spangles and is soluble in water from which it is reprecipitated by ammonium chloride. Nitric acid acting on a-isodypnopinacolene dissolved in acetic acid converts it into a nityo-derivative C,,H,,O,N ; this crystallises from dilute acetic acid or nitrobenzene in hard yellow crystals and melts a t 272'. On reduction a-isodypnopinacolene does not yield definite products but on oxidation by chromic acid in presence of acetic acid a small quantity of benzoic acid is formed.When the hydrocarbon is dissolved in carbon disulphide and treated with a molecular proportion of bromine a bromo-derivative C,2H25Br is produced which crystallises in pale yellow needles melts at 199-200° and on reduction with sodium amalgam in presence of alkalis furnishes a series of crystalline products. When chloroform is employed as the solvent an isomeric 6romo-derivative is obtained ; this crystallises in tablets melts at 192O and furnishes a crystalline reduc- tion product with sodium amalgam When the bromination is carried out in presence of acetic acid a crystalline product of indefinite com- position is formed.A dibromo-derivative forniiiig large cubical crystals is obtained when bromine (2 mols.) is added to a-isodypnopina- colene dissolved in carbon disulphide. When the hydrocarbon is mixed with reduced iron and excess of bromine added a vigorous reac- tion ensues and the principal product is the compound C3,Hi4Brl,,; this crystalliseg from chloroform on addition of ether in straw-coloured tablets retains chloroform tenaciously develops a violet colour on exposure to sunlight evolves hydrogen bromide and becomes resinous W. A. D.130 ABSTRACTS OF CHEMICAL PAPERS. when 'heated and when warmed with potassium hydroxide in alcohol furnishes a bright red solution. T A.H. Constitution of Anthranil.GUSTAV HELLEH. (J. pr Chena Compare Abstr. 1902 i 779; 1903 i a. Y. 1904 [ii] 70 616-520. 827 ; 1904 i 160).-A reply to Barnberger (Abstr. 1904 i 442). Chloralamino-compounds. 11. SIMDN GARTNER (AnnaTeiz 1904 336 229- 266. Compare Abstr. 1904 i 788).-TrichloroetEiylidene- anthranilic a :id and potassium cyanide react in aqueous solution a t the ordinary temperature t o form a product which when boiled with water yields dichloroacetylanthranilic acid (Jackson Abstr. 188 1 735); this is also formed by the action of dichloroncetic chloride on anthranilic acid ; i t crystallises in colourless needles or large colour- less plates melts a t 176-177" is hydrolysecl by aqueous sodium hydroxide or less easily by dilute sulphuric acid to anthranilic dichloroacetic and glycollic acids and is reduced by sodium amalgam in aqueous solution to anthranilic acid.C9H,0,NCl,A g crystallises in rosettes o€ needles ; the ethyl ester C',,H,,O,NCl2 crystallises in rhombic plates melts a t 58-60' and boils a t 180 -190' under 13 mm. pressure. The silvev bal'iuua and calcium salts of anthranilic acid are described. When boiled with acetic anhydride dichloroacetylanthranilic acid The siZve~ salt N=$WHCl which cog0 forms the lactone of its titutomeric form C,H,< crystallises in long colourless prisms melts a t 1 7 5 O is easily soluble in acetone or chloroform and is hydrolysed when boiled with water t o the dichlmo-acid. When boiled with 20 per cent. ammonia in a reflux apparatus the lac tone forms dichloroacetylanthranilimine (4-keto- which crys- 2-dichloromethyldihydroquinazoline) C,H,< tallises in thick rhombohedra melts a t 210° sublimes without decom- position and when dissolved in warm aqueous sodium hydroxide is converted into an amino-acid.The action of phenylhydrazine on the lnctone leads to the formation of two substances a cldoro-compound C21H180N5t21 which crystallises in red plates and melts and decom- poses a t 24S0 and a derivative C,,H,,ON which crgstallises in glisten- ing needles and melts and partly decomposes at 232'. BADISCHE ANILIN- & SODA- FABRIK (D.R.-P. 155628).-Formddehyde and anthranilic acid com- bine in aqneous suspension or ethereal solution to form a condensation product separdting in yellowish-white crystals melting a t about 115-150° insoluble in water or dilute acids readily soluble in acetone.The compound becomes luminous on rubbing. Sodium sulphite converts it into w-su~~~omethylant~~racnilic mid (sulphite coin- pound of methyleneanthranilic acid) which reacts vith metallic cyanides t o form W-cyanomethylanthranilic acid (compare Abstr. 1903 i 336). iY=? *CHCl CO*NH G. Y. a-Sulphome thylanthranilic Acid. C. H. D.ORGANIC CHEMISTRY. 131 a-Amino-acids. EMIL ERLENMEYER jun. (Annnlen 1904 337 205-221).-An account is given of the various methods of preparing a-amino-acids including some recent and new methods devised by the author in which aldehydes are condensed with glycine and analogous substances. The synthesis of a-amino-P-hydroxg-acids by similar methods is also described. The paper concludes with a discus- sion of the state of our knowledge of the property exhibited by the methylene group of inducing condensation with various substances.K. J. P. 0. Synthesis of some a-Amino-P-hydroxy-acids. EMIL ERLEN- MEYER jun. and F. BADE (Annalen 1904 33'7 222-235. Compare preceding abstract).-The number of aldehydes which are able to condense with glycine forming a amino-P-hydroxy-acids is very limited. Neither vanillin nor salicylaldehyde will condense in this manner o-Met hoxybeiizaldehyde (2 mols.) however condenses with glycine (I mol.) when they are shaken together in the presence of a 50 per cent. solution of sodium hydroxide to which alcohol has been added; the product solidifies a mixture of two substances being formed which are separated by crystallisation from alcohol.The less soluble is the sodium salt OMe~C,H4*CH(OH)*C(N:CH*C,H,*OMe)*C0,Na,~EtOH which forms rhombs. The free acid could not be obtained but its acetyl derivative OMe*C,H;CH(OAc) C(N:CH* C,H,-ONe) *CO,H H,O is obtained together with a neutral yellow substance when the sodium salt is heated with acetic anhydride at 100'; it forms crystals becoming yellow at 210" and decomposing a t 216'. When a solution of the sodium sdt is treated with dilute acetic acid o-methoxyphen~l~deil.ine OMe.C,H;CH( OH)*UH (NH,).CO,H,H,O i 3 obtained o-methoxp- benzaldehydo being eliminated ; this acid crystallises in leaflets very soluble in water and melting and decomposing a t 179" ; the hydro- chloride is a crystalline powder and the coppep. salt a greyish-blue insoluble powder.When heated with acetic anhydride the amino-acid is converted into t,he oxaxole which crystallises in yellow leaflets melting a t 156"; it is identical with the yellow substance formed when the sodium salt is heated with acetic anhydride. On boiling the oxazole with sodium hydroxide it is converted into the acid OMe*C,H,i*CH:C(NHAc)*CO,H which crystal- lises in small neejles melting and decomposing a t 214O. The soluble substance formed in the condensation is best prepared by usirig 3 mols. of the o-methoxybenzaldehyde and is a com- pound formed by condensation of 3 mols. of the aldehyde with glycine 0 Me -C,H,* CH( OH) CH( C,H 0 Me) - N CH CgH 0Me ; it cry stallises in needles melting a t 134" and in alcohol gives an alkaline reaction. When heated with acetic anhydride it yields an cbcetyl derivative melting a t 170'.On warming with hydrochlo5ic acid at loo" the free base OMe*C,H4*CH(OH)*CH(NH,)*C,H,~DMe; is obtained crystallising -in needles me1 ting at I 36" ; the platinichloride crystallises from alcohol and melts a t 197". When heated the base decomposes into o-methoxybenzaldehyde and o-methoxybelzxylamirie (0-anisarnine) which is an oil ; the hydrochloride crystallises in long needles melting132 ABSTRACTS OF CHEMICAL PAPERS. a t 1 4Y0 and the platinichloride (C',I€,,ON),,1II2PtCl6,2~H,O in dark yellow leaflets melting and decomposing a t 189'. Unsaturated Compounds. 11. F. WILLY HINRICHSEN (Armalert 1904 336,323-344. Compare Abstr. 1902 i 129 ; 1904 i lola).- [Wit,h OSCAR Lo~s~.]-When acted on by bromine in chloroform soh- tion ethyl a-cyanocinnamenylacrylate forms a dibromide CHPliBr-CHBr.CH C(CN)*CO,Et which melts a t 98" and is oxidised by chromic acid in glacial acetic acid solution to the dibromide of cinnamic acid. The &bromide of cyanocinnainenylacrylic acid melts a t 187" and yields the ethyl ester melting a t 98'. Cinnamylidenenaaloizonitrile CHPh:CH*CH:C( CN) obtained by the condensation of cinnamaldehyde with methylene dicyanide in pre- sence of sodium ethoxide crystallises in slender yellow needles melts a t 12So and forms a white crystalline dibromide CHPhBr- CHBr- CH C( CN) which melts at 130° and on oxidation yields benzoic and dibromo- hydrocinnamic acids. [With MARIE R~msR.]-When oxidised with potassium perman- ganate in ace tone solution me thy1 a-nitrophenylcinnamenylacrylate yields dibromohydrocinnamic acid p-nitrobenzoic acid and an acid which melts at 110- 120" and may be phenylbromolactic acid.[With OSCAR Lo~s~.]-Cinnamddehyde neither reacts in presence of sodium ethoxide with a methyl group except in the casesof acetone and acetophenone nor with methylene unless i t is combined with two nitrile groups or with one nitrile and one other slightly acid group. Other aldehydes also take part in the reaction. The following new substances prepared by this reaction are described a-Cynnocitrylicleneacetic acid C,,H,;O,N obtained by the action of citral on ethyl cyanoacetate and hydrolysis of the product forms small yellow crystals and melts a t 150". 0- Hydroxybenxylidenernalononitrile OH- C,H;CH C(CN) obtained from salicylaldehyde and malononitrile forms yellow crystals and melts a t 183-184'.Methoxybenxylidenemalononitrile OMe* C,H; CH C( CN) from anis- aldehyde and malononitrile crystallises in slender white needles and melts a t 11 0'. On addition of sodium ethoxide t o the alcoholic solution of cinnam- aldehyde and chloroacetonitrile a precipitate of sodium chloride is formed and a dark oil is obtained on evaporation of the alcohol. K. J. P. 0 G. Y. Isomeric Esters of Orthoketo-acids. GUIDO GOLDSCHMIEDT and ALFRED LIPSCHITZ (Monatsh. 1904 25 1 164-1 176. Compare Abstr. 1904 i 168 ; Meyer Abstr. 1904 i 747).-When heated with acetic anhydride o-fluorenoylbenzoic acid forms an acetyl derivative which crystallises in matted white needles sinters a t 120° and melts and is converted into fluorenoylbenzoic anhydride a t 150-160'.The oxime of the anhydride melts and decomposes at 237-238" is insoluble in dilute aqueous potassium hydroxide and dissolves in concentrated sulphuric acid to a lemon-coloured solutionORGANIC CHEMISTRY. 133 I,'luowLonoyEbenzoic m i d obtained by oxidation of o-fluorenoyl- benzoic acid with a1 kaline permanganate is yellow and crystalline and melts at 248-250'. Hethyl Juorenonoylbenxoate C,oH,10,*C02Me obtained by the action of methyl iodide on the silver salt or of methyl-alcoholic sulphuric acid on the acid melts a t 160-162' and dissolves in concentrated sulphuric acid to a lemon-yellow solution An isomeric methyl ester is formed by warming the acid with thionyl chloride and treatiog the product with methyl alcohol; it melts at 184-186' and dissolves in concentrated sulphuric acid to a red solu- tion.The acetyl derivative obtained by heating the acid with acetic anhydride melts a t 178-180,' and dissolves in concentrated sulphuric acid to a red solution. Methyl naphthoylbenxonte C,H ,O*CO,RIe obtained by es terifyin g the acid with methyl alcohol and concentrated sulphuric acid or hydrogen chloride by treatment of the silver salt with methyl iodide or by the action of methyl alcohol on the acid chloride obtained by means of thionyl chloride forms large glistening monoclinic crystals [a b c = 1.3561 1 1.0897 ; p= 74O] melts a t 117-120") and dis- solves in concentrated sulphuric acid to an intensely yellow solution which slowly becomes red.The isomeric methyl ester is formed by the action of methyl alcohol on the acid chloride obtained by means of phosphorus ti ichloride or pentachloricle ; it separates from methyl alcohol in monoclinic crystals [a b c = 0.6138 1 1.5430; /3= 67'16'1 melts at 134-137"; and dissolves as does the free acid in con- centrated sulphuric acid to a violet solution. Ethyl fluorenonecarboxylate which melts a t 84-86" (Abstr. 1 903 i 161) is also obtained by the action of ethyl iodide on the silver salt by esterification with alcohol and sulphuric acid or by treatment with alcohol of the acid chloride prepared by means of phosphorus trichloride. The methyl ester C,,H70*C0,1Ue prepared by the various methods crystallises in glistening yellow needles melts a t 86-89O and dissolves like the free acid in concentrated sulphuric acid to a red solution. No second ethyl or methyl ester of flnorenonecarboxylic acid coulcl be obtained. G.Y. Isomeric Esters of Aromatic-Keto-acids. HANS NEVER (Monatsh. 1904 25 1177-1195. Compare Abstr. 1904 i 747; Goldschmiedt and Lipschitz preceding abstract).-0-Benzoylbenzoic chloride prepared by the action of thionyl chloride on the acid and the excess of the reagent removed by a current of dry air a t 50' uucler reduced pressure is a colourless viscid oil which does not solidify when strongly cooled or on addition of a crystal of the acid chloride which melts at 68-71". It distils at 33V-35O0 decomposing into hydrogen chloride and anthraquinone and when treated with concen- trated aqueous ammonia at 0' yields the amide which is also formed by the action of ammonia oneither of the methyl esters.I n the pre- sence of aluminium chloride the liquid acid chloride reacts with benz- ene to form phthalophenone. o-Benzylbenzoic acid prepared by Ullmann's method (Abstr. 1896 i 563),crystallisesinlongneedles; the silver salt crystallises in needles and with inethyl iodide forms the methyl ester which is also obtained by134 ABSTRACTS OF CHEMICAL PAPERS. conversion of the acid into its chloride by means of thionyl chloride and treatment of the product with methyl alcohol. It is a colourless liquid which has a pleasant odour and is ovidised by chromic acid to the d,lactone of dihydroxytetraphenylethanedicarboxylic acid (Ull- mann Zoc. cit.). The esters of o-benzoylbenzoic acid are reduced by zinc and acetic acid to the lactone of benzhydrylbenzoic acid and a small amount of a less fusible product which contains no niethoxy- group. The action of phenylhydrazirie on the isomeric esters in ab- sence of a solvent leads to the formation of Roser's phenylhydrazone (Abstr.1885 797) which nielts a t 162-163'instead of a t 180-182' as stated by that author. Methyl p-toluoyl-o-benz mte obtained by the action of alcohol and sulphuric acid on the acid or of methyl sulphate on the potassium salt melts at 61"; p.revious authors have given the melting point as 64" and 66". The isomeric metliyl estrr formed by the action of methyl alcohol on the liquid acid chloricle which is obtained by means of thionyl chloride nielts at 71-72' is leas soluble than its isomeride and gives an intensely yellow coloration with concentrated sulphuric acid.A mixture of equal amounts of the two isomeric esters melr,s a t 48-49". Methyl p-h2/droxybe.rzxoy?beizxoate formed by the action of sulphuric acid and methyl alvohol on the acid melts at 134". The isomeric estey obtained by the thionyl chloride method melts a t 134-135' and drs- solves i n concentrated sulphriric acid to an intensely orange-yellow solution A mixture of the two esters inelts a t 11 2-1 14'. The methyl ester of tetraclilorobenzoylbenzoic acid which is obtained by shaking the potassium salt with methyl sulphate in aqneous solu- tion crystallises in needlesand melts at 92'. The chloride formed by the action of thionyl chloride on the acid is crystalline melts a t 179-180' and when boiled with inethyl alcohol yields the second methyl ester which crystallises from a mixture of chloroform and methyl alcohol and melts at 1.54' (Kircher Abstr.188'7 831). The action of diazomethane on o-benzoylbenzoic p-toluoyl-o-benzoic ancl tetrachlorobenzoylbenzoic acids leads t o the formation of the more fusible methyl esters. It is probable that the free o-keto-acids ancl their more fusible esters which are therefore the $-esters have the lactonic constitution. G. Y. Introduction of Nitrogen into the Santonin Molecule and the Physiological Behaviour of Certain Santonin Derivatives. EDGAR WEDEKIND (Zeit. physiol. Chem. 1904,43 240-248. Compare Abstr. 1904 i 60).-Benzene azodesmotroposantonin (Abstr. 1903 i 542) on reduction with stannous chloride and hydrochloric acid yields the AydrocJdoride of d-aminosantonous acid ~H,*CH,*~*CMe:S-NH2 CO,H*CHMe*CH-CH,*C*CMe:C*OH It crystallises in plnt,es which tend t o turn red on exposure to the air is dextrorotatory and its aqueous solutions have a strong acid re- action.The amino-acid crystallises from alcohol in colourless needles melting a t 206" and is only sparingly soluble in water. Santonin desmotroposantonin santonic acid and the above hydro-ORGSNIC CHEMISTRY. 135 chloride have been examined from a physiological point of view. Although santonin acts as a strong poiyon when taken into the human system none of these four coalpounds has any appreciable toxic effect on lower anirna.13 and only santonin itself appears to be capable of destroying ascarides.J. J. S. Gtlycollic Acid Derivatives of Pyrogallol and its Alkyl Ethers. Pyrogallol and its alkyl ethers combine with chloroacetic acid on bail- ing with sodium hydroxide in a reflux appardtus or in an open vessel the volume of the solution being maintained constant. The condensa- tion prdduct separates on acidifying with hydrochloric acid and may be recrystallised from water. P~ogatlolylycolllic acid C,H,( OH),*O.CH,*CO,H melts a t 153-154' an11 dissolve readily in alcohol or hot water sparingly in cold water ether or benzene ; the alk dine solution becoiiies brown in air. PY7.0- gltlloldiglycollic acid OH.C,H ,(O*CH,*C0,H)2 is similar but its alkaline solution does not d;irkeii in air. Py~~ogccZZoZ ethyl ether diglycollic ucid OEt*C,,H,(O*~H,*CO,H)z crys- tallisea from benzene and melts at 108-109' ; pyrogallol diethyl e t h w gZyc Jlic acid C,,H,~(OEt),O.CH,*CO.LH nielts a t 82-433".The poison- ous character of pyrogtllol disappears in these derivatives. C. H. D. FKANZ UTZ (Cizem. Zeit . 1905 29 31).-When tannin is boiled with dilute hydrochloric acid dextrose is first formed and on further boiling 1,levulose and furfur- aldehyde. A. McK. Interaction of Pae nylcarbimide with 1 3-Dicarbonyl Compounds. WALTER DIECKMANN J. HOPPE and RICHARD STEIN (Bw. 1904 37 46.37-4638. Compare Abstr. 1904 i 847 87 3).-The majority of acyclic 1 3-Jicarbonyl compounds for example ethyl benzoylacetate acetylace tone benzoylacetone dibenzoylmethane and ethyl mdonate,interact with pheuylcarbiniide giving C-carbanilides according to the eqnation R*CC>*CH,.CO*R + PhN:CO = R*CO*CH(CO*R).CO*NHPh ; that the products are not 0-carbsnilides as has been assumed previously in several cases for instance those of dibenzoylmethane and benzoylacetone is shown by the fact that they have an acid character give the ferric chloride reaction and are hydrolysed aciborcling to Chisen's rule exemplified by the equation These C-carbanilides however are produced either at the ordinary temperature or a t 100" only in presence of traces of alkali for example that imparted by soda-glass.I n the case of alkyl-substituted ethyl acetoacetates and acyclic 1 3-diketones the interaction with phenyl- carbimide even in pre jence of alkali takes place extraordinarily slowly but traces of a C-carbanilide appear to be formed.I n all these cases the formation of an 0-carbanilide could not be detected. On the other hand the dihydroresorcins like phenols in absence of alkali give at once 0-carbanilides ; the hydroxymethylene- compounds however although giving 0-carbanilides require the pre- AKTIEN-OESELLSCHAFT FUR ANILIX-FABRIKATION (D.R -P. 155568).- Decomposition of Gallotttnnic Acid. CH,*CO.CHBz*CO*NHPh + KOH = CH;C02K + CH,Bz*CO*NHPh.136 ABSTRACTS OF CHEJIZCAL PAPERS sence of traces of alkali to initiate the action. When an alkali is used in the case of the dihydroresorcins instead of getting an 0-carbanilide a C-carbanilide is produced ; an alkali transforms for instance CH :C( O*CO*N HPh) Co<CH,--CBph>CH2 analogous trar&formation of the 0-carbanilide of hydroxymethylene acetophenone into the C-carbanilide CHBz:CH*O*CO*NHPh -+ OH*CH:CBz*CO*NHPh can be effected by heating it in ethereal solution with dry potassium carbonate.In the case of phloroglucinol no interaction with phenylcarbimide occurs a t 100" when an alkali is absent; the addition of a trace of sodium carbonate gives rise to a substance which differing from Goldschmidt's tricarbanilide is undoubtedly the 0-tricarbanilide. These facts show that the use of phenylcarbimide in ascertaining the structure of isodynamic substances is subject to considerable limita- tions. The new compounds obtained in investigating the foregoing cases are as follows Ethyl benxoylmalonunilata OH*CPh:C(CO,Et)*CO*NHPh obtained from ethyl benzoylacetate and phenylcarbimide crystallises from alcohol in co10ui-le3s needles and melts a t 142-143' ; on hydrolysis with alcoholic potassium hydroxide it gives beiizoic acid and malonanilic acid.Ethyl acet~lbenxylmalonanilate CH,Ph CAc( C0,Et) CO*NH Ph could not be isolated in the case of the interaction of ethyl benzyl- acetoacetate with phenylcarbimide but its formation is evident from the fact that the product on hydrolysis gives a-cccrboxydil~yclrocin~a~- unilide CH,Ph*CH(CO,H)*CO*NHPh which ci-ystallises from alcohol in colourless needles and decomposes on melting giving dihydrocinnam- anilide ; tho latter melts at 97' not at 92" as previously stated. Diacetylacetanilide CHAc,*CO*NHPh prepared from scetylacetone crystallises from alcohol in colourless needles and melts at 117-1 19".Benxoylucetylucetu~~ilidc CH,* C( OH) :CBz*CO*NHPh obtained from benzoylacetone forms colourless needles melts a t 126") and on hydrolysis gives benzoylacetanilide. Dibenzoylacetanilide CH h,*CO-NHPli obtained by the action of phenylcarbimide on dibenzoylmethane gives on hydrolysis benzoic acid and benzoylacetanilide. DicarbethoxyucetaniZide (ethyl C-car banilinomalonate) CH( CO,Et),*CO.NHPh separates from alcohol in colourless crystals nielts a t 122') and on hydrolysis gives malonic acid monanilide. The 0-car banilide of dime t h y ldi hydroresorcin >CH CH:C(O*CO*NHPh) co<(JJl&- CMe crystallises from benzene in colourless needles melts at 105-106° and on hydrolysis gives methyl phenylcarbamate and dimethyl- di h ydroresorcin. l)imetl~yldihydrorerorcin C-carbu?dide <CH,--(,j C(CO*NHPh):C(OH)>,H Me,ORGANIC CHEIMISTRT. 137 crystallises from alcohol melts at 03-94O and is not attacked by methyl alcoholic potassium hydroxide.Phen y Zdih ydro yesorc in 0- carbccnilide CH C (0 CO N H Ph) "O<cH2- CHPh>CH2' crystallises from benzene and melts between 130' and 184' decompos- ing into its components. The C-cadanilide C( CO*NHPh):C(OH)> co<CH2-- CHPh cH2' melts at 136" and is not hydrolysed by alcoholic potassium hydr- oxide. The isomeric C-cccrbnnilide C O < ~ ~ 2 . ~ ~ ~ ~ > C H * C O * ~ H P obtained from ethyl cinnamate and sodioacetoacetylanilide crystallises from alcohol and melts a t 196-19'7'. From hydroxymethyleneacetophenone the O-carbnnilide CHBz CH*O*CO*NHPh is obtained ; it crystallises from benzene in colourless needles melts at 123-1 25' and is easily hydrolysed into its constituents.The C-cccrbnnilide NHPh*CO*CRz:CH*OH crystallises from benzene melts at 93-94" and is only very slowly hydrolysed by alcoholic potassium hydroxide giving then formic acid and benzoylacetanilide. Phloroglzcc inol-O-t?.icccl.ba?~ilide C, H3( 0 CO*NHP h)3 crys tallises froin alcohol or glacial acetic acid melts a t 190-191' and is easily hydrolysed into phloroglucinol and methyl phenylcarbamate. Diethyl p~ZoroglzLcinolcl~ca~~box~lc~te O-t?-iccc~bc~nilide melts at 150 -155" and is also easily hydrolysed. Esterification by means of Sulphuric Acid. 11. HANS MEYER (illoncctsh. 1904 25 1201-1214. Compare Abstr. 1904 i 216).- Methyl anthrsnilate is formed in 92 per cent. yield when anthranilic acid is dissolved in concentrated sulphuric acid.Methyl paminomesityl- ate formed by the same method melts a t 93'. Methyl o-aminomesityl- ate melts at 39' and has a slight odour resembling that of ethyl benzoate. By this method of esterification 4 grams of heniimellitic acid yields 2-3 grams of the trimethyl and 1.2 grams of the diethyl ester. The esters were obtained in the same proportion when 5 grams of the acid were boiled with 10 grams of sulphuric acid and 50 grams of methyl :~lcohol (compare Graebe and Leonhardt Abstr 1896 i 437; Meyer Abstr. 1896 i 547). When treated with thionyl chloride dimethyl hydrogen hernimellitate is converted into its crystal- line chloride which melts a t 84-87O and when treated with absolute alcohol and barium carbonate forms the dimethyl eth$ ester (C02Et),* C,H(O*CO*NHPh) W.A. D. This is a colourless oil having an o d k of apples and when shaken with N-sodium hydroxide solution yields ethyl dihydrogen hemimellitate cH* c(co2H)>C*C0,Et which crystallises in needles melts at 175" and is formed when hemimellitic anhydride is boiled with alcohol. C H % ~ C(CO,H)138 ABSTRAC'l'S OF CHEMICAL PAPERS. When dissolved in sulphuric acid and heated with methyl alcohol in a benzene-bath mellitic acid forms the pentamethyl ester ; a t 100° a mixture of this with the hexamethyl ester is obtained whilst a t 120-1 25" the latter preponderates very lai gely. Pentamethyl hpdrogsn mellitate crystallises in long silky glistening needles and melts a t 141-144".G. Y. Lichens and their Characteristic Canstituents. IX. O~WALD HEME (S. p*. Chenz. 1906 [ii] '70 449-502 561. Compare Abstr. 1898 i 378 531 679 ; 1899 i 331 ; 1901 i 85 149 595; 1902 i 689 ; 1903 i 702).- Clccdonicc S Q Z G C ~ I ~ O S ~ (C. froncloscbc) was gathered from a boulder in the upper Rsnnbnch Thal mar Wilclbad ; as with the var. venthosa the only characteristic constituent found was squamatic acid. When treated with concentrated aqueous potassium hydroxide this acid forms delicate white needles probably of the potassium salt. which gradually redissolve when on addition of water the solution becomes blood-red ; the bc~rium salt forms a white voluminous floccu- lent precipitate Cladonia (Ctadincc) destrictcc contains Z-usn:c and squamatic acids a pigment which forms a blue compound with aqueous sodium hydroxide and an indifferent compouncl cladestin which forms a white micro- crystalline powder becomes yellow a t 240° melts a t 2 5 2 O and gives a dark red coloration with ferric chloride in alcoholic solution.Zopf's destrictic acid (Abstr. 1903 i 763) was possibly sqnamatic acid ; no trace of a colourless compound crystallising in leaflets could be found. Clccdonicc furcata (6'. rctcernosa C'. recuwa) mas obtained from the woods in the neighbourhood of the Waldeck Ruin between Talmiihle and Teinach stations in Wurtemberg ; it yields traces of an ncid which crystallises in small colourless scales and gives a red coloration with ferric chloride and a wax-like substance which is soluble in ether.Cetrariu islandica of various origins yields proto-a-lichesteric acid which is monobasic forms the barium salt (C,,H,,O,),Ba and when heated with hydriodic acid of sp. gr. 1.7 yields no alkyl iodide but is almost entirely converted into a substance which melts a t 70-80'; no lichesteric acid was obtained from the moss (Bohme Abstr. 1903 i 316). I n the Iceland moss fumaric acid is present in combination with protocetraric acid as fumaroproto- cetraric acid C,2H46033,2 H,O previously considered to be identical with protocetraric acid (Abstr. 1898 i 534). It crystallises in small white needles commences to decompose a t 240° and a t 260' has become black without having melted ; at higher temperatures a sublimate of fumaric acid is formed; i t is sparingly soluble in water ether alcohol or acetone ; the alcoholic solution has an acid reaction and gives a purple coloration with ferric chloride ; in concentrated sulphuric acid it dissolves to a dark red solution.When dissolved in aqueous alkali hydroxide precipitated by the addition of hydrochloric acid and again neutralised with the alkali hydroxide fumaroproto- cetraric acid is hydrolysed to fumaric and protocetraric acids or to diethylprotocetrai*ic acid if the reaction takes place in alcohol. Yroto-ORGANIC CHEMISTRY. 139 cetraric acid CJ4H42027 forms spherical crystalline aggregates decom- poses without melting a t 250° gives a purple coloration with ferric chloride in alcoholic solution and dissolves in concentrated sulphuric acid to a red solution. The barium (C5,H?,0,7)2Ba the caZcium ( C54H,g0,7)ZCa3 and the yellow amorphous szlver salt are described.When heated with methyl alcohol in a sealed tube a t loo" proto- cetraric acid forms the ti-imethyl ether C5,H3,0,,( OMe) which crys- tallises in short colourless prisms becomes black a t 240" without having melted and gives a purple coloration with ferric chloride in alcoholic solution. The potas.siunz salt C,7H,50,7K is a white powder and on treatment with warm alcoholic potassium hydroxide forms the salt C57H,30,7K which crystallises in white needles. When heated with methyl alcohol and concentrated sulphuric acid in a sealed tube a t loo" trimethylprotocetraric or furnaroprotocetraric acid yields tri- methylcetrol C H 46020 which forms greenish blue masses. Dimethylprotocetreric acid C54H40085(0Me)2 obtained by boiling fumaroprotocet raric acid with potassium hydrogen carbonate and methyl alcohol in a reflux apparatus forms small yellow prisms commences to decompose a t 40° and is blackened without melting a t 260"; i t dissolves in concentrated sulphuric acid t o a yellow solution which changes to blood-rcd.The potassium salt crystallises in small colour- less prisms. Triethj lprotocetraric acid C54H3902,(OEt)3 is identical with cetraric acid ; the potassium salt C5,H 36024(OEt)SK3 crjstallises in small white needles. Dieth ylpotocetraric acid C'~4H,o0,,(OEt) obtained froiii fumaro- protocetraric acid crystallises in stellate groups of white needles and is complt tely decomposed without having melted a t 250" ; the potassium salt C51 H,70,5(OEt),K3 crystallises in white needles.Diethylce- trol C Hf80,,(OEt) separates from water as an amorphous floccu- lent precipitate and sinters and decomposes a t 2.50". BisdiethylcetroZ ( C55H48020)2,. formed a1 ong with diethylcc t rol by the action of alcoholic sulpburic acid on fumaroprotocetraric acid is a dark blue substance which when heated to high temperaturc s burns with- out previous melting and dissolves in aqueous sodium hydroxide to a yellow solution. The acid previously obtained from Parmelia s~xatilis var. sulcata and pa?ingormis (Abstr. 1901 i 151) and termed protocetraric acid neither yields fumaric acid when sublimed nor alkylcetrols when heated with alcoholic sulphuric acid; it is to be distinguished as parmatic acid. Contrary to Zopf's statement (Abstr.1901 i 87) Parnzelia Borreri contains stranorin as well as lecanoric acid. Parmelia tinctorurn from .Madras cinchona bark yields lecanoric acid and atranorin. P. perlata contains atranorin and perlatic acid C,7E12,0g*OMe,2H20 which crystallisps in small white needles loses 2H,O at 80° melts when slowly htated a t 100-105" when quickly heated a t 125-130° gives a red coloration with bleaching powder in alcoholic solution a dark blue coloration with ferric chloride and dissolves in concen- trated sulphuric acid to a colourless solution which becomes greenish- brown on warming. The potassium salt C,,H,,O,,K 2H,O crystallises140 ABSTRACTS OF CHEMICAL PAPERS. in white prisms ; the bayium coppw ( C,8H,,010)2C u silver C28H29010Ag and the basic lead 5(C,,H,,O,,),Pb,PbO are described.The ethyl ester C27H2,0,*C0,Et is obtained as a colourless strongly refractive oil which slowly solidifies to white needles melts at 56-58' and with bleaching powder in alcoholic solution gives an intensely red with ferric chloride a dark blue coloration. When warmed at 85' with acetic anhydride anhydrous perlatic acid yields dicccetylperlutide C28H2,0E Ac? which forms a white powder and melts at 55". When boiled with aqueous bnryta perlatic acid forms barium carbonate and perlatol C,iH,,O which sinters at 60' and melts a t 80'. Along with perlatic acid there occurs in P. perlutu an acid which crystallises in small white needles melts at a little above loo' gives a bluish-violet coloration with ferric chloride red with bleaching powder in alcoholic solution and forms a n amorphous potassium salt.P. cccpemta from a sandstone wall from Castanea vesca near Neu Schloss in Baden-Baden and from beech trees in the neighbourhood of Solitude near Stuttgart yields d-usnic capraric and caperatic acids. Sticta pulrnonaria contains stictaic acid (stictinic acid Knop and Schnedermann J. pr. Chem. 1846 39 365) and not protocetraric acid as previously stated (Abstr. 1898 i 681). Stictaic acid C,,H,,O;OMe crystallises in small yellow needles containing 2-6 per cent. of water of crystallisation lost at looo melts and decomposes a t 264O gives a purple coloration with ferric chloride in alcoholic solution and dissolves in sulphuric acid to an orange- coloured solution. The potussium C,,H1,09K and the ba~iunz (C1,H,,O,),Ba salts have been analysed.Aspicilia gibboscc yields nspicilic m i d which crystallises in coloIdess flat needles melts a t 119" and with bai.ium chloride in ammoniacal solution gives (1) a white flocculent precipitate aspicdin which crystal- lises in long colourless glistening leaflets melts a t 150' distils with- out decomposition and dissolves in concentrated sulphuric acid to a colourless solution which becomes brown when heated and (2) a small amount of an acid which gives a blue coloration with ferric chloride. Traces of atranorin are now found along with lecanoric acid in Urceolarin scruposa var. vulgcc?*is. Sodium lecccnomte C1,H,,O7Na,4H,O crystallises in small white needles. Chiodecton sungzcifieum (C. rubrocinctztrn) from Bolivian calisnya bark contains chiodectonic acid C,,H,,O which forms a scarlet floc- culent precipitate dissolves in alcohol to a blood-red solution decolor- ised by bleaching powder and gives a black coloration with ferric chloride and chiodectin which crystallises in long needles melts at 120° and is neutral.Contrary to the statements of previous authors Pertusccric6 tlealbccta does not contain orcin. G. Y. Some Archil Lichens and their Chromogens. OSWALD HESSE (Bey. 1904 37 4693-4696. Compare Abstr. 1898 i 531).- Contrary to Ronceray's statements (Abstr. 1904 i 897) erythriii (erythric acid) melts at 148O (see Zoc. cit. and Juillard Abstr. 1904 i 593) and lecanoric acid at 166'; the Maquenne block is evidently notORGANIC CHEMISTRY. 141 suitable f o r these substances.Erythrin is found in Roccellcc Montagnei I?. fuciformis and R. fructicosa (R. cacticoZn ; R. peruensis) but not in R. tinctoria which contains lecanoric acid. Ronceray ’s supposed Bendrographa Eeucoplmu was R. fbucticosa. Erythrin is not obtained from any Pertusaria ; Ronceray’s erythrin was probably lecanoric acid. The vanillin-sulphuric acid test is not trustworthy for orcinol in the lichens. Juillard’s anhydroerythric acid and ‘‘ simple erythrin ” (Zoc. cit.) were impure erythric acid to which the author assigns the formula C,H,( OH),~O*C,H,Me(OH)*CO*O*C~H21Me(OH)*C02H ; picroerythric acid then becomes C,H,( OH),. 0. C,H,Me(OH)*CO,H. G. Y. [Sulphonic Acids of Benzaldehyde.] CHEMISCHE FABRIK VORM SANDOZ (D.R.-P. 1545%). -On dissolving toluenesulphonic acids in fuming sulpliuric acid and adding manganese dioxide oxidation to the corresponding benzaldehyde-sulphonic acids takes place the aldehydic group remaining unattacked even when a large excess of oxidising agent is employed.Sulphur trioxide is added from time to time to take up the water formed ; the product is then poured on to ice a.nd separated by means of sodium hydrogen sulphite. The sodium salts of benzaldehyde-p-sulphonic and benzaldehyde-2 4-disulphonic acids are described. The salts yield white and yellow phenylhydrazones respec- tively and the latter gives rise to the disulphonated leuco-base of malachite green when condensed with dimethyl- or diethyl-aniline. C. H. D. Preparation of Aromatic Dihydroxyaldehydes. RUDOLF SOMIVIER (D.R.-P.15573 l).-Hydrogen peroxide oxidises aromatic monohydroxyaldehydes in the presence of ferrous sulphate to cli- hydroxyaldehydes. After removing the iron by means of barium hydroxide the aldehyde is precipitated by lead acetate. The new hydroxyl group takes the ortho-position to that already present the aldehydic group not being attacked. Thus nz- and p-hydroxybenz- aldehydes yield protocatechualdehyde and salicylnldehyde yields 2 3-dihydKoxybenzaldehyde together with a small quantity of resorcylaldehyde (compare Fenton and Jones Trans. 1900 77 69 ; Cross Bevan and Heiberg Abstr. 1900 i 534). C. H. D. Cyclic Compounds. Oxidation of 2-Methylcyclohexanone. WLADIMIR B. MARKOWNIKOFF (Anmden 1904 336 299-309. Com- pare Abstr. 1903 i 836).-The product of the oxidation of 2-methyl- cplohexanone contains in addition to the three acids previously mentioned (Zoc.cit.) an acid which is very soluble in water and melts at a lower temperature than does pyrotartaric acid. Bouveault and TBtry’s dianilide method of separating p- and a-methyladipic acids (Abstr. 1901 i 364) is unsatisfactory as contrary to these authors’ statement (Zoc. cit.) a-methyladipic dianilide which melts at 174-175’ is slightly more soluble in alcohol than is the /3-dianilide. The pyrotartaric acid formed in the oxidation probably becomes inactive during the distillation as the active anhydride which melts VOL. LXXXVIII. i. I142 ABSTRACTS OF CHEMICAL PAPERS. at 67-67*5" after distillation under 760 mm. pressure melted a t 42-45" and when boiled for five minutes was completely converted into the inactive anhydride.G. Y. Action of Ammonium Sulphide on Ketones and the Con- version of Thiopinacones into Hydrocarbons. WILHELM MANCHOT and PAUL KRISCHE (Annulen 1905 337 170-204).-The earlier experiments of Behr Engler and Baumann and Fromm on the action of hydrogen sulphide or hydrosulphides on acetophenone and benzophenone is discussed. Besides repeating their experiments the authors have investigated the reaction of ammonium sulphide on other aromatic ketones. p-Dinitrodibenzyl ketone prepared by nitrating dibenzyl ketone with fuming nitric acid forms microscopic crystals melting at 1 0 5 O ; it is oxidised to p-nitrobenzoic acid by nitric acid and gives a very delicate red coloration with alkali hydroxides. The oxime crystallises in needles melting at 133" and gives a red coloration with alcoholic potassium hydroxide.The phenyZAydraxone crystallises in needles melting a t 136'. On reduction with stannous chloride basic sub- stances are formed but when suspended in alcohol and treated with alcoholic ammonium sulphide containing excess of hydrogen sulphide it is converted into p-dinitrodibenxylthioketone Cs(CH,*C,H,*NO,) (or the corresponding mercaptan) which crystallises in needles melting at 137". Dibenzyl ketone is readily converted by the Eiame reagent into tetrabenzylthiopinacone SH*C(CH,Ph),*C(CH,Ph),*SH which crystallises in long needles melting a t 11 7". The investigation of the action of ammonium hydrosulphide on alcoholic solutions of acetophenone led to results differing widely from those of Baumann and Fromm who obtained two isomeric diphenylthiophens melting respectively a t 119' and 1 5 2 O whereas the authors obtained d ipheny 1 dimethyl thiopinacone SH*CMePh*CMePh*SH which forms scales melting a t 1 1 8 O .The substance obtained by Engler from benzophenone was found to be tetraphenylthiopinacone and not a disulphide. Did~p~.fylenethiopinacone c,,H sS,! was prepared from diphenylene ketone (fluorenone) by treatment with alcoholic ammonium hydro- sulphide and crystallised in long needles melting at 165'. ~ e t r a b e ? 2 x y l t e t r a ~ ~ t J ~ y l t ~ ~ ~ o ~ ~ ~ ~ c ~ c o n e C,&K,,S was prepared in a similar manner from diphenylpentanone in quantitative yield ; it crys- tallised in needles melting a t 112'.Tetru benxyZetlqZene C (CH,Ph), C( CH,Ph) was obtained from the tetrabenzylthiopinacone by heating with copper powder and fraction- ating the oily product which boiled a t 304" had a faint violet fluorescence and formed an additive product with bromine. On nitration it yielded a tetranitrotetrabenzylethylene C,,H,,O,N which crystallised in needles melting a t 156O. On heating the thlopinacone for several hours at 180° hydrogen sulphide is evolved and tetra- benzylthiopinacone formed together with sulphur. Tetraphenylthiopinacone is converted into tetraphenylethane when heated with copper but when heated alone into tetraphenyl-ORGBNIC CHEMISTRY. 1.43 ethylene which crystallises in leaflets melting at 224" and does not yield a picrate but forms a tetrabromo-derivative (m.p. 253'). Didiphen y lene thiopinacone is converted into did iphen y lene-et hane (m. p. 249') on boiling its alcoholic solution with copper powder ; if the pinacone is heated directly with copper a very small quantity of a sub- stance crystallising in brownish-red needles and melting a t 203" is - obtained together with di~~~enyZe?2e-et~yZe?ze FGH4>C:CH ; the latter P a 4 V" = forms orange-red crystals with an aromatic odour which melt a t 104-1 06". When heated alone a t 300° this pinacone decomposes hydrogen sulphide being evolved and a hydrocarbon (diphenylene-ethyl- ene ?) melting a t 106' formed. Since it was possible that the formation of diphenylene-ethylene was due to the decomposition of didiphenylene- ethane the latter was heated with copper; a small quantity of diphenylene-ethylene was produced.Since Graebe obtained M i - phenylene-ethylsne by distilling fluorene with lead oxide it was pro- bable that lead oxide could be used to remove the sulphur from didi- phenylenethiopinacone and that it would also lead to the formation of diphenylene-ethylene; such was found to be the case. Further on heating fluorens with lead oxide it was converted to a very large extent into diphenylene-ethylene. The diphenylene-ethylene from various sources yielded the same dibromide CI4HJDBrP which crystal- lised in needles melting a t 1-58'. When distilled with nickel in a current of hydrogen the hydrocarbon is converted into fluorene. K. J. P. 0. Certain Reactions of Benzoin. J. BERT. GARNER (Anzer. Chena. J. 1904 32 583-606).-The reaction between benzoin and alcoholic potassium hydroxide or sodium ethoxide has been studied by Zinin (J.pr. Chew. 1867 98 495) Jena and Limpricht (Ammlem 1870 155 93) Limpricht and Schwanert (Abstr. 1871 536) Japp and Owens (Trans. 1885 47 go) and others. Pipcke (Abstr. 1888 701) found that when a solution of sodium ethoxide was added to a solution of benzoin in boiling alcohol a mass of blue crystals was produced which became colourless when heated but on shaking in contact with air again became coloured. On repeat- ing this experiment it has been found that a substance C42H3205Na2 is produced which crystallises in long white silky needles and is decomposed by water and most other solvents. When this compound is treated with water at 20° benzoin sodium hydroxide and benzoic acid are produced.The substance is also decomposed by glacial acetic acid with formation of benzoin benzoic acid and sodium acetate. On heating benzoin with alcoholic potassium hydroxide in a sealed tube for 6 hours at 150-160" the following substances were obtained the quantities stated being those produced from 16 grams of benzoin. Ethylbenzoin 1 a 7 5 grams ; hydrobenzoin isohydrobenzoin and their dimolecular anhydrides 4.9 grams ; benzyl alcohol 1.9 grams ; benzoic acid 2.2 grams; benzilic acid 0.1 gram; and ethylbenzilic acid 4.2 grams. The last substance resembled the ethylbenzilic acid of Jena and Limpricht (Zoc. cit.) but when heated to 70" suffered violent L 2144 ABSTRACTS OF CHEMICAL PAPERS. decomposition with evolution of carbon dioxide and formation of a dark red viscous oil.I n another experiment an alcoholic solution of benzoin was heated with sodium ethoxide for 26 hours in a reflux apparatus. The products obtained from 15 grams of benzoin were as follows hydrobenzoin 4 2 grams ; isohydrobenzoin 2.2 grams ; dimolecular anhydride of hydrobenzoin 0.8 gram ; dimolecular anhydride of isohydrobenzoin 0.5 gram ; benzoic acid 2.2 grams ; Jena and Limpricht's so-called ethylbenzilic acid 4.9 grams ; benzilic acid a Grace ; and a tetrahydro- f uran derivative 1 -9 grams. When dry oxygen is passed into a boiling alcoholic solution of benzoin and sodium ethoxide benznldehyde benzoic acid the tetra- hydrofurnn derivative and traces of benzilic acid are produced. These experiments have shown that Jeiia and Limpricht's so-called et hglbenzoin is a mixture of hydrohenzoin isohydrobenzoin and their dimolecular anhydrides ; that the isodesoxybenzoin pinacone described by the same authors is a mixture of ethylbenzoin isohydrobenzoin and its dimolecular anhydride ; that the so-called ethyldibenzoin obtained by Jenn and Limpricht Limpricht and Schwanort and Jnpp and Owens is 2-benzoyl-2 3-diphenyl-5-hydroxytetrahydrofuran ; and that the substance to which Jena and Limpricht assigned the formula C,,H,,O is impure isohydrobenzoin dimolecular anhydride.5-Hpdroxy-2- bevxoyl-2 3-di2112enyktetrahy~~.ofici.n.n YH2* CH(0H) CHPh*CPhEz>" crystallises from hot ethyl alcohol in large prismatic crystals melts a t 195" and is soluble in hot benzene ether acetic acid or chloroform gives a deep red coloration with ferric chloride and when fused with potassium hydroxide is converted into benzoic cinnnmic and acetic acids ; its acetyl derivative forms large transparent plates and melts at 145O.The tetrahydrofuran compound is oxidised by chromic acid with formation of benzoic acid and carbon dioxide; it is converted by an alcoholic solution of hydrogen chloride into ethyl cinnamate and benzil. On oxidising the compound with alkaline permanganate or with nitric acid y-benxoyl-fly-diphenylbutyrokcictone is produced which crys- tallises from ethyl alcohol melts a t 138*5" and is soluble in ethyl acetate benzene or chloroform. 5 -Hydroxy-2- benzoyl-2 3-diphenyl t et rahydrofuran can also be pre- pared by the action of cinnamaldehyde on benzoin in presence of dilute sodium ethoxide another substance being simultaneously prodnced which mystallises in needles and melts a t 160-161°.E. G. o-Benzoquinone. RICHARD WILLSTATTER and ADOLF PFANNENSTIEL ( Bey. 1904 37 4744-4746).-o-Benzoquinone CGH,O is easily obtained by oxidising catechol a t the ordinary temperature with freshly prepared purified siiver oxide in pure dry ether containing ignited sodium sulphate ; it crystallises in dark red transparent plates decom- pwes between 60' and 70" has no smell and is not volatile. On re- duction with sulphurous acid catechol is a t once regenerated. W. A. D.ORGANIC CHEMISTRY. 145 Action of Azoimide on p-Beneoquinone. RICHARD ESCALES (Chem. &it. 1905 29 31).-By the action of azoimide on p-benzo- quinone a substance is obtained which melts at 14s-153'; when crystallised from ethyl acetate the melting point is about 25" lower.A. ISlcK. P r e p a r a t i o n of Methylaminoanthraquinones. FARBENFABRII~EN VORM. FRIEDR. BAYER 8t Co. (D.R.-P. 156056).-Amino-derivatives of anthraquinone react with formaldehjde in strong mineral acid solution to form methylaniino-derivatives. The substances may be dissolved in concentrated sulphuric acid and warmed to 55-60'. The preparation of a-methylaminoanthraqninoue and of 1 6- and 1 9-di- rnethyldiaminosntliraquinones is described (compare Abstr. 1 90 1 i S39) C. 1%. D. C o n s t i t u t i o n of Dibromo-1 6-diaminoanthraquinone. ROLAND SCHOLL and A. KRIEGER (Ber. 1904 37 4681 -4686).~-Sclioll and Berblinger's dibromo-1 6-diaminoanthraquinone (this vol.i 88) must be the 2 7-dibromo-compound as the dibromotetraminoanthraquinone obtained on reduction of Scholl's dibromodinitro-1 6-dinitroamino- antbrayuinone (this vol. i 70) does not react with phenanthraquinone and therefore cannot hare amino-groups in the ortho-position to each other. 2 7-Dibromo-4 9-dinitro-1 6-dinitroaminoanthraquinone is best prepared from crude 2 7-dibromo-1 6-diaminoanthraquinone and is purified hy treatment with alcohol and hydrogen chloride and re- crystallisation from dilute ammonia. 2 7-Dibromo-1 4 6 9-tet~*aniinoantlwaquinone YH C ( N H ) . ~ . ~ O * ~ * C ( N H ) ~ B ~ ~ CBr C ( N H ,) C * C 0- C . C (NH,) C Br ' is obtained by reduction of 2 7-dibromo-4 9-dinitro-1 6-dinmino- anthraquinone with aqueous potassium sulphide or of the ammonium salt of the dinitroamino-compound with hydrogen sulpbide or phenyl- hydrazine in aqueous solution.It cr ystalliaes in violet glistening needles does not melt at 360' is insoluble i n solvents of low but sparingly soluble in those of high boiling point dissolves in concen- trated sulphuric acid to a brown solution which becomes red and finally blue on dilution and forms a tetmbenxo9Z derivative C42H,fjOfjN4%?- G. Y. Action of Aromatic Bases on the Nitroamino-g roups of 2 7-Dibromo-4 9-dinitro-1 6dinitroaminoanthraquinone. ROLAND SCHOLL and A. KRIEGER (Ber. 1904 37 4686-4692. See foregoing abstract).-When boiled with aniline 2 7-dibronio- 4 9-dinitro-1 6-dinitroaminoanthraquinone yields azophenine and 2 'I-dibronzo-1 6-diamino-4 9-dianiZinoantJAraquinone YH C(NHPh) *c*CO*g*C(NH2)=$JBr CBr:C( NH,)-C.CO*C*C(NHPh) CH ' which crystallises from nitrobenzene in blue needles dissolves in cold concentrated sulphuric acid t o n violet-blue solution and wheni4e ABSTRACTS OF CHEMICAL PAPERS.warmed with sulphuric acid forms a suZpThonic acid which dissolves in water and dyes wool a greenish-blue colour. When heated with aniline on the water-bath the dinitroarnine yields 2 7-dibronio- 4 9-dianili.laoantl~rc~~uino.rze-1 ; 6 - b~sdiaxonm~nobenxene $?H C(h’HPh)-E* C0.E. C( N,HPh) YBr CBr:C(K,HPh)*C*CO*C*C(NHPh)=CH ’ which forms a bluish-green powder melts on the boiling water-bath and resolidifies to a violet glistening mass unmelted a t 300° and aminoazobenzene.formed by the action of boiling ptoluidine on the ammonium salt of the dinitroarnine crystallises in microscopic blue needles. The action of boiling dimethylaniline on the ammonium salt of the dinitroamine leads to the formation of 2 7-dibronzo-4 9-dinitroanthra- puinone-l 6-bisaxozydinzetJiylaniline which crystallises in blue ball- like aggregates and yields 2 7-dibromo 4 ; 9-dinitro-1 6 diamino- anthraquinone when strongly heated or when boiled with nitro- benzene. . G. Y. Sulphonic Acids of p-Aniinohydroxyanthraquinones. FARB- ENFABRIHEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 155440).-The introduction of ap-hydroxy-group into a-amino- or a-alkylsmino-ant hra- quinones by the action of fuining sulphuric acid (Abstr. 1904 i 1032) is also applicable to the snlphonic acids of those compounds.The preparation of 1 -amino-4-hydroxy-7-sulphonic acid and its methyl and ethyl derivatives is described. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-.P. 155045).-Anthraquinone-a-sulphonic acid (Abstr. 1904 i 513) is converted by fuming sulphuric acid into a new puqmrin-a-(6- or 9-)suZpimaic acid. A sulphuric ester is first formed and may be salted out by means of potassium chloride and this intermediate product is then hydrolysed to purpurin-a-sulphonic acid by dissolving in hot potassium hydroxide acidifying with hydro- chloric acid and boiling. 2 4-~ibromo-l 1 6-diamino-4 9-di-p-toluidiizonnt?Li.a~ui~io~i~ C. H. D. A New a-Sulphonic Acid of Purpurin. The alkali salts are red in colour. C. H.D. [A New Purpurinsulphonic Acid.] BADISCHE ANILIN- & SODA- FABHIK (D.R.-P. 154337).-Anthraquinone-P-sulphonic acid is con- verted by concentrated sulphuric acid containing a mercury salt and arsenic 01- phosphoric and nitrous acids into a new purpurinsulphonic acid which differs from the products obtained by direct sulphonation of pnrpurin. The acid dissolves in water to a red solution from which it is precipitated by mineral acids; the alkaline solutions are red. Soluble dyes containing the sulphonic acid group are obtained on heating the acid with aromatic amines a t 120-190° with or without the addition of condensing agents. The products are mixtures of compounds containing one and two amine residues. C. H. D. FARBWERKE YORM. MEISTER LUCIUS & BRUNINU (D.R.-P.155633. Compare Abstr. 1903 i 84O).-The nitro- and halogen derivatives of mnthra- Dialkyl Ethers of Anthrachrysone Derivatives.ORGANIC CHEMISTRY. 147 chrysone react with methyl sulphate to form ethers only two methyl groups being introduced. Binitroanthrccc?wg/sone dimethyl ether is a yellow crystalline powder insoluble in most solvents and melting above 300'. Diccminoccnth~u- chrysone dimethyl ether obtained by reduction of the dinitro-compound is blue in colour. Tetrccbromourztl~ruc~r?lsone prepared by the addition of bromine in excess to an aqueous solution of anthrachrysonedisulphonic acid is an insoluble orange powder ; the climethpl ether forms an insoluble orange crystalline powder. a-Derivatives of Geraniol. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co.(D.R.-P. 154656. Compare Abstr. 1904 i 842).-The compounds obtained from citral and magnesium alkyl or aryl haloids may be decomposed by means of concentrated organic acids instead of dilute mineral acids. The preparation of a-methyl- and a-ethyl- geraniols is described. Terpenes and Ethereal Oils. LXX. Compounds of the Thujone Series. OTTO WALLACH (Artnalen 1904 336 247-280. Compare Abstr. 1893 i 105 ; 1895 i 619 ; 1897 i 246 ; 1902 i 801 ; 1903 i 103 ; 1904 i 104).-[With E. Bo~!~~~.]-Thujone is obtained in two chemically identical but physically isomeric modifications which are best obtained in a state of purity by conversion into their semicarbazones and hydrolysis of these by means of phthalic anhydride. a-Thujone has [ a ] - 10.23'; it forms a Isevorotatory oily oxime and two semicarbazones the one of which crystallises in rhombic prisms [a b c = 0.7157 1 0,48951 melts a t 186-188° has [ a ] D + 59*5' and is only slightly soluble in cold ether or methyl alcohol ; the other semicarbazone is amorphous melts at about 1 loo and has [.ID approximately the same as the crystalline modification than which i t is more easily hydrolysed.a-Thujone is partially converted into the ,&modification by warm alcoholic potassium hydroxide ; it is trans- formed completely into /3-thujone and afterwards into isothujone by alcoholic sulphuric acid. P-Thujone has [a]Df76'16'; it forms a crystalline oxime which melts at 64-55' and has [ aID + 105*1' and a dimorphous semicarb- azone which has [ a ] + 215.76' to + 221.47' ; the hexagonal modifica- tion [a c = 1 4,0631 obtained on rapid cooling of the methyl-alcoholic solution melts a t 174-175* and in solution a t the ordinary tempera- ture gradually changes into the stable modification which crystalliees in rhombic prisms [cc b c = 0.252 1 0.7051 melts at 170-172' has n sp.gr. 1.11 a t 25" and is more easily soluble in methyl alcohol than the crystalline semicarbazone of a-thujone. Both a- and P-thujones yield u-thujaketonic acid which has [ a ] D + 191.99' when oxidised with potassium permanganate. At certain temperatures and concentrations solutions of the semicarbazones of a- and P-thujones deposit mixed crystals of varying melting points especially a form which crystallises in needles and melts at 150-152' As P-thujone also is converted into a mixture of a- and /3-thujones when warmed with alcoholic potassium hydroxide these two modifica- C.H. D. C. €1. D.1.48 ABSTRACTS OF CHEMICAL PAPERS. tions differ only in regard to the asymmetric carbon atom to which the methyl group is attached and the conversion of one into the other takes place owing to momentary formation of *the enol-form YH-CMe cH2<c PrP-CH Oil of thuja contains principally a-thujone oil of tansy principally P-thujone in each case with traces of the other modification; oil of absinth contains /I-thujone with smallw quantities of the a-form whilst the oils of sage and of Artemisicc Hc6rreZiei.i contain the two modifica- tions in about equal amounts. [With w. FRITZSCHE.]-T~~ oxime of P-thujone when treated with benzoyl chloride according t o the Schotten-Baumann method yields a benxoyl derivative which separates from methyl alcohol in colourless crystals and melts a t 52-53'.The action of phosphorus pentachloride on the oxime in chloroform solution leads t o the formation of the isooxime which melts a t go' boils a t 155-175O under 11 mm. pressure and is reduced by sodium and alcohol to the secondary base U,,H,,N. This forms a nitrosounaine C,,H,,N*NO which melts at 55-56". The pZatinicldos.ide of the base (CloH1,NMe,C1),PtC1 was analysed. When acted on by benzoyl chloride in alkaline solution the oxime of isothujone yields a benxoyl derivative C,oH160NBz which crystallises in needles and melts a t 139-140'. With hydrogen chloride in ethereal solution isothujoneoxime forms the crystalline hydrochloride C,,€€,,ON,HCl.isoThujoneamine obtained by reduction of the oxime forms a benxoyl derivative CI,Hl8NBz which melts a t 127-1 28'. When reduced with sodium in alcoholic Solution the oxime yields 56 per cent. of isothujoneamine the remainder being converted into isothujone with evolution of ammonia. The benxoyl derivative of thujamenthone C,oH,qONBz melts and decomposes at 135-136". The liquid product obtimed in the thujn- menthone oxime is now shown to be a mixture of the oxime with tho isooxime. When oxidisod with potassium permanganate in warm aqueous solution the isooxirne yields hydroxythujamenthone isooxime $.! HPrs*CHMe' 7 Me.oH which melts st 173 -1 74" and isopropyl- C H,- CO -NH l ~ v u l i c acid. When the hydroxyisooxiine is boiled with 20 per cent.hydrochloric acid it is converted into thujamenthoketonic acid. >C!*OH under the influence of the alkali hydroxide. G. Y. Essential Oil of the Wood of Thuja Articulata of Algeria. EMILIEN GRIMAL (Compt. vend. 1904 139 927-928).-The essential oil of the wood of TrLuja articdata contains carvacrol thymoquinol and thymoquinone. N. H. J. M. Condensation Product from Haematoxylin and Form- aldehyde. ROBERTO LEPETIT (D.R.-P. 155630).-H~matoxylin con- denses with formaldehyde on heating with acids a t loo" or without acids at 110-115' under pressure. The product is an insoluble brownish-red powder with metallic lustre and dissolves readily in dilute alkalis to a bluish-red solution or in alcohol acetic acid,ORGANIC CHEMISTRY.149 glycerol or acetone to dark brownish-red solutions. non-poisonous and possesses astringent properties. AKTIEN-GESELLSCHAFT FUR A NILIN- FAnRrKATroN (D.R.-P. 155541).-The alkyl haloid compounds of methylated quinolines are oxidised in alkaline solution by potassium ferricyanide or potassium persulphate forming dyes of the cyanine series. No similar dye is obtained from quinoline alkyl iodides the presence of a methyl group in the yuinoline ring being essential. The products dissolve in alcohol t o blue solutions and may be employed to increase the sensibility of photographic plates. The absorption- spectra of the dyes from quinaldine lepidine p-toluqninaldine and a mixture of the latter with 13-tolnquinoline are described. [Formation of Furoyl Derivatives by means of Pyromucic Chloride,] ERICK BAUM (Uer.1904 37 4756).-A correction (com- pare Abstr. 1904 i 910). Halogen Derivatives of Fluoran. BADISCHE ANILJN- & SODA- FABRJK (D.R.-P. I 56333).-DichIorofluoran may be readily prepared by heating phthalic anhydride and m-chlorophenol with zinc chloride. Condensation tlhen occurs with the formation of a pyrone ring. The reaction is also applicable to the homologues of m-chlorophenol or m-bromophenol and to the halogen derivatives of phthalic nn- hydride. 0- CAZop.0-p-cresol (2-cAZoro-4 -liydro.rgto Zuene) prepared by boiling the dinzonium compound of 2-chloro-p-toluidine forms colourless needles melting at 5 5 O and boils a t 228' ; i t dissolves very readily in alcohol or ether and separates from water i n spear-like crystals.o-Bronzo-p-eresol melts at 55-56' boils at 245-246' and dissolves sptringlg in water. 3 4-Dichloropl~enoZ forms colourless needles ; i t melts at 64-66" and boils at 146-146O. Y k t m cldorofluora?z from dichlorophen ol and plit halic anli y drid e melts a t 265" ; dicllilo1.otlimetiLy~uorun forms small colourless crystals and melts at 385' ; clibronaodimat?LylJIuol.an melts at 284-285'. It is tasteless and C. H. D. Dyes of the Cyanine Series. C. H. D. W. A. D. C. H. D. Ethylacetylacetone and its Condensation Products with Polyvalent Phenols. CARL BULow and Ivo DEIGLbIAYR (Bey. 1904 37 45%-4531. Compare Biilom Abstr. 1903 i 272; Biilom and Deiglmayr Abstr. 1904 i 609).-When hydrogen chloride is passed into a solution of methylacetylacetone and resorcinol in glacial acetic acid containing a little acetic anhydride ether being added when the dark brown mass becomes viscous glistening greeni~h- ello ow crystals of the hydrochloride of 7-~~ydroxy-2-metliyZ-3-et~~yl-4-~et~~Ze?~e- 4- benxopyran oH*?=CH'fi*o(HC1).fiMe separate. The picrate pre- pared by adding picric acid t o a boiling alcoholic solution of the hydrochloride crystallises in yellow needles and dissolves in con- centrated aulphuric acid to a yellow solution with slight blue fluorescence.The constitution of 7-hydroxy-2-methyl-3-ethyl-4-methylene-1 4- CH:CH*C.C(:CH,).CEt '150 ABSTRACTS OF CHEMICAT PAPERS. benzopyran was proved by the isolation of methyl propyl ketone resacetophenone and acetic acid from the products of the action of potassium hydroxide on the hydrochloride.C. H. D. Three Position isomeric Hydroxyl Derivatives of Resacetein. CARL BULOW and CONSTANT. SAUTERMEISTER (Bey. 1904,37,4715-4723. Compare Abstr. 1904 i 262 609 6lO).-The hydrochloride of 5 7- dihydroxy-2-op-cliet?~oxyph.enyZ-4-methyZene-I 4-benxop~ran is obtained by the condedsati;; of diethoxybenzoylacetone with phloroglucinol in acetic acid solution and in presence of hydrogen chloride a t 30-40'. It crystallises from a mixture of alcohol water and concentrated hydrochloric acid in anhydrous orange-red needles which are hydrolysed to the base when boiled with water. The picrate C26H230i2N3 crystallises in orange-red needles is sparingly soluble begins to melt a t 216' and is completely decomposed a t 225'. The plcbtinichloride (C20H,,05),,H2PtC16 forms a yellowish-brown crystalline precipitate and the base itself crystallises from alcohol in small dark reddish-brown needles which melt and decompose a t 170-180'.I t s solution in concentrated sulphuric acid exhibits a feeble green fluorescence. An isomeric 7 8-dihyclroxy-derivative is obtained by the con- densation of diethoxybenzoylacetone with pyrogallol ; it crystallises in violet-black glistening needles containing 1 H20 is moderately soluble in most organic solvents and melts and decomposes a t 196-201'. The hydroc?iZoride crystallises in dark red needles the suZphate C,oH2,0,,H,S0 forms dark red glistening needles melting a t 236-242' and its solution in concentrated sulpliuric acid does not fluoresce. The picrate decomposes at about 215O and the diacetyl derivative C2,H,,0 crystallises in orange-red plates very sparingly soluble in the usual solvents The 6 7-cli?~yds.osy-derivative obtained from hydroxyquinol crys- tallises from alcohol in garnet-recl quadratic plates with a blue lustre melts and decomposes a t 198-211' is readily soluble in most organic solvents and its solution in concentrated sulphuric acid exhibits a deep green fluorescence.The hydrochloride crystallises in golden-yellow glistening needles containing 1 *5H2O. The picrate also forms golden- yellow crystals which melt and decompose a t 195-208'. The sulpficcte forms glistening brown needles which melt at 204-214" and the dicccetyl derivative forms dark red glistening needles melting a t 235-250'. I t s solution in sulphuric acid does not fluoresce.The dyeing properties of the 5 7- and 7 8-dihydroxy-compounds have been tested. J. J. S. Influence of Alkaloids on Certain Processes of Oxidation. E. FEDEI~ (Amh. Pharz. 1904 242 680-704).-1t is known that certain metallic salts (namely copper sulphate mercuric chloride silver nitrate ferric chloride gold chloride and platinum chloride) are able to oxidise the solutions of certain organic substances (namely guaiacum resin or guaiaconic acid aloin indigocarmin pgrogallol catechol,ORGANIC CHEMISTRY. 151 quinol orcinol) with production of a coloration. This action often slow in itself is frequently much accelerated by the presence of an alkaloid. The influence of many alkaloids in this direction has been investigated ; for details the original paper must be consulted.The influence of alkaloids on the reduction of copper salts by dextrose and on the biuret reaction has also been examined. C. F. B. A New Series of Bases derived from Dihydroberberine. MARTIN FREUND and HEINRICH BECK (Ber. 1904 3'7 4673-4679. Compare Abstr. 1904 i 915).-In addition to berberinal the salts of berberine also react with magnesium alkyl or aryl haloids yielding a-derivatives of dihydroberberine. a-Benzyldihydroberberine forms a Iqdyochloy.ide C,;H,,O,N,HCl crystallising from alcohol and ether and melting a t 165-166'. The methiodide separates from alcohol as a yellow crystalline powder and sinters a t 170" and decomposes at a-1~~tJ2yZdil~ydroberberiyze from berberine hydrochloride and mag- nesium methyl iodide separates from dilute alcohol in yellow crystals and melts at 134-135O.The hydriodide separates from dilute alcohol in bright yellow leaflets and melts a t 249O ; the crystalline hydrobromide rapidly darkens. a-Pheny2di?~ydroberberi?ie is precipitated by ammonia from its solution in alcohol and acetic acid in.brownish-yellow glistening tablets melting at 195O. 181-182'. C. H. D. Normal Quinine Hydrochloride. CARLO ERBA (J. Pharm. Cl~im. 1904 [vi] 20 550-551).-The author draws attention to his study of the subject published in the Boll. farm. 1901. According to his observations the salt crystallises from 95 per cent. alcohol is hydrated arid has the formula C,3H2,0,N,,2HC1,C6H,0,H20 whilst Carette (Abstr. 1904 i 1044) stated that it contained 1.5 mols. of alcohol.G. D. L. Constitution of P-isoCinchonicine. KARL KAAS (iMoncctsh. 1904 25 1145-1 152. Compare Abstr. 1900 i 605).-/3-iso-+-Cinchonicine is now found to be a keto-base like cinchonicine (compare Miller and Rohde Abstr. 1894 i 431 432) and is therefore to be called p-iso- cinchonicine. The action of phosphorus pentachloride on p-iso- cinchonicine in chloroform solution leads to the formation of hydrogen chloride and the hydrochloride of a chloro-base C,,H2,N,CI,2HCl which crystsllises in short yellow prisms melts at 150" and is hygroscopic ; the chloro-base like cinchonine chloride does not lose chlorine when the salt is shaken with silver acetate in glacial acetic acid solution. obtained by shaking the base with benzoyl chloride in benzene solution crystallises in needles melts a t 228O and is not hydrolysed when boiled with potassium hydroxide for half an hour.The action of acetic anhydride on the base leads to the formation of an oily ucetyl derivative. When treated with methyl iodide in methyl-alcoholic The hydrochloride of the benzoyl derivative C,(3H,5.0,N,,HC1,H,0,152 ABSTRACTS OF CHEMICAL PAPERS. solution P-isocinchonicine forms the hydriodide of the methyl base C,,H,,ON,Me,HI which crystallises in short yellow prisms de- composes at 268O and when treated successively with ammoniacal methyl alcohol and hydrochloric acid is converted into the hydrochloride. This is also obtained by heating P-isocinchonine methiodide with aqueous potassium hydroxide and treating the product with hydro- chloric acid G.Y. Creatinine. GEORG KORNDORFER (Arch. Pharm. 1904 242 641-648).-The creatinine used was prepared from urine. When heated with methyl iodide and methyl alcohol i t formed a methylcreatinine hydrioclide C,H ,ON,,HI me1 ting a t 2 12' ; the cor- responding hydrochloride aurichloride melting a t 174" platinichloride with ;tH,O and picrate melting a t 183" were also prepared. By decomposing the hydriodide with silver oxide the base was obtained in an amorphous state. The liydrochloride however could be decom- posed with potassium carbonate (and therefore cannot be a quaternary ammonium salt); obtained in this way the base forms crystalline hygroscopic needles of the composition C,H,ON,,H,O. The base (methylcreatinine) was heated with methyl iodide and methyl alcohol and from the product a dirrtell~ylcrecctinine p2atini- chloride ZC,H,,OK,,H,PtCl was isolated and also a small quantity of a salt which contained a percentage of platinum approaching that in a trimethylcretctinine platinichloride 2C7H,,0N,,H,PtC1,.C. F. B. Suprarenine [Epinephrine] the Substance of the Suprarenal Glands which causes Increase of the Pressure of the Blood. E. WevRIctr (Chem. Cents.. 1904 ii 15'75-1576; from verb. Ges. Beut. Taturfor. Aeyxte 1903 ii 127).-Suprarenine prepared from fresh suprarenal glands of oxen by extracting with water which has been rendered faintly acid forms a pale brown to yellow or greyish- white sandy powder. The presence of extremely small crystals may be detected. Suprarenine is sparingly soluble in hot or cold water and is insoluble in alcohol or ether.The hydrochloric acid solution is emerald-green but on the addition of dilute ammonia becomes carmine- red. The hydrochloride is precipitated by ammonia or alkali carbon- ates but not by alkali acetates; i t does not give any of the reactions of albumin and its concentrated aqueous solution is not precipitated by alcohol. One gram of the base is sufficient to neutralise 0*195-09 gram of hydrogen chloride. The composition C,,H1,O,N,$H,O is ascribed to suprarenine and it is assumed to have a constitution similar to that of aminocatechol. Skimmianine an Alkaloid from Skimmia Japonica. J. HONDA (Chem. Centr. 1904 ii 1511-1512 ; from Arch. exp. Puth. Pharm. 52 83-94).-A poisonous alkaloid skimmianine has been found to be present in all parts of Shimrnicc japonica but most abun- dantly in the leaves.It was isolated from the latter by extracting with 96 per cent. alcohol. Skimmianine C,,H2,0,N crystallises from alcohol in yellow four-sided prisms melts at 175*5O and is readily soluble in chloroform or alcohol moderately so in methyl alcohol very E. w. w.ORGANIC CHEMISTRY. 153 sparingly so in ether amyl alcohol or carbon disulphide and insoluble in water or light petroleum. All the solutions are neutral to litmus. The solutions of the base are almost tasteless but those of the salts are very bitter. Skimmianine is only dissolved by dilute mineral acids when present in excess and the solutions on evaporation yield the salts which crystallise in needles. When the excess of acid is neutralised by alkali carbonates or when the salts are dissolved in water and the solutions Concentrated the base is precipitated.Even after boiling with dilute acids skimmianine does not reduce alkaline copper solutions. A solution of the alkaloid in hydrochloric acid gives voluminous precipitates with the ordinary alkaloid reagents and forms a ylutinichloyide which crystallises in rhombic plates and is moderately soluble in water but only sparingly so in alcohol. The precipitate formed with gold chloride is easily decomposed. Crystals of skimmianine dissolve in concentrated sulphuric acid forming a brownish-yellow solution which on the addition of potassium chlorate becomes reddish-brown. By the action of the alkaloid on Frohde's reagent a green coloration is formed which afterwards becomes blue ; a solution of potassium permanganate in sulphuric acid becomes violet and then yellowish-brown and concentrated nitric acid forms a yellow solution which changes to oraage-red.Injection of skimmianine into the femoral lymphatics of Raiza esculentrc or Rana temporaria affects the appearance of the muscles a t the place of application and renders them stiff and brittle. The neighbouring muscles are also affected by larger doses. Voluntary motion becomes sluggish the breathing superficial and the pupils contract. Reflex sensibility appeared as LZ rule to increase only in the case OF Rana esculenta. The absolute strength and the work per- formed by the muscles were apparently diminished. The alkaloid has probably a direct action on the muscles of the heart decreasing the pulsations and causing disturbance of the diastole.The pulse is similarly affected even when atropine bas been previously administered. Intravenous injection in the case of rabbits causes general symptoms of poisoning. Slight poisoning is accompanied by feeble spasms. The preesure of the blood falls even when chloral has been administered but after a time it increases again probably owing to the compensating contraction of the peripheral vessels. Skimmianine has no effect on the secretion of urine. E. W. W. Pharmacological Studies on Synthetical Bases of the Piperidine Series HERMANN HILDEBRANDT (Zed. physiol. Chenz. 1904 43 249-289. Compare Abstr. 1900 ii 676 and this vol. i 80).-Dimroth's thymolmercury chloride C,H7*C,H2Me( OH)*HgCl (Abstr.1902 i 656) does not react with formaldehyde and piperidine in the cold but on warming the methyle?te~iye;*idide deiivative CH~c(HfiC1)=CD;Ie~C.CH2"H,o C(C,H,)*C(OH) is obtained. This has very much the same physiological properties as other compounds containing m er- cury directly attached to the benzene nucleus. The methylenepiperidide derivative of thymotic alcohol melting a t154 ABSTRACTS OF CHEMICAL PAPERS. 141" (thisvol. i SO) is very hygroscopic and readily yields a pZatini- chloride ( C,7H,50N),PtC1,,H20 which crystallises in orange plates. o-Thymotinpiperidide (Base a) melting at 141° is isomeric with p-thymotinpiperidide (Base 1) (Abstr. 1900 i 676) and when taken into the animal system is eliminated as a glycuronic acid derivative which on hydrolysis with 8 per cent.sulphuric acid yields the methylated base C,7H270N (Base 3) melting a t 144'. This can be distinguished from Base 2 by means of its pkatinichloride (C,7H,70N)2,H2PtC1 which separates i n the course of a few hours. Bases 2 and 3 but not Base 1 give characteristic thymol reactions with acetic and sulphuric acids. p-Thymotic aldehyde and the corresponding acid and o-thymotic acid do not condense with piperidine and formaldehyde. When taken into the animal system the ortho-acid is partly eliminated as such and partly in combination with glycnronic acid. I t is a milch more effective poison than the para-acid which is entirely eliminated in combination with glycuronic acid. Dannenberg's p-bromothymol (Abstr. 1903 i 338) yields a metlhylene- piperidide derivative melting at 59".The corresponding o-bromo- derivative melts a t 76". They are not poisonous and are excreted in combination with glycuronic acid. The glycuronic acid derivatives of 0- and p-thymotinpiperidides cannot be precipitated from urine by the addition of basic lead acetate whereas the derivatives of piperidides which are physiologically inactive are readily precipitated. Auwers and Marwedel's dibromo-p-hydroxy-+-cumyl piperidide (Abstr. 1896 i 149) is physiologically inactive whereas dibromo-p- cresylpiperidide melting at 1S2' is as active as 0- and p-thymotin- piperidides. The results of varions experiments tend to show that the condensation products obtained from piperidine and phenols by means of formalde- hyde exhibit an acute physiological action only when the para- or one of the ortho-positions with respect to the hydroxyl group is not substi- tuted.The meta-position with respect to the hydroxyl has an influence on the physiological action only when both meta-positions are unsub- stituted and when the methylenepiperidine residue is adjacent. A further generalisation is that only those condensation products of piperidine with phenols and formaldehyde which have an urisubstituted ortho- or para-hydrogen atom in the benzene ring undergo methylation in the animal system; it would thus appear that it is only physio- logically active compounds which undergo methylation. The organism does not appear to be capable of introducing methyl in place of a hydrogen atom in the ortho- or para-position with respect t o the hydroxyl groups and thus forming an inactive compound hence it is the nitrogen atom which is niethylated and the hydroxyl group reacts with the glycuronic acid forming a compound which is physio- logically inactive.Experiments have been conducted in order to determine the effect of introducing various substituents into the piperidine ring of the con- densation products. Scholtz's iso-3 6-diphenylpiperidine condenses with formaldehyde and tliymol when the mixture is heated yielding a product which melts at 1 62". It is physiologically inactive. 2-Methylpiperidine itselfORGANIC CHEMIS1'1ET. 155 is largely oxidised in the animal system to the corresponding carb- oxylic acid which then unites with glycine. Thymotin-2-methylpiperidide C,pH2pON crystallises in irregular cubes melts at 118' and is not so physiologically active as the simple piperidide.It is eliminated in the form of a neutral derivative of glycuronic acid which on hydrolysis yields a methyl derivative C,,H,,ON crystallising in needles and melting a t 116". This is much less active than the original methylpiperidide. Carvacryl-2-naethyzpiperidide crystallises in needles melts a t 15 lo and is extremely active. I t s platinichloride ( C'17H,70N)2,H,PtC1 crystallises readily from alcohol in fla f needles. The metlqlated base obtained by the decomposition of the excreted glycuronic acid deriva- tive is not so active. T l q n o t i n copellidide OH~C,H,&IePr*CH,*C,NH8MeEt( 1 4) melts at 1 15' and is still less poisoncus than the 2-methylpiperidide whereas copellidine itself is about three times as poisonous as 2-methylpiperidine.Dib~~omoc~esyl-2-nzetl~y~iperidide is still less active. J. J. 8. Dimolecular Nitriles. ERNST VON MEYER (J. p. Chern. 1904 [ ii] 70 560-561).-3-Cya~zo-2-pl~enyl-6-met~yZ-4~yr~do~ze ,,<c(cN):cph>N CH,-CMe ' or 3 -cyano-4-hydrox y-2 phen yF6-metj~yZp yridine OH. C<C(CN) CPh>N 'CH-CMe is formed when a solution of benzoylacetonitrile in ethyl acetoacetate is saturated with hydrogen chloride. It crystallises in leaflets melts at 244'; and when heated with hydrochloric acid at 200° yields 4-f~ydi.oxy-2-pl~enyl-6-naethylpyridine which crystallisea in needles and melts a t 178.5O. The action of cyanogen bromide on benzoylacetonitrilo in benzene solution a t 100' leads to the formation of a bronzo-derivative CN*CH,* CPh:NBr which crystallises in white needles and melts a t 114'.The bromo- derivative of diacetonitrile is similarly formed by bromination with cyanogen bromide in benzene solution. G. Y. 2 6-Substituted Pyridinecarboxylic Acids. HANS MEYER (Jfonatsh. 1904 25 1196-1300. Compare Abstr. 1903 i 364).- When warmed with methyl iodide and aqueous sodium carbonate 6-methylpyridine-2-carboxylic acid and quinoline-2-carboxylic acid do not form the respective betaines but after evaporation are recovered unchanged. The action of thionyl chloride on qninoline-2- carboxylic acid leads to the formation of its crystalline chlokle which melts and decomposes a t 175-177" and when treated with methyl alcohol yields the methyl ester crystallising in matted needles melting a t 7s'.The amide formed by the action of aqueous ammonia on the chloride or the ester crystallises in slender glistening needles melts at 123O and forms an aurichloride which crystallises in needles and melts a t 210'. The n i t d e is formed when the amide is boiled with thionyl chloride; it crystallises in long needles melts a t 89" is very156 ABSTRACTS OF CHEMICAL PAPERS. easily volatile has a pleasant odour and is more easily hydrolysed than 4-cyanoquinoline. The aurichloride crys t allises in needles and melts and decomposes a t 158". G. Y . Conversion of Tetrahydroquinoline into SMethyldihydro- indole. JULIUS VON BRAUN and A. STEINDORFP (Bey. 1904 37 4723-4730).-Tetrahydroquinoline may be transformed into %methyl- dihydroindole by means of the following reactions.Benzoyltetra- hydroquinoline is converted into benzoyl-o- y-chloropropylanilide ( Abstr. 1904 i 918). This is stable towards quinoline is reconverted into the tetrahydroqninoline derivative on treatment with sodium ethoxide but when distilled under 12 mm. pressure is mainly transformed into benzo?lZ-o-ccZl?lZicnilide COPh NH*C,H,* C H,*CH :CH a1 though benzoy 1 chloride and tetrahydroquinoline are formed at the same time. The benzoylall ylanilide crystallises from alcohol in long needles melts at 123-124' and is only slowly hydrolysed by alkalis. It readily combines with hydrogen chloride when heated with three times its weight of fuming hydrochloric acid a t 70-80° yielding benzoyl-o- p-chloropropylanilide (this vol.i 81). o-P-CfLZoroiuro;llz/ZnniZ~~~e NH,*C,H,*CH,*CHClMe is obtained when the P-chlorinated anilide or benzoyl-o-ally lanilide itself is heated with fuming hydrochloric acid for several hours at 1 2 5 O and when heated with water it is transformed into 2-methvldihydroindole bvdrochloride . I J. J. 8. A Method for the Preparation of Compounds derived from Pseudo-bases by the Replacement of the Hydroxyl Group by Hydrocarbon Residues. MARTIN FREUND [with EDMUND SPEYER] (Ber. 1904 37 4666-4672).-Such salts of organic bases as yield pseudo-bases with alkali hydroxides react with magnesium alkyl or aryl haloids forming compounds which may be regarded as derived from the pseudo-bases by the replacement of hydroxyl by a hydrocarbon residue. Quinoline methiodide reacts vigorously with magnesium phenyl bromide in ethereal solution to form 2 - p f ~ e i a ? / Z - l - ~ ~ a e t f ~ ~ ~ l d i f ~ ~ ~ ~ r o The reaction is a general one.- - - - - -,CH =YH which crystallises from alcohol in prisms melting a t 4\NMe*C HPh' C6H 89-90G and dissolves readily in acetone or chloroform but is insoluble in water. It dissolves in hydrochloric acid and is reprecipitated on dilution. Calcium permanganate oxiclises it to benzoylmethyl- anthranilic acid CO,H*C,H,*NMe*COPh. Sodium reduces the base in alcoholic solution to 2 -phengZ-l -meth yltetr~~~ydroquinoline crystallising from alcohol in rhombic tablets melting a t l06-107" and possessing weak basic properties. Bromine reacts with 2-phen y 1-1 -met h yld ih y droquinoline in chloro- form solution forming %(or 4-)bromo-S-pl~en?/lr/uinoliiae methobyonaide - .- - C H Z y B r c Br== YH crystallising from water in N MeBr CP h' C6H4<meBr*~~11 or C,H,<ORGANIC CHEMISTRY. 157 yellow needles and melting and decomposing a t 248-260'. Sodium hydroxide precipitates the pseudo-base as an amorphous yellow mass dissolving readily in alcohol or ether. The anamoniuna base may be obtained by the action of moist silver oxide on tlie bromide its aqueous solution limy be evaporated without decomposition and sodium hydroxide converts it into the insoluble pseudo-base. The bromide clecoiiirsoses on fusion into methyl bromide and crystallising from dcohol in white needles and melting a t 120-121'. Magnesium methyl iodide and quinoliiie methio dide react vigorously to form 1 2-dinzsthylJi?~ydroqui~zolisze an oil becoming yellow on exposure to air and boiling a t 255-256O.It dissolves readily in acids but does not yield crystallisable salts. Magnesium ethyl ioclicle and phenylacridine methiodide react to form p?Len?llet~~?jZmst~~Z~il~~cl~oacrid~s~c CtiEt,<NMe->C,H crystal- lising from alcohol or light petroleum in yellowish-white needles melting a t 112' after sint8ering. A P h E t The product lias no basic properties. C. H. 11 Hyposulphites of Aromatic Bases. h G U S T E LURII~RE LOUIS LUICII~RE mid ALPIIONSE SEYEWETZ (BUZZ. S'oc. cliinz. 1905 [ iii] 33 67-69).-2 4-Diaminopl~enol ?qposuZplde obtained by a mixture of molecular solutions of diaminophenol hydrochloride and sodium hyposulpliite in water crystallises in white spangles and is slightly soluble in cold water (1 in 600) and alcohol.The lqposuZplLites of diamiuoresorcinol and 2 4 6-triaminophenol resemble the fore- going but that of p-phenylenecliamine is less stable and more soluble in water. The monoamines and pyridines also yield crystalline hypo- sulphites. T. A. H. [ Indophenol from 1,-Phenylenediamine and o-Acetylamino- phenol.] KALLE & Co. (D.R.-P. 156478).-Potassium ferricyanide oxidises a mixture of p-phenyleiiediamine and o-acetylarninophenol forming a blue indophenol. On dissolving in sodium sulphide and passing a current of carbon dioxide the pure leuco-indophenol is precipitated and may be crystitllised from organic solvents. It dissolves sparingly in water readily in acids or alkalis. The indo- phenol yiefds a 6liie dye on fusion with sodium sulphide and sulphur. C.H. I>. Formation of Chains. LX V. Reactions of Di-a-bromoiso- valeryldiarylethylenediamines. CARL A. BISCHOFF [and in part BILSEN,VONMEYSTOWICZ PAPKE RADIK ROSSI SCHUBETSKI TELETOFF and WULFFIUS] (Bey. 1904 37 4653-4666). - Di-a-bromoisovaleryl- diphenylethylenediamine from a-bromoisovaleryl bromide and diphenyl- ethylenediamine in presence of pyridine (compare Abstr. 1899 i 278) is converted by sodium phenoxide or naphthoxide into di-dinzethyl- acryZodi~~~enyZet~~ylenedianzi,2e CdH (NPb GO* CH:CMe,) which forms VOL. LXXXVIII. i. m158 AlJSTXACTS O F CHEMICAL PAPERS. silvery needles melting a t 177" and dissolving readily in chloroform acetone or acetic acid less readily in alcohol or benzene.I n similar manner di-a-bromoisovaleryldi-o-tolylethylenediamine yields cli-dimet?~~lac~yZddi-o-tolyZeth~Zened~c~~~~~e crystallising from alcohol in glistening needles me1 ting a t 1 78". Di-dirneth~lc~cryl- di-p-toZylet?~yZenedianzine crgst.rllises from dilute alcohol in glistening needles and melts a t 1 7 P . Di-a-bromoisovaleryli-~-n~~?~t~~~Zet?~~Zene~~~nzine crystaliises from ethyl oxalate in long four-sided leaflets melting a t 211-212" and dissolves very sparingly iii most organic solvents readily in nitro- benzene. ~i-~imet?~ykc~cryk2i-a-.1zccp~it~~y~et~~ylbnedie~?nine crystallkes from glacial acetic acid in small colourless prisms melting a t 206 -208". Di-~~imetl~~kacr~l~i-~-na~ht?~ylethylenecliamine separates from alcohol as sparingly soluble silky needles melting a t 1 8 7 O and dissolves readily in chloroform.C. H. D. Diamines. ADOLF LOEWY and CARL NEUBEBG (Zed. plqsiol. Chsm. 1904 43 35;5-357).-Diamines are usually isolated from urine either as benzoyl derivatives (von Udrhnszky and Baumann Abstr. 1889 33 1024) or as mercurichlorides (Brieger and Stadthagen Bed. IL5n. JTocl~ 1889 345). The authors employ the phenylcarbimide deriva- tives. Tetramethy ZerLedianaine~laenylcarbinai~~ NHPh*CO*NH*[CH,I,.NH*CO*NHPh obtained by mixing the components in ethereal solution crystallises from a mixture of pyridine and acetone in needles melting a t 240" (corr.) and is insoluble in the ordinary solvents. The corresponding derivative of pentantetlLylenedinmine CIYH2,,OSN4 melts at 207-209" (corr.) and is more readily soluble in a mixture of pyridine and acetone.The ethylenediamine derivative melts a t 2 63'. J. J. S. Action of Secondary Asymmetric Hydrazines on Sugar I. RUDOLF OFNER (Monatsh. 1904 25 1153-1163. Compare Abstr. 1904 i 798 936).-Whilst phenylmethylosazone is formed by the action of phenylmethylhydrazine on dextrose or laevulose no osazone is formed by the action of pure as-phenylbenzylhydrazine on either of those substances. Neuberg's supposed l=vulose-phenylbenzylosazone (Abstr. 1902 i 264) is phenylbenzylphenylosazone which is obtained by the action of phenylbenzylhydrazine containing phenylhydrazine on dextrose or lmulose or of pure phenylbenzylhydrazine on pheuyl- glucosazone. G. Y. [Chloroindanthrene.] BAUISCHE A NILIN- & SODA-FABRIK (D.E.-P.155415).-A mixture of concentrated nitric acid and fuming hydrochloric acid converts indanthrene a t 50" into chloroanthru- pwinoneaxine a yellow fairly stable compound which is reduced by sodium hyposulphite to chloroindanthrene dissolving in nitrobenzene or aniline t o green solutions insoluble in water or sodinm hydroxide. C. H. I).ORGANIC CHEMISTRY. 159 Study and Synthetical Preparation of Aryl Thiohydantoins. &I. EMMANUEL POZZI ESCOT (Compt. s'end. 1904 139 1031-1032).- Disubstituted +thiohydantoilis readily prepared by the action of monochloro- or monobromo-acetic acid on the s-arylthiocarbamides (compare Abstr. 1904 i 869 j are crystalline compounds decomposed by alkalis yielding the corresponding s-mylcarbamides according t o the equations SH S-YH NR*CO ' RX:C<NHR + CH,C1*COpH = RN:C< RN:C<.&-~~2 + 2H,O = CO(NHR) + HS*CH,*CO,H.Bi-o-toZyZ-t,b-tlbiohydantoin forms slightly yellow octahedral crystals nielting 4" lower than the correspoiiding thiocarbamide is slightly soluble in water and readily so in boiling alcohol or cold xylene toluene or cblorof orm. B i-p-to 2 y 2-$- thiohydantoin crys t allises f roni alcohol in almost colourless small square plates and melts at 115". Di-a-)zapl~thyZ-$-t~~~o~~yda~atoiiz crystallises from alcohol in white prisms and melts a t 183' ; the P-isomeride possesses similar properties. Diphenyl-$-thiohydaiitoin crystallises from alcohol and melts a t 174'. M. A. W. Action of Magnesium Benzyl Chloride on Crystal-violet. MARTIN FREUND and HEINKICH BECK (Bey.1904 37 4679-4680). -Crystal-violet suspended in ether reacts vigorously with magnesium benzyl chloride. to form hexun~eti~yltriarninot~~i~~enyZ~e~izyZmethane CH,Ph*C(0,H,*NMe2) separating from chloroform and alcohol in small slightly blue crystals melting at 181-1 82'. Potassium iodide precipitates the crystalline hydriodide melting and decomposing at 267-268" from its solution in hydrochloric acid. No dye is obtained on oxidation with chloranil or lead peroxide and hydrochloric acid. C. H. D. 2-Alkyloxypyrimidine Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 155732).-The hydrochlorides of the ethers of isocarbamic?e R*O.C(NH,):NH,HCl prepared by the action of alcohols and hydrogen chloride on cyanamide (Stieglitz and McKee Abstr.1900 i 340 431) react with the metallic derivatives of alkyl cyaiioacetstes to form 2-a1 kyloxy-derivatives of pyrimidine YH*CO*CH OR.& :N--&NH' The 2-~~zethoz~~~yrinzidine derivative prepared by adding sodium to a solution of ethyl cyanoacctate and isocarbamide methyl ether hydro- chloride in absolute methyl alcohol crystallises from hot water or alcohol in colourless needles melting a t 228-220O and dissolving readily in alkalis or acids. The 2-ethoxy-derivative is similar and melts at 247". These compounds may be converted into derivatives of hgpoxanthine by Traube's method (Abstr. 1900 i 416). C!. H. D.Preparation of Die thylxanthins. GEORG Scmr,m ( C ' I ~ L . C'entr. 1904 ii 1497 ; from Bull. Soc. Ski. Hucccrest 13 155-159).- By the action of phosphorus oxychloride on the solution obtained by heating together a mixture of pyridine and cysnoacetic acid with finely powdered diethylcarbamide the hydrochloride or phosphate of is obtained as a syrup.The base prepared from the 'salt by evaporating with ammonia crystallises from water in needles and melts a t 137". The isomnityoso-compound C,H,,O,N,,-H,O crystallises in small dark red plates and is sparingly soluble in water. 5 6- Bianzino-2 4-clioxy-1 3-dietl~y~~rimitli.lae obtained by warming the preceding compound with yellow ammonium sulphide forms yellow crystals and when boiled with anhydrous formic acid yields 6-amino- 5-Jbr.nuylicmino-2 4-dioxy-1 3-diethylp~i.inaidine C,H,,O,N which crystallises from absolute alcohol in white needles and is readily soluble in water or alcohol ; it melts and decomposes a t 235O forming 1 3-diethylxanthine rEt*Co *g'R'H>CH miti elimination'of water CO*NEt-C -N Diethylxanthine crystallises from water.in yellow prisms and melts a t 208'. SJEt-CO .$*XEt 1 3 7-Triethylxanthine >CH prepared by the C 0 - N E t C--N action of ethyl iodide and sodium ethoxide ( 2 mols.) on diethyl- xanthine melts a t 115' and is readily soluble in alcohol. E. W. W. Acetyl Derivatives of Phenylurazole. Sa~onrox F. ACREE (Arner. Chem. J. 1904 32 606-611. Compare Abstr. 1902 i 242 ; 1903,i,867).-1t has been shown (Abstr. 1903 i 867) that whenacetyl- phenylurazole prepared by Cuneo's method (Abstr. 1899 i 9) is treated with diazomethane 2-acetyl-l-phenyl-4-methylurazole is pro- duced which melts a t 94" but after heating a t 140' melts a t 113-115".The same change takes place when the substance is left for a few months at the ordinary temperature. The product melting at 113-115" is identical with the compound which mas obtained by Busch (Abstr. 1901 i 617) by the action of acetic anhydride and sodium acetate on 1-phenyl-4-methylurazole and was inadvertently stated to melt at 129". A few months after the first experiments had been carried out an attempt was made to prepare a further quantity of the substance melting at 94" from the same sample of acetylphenylurazole which still showed the same melting point (173') as before but only the isomeride melting a t 11 3-1 1 5 O could be obtained. Numerous experiments have been made with acetylpbenylurazole prepared in various ways but in no case has the labile form of the methyl derivative melting a t 94" again been obtained.It is probable that acetylphenylurazole prepared by Cuneo's method consists of a mixture of two substances,ORGAN I C C H EM ISTR Y. 161 rPh-N CO*NH >C*OAc and the stable modification the labile modification rPh*NAc C 0--NH >co. The action of acetyl chloride on the silver salt of phenylurazole has been reinvestigated. It is found that acetylphenylurazole is the chief product of the reaction a small amount of diacetylphenylurazole which melts a t 165" also being produced. The labile diacetylphenylurazole described by Wheeler and Johnson (Abstr. 1903 i 693) could not be obtained. The action of ethyl iodide on silver phenylurnzole has also been re- examined (compare Wheeler and Johnson Zoc.d.) and i t has been found that 3-ethoxy- 1-phenylurazole is produced together with a smaller quantity of 3 5-diethos~-l-phenylurazole. 32. G. [Relations between Quinonehydrazones and p-Oxyazo-corn- pounds.] WALTHER BORSCHE (Arznalen 1904 336 346).-The author had overlooked (Abstr. 1904 i 1056) Hewitt and Pope's descrip- tion of p-hydroxyazobenzene hydrochloride (Abstr. 1897 i 5 17). G. Y. [Azo-compounds from 3-Hydroxydiphenylamine.] K. OEHLER (D.R.-P. 155014).-The diazonium compounds of naphthionic acid or P-naphthylamine-5 7-disnlphonic acid combine with 3-hydroxy- cliphenylamine t o form azo-compounds which yield very fast brown dyes on treatment with chromium salts the hydroxy-group probably occupying the ortho-position with respect to the azo-group.C. H. D. Azo-compounds from Sulphonic Acids of a-Amino-P-naphthol. CHEMISCHE FABRIKEN VORM. WEILER-TER-MEER (D.R.-P. 155083).- Azo-compounds of acid chwacter yielding dark lakes with sodium dichromate or ferric acetate are obtained on diazotising the mono- or di-sulphonic acids of a-amino-/3-naphthol in the presence of organic acids only and combining the diazo-compouncls with resorcinol in alkali hydroxide solution. C. H. D. The Copper Compound of p-Nitroaniline-Red. WLADIMIR SCHAPosCHN IKOFF and v. SVIENTOSLAVSKI (xed. pcirb. Text. bad. 1904 3 422-426).~-The same deep brown dye is obtained by boiling p-nitroaniline-red with aqueous copper sulphate containing ammonia as is formed on adding a mixture of alkaline sodium p-naphthoxide tartaric acid and aqueous cupric chloride to diazotised p-nitroaniline ; after suitable purification the compound has the composition of the copper salt ( NO,*CGH,* N;C,,H,* O),Uu of p-ni trobenzeneazo-P-naphthol.In a similar way the copper salt of benzeneazo-P-naphthol may be prepared. That these substances are merely the copper salts as supposed is shown by the fact that on decomposition with hydrochloric acid they regenerate the hydroxyazo-compounds. W. A. D.162 ABSTRACTS OF CHEMICAL PAPERS. Azodiphenylmethane a Correction. PAUL FREUNDLER (Bull. Soc. chinz. 1905 [iii] 33 80-81. Compare Abstr. 1903 i 585).-It is shown that the substance obtained by the anthor by heating benzene-o- azobenzyl alcohol a t 1 30° is not as was supposed azodiphenylmethane but a niolecular combination of nxobenzene and phenylindazole.The presence of azobenxene is probably due to the formation of a hydroxyl- amine derivative along with benzeiie-o-azobenzyl alcohol in the con- densation of nitrosobenzene with o-nininobenzyl alcohol and the subsequent dehydration of this. T. A. H. pNitrobenzeneazo-o-tolueneneazo-p-naphthol. FARRWERKE VORM. MEISTER LUCIVJB & BR~NING (I).R.-P. 155396).-pNitro- benzeneazo-o-toluidine may be diazotised a t 15-20” and then yields n garnet-red ago-compound with ,%naphthol. If the fabric is first treated with ,@naphthol and afterwards with the diazo-solution the dye is deposited in the fibre and then resembles ‘‘ alizarin garnet.” The colour is completely removed by means of formaldehyde-sodium hjdrogen sulphite.C. H. D. Disazo-dyes from 6-Amino-a-naphthol-3-sulphonic Acid. K. OEHLER (D.R.-P. 155740). -In the preparation of disazo-com- pounds from 6-amino-a-naphthol-3-sulphonic acid (Abstr. 1904 i SOS) nitro-o-aminophenol may be replaced by chloro-o-aminophenol. The combination occurs more slowly than when nitro-comDounds are employed but the properties of <he dyes produced are simfiar. C. H. D. Formation of Hydrogen Cyanide by the Oxidation of Proteids. R. Hi. ADERS PLIMMER (J. Yhysiol. 1904 32 51-58. Compare Rbstr. 1904 i 53S).-By the oxidation of albumins with chromic acid a constant amount of hydrogen cyanide is evolved which varies for each albumin; the amount thus obtained is usually greater than in oxidation by Neumann‘s nitric acid mixture.The pro- ducts of proteolysis give a rather greater amount than the albumins themselves. The hydrogen cyanide arises from the glycine and aspar- tic acid but the other amino-acids also give rise to a small quantity which however is negligible in comparison. W. D. H. Amyloid. CARL NEUBERG (CiLenz. Cen.fr. 1904 ii 1576-1577 ; from Verb. Ueut. Path. Ges. 1904 19-32).-According to Kraw- kow amyloid is a compound of chondroitinsulphuric acid with- a pro- teid. The latter differs materially from the albumin of the cell and more nearly resembles the protamines or histones. The results of the hydrolysis of a liver amyloid showed that it yielded 0.8 per cent. of glycollic ;wid 22-2 of leucine 3.8 of glutamic acid 4.0 of tyrosine 3.1 of pyrollidine-2-carboxylic acid 13.9 of arginine and 11.6 of lysine ; histidine was not present.The leucine consisted of a mixture of aminoisobutylacetic acid and F. Ehrlich’s isoleucine. Complete precipitation of pyrollidine-2-carboxylic acid from a solu- tion in methyl alcohol may be effected by means of a solution of mercury acetate in methyl alcohol to which potassium methoxide hasOKGANIC CHEMISTRY. 163 Percentage of total N present as been added. Since i t is improbable that d-tyrosine is a component of amyloid or that racemisation takes place in the process of decomposition i t must be assumed that the fundamental constituent is a substance which is comparatively stable towards acids and resembles the protamines or Siegfried’s kyrines. The monoamino- acids which are only feebly combined with this substance are liber- ated a t once and a portion of them is rendered inactive by the action of boiling snlphuric acid. The resemblance t o the histones is supported by the fact that ainyloid is always found in COM- bination with an acid.Amyloid can no longer be regarded as a particular coagulation form of albumin. It has been shown that it is attacked by pepsin and trypsin in the ordinary way although the action is somewhat slower than in the case of normal dbumin- ous substances. Amyloid livers are thus subject t o autolysis in the typical way and the possibility of resorption cannot be doubted. Whilst the percentage composition of amyloids from different sources varies but little the forms in which the nitrogen and sulphur are contained me by no means the same in each case; the latter may be present not only in the sulphate form but also in a state of combination similar to that in which it is found in cystine.In the following table the samples (l) (a) and (3) refer respectively to amyloids from liver spleen and a normal human aorta Total S coiisists of C. 13’8 30% 54.9 51’2 4.9 1.7 0.0 57-0 11.2 1.8 0.0 36.0 8’8 0.4 1’9 - H. 1 2 3 - N. 50.1 49-3 49.6 14-1 14’1 11’4 - - S. 2.6 1.8 2.3 - Proteids of a pronounced basic character always occur in places where normal tissuo is undergoing change and smyioid is a product of the metamorphosis of albuminous substances. Amyloids from the liver spleen and aorta may possibly represent different phases of the process of change which cultninates in the formation of the typical liver amyloid.Preparation of Bromolecithin AKTIEN-GESELLSCHAFT FUR ANILIN-FABRIKATION (D.R.-P. 1561 lo).-Lecithin readily combines with bromine in chloroform solution the amount of bromine taken up vasy- ing with the source of the lecithin employed. Lecithin obtained from egg-yolk absorbs 30 per cent. of its weight of bromine. On evaporn- tion under reduced pressure the product is obtained as a colourless waxy mass. Unlike lecithin bromolecithin is not hydrolgsed by the intestinal juice. C. H. I). E. W. W.164 ABSTK ACTS 0 F C H Ehl IC A T l'h 1'E 1Z S Iodo-derivative8 of Lecithin. J. D. RIEDEL (D.R.-P. 155629).- Iodo-derivatives of lecithin are obtained by the action of iodine chloride or of mixtures producing iodine chloride on lecithin. The products dissolve readily in ether or warm alcohol and swell in water ; they may contain as much as 50 per cent. of iodine. Alkalis decom- pose them y!elding choline,. glycerolphosphoric acid and fatty iodo- acids The iodine is contained in the fatty acid residue. Choline yields only an unstable additive compound with iodine chloride. Products containing 5-20 per cent of iodine find therapeutic application. C. H. D. Hernocyanin. 11. MARTIN HENZE (Zeit. physiol. C'hent. 1904 43 290-298. Compare Abstr. 1901 i 783).-The distribution of the nitrogen in the hteniocyanin molecule has been determined by Hausmann's method with the following results total = 16-09 ; as ammonia 0.93 ; as humin 0.43 ; dialvicle nitrogen 4.45 ; and monamicle nitrogen 10.20 per cent. When liydrolysed with 33 per cent. sul- phuric acid the following products aye obtained histidine lysine glutamic acid tyrosine and leucine. Arginine could not be isolated and a reducing sugar could not be detected ,zmong the products of hydrolysis. J. J. S. Velocity of Enzymatic Reactions. 11. KEGINALU 0. HERzoa (Zeit. physiol. Chena. 1904 43 222-227. Cornpaw Abstr. 1904 ii 164 506).-Largely a reply t o Henry (Conept. rend. SOC. Bid. 1904 57 173). Further experiments are described which tend to show that in solutions of equal viscosity the rate of inversion of sucrose by invertase is practically the same. Diastasic Coagulation of Starch. AUGUSTE FERNEACII and JULES WOLFF (Conapt. Tend. 1904 138 1217 -1.219. Compare Abstr. 1904 i 211 228 291 374).-The cliastasic coagulation of starch is only possible when the starch is in a state of liquefaction produced either by a liquefying diastase such as amylase or artificially by heating under pressure. A 4.6 per cent solution of starch is coagulated by an extract of malt which has not been heated or by a mixture of extracts of barley wheat or rye whicli have not been heated with a malt extract which has been heated at 75" a tempera- ture at which the amylo-coagulase is destroyed whilst the liquefying property OF the amylase is preserved. Further starch paste which has been liquefied by heating under pressure at 145" is coagulated by barley extract. 35. A. W. Phenyl Derivatives of Elements of the Phosphorus Group. PAUL PFE~FFER [with IDA HELLER and H PIETSUH] (Bey. 1904 37 4620 -4623. Compare Pfeiffer and Schnurmann Abstr. 1904 i 232 ; Pfeiff er and Truskier ibid. i 544)-Triphenylphosphine is conveniently prepared by the action of magnesium phenyl bromide on phosphorus trichloride in ethereal solution; it crgstallises from a mixture of alcohol and ether in colourless prisms or plates and melts at 78.5". Triphenylarsine triphenylstibine tri-p-tolylstibine and triphenyl- bismuthine mere all prepared wit11 a good yield by a similar method. J. J. S. W A. D.

ISSN:0368-1769    

DOI:10.1039/CA9058800109

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 115 Analytical Chemistry. Sodium Nitrate containing Perchlorate. HENRI PELLET and G. PRIBOURG (Bied. Centr. 1904 33 798-803; from Ann. 8ci. Agron. 1902-1903,8 ii 199).-The amounts of perchlorate vary from traces to 1.5 per cent. but as much as 3.2 and even 6 per cent. reckoned as potassium salt have been found. According to de Caluwe less than 1 per cent. of sodium perchlorate is injurious to vegetation whilst potassium perchlorate and chlorate are much less injurious. When sodium nitrate contains perchlorate the chlorate is present only in small quantity. Potassium is always present but seems to have no relation to the amount of perchlorate. Vincente and Lafitte detect chlorates in presence of chlorides perchlorates and nitrates by adding to the solution a few drops of a solution of aniline in water (1 40) and an equal volume of hydro- chloric acid of 22' B.A reddish-violet coloration which turns to an intense blue is produced when traces of chlorate are present. N. H. J. M. Use of Chromates of Barium and of Silver in the Estima- tion of Sulphates and Chlorides. LAUNCELOT W. ANDREWS (Amer. Chem. J. 1904 32 476-480).-Estintation of Sulphates.- The process published by the author in 1890 consisted in precipitat- ing the alkali sulphate with a solution of barium chromate in dilute hydrochloric acid ; after removing the excess of barium chromate by neutralisation the alkali chromate formed in the reaction was estimated iodometrically. The author now states that in practice it will be found more convenient to use a solution of barium chromate in N-trichloroacetic acid which unlike the hydrochloric acid solution is perfectly stable.Estimation of Chlorides.-Silver chromate is a valuable reagent for the estimation of very small quantities of chlorine say in drinking- waters. On agitating the water with this rea.gent silver chloride is formed and the filtrate contains alkali chromate which may then be estimated calorimetrically. L. DE K.116 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Tellurium. ALEXANDER GUTBIER (Chem. Centr. 1904 ii 1554-1555 ; from Sitxungsber. phys. med. SOC. 1904 130-1 33),-The tellurium is separated by reduction with hydraxine hydrate washed with lukewarm water and dried preferably in a current of hydrogen. L. DE K. Iodometric Estimation of Telluric Acid. ALEXANDER GUTBIER and E.RESENSCHECR (CJLem. Centr. 1904 ii 1555; from Sitxungsber. phys. nzed. SOC. 1904 138-142).-Telluric acid cannot be accurately estimated by distillation with hydrochloric acid and subsequent iodometric estimation of the chlorine evolved L. DE K. Estimation of Nitrogen in Organic Compounds. HENRY C. SHERMAN and M. J. FALK (J. Amer. Chem. Soc. 1904,26 1469-1474). -The authors stat,e that even in the case of alkaloids the Kjeldahl method as modified by Dyer may be successfully employed if the boiling be continued for at least two hours after the liquid has become colourless (compare Dyer Trans. 1895 6’7? 812). L. DE K. Volumetric Estimation of Hydroxylamine by means of Tervalent Titanium. ARTHUR ST~HLER (Ber. 1904 37 4732-47 33).-Hydroxylamine is quantitatively reduced to ammonia by t,itanium trichloride or trisulphnte and since the excess of the titanium salt can be easily estimated by titration with perrnanganate o r ferric chloride a convenient method of estimating hydroxylamine especially in organic compounds is obtained.Hydrazine sulphate is uot acted O L ~ by titanium salts under like conditions. E. F. A. Estimation of Phosphorus in Iron Ores. JAMES S. ROWLAND and LLEWELLYN J. DAVIES (.I SOC. Clmn. iyzci?. 1904 23 (24) 1186-1 187. Compare Trans. 1866 19 14S).-One to two grams of the finely powdered ore are mixed with one gram of calcined magnesia and heated in a muffle furnace at a bright red heat for about an hour The cooled mass is boiled with 50 per cent. nitric acid when a solution containing all the phosphorus is obtained.The phosphorus is then precipitated by ammonium molybdate and the washed precipitate dissolved in a definite volume of standard sodium hydroxide solution which is then titrated with nitric acid using phenolphthalein as indicator. Results are given to show the accuracy of the process. H M. D. Estimation of Phosphoric Acid in Food-stuffs. EMILE FLEURENT (Bull. SOC. chim. 1905 [ iii] 33 101-103).-The author finds that Garola’s process (Abstr. 1897 ii 596) for the estimation of phosphoric acid in wheat flour is inconvenient. Larger quantities of material may be used and the operation carried out more rapidly if the flour is destroyed with fuming nitric acidand the product from this opera- tion treated with sulphuric acid as in the Kjeldahl process for the final destruction of the organic matter.The residue so obtained is diluted,ANALYTlCAL CHEMISTRY. 117 neutralised with ammonia some ammonium chloride added and the phosphoric acid estimated with ‘‘ magnesia mixture.” OSWALD SCHREINER and BATLEY E. BROWN (J. Alriie~. Chenz. Soc. 1904. 26 1463-1468. Compare Abstr. 1904 ii S5).-Tlie process may be briefly summarised as follows. The solution drinking water for instance is mixed with a drop of ammonia and a few drops of ammonium oxalate and evaporated to dryness. The residue is moistened with magnesia mixture and after a few hours i t is washed several times with small quantities of ammonia mster and finally once with plain water. The precipitate which now contains any phosphoric acid as triple phosphate is dissolved in nitric acid and tested colorirnetrically by the T.A. H Colorimetric Estimation of Phosphates. authors’ improved molybdate process. L. DE K. Estimation of Arsenic. R. C. COWLEY and J. P. CATFORD (Ylmrm. J. 1904 73 897).-The following manner of applying Reinsch’s test is described. A fine copper wire coiled into a helix is immersed i n 10 C.C. of the liquid to be tested to which 2 C.C. of hydrochloric acid have been added. The liquid is con- tained in a test-tube and the copper helix should reach from the bottom of the liquid to above its surface. The test-tube and its contents are placed for 1 hour in a salt-water bath kept at a temperature just below its boiling point. At the end of this time the exposed length of wire is pressed down below the surface and the heating continued for a further 15 minutes.If all the arsenic has been removed from the liquid this upper portion of the wire will remain bright The helix is then removed washed and the arsenical deposit dissolved off by 1 C.C. of bromine water containing a little hydrobromic acid. After washing the wire the arsenical solution is treated with 1 C.C. of potassium hydroxide solution and boiled until the light green copper compounds are decomposed. The copper oxides are collected on a filter the anenate in the filtrate reduced to arsenite and titrated with ,1’/100 iodine solution. The latter should be standardised with an arsenical solution of known strength. It is asserted that the method is capable of measuring 0.033 milligram of arsenic.w. P. s. Examination of Drugs for Arsenic. WILLIAM A. H. NAYLOR and E. J. CHAPPEL (Phawn. 2 1905 74 33 34)-The authors have examined most of the drugs of the British Pharmacopceia in order to see whether they complied with the limits proposed in the recently issued report presented to the Pharmacopoeia Committee of the General Medical Council. The methods employed were those recommended in this report. A large proportion of the drugs &c. came within the prescribed limits for arsenic the exceptions being antimony oxide 1000 ; bismuth carbonate 5 ; glycerol 4 ; iron 500 ; potassium carbonate 4 ; reduced iron 100 ; sulphonal 6 ; and tartar- ated antimony 500 parts of arsenic per million. The drugs were purchased through the ordinary channels the only stipulation made being that they should answer the requirements of the Pharmacopoeia.The inference drawn from the results of the experiments is that the VOL. LXXXVIII. ii. 9118 ABSTRACTS OF CHEMICAL PAPERS. recommendations as to the arsenic limit are except in the case of a few drugs capable of practical fulfilment.. w. P. 8. Rapid E s t i m a t i o n of Silicon in Ferrosilicon. LOUIS LUCCH~SE (Ann. Cl~,in&. CC~KCZ. 1904 9 452-453).-0.5-1 gram of the finely powdered sample is treated in a weighed platinum crucible with 1 C.C. of hydrofliioric acid 1 C.C. of nitric acid is added and the whole evaporated to dryness. After adding another C.C. of hydro- fluoric acid and evaporating the mass is calcined. After another treatment with hydrofluoric and nitric acids the mass is finally ignited to constant weight and the resulting ferric oxide multiplied by 017 represents metallic iron which deducted from the original weight gives the silicon.The impurities present in commercial samples are not sufhiently large to affect the result. L. DE K. The Microscopic Examination of Metals. JOHN H. I;. JENKINS and I>. G. RIDDICK (Arzcdyst 1905 30 2-15).-This paper deals mainly with the microscopic examination of mild steel. The methods of preparing the sections are fully described and inclnde the polishing etching heat-tinting and mounting of the specimens. Forty-one photo-micrographs are given to illustrate the specimens mentioned in the paper comprising iron crystals pig iroris mild steels cemented steels manganiferous steels pearlite copper " burnt " copper annealed steel flaws in steel cast-steel &c.w. P. s. Precipitation of Barium Bromide by Hydrobromic Acid. NORMAN c. 'IHORNE (Ante?.. Sci. 1904 [iv] 18 441-444).-If a concentrated solution of barium bromide or chloride is treated with an excess of a mixture of equal parts of hydrobromic acid and ether the barium is precipitated quantitatively as bromide. It is advisable to saturate the mixture with hydrogen bromide which is conveniently made by dropping liquid bromine into a solution of naphthalene in petroleum and passing the evolved gas through a purifying tower charged with glass wool and red phosphorus. The precipitate is collected on a weighed asbestos pad washed with the acid ether mixture mixed with a little ammonium bromide and finally heated a t 250' to constant weight.The process may be used in the presence of calcium and magnesium. If however barium bromide is treated with hydrochloric acid and ether it is practically precipitated as chloride. If barium chloride is partially precipitated with hydrochloric acid and then mixed with an amount of hydrobromic acid which by itself would not have caused any precipitate a mixture of barium chloride and bromide is obtained. L. DE K. Estimation of Lead and Antimony as Sulphides. JOSEPH A. MULLER (Bui,?. SOC. chinz. 1904 [ iii] 31 1300-13U3).-1t is proposed t o precipitate the snlphides of these metals in warm slightly acid solu- tion and to mash the precipitates previously collected on tared filters successively with (1) a solution of hydrogen sulphide in water (2) alcohol (95 per cent.) (3) a mixture of equal volumes of alcohol ether,ANALYTICAL CHEMISTRY.119 and carbon disulphide and (4) ether and then to dry them under re duced pressure over sulphuric acid. The results of a number of trials of this method quoted in the original indicate that i t gives trustworthy results. T. A. H. Analysis of Lead Minerals. JOSEPH A. MULLER (Bull. Xoc. chirq. 1904 [ iii] 31 1303-1 306). -The finely owdered mineral is warmed the excess of acid treated first with warm mttter and then with hydro- chloric acid at SOo. From the aqueous solution the iron is precipitated by the addition of sodium acetate and subsequent ebullition and the silver as the chloride. To the filtrate are added ( a ) the hydrochloric acid solution prepared from the original residue and ( b ) the precipitate of basic ferric acetate previously dissolved in hydrochloric acid and the whole i s largely diluted with water then warmed and saturated with hydrogen sulphide. The precipitate is first washed with a solu- tion of sodium or ammonium sulphide arsenic being estimated as magnesium ammonium arsenate and antimony as the sulphide (com- pare preceding abstract) in the washings ; next the residue is washed with alcohol &c.as already described (Zoc. cit.) and weighed. If copper is present this is determined by treating an aliquot portion of the precipitate with nitric acid followed by suiphuric acid and estimating the copper in thc soluble portion by one of the usual methods.The lead sulphide precipitate may also contain a small quantity of silver sulphide ; this may be estimated by reduction and cupellation. The remaining constituents of the mineral are determined in the usual way. Analysis of Ferrosilicons; Use of Sodium Peroxide in Platinum Crucibles. LOUIS LUCCH~SE (Ann. China. anal. 1904 9 450-451).-When copper or nickel crucibles are used for fusions with sodium peroxide the fused ma68 is always contaminated with copper or nickel oxides which complicates the analysis. KO such inconvenience is experienced when using a platinum crucible. For the assay of ferrosilicon 1 gram (or less) of the finely powdered sample is mixed by means of a spatula with 2 grams of dry sodium carbonate and 2 grams of sodium peroxide contained in a platinum crucible.After heating for 5 minutes very gently over a small Bunsen flame or a spirit lamp the crucible is seized with a pair of nickel tongues and with constant rotary movement heated to dull redness for 15 minutes when the fused mass is a t once turned out. The mass which contains the silicon as silicate is then analysed as usual. Estimation of Chromium in Steel. FRED IBBOTSON and R. HOWDEN (Chem Akws 1904 90 320-32 I).-The sample is dissolved in a small smoiint of nitric acid of sp. gr. 1.20 and heated to expel nitrous fumes. After copious dilution 2-3 grams of ammonium per- sulphate and about 0.01 gram of silver nitrate are added and the solution heated until the chromium and manganese are completely oxiclised. If the quantity of the latter metal be large manganese dioxide may separate and must be removed by filtration.The solu- tion is cooled treated with excess of ammonium acetate and lead with nitric acid for 12 hours and the reei i ue left after evaporatiop of T. A. H. L. DE K. 0-2120 ABSTRACTS OF CHEMICAL PAPERS. acetate solution is added. The precipitated lead chromate is collected on an asbestos filter washed with dilute ammonium acetate solution and then dissolved off the fi!ter with nitric acid. After diluting the solution an excess of standard ferrous slulphate solution is added and the estimation completed by titration with A720 potassium perman- ganate solution. Steels containing large quantities of tungsten cannot be completely decomposed by nitric acid alone. I n this case 0.5 gram of the sample is heated with 10 C.C.of sulphuric acid (1 4) until nearly dissolved 2 C.C. of nitric acid of sp. gr. 1.2 are then added and after boiling 200 C.C. of water. To this solution containing much of the tungsten as precipitated oxide 20 C.C. of the nitric acid and 20 C.C. of a 0.2 per cent. silver nitrate solution are added together with 3 grams of ammonium persulphate. The mixture is gradually brought to boiling then cooled ferrous sulphate solution is added and the titra- tion completed as above described. w. P. s. Estimation of Chromium in Steel. FRED IBBOTSON and R. HOWDEN (Chenz. i%ews 1905 91 3)-Cbromium and manganese may be estimated in one portion of a sample of steel according to the following method. The manganese is oxidised in a cold nitric acid solution of the steel by means of sodium bismuthate and tjtrated in the usual manner.About 50 C.C. of nitric acid of sp. gr. 1.2 and 10 grams of sodium bismuthate are then added and the mixture boiled. A small quantity of rnsnganous sulphate is added and the boiling con- tinued for a minute or so. The manganic oxide is then collected on a filter and the chromic acid estimated in the filtrate. w. P. s. Electrolytic Estimation and Separation of Antimony and Iron. The Trisulphide Method for Estimating Antimony. ARTHUR FISCHER (Zed. nn0r.g. Chem. 1904 42 363-41 7. Compare Abstr. 1903 ii 6l6).-The electrolytic reduction of tin from the solution of the tin ammonium thio salt is easiIy accomplished by means of a platinum cathode covered by a layer of tin on the addition of sodium sulphite to the ammonium sulphide used.The use of a platinum iridium anode is recommended. Antimony may be quantitatively separated from a solution of the thioantimonite o r from the thioantimonate in sodium sulphide on the addition of potassium cyanide. The presence of polysulphides in the solution prior to electrolysis is immaterial since they are easily reduced by the potassium cyanide present. A platinum iridium anode is also preferable in this case to a platinum anode. The electrochemical equivalent of antimony in thioantimonite is Sb/3 and in thioantimonate Sb/5. The quinquevalency of anti- mony favoilrs the reversibility of the reaction whilst the tervalency does not. The separation of antimony from tin may be effected from sodium sulphide solution to which potassium cyanide is added.The separation is accomplished both when tervalent and quinquevalent antimony com- pounds are employed. The solution mwt be saturated at 30'with sodium sulphide and must contain from 2 to 4 grams of sodium hydr-ANALYTICAL CHEMISTRY. 121 oxide. The temperature must not exceed 30" uor the tension 1.1 volts. I n the absence of potassium cyanide only tervalent antimony can be separatecl from tin with accuracy. The electrolyte must in this case be saturated a t 50' with sodium sulphide and the tension must not exceed 0.9 volt. Sodium hydrosulphide is unsuitable for the separation since the potentials of antimony and tin towards its solution are only very slightly different. The addition of sodium hydroxide to the electrolyte as recommended by Classen is absolutely essential.The trisulphide method for estimating antiiiiony gives results lower than those obtained by the electrolyt,ic method. A. McK. Estimation of Chloroform Vapour by a Tonometric Method. B. J. COLLINGWOOD (Proc. physiol. Soc. Nov. 1904 ii-iii ; J. Physiol. 32).-The principle of. the method is as follows one chamber contains the mixture of air and chloroform another air only; the two are connected by a manometer. An equal amount of chloroform is added to both and the difference in the levels of the water or mercury in the two limbs of the manometer is proportional to the percentage of the chloroform originally present. The method gives good results and these are not affected by the presence of carbon dioxide. W. D.H. Estimation of Chloroform Vapour in Air. ALFRED G. LEVY (Proc. physiol. Soc. Nov. 1904 iii-iv ; J. Physiol. 32).-Waller's densimetric method was compared wihh Vernon Harcourt's corn- bustion method The results agree very closely the former method giving as a rule slightly higher results. W. D. H. Estimation of Glycerol in its Solutions by means of the Specific Gravity. C. ST~EPEL (Chenz. Centr. 1904 ii 1626-1627 ; from Seifensiederzeit. 31 818).-The amount of glycerol in a crude sample which is reasonably free from other organic matters may be determilied by subtracting from the percentage as deduced from the sp. gr. the percentage of ash multiplied by 3.33. This however only holds good for small amounts of salts If the sample is very concentrated the determination of the sp.gr. is somewhat troublesome. I n this case it may be slightly diluted with a known weight of water. L. DE K. Assay of Glycerol. TAUREL (Clwm. Centr. 190.1 ii 1258 ; from MOR. Xci. 18 574-577).-When testing crude glycerol by means of Hehner's dichromate process it is necessary to first remove certain objectionable matters by addition of basic lead acetate. The author prepares this by dissolving 1 mol. of lead acetate and adding half a mol. of sodium hydroxide. Any excess of lead in the filtrate must be care- fully removed by sodium sulphate. Alkaline samples should be first neutralised with acetic acid before clarifying with the lead. If there is much sodium chloride present there is a risk of chlorine escaping during the heating with potassium dichromate and sulphuric acid.122 ABSTRACTS OF CHEM1CA4L PAPERS.The author therefore recommends connecting the flask with a bulb tube containing a standard solution of arsenious acid and in this way estimating the chlorine and allowing for it. When testing glycerol for sulphides acetic acid should be used in the cold. When testing for arsenic by Gutzeit’s test any sulphur compounds should be first fully oxidised with potassium permanganate before adding zinc and hydrochloric acid. L. D E K . New Test for Cholesterol. CARL NEUBERG and DORA RAUCH- WERGEH (Chem. Ceyatr. 1904 ii 1434-1485 ; from Festschr. fur Ernst XaZkowski 379-285).-A trace of cholesterol is heated with 1.5 C.C. of absolute alcohol and a minute particle of rhamnose or a drop of solution of 8-methylfurfuraldehyde is added.When quite cold an equal bulk of sulphuric acid is allowed to run down the sides of the test-tube when a characteristic raspberry-red ring will a t once be noticed. If the tube is well cooled and shaken the whole liquid becomes red and shows after being diluted with alcohol a character- istic dark absorption band between E and C. If the mixture becomes overheated the liquid assumes a brown colour and then shows a second absorption band in the neighbourhood of B. Phytosterol does not give the reaction or a t most a rose colour which gives an absorp- tion band in the yellowish-green. The reaction is however shared by some hydroaromatic compounds such as biliary acids also by camphor borneol menthol and similar substances. L. DE K. Corrections to be Applied in the Estimation of Lactose in Cows’ Milk and Human Milk.GUSTAVE PATEIN (J. Pharm. Chirn. 1904 [vi] 20 501-505).-Attention is drawn to the necessity of correcting for the volume of the precipitated casein and fat in this estimation particularly when the analysis is made on the undiluted milk. Lactose cannot be estimated polarimetrically in human milk on account of the presence of a lzevorotatory substance which is not pre- cipitated by mercuric nitrate or by picric acid. As this substance however does not reduce Fehling’s solution the volumetric met’hod may be used. w. P. s. New :Reaction for Lactose ( a n d Maltose). ALFRED WORLK (Zeit. anal. Chenz. 1904 43 670-679).-Lactose or maltose heated with 10 per cent. ammonia for 15-20 minutes develops a bright madder-red colour of considerable permanence.Other carbohydrates give either no colour or a yellow to yellowish-brown one and do not obscure the lactose reaction. The reaction is however inhibited by various substances such as tartrates citratcs and ammonium salts. M. J. S. Composition and Analysis of Maple Syrup and Maple Sugar. JuLrrrs HORTVET (J. Amer. Chern. h’oc. 1904 26 1523-1545).-A lengthy paper giving the results of the analysis of a large number of pure and adulterated samples of maple sugar and syrup. For full particulars of the analytical operations and results the original paperANALYTICAL CHEMISTRY. 123 should be consulted. Considerable importance is attached t o the volume occupied by the precipitate formed on adding basic lead acetate The amount of malic acid and the alkalinity of the ash also give valuable indications as to the genuineness of the samples.L. D E K. Table for the Rapid Calculation of the Original Extractive Matter of Beer Wort. PAUL LEHMANN and HERMANN STADLINGER (Zeit. anctl. Chem. 1904 43 679-687).-The formula lOO(E + 2.0665A) for € = 100 + 1.0665A the calculation of the original extractive matter E from the percentage of alcohol A and the extractive matter of the beer F may be expressed i n the form ZOO 206.65A 100 + 1+0665A+ 100 + 1.06658’ Or z=E,(Aa)+(AP). The table gives the values for Aa and AP for each 1/100 per cent. of alcohol from 1.5 to 4.99 per cent. and the cal- culation is thereby resolved into the multiplication of the factor A a by E and addition of the corresponding number AP.Estimation of Carbamates. JOHN J. R. MACLEOD and H. D. HASKIKS (Anzer. J. Physiol. 1 904 12 444-456).-Carbamates are present in the ui.ine when urea formation is interfered with. Previous methods for detecting these salts are unsuitable for quantitative work. The present paper is limited t o a description of a new method and proofs of its accuracy. The principle of the method is to determine the yield of carbon dioxide from the liquid by the Barcroft-Haldane method and again in the same liquid after precipitation of the carbon- ates by barium hydroxide and ammonia. I n liquids which contain proteid a slight modification is necessary. € = E AX. J. S. TV. D. H. Detection of Acetates Cyanides and Lithium. STANrxY R. BENEDICT (A9)2e9*.Chenz. J. 19@4,32 480-483).-Detection of Acetates. -The process is based on the fact that a solution of cobalt nitrate containing a little free acetic acid gives practically no precipitate with hydrogen sulphide but does so a t once when an alkali acetate is added ; also on the fact that silver acetate is slightly soluble. The solutioii is mixed with slight excess of sodium carbonate and then with slight excess of silver nitrate. After carefully removing this by sodium chloride the filtrate is saturated with hydrogen sul- phide. On pouring the liquid into 2 C.C. of N-cobalt nitrate containing a fern drops of acetic acid and saturated with hydrogen sulphide a more or less heavy precipitate of cobalt sulphide will be formed should a n acetate be present. Detection of Cynizides in the peseiace of 3’errocyunicZe.s.-The solution is made alkaline with sodium hydroxide and about 1 C.C.of N/25 mercurous nitrate is gently poured over it. A ring of black mercurous oxide is thus formed which however in the presence of a trace of cyanide will on shaking partly dissolve whilst the rest turns a light grey.124 ABSTRACTS OF CHEMICAL PAPERS Retection oJ Litl&cm in the presence of S o d i u m -To the solution is added a little ammonia and then one-tenth of the volume of &-/5 sodium phosphate and finally enough alcohol to produce a fairly heavy per- inanent precipitate which may be simply sodium phosphate o r contain admixed lithium phosphate. The solution is now heated to boiling when should lithinm be absent. i t will become perfectly clear but in the presence of lithium its phosphate remains undissolved.L. DE K. Detection and Estimation of Citric Acid in Wines. LUCIEN ROBIN (Ann. Chirn. ancd. 1904,9 453-456) -The following reagents are required (1) a 40 per cent. solution of lead acetate (2) a mixture of 1 vol. of glacial acetic acid and 9 vols. of water (3) a strong solution of potassium hydroxide (4) a mixture of 1 vol. of glacial acetic acid and 9 vols. of alcohol (5) a hot saturated alcoholic solution of cadmium acetate. Twenty-five C.C. of wine are heated to boiling 3 C.C. of (1) are added and after boiling for a few minutes the precipitate is collected washed and then heated f o r 5 minutes a t 90' with 10 C.C. of (2). After washing the residue with the acid water the filtrate is freed from lead by means of hydrogen sulphide and evaporated to incipient dryness.The residue is now dissolved in 5 C.C. of alcohol and after being neutralised with (3) 0.5 C.C. of glacial acetic acid is added and after stirring the liquid is passed through a filter and the deposit washed twice with 5 C.C. of (4). After the last traces of potassium hydrogen tartrate have separated and been removed by filtration the citric acid i a precipitated by adding 6 drops of ( 5 ) collected on a tared filter washed with alcohol dried a t loo" and weighed. The weight multiplied by 0.5378 = citric acid. After weighing it may be further identified as a citrate by DenigAs' mercurial reagent. L. DE K. Estimation of Amino-acids in Urine. FRANZ ERBEN (Zeit. physiol. Chem.1904 43 320-324).-An adaptation of the method already employed by E. Fircher and Bergell and by Ignatowski in which naphthalene-P-sulphonic chloride is the reagent employed. Normal urine contains a conjugated amino-acid hippuric acid which does not give the reaction in question. I n the investigation of urine it is first necessary to remove and estimate the hippuric acid. When this is done normal urine and many pathological urines give no further evidence of amino-acids. From experiments with mixtures of urine and amino-acids (glycine alanine leucine tyrosine) the method is shown not to be accurate quantitatively from 5'7 t o 80 per cent. only of the added acid being recoverable. W. D. H. The Reactions Concerned in the Estimation of the Iodine Value. FREDERIK H.VAN LEENT (Zeit. anal. Chem. 1904 43 661-670).-From a discussion of the work of von Hubl Waller Ephraim Marshall Wijs and others the author draws the following conclusions (1) the active constituents of the solutions of von Hubl Ephraim and Wijs are iodine monochlorido and hypoiodous acid ;ANALYTICAL CHEMlSTRY. 125 both of these form additive products and are iodometrically equivalent (2) no combination or liberation of hydrochloric acid takes place during the iodine absorption (3) the hydrochloric acid which becomes free during the reaction is a product of the hydrolytic decomposition of iodine inonochloride (4) no substitution of hydrogen by halogens takes place ( 5 ) the iodine value is a measnre of the unsaturated com- pounds present in the fat (6) the ’IVijs solution of iodine monochloride in 99 per cent.acetic acid is to be preferred for the reaction. M. J. 8. A Simple Method for the Estimation of the Fat in Butter. A. HESSE (Zeit. hTdur. Genussnz. 1904 8 673-675).-From 1-5 to 2 grams of the well-mixed sample are placed in a Gottlieb’s cylinder and treated with 8 C.C. of hot water. If necessary the cylinder is placed in warm water until the butter is melted. One C.C. of ammonia and 10 C.C. of alcohol are then added and the mixture shaken to dis- solve the casein. After cooling 25 c . ~ . of ether and 25 c . ~ . of light petroleum are added and the whole thoroughly mixed. When the ethereal solution of the f a t has separated it is drawn off and the residue again treated with 50 C.C. of ether which is drawn off without having been shaken up and finally with 50 C.C.of the mixture of ether and petroleum. The united ethereal solutions are evaporated and the residue of f a t weighed. w. P. s. The ‘( Sinacid ” Butyrometer Jlu 1201 and KOEHLER (iMiZch. Zeit. 1904 33,787-790).-Thisinstrument devised by A. Sichler isintended for the estimation of fat in milk the methodof procedure resembling that of Gerber. Its name is derived from the fact that the sulphuric acid of the latter process is dispensed with (sine acido) a salt solut,ion being used instead. The composition of this solution is not given as the patent rights have not yet been secured but it has an alkaline reaction. The amyl alcohol of the Gerber process is replaced by another higher alcohol. The new method gives results closely agreeing with those yielded by Gerber’s process but the authors consider that the latter is to be preferred where many samples of milk have to be examined on account of it’s rapidity.w. P. s. Colour Reaction of Cotton Seed Oil. GEORGES HALPHEN (BUZZ. SOC. chirn. 1905 [iii] 33 108-llO>.-It is shown that after cotton seed oil has been fully brominated it does not give Halphen’s colour reaction (Abstr. 1898 ii 358) but that oil coloured by the reagent retains its colour on subsequent bromination. The substance t o which the production of the colour is due is not present in the “unsaponifi- able matter,” and is probably an unsaturated acid. When cotton seed oil is treated with water the “active principle ” is not removed but wet oil gives an orange-brown colour instead of the normal rod colour with Halphen’s reagent.The passage of hydrogen sulphide through cotton seed oil produces no coloration. These observations do not support Raikom’s view (Abstr. 1900 ii 698 and 1902 ii 366) that the production of the red colour is due to the formation of126 ABSTRACTS OF CHEMICAL PAPERS. a t hio-derivative and its disappearance on exposure to sunlight to the loss of sulphur and polymerisation of the product formed. T. A. H. Detection of Cotton-aeed Oil in Olive Oil. E. MILLIAU (Compt. rend. 1904 139 807-809. Compare Abstr. 1904 ii 456). -The chemical tests applied in the detection of cotton-seed oil namely the reduction of warm alcoholic silver nitrate solution and the produc- tion of a red colour on treatment with a solution of sulphur in carbon disulphide ape both given by ‘‘ capoc” oil and baobab oil.These oils are indeed more sensitive towards both reagents than cotton-seed oil and a method of distinguishing the two former from cotton-seed oil is based on the observation that the fatty acids from ‘‘ capoc” oil and baobab oil give an intense brown coloration with alcoholic silver nitrate in the cold whilst cotton-seed oil in similar circumstances has no re- ducing action. The oils themselves if chloroform is added to bring them into solution may be used instead of the free acids but the difference of behavionr is less marked H. 31. D. Fat of the Fruits of the Dipterocarpus Species. IBIDOR KLIMONT (Xonntsh. 1904 25 929-932). -A specimen of Borneo tallow from the Austrian €iandelsniuseum melts a t 34.5-34-7” and has a n acid number 15.8 an iodine number 3011 and a hydrolysis number 194.6.It contains tristearin tripalmitin (?) oleodistearin (Henriques and Kunne Abstr. 1899 i 330) oleodipcdnzitiu which melts when freshly recrystallised a t 33-34’ when fused and resolidified at 28-2ga has an iodine number 30.2 a hydrolysis number 202.7 and other mixed glycerides of fatty acids with smaller carbon nuclei and with unsaturated fatty acids. Oleodipalmitin is found also in oxao fat (compare Fritzweiler Abstr. 1902 ii 470). c:3H5(c&310.J.yc YH330.y G. Y. Assay of Beeswax. GEORG BUCEINER (Chenz Zeit. 1905 29 32-33).-A slight modification of the author’s process (Abstr. 1892 ii 665). After determining the acidity number of 3.6 grams of the sample 35 C.C.of iV/2 alcoholic potassium hydroxide are added and after connecting the Erlenmeyer flask with a Soxhlet tube and condenser the contents are boiled briskly for one hour. I n this way the liquid in the flask gets temporarily concentrated and the saponifi- cation is more complete ; a portion of the alcohol also can be recovered from the Soxhlet tube When very refractory samples have to be tested the author uses absolute alcohol or pure aniyl alcohol (Werder’s process). L. DE K. Saponification Number and Dry Residue of Oil of Lemon. ENRICO BERT^ (Chenz. Centr. 1004 ii 16’70 ; from 13011. Chiai. F(mn. 43 709-7 13). -Adulteratioii of oil of lemon may be detected by nieaiis of the saponification number a i d by the amount of residue left on evaporation on the \I ater-bath.The saponification number of the pure oil does not exceed 3.5 and the residue variesANALYTICAL CHEMISTRY. 127 from 2-3-5 ; i t is therefore possible to detect the presence of excessive quantities of fatty 01' resinous matters. A table is also given showing the constants of a pure oil; of a mixture containing 25 per cent. of terpene and 2 per cent. of fatty oil and another mixture containing 50 per cent. of terpene and 4 per cent. of oil. The data include the rotation a t 20° the rotation of the distillate at 20° the rotation of the residue a t 20" sp. gr. a t 15" dry residue and the citral. L. DE K. Detection of Saccharin. E. VON UAHLEK. (C'henz. Zeit 1905 29 32).-The ethereal solution containing the saccharin is evaporated to dryness and the residue is transferred to a small reduction tube in which a sm:tll piece of metallic sodium or potassium lias bwii placed.The whole is heated and after the action is over the tube while still hot is immersed in a freshly-prepared solution of sodium nitroprnseide. If saccharin was originally present the mass now contains alkali sulphide which gives the characteristic violet colour. L. DE I(. The Pgrrole Reaction. CARL NEUBERC ( C I m i . C'eiztr. 1904 ii 1435-1457 ; from Fesfsclu. fiir Ernst S(dkozoski 27 1-278).-A table containing the names of 47 organic compounds which give the pyrrole reaction either directly or after addition of zinc dust or zinc dust and ammonia. L. DE K. Reactions of Cocaine and Morphine. C. REICHARD (Clm2. Centy. 1904 ii 1257 ; from Pl~ctrm.&it. 49 855. Compare hbstr. 1904 ii 374).-A i per cent. solution of uranium nitrate containing a few drops of potassium thiocyanate gives an intensely yellow precipi- tate with salts of cocaine. If a little of a mixture of 5.04 parts of uranium nitrate and 6-5s parts of potassium ferricyanide is dissolved in a few drops of water and added to a few crystals of a cocaine salt the latter assume a dark colour and gradually yield a dark brown liquid. Morphine crystals at once turn brownish-black and yield a dark red liquid which on drying gives an almost black residue. A mixture of 2.5 parts of crystallised copper sulphate and 6.6 parts of potassium ferricyanide rubbed with a fern drops of water and a little solid or dissolved morphine a t once turns dark brown.Cocaine gives no reaction. A mixture of powdered copper sulphate and morphine when heated with sulphuric acid yields a beautiful dark violet liquid. L. DE I<. Composition of Turmeric. ALBERT E. LEACH (J A7ue~. C'lm2. Xoc. 1904 26 121@-1211).-The author has analysed three varieties of turmeric China Pubiia and Alleppi. The average composition is as follows Moisture 8.73 ; total ash 7-07 ; ash soluble in water 5-36 ; total nitrogen 1.42 equal to 8.88 proteicls ; total ethereal extract 11.17 ; volatile ethereal extract 3.19 ; alcoholic extract 6.96 ; crude fibre 5.37 ; reducing matters by acid methocl calculated as starch 49.73 ; starch by diastase method 34.2 1 per cent L DE I<.128 ABSTRACTS OF CHEMlCAL PAPERS. New Reagent for the Detection of the Colouring Matters of Blood or their Products of Decomposition.E. RIEGLER (Zeit. ccnccl. Chem. 1904 43 539-544).-The two absorption bands in the spectrum of an alkaline solution of Hoppe Seyler's haemo- chromogen are exhibited with great intensity by an alcoholic solution and such a solution is very readily obtained by treating blood pig- ments with an alkaline alcoholic solution of liydrazine. Sodium hydroxide 10 grams and hydrazine sulphate 5 grams are dissolved in 100 C.C. of water and the solution is mixed with 100 C.C. of strong alcohol and filtered. By shaking a little blood or hzmoglobin with this reagent a rich purple solution of htemochromogen is obtained. When shaken with air this solution becomes transiently green and in this condition shows the single band of a n alkaline haematin solution.In testing urine for blood a trace of white of egg is added and coagulated by boiling after adding a drop of acetic acid. The albumin carries down the hxmatin and after collection on a filter and washing is shaken with the hydrazine reagent. Blood stains on linen can be treated directly with the reagent and examined with a micro- spectroscope. B'l. J. s. Simulation of Traces of Albumin by Substances which interfere with the Ferrocyanide Test especially in Liquids re- quiring Clarification. BRUNO BARDACH (Zed. c6ncd. C'hem. 1904 43 554-557).-1n cases where proteids have been precipitated by ammonium sulphate i t is customary to confirm the completeness of the precipitation by testing the filtrate with potassium ferrocyanide. In these circumstances a trifling turbidity is always observed and this the author has traced to impurities in the ammonium sulphate which cannot be removed by any of the ordinary methods of purifica- tion. It is necessary therefore to employ the purest ammonium sulphate obtainnble and to test the specimen with ferrocyanide and make allowance for the turbidity which is obtained in the absence of albumin. A similar deceptive turbidity is produced by ferrocyanide in liquids which have been clarified by infusorial earth in consequence of traces of iron from the kieselguhr passing into solution. Neither ignition nor treatment with hydrochloric acid improves the kieselguhr in this respect. The only satisfactory method of clarification is to pass the liquid through several thicknesses of filter-paper which however must be absolutely free from iron. M. J. S,

ISSN:0368-1769    

DOI:10.1039/CA9058805115

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

129 General and Physical Chemistry. Refractive Indices of the Elements. CLIVE CUTHBERTSON ( Proc. Roy. Xoc. 1904 74 283-284).-Attention has been previously drawn to the fact that the refractivities of (1) helium neon argon krypton and xenon (2) chlorine bromine and iodine are in the ratio of small integers. With a Jamin’s refractometer adapted for high tempera- tures the refractivities of mercury phosphorus and sulphur have been determined and it is shown that the simple relationship found in the cases of the inert atmospheric gases and of the halogens holds also in the case of (1) nitrogen and phosphorus (2) oxygen and sulphur ; an atom of the second element in each case retards light four times as much as an atom of the first On these lines one may regard the two series N 0 F Ne and P S C1 A as in some sense homologous.I n the latter series the power. to retard light increases with the valency in spite of the simultaneous decrease in atomic weight. The same relationship is found for the aeries Ne 0 N. J. C. P. Spectra of the Metals in the Electric Arc. VII. Spectrum of Tungsten. BERNHARD HASSELBERG ( K . Xvenska Vet. Akad.HandZ. 1904 38 No. 5 1-47. Compare Abstr. 1903 ii 706).- Although on the whole the same lines occur in the arc spectrum of tungsten as appear in the spark spectrum recently recorded by Exner and Hnschek there is very marked difference in the relative intensity of the lines. The lines in the arc spectrum which are apparently due to iron chromium titanium cobalt nickel manganese vanadium and molybdenum have been eliminated and the lines regarded by the author as characteristic of tungsten are fully recorded the discussion being illustrated by reproductions of the spectra. A number of lines in the tungsten spectrum coincide with feeble lines in the solar spectrum and the author regards i t as proved that tungsten is present in the absorbing envelope of the siin.J. (2. P. The Group IV. Lines of Silicon. Sir J. NORMAN LOCKYER and F. E. BAXANDALL (PYOC. Roy. Xoc. 1904 74 296-298).-1n previous papers (Abstr. 1900 ii 181 ; Proc. Roy. Xoc. 67 403) it was shown that the silicon lines might be divided into four distinctive groups. The genuineness of the lines of the fourth group has been questioned by de Gramont (Abstr. 1904 ii 641) but the authors adhere to the conclusion previously reached and the photographic evidence on which it was based is now reproduced.Infra-red Absorption Spectrum of Carbon Dioxide aa affected by Pressure. CLEMENS SCHAEFER (Ann. Physik. 1905 [iv] 16 93-105).-Under high pressure the bands are widened and the maximum absorption is intensified. This result cannot be attained merely by increasing the thickness of the absorbing layer J. C. P. VQL LXXXVIII. ii 10130 ABSTRACTS OF CHEMICAL PAPERS. hence the character of the absorption depends not on the number of absorbing molecules but on their density. J. C. P. Rotation of Optically Active Substances. PAUL WALDEN (Hey. 1905 38 345-409).-A lecture delivered before the German Chemical Society. C. H. D. Dissociation of Strychnine Salts determined by their Rotatory Power.Rotatory Power in Homologous Series. Influence of the Double Linking. JULES MINGUIN (Compt. rend. 1905 140 243-245).-The author has measured the rotation of a number of strychnine salts obtained by dissolving 0.334 gram of strychnine and a molecular proportion of the acid in 25 C.C. of a mixture of parts of benzyl alcohol and ethyl alcohol (2 1) and the change in the rotatory power caused by the addition of excess of acid has also been studied. The results show (1) that the salts are partially hydrolysed by the addition of excess of acid and the hydrolysis as measured by the increase in the rotatory power is greater in the case of the weak than of the strong acids; ( 2 ) that the salts of a homologous series of acids have practically the same rotatory power (compare Tschugaeff Abjtr.1898 i 274 495 ; 1899 ii 3 ; and lSlinguin and de Bollernent Abstr. 1903 i 352) ; (3) that the salts of the unsaturated acids have a higher rotatory power than those of the saturated acids containing the same number of carbon atoms (compare Haller Abstr. 1903 i 503 563 628; Zelinsky Abstr. 1902 i 597; Rupe Abstr. 1903 i 565; Ninguin 1903 i 428). M. A. W. Specific Rotatory Power of Nicotine dissolved in Mixtures of Water and Ethyl Alcohol. 1'. GNESOTTO and G. CRESTANI (Nuowo Cinz. 1904 [v] 8 365-381).-The authors have measured the specific rotation of nicotine in various mixtures of water and ethyl alcohol all the solutions having approximately the same concentration namely 12.1 grams of nicotine per 100 C.C. of the solution. The results which are given in the form both of tables and of curves show that the values of the specific rotatory power of nicotine a t 20' in aqueous alcohol are all inferior to those of the specific rotatory power of the substance itself supposing that each component of the mixture exercises on the active substance an influence proportional to the quantity by weight in which it occurs in the mixture.The differences A between the absolute values of the specific rotatory power of nicotine determined experimentally and the absolute values calculated on the above supposition starting from an alcoholic solution of nicotine increase rapidly with the amount of water substituted for alcohol and reach a maximum for a mixture of water and alcohol con- taining about 80 per cent of the latter ; from this maximum point the diEerences vary practically rectilinearly with the proportion of water present.From these and previous results it is concluded t h a t the ttct'ion of mixtures of water and alcohol on alkaloids shows itself by producing an increase or a diminution in the specific rotatory power of the active substance in solution (with reference t o that obtained byGENERAL AND PHYSICAL CHEMISTRY. 131 calculation from the additive formula) according as dilution of the solution of the substance in the two separate solvents produces an increase or a diminution in the specific rotatory power. T. H. P. Fluorescence of Sodium Vapour. L. PUCCIANTI ( A t t i a. dccnd. Lincei 19Q4 [v] 13 ii 433-440).-The author shows that the lines D and D exist in the fluorescence spectrum of sodium vaponr.The exciting light from which they originate is that of these usually broad lines themselves but in the small spectral interval occupied by each of them light of a given wave-length can excite the emission of waves of different lengths. Indications are given of the construc- tion of a model of the phenomenon on the basis of secondary waves taking into accoiint the annulment or collision of the vibrations. T. H. P. Solvent and Fluorescence. HUGO KAUFFMANN and ALFRED BEISSWENGER (Zed. physiknl. Chem. 1904 50 350-354. Cornpzre Abstr. 1904 ii 528).-An example of the way in which fluorescent amines exhibit a different fluorescence colour according to the solvent in which they are dissolved has already been given (Toc.c i t . ) . The same phenomenon is exhibited in an exceptional degree by dimethyl- naphtheurhodine also by o-aminocinnamic acid and its esters dimethyl- aminocliphenylquinoxaline aminobenzoxazole and ethyl succinylsuccin- ate (compare also Kehrmann and Messinger A bstr. 1892 889). It appears that dissociating solvents affect very slightly the fluorescence colour of the solid substance but the cause of the change of fluorescence cannot be association in benzene and similar solvents because dimethylaminodiphenylquinoxaline for example has a normal molecular weight in benzene It is shown however that in general the displacement of the fluorescence colour from that exhibited by the solid increases as the dielectric constant of the solvent decreases. The order of the solvents is however not always the same so that the nature of the fluorescent substance is also a determining factor.It is noted that the colour of tbe solutions of these fluorescent substances changes with the solvent in a manner very similar to the fluorescence colour. J. C. P. Action of Very Low Temperatures on the Phosphores- cence of- Certain Sulphides. P. LE Roux (Compt. rend. 1905 140 84-85 239-241).-The diminution in the brightness of the phosphorescence of certain sulphides at low temperatures has been observed by Recquerel (Abstr. 1891 776) Pictet (Compt. ?*end. 1894 119 527) Dewar (Chem. ATews 1894) Henry (Contyt. rend. 1896 122 662) and A. and L. Lumikre (ibid. 1899 125 549) and the author finds that a t the temperature of liquid air phosphorescent calcium sulphide becomes non-luminous but recovers its original luminosity when removed from the liquid air and allowed to regain the ordinary temperature.At the low temperature the phosphores- cence is in a potential state for the light emitted by the cooled sulphide on regaining the ordinary temperature is more intense than that of a similar specimen which has not been cooled; further if a 10-2132 ABSTRACTS OF CHEMICA4L PAPERS. non-luminous specimen of calcium sulphide is placed in liquid air and exposed to the light of burning magnesium it becomes luminous when heated to the ordinary temperature. M. A. W. Triboluminescenoe. 11. L. A. TSCHUGAEFF (J. Russ. Phys. Chem. Soc. 1904 36 1245-1253. Compare Abstr. 1901 ii 489)- The author has examined a number of crystalline compounds and finds that in addition to the six compounds already given (Zoc.c i t . ) benzoyl-/3-naphthylamine and benzoyl-m-toluidine also exhibit tribo- luminescence of the first order. With the former of these two com- pounds this property can be observed in ordinary daylight and under favourable conditions the emission of light continues for some six or eight seconds. The results obtained with a number of amino-compounds show that in many cases of two closely-related compounds such as homologues or isomerides one exhibits triboluminescence whilst the other does not. Similar observations have been made on other classes of compounds. Triphenylmethane is triboluminescent but its compounds with benzene or thiophen of crystallisation do not exhibit this property ; on heating these compounds for a short time above their melting points and recrystallising the residues from ether or toluene tribo- luminescent crystals are again obtained.Aniline hydrochloride exhibits strong triboluminescence but the basic salt 2NH,Ph,HCl does not do so. Uranium nitrate completely loses its power of triboluminescence if the crystals are recrystallised from ethereal solution over phosphoric oxide. A number of optically active compounds mere examined and i t was found that these exhibit triboluminescence whilst the corresponding racemic compounds do not. T. H. P. Radioactivity of Underground Air. H. M. DADOURIAN (Amw. J. 8&. 1906 [iv] 19 16-22).-Bumstead has recently shown (Amer. J. Xci. 1904 18 1) that the excited activity obtained by exposing a negatively charged wire in the open air may be fairly accounted for by assuming the presence of radium and thorium emanations in the air. The author now finds that the slowly decaying activity obtained by exposing a negatively charged wire to underground air (that is air which has passed through the soil) is attributable to thorium.J. C. P. Occurrence of Radium and of Radioactive Noble Earths in Fsngo Mud and Soil from Capri. FRIEDRICH GIESEL (Ber. 1905 38 132-133).-The small amount of crude barium sulphate ob- tained from Fango mud contains radium. As Capri soil contains no sulphuric acid i t was fractionally extracted with hydrochloric acid ; radium was found to be present chiefly in the fraction obtained by extraction of the earth with a large excess of hydrochloric acid No uranium was found in either earth.G. Y.GENERAL AND PHYSICAL CHEMISTRY. ‘1 33 A New Radium Mineral. J. DANNE (Conzpt. rend. 1905 140 241 -243).-The pyromorphite in lead ores found at Issy-l’Ev6que contains radium in variable quantity some specimens having a radioactivity several$imes as great !s that of uranium and 1000 kilos. of the mineral yield one centigram of radium bromide. As the mineral contains no uranium (compare Boltwood Abstr. 1904 ii 666) the radium has probably been recently deposited by waters charged with radium salts for from the waters of springs in the neighbourhood a radioactive gas containing radium emanation has been extracted and the barium sulphate precipitated by sulphuric acid from a solution of barium chloride in the radioactive water has a permanent although feeble radioactivity.M. A. W. Potential of the Hydrogen-oxygen Cell. FRANCTS JOSEPH BRISLEE (l’rans. Paraday Xoc. 1905 1 65-74. Compare Wilsmore 1901 ii 2 ; Luther and Inglis 1903 ii 406).-The influence of small quantities of hydrogen peroxide persulphuric acid and ozone on the oxygen potential has been investigated. Two different methods of operation were employed. I n the first the electrodes were polarised by electrolysis extending over two to three days in the second they were freed from gases as completely as possible to begin with and the respective gases were then passed through the solution (normal acid or alkali) the potential as in the first method being measured a t intervals until a constant value was reached. This condition having been attained the effect of the addition of the various substances was tried.The oxygen potential is lowered by the addition of small quantities of hydrogen peroxide. The presence of persulphuric acid or ozone raises the oxygen potential. I n one experiment in which the concen- tration of the added persulphate was 1 gram-molecule in 5000 litres the E.M.F. rose from 1.081 to 1.122 volts and remained constant a t this value for five days. Persulphuric acid and ozone appear further to hinder the separation of oxygen from the supersaturated electrodes and this perhaps accounts for the high potential observed and main- tained for a comparatively long period in electrolytically polarised electrodes. A very thin platinum electrode was prepared by coating a glass tube with “Glanz Platin,” heating in a muffle furnace and platinising in the usual way.When this mas polsrised for 72 hours in normal sodium hydroxide solution the original E.M.F. of the cell was 1.366 but on passing a current of oxygen gas through the solution this rapidly fell to 1.073 (the normal value). Under the same con- ditions but with the addition of potassium persnlphate (1 gram-mol- cule in 500 litres) after polarisation the original E M.F. of 1.350 volts only sank to 1.328 volts a t the end of ten days. The E.M.F. of cells provided with very thin platinised electrodes prepared in the manner described is in very good agreement with that calculated from the Helmholtz formula. H. M. D. Reduction of Mercurous Chloride by Silver.J. N. BRONSTED (Zeit. physikal. Chem. lY04,50,481-486).-As shown by Ogg (Abscr. 1899 ii la) the potential difference of the cell134 ABSTRACTS OF CHEMICATJ PAPERS. HgNO *g [ $:%No3 1 N/10*HNo3 1 L$7/10.HN0 I Hg alters its sign with the concentration of the silver and mercurous salts and in the most dilute solutions studied by him the current passed in the cell from silver to mercury. This must therefore be the case also with the cell Ag I AgCIKC?gC1 1 Hg and the change going on in this cell may be represented by the equation Ag + HgCl = Hg + AgCI. This however is an endothermic reaction for according to the work bf Thomsen and of Nernst the heat of formation of mercurous chloride is greater than that of silver chloride. With the help of Helmholtz's equation F(dx/dT) = T - U the heat effect of the reaction may be calculated from the E.M.F.and the temperature-coeEcient of the E.M.3'. of the corresponding cell. The author has determined the.se quaritities for the cell and is able to calculate the heat absorbed 6y the reaction Ag+WgC!l = Hg + AgCl in good agreement with the calorimetric data. J. C. P. The Measurement of the Potential of the Electrodes in Stationary Liquids. The Determination of Changes of Con- centration at the Cathode during Electrolysis. HENRY J. s. SAND (lkans. Faraday Xoc. 1905 I 1-23. Compare Abstr. 1901 ii 82).-In the cells used for the measurement of the electrode potentials arrangements were made t o have the electrode not under examination as non-polarisable as possible to avoid the evolution of gases and to permit of the continuous measurement of the difference of potential between the electrode and the layer of solution in contact with it during the passage of the current. The variation of the electrode potential with the time of passage of the current is shown in a series of curves.With solutions of silver nitrate copper sulphate and zinc sulphate the removal of the dissolved substance from the immediate neighbour- hood of the cathode is indicated by a sudden drop in the electrode potential. I n the case of copper sulphate the fall amounts to one volt and the potential then becomes fairly constant at this lower value. In the case of silver nitrate the fall is onlyabout 0.2 volt and afterwards the potential rises more or less rapidly to its original value the cathode being then found to have become covered with minute silver crystals which grow out into the solution Zinc sulphate behaves in similar manner to copper sulphate.Diffusion coefficients for the first two salts are calculated on the assumptiom that the breaks in the curves may be taken as measuring the time which elapses before the concentration of the liquid bathing the electrode becomes zero and the numbers obtained agree satisfactorily with the known data. Curves obtained for alcoholic cuprous chloride solutions show two breaks one corresponding with the reduction of the small quantities of contained cupric salt the other to the deposition of copper from the cuyrous chloride; the latter process begins at 0.45 volt the electrodeGENERAL AND PHYSICAL CHEMISTRY.135 potential rising however gradually to 0~65-0*70 volt a t which it remains fairly constant. The curves for the electrode potential when nitrobenzene is under- going reduction in acid and alkaline solutions are also given. I n acid solution and with a platinum cathode the potential rises a t first then falls and again rises becoming finally stationary The retrogression appears to be due to temporary alteration in the nature of the electrode as a consequence of the electrolysis. With a copper cathode similar phenomena are observable but whilst the original electrode potential has a lower value (corresponding with less absorption of energy) the final stationary potential is higher than for the platinum cathode on account of the higher ' r over-voltage " necessary to liberate hydrogen.According to calculations made by the author the variations of electrode potential with current density observed by Haber (compare Abstr. 1900 i 281 ; RUSS Abstr. 1903 ii 631) cannot be explained as the result of concentration changes at the cathode. H. AX. D. Anodic P.D.-Current Curve for Hydrochloric Acid at Platinum Electrodes. ROBERT LUTHER and FRANCIS J. BRISLEE (Zeit. physikal. Chent. 1905 50 595-601. Compare Abstr. 1903 ii '708).- A reply to Bose's criticism (Abstr. 1904 ii 697). J. C. P. Electrical Conductivity of Ethereal Solutions of Phosphoric Acid. WLADIMIR A. YLOTNIKOFF (J. Buss Phys. Chenz. Xoc. 1904 3'7 1282-1 288).-Ethereal solutions of phosphoric acid possess consider- able conductivity. An aqueous 87 per cent.solution of the acid has only three times as great a conductivity as the ethereal solution of corresponding concentration ; a t higher concentrations the difference becomes still less. With diminution of the concentration the con- ductivity in ethereal solution falls much more rapidly than in aqueous solutions. A similar rapid fall in conductivity is observed on diluting other non-aqueous solutions and it remains an open question what concentration should be employed in estimating the dissociating power of a solvent. The molecular condiictivi ty diminishes continuously as the concentration diminishes. With rise of temperature the specific conductivity increases. The considerable development of heat occurring on dissolving phosphoric acid in ether and transforming the 90 per cent.solution to the crystalline condition at 25" may be an indirect indica- tion of the existence of a chemical compound of ether with phosphoric acid. T. H. P. Electrical Conductivity and other Properties of Sodium Hydroxide in Aqueous Solution as elucidating the Mechanism of Conduction. WILLIAM ROBERT BOUSFIELD and THOMAS M. LOWRY (Proc. Roy. Xoc. 1904 74 280-283).-The conductivity of sodium hydroxide solutions touched on in an earlier paper (Abstr. 1903 ii 52) has been further studied. The con- ductivity-temperature curve exhibits an inflection (see Zoc. c i t . ) bet ween 0' and 100" only in the case of solutions which are moderately dilute. The temperature of inflection varies regularly with the sodium136 ABSTRACTS OF CHEMICA4L PAPERS.hydroxide concentration from 48' for a normal (4 per cent.) solution t o 100' for a 30 per cent solution When the sodium hydroxide solutions are very dilute or concentrated no inflection occurs in the conductivity-temperature curve and there is a masked parallelism between the change of conductivity and the change of viscosity with temperature. The inflected conductivity-temperature curves can be represented by the equation Kt = KO + at + y(t - T)3 where I' is the temperature of inflection but the more general formula Kt/Ko= pulpo( 1 + bt)ne-at is applicable to conductivity-temperature curves of all kinds. With the help of this formula it is possible to make some approximation to resolving the two opposing influences (decay of ionisation and increase of ionic mobility with rising temperature) which determine the form of the conductivity-temperature curve.The conductivity-concentration curve for sodium hydroxide solutions a t 1s' is similar to that given by Kohlrausch. The maximum con- ductivity a t this temperature is 0,3490 (Kohlrausch's value = 0.3462) in a 15 per cent. solution. At higher temperatures the maximum conductivity is greater rising to 1.4 a t loo" and occurs in more con- centrated solutions. The densities of sodium hydroxide solutions of different concentra- tions have been very carefully determined the plan being to start from a large weighed quantity of sodium and to convert this quanti- tatively into the hydroxide. Eleven determinations made with six different standard solutions gave as the density of a 50 per cent.solution the value 1.5268 with an average error of O*OOOl. The other solutions the densities of which were t o be determined were prepared by diluting the strong standard solution. Such a density- concentration table having been drawn up it is possible to deduce the Concentration of any given sodium hydroxide solution more accurately from its density than from a titration of the solution. The variation of density with temperature becomes simpler in character as the concentration of the solution studied increases. Thus when the equation pt = po + at + Pt2 + yt3 is taken t o represent the influence of temperature on the density of water and aqueous sodium hydroxide solutions y vanishes when the concentration of 1 2 per cent.of alkali is reached and /3 vanishes a t 42 per cent. concentration. The viscosity of a 50 per cent. sodium hydroxide solution is about 70 times that of water. The influence of this factor on the ionic mobility may be to some extent eliminated by dealing with the ratio of molecular conductivity to fluidity. The molecular conductivity of sodium hydroxide solutions decreases with increasing concentration but the foregoing ratio termed the '' intrinsic conductivity," falls to a minimum a t about 8 per cent. sodium hydroxide and then rises attaining at 50 per cent. concentration a value considerably greater than that found for the most dilute solutions. This is associated with the fact that liquid caustic soda is an electrolyte and in con- centrated solutions the caustic soda probably conveys the current partly as such.The molecular volume of sodium hydroxide in dilute aqueous solution has a large negative value a litre of water dissolving 140 grams at O' 100 grams a t 18" or 60 grams at 50° without;GENERAL AND PHYSICAL CHEMISTRY. 137 increasing in volume. The molecular volume does not increase con- tinuously with rising tomperature but reaches a maximum a t about 70'. I n a 50 per cent. solution however the temperature has little effect on the molecular volume. J. C. P. Electrolysis with Alternating Currents. Passivity of Metals MAX LE BLANC (Zeit. Elektrochem. 1905 11 8-lo).- Remarks on papers by Brochet and Petit (this vol. ii 27) and by Sackur (Abstr. 1904 ii 802). T. E. Electrolysis with Alternating Current.CARLO Rossr (Chenz. Centr. 1905 i 61 ; from L'Indust. Chinz. 1904 6 333-335. Com- pare Le Blanc and Schick Abstr. 1904 ii 229).-Solutions of potassium chlorate acidified with sulphuric acid exhibit complicated phenomena when subjected to the action of an alternating current between copper or iron electrodes. The copper electrodes become coated with cuprous chloride copper dissolves and a bluish-green basic c hlorat e Cu( ClO,) 3 C u(OH)2 separates from the solution. When a direct current is used cuprous chloride is formed at the anode together with smaller quantities of basic chlorate and chloride ; the solution from which a complex mixture of cupric hydroxide cupric oxide copper and ctipric chloride separates out does not contain dissolved copper. It is supposed that the copper passes into solution at the anode as cuprous ion which reduces the chlorate cupric copper being then precipitated by the alkali formed a t the cathode.The non-reversibility of the change at the electrodes when alternating currents are used is probably due t o the rapid removal of the cuprous ions in this manner. When on the other hand the potassium chlorate is replaced by sodium chloride the alternating current dis- solves very little copper. With iron electrodes similar phenomena were observed. H. M. D. Determination of the Electrochemical Equivalent of Silver. G. VAN DIJK ( A T c ~ . N&erZand 1904 ii 9 447-525. Compare Abstr. 1904 ii 255).-The present paper gives detailed descriptions of the methods and apparatus employed in the determination of this constant the substance of the results having been already published (Zoc.cit.). An investigation into the influence of the form and manipulation of the voltameter on the value of the equivalent has also been made and the author considers that the value of the equivalent is best represented by 0.011180. T. A . H. Electrolytic Solution of Platinum. RUDOLF RUER (Zeit. EZektrochem. 1905 ii lO-l2).-The author considers that his theory of the dissolution of platinum by alternating currents (Absh. 1903 ii 407) gives a much more satisfactory explanation of the phenomena than that advanced by Brochet and Petit (this vol. ii 27 and 28). Several new experiments are described in which platinum anodes are polarised for a few seconds and then left exposed to a solution of sulphuric acid containing ferrous sulphate or sulphur dioxide for a few138 ABSTRACTS OF CHEMICAL PAPERS.seconds Considerable quantities of platinum are dissolved which would be quite inexplicable on the theory of Brochet and Petit but is quite in accordance with that of the author. T. E. Theory of Amphoteric Electrolytes. 11. JAMES WALKER (Proc. Roy. Xoc. 1904 74 271-28O).-The correction of a slight error in the calculations of the earlier paper (Abstr. 1904 ii 309) leads to a still better agreement between the theoretical and experimental values of the conductivity for the aminobenzoic acids. Formulx? are deduced connecting the concentrations of the various components in the solution of an amphoteric electrolyte which is largely ionised. From a consideration of these formulx? it appears that the non-ionised proportion is unaffected by a simultaneous change of l/ka kb and v in the same ratio [k = dissociation constant of the electrolyte as acid k b = dissociation constant of the electrolyte as base v = dilution].This result is of importance in dealing with any series of amphoteric electrolytes for which the product ka.kb is a constant. Here it may be shown that as ka diminishes and kb increases the total ionisation falls off rapidly a t first then more slowly until over a considerable range it is practically constant a t the minimum value actually reached when ka = kb. The further increase of kb and decrease of ka is accompanied by corresponding changes in the ionisation until finally the electrolyte under consideration acts really as a simple base.The author’s theory has been further tested with satisfactory results in the cases of cacodylic acid (see Johnston Abstr. 1904 i 984) and asparagine. From Winkelblech’s values of k and kb for asparagine (Abstr. 1901 ii 370) the molecular conductivity a t v = 16 is calculated in good agreement with an actual determination for which specially purified water and asparagine were employed. The acidic or basic ionisation of an amphoteric electrolyte increases the freezing point depression whereas the ‘‘ saline ” ionisation does not. I n conjunction with the conductivity the cryoscopic method should give useful results with soluble electrolytes which are largely ionised. J. C. P. Contact Ellectrification and Colloidal Solutions.JEAN PERRIN (J. Chim. phys. 1904 2 601-651).-The phenomenon of electric osmosis was first observed by Reuss and subsequently investigated by Wiedemann who showed that in a given liquid the loss byelectric osmosis across a diaphragm varies with the current is proportional to the cross section of the diaphragm and independent of its thickness. I n the case of capillary tubes Quincke showed that the transference is proportional to the square of the diameter and also showed that some substances exhibit osmosis in the reverse sense. Quincke sought to explain the phenomenon by the existence of a double electrified layer a t the walls. The t.angentia1 force of the field causes motion of the liquid layer and hence by friction of the inner mass of liquid also and Helmholtz proved that this explanation was in accord with the quantitative results.This explanation also holds for the E.M.F. of filtration and leads to the result that if a liquid filters under pressure across a given diaphragm the E.M.F. is proportional to the pressure and that this ratio dependsGENERAL AND PHYSICAL CHEMISTRY. 139 solely on the liquid being independent of the thickness of the diaphragm or of the diameter of its pores. From observations of either the electric osmosis or the E.M.F. of filtration determination may be made of the difference of potential between the liquids and walls. Similar reason- ing also explains the motion of small suspended solids in the opposite sense. I n the author’s own experiments although the diaphragm was varied and the field taken to 90 volts per cm.no osmosis was observed for chloroform ether petroleum benzene turpentine or carbon ciisulphide whilst with all diaphragms and in a field of 10 volts per cm. osmosis was readily found for water ethyl alcohol methyl alcohol acetone acetylacetone and nitrobenzene. He hence concludes that electric osmosis is only easy in the case of liquids of high specific in- ductive capacity that is f o r ionising liquids whilst low viscosity is also necessary. The influence of traces of dissolved electrolytes was then investigated and it was found thsit powdered carbon becomes positively charged in slightly acidified water and negatively in water ren- dered feebly alkaline. Similar results were obtained when anhydrous chromium chloride and other insoluble solicls were used in place of carbon.The results are sometimes masked by a slight solubility of the compounds employed but the results indicate the following general rule. The potential of any wall in an aqueous solution is always raised by the addition of a univalent acid to the solution and lowered by the addition of a univalent base. This influence is ascribed to the hydrogen and hydroxyl ions other univalent ions having comparatively little in- fluence. The great effect of these ions may possibly be due to a small diameter or sphere of molecular attraction. Polyvalent ions appear t o diminish the electrification the addition of sulphuric acid lowering the effect due t o hydrochloric or nitric acids. The result is still more marked with tervalent or quadrivalent acids.This action may occa- sionally be of service in indicating the existence of polyvalent ions in solution. It seems probable also that a study of the laws of cont.act electrification may provide a means for evading or inducing the dragging down of soluble matter by precipitates. L M. J. Recent Investigations bearing on the Theory of Electrolytic Disaociation. LOUIS KAHLENBERG (Tmns. Paraday Soc. 1905 I 42-53).-Experimental observations made by the author in connec- tion with the properties of aqueous and non-aqueous solutions are summarised. Their bearing on the theory of solution and of electro- lytic dissociation is discussed and the conclusion is drawn that these theories are untenable. No general agreement between the values of electrolytic dissociation as calculated from the conductivity and from the vapour pressure boiling point or freezing point has ever been established.Whereas Arrhenius’s theory requires that the molecular conductivity shall always increase with dilution cases are known where it diminishes or remains practically constant. The Nernst-Thomson rule which ascribes the cause of dissociation to the high specific inductive capacity of the solvent is not confirmed by later experiments. The additive properties of solutions of electrolytes which are140 ABSTRACTS OF CHEMICAL PAPERS. frequently regarded as evidence in favour of the dissociation theorg really form no argument for in the case of pure liquids additive relationships are known to exist for example in the case of molecular volume and of molecular refractive power.The theory refers the colours of solutions say of copper nickel and cobalt salts to the ions but non-conducting benzene solutions of the oleates of these metals are also blue green and red respectively and the red cobalt solution turns blue on heating just like the aqueous solutions. Instantaneous reactions cannot be ascribed to ions for non-conduct- ing benzene solutions of hydrochloric acid and of copper oleate precipitate copper chloride practically instantaneously. The behaviour of acids towards metals in non-aqueous solutions is not in accord witb the assumption that the substances owe their char- acteristic properties to hydrogen ions for non-conducting solutions of trichloroacetic acid in allylthiocarbimide attack dry magnesium rapidly and decompose the dry alkali carbonates. Thermal data offer difficulties also and the fact that Ostwald’s dilution law holds good for certain organic acids in aqueous solutions is not of general significance.The essential electrolytes do not fit in with the law of mass action in aqueous solution and in non-aqueous solvents it has yet to be shown that the mass action law is applicable. These and other facts lead the author to conclude that Arrhenius’s dissociation theory is useless and misleading. An acceptable theory of solution must not differentiate between the processes of solution and chemical action. A careful consideration of facts shows that these are “identical in character and chemical compounds are merely the cleavage pieces of solutions placed under special stress or duress represented by the so-called purifying pro- cesses.” The process of solution thus represents the general case of interaction of substances union resiilting when the specific attraction between them is under the existing conditions sufficieut to cause a fusion or blending of their masses.I n the further investigation of solutions the most concentrated should receive first consideration the dilute solutions only appearing as limiting cases. By means of vapour pressure freezing point and conductivity measurements carried out systematically on these lines it should be possible to elaborate a theory of solutions on the basis of chemical affinity acting between solvent and solute. H. M. D. Ionisation in Flames Pmnm MASSOULIER (Conzpt.Tend. 1905 140 234-236).-Using the flame of burning ether instead of coal gas the author has measured the conductivity of a flame by Townsend’s method (compare Abstr. 1901 ii 221) at a lower temperature than that employed by Wilson (Abstr. 1899 ii 722) or Moreau (Abstr. 1903 ii 125 196) and finds contrary to the experience of these investigators that the electrodes play only a secondary part in the ex- periment. Experiments are in progress to determine if the ionisation which is the cause of the conductivity of the flame is of chemical origin or merely due to the dissociation of the molecules at the high tempera. ture. M. A. W.GEKERAL AND PHYSICAL CHEMISTRY. I41 The Ions of the Atmosphere. P. LANGEVIN (Compt. rend. 1905 140 232-234).-The author has extended his investigations on ionised gases (compare Abstr.1902 ii 301 ; 1903 ii 263 587) to the ions in the atmosphere a t the top of the Eiffel Tower and finds that in addition to the ordinary ions having a mobility of 1.5 cni. for one volt per centimetre there are others having a mobility several thousand times smaller and of the same order as those observed by Townsend in freshly prepared gases (Abstr. 1901 ii 221) and by Bloch in the ions of phosphorus (Abstr. 1903 ii 206 ; 1904 ii 117 ; this vol. ii 72) ; but the electric charge of the latter ions is fifty times as great as that of the ordinary ions. M. A. W. Registration of the Ions in the Atmosphere. P. LANGEvrx and M. MOULIN (Compt. rend. 1905 140 305-307).-An arrange- ment for the automatic registration of the ionic condition of the atmosphere is described.By means of a small water turbine or electro-motor a current of air is made to pass through a cylindrical condenser charged to constant potential an electrode within the cylinder being connected with one of the quadrant pairs of a Curie electrometer. The air then passes through a meter or anemometer which sets in action a clockwork mechanism a t intervals correspond- ing with the passage of a definite volume of air through the apparatus. For a description of the mechanical arrangements by means of which this apparatus makes i t possible to have the concentration of both positive and negative ions recorded automatically two or three times per hour the original must be consulted. H. M. D. Cause of tho Ionisation of Air in Contact with Phosphorus.EDGAR MEYER and EXKST MULLER (Chew,. Cent?.. 1905 i 61-62; from Ve&. Deut. Phys. Ges. 1904 2 332-336).-The object of these experiments was to determine whether the ionisation of the air in contact with oxidising phosphorus is due to the light emitted in the process or to the oxidation itself. I n presence of substances such as chlorine ether and turpentine which inhibit the glowing of phosphorus there is no oxidation and no ionisation so that these experiments furnish no information. If phosphorus is allowed t o oxidise in thin. walled quartz vessels which are transparent to ultra-violet radiation no ionisation of the air can be detected. Examination of the spectrum of the radiation emitted by phosphorus undergoing oxidation shows it to be free from ultra-violet rays.The ozone produced in the oxidation cannot be the cause of the enormous conductivity imparted to the a i r ; after removal of the ozone the air retains its conducting power. H. 31. D. High Temperature Measurements. THOMAS GRAY ( J . SOC. Chem. Ind. 1904 24 1192-1197).-The author gives a description of his own experience with various types of pyrometer. The calorimetric method using an iron cylinder gives results which are usually within 10' of the truth at temperatures not exceeding about 1000°. Several forms of direct reading and registering thermo-electric142 ABSTRACTS OF CHEMICAL PAPERS. pyrometers are described ; calibration is most conveniently and accu- rately effected by direct comparison with a standard conple the E.fi.B'. being measured by means of a potentiometer but it may also he carried out by means of the boiling point of sulphur the melting point of sodium carbonate ( 8 5 2 O ) and that of potassium sulphate (1066").Convenient methods of working are described together with the precautions needed to ensure accuracy. The platinum resistance thermometer is more sensitive and accurate than the thernio-e!enient but it is more easily damaged by contact with furnace gases if its protecting porcelain tube breaks and it is more difficult to repair and restandardise. The Wanner optical pyrometer is described the light from the hot substance and the light from a small incandescent lamp pass through the same train of prisms (only the red rays being used for comparison) and then through a Nicol prism.By means of a double prism and lens of special construction the extraordinary ray corresponding with the one source of light and the ordinary ray corresponding with the other are focussed together on a slit in the eye-piece; they are there- fore polarisen a t right angles to each other and the rotation of a Nicol prism in the :eye-piece makes i t possible to:diminish the brightness of one and increase that of the other until they appear of equal brightness. The temperature is then obtained from the amount of rotation required. The great advantage of a pyrometer of this form is that no part of it is exposed to the high temperature and therefore the frequent repairs and restandardisations needed with other pyrometers are avoided.T. E. New Laboratory Burners and their Adaptation to the Pro- duction of High Temperatures. GEORGES N~KER (Bull. Soc. chirn. 1905 [ iii] 33 210-215).-The burners are of the usual air-gas type but the gas enters the chimney through an injector of special form and the chimney is capped by a network of partitions of square section. This network presents a large cooling surface and so diminishes the tendency to '' strike back." At the same time it breaks up the air-gas stream pToducing a large number of small jets which unite above to form an intensely hot homogeneous flame. A labora- tory burner of this type in action is figured in the original which also gives particulars of the temperatures obtainable with these burners working under different conditions.T. A. H. New Regulator for Thermostats. OCTAVE DONY-HBNAULT (Zeit. Elektrochem. 1905 11 3-5).-1n the well-known Ostwald form of regulator toluene cannot be used in the bulb which is placed in the thermostat because it creeps between mercury and glass and so causes a constant rise of temperature. This is avoided by making the part of the regulator which is outside the bath in the form of a double U-tube connecting the toluene bulb to the top of the middle bend and placing a layer of salt solution between it and the mercury. When the temperature of the air is constaiit the temperature of the thermostat varies less than O.O0lo ; the influence of fluctuations of the external temperature is diminished by making the volume of theGENERAL BND PHYSICAL CHEMISTRY.143 external tubes small in comparison with that of the immersed toluene bulb. T. E. Vaporisation of Solid Substances at the Ordinary Tempera- ture. CONSTANTIN ZEKGELIS (Zeit. physikal. Chern. 1904 50 219-224).-When silver leaf is suspended over a layer of a metallic oxide in a closed vessel the leaf after a longer or shorter interval begins to assume a yellow colour and traces of the metal originally present in the oxide may be detected in the silver. I n some cases the increase in weight of the silver can be determined. The oxides found to act in this way were those of copper zinc iron chromium manganese lead cobalt uranium molybdenum arsenic and antimony. The action is favoured by partial exhaustion of the containing vessel by the presence of moisture and of a reducing substance such RS hydrogen o r alcohol vapour.Comparative experiments with nickel copper and aluminium foil led to negative results but gold leaf exposed t o zinc oxide for six months mas found to contain a trace of zinc. Other substances which melt only a t a high temperature may be similarly shown to vaporise a t the ordinary temperature; for example sulphur selenium lead copper red phosphorus tin anti- mony and arsenic sulphides iron copper and chromium hydroxides copper carbonate zinc chloride and lead iodide. That such substances vaporise may be shown also by other methods thus if a watch-glass coiitaining potassium ferrocyanide solution is kept along with copper or copper oxide in a closed vessel the ferrocyanide gradually turns to a brownish-red colour.J. C. P. Molecular Weight Determination by the Rise of the Boiling Point in Cathode Ray Vacuum FRIEDRICH KRAFFT and PAUL LF-HMANN (Bey. 1905 38 242-253. Compare Abstr. 1896 ii 89 464 635 ; 1899 ii 464).-In previous papers it mas established that the boiling point of high molecular liquids in the vacuum of the cathode light depended on the height of the vapour column above the liquid and also on the molecular weight of the substance. A number of improvements have been introduced into the apparatus for which the original should be consulted among the most important being an arrangement allowing the thermometer to be moved so that the temperature a t any position from immersion in the liquid to the very top of the column of vapour can be read at will. The work performed by each layer of vapour in raising up that over it causes an absorption of heat so that in the case of mercury the temperature falls from 174' in the liquid to 152' a t the top of the column of vapour 195 mm.high ; a difference of 22'. The difference of these two temperatures has been determined for various substances in the case of pnlmitic and lauric acids and mercury the differences observed namely 28.4' 2 2 - 2 O and 2 2 O respectively are exactly proportional to the molecular weights. This relationship has been satisfactorily tested for a number of substances. The method has been extended to the metals the experiments being carried out in quartz vessels Cadmium showed a fall of 5' f o r a144 ABSTRACTS OF CHEMICAL PAPERS. column of 80 mm. of vapour zinc a fall of 3' and lead one of 2-3' these figures being in agreement with their molecular weights.E. F. A. Lowest Temperature of Evaporation of Metals in the Vacuum of the Cathode Light. FRIEDRICH KRAFFT and LUDWIG BERGFELD (Bey. 1905,38 254 -262. Compare Demargay Compt. rend. 1882 95 183).-Attention has been paid to the accurate determina- tion of the temperature a t which metals heated in the vacuum of the cathode light first begin t o evaporate. The experiments were per- formed in a horizontal tube 25 em. long connected a t one end to the pump and cooled receiver whilst the other was surrounded by a mantle in which the heating fluid was circulated; in some cases a quartz tube was employed. I n this way the temperature of evaporation of cadmium was determined to be at 156-5' silver a t 680' and similarly for a number of metals.For the details the original should be con- sulted. E. F. A Boiling Point in Vacuum ; a New Constant and its Mean- ing FRIEDRICH KRAFFT (Ber. 1905 38 262-266. Compare pre- ceding abstracts).-It is pointed out that mercury begins to evaporate a t about - 40' boils in vacuum a t 155' and under the ordinary pressure a t 357'. The interval (195') between the commencement of evaporation and the point a t which the substance boils in vacuum during which work is done in overcoming gravity is approximately equal to that (202') between the boiling point in vacuum and a t the ordinary pressure during which work is done in overcoming the pressure of the atmo- sphere. The same relationship holds for all the metals experimented with; as a general rule as much heat is required starting from the beginning of evaporation to overcome the resistance of gravity as is further required to overcome the pressure of the atmosphere or in other words gravity and atmospheric pressure are equivalent.The results are summarised as follows column I giving the tempera- ture at which evaporation begins in the vacuum column 111 the boil- ing point in the vacuum and column V the boiling point under 760 mm. pressure. I. Diff. 111. Diff. v. Mercury ............ - 40" 195" 155" 202 357" Cadmium ......... 156 294 450 299 749 Ziac ................. 184 366 550 37 0 920 Potassium ......... 63 302 365 302 667 Sodium ............ 98 320 41 8 324 742 Bismuth ...........270 723 993 707 1700 Silver ............... 680 680 1360 680 2040 E. F. A. Conductivity of Nitrogen Dioxide for Heat. C. FELICIANI (Chem. Centr. 1905 i 331 ; from Physikal. Zeit. 1905 6 20-22).- The conductivity of nitrogen dioxide was examined by the method of cooling at different pressures and temperatures (18' to 131'). Allow- ance being made for convection there is an increase in the con-GENERAL AND PHYSICAL CHEMISTRY. 145 ductivity at all pressures a t 65" followed by a decrease to a minimum and a second increase between 120" and 130". The conductivity increases with the pressure and the conductivity and dissociation curves follow similar courses. Up to 90' and for pres- sures of not less than 60 mm. the conductivity of nitrogen dioxide is larger than that of any non-dissociating gas examined previously Magnanini's numbers used by Nernst (Boltxmanr~ Festschrzyt 1904),are not quite trustworthy.The value for the conductivity of a mixture of NO and N,O cannot be taken as equal to that of CO the author obtaining somewhat higher values than those calculated by Nernst. G. D. L. Heats of Combustion of Atoms and Molecules. LAWRENCE J. HENDERSON (J. PhysicaE Chem. 1905,9 40-56).-F'rom considera- tion of the values of the heats of combustion of a number of substances the author shows that the same substitution affects the heat of com- bustion to different extents. Thus the substitution of -OH for *H diminishes the heat of combustion by 40 csls. when it converts a paraffin hydrocarbon into a primary alcohol but by 72 cals.when it converts an aldehyde into an acid. These values .are not however absolutely constant but the differences vary in a regular way and the author considers that every atom of a molecule in a degree dependent upon its position influences the heat of combustion of every other atom of the molecule whether or not it is united to that atom. L. M. J. Depression of the Freezing Point in Dilute Solutions of Highly Dissociated Electrolytes HANS JAHN (Zeit. physikal. Clmn. 1904 50 129-168. Compare Abstr. 1900 ii 707; 1901 ii 491 592).-With an apparatus similar to that used by Hausrath (Abstr. 1903 ii 61) the author has very carefully determined the freezing points of dilute solutions of lithium sodium potassium and czsium chlorides sodium and potassium bromides. Lithium chloride is peculiar in that the molecular depression exhibits a minimum whildt in all the other cases the molecular depression increases regularly as the concentration decreases.A the freezing point depression and A! the number of gram equivalents of salt in 1000 grams of water are connected by the following equations which give numbers in very good agreement with experiment N having values from 0.1 downwards (1) for potassium chloride A = 35605N- 0*98196N2 ; (2) for sodium chloride A = 3.5582N- 0*87452N2 ; (3) for lithium chloride A = 3-6116N- 0*8857:V2. The values for the ionic concentration (wJ deduced from the freezing point depression agree very well with those deduced from the conductivity in the cases of sodium and potassium chlorides ; for lithium chloride the conductivity method gives smaller values for czsium chloride and potassium bromide greater values of nl than the freezing point method.Even sodium and potassiuin chlorides however are very far from following the formula nl?/(N- nl) = const. and the author concludes that the values of m based on the validity of the siinple solution laws are wrong. He further contends that the accepted values of pcx are probably too high on account of hydrolysis VOL. LXXXVIII. ii. 11146 ABSTRACTS OF CHEMICAL PAPERS. in very dilute solutions and the impurities of the water and the glass of the containing vessel. If 106.85 is taken as the value of pm for sodium chloride instead of the usual 108.1 the dissociation equation given above is applicable in dilute solutions and the constant = about 0 160.A similar value is found independent of the dilution when m is deduced from the aathor's expanded formula for the freezing pointldepression (see Abstr. 1902 ii 597). The B.M.F. of sodium chloride concentration cells may be calculated with the aid of the fore- going constant and the values so found are in good agreement with experiment. Similar remarks apply to the other electrolytes studied. The attempt made in this paper to reconcile the dissociation theory with the laws of thermodynamics in the case of highly dissociated electrolytes leads further to the conclusion that the ionic mobility must increase with increasing concentration of the solution. It is necessary also to regard Arrhenius' formula a = p/pm as valid only in very dilute solutions.Specific Volume as the Determining Criterion of Chemical Combination in Metal Alloys. 11. E. MAEY (Zeit. physikal. Chem. 1904 50 200-218. Compare abstr. 1901 ii 633).-1n the case of alloys where there is no chemical combination the specific volume can be calculated by the mixture formula to within 1 per cent. of its true value. A greater deviation than this is due generally to the formation of a compound or sometimes if less marked to that of solid solutions only. The specific gravity of a large number of alloys of different composition has been determined and from the break in the curve obtained by plotting specific volume against composition it appears that in eight out of the thirteen binary alloys investigated chemical combination of the component metals takes place.The compounds thus indicated are Sb3Zn2 Sb,Cd SbAg SbCu AgZn4 AgCd or AgCd CuCd AgHg. The existence of several of these has been indicated by other methods (compare for example Hersch- kowitsch Abstr. 1898 ii 582 ; Heycock and Neville Abstr. 1897 ii 245) but the exact formula adopted differs in some cases. With the combinations Zn-Hg Cd-Hg Cd-Zn Bi-Zn and Pb-Zn there was no certain indication of the existence of a compound. Stress is laid on the treatment of the specific volume and not the specific gravity as an additive property. Vapour Pressure by Air-bubbling. EDGAR P. PERMIAN (J. P?AysicaZ Chem. 1905 9 36-39).-Doubts regarding the accuracy of the method of air-bubbling for the determination of vapour pressure have been raised by Carveth and Fowler (Abstr.1904 ii 541). The tuthor defends the method and quotes results obtained previously by himself t o show that with sufficient care accuracy is obtainable a t any rate in the case of water as solvent. He further raises objections to the methods employed by Carveth and Fowler in their experiments (compare Trans. 1903 83 1168). 111. GIUSEPPE BRUNI and B. SALA (G'uxxetta 1904 34 ii 479-485. Com- pare Bruni and Berti Abstr. 1900 ii 591 and 592).-Determinations of J. C. P. J. C. P. L. 111. J. Dissociation of Nitro-derivatives in Certain Solvents.GENERAL AND PHYSICAL CHEMISTRY. 147 the elevations of the boiling points of solutions of naphthalene diphenyl dibenzyl and trichlorobenzene in acetonitrile give the mean value 17.3 for the molecular elevation of the boiling point of this solvent.The number given by Kahlenberg (Abstr. 1902 ii 310) namely 14.39 is hence low. I n boiling acetonitrile picric acid picryl chloride [ 1 3 5-tri nitro-2-chlorobenzene] 2 4 6-trinitrotoluene trinitro-p-xylene and dinitromesitylene all undergo a considerable amount of dissociation whilst bromodinitromesitylene exhibits normal ebullioscopic relations. The behaviour of the last-named compound in which the hydrogen atoms of the benzene nucleus are all substituted is in accord with that of trinitromesitylene in formic acid solution (Bruni and Berti Zoc. cit.). I n methyl-alcoholic solution picryl chloride trinitro-p-xylene and dinitromesitylene all undergo dissociation. I n boiling ethyl alcohol or acetone however picryl chloride gives perfectly normal molecular weights.The theory put forward by V. Meyer (Abstr. 1896 i 419) to explain the dissociation of nitro-compounds supposes that under the electro-negative action of the nitro-groups one of the hydrogen atoms of the aromatic nucleus becomes capable of dissociation without the intermediate formation of isonitro-groups. To ascertain whether other electro-negative groups exert a similar influence to that of the nitro-group the author has determined the molecular weight of s-trichlorobenzene in boiling acetonitrile and methyl alcohol. The numbers obtained are quite normal showing that the power of exciting dissociation is a specific property of the nitro-group and not a general one of all electro-negative groups. J. C. GRAHAM (Zeit.physikal. Chenz. 1904 50 257-272).-Yertical columns of salt solution and pure water of the same section are brought together so that there is no initial mixing at the common surface. After some time the salt concentration at various levels both above and below the common surface is determined. The author takes Fourier’s series as the groundwork of his computations and concludes from his experiments that the diffusion of salts follows the same laws as the conduction of heat. The diffusion constant for each salt is independent of the density of the solution and of the time during which diffusion has taken place. The salts employed in the author’s experiments were the chlorides of sodium potassium ammonium zinc and manganese the nitrates and carbonates of sodium and potassium and ammonium sulphate. The results obtained indicate no evident connection between the value of the diffusion constant and the molecular weight.When sodium and potassium chlorides and sodium and potassium nitrates are allowed to aiffuse in dilute hydrochloric acid and dilute nitric acid respectively instead of in pure water slightly higher values are obtained for the diffusion constant. T. H. P. Diffusion of Salts in Solution. J. C. P. Diffusion of Electrolytes in Water. L. WJLLIAN HOLM (Zeit. physikal. Chem. 1904 50 309-349).-The electrolytes studied were 11-2148 ABSTRACTS OF CHEMICAL PAPERS. the chlorides of lithium sodium and potassium the hydroxides of sodium and potassium potassium iodide and hydrochloric and acetic acids. I n all cases there was found a certain concentration below which the diffwion-coefficient increases as the solutions become more dilute.From the same point the coefficient increases also with increasing concentration and consequently exhibits a minimum provided that the formation of complex molecules a t higher concentrations does not mask the true variation of the diff usion-coefficient. The concentration a t which the minimum occurs is different for different electrolytes. The temperature-coefficient of the diffusion constant varies also with the electrolyte studied and is equal to the sum of the temperature- coefficients of the osmotic pressure and the electric conductivity. The author’s experiments are in harmony with Nernst’s theory dealing with the calculation of diff usion-coefficients at infinite dilution (Zeit. physikal.Chem. 1888 2 613) and with Arrhenius’ views on the variation of the diff usion-coefficient with the dilution (Abstr. 1892 1265). It is shown that the internal friction of the molecule is somewhat less than the sum of the corresponding quantities for the ions. J. C. P. Verification of a Recent Equation of Van der Waals. JOHANNES J. VAN LAAR (Arch. Nierlalzd 1904 [ ii] 9 389-417. Com- pare Van der Waals Abstr. 1901 ii 644).-1. Varicbtion of b ilz the Case of Hydrogen.-Van der Waals has asserted (loc. cit.) that in the case of a diatomic gas the relationship ( b + b,)/(v - b) = 1 - [(b - 6,)/(6 - 6,)]2 holds where b is the least value of b (reached when the atoms are in contact) and b,-its greatest value (obtained when the volume of the gas is infinitely great). Comparing the values of b calculated from this relationship with those deduced directly from Amagat’s results it is found that the two values only become concordant for pressures above 300 atmospheres a t O” above 400 atmospheres at loo” and above 250 atmospheres a t 200’.Further the critical constants calculated on the assumption that the values of b and 6 are independent of the temperature as is implied by Van der Waals’s hypothesis that the value of a is directly proportional to the absolute temperature are not in good agreement with those determined experimentally in particular there is lack of concordance in the calculated and observed critical volumes. From his results the author draws the conclusion that (6 - b,)2 is proportional to the absolute temperature 6 being constant and 6 variable while a is independent of temperature.11. Specific Heats of Liquids at Low Temperatures.-It is shown that specific heats a t constant volume calculated from the relation Cu = RT[B/T- l / ( w - b)(db/dT) + l / ( b - b,)(d{b - bo)/dT)8] on the as- sumption that 6 - 6 = J y T (see above) are in good agreement with those determired experimentally. The concordance of the calculated and observed results for liquids affords a further proof that the varia- tion in vaiue of (hl - b,) with temperature is due to change in b b remaining constant.GENERAL ANT) PHYSICAL CHEMISTRY. 149 I t is pointed out that for many diatoniic and for some inore com- plex substances the quotient of melting point by critical temperature both being expressed on the absolute scale is approximately 0.5.T. A. H Validity of the Law of Corresponding States for Mixtures of Methyl Chloride and Carbon Dioxide. H KAMERLINGH ONNES and C. ZAKRZEWSICI (Proc. K. Akncl. Vetensch. dmste~dccm 1904 7 385-290 ancl 377-382. Compare Abstr. 1904 ii S07).-From a study of the conditions of coexistence it appears that for mixtures of methyl chloride and carbon dioxide there are deviations from the law of corresponding states which become very marked for liquid densities and low temperatures. More Exact Equation of Condition for Gases. 111. J. B. GOEBEL (Zeit. physikaZ. Chem. 1904,50 238-240).-A supplementary note to earlier papers (see Abatr. 1904 ii 311 706). Kinetic8 of the Nitration Reaction.HAAVARD MARTINSEN (Zeit. physilal. Ciie~n. 1904 50 385-435).-The nitration of nitrobenzene to m-dinitrobenzene in concentrated sulphuric acid solution is shown by experiments a t Oo and 35" to be a reaction of the second order although the velocity-coefficient a t 0' falls off slightly with the time probably because part of the nitrobenzene undergoes sulphonation during the long time required for the experiments at the lower tem- perature. The velocity of nitration is more than trebled for a rise of 10". The velocity varies also with the strength of the sulphuric acid used as medium ancl reaches a maximum when the molecular ratio of sulphuric acid to water is about 1.0 0.7. The course of the change was followed by taking portions of the reaction mixture from time to time and either extracting the nitro-compound with ether and determining the amount of stannous chloride oxiclised by it or estimat- ing the amount of unconsumed nitric acid in a nitrometer.The nitration of 2 4-dinitrotoluene or of 0- wi- and p-nitrobenzoic acids follows the course of a bimolecular reaction. The introduction of a methyl group in the nitrobenzene molecule increases the velocity of nitration. A carboxyl group has the opposite effect but the extent of its influence depends on its position and is lessened by converting the acid into ester. The introduction of a nitro-group diminishes the rate of nitration to a greater extent than the introduction of a carboxyl group. When p-nitroaniline is nitrated two nitro-groups are intro- duced a t nearly*the same rate and the reaction results in the forma- tion of picramide. The rate of nitration of a-nitronaphthalene is greater than that of nitrobenzene. The nitration of phenol in aqueous solution is a complicated auto- catalytic reaction the velocity increasing with increasing acid concen- tration but decreasing with increasing phenol concentration.The velocity of nitration is increased markedly by the addition of potassium nitrate or sulphuric acid to a less extent by the addition of sodium and strontium nitrates. Nitrous acid acts as a catalytic agent and the autocatalytic character of the reaction is to be attributed to the production of this substance during the nitration process ; the rate of J. C. P. J. C. P.150 ABSTRACTS OF CHEMXCAL PAPERS.nitration and the rate of production of nitrous acid run parallel and when the production of nitrous acid is pievented no nitration takes place at l a s t when the nitric acid concentration is not too great. Nitrosophenol increases the velocity of nitration but its effect is almost independent of its concentration. The nitration of pcresol is very similar to that of phenol. J. C. P. Chemical Kinetics of the Benzoin Synthesis (Catalysis by Clyanide Ions). ERNST STERN (.&it. physikd. Chem. 1905 60 513-559. Compare Lapworth Trans. 1903 83 995).-The gradual conversion of benzaldehyde in to benzoin in aqueous alcoholic solution under the influence of potassium cyanide may.be followed by taking samples of the reaction mixture from time to time and estimating their reducing power with Fehling’s solution.The change for the first half of its course at least and within certain concentration limits is regular and follows the course of a bimolecular reaction. The rate of change is further proportional to the concentration of the potassium cyanide and a similar statement applies when other ionised cyanides are used ; when however the -CN group is in a complex it is without influence. It thus appears that the reaction is one in which the catalytic agent is the cyanide ion. Free hydrocyanic acid and free alkali are without catalytic eff ect although in certain circumstances they may give rise to secondary reactions. When the percentage of water in the aqueous alcohol is raised the rate of change increases. The variation of the reaction velocity with temperature is in accordance with the usual law.The influence of benzaldehyde on the conductivity of an aqueous alcoholic solution of potassium cyanide is inappreciable at higher temperatures but is considerable a t Oo and the experiments made in this connection indicate a reversible interaction between benzaldehyde and potassium cyanide. The various theories of the benzoin synthesis that have been advanced are discussed and those which refer the synthesis solely or chiefly to the presence of alkali or hydrocyanic acid are regarded as discounted by the author’s ex- periment 9. J. C. P. Mechanism of Ether Formation from Alkyl Haloid (or Halogen Dinitrobenxene) and Sodium Alkyloxide. C. A. ~ B R Y DE BBUYN and S. TIJMSTRA (Zeit. physikccl.Chem. 1904 50 436-442. Compare Hecht Conrad and Hriickner Abstr. 1889 931 ; 1890 4 327 1046; de Bruyn and Steger Abstr. 1899 i 744 745; Nef Abstr. 1900 i 4 ; Luloffs Abstr. 1902 i 87 ; Burke and ,Doman Trans 1904 85 555).-To explain the peculiarities in the rate of formation of ethers as observed and discussed by the above-mentioned investigators the authors suppose that the alkyl haloid is dissociated to a alight extent This would account for the influence of added sodium haloid in lessening the rate of change. The fact that a velocity constant is obtained at all in spite of the sodium haloid produced during the change might be attributed to the formation of a compound between the ether and the sodium haloid but some experiments made by the authors are unfavourable to this explanation.The reactionGENERAL AND PHYSICAL CHEMISTRY. 151 mixture becomes more dilute with respect to alkyl haloid as the change proceeds and possibly the consequent increase of dissociation of the alkyl haloid is exactly neutralised by the effect of the sodium haloid produced. J. C. P. Periodic Contact Catalysis. 11. GEORG BREDIG and E. WILKE (Chem. Centr. 1905 i 64 ; from Verh. Heidelberg Natuy-hist. med. Ver. 1904,[N.F.],8,165-181. Compare Bredigand Weinmayr 1903,ii 279). -In strongly alkaline solution hydrogen peroxide is rapidly and continuously decomposed in contact with mercury which acts cntalyt i- cally. In acid solution the mercury is slowly oxidised whilst in feebly alkaline solution the action is of periodic character and oxygen is intermittently evolved.The best results are obtained when the con- centration of the alkali is to gram-mols. per litre. The rate of intermittence increases during an experiment ; it diminishes with fall of temperature whilst rise of temperature beyond a certain limit causes the action to become aperiodic. The periodicity is also affected by pressure and by light. When the mercury surfaceis made a n anode or a cathode in contact with alkaline hydrogen peroxide solut.ion the periodic phenomena are still observable. The quantity of alkali necessary for the effect varies with the potential of the mercury. The effect is diminished by extremely small quantities of alkali chloride (l/25000-1/50000 mols. per litre) probably in consequence of the formation of a thin layer of mercurous chloride.Nitrates are without action ; sulphates diminish the pulsation when added in larger quantity. The character of the pulsations has been studied in a similar manner to that adopted in Ostwald’s experiments on the solution of chromium in acids. The regular curves obtained indicate a slow continuous change during the active period and a rapid fall when the maximum has been reached. The form of these curves is altered when any foreign substance is added to the solution. The addition of colloids causes the apices of the curves to assume a much more pointed character. The action of the colloids probably consists in altering the rate of formation and the stability of the oxide layer on which the periodic phenomena depend. H. M. D. Influence of Metals on the Hydrolysis of Sucrose.RUDOLF VONDRGEK (Zeit. physikal. Clzem. 1905,50 560-566).-The influence of platinum in compact form on the rate of inversion of sucrose is very slight (see also Kafman and Sulc Abstr. 1897 ii 136; Lindet Abstr. 1904 i 293 ; PlzBk and Husek ibid. ii 391). Fresh platinum black however has a marked accelerating effect but the author has observed that a sample of platinum black once used to induce inversion is without effect on a second sucrose solution. Dry- ing a t 150° restores its activity (compare Purgotti and Zanichellr Abstr. 1904 ii 329) which is therefore probably due to the presence of oxygen. When a sucrose solution is heated for a short time with platinum black and then filtered the inversion proceeds according to the formula for a unimolecular reaction the inverting agent being the oxidation products of the sugar.Indeed evidence of the presence of152 ABSTRACTS OF CHEMlCAL PAPERS. H e ions in a sucrose solution treated with platinum black can be deduced from measurements of tho conductivity. J. C. P. Solubility of some Sparingly Soluble Salts in Water at 18'. FRIEDRJCH KOHLRAUSCH (Zeit. physikal. Chena. 1904 50 355- 356. Compare Abstr. 1903 ii 528).-Vnlues for tho solubility deduced from the conductivity of the saturated solutions are here recorded for a num- ber of sparingly soluble salts. The list has been prepared for the new edition of Landolt and Bornstein and is almost complete although some points still remain to be examined such as the influence of temperature on the solubility.The temperature for which the present numbers are valid is 18' except in the cases of silver bromide and iodide where the temperature is 2 1 O . I n the following list the first number after the name of the substance is the specific conductivity of the saturated solution the second in brackets is the weight in milli- grams of the substance per litre of the saturated solution barium fluoride 1530 (1630) ; strontium fluoride 172 (117) ; calcium fluoride 40 (16); magnesium fluoride 224 (76); lead fluoride 431 (640) ; silver chloride 1-35 (1.6) ; silver bromide 0.075 (0.107) ; silver iodide 0.002 (0.0035) ; thallium chloride 1514 (3040) ; thal- lium bromide 192 (420) ; thallium iodide 22.3 (56) ; mercurous chloride 1.2 (2); mercuric iodide 0.2 (0.4) ; silver iodate 11.9 (40) ; lead iodate 6.2 (19) ; Barium sulphate 2.4 (2.3) ; strontium sulphate 127 (114) ; gypsum 1885 (2040) ; lead.sulphate 32.4 (41); barium chromate 3.2 (3.8) ; silver chromate 18.5 (25) ; lead chromate 0.1 (0.2) ; barium oxalate (BaC20,,2H,O) 78.3 (86) ; strontium oxalate (SrC,O,) 54 (46) ; calcium oxalate (CaC,O,,H,O) 9.6 (5.6) ; magnesium oxalate (MgC,0,,2H20) 200 (300) ; zinc oxalate (ZnC20,,2H,0) 8 (6.4) ; cadmium oxalate (CdC,0,,3€120) 27 (33); silver oxalate (Ag,C20,) 25.5 (35); lead oxalate (PbC,O,) 1.3 (1 -5). In some of the foregoing numbers the last number is uncertain. J. C. P. Molecular Attraction (3). J . E. MILLS (2 Physiccd Chem. 1904 8 593-636).-1n the two previous papers (Abstr. 1903 ii 596 ; 1904 ii 642) the equation L - E = k( ug- IF) was applied to 21 different substances employing values for L calculated from dp/dT the latter ratio being obtained not from vapour pressure observations themselves but from these results smoothed by Biot's formula.The constant 6 of the equation p = b2'+ cc proposed by Kamsay and Young is a dP/dY' and a t the critical temperature is identical with the dP/dt of the thermodynamical equation. It was found that by use of b instead of the Biot dP/dl'better agreement was obtained a t the critical temperature in those cases where the accord had previously been unsatisfactory. It was also found that in the cases where divergencies in the values of the constant occur irregularities also occur in the curve representing PV against temperature. The author gives a number of curves for L - E against Jd- YB which indicate very clearly the agreements of the constants.Three equations are nowGENERAL AND PHYSICAL CHEMISTRY. 153 available for calculating lateiit heats. - (1) The thermodynztmical L = T/J.( Y - v)dP/dl’; (2) L = p’( Jd - 33) + 8 and (3) Crompton’s equation L=2Rl’logd/B. The values of L for the different sub- stances examined are calculated from these equations ; it is seen that as a rule Crompton’s equation a t low temperatures gives high results but a t high temperatures gives results in better accord with (2) than those calculated by equation (1). For high temperatures therefore Crompton’s equation should prove of corisiclerable value as owing to the uncertainty in the values of dP/dl’ the values obtained thermo- dynamically are untrustworthy.Curves are given for the variation of internal latent heat with temperature; it is seen that all are concave towards the temperature axis but no simple empirical formula could be obtained. From the equation previously given the value of a in Ramsay and Young’s expression may be calculated. I n t-he case of isopentane the value obtained is 159,400 the volume P being 4.266. Young obtained the value 157,880 a t V= 4.3 from the drawn isochors and 162,890 by calculation. It is shown also that a t the critical tem- perature the following relations hold (1) P= dP/dT. T - 10,47lp’/ Y413 ; (2) dP/dT= 124,S60/mY and (3) mp’ @/T = constant. L. M. J. Theory of Colloids. EDUARD JORDIS (Ckem. Cent?.. 1904 ii 1683-1686 ; from Man.S’ci. [iv] 18 797-818. Compare Abstr. 1904 ii 7 14).-According to the theory propounded colloidal solutions do not differ essentially from ordinary solutions. A comparison of the properties of colloids with those of crystalloids indicates that no sharp line of demarcation can be drawn between the two classes. As yet a pure hydrosol has not been prepared and it is probable that purification leads in all cases to the formation of a hydrogel. The hydrosols therefore are not pure substances but are to ba regarded as combinations which the author designates as ‘‘ chemical colloids.” The process of neutralisation of acid and basic colloids the precipi- tation of albumin by alkali halogen salts in acid and alkaline solution the influence of concentration on the precipitation of colloids the causes of hydrogel formation the electrolysis of hydrosols the different hypotheses relative t o the structure of hydrogels and many other points are discussed for which the original must be consulted.Incidentally the author divides the colloids into six groups according to their modes of formation. These are (1) precipitation by alkali by hydrolysis or by acids ; (2) precipitation by hydrogen sulphide ; (3) formation of halogen colloids from metallic hydrosols ; (4) forma- tion of complex substances such as Yrussian blue; (5) reduction of salts of heavy metals ; (6) electrical disintegration of metals under water. H. M. D. Solid Solutions and Isomorphism. GIUSEPPE BRUNI and A. TROVANELLI (Gaxxetta 1904 34 ii 349-357).-Thioacetic acid gives abnormally small freezing point depressions in acetic acid solution.Thioacetamide on the other hand gives depressions greater than the normal values in solution in acetamide (the constant of which was deter- mined t o be 36.3). I n formamide (the freezing point constant of154 ABSTRACTS OF CHEMICAL PAPERS. which was found to be 38*5) thioacetamide gives normal depressions showing that here the thioacetamide is not appreciably dissociated and that mixed crystals are not formed with acetamide. I n urethane solutions ethyl thiocarbamate gives depressions smaller than the normal values whilst xanthamide or ethyl sulphocarbamate gives depressions slightly greater than the normal ones. Compounds of the aliphatic series containing the group iC*SH hence form solid solutions with the corresponding compounds containing the complex IC -OH but those with the grouping :C:S are not able to crystallise with the corresponding oxygen compounds Thiophenol exhibits normal cryoscopic behaviour in phenol solutions.p-Fluoronitrobenzene gives depressions somewhat higher than the normal values when dissolved in p-chloronitrobenzene the molecular freezing point depression for which is 108. This is the first observed case of isomorphism between fluoro- and chloro-organic derivatives. T. H. P. Decomposition of Hydrated Mixed Crystals. 11. REINHARD HOLLMANN (Zeit. physikal. Chem. 1905 50 567-594. Compare Abstr. 1902 ii 446)-A theoretical paper. J. C. P. Mixed Crystals in Systems of Three Substances. ERANS A. H. SCHREINEMAKERS (Zeit.physikal. Chem. 1904 50 169-199).-A theoretical paper. J. C. P. Method for the Determina.tion of the Affinities of Acids Colorimetrically by means of Certain Vegetable Colouring Matters. JOSEPH H. KASTLE (Amer. Chem. J. 1905 33 46-59).- It is shown that dilute solutions of certain vegetable colouring matters can be used for determining the relative strengths of acids. The following materials have been found to contain colouring matters capable of employment for this purpose the skin of the purple grape and of the wild grape (Vitis wulpina) the flowers of the red geranium purple petunia the scarlet sage (Xalwia fuZgens) and the red rose. The reagent is prepared by macerating the grape skins (or other material) with water boiling filtering adding a small quantity of solution of egg albumin to clear the liquid which is afterwards boiled and filtered.A current of sulphur dioxide is then passed into the liquid until the colour is almost discharged and the excess of sulphur dioxide is removed by boiling a little toluene being added as a pre- servative. The effect of varioiis acids on the reagent has been studied and it is found that the colouring matter is regenerated on the addition of an acid the intensity of the colour varying according to the affinity of the acid. On arranging the acids in order of their affinity as determined by this process it is found that this order agrees closely with that obtained by Ostwald's methods. It has not been found possible to exhibit the difference in strength between the very weak acids such as acetic propionic and butyric acids by this colorimetric method but it is thought that possibly this may be effected by varying the concentration.E. G.GENERAL AND PHYSICAL CHEMISTRY. 155 Sixth Report of the Committee [of the German Chemical Society] for Fixing Atomic Weights. HANS LANDOLT WILHELM OSTWALD and OTTO WALLACH (Ber. 1905 38 13-22. Compare Abstr. 1902 ii 129; 1903 ii 68; 1904 ii 20).-This report deals with the replies to a circular addressed to the members of the Inter- national Committee relating to the basis of the atomic weights. Of the fifty-nine members thirty-nine recorded their votes and of these thirty-two were in favour of the exclusive publication of the table based on O = 16 two were in favour of the table in which H= 1 whilst five were in favour of both tables being given. The committee therefore proposes the exclusive use of the values based on 0 = 16. C. H. D. Theory of Valency. RICHARD ABEGG (Zed. anorg. Chem. 1905 43 116-121. Compare Abstr. 1903 ii 536; 1904 ii 475).- A theoretical paper in which the following problem is discussed. If an uncombined polyvalent atom of an element is present in a system containing an amount of another element insufficient to form the compound corresponding with the lowest stage of combination will one valency of the atom in question be concerned in the forma- tion of the compound or will all the valencies take a part S Although experience appears to favour the first alternative the latter is con- sidered to be the more correct especially since the affinities of the different valenciea of one atom have not all the same value. A. McK. Conception of Valency. RICHARD ABEGG and F. WILLY HINRICHSEN (Zeit. anorg. CIwrn. 1905 43 122-124).-A criticism of the views of Billitzer (Abstr. 1904 ii 720) who considers that the valency of an element is a function of the temperature. The authors draw a sharp distinction between the valency of an element and its ‘‘ affinity.” A. McK. Hydration and Hardening. EDUARD JORDIS (Zeit. A’lektroclmh. 1904 10 938-940).-The views regarding the hardening of Port- land cement and gypsum expressed by Rohland (this vol. ii 19) are adversely criticised. The acceleration of the setting of cement by the addition of salts is not a catalytic process since the salts added react with the cement and undergo permanent change. T. E. Siphon with a Mercury Valve. FERDINAND PJLZ (Chem. Centr. 1905 i 133; from Zed Landw. Vers.-bVes. Oestew. 7 819).-The delivery tube is bent in a U-form and is connected by a tube from the bottom of the bend with a pear-shaped glass bulb which is attached by a ground glass joint and is capable of rotation. The bulb and U-tube contain mercury and by rotating the bulb down- wards the level of mercury is depressed so that the liquid may pass the bend of the delivery tube. The valve is designed for use with alkaline liquids for which glass or rubber is undesirable. G. U. L.

ISSN:0368-1769    

DOI:10.1039/CA9058805129

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

156 ABSTRACTS OF CHEMICAL PAPERS Inorganic Chemistry. Hypochlorous Acid. 111. Formation and Decomposition of Chloric Acid. JULIUS SAND (Zed. phpikal. C'hem. 1904 50 465-4S0. Compare Abstr. 1904 ii 612).-The slow liberation of chlorine at 70" in a solution containing potassium chlorate and hydro- chloric acid has been quantitatively followed. It appears that the reaction is quinquemolecnlar and that the rate of change at any moment is given by the equation dx/dt =k[C10,'].[H']2[C1']2. The velocity actually measured is probably that of the action C10,' + 2H' + 2Cl' = C10' + 2HOC1,'the hypochlorous acid then reacting instantaneously with hydrochloric acid to produce chlorine. The absolute value of kY0 works out to 0.56 x 10-s. The action represented by the foregoing equation is reversible as shown by Foerster who has also determined the velocity of the change C10 + 2HOC1= C10,' + 2H' + 2C1' (see Abstr.1901 ii 309). The author also has determined the velocity L' of this change and finds L,,'=53*1. From the values of k and L' it is possible to deduce the equilibrium constant K of the reversible reaction C10,' + 6H' + 5Cl',3H20 + 3C1 ; the value thus obtained is KT0 = 0.995 x From the known heat {effect of the reaction the author then calculates Kzo= 0.54 x 10-11. Further it can be shown that an electrode im- mersed in a solution containing the ions IT Cl' and ClO; in equilibrium would assume the potential 1.434 volts against the normal hydrogen electrode (compare Luther Abstr. 1902 ii 641). J. C. P. Atomic Weight of Iodine PAUL KOTHNER and E.AEUER (Annalen 1904 337 362-369. Compare Abstr. 1903 ii 560-566 and this vol. ii 81).-Baxter's recent determination of the atomic weight of iodine (this vol. ii S l ) is discussed. It is pointed out that Stas' erroneous result cannot be attributed to an admixture of silver nitrate in the silver iodide since the same result was obtained with the sulphate. The suggestion that the iodine is possibly admixed with a small quantity of a new element is very doubtful. If the atomic weight of iodine is calculated from Ladenburg's results using the new value found by Richards and Wells for chlorine the number 126.985-136.991 (0 = 16) is obtained. Baxter's calculation I = 126.964 is incorrect. The most probable value for the atomic weight of iodine deduced from these two researches is 126.98.The mean of the 41 determinations made by Scott Ladenburg Baxter and the authors is 126.97 (0 = 16). K. J. P. 0. Polysulphides. I. FRIEDRICH W. KUSTER and EDUARD HEBER- LEIN (Zeit. anorg. Chem. 1905,43 53-84).-The solubility of sulphur in a solution of sodium sulphide is almost independent of the tempera- ture between the limits of 0" and 50° its solubility diminishing very slightly with increase of temperature. The solubility of sulphur in a solution of sodium sulphide depends greatly on the dilution of theINORGANIC CHEMISTRY. 157 latter. It is greatest in a iV/16 solution where the constitution of the solution approximates to the formula Na2S,.24. There is evidence that in the solutions examined no uniform compounds are present but that various substances are in a condition of complex equilibrium with one another.All sulphides and polysulphides undergo much hydrolysis in aqueous solution. The extent of hydrolysis diminishes regularly with increasing amount of sulphur in the solutions. The representation of polysulphides as thio-salts of thio-oxy-acids is untenable as also is Geuther's representation of them as sulphides of polyvalent metals. The formula advanced by Spring are also inadequate.' Polysulphides are salts of complex thio-acids of the type H2S,So which are analogous to the complex iodides €€I,I and HI,14. A. McK. Theory of the Lead Chamber Process. angew. Chem. 1905 18 60-'71).-Polemical. (this vol. ii 23). GEORG LUNGE (Zeit. A reply to Raschig A. McK. Density and Expansion of Sulphuric Acid in Aqueous Solution.J. DOMKE and W. BEIN (Zeit. anorg. Chem. 1905 43 125-181).-The authors have investigated the relationships between concentration density and expansion of aqueous solutions of sulphuric acid and also the physico-chemical nature of sulphuric acid in various concentrations. The maximum density 1.8415 a t 15'/4O was attained with a 97.25 per cent. of acid. The formation of hydrates in sulphuric acid solutions is discussed. The existence of hydrates in solution cannot be deduced from density determinations alone. Examination of freezing point curves does not prove the existence of hydrates containing 1 2 4 and 6H,O respectively. Hydrates containing 1 and 2H,O respectively certainly exist (Lespieau Jones). Sulphuric acid (99.52 per cent.) has a sp.gr. 1.8377 a t 15"/4". The density determinations of the authors are contrasted with those of others and extracts are given from the complete tables of the sp. gr of aqueous solutions of sulphuric acid a t various temperatures. The paper includes a very complete bibliography. A. McK. Constitution of Hyposulphites. MAURICE PRUD'HOMME (Bull. SOC. chirn. 1905 [iii] 33 129-1 31).-Baumann Thesmar and Frossard prepare formaldehyde sodium hydrogen hyposulphite H.CHO,NaHSO 2 H,O by the reduction of sodium hydrogen sulphite with zinc and sulphuric acid and precipitation with sodium chloride after removal of the zinc. The precipitate is dissolved in a 40 per cent. solution of formaldehyde when a mixture of the desired proclnct with formaldehyde sodiuin hydrogen sulphite crystallises out.From this the hyposulphite additive product may be obtained in large monoclinic crystals by158 ABSTRACTS OF CHEMlCAL PAPERS. recrystallisation from dilute alcohol. It is like all the additive pro- ducts of formaldehyde with the hyposulphites quite stable and is only resolved into its generators by steam at looo and under these conditioiis forms a powerful reducing agent (Rev. Gen. Mat. Col. 1904 353). The formulae ascribed to these compounds support Schutzenberger’s view (Conapt. rend. 1869 69 196) that the composition of sodium hyposulphite is represented by the formula NaHSO (compare Eernthsen and Bazlen Abstr. 1900 ii 203). I t is suggested that the salt K2S204 obtained by Moisssn by the action of sulphur dioxide on potassium hydride (Abstr.1903 ii 75j is derived from a new sulphur acid and that it is hyclrolysed by water according t o the equation K,S,O + H,O = KHSO + KHSO,. In support of this view it is stated that the product recrystallised from water contains both needles and stellate groups of acicular crystals. T. A. H. Colloidal Selenium. CARL PAAL and CARL KOCH (Rer. 1905 38 526-534. Compare Schultze Abstr. 1886 302 ; Gutbier Abstr. 1902 ii 652).-The liquid hydrosol of selenium is obtained by reducing selenious acid dissolved in aqueous sodium protalbate or lysalbate with hydrazine hydrate and hydrochloric acid or with hydroxylamine hydrochloride and dissolving the precipitate so obtained in :aqueous sodium carbonate. The liquid hydrosol after purification by dialysis is blood-red by reflected-light or when strongly diluted red by trans- mitted light.The solid hydrosol obtained in dark red glistening flakes when the solution is evaporated by gentle heat and finally over sulphuric acid contains 32-50 per cent. of selenium and is easily soluble in cold water. This form is much more stable than the Eiydrosols previously obtained ; in aqueous solution i t remains un- changed on repeated alternate treatment with acetic acid and sodium hydroxide or when boiled with an excess of 10 per cent. sodium chloride or phosphate solutions but is gelatinised on addition of an excess of calcium chloride solution in the cold. A specimen of this solid hydrosol after preservation for 24 years dissolved almost com- pletely in water. Colloidal selenium containing up to 90 per cent.of selenium is obtained by dissolving the solid hydrosol in water and adding acetic acid as long as precipitation takes place. G. Y. The Brown a n d Blue Modifications of Colloidal Tellurium. CARL PAAL and CARL KOCH (Bey. 1905 38 534-546. Compare Gutbier Abstr. 1902 ii 653 ; 1904 ii 613).-The brown modification of colloidal tellurium is easily obtained by warming an alkaline aqueous solution of telluric acid containing protalbic or lysalbic acid with hydrazine hydrate on the water-bath; in neutral or alkaline solution containing sodium protalbate or lysalbate telluric acid is reduced by hydroxylamine only on boiling as is tellurium dioxide by hydrazine hydrate; in these cases the brown modification a t first formed changes into the blue as the boiling proceeds.Gutbier and Resenscbeck’s brownish-violet tellurium hydrosol is probably a mixture oE the brown and blue modifications. As in the case of colloidal selenium the liquid hydrosols of tellurium containing sodiumINORGANIC CHEMIISTRY. 159 protalbate or lysalbate are very stable and on careful evaporation yield the solid hydrosols which are soluble in water and remain unchanged when heated t o 100’ in a vacuum. On addition of acetic acid to the liquid hydrosois the solid hydrosols containing protalbic or lysalbic acid are precipitated ; these contain upwards of 80 per cent. of tellurium and are very stable when protected from the atmos- pheric oxygen the brown modification retaining its solubility after three years. G. Y. Radiotellurium.IV. WILLY ~ ~ A R C K W A L D (Bey. 1905 38 591-594. Compare Abstr. 1902 ii 508; 1903 ii S l 733).-A quantity of crude tellurium obtained from 15 tons of pitchblende was treated as previously described. The product thus obtained was purified as follows. It was dissolved in dilute nitric acid and the filtered solution repeatedly evaporated with hydrochloric acid in order that the nitric acid should be expelled. A current of sulphur dioxide was then passed into the solution of the residue in dilute hydrochloric acid. The resulting precipitate consisted of a mixture of selenium tellur- ium and radiotellurium. It follows from this result that radiotellurium chloride is reducible by sulphurous acid. Radiotellurium is precipi- tated by sulphurous acid relatively with greater difficulty than the other substances.The precipitate (16 grams) obtained by means of sulphurous acid was dissolved in dilute nitric acid the solution evaporated to dryness and the residue warmed with ammonia a method of separation of radiotellurium from selenium and tellurium which was based on the supposition that radiotellurium oxide is not an acid anhydride and is quite insoluble in ammonia. Three milligrams of a very radio- active product were thus obtained Measurements showed that the radioactivity of this product dim- inished with time. The rate of decay accords with the formula for unimolecular reactions as is the case with all uniform radioactive substances. After 139.8 days the intensity of the radioactivity sunk to one-half of the original.Kadiotellurium is a uniform radioactive substance and is not identical with polonium which without doubt is a mixture of radio- active substances. The rate of decay of Madame Curie’s polonium as measured by her does not accord with the formula for unimolecular reactions. Rutherford’s Radium E is also not identical with radiotellurium. A. McK. Formation of Ammonia from its Elements. FRITZ HABER and G. VAN OORDT (Zeit. anorg. Chem. 1905 43 11 1-1 15)-The authors have studied the equilibrium between nitrogen hydrogen - and am- monia. A current of ammonia was passed over finely-divided iron at a high temperature and the resulting gas after having been freed from ammonia passed over a fresh quantity of iron which was main- tained at the same temperature as in the*initial case. A fresh amount of ammonia was produced by the latter treatment; this was again separated from the mixture which was now found to be a mixture 91 nitrogen (1 vol.) and hydrogen (3 vols.).160 ABSTRACTS OF CHEMlCAL PAPERS.The experiments were conducted with dry gases at pressnres approxi- mating to atmospheric. The temperature was about 1000". Nickel is not so active a catalyst as iron. A. McK. Action of Hydrogen Fluoride on Nitrogen Sulphide and a New Method of Formation of Thionyl Fluoride. OTTO RUFF and CURT THIEL (Bey. 1905 38 519-553. Compare Abstr. 1904 i 396).-When heated a t 120' in a closed platinum vessel hydrogen fluoride and nitrogen sulphide unite to form a red liquid which easily decomposes again into its components ; in presence of traces of moisture thionyl fluoride is formed.This may be prepared almost quantitatively by heating nitrogen sulphide hydrogen fluoride and copper oxide together a t 100" in a copper bomb. I n presence of carbon or of sunlight a mixture of chlorine and thionyl fluoride in a sealed glass tube react with the silica of the latter to form silicon tetrafluoride and sulphuryl fluoride. Thionyl fluoride and nitrogen trioxide in presence of traces of moisture react with silica to form nitrosulphonic acid and silicon tetrafluoride. Thionyl chloride is not changed when repeatedly passed through a white hot platinum tube filled with platinum sponge. New Experiments on the Preparation of Diamonds. HENRI MOISSAN (Cornapt. rend. 1905 140,277-283. Compare Abstr. 1897 ii 549).-The appearance of the cross-section of the block of meteoritic iron from Caiion Diablo (this vol.ii 43) seemed to indicate that the separation and crystallisation of the carbon had been influ- enced by the sulphur silicon and phosphorus present in the meteorite. The author's previous experiments have therefore been repeated with a view of testing whether the presence of these metalloids affects the crystallisation of the carbon under laboratory conditions. One hundred and fifty grams of Swedish iron were melted in a crucible in the electric furnace with excess of sugar charcoal and a t the end of two or three minutes when the molten iron had become saturated with carbon t'he crucible was withdrawn five grams of ferrous sulphide were added and the whole was then rapidly cooled by immersing the crucible in cold water.Carbon separated in crystalline form from the central portions of the molten mass and the yield was increased as a con- sequence of the presence of sulphur. KO diamonds were obtained on the addition of sulphide if the mass was not rapidly cooled. The pre- sence of silicon also appears favourable to the crystallisation of the carbon whereas experiments in which phosphide of iron was added gave no result. The synthetical diamonds are always feebly doubly refracting but the amount is variable and bears no relation to the external form. This observation is in agreement with the optical behaviour of most natural diamonds. H. M. D. G. Y. Combustible Gaseous Carbon Compounds in t h e Air. HEINRICH WOLPERT ( A d .lfigiene 1905 52 151-178).-1n the free outer air there exist cer tain incompletely oxidisecl carbon compounds. The amount of these materials in the Berlin atmosphere averages a tINORGANIC CHEMISTRY. 161 least 0.015 volume per 1000 that is about 4-5 per cent. of the amount of carbon dioxide. The air of rooms contains a t least as much but if this is rendered still more impure by the burning of oils or gas or by respiration these gaseous compounds of carbon increase. W. D. H. The Action of Silicochloroform on some Fluorides and the Preparation and Properties of Silicofluoroform. OTTO RUFF and CURT ALBERT (Rer. 1905 38 53-64. Compare Ruff and Plato Abstr. 1904 ii 265).-Silicochloroform does not react with silver fluoride or lead fluoride even on prolonged heating.Antimony trifluoride and silicochloroform react in a sealed tube according to the equation 3SiHC1 + 4SbF3 = SSiF + 2Sb + 2SbC1 + 3HC1. The same reaction occurs very vigorously in the case of arsenic trifluoride. Tin and titanium tetrafluorides however react in a different manner for instance 3SnF + 4SiHC1, 4SiHF + SSnCl,. To propare silicofluoroform molecular quantities of silicochloro- form and titanium tetrafluoride are heated toget'her in a closed copper vessel or glass tube for 18 hours at 100-120°. The vessel is then cooled in liquid air and allowed to become warm slowly 'the gases evolved being condensed by means of liquid air. Silicofluoroform SiHF boils a t - 80.2' under 758.5 mm. pressure (corr.) and melts at about - 110'. It slowly decomposes in a sealed glass tube even at the ordinary temperature according to the equation 4SiHF = 2H + SSiF + Si the decomposition being greatly accelerated by heat.It burns in air with a very pale blue flame the temperature of ignition being higher than that of silicochloroform 12SiHF + 60 = SSiF + 3Si0 + 4H,SiF + 2H,Si03. Water and sodium hydroxide decompose it thus ZSiHF + 4H,O = Si(OH) + HzSiF6 + 2H,. Alcohol forms ethyl orthosilicate Si(OEt) ; ether forms ethyl silico-orthoformate SiH(OEt) and ethyl fluoride. Toluene dissolves its own volume of silicofluoroform. The properties of the silicohalogenoform series are tabulated and compared. C. H. D. silicates. V. EDUARD JORDIS and E. H. KANTER (Zeit. anorg. Chem. 1905 43 48-52 Compare this vol. ii 88).-The influence of the length of time duiing which boiling is contiuued in the action of calcium hydroxide solution either alone or in presence of calcium ions on silicic acid has been examined.The analyses quoted show that at first calcium from the hydroxide quickly combines with the silica after- wards it is partly removed from the compound formed and then again combined with it to a greater extent than before. The anion is in some way or other transformed. A. McK. Potassium and Ammonium Nitrates and the Law of Bravais. FR~DERTC WALLERANT (Compt. rend. 1905,140 264-266). -Potassium nitrate like ammonium nitrate exhibits polymorphism (Abstr. 1904 ii 31) the normal orthorhombic form a t 129' passing into an a-rhombohedra1 form which on superfusion is converted into a P-rhombohedra1 variety.M. A. W. VOL. LXXXVIII. ii. 12162 ABSTRACTS OF CHEMICAL PAPERS. Some Physical Charaoters of the Sodium Borates with a New and Rapid Method for the Determination of Melting Points. CHARLES H. BURGESS and ALFRED HOLT jun. (PTOC. Roy. Soc. 1904 74 285-295. Compare Proc. 1903 221).-When pure borax glass is kept for some hours a t such a temperature that it has the consistency of a viscid syrup it gradually changes to a mass of colourless crptals. The latter are about as soluble in water as borax glass are not hygroscopic and melt a t a higher temperature than the glass into which they are reconverted on melting and then cooling quickly The phenomenon of crystallisation on reheating moreover is exhibited by all mixtures of boric anhydride and sodium carbonate in which the ratio B,O Na,CO lies between 6 1 and 8 5.With the idea that the change was probably due to the crystallisation of some borate rich in sodium the authors fused boric anhydride with a large excess of sodium carbonate and found that the greatest proportion in which boric anhydride combined with sodium oxide is given ap- proximately by B2O3 Na,O 1 1.3. The product obtained is therefore neither NaBO nor Na3B0,. The melting points of glasses and crystals of varying composition were determined with the view of discovering what compounds if any existed. A glass bead was used to attach a vertical weighted wire to a horizontal platinum wire suitably heated by a current. When the horizontal wire was raised to a sufficiently high temperature (which could be deduced from its resistance) the vertical wire dropped and in this way the melting point of the glass was determined.The melting points of the glasses were well defined but the melting point curve is irregular and difficult of interpretation. The melting point curve for the crystals exhibits a maximum about the composition 5Na20,4B,0 which agrees with the ratio referred to above. It would appear that borax (Na20,2B,0,) is not a definite compound under these conditions but approximately a eutectic mixture of the compounds 5Na20,4B20 and Nn20,4B,0 for the latter of which there is other evidence. Experiments were also made in which after powdering roughly the crystals were picked out from the accompanying glass and analysed. With mixtures between Na20,4B,F) and Na20,2B,03 the crystals and the glass have the same composition and it is probable that in this case formation of mixed crystals or a solid solution from a superfused liquid has taken place.With mixtures containing more boric anhydride than Na20,4B,03 only a part crystallises and the crystals have approximately the composition Na,0,6B20,. If the crystals could be freed from glass the compo.-ition would probably be Na,O 4R,O,. The glass must be regarded as a superfused and therefore meta- stable form of the crystals behaving in several respects as if it were a liquid of enormous viscosity. J. C. P. Pentasulphides of Rubidium and Cesium. WILHELM BILTZ and ERNST WILKE-DORFURT (Bey. 1905 38? 123-130).-Rubidium and caesium pentasulphides are formed by warming the monosulphides with powdered sulphur and aqueous alkali hydroxide solution in an atmosphere of hydrogen.INORGANIC CHEMISTRY.163 Rubidium pentccsulphide Rb,S crystallises in dark red rhombic prisms commences to blacken at 170-185O melts at 223-224" and has a sp. gr. 2.618 a t 15". When exposed to the air it deliquesces to a red liquid from which sulphur crystallises out; it remains unchanged under cold alcohol hot ethyl sulphide or chloroform but is decomposed by hot nitrobenzene or more energetically by a mixture of nitro- benzene with ethyl or amyl alcohols ; in contact with carbon disulphide the red crystals slowly become yellow the change being accompanied by absorption of carbon disulphide. Cesium pentaszclphide Cs2S5 H,O forms red crystals melts at 202O is not hygroscopic and can be recrystallised without change from 70 per cent.alcohol. G. Y. Some Physical Constants of Calcium and Calcium Amalgam. HENRI MOISSAN and CHAVANNE (Compt. rend. 1905 140 122-127. Compare Abstr. 1900 ii 76).-The authors have redetermined some physical constants of calcium using for the purpose the metal prepared by the Bitterfeld electrolytic process containing from 99.3 to 99.6 per cent. of calcium the impurities consisting of calcium chloride silicon aluminium and traces of sodium and iron and dissolving slowly in pure water but rapidly in water containing a trace of iron gold or platinic chloride. The electrical conductivity of calcium measured in wires of 0.51 and 0.77 mm. diameter is 15.6 at ZOO that of silver being taken as looo.Calcium becomes pasty at 790-795' and melts at 810' (compare Arndt this vol. ii 87) and has a sp. gr. 1.548. Calcium dissolves slowly in mercury to form a solid crystalline mass from which prismatic crystals of definite composition Hg,Ca are isolated by fractional crystallisation in a vacuum ; this amalgam is stable in dry air at the ordinary temperature and dissolves slowly in water thus forming a convenient reducing agent capable of reducing alkali nitrates to ammonia and traces of nitrites ammonium sulphate to ammonium amalgam and acetone to a mixture of pinacone and isopropyl alcohol. M. A. W. Red Coloration of Bleaching Powder. NAZARENO TARUGI (Gaxxetta 1904 34 ii 466-468).-1t is generally stated that the red coloration sometimes produced in bleaching powder by subjecting it to the action either of carbon dioxide or of gentle heat depends on the presence of small quantities of manganese which become trans- formed by the oxidising action of the bleaching powder into a calcium salt of permanganic acid.The author shows however that this is not the case the red colour being due to the presence of a salt of ferric acid. T. H. P. Alkaline Reaction of Strontium and Calcium Carbonates. L. BLUM (Zeit. anal. Chem. 1905 44 12-13).-The carbonates of strontium and calcium wetted with water on red litmus paper change the colour t o blue Marble behaves in the same way. M. J. S. 12-2I G P ABSTRACTS OF CHEMICAL PAPERS. Action of Barium Amalgam on Solutions of Sodium and Potassium Salts. GEORGE McP. SMITH (J. PhysicaZ Chem.1905 9 13-35).-A controversial paper in which the author replies to Fernekes (this vol. ii 33). The author’s experiments show that barium in barium amalgam may be replaced by potassium or sodium by the action of solutions of the hydroxides of these metals on the amalgam. The question of such replacement is briefly discussed a t the end of the paper and it is pointed out in the case of the action of barium amalgam on solutions of potassium salts that the separation of potassium or of hydrogen depends on the relative values of the ratios .2JPBa/pBa PK/pK and P H / p H where F and p are the electrolytic solution pressure and the osmotic pressure of the indicated elements. L. M. J. Metals found in the Archeological Excavations in Egypt. MARCELLIN BERTHELOT (Conapt.rend. 1905 140 183-185).-Two metallic specimens obtained from Egyptian tombs consist essentially of an alloy of tin and copper. The first specimen datingfrom the end of the IInd or the beginning of the IIIrd dynasty was much corroded and largely converted into copper oxychloride and carbonate and con- tained 56.7 per cent of copper 2 per cent. of tin and traces of zinc. The second specimen also from the tombs of the Pharaohs was well preserved and contained 87.44 to 87.52 per cent. of copper 11.47 per cent. of tin and traces of lead Neither specimen contained arsenic silver or iron. M. A. W. Reduction of .Metallic Oxides by means of the Cerite Metals. L. WEISS and 0. AICHEL (Anncden 1904 33’7 370-389).-The alloy of the cerite and yttrium metals the ‘‘ Mischmetall,” obtained from the oxides in the residue of the manufacture of thorium nitrate has all the requirements of a good reducing agent as it has n high heat of com- bustion and forms easily fusible and stable oxides It cannot be obtained as a powder but in filings which however cannot be kept. I n compact pieces it can be kept unoxidised for months.Iron nickel cobalt manganese and chromium can easily be obtained pure by its means. Molybdenum was prepared in a pure state from molybdic acid and forms a silver-white metal with crystalline fracture; it is not magnetic. Tungsten and uranium could not be prepared pure. Vanadium niobium and tantalum were easily prepared from the pent- oxides. Vanadium forms a silver-white regulus the surface of which showed crystalline structure; its hardness is 7 and it is brittle but not magnetic insoluble in potassium hydroxide bromine water hydro- chloric acid or dilute sulphuric acid but soluble in concentrated sulphuric acid hydrofluoric or nitric acid.It is oxidised to vanadates by molten alkali hydroxides carbonates or saltpetre and when heated in the air is converted into the pentoxide. Columbium shows no sign of crystalline structure is brittle of a silver-white fracture insoluble in hydrochloric or nitric acids or aqua regia but slowly soluble in boiling sulphuric or hydrofluoric acids. It is converted by molten alkali hydroxides into columbates and is oxidised by the air into the pentoxide. Tantalum could not be obtained free from dross. It isINORGANIC CHEMISTRY. 165 pure white and very hard is completely insoluble in acids but con- verted by alkali hydroxides into tantalatcs.It burns in the air to the pent oxide. Pure metals could be obtained from the oxides of silicon boron tin lead titanium or zirconium. Bismuth oxide reacts explosively with the alloy. K. J. P. 0. Combinations of Samarium Chloride with Gaseous Am- monia. CAMILLE MATIGNON and R. TRANNOY (Compt. rend. 1905,140 141-143).-When anhydrous samarium chloride (Abstr. 1902 ii 505) is sealed in a tube with liquid ammonia i t is converted into a white bulky compound SmCl3,11.5NH which on being progres- sively heated gives off its ammonia a t eight different temperatures which are the dissociation temperatures of the eight compounds that samarium chloride forms with ammonia; the formuh of the com- pounds their dissociation temperatures ( t ) and heats of formation (Q) are as follows SmC13,NH3 ( t ) 375" (Q) 20.7 Gal.; SmCI3,2NH ( t ) 240° (Q) 16.4 Gal. ; SmU13,3NH ( t ) 200° (Q),15.1 Cal. ; SmC1,,4NH3 ( t ) 155O (Q) 13.7 Csl. ; SmC1,,5NH3 ( t ) 1 0 5 O (Q) 12.1 Gal. ; SmCl,,$NH ( t ) 76O (&) 11.2 Cal. ; SrnCl3,9*5NH ( t ) 40° (&) 10.0 Cal.; SmCI3,11.5NH ( t ) 15" ( Q ) 9.2 Cal. M. A. W. Double Silicides of Aluminium. WILHELM MANCHOT and A. KIESER (Annden 1904 337 353-36 I).-A chromium aluniinium silicide CrzA1Si3 is obtained by heating chromium potassium dichromate or potassium chromifluoride with a very large excess of potassium silicofluoride and aluminium in a Perrot's furnace to the highest attainable temperature for half an hour and dissolving the regulus in dilute hydrochloric acid.It forms greyish-white hexa- gonal crystals with a metallic lustre which are conductors of elec- tricity; their hardness is 5 and sp. gr. 4.7 I t is insoluble in sodium hydroxide boiling hydrochloric acid nitric acid aqua regia or sulphuric acid but dissolves easily in hydrofluoric acid and molten alkali hydroxides. A t a high temperature chlorine bromine and iodine attack the material; hydrogen chloride has a feeble action and oxygen none. If the proportions are so chosen that the regulus contains from 34.4 to 50 per cent. of free silicon then a second silicide Cr2AlSi is formed. It forms small crystals of a hardness somewhat greater than 5 and a sp. gr. 4.S. It is partly dissociated at the temperature of formation. Tungsten aluminium silicide forms black hexagonal crystals which are not attacked by acids aqua regia or sodium hydroxide and only by hydrofluoric acid on evaporation but readily by hydrofluoric and nitric acids and by molten alkali hydroxides.K. J. P 0. Indium and Rubidium Fluorides. CAMILLE CHABRIE and A. BOUCHONNET (Compt. rend. 1905,140 90-91. Compare Abstr. 1901 ii 102 242 314 600).-lndium JEuoride In,F6,18H,0 obtained by slowly evaporating a heated solution of indium hydroxide in hydrogen fluoride forms white crystalline needles very slightly soluble in cold166 ABSTRACTS OF CHEMICAL PAPERS. water insoluble in alcohol or ether soluble in cold hydrochloric or nitric acid and slowly decomposed by boiling with water or exposure to the air ; it loses its water of crystallisation when heated and at a red heat is completely deconiposed into indium sesqnioxide and hydrogen fluoride.Rubidium hydrogen juoride RbF H F obtained by slowly evaporating an aqueous solution of rubidium carbonate and hydrogen fluoride forms small deliquescent crystals insoluble in alcohol or ether and partially converted into rubidium3uoride RbF when heated with excess of ammonium hydrogen fluoride. M. A. W. Interaction of Hydrochloric Acid and Potassium Per- manganate in the Presence of Ferric Chloride. JAMES BROWN (Amer. J. Xci. 1905 [iv] 19 31--38).-Experiments have been made in which known quantities of hydrochloric acid and of standard potassium permanganate solutions have been kept a t 50' for a definite time A known volume of standard oxalic acid was then added and standard permanganate run in until the coloration was permanent.The amounts of permanganate apparently reduced during digestion are found constant in different experiments only when the chlorine produced during the digestion is expelled by a current of air or carbon dioxide before the addition of the oxalic acid. Ferric chloride was thought by Wagner (Abstr. 1899 ii 275) to have a catalytic influence on this reaction but the author's experiments are opposed to this view. J. C. P. The Increase in Volume of Molten Cast Iron saturated with Carbon in the Electric Furnace at the Moment of Solidifying HENRI MOISSAN (Compt. rend. 1905 140 185-192) -Pure iron or iron containing only a small quantity of carbon behaves normally on passing from the liquid to the solid state that is its volume diminishes and its density increases ; iron saturated with carbon in the electric furnace behaves like water on solidifying that is its volume increases and its density diminishes j when however fused cast iron of this type is rapidly cooled by immersion in water in fused lead or in iron filings a solid crust is formed and the liquid in the interior is subjected to increased pressure due (1) to the gas evolved during the change from the liquid to the solid state (2) t o the contraction of the solid crust on cooling (3) to the increase in volume of the interior portion on passing from the liquid to the solid state and in these circumstances microscopic diamonds are formed in the interior of the mass due to the cooling of the fused iron saturated with carbon under increased pressure (compare Abstr.1894 ii 189 ; 1896 ii 644). If however as sometimes happens the interior pres- sure is released by the escape of gas through a weak place in a solid crust no diamonds are formed. M. A. W. A Colloidal Iron Hydroxide obtained by Electrodialysis and some of its Properties J. TRIBOT and H. CHRETIEN (Compt. rend. 1905 140 144-146).-The colloidal ferric hydroxide obtained by dialysing a solution of ferric hydroxide on ferric chlorideINORGANIC CHEMISTRY. 167 always contains a considerable quantity of chlorine which can how- ever be removed by an electrolytic process the colloidal solution con- taining the cathode being placed in the inner cell the outer vessel containing water which is frequently renewed. The colloidal ferric hydroxide thus obtained possesses all the properties of Graham's hydroxide ; each form behaves as a ferment towards proteid matter in alkaline medium breaking it down into albumoses but the colloidal ferric hydroxide prepared as above is more active in this respect than that of Graham as is shown in the following table Percentage of A1 bumose Weight of 2 C.C.of -____ 1.5KOH Colloidal Solution. Proteid. Alkali added. formed. 50 C.C. electrodialytic hydroxide 5.021 27.02 1000 50 C.C. 7 5.014 2 C.C. of 1'2KoH 24~62 1000 15KOH 8,16 50 C.C. Graham's hydroxide . . . 5.073 2 C.C. of 1000 50 C.C. 7 7 1.2KOH 6.23 . 5 041 2 C.C. of 1000 M. A. W. Colloidal Ferric Oxide Brown Modification. PAUL NICOLARDOT (Compt.rend. 1905 140 310-312).-The fact that the majority of the crystallised ferric salts are white leads the author to conclude that the normal sesquioxide should also exhibit this colour. It is in fact obtained in this condition when a freshly prepared and concentrated ferric solution is added to a cooled solution of ammonia but it rapidly becomes coloured. To explain the differently coloured forms of the oxide it is suggested that the normal colourless oxide undergoes molecular condensation. According to the author's statements four such modifications can be recognised. H. M. D. Ferrous and Ferric Arsenates. WILLIAM DUNCAN (Phurm. J. 1905 [iv] 20 71-72).-Ferrous arsenate prepared by the B.P. method gradually undergoes oxidation. This change is due to the action of moisture air and heat which results in the formation of ferric arsenate and oxide.Ferric arsenate when freshly precipitated is a dull white insoluble substance which becomes grey when dried at looo and if heated above this temperature gradually turns red. The air-dried salt has the composition FeAsO,,H,O but becomes anhydrous if heated at 100'. When either the hydrated or anhydrous salt is treated with sodium hydrogen carbonate effervescence takes place and a soluble compound is produced. Hydrated ferric arsenate is therefore an acid and determinations of its basicity have shown that it may be represented by the formula AsO,(FeO)(OH),. A ferrous ammonium ursenwte has been prepared but its stability has not yet been investigated. E. G.168 ABSTRACTS OF CHEMICAL PAPERS.Reduction of Molybdenum Compounds in Sulphuric Acid Solution by Magnesium. BORIS GLASMANN (Bey. 1905 38 604 -605).-Molybdic acid in sulphuric or hydrochloric acid solution is quantitatively reduced by magnesium to molybdenum trioxide. A. McK. Physico-chemical Researches on Tin. VI. ERNST COHEN and E. GOLDSCHMIDT (Zeit. physikal. Chem. 1904 50 225-237. Compare Abstr. 1904 ii 567).-Besides grey tin the following modifications are mentioned in older chemical literature (1) rhombic tin ; (2) tetr- agonal tin ; (3) recently fused tin. Special determinations of the specific gravity show that no difference can be detected between tin prepared electrolytically and tin obtained in the usual way from the fused metal. I n both cases the tin crystal- lises in the tetragonal form.The specific gravity of recently fused tin is 7.287 at 15" and it appears that the very low and irregular values obtained by earlier observers for the specific gravity of electrolytic tin were due to the enclosure of varying quantities of impurity such as stannous chloride. At the ordinary temperature rhombic tin appears to be metastable the transition temperature lying about 170'. No indication of this is given by a dilatometer but there is a marked change in the rate of flow of compressed tin about that temperature (compare Ann. Ptqsik 1903 [iv] 10,647). The various stable forms of tin and the temperature limits of their stability are indicated as follows Electrolvtic Grey tin 3 tetragonal tin. Tetragonal tin 2' rhombic tin. Rhombic tin fused tin J.C. P. Recovery of Tin. F. GELSTHARP (l'ranns. Faradag Xoc. 1905 i lll-l12).-When tin plates immersed in a solution of sodium hydroxide of sp. gr. 1-05 and at 80' were connected up with a battery polarisation set in and the anode surface was found to be covered with a layer of some brown substance. On reversing the direction of the current for a moment and again connecting up in the original manner the polarisation disappeared and the tin dissolved regularly from the anode. The same eff'ect was obtained by placing a piece of clean iron in contact with the anode for a short time. Investigation of various pieces of tin plate showed that the phenomenon was exhibited by all bright clean samples but not by old and tarnished (oxidised) pieces. The brown layer formed on the anode is supposed to be an oxide insoluble in sodium hydroxide solution; the effect of reversing the current or making contact with iron is to reduce this to finely divided metal which under the influence of the current oxidises to form a soluble oxide.H. M. D. Tempering of Bronzes. L ~ O N GUILLET (Compt. rend. 1905 140 30'7-310).-Copper tin alloys containing 5-21 per cent. of tin have been tempered a t temperatures varying from 300-800" and the effect of the treatment on the mechanical properties determined. TheINORGANIC CHEAIISTRP. 169 breaking weight and the elongation are slightly increased in the case of alloys containing more than 92 per cent. of copper by tempering at 400-600°. Por alloys containing less than 92 per cent.of copper these properties increase very distinctly when the temperature employed reaches 500'. This behaviour agrees with the facts brought forward by Heycock and Neville (Abstr. 1901 ii 508; 1902 ii 261). The maximum breaking weight is reached by tempering a t 600'; the temperature which gives the maximum elongation varies with the composition of the alloy being 800° for a bronze containing 91 per cent. copper and 600" for one containing 79 per cent. H. M. D. Copper Tin and Oxygen. E. HEYN and 0. BAUER (Chem. Centr. 1905 i 76-77 ; from Mitt. Tech. Vers.-A. Berlin 1904 22 137-147).-The investigations of Heyn (compare Abstr. 1904 ii 406) on the equilibrium between copper and oxygen have been extended to the system copper tin and oxygen. Oxygen is only met with in copper tin alloys in the form of tin dioxide crystals which are insoluble in the alloy.Occasionally the crystals unite to form pellicles and as solidification proceeds the dioxide accumulates in the melted portion of the system increasing its viscosity considerably. The tin dioxide pellicles resemble those of alumina in molten iron deoxidised by aluminium. Cuprous oxide and tin cannot exist together in the molten alloy reaction taking place according to the equation 2Cu,O + Sn = 4Cu + SnO,. Addition of phosphorus is recommended for the removal of tin dioxide. For the analytical separation of the metallic tin from the dioxide the alloy is made the anode in dilute sulphuric acid when the tin present as metal passes into solution. Tin dioxide is insoluble in liquid tin.The grey and yellow spots observable on tin bronze fractures are due to the coarse structure consequent on slow cooling ; if cooled rapidly the colour of the fracture is quite uniform in consequence of the very intimate mixing of the particles. H. M. D. Electrolytic Preparation of Titanous Sulphate. W. H. EVANS (Men%. ManelLester PIL~E. SOC. 1905 49 Mem. 11 1-3. Com- pare Abstr. 1904 ii 412).-'l'he effect of current density concentra- tion of solution and temperature on the electrolytic reduction of titanic sulphate was examined. Good yields of titanous sulphate could be obtained without the use of a diaphragm. If the current density a t the anode is kept fairly high oxygen is evolved without effecting any marked oxidation of the titanous salt. The yield diminishes rapidly with increase of current density.Rise of tempera- ture increases the yield. A. McK. Condition in which Chlorine exists in Colloidal Solutions of Metallic Hydroxides. RUDOLF RUER (Zeit. anorg. Chem. 1905 43 85-93).-Colloidal solutions of zirconium hydroxide prepared by dialysis of a 3 per cent. aqueous solution of zirconium oxy- chloride contain chlorine. When silver nitrate is added to such solutions only a faint opalescence appears the solution becoming170 ABSTRACTS OF CHEMICAL PAPERS. gelatinous after a few minutes. When nitric acid is added along with silver nitrate a slight turbidity appears which becomes more marked when the solution is boiled until finally all the silver is deposited as chloride. From this and from the analogous behaviour of ferric hydroxide the conclusion is drawn that the colloidal solutions in question contained chlorine in the form of hydrochloric acid or metallic chloride or oxychloride dissociation having occurred partially.The behaviour of tho solutions towards silver nitrate is attributed to a specific action of the colloidal hydroxide by which the silver chloride formed is retained in solution in the colloidal form. The author's views are opposed to those of Hantzsch and Desch (Abstn 1902 i 708) who suppose that solutions of colloidal ferric hydroxychloride contain a complex chloro- ferric acid. A. McK. Radioactivity of Thorium. FRITZ ZERBAN (Ber. 1905 38 557-559. Compare Abstr. 1903 ii 532 ; 1904 ii 41 ; Wiukler Abstr. 1904 ii 462).-Uranium has been found in all monazite sands which have been specially examined for that element.To ascertain if the monazite itself contains uranium a well-crystallised Norwegian monazite was examined and found t o contain uranium and it yielded radioactive thorium. Minerals free from uranium yield inactive thorium (compare Baskerville and Zerban this vol. ii 95). G. Y. The Spitting of Alkali Vanadates. WILHELM PRANDTL (Ber. 1905 38 657-662).-When a mixture of vanadium peritoxide and sodium carbonate along with a small quantity of phosphoric acid is melted in the blow-pipe flame and allowed to cool slowly a marked evolu- tion of oxygen takes place the whole mass spitting violently much as solidifyingsilver does. Sodium hypovanadovanadate 5 V,C),,V,O,,Na,O is formed crystallising in dark steel-blue glistening rhombic needles quite insoluble in water ; potassium hppovanadovanadate 8V,0,,V,0,,K20 has similar properties.This is an interesting case of dissociation of a compound rich in oxygen into oxygen and a substance containing less oxygen as the temperature falls. E. F. A. So-called Explosive Antimony. 11. ERNST COHEN EDWARD COLLINS and TH. STRENGERS (Zeit. physikal. Chem. 1904,50,291-308. Compare Abstr. 1904 ii 345).-According to earlier work of Pfeifer and Popper the quantities of metallic antimony deposited by a current from solutions of the trichloride are always proportional to the quantities of silver deposited by the same current ; it was found also that this ratio was independent of the concentration of the antimony trichloride solution and of the varying quantities of the trichloride enclosed in the antimony deposit.The authors show that the influence of varying temperature and of varying hydrochloric acid concentration on the electro-chemical equivalent found for antimony is practically negligible. Their experi- ments show however that the ratio S b Ag does increase with the concentration of the trichloride in the solution which is electzo- lysed ; thus as the said concentration rises from 2.3 to 83.3 per cent.INORGANIC CHEMISTRY. 171 the antimony equivalent increases from 40.29 to 40.63. A similar increase of the equivalent was found with solutions of antimony trichloride in methyl alcohol and of the tribromide and trifluoride in water. It is noteworthy that in the last case the antimony deposited is not explosive nor does it enclose any appreciable quantity of the trifluoride.On t,he other hand all the samples of antimony obtained by electrolysing the tribromide solutions (4.3-68.4 per cent. con- centration) were explosive and were found to contain large quantities of t ri bromide. J. C. P. Alloys of Zinc and Antimony K. MONKEMEYER (Zeit. anorg. Chem. 1905 43 182-196).-Since many of the results quoted in the literature concerning the compounds formed by melting together zinc and antimony are discordant the author has studied the curve of cooling of mixtures of these metals. The temperatures were measured by a thermo-element the wires of which consisted of platinum and an alloy of platinum with rhodium and were connected by means of copper wires with a volfmeter.The temperatures were read every 10 seconds. Zinc melts a t 410' and antimony at 630.6'. From one series of experiments the following are recorded the composition of the molten mixture the temperature at which crystal- lisation began (corresponding with the breaks in the curves of cooling) and the temperatures of the eutectic crystallisation (the simultaneous separation of two crystalline forms). The number of seconds is also noted during which each eutectic cry stallisation lasted. The curve shows two maxima three eutectic points and the two melting points of the pure metals. The evidence for the existence of the compound Zn,Sb is as follows. The curve exhibits a distinct maximum corresponding with 45 per cent. of zinc. At 561" the temperature corresponding with this maximum the solid which separates is uniform.The crystallisation of the fused masses con- taining 50 and 40 per cent. of zinc respectively ends a t 411" and 539' respectively. The presence of the compound Zn,Sb is also deduced from the structure of the alloys containing from 40 to 50 per cent. of zinc. The evidence for the existence of the compound ZnSb is as follows. The curve exhibits a maximum corresponding with 35 per cent. of zinc whilst at 544' the temperature corresponding with t h i s maximum the solid which separates is uniform. The crystallisation of the fused masses containing 40 and 30 per cent. of zinc respectively ends at 539" and 507" respectively. The structure of the alloys is also evidence for the existence of this compound.A. McK. Gold Hydrosols. LUDWIG VANINO (Ber. 1905 38 463-466. Compare Abstr. 1904 ii 80S).-Gold hydrosols may be prepared by warming alcoholic solutions of gold chloride with water. Sodium aurichloride is not reduced so readily. Hydrosols with different characteristic colours may be obtained by working under varying conditions of temperature and concentration. Methyl alcohol may be172 ABSTRACTS OF CHEMICAL PAPERS. used in place of ethyl alcohol and the reaction may be carried out at the ordinary temperature but proceeds very slowly &der these conditions. J. J. S. Supposed Solubility of Aurouls Oxide in Water. LUDWIG VANINO (Bey. 1905 38 462-463).-The so-called solution of aurous oxide in water is in reality a colloidal suspension as the oxide may be precipitated together with barium sulphate or silicic acid (Vanino and Hartl Abstr. 1904 ii 808) and cannot pass through a Puckall filter. It may also be recognised as a suspension by means of gum arabic (Dluthmann Abstr. 1887 636). J. J. S. Comparative Absorption of Hydrogen by Rhodium and Palladium. L. QUENESSEN (Bull. SOC. chim. 1905 [iii] 33 191--193).-The author finds that Wilrn’s statements (Abstr. 1881 514) ( I ) that rhodium absorbs hydrogen more readily than palladium (2) that the absorption capacity of rhodium for hydrogen varies with the method of preparation of the metal and (3) that rhodium exhibits an a s n i t y for hydrogen are inaccurate. Rhodium heated in a current of hydrogen absorbs a little of the gas and on exposure to air the metal so treated gives rise to a small quantity of moisture but no moisture is produced if before the air is admitted a current of dry cold carbon dioxide is passed over rhodium which has been heated in hydrogen. Further rhodium previously heated in hydrogen evolves none of this gas when subsequently heated under reduced pressure. Palladium which has been heated in hydro- gen and subsequently exposed t o a current of cold dry carbon dioxide still retains the property of forming moisture when brought into con- tact with air. T. A. H.

ISSN:0368-1769    

DOI:10.1039/CA9058805156

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

Organic Chemistry. Action of Acetylene on Solutions of Mercuric Chloride. HEIN~~ICII BILTZ (Bey. 1905 38 133-136. Compare this VO~. i 2 ; Hofniann Abstr. 1898 i 635 ; 1899 i 97 485; this VOL i 2).-A criticism of Hofinann's work and a claim for priority. G. Y. Tetraiodoethylene and Di-iodoethylene. ERNST ERDMANN and HUGO ERDMANN (Ber 1905 38 237-240).-Tetraiodoethylene is conveniently prepared in quantity by a modification of Maquenne's method (Abstr. 1893 i 449). Water is slowly allowed to drop into a well-stirred mixture of iodine calcium carbide and benzene the temperature being kept below 4 5 O . The product is freed from di-iodoethylene by distillation with steam and recrystallised from benzene. The authors agree with Biltz (Abstr. 1897 i 389) that the di-iodoethylene is formed as a by-product.Unfavourable results were obtained on using tetrdiodoethylerle in place of iodoform in the treat- ment of wounds. E. F. A. Action of Chlorine on isoButylene. S. A. POGOR~ELSKY (J. Russ. Php. Chem. Soc. 1904 36 11 29-1 184).-The author's experiments described in detail in this paper show that the reaction between chlorine and isobutylene may so far as the products first formed are concerned be represented as follows mCMe,:CH + .nC1 = CMe,Cl .t CH,Cl*CMe:CH + CBle,Cl*CH,Cl + CH,Cl*CMe:CHCl + CH,Cl*CMeCl*CH,Cl+ . . . . The first of these products CMe,Cl requires for its formation the presence of hydrogen chloride but i t appears as a product of the total interaction of chlorine and isobutylene The water in presence of which the chlorination of the isobutylene took place was found to contain small quantities of trimethylcarbinol isobutenol and is0 butyleneglycol.T. H. P. Addition of Iodine Chloride to isoButylene. A. W. ISTOMIN (J. Russ. Plqs. Chenz. Soc. 1904 36 1199-1208).-The addition of iodine monochloride to isobutylene in the cold avoiding an excess of the latter yields a small quantity of isobutylene chloride but mainly isobutplene chloroiodicle [p-cl~ loi.o-a-iodo-P-nzet~p~ropc~ne] CMe,Cl. CH,I which boils a t 69-63' under 20-22 mm. pressnre and has the sp. gr. 1.7502 a t 15"jb". On heating with methyl alcohol i t yields the ether OBSe*CR.le,*CH,I wliicli boils atc 69-70' under 20-22 mm. pressure or with decomposition a t 165-166" under 760 nini. pressure. This ether 1-eacts with magnesium in presence of a small quantity of magnesium methiodide yielding PE-tlinzeth?ll~~exylen~-p€-glycol clinzetlql ethes.OISle*C~~e,.UH,.CH,*C~e~.OnSe which boils at 190-192' under 780 mm. pressure and has the normal molecular weight in VOL. LXXXVIII. i. 1.L166 ABSTRACTS OF CHEMICAL PAPERS freezing benzene ; when treated with hydrobromic acid this compound yields diisocrotylic bromide (Pogorielsky Abstr. 1899 i 785). T. H. P. Action of Water on Hexylene Dibromide (from Mannitol). HEINRICII KLARFELD (Monutsh. 1905 26 83-88. Compare Hecht Annalen 1881 209 311).-When heated with water in a sealed tube a t 160-170O for nine hours hexylene dibromide (b. p. 91' under 17 mm. pressure) yields hexylene and a mixture of methyl butyl ketone and ethyl pi-opyl ketone.Tridecyl Alcohol. J. BLAU (Moncctsh. 1905 26 89-log).- Myristamide (Reimer Abstr. 1885 1197) prepared by Aschan's method (Ab:tr. 1889 i 14) melted a t 105-107' or after recrystallisation at 102 . Some preparations made with commercial phosphorus trichloride melted a t S5". The action of bromine in carbon tetrachloride solution on myristamide dissolved in methyl alcohol followed by sodium meth- oxide leads to the formation of methyl tridec?/Zcurbu1?icite C13H,7-NH*C0,Me which crystallises in small white leaflets and melts a t 53-54' and m yristyltridecylcarbamide C,,H,7*NH.COgNH*CO*C~3H2~,. which crys- tallises in large silky leaflets and melts at 103'. Tridecylamine C,,H,,*NH formed by distilling the urethane or the carbamide with potassium hydroxide absorbs moisture and carbon dioxide from the atmosphere and solidifies to a white mass ; the hydrochloride C,,H,,N,HCl crystallises in small needles and decomposes a t 160' ; the platinichloride (C,,K,,N),,H,PtCl crystallises in yellow spangles and decomposes a t 205' [compare Reimer and Will Abstr.1885 1197 ; Lutz Abstr. 1886 6851. Tridecyl aZcohoZ C,3H27*OH pTepared by the action of silvef nitrite and hydrochloric acid on the amine in aqueous solution melts a t 30.5" boils a t 155-156' under 15 mm. pressure and has a sp. gr. 0,8223 a t 31"/4". On oxidation with potassium dichromate and sulphnric acid the alcohol yields tridecoic acid which melts a t 40'. Reduction of Dimethyltrimethylene Glycol (&3-Dimethyl- propan-ay-diol) by means of Fuming Hydriodic Acid. PAUL MEYERSBEBC (Monatsh.1905 26 41-51. Compare Ape1 and Tollens Abstr. 1896 i 115 ; Just Abstr. 1896 i 403).-When heated with an excess of fuming hydriodic acid in a sealed tube a t 100-1 10" for about 30 hours PP-dimethyltrimethylene glycol yields the iodohydrin and tert.-butylcarbinyl iodide (Tissier Abstr. 1893 i 543). The iodide distils unchanged a t 42-44' under 20 mm. at 52" under 35 mm. pressure has a sp. gr. 1.6317 at 13" or 1.463 at 26" and on treatment with silver acetate in glacial acetic acid solution and hydrolysis of the product with dilute aqueous potassium hydroxide yields tert.-butylcarbinol. When boiled with aqueous potassium car- bonate in a reflux apparatus the iodide yields only a small proportion of the carbinol the remainder being converted probably into the volatile smylene.G. Y. Preparation of Xanthogen Compounds. L. A. TSCHUGAEFF (J. Russ. Phys. Chem. sbc. 1904 36 1253-1258).-The preparation of xanthogen compounds by the formation of the sodium alkyloxide G. Y. G. Y.ORGANIC CHEMISTRY 167 and subsequent action of carbon disulphide and an alkyl iodide requires a long-continued heating of the alcohol with sodium a t a high tem- perature and is often accompanied by isomeric change and the forma- tion of resinous products. The author finds that by usiiig potassium in place of sodium the time required for the reaction is considerably shortened. The fact that primary and secondary alcohols liberate tert. -amyl alcohol (dimethylethylcarbinol) from potassium twt. -amyl- oxide may also be used to simplify the method of preparation of xanthogen compounds as the potassium compounds of alcohols of the terpene series may be prepared in this way.T. 13. P. Action of Dilute Acids on Pinacones. ADOLF I m B E x (Moncctsl~. 1905 26 35-39).-Contrary to what might be expected from Erlen- meyer's theory (Bey. 1851 14 322) the results obtained by Zuinpfe (Abstr. 1904 i 291) and Kohn (following abst.rnct) suggest that the pinacolin formation takes place with those pinacones only which con- tain the grouping :CMe*OH. G. Y. Action of Dilute Sulphuric Acid on Propionepinacone. SIEGFRIED KOHN (Monatsh. 1905 26 11 1-1 18. Compare Zumpfe Abstr. 1904 i 291 ; Lieben preceding abstrmt).-When boiled with dilute sulphuric acid for five hours in a reflux apparatus propione- pinacone yields two products.(1) A hydrocarbon CIOHlS which is a colourless liquid with a pleasant odour boils a t 153-154' is insoluble in water but easily soluble in alcohol ether or chloroform and forms an additive com- pound with 1 mol. of bromine. (2) An oxide C,,H,,O which is a yellow mobile liquid with a characteristic odonr ; it boils at 159-190° does not form an oxime does not react with zinc ethyl a t 100' or with water at 210-220' and when oxidised with potassium permanganate in alkaline solution yields a-ethylbutyric acid and an acid C9H1603 which forms a silvei- salt crystallising in long white needles and therefore is probably an as-oxide. G. Y. Action of Organic Acids on Metals of the Cerium and Yttrium Groups. THEODOR H. BEHEENS (Rec. t m w . chim. 1904 23 413-418.Compare Abstr. 1902 ii SO).-The formates of metals of the yttrium group crystallise in pentagonal dodecahedra. When aqueous solutions of the salts are evaporated at the boiling point until of syrupy consistence they become turbid after some hours and then on addition of water deposit crystals which are from 5 to 8p long dissolve with difficulty in water and readily in formic acid and leave a yellow oxide on ignition. These reactions are similar to those of Marignac's terbium the existence of which the author doubts. Erbium can be detected by examining the absorption spectrum and iron by the usual colour reactions. When acetic acid is added to aqueous solutions oE formates of the yttrium group double salts are precipitated in the form of transparent rhombs 30 to 50p long with an acute angle of 63" optically negative n 2168 ABSTRACTS OF CHEMICAL PAPERS.in the direction of the long diagonal and showing well-marked colours with polarised light. The metals of the yttrium group give salts with the aliphatic hydroxy-acids crystallising in radiating spheroids 50 to 8Op long brown by transmitted light and showing a cross when placed between the nicols. Keedles 120p long can be obtained from dilute solutions. Metals of the cerium group as well as thorium and zirconium give readily soluble salts with these acids. Ammonium fumarate gives precipitates of rhomboidal tablets with both the cerium and yttrium groups the crystals in the former group being from 50 t o 70p and in the latter froin 120 to 150p long. I n both cases the acute angles of the rhombs are 64-66' and the angle of extinction 1 9 O but the fumarates of the yttrium group are the more soluble.Mesaconic acid gives with cerium or lanthanum nitrate spheroidal aggregates of rod-like crystals 15p long and with yttrium or erbium nitrate rectangular rods 20 t o 30p long with angle of extinction 36" and often grouped into bwches. The mesaconates of the last two metals are more soluble than those of the former two. T. A. H. Preparation of Anhydrides of Chloroacetic Acids. THOMAS S. PATTERSON (Bey. 1905 38 2 10 -2 13. Compare Buckney and Thomsen Be?.. 1S77 10 698 ; Antoine J. Pl~ccrn~ Chim. 1883 [v] 8 417 ; Bisclioff and Walden Abstr. 1895 i l'i).-Perfectly anhydrous sodium carbonate has no action on frejhly-prepared chloro- acetyl chloride but when the carbonate has been exposed to the air for a short time it reacts vigorously with the chloride yielding varying amounts of anhydride. The following boiling points for the anhydride are given Pressure .............. 24 36 51 62 104 116 mm.Boiling p i n t ...... 126" 135" 144" 149" 161" 163" For cliloroacetic acid Pressure.. ............ 18 36 68 101 153 207 mm. I3oIling point ..... 93" 108" 121" 130.1" 140.5" 149" For dichloroacetic acid Pressure.. . . . . . . . . 2 1 24 36 71 88 142 164 mill. 1Soiling point ... 99" 102.5" 111.5" 125" 129" 140" 144" J. J. S. Migration of the Ethylenic Linking in Unsaturated Open- chain Acids. EDMOND E. BLAISE and A. LUTTHINGER (Compt. rend. 1905 140 14S-l50).-Fittig has shown (Abstr. 1895 i 204) that the aP-unsaturated acids are converted by the action of alkalis into the corresponding py-isomerides ; in the present paper the authors show that the action of concentrated or SO per cent.sulphuric acid a t 0" on the a-ethyl- a-propyl- a-isopropyl- a-butyl- a-heptyl-acrylic acids on a-methyl-P-ethylacrylic acid or on ap-heuenoic acid causes the ethyleiiic linking to migrate from the shorter into the longer carbon chain giving an up- or a py-unsaturated isorneride the latter formingORGANIC CHEMISTRY. 169 a y-lactone (equation 1). The mechanism of the reaction appears t o involve successive hydrations and dehydrations and in certain cases the ketone resulting from the decomposition of the intermediate a- hydroxy-acid has been isolitted (equation 11) I. CH,R*CH,*C( CO,H):CH -+ CH,R*CH,*CJfe(OH).CO,H -+ CH,R*CH:C;lle*CO,l?C -+ CH,R-CH(OH)*CUIISle.CO,H -+ CHR:CH.CHAle*CO,H -+ CHR(OH)*CH,*CHMe*COsH -+ >o.YHMe-CO CH,-CHR 11. C H,R* CH2* C( CO,H) :CH -+ CH2R* CH,* CMe(0H) CO H -+ CH,R*CH,*CO*CH,. When the carbon atom in the 7-position to the carboxyl groups is primary the ap-unsaturated acid is formed thus a-ethylacrylic acid yields tiglic acid and methyl ethyl ketone ; when the carbon atom in the P-position is tertiary the corresponding ketone is the only product and a-isopropylacrylic acid gives methyl isopropyl ketone and when the carbon atom in the y-position is secondary a ketone and a y-lactone are produced. 35. A. W. Condensation Products from Fatty Aldehydes and Nega- tively-substituted Acetic Acids. EMIL KNOEVENAGEL (D.R.-P. 15 65 60).-F;ttty aldehydes combine with negatively substituted acetic acids such as malonic cyanoacetic acetoace tic benzoylacetic and acetonedicarboxylic acids in the presence of small quantities of ammonia or primary or secondary amines. Valeraldehyde and malonic acid with a little piperidine yield 6-met7uyZhexenoic mid consisting of a mixture of the Aa- and A@-acids boiling at 12'7-132" under 25 mm. pressure. When 2 mols. of malonic acid are employed the product is P-isobzctylglutciric mid which melts at 48" and boils at 205-210" under 15 mm. pressure. Valeraldehyde and cyanoacetic acid yield a-cpno-8-methyl-Aa-hexenok acid melting at 53" and aa-dicya92o-P-isob.tctylgZutaric cicid melting a t 162". Heptalde- hyde and malonic acid yield nonylenoic acid ; heptaldehgde and cyano- acetic acid yield ay-clic?/uiLo-P-~~exyZglzitaric acid which melts at 142'.Citral also condenses with malonic or cyanoacetic acid t o form citrylidene derivatives. The condensation of aromatic aIdehydes with these acids (Abstr. 1899 i 144) requires the addition of a larger quantity of the base. C. H. D. Changes effected by Time on Hydrocarbon Substances of Organic Origin. MARCELLIN BERTHELOT (Con2pt. rend. 1905 140 177- 183).-From the viscous fatty matter extracted from an Egyptian vase belonging probably to the XT7111th Dynasty (B.c. 1600 t o 1370) the author has isolated the acids C,H,,O and C4H803 of the hydroxystearic series in the form of their soluble crystalline calcium salts the ,insoluble residue consisting of a mixture of acids of the hydroxyoleic series CnH2n-293 and of bitumens or resins (C,H,,O),; these acids are possible products of the gradual oxidation of oil of ricirius and it is probable that this oil together170 ABSTRACTS OF CHEMICAL PAPERS.with balm resins bitumens &c. constituted the original contents of the vases. M. A. W. Sodium Acetoacetate and the Formation of Analogous Salts in Solution. JULIUS W. BRUHL and HEINRICEI SCHROEDER (Bey. 1905,38 220-226. Compare Abstr. 1904 i 646 969).-Ethyl aceto- acetate was mixed with the equivalent quantity of sodium ethoxide in absolute alcohol and the spectrocheinical functions of the coniponents of the mixture deterniinecl before and after mixing. A very great change in the dispersion takes place on mixing. Taken in conjunction with the results obtained with the esters of camphorcarboxylic acid (Zoc.cit.) it is beyond doubt that ethyl acetoacetate during salt forma- tion is completely enolised change taking place from a non-conjugated linking to a conjugated system 0 CMe*CH2*C02Et -+ ONa*CMe:CfH*CO,Et. This is discussed a t some length in connection with the theory of WillstPtter and Pummerer (Abstr. 1904 i 1043) that the salts of ethyl acetoacetate with sodium ethoxide are additive compounds of the type CO,R*CH,* CR(0Et) *ONa. It is shown however that the whole optical behaviour of sodiuin acetoacetate can only be explained on the theory that isomeric change takes place. I n general the esters of P-ketonic acids are instantly enolised when they form salts. E. F. A.Ethyl Citrylideneacetoacetate. EMIL KNOEVEKABEL (D.R.-P. 156115).-Ethyl citrylideneacetoacetate (Abstr. 1902 i 342) does not yield a perfume on inversion with acids. If heated for several hours at 160" with or without the addition of water however the ester undergoes a change the boiling point and specific gravity being raised. On inverting the product by means of acids a compound is obtained boiling a t 150-190" under 12 mm. pressure which may be employed as a perfume. C. H. D. Intramolecular Migration of Acyl Groups. WILHELM WIS- LICENUS (Bey. 1905 38 546-548. Compare Abstr. 1901 i 187; 1902 i 72; Bouveault and Bongert Abstr. 1903 i 145; Dieck- mann and Stein Abstr. 1904 i S73).-The author has heated ethyl 0-acetylacetoacetate in total absence of any alkali in a platinum tube a t 240" for three hours and confirms the previous statement that under these conditions about 1 per cent.of the 0-acetyl ester is con- verted into the C-derivative. G. Y. Action of Bases on Chloral Hydrate. JOHANNES E. ENKLAAB (Rec. trav. clkirn. 1904 23 419-439).-Reicher has shown that the rate of decomposition of chloral hydrate by bases is proportional to the excess of base used over that necessary to form with the chloral hydrate a salt of the type CCl,*CH(OK)*OH (ilfaandblaad 1885 18). The author confirms this observation and suggests that the mechanism of the reaction is either that this salt breaks down into chloroform and a formate or that the complex negative ion CCl,*CH(OH)*O* produced by its dissociation gives rise to chloroformORGANIC CHEMISTRY.171 and the negative ion of formic acid the reaction in either case being unimolecular and brought. about by catalysis under the influence of the -OH ions of the excess of the base used. The former explanation is considered the more probable since the reaction velocity is greater in presence of neutral salts of the base used. It is assumed that the addition of such salts diminishes the dissociation of the chloral hydrate salt and iiicreases the total number of positive ions of the base and that these positive ions act as accelerators of the catalysing action of the -OH ions. T. A. H. Condensation of 9%-Butaldehyde by means of Dilute Sulphuric Acid. ADOLF GORHAN (~l4onatsh. 1905 26 73-82. Compare R:iuer Abstr. 1904 i 279; Kadiera Abstr. 1904 i 466).-When heated with 10-40 per cent. sulphuric acid a t 100-200' for 8-30 hours or when heated with fuming hydrochloric acid a t 90' for four hours or when heated in a reflux apparatus a t 85-90' for eight hours rz-butaldehyde is partially converted into Raupen- strauch's a-ethyl-P-propylacralclehyde (Abstr. 1887 794) and an un- saturated ccldelyde C,,H,,O which is a viscid oil and boils a t 160-162' under 1 2 mm. pressure. It has a pleasant odour reduces ammoniacal d v e r solutions forms a crystalline precipitate with pheuylhydrazine and with bromine in chloroform solution a t low temperatures yields the addit ice compound O1,H 2202Br2. G. Y. Condensation of Formisobutaldol with Acetaldehyde. ALOIS SCHACHNER (Monatsh. 1905 26 65-72. Compare Wessely Abstr. 1900 i 428).-The action of formisobutaldol on acetaldehyde in presence of aqueous potassium carbonate leads to the formation of the product OH*CH;CMe,*CH(OH)*CH,*COH which in the solid state has the bimolecular formula (C,Hl,03)2 (compare Kohn Abstr.1900 i 274). It crystallises in sheaves of white needles melts a t 8 4 O is more soluble than formisobutsldol in water or the ordinary organic solvents does not form an additive compound with broinine and on distillation decomposes into forivisobutaldol and acetaldehyde G. Y. Chloromalonaldehyde. WALTER DIECKMANN and LUDWIG PLATZ Compare this vol. i 117).-An acknowledg- (Bey. 1905 38 339. ment of priority. W. A. D. An Isomeride of Trichloroacetone. GUSTAVE PERRIER and EUG~NE PROST (Compt. rend. 1905 140 146-148).-An attempt to replace the chlorine in chloral by the grouping OEt by the action of aluminium ethoxychloride Al,Cl,(OEt) (compare Perrier Abstr.1901 i 442) was unsuccessful the product obtained being an isomeride of trichloroacetone C,H,OCl boiling a t 182-187" under 764 mm. or a t 101-103" under 30 mm. pressure having a sp. gr. 1.423 a t 15' and an odour similar to that of the terpenes. It yields chloral when warnled with sulphuric acid chloroform when oxidised by chromic mixture or carbylamine when heated v i t h a mixture of potassium hydroxide aniline and alcohol. All these reactions show172 ACSTRACTS OF CHEMICAL PAPERS. that the three atoms of chlorine in the compound are associated with the same carbon atom and as it differs from trichloroacetone in respect of its insolubility in water and in not being attacked by hot or cold ammonia the authors suggest the following provisional constit u- CH tional formula for the compound CCI,*CH< I .0 31. A. W. Chlorination of Methyl Ethyl Ketone. ANDR~ KLING (Con@. rend. 1905 140 312-314. Compare Vladesco 1892 424 810; Reymenant 1901 i 126).-The action of chlorine on methyl ethyl ketone in presence of water and calcium carbonate leads to the forma- tion of two monochloro-substitution products. The action takes place most regularly at 60-70'. At low temperatures the action frequently only begins when a considerable quantity of chlorine has been absorbed by the solution and there is then danger of explosion. The products of incomplete chlorination are the same when t.he ketone is acted on by sulphuryl chloride by free chlorine or by chlorine in presence of iodine but the bes0 results are obtained by the first method.The two products can be separated by repeated fractionation. The one which boils a t 40-41' under 30 mm. and a t 114-117' under 760 mm. pressure is nzet?Lyl a-chloroethyl ketone CH,*CBCl.COMe. The other boils a t 59-60' under 30 mm. and a t 134-136' under 760 mm. pressure and is chloronzethyl ethyl ketone COEt CH2Cl for on converting it into the corresponding alcohol and reducing this the glycol OH*CHEt* CH,. OH is obtained. a t 125* was probably a mixture of these two substances The substance obtained by Reymenant and stated to boil H. M. D. New Method of Synthesising Saturated Ketones by Catalytic Reduction. GEORGES DARZENS (Cornpt.rend. 1905 140 152-1 53).-Aliphatic unsaturated ketones of the type C,,H2n- ,O are converted into the saturated ketones C,H,,O by direct hydrogenation a t 180-190° in the presence of nickel obtained by reducing nickel oxide at 245-250' (compare this vol. i 66) and the following ketones were thus prepared methyl isobutyl ketone from mesityl oxide ; methyl isoamyl ketone from methylhexenone and methyl isohexyl ketone from natural methylheptenone or from the synthetical com- pound M. A. W. Addition of Hypochlorous Acid to Allene Hydrocarbons. 11. F. W. SMIHNOFF (J. Buss. Plqs. C'l~enz. Soc. 1904 36 1184-1199. Compare Abstr. 1904 i 214).-The action of hydro- chlorous acid on unsymmetrical dimethylallene yields as principal product chlorometlyl ?h ydrole~iso~)ro~~yZketone OH C Me CO * CH2Cl which boils a t 84-85' under 10 mm.pressure; the ncetpZ derivative OAc*CMe,*CO-CH,Cl forms crystals melting at 47.5" and boiling at 102-104' under 10 mm. pressure and the pl~enylosaxone OH*CMe,.C(N,HPh)*CH:N,HPh separates from alcohol in golden-yellow crystals melting at 141'. The other products of the reaction are (1) chloromethyl chloroiso-ORGANIC CHEMISTRY. 173 propyl ketone and (2) /3/3-dichloro-a&dihydroxy-y-rnethylbutane O H * CMe,*CCI a*CH,* OH which forms crystals melting a t 151' dissolves readily in alcohol or ether and to a less extent in benzene or water and reduces Fehling's solution in the cold. The above products are what would be expected according to theory to be formed in this reaction. T. H. P.Birotation of Galactose. GUNNAR HEIKEL (Anncden 1905 338 71-104).-The most probable cause of the birotation of an aldhexose is the existence of two stereoisomeric lactone forms which are very readily transformable into one another possibly through the inter- mediary stage of the aldose. This supposition has found support in the fact that pyridine solutions of dextrose of different rotatory powers yield two penta-acetates (Abstr. 1904 i 667). On investigating galactose i t mas found that an aqueous solution had [aIu 80.8" a t 20" but in anhydrous pyridine a t first [a] 170" and finally [.ID 55.6' Solid galactose when acetylated in pyridine solution at O" yielded a penta-acetate C6H7O8Ac5 which could not be crystallised and had La] + 71*B0 in benzene a t 20". The already known P-penta-acetate prepared by acetylating a t the ordinary tem- perature melts at 141*5-142" and has [a] 59*2" whilst an amor- phous substance formed a t the same time has [a] 60.S'.When the acetylation is carried out a t loo" the same /3-acetate and a product having [.ID 38*6" and when the acetylation is carried out in pyridine a t 50-60" the p-acetate and a product having 49.7" are obtained. The acetate having [a] 71.8" is probably the pure isomeric a-acetate whereas the other amorphous forms are taken to indicate the existence of a third y-acetate. The behaviour of galactose dissolved in boiling pyridine confirms this supposition since an initial rotation of [.ID 31" changes slowly into the rotation of [.ID 59.26' when the solution has cooled. It seems probable that the y-penta-acetate corresponds with the aldehyde form of the sugar.I n aqueous solution the a-galactose with the high rotatory power changes into a mixture of the P- and 7-galactoses. A t a higher temperature the equilibrium changes in favour of the y-galactose!. Attempts to convert the penta-acetates into different methylglucosides yielded only the mixture of known glucosides. K. J. P. 0. ROBERT BEHREND (Annalen 1905 338 105-1 07. Compare preceding abstract).-Since Heikel has shown that a t least three modifications of galactose exist it is probable that dextrose also possesses an aldehyde form. In order t o demon- strate that the birotation of dextrose is not due to hydration dextrose was dissolved in anhydrous pyridine at 0" and the rotatory power determined after given intervals of time.The change was found to be a reaction of the first order ; if it was a case of hydration the reaction would have been one of the second order ; further it is not probable that dextrose would take up water from pyridine which potassium hydroxide was not capable of withdrawing. [Birotation of Dextrose.] I(. J. P. 0.1'74 ABSTRACTS OF CHEMICAL PAPERS. Influence of Inactive Substances on the Optical Rotation of Dextrose. INA A. MILROY (Zeit. physikal. Cl~em. 1904 50 443-464).-The following substances when added to an aqueous solution of dextrose are found to increase the specific rotation the dextrose solution being first kept for 2.t least 24 hours after its preparation phosphoric arsenic and boric acids aluminium acetate cerium sulphate lead acetate sodium tungstate ammonium molybdate methyl ethyl n-propyl and isopropyl alcohols acetone acetaldehyde and glycerol.In general the increase OE the specific rotation is approximately proportional to the amount of added substance. When methyl and ethyl alcohols are added the rotation does not a t once assume a steady value but gradually increases with the time becoming constant after 48-72 hours. I n the case of n-propyl alcohol and acetone the same phenomenon is observed only for the larger additions of these substances; when the added quantities are smaller the rotation falls off with the time finally reaching a constant value which however is still greater than that for dextrose alone. The following substances added to dextrose solutions diminish the specific rotation potassium sodium and barium hydroxides ethyl- amine diethylamine triet hylamine pyridine borax mercuric chloride aniline hydrochloride dimethylaniline hydrochloride phenol and pyrogallol. So far as the bases in this list are concerned the diminution of rotation is more extensive and more rapid the stronger the base.It will be observed that in general the effect of acids is t o increase the effect of bases is to diminish the rotation of dextrose. The following substances are found to be without effect on the rotation magnesium sulphate ammonia alum thorium uranium and copper nitrates and ferric chloride _ - [Compare somewhat similar work on lactose Trey Abstr. 1904 i 292.1 J. C. P. ' Casium Methylamide. ETIENNE RENGADE (Compt.rend. 1905 140 246-248).-Moissan has shown that cmium reacts with ammonia at 40" to form casium-ammonium (compare Abstr. 1903 ii 477) and the author finds that although the metal dissolves in methylamine at - 20° the solution of casium-methylammonium thus obtained decomposes readily giving off hydrogen and forming caesium- methylamide NHMeCs in white silky crystals which decompose explosively on being rapidly heated or on contact with moist air ; at 115' to 120° however they are gradually decomposed with the formation of caesium cyanide and the liberation of hydrogen and they are slowly decomposed by water yielding methylamine and casium hydroxide. A$. A. W. Diaminoguanidine. GUIDO PELLIZZARI and C. CAKTONI (Ber. 1905 38 283-284).-A claim for priority (compare Stoll6 and Hofmann this vol.i 28). Condensation of some Esters with Ethyl Carbamate and with Ethyl Aminoacetate. OTTO DIELS and 1jANS HEINTZEL (Ber. 1 9 05 38 2 9 7-30 5).-Ethyl bromoacet ylcarbamcite W. A. D. CH,Br* CO*NH*CO,Et,ORGSNIC CHERIISTRP. 175 prepared by boiling an ethereal solution of ethyl bromoacetate and ethyl sodiocarbamate CHNa*CO,Et crystallises from dilute alcohol in long slender needles and melts a t 120-121". Ethyl a-bronto- propio?L~Zcarbumate CHMeBr*CO*NH-CO2Et prepared in similar manner from ethyl a-bromopropionate crystallises from dilute alcohol or from ethyl acetate in short thick prisms sinters a t Y7" and melts at 100-101". Ztl~yZ a-bromobut~rylcarba~~z~~te is similar and melts a t 80-81" ; e t i q l a-b~~orrzoisobuty~~ylcurb~~~~zute melts a t 63--64O.As the length of the carbon chain of the halogen acid increases the ease of interaction with ethyl carbamate diminishes. Ethyl cinnu~zoylcarbuntc~te CHPh:CH* CO*NH*CO,Et prepared from ethyl cinnamate and ethyl carbamate crystallises from a mixture of light petroleum and ethyl acetate in long needles melts at l l O - l l l o and combines with bromine forming the dibromide CHPhBr*CHBr*CO*NH* CO,E,t which melts at 131-132'. Ethyl sodiocarbamate simply eliminates 2HBr from two molecules of ethyl bromomalonate giving rise to ethyl ethylenetetracarboxylate C(C02Et)2:C(C0,Et)2. I n presence of potassium hydroxide ethyl aminoacetate combines with ethyl chloroacetate alcohol being eliminated to form ethyl c7~Zo~oucetylanzinoacetute CH2C1*CO*NH*CH2*C02Et which crystal- lises from a mixture of ethyl acetate and light petroleum in thin rectangular plates and melts at 62-43'.Ethyl cyanoacetylanziizo- ucetute obtained in similar manner from ethyl cyanoacetate crystal- lises from water and melts a t 100-101". Ethyl aminoacetate combines with ethyl sodiocarbamate alcohol being eliminated t o form ethyl hydantoate which was not isolated but characterised by i t s giving rise to hydantoin. W. A. D. Internally Complex Metallic Salts. [Copper Glycine.] HEIN- RICH LEY (Zeit. EZektroclLem. 1904 10 954-956).-The molecular weight of copper glycine dissolved in water as determined by the freezing point method is almost normal and its conductivity in aqueous solution is very small. The copper in this salt has been represented as replacing the hydrogen of the carboxyl groups or that of the amino-groups.The latter formula is doubtful because diethylaminoacetic acid forms a salt which is quite analogous to the copper salt of glycine. The following experiments prove that the copper is linked to oxygen and not to nitrogen. When ammonia is added to a solution of copper glycine no change in the deep blue colour of the solution takes place but by determining the co- efficient of partition of the ammonia between the solution and chloro- form it is shown that the ammonia has combined with the salt. The combination might yield the salt Cu(NH*CH,*CO,NH,) or the com- plex cathion [Cu(NH,),,] and the anion NH2*CH,*C02. An experiment showed that the blue colour moves toward the cathode when the solu- tion is electrolysed proving that the copper exists in the cathion.In order to explain the dark blue colour of the solutions the author supposes that the salts are internally complex the NH2 groups playing It is therefore very little dissociated.176 ABSTRACTS OF CHEMICAL PAPERS. the same part as the MI molecules attached to copper in the complex copper ammonia compounds. T. E. Hydrolysis of Leucine Ethyl Ester by the Pancreatic Fer- ment. OTTO WARBURG (Ber. 1905 38 187-188. Compare E. Fischer and Bergell Abstr. 1903 i 694; 1904 i 867).-When the synthetical racemic ethyl ester of leucine is left in contact with water and crude pancreatin a t the ordinary temperature the d-ester is not hydrolysed whereas the Lester yields I-leucine. Fresh pancreas juice has the same effect.This affords a further example of ' I asymmetric hydrolysis." J. J. S. Betaine Ethyl Ester Hydrochloride. ALBERT KOEPPEN (Uer. 1905 38 16'1-1 69).-Betuine ethyl ester Iigdrochloride prepared by the action of 33 per cent. alcoholic solution of trimethylamine on ethyl chloroacetate separates from ethyl alcohol in deliquescent crystals and melts a t 143.5'. Its ylutinichloride (NMe,*CH2*CO,Et),PtCl forms glistening orange-coloured crystals. When boiled for two hours with hydrochloric acid betaine ethyl ester hydrochloride forms betaine hydrochloride which was identified by its crystalline form and by its platinichloride. Betaine ethyl ester itself could not be prepared by the action of moist silver oxide on its hydrochloride. A.McK. Formation of C-Acyl Derivatives from Ethyl Cyanoacetate by means of Pyridine and Quinoline. ARTHUR MICHAEL and 0. ECKSTEIN (Be?,. 1905 38 50-53. Compare Dieckmann and Breest Abstr. 1904 i 845).-The experiments of Claisen and Haase (Abstr. 1900 i 373) make it probable that the question whether an 0- or a C-derivative is formed in the acylation of ethyl acetoacetate and similar compounds by the pyridine method depends on the stability of the primary additive product towards the base. Ethyl cyanoacetoacetate prepared by the action of acetyl chloride and pyridine on ethyl cyanoacetate in the cold forms a semicccrbuxone crystallising in colourless needles and melting at 190'. When benzoyl chloride is added to a mixture of ethyl cyanoacetate and pyridine even at a low temperature a brown substance is produced.On replacing the pyridine by q uinoline however ethyl cyanobenzoyl- acetate is obtained (compare Haller Abstr. 1886 240). A netitral compound containing nitrogen but of unknown constitution was also obtained crystallising from dilute alcohol in almost colourless microscopic needles melting at 178" and dissolving readily in organic solvents. Ethyl ethylacetoacetnte and ethyl methylacetoacetate do not yield acetyl derivatives with acetyl chloride and pyridine. C. H. D. Supposed Existence of Thiocyanate of Iron and Probable Constitution of the Hsemoglobin of the Blood. NAZARENO TARUGI (Gaxxettu 1904 34 ii 326-348. Compare Abstr. 1903 ii 460 and 1904 ii 320; and Vitali Abstr. 1904 ii,,104 and 600).- Free thiocyanic acid does not give van Deen's reaction because this isORGANIC CHEMISTRY 177 characteristic of the normal thiocyanogen group while the free acid contains the iso-form which when introduced into a salt is converted wholly or partially into the thiocyanogen group.The red coloration formed by the action of ferric chloride on a thiocyanate is due to the formation of the iron salt of a peroxyt?biocyanic acid according to the reversible equation 12FeC1 + 6H20 + GKCNS 2FeHC,N30,S + 6KCl+ lOFeCI + lOHC1. The free acid C3H303N3S3 as well as all its acid salts have a red colour. Solutions of oxalates tartrates &c. decolorise the acid and convert it into the corresponding normal salts which are again decomposed by mineral acids with liberation of the peroxy-acid and formation of a red coloration.When a dilute solution of the free acid is heated it becomes decolorised and oxygen is liberated from the acid while the sulphur present is oxidised t o sulphuric acid. With concentrated solutions heating produces an increase in the depth of colour. Peroxythiocyanic acid may also be prepared by the oxidation of thiocyanates in ethereal solution by means of nitric or chromic acid. The ethereal solution of the acid is decolorised by reducing agents. The author expresses the structure of hzmoglobin as (x)-N,C,S,* Fe*Fe*N,C,S,* (x) and that of oxyhzmoglobin as (x)*N,C,S,O,*Fe*Fe*N,C~S~O~* (x) where ( x ) represents an albumin group. T. H. P. Two Complex Salts of Molybdenum. ALBE RTO CIHLESOTTI (Guxxettcc 1904 34 ii 493-503).-The interaction of the double chloride of molybdenum and potassium (Abstr.1903 ii 730) with potassium thiocyanate yields a thiocpnute of molybdenum and potussium K3Mo(CNS),,4H,O which forms orange-coloured crystals readily soluble in water and readily loses water of crystallisat ion becoming dark red or if completely dehydrated in a desiccator over phosphoric oxide or by heating almost black in colour. I n the neutral solution of the double salt hydrogen peroxide produces a green coloration which changes to blue and finally to yellow; hydrogen cyanide appears to be formed in this oxidation. Bromine added to an alkaline solution of the salt produces the same changes of colour. Lead acetate gives an orange-yellow precipitate insoluble in acetic acid silver nitrate a flocculent yellow precipitate and mercuric nitrate a brick-red precipitate which becomes black on boiling the solution.Mercuric chloride yields a vivid red precipitate which turns yellow and has probably the composition [ Mo( SCN),],Hg3. With potassium cyanide the double chloride of potassium and molybdenum yields the double cyunide Mo( CN),K 2 H,O which forms yellow crystals readily soluble in water yielding a neutral solution. The solution is stable when kept away from strong light but when exposed to the direct action of the sun’s rays its colour changes almost instantaneously to red and then to pale green hydrogen cyanide being simultaneously formed. That the formula of the salt is that given above and not a multiple of it is shown by conductivity determina- tions. Even in extremely dilute solution ferric chloride is coloured an intense blue by solutions of the double cyanide.Solutions of silver and mercurous salts give voluminous pale yellow precipitates178 ABSTRACTS OF CHEMICAL PAPERS. insoluble in dilute acids. This double cyanide presents the first known case of a complex ion which is stable in solution and which contains a metal combined with eight halogenic residues. T. H. P. Condensation of Natural Leucine and Carbamic Acid. Lours HUGOUNENQ and ALBERT MOREL (Compt. rend. 1905 140 150- 15 1 ).-is0 Butyll~ydantoic acid NH,*CO*NH*CH( CH2Prp).C0,H obtained by dissolving leucine in excess of carbamide at 130-135" crystallises in very white needles decomposing at 200-210° is slightly soluble in cold readily so in boiling water or alcohol insoluble in mineral acids but dissolves in acetic acid forms soluble salts with the alkali metals and is decomposed by sodium hypobromite forming NH- QH- C H P ~ - obtained byheat- NHsCO leucic acid.isoButylhydantoin CO< ing isobutylhydantoic acid a t 250° crystallises in silky needles melting a t 200-2 1 Oo is slightly soluble in cold water readily soluble in cold alcohol insoluble in mineral acids but soluble in alkalis owing to the acid nature of the hydrogen atom of the imino-group situated between two carbonyls ; it is not acted on by sodium hypobromite and on prolonged boiling with water it is converted into isobutyl- hydantoic acid. M. A. W. Cyanodialkylacetylcarbamides. FIRMA EMANUEL MERCK (D.R.-P. 156383. Compare this vol. j i 179).-M7hen the esters of dialkylcyanoacetic acids react with carbamide or its alkyl deriva- tives in the presence of a metallic ethoxide a t the ordinary tempera- ture c yanodial kylace tylcarbamides are f orrned which condense on heating to form iminodialkylbarbituric acids.Thiocarbamide or guanidine map also be employed in place of carbamide. a-Cyano-a-ethylbutyrylcarbc~~ide CN*CEt,*CO*NH.CO*NH from ethyl a-cyano-a-ethylbutyrate carbamide and sodium ethoxide crystal- lises from hot water melts a t 118O and dissolves in alcohol ether or ethyl acetate. Cyanoetl~~l~ulyrylthiocarbcc.nzide forms slender yellow needles and melts and decomposes at 2 6 1 '. Cyaizoethylbutyrylguccrtidine dissolves readily in water. a-Cyano-a-popylvalerylcarbumide crystallises from alcohol in colourless prisms and melts a t 101".Cyanoet/ql- butyrylphenylcarbanaide from ethyl cyanoethylbutyrate and phenyl- carbamide forms long flat prisms and melts a t 156". C. H. D. Preparation Use and Recovery of Semicarbazide. LOUIS BOUVEAULT and RENI~:LOCQUIN (Bull. Soc. chim. 1905 [iii] 33 162-165).-Details are given of a method of preparing semicarbazide which is a slight modification of that used by Thiele and Stange (Abstr. 1894 i 165). I n the preparation of semicnrbazones the authors dissolve free sernicnrbazide in as little water as possible add to the solution a few drops of acetic acid and finally the aldehyde or ketone and suficient methyl or ethyl alcohol to give a clear solution which is finally warmed on the water-bath for 15 minutes This process gives better results than the use of semicarbazide hydrochloride in combinafion with sodium acetate.ORGANIC CHEMISTRY. 179 I n regenerating a ketone or aldehyde from its semicarbazone the latter is boiled for one hour in a reflux apparatus with a slight excess of dilute sulphuric acid (15 per cent.) and the aldehyde or ketone finally distilled off in a current of steam.The residue contains hydr- azine sulphate and semicarbazide sulphate. On concentration and cooling the former crystallises out from the mother liquor; after neutralisation with potassium carbonatme and concentration under reduced pressure two-thirds of the hydrazine initially used may be recovered as the sulphate by extraction with alcohol. T A. H. Imino-CC-dialkylbarbituric Acids. FIRMA EMANUEL MERCK (D.R.-P.156384. Compare Abstr. 1903 i 799 ; 1904 i 380 ; this vol. i 17S).-Carbamide reacts with the esters of dialkplcyanoacetic acids on warming with sodium ethoxide in alcoholic solution on the water- bath f orming iminodialkylbarbituric acids CR R t < ~ ~ x ~ ~ ~ > C O from which the corresponding dialkylbarbituric acids are readily obtained by heating with dilute acids. Inainodiethy?,barbituric acid from carbamide and ethyl cyanoethyl- butyrate melts and decomposes at 195' and dissolves in 136 parts of water a t 20' and in 23.5 parts at 100'. Inzinodipropylbarbituric acid melts and decomposes a t 305' ; iminodibenz~lbarbitur~c acid crystal- lises from hot alcihol ; i7,ainoeth~l~ro~~y~b~rbi~~iwic acid melts at 302'. c1. H. D. Preparation of Barbituric Acid and its Homologues.FIRMA EMANUEL MERCK (D.R.-P. 156385. Compare preceding abstract).- Dilute acids hydrolyse the alkyl derivatives of iminobarbituric acid on heating yielding alkylated barbit uric acids. Bipropglbarbituh acid melts a t 146' ; dibenzylbarbituric acid melts a t 222' ; pi-opylbccrbituric acid (from inaino~rop~~bcci.titu~i~ acid melt- ing at about 300') melts a t 207'; etl~y~ropylbarbituric acid forms large colourless needles and melts at 145'. C. H. D. Nitriles of Hydroxy- and Amino-carboxylic Acids. EMIL KNOEVENAGEL (Ber. 1905 38 213-217. Compare Trans. 1904 i 981 989 994 1024 1027 1028).-Polemical. A reply to Bucherer's criticisms (this vol. i 59). J. J. 8. Copper Double Cyanides. HERMANN GROSSMANN and PETER VON DER FORST (Zeit.ccnorg. Chem. 1905 43 94-110. Compare Abstr. 1904 i 983).-The sodium salt NaCu2(CN),,2H2O prepared by the action of cuprous cyanide on a concentrated solution of sodium cyanide forms glistening rnonoclinic crystals. The ammonium salt NH,Cu2( CN),,H,O forms prismatic needles. LiCu,( CN) 3H,O forms prismatic needles. These three salts are readily decomposed by w a t er . The ru6idCurn salt Rb,Cu,(CN) crystallises in octahedral leaflets. The ccesium salt Cs2Cu,(CN) separates in tetragonal or hexagonal The Zithium salt,180 hBS'1'R AC'I'S 0 F CII E ICI IC A L P APE RS . cubes. The cnlciuna salt CaCu,(CN)5 forms rhombic prismatic needles. The ammonium salt NH,CU(CN)~ prepared by careful evaporation a t 70' of the liquid from which the salt NH,Cu,(CN),,H,O has been removed separates in nacreous leaflets.The rubidium salt RbCu(CN) prepared by the interaction of rubidium carbonate cuprous cyanide and hydrocyanic acid forms rhornbic plates. CsCu(CN) 1$H,O forms glistening needles. tallises in plates and in rhombic pyramids. forms monoclinic plates. The magnesium salt MgCu2(CN),,11 H,O separates in monoclinic needles. The cmium salt Cs,Cu(CN),,H,O crystallises in leaflets. The 6ariunt salt FaCu2( CN),,3H20 forms prismatic needles. 'l'he calcium salt CaCu( CN),,4H20 forms prismatic needles. The authors have obtained these salts from mother liquors from which other salts had been removed. From determinations of the lowering of freezing point the conclu- sion is drawn that the salt K,CU(CN)~ undergoes hydrolytic dissocia- tion in very dilute solution.The sodium salt Na,Cu(CN),,3H20 fornis hygroscopic hexagonal leaflets. Crystallographic measurements of most of the salts examined are given. A. McK. The cmsiu,na salt The bariunz salt BaCu,( CN),,4H20 crys- The strontium salt SrCu( C"),,8H20 Its eIectrolytic conductivity was measured. Derivatives of Formhydroxamic Acid and the Possible Existence of Esters of Fulminic Acid. HENRY C. BIDDLE (Amer. Chem,. 2 1905 33 60-68).-Attempts have been made to prepare benzyl fulminate and the corresponding benzoyl and acetyl derivatives by the elimination of hydrogen chloride from the benzyl benzoyl and acetyl derivatives of chloro-formoxime (Abstr. 1900 i 137) but without success. Methyl formhydroxccmate COH*NH*OMe prepared by the action of formic acid on a-methylhydroxylamine is a colourless liquid which boils at 116-117° under 33 mm.a t 123-124' under 45 mm. and a t 126-127" under 50 mm. pressure; i t solidifies in colourless prisms and melts a t 38-39O. The ester is deliquescent and is decomposed by hydrochloric acid with formation of formic acid and a-methylhydr- oxylamine hydrochloride. When treated with solution of platinic chloride the ester undergoes dissociation and the platinichloride of a-methylhydroxylamine is produced. The s i l v e r salt of methyl form- hydroxamate forms white leaflets and reacts with acetyl and benzoyl chlorides and with methyl and ethyl iodides with formation of the corresponding acyl and d k y l derivatives. When nioleculm propor- tions of methyl forinhydroxamate and phenylcarbirnide are .warmed together an additive cornpound is produced which cry stallises in colourless leaflets melts a t 123-123.5" and is readily soluble in chloroform and sparingly so in ether alcohol or hot water.By the action of phosphorus pentachloride on methyl formhydr- oxamate nhet7LglZ chhroformoxinae CHCl:N*OXe is producd as aORGANIC CHEMISTRY. 181 volatile liquid which boils a t 6S0 has an odour like that of chloro- form,and is slightly soluble in water. When this substance is treated with potassium hydroxide small quantities of a neutral unsaturated compouzad are produced which has a strong orlour resembling that of isonitriles boils a t about 50-60° and is probably methyl fulminate C:N*OMe but has not yet been isolated in sufficient quantity to admit of its identification. Methyl fulminate also appears to be formed by the interaction of a-methylhydroxylamine hydrochloride chloroform and alcoholic potassium hydroxide the same isonitrile-like odour being produced E.G. ROLAND SCHOLL (Annulen 1905 338 1-35).-The ketoximes of the fatty series are converted by nitrous acid or nitrogen peroxide into $-nitroles but in the case of the oximes of yinscolin camphor camphenone fenchone menthone tanxcetone mesityl oxide and santonin the oxime group is exchanged for the group N,O,. This reaction is confined to ketoximes in which tlie group >C:N*OH is linked to a tertiary o r quaternary carbon atom. The group C,HN,O which is produced in this reaction must either have the constitution >C:&NH*NO an enylnitroamine or >CH*b:N.-\O a nitroimine.Since the compounds do not react with phenylcarbimide and diazomethane the latter formula is the more probable. The nitroimines are $-acids and yield a series of salts which Nitrimines and Nitriminic Acids. correspond with an acid of the formula >C:C*N:NO.OH or When the acid is set free from its salts it is immediately reconverted into the nitroimine but since the salts yield the two series of alkyl derivatives >C:C!*N<r'oR and >(::C*NR*NO it is probable that an enylnitroamine is intermediarily produced in the conversion. Of the two possible constitutions of the group present in the salts N,O*OH the expression N<b is preferred since it represents more simply the cleavage of the mesitylnitroiminic acid into nitrous acid and a-mesityloximc and a t the same time the formation of nitro- imines froin oximes and nitrous acid. Only those oximes are capable of undergoing this reaction which have a loosely bound hydrogen atom on the P-carbon atom relatively to the oxime group thus This hydrogen atom together with the hydrogen atom of the oxime group combines with the oxygen of the nitrous acid in the condensa- tion; a group >? >N*OH is thus formed which then by re- arrangement passes into the group >C:b*N< I I 0 N-OH >CHA:N-OH.-C:N-O N*OH 0 - [With A. 0. WEIL and K. HOLDERMANN.]-PinsCOlinOXime on VOL. LXXXVIII. i. 0182 ABSTRACTS OF CHEMICAL PAPERS. treatment with phosphorus pentachloride in dry ether is converted into acetyl-tert.-but&micZe CMe *N€€Ac which crystsllises in needles melts a t 95" sublimes very readily and Soils at 1!)4O ; its Iqdrochloride formed from the ethereal solution is very Iiygroscopic.From this tmnsforination it follows that the oxinie 'has t h e anti-configuration Pinncohnoxime reacts with phenylcnrbamide yielding the conbpound C,Hrl,:NO*CO*NHPh which crystallises in needles melting a t 131 -5O. L'he a c e t y l derivative of the oxime C,H,,:N 'OAc is an oil boiling a t 83-84" under 10 nim a t 100-lO1° under 25 mni. and a t 208-21Q0 under the atmospheric pressure. Pi?zrCcoZin-nitroiniine C Me,*CMe:N-NO is prepared by dissolving pinacolinoxime in ether and adding nitrogen peroxide and by fractiona- ting the product after removal of the acid by water and alkali. It boils at S0*5-8lo and is always mixed with oxime and methyl-tert.-butyl- dinitromethane CMe;CMe(NO,) which separates as a crystalline hydrochloride when the nitroilnine is dissolved in concentrated hydro- chloric acid ; it forms very volatile crystals smelling of camphor melts a t 173-174' and boils a t 101-103° under 34 mm.pressure. The salts of the nitroimine are formed when it is heated with concen- trated alkali hydroxides but the ammonium salt is not produced by passing dry ammonia into a solution in anhydrous ether. It is oxidised by permanganate and reduces ammoniacal silver solutions. It does not react with diazomethane or phenylcarbimide and when distilled under the ordinary pressure decomposes into pinacolin. On broniina- tion it yields dibroniopinacolin C,H,oOBr2 (m. p.74*5") which is identical with the substance obtained from 66-dibromo-PP-climethyl-y- butanone. On reduction with aluminium amalgam in moist ether the nitroimine is converted into the oxime. The sodium salt obtained from the nitroimine by the use of sodium ethoxide crystallises in silky hygroscopic needles which are hydrolysed in aqueous solution ; the potassium salt forms hygroscopic needles and the silver salt a greyish-white precipitate. When the sodium salt is heated in methyl-alcoholic solution with methyl iodide for 2 hours a N-methyl derivative CMe,*C(CH,)*N Ne*NO is obtained in the form of volatile crystals melting a t 39" and decomposed by hydrochloric acid methylamine being produced ; it is not oxidised by permanganate. The corresponding ethp? isopropyl and n-butyl derivatives are oily liquids of peculiar odour. IS*OMe CMe,*C(CH,)*N<b is prepared from the silver salt and methyl iodide a t a low tempera- ture in ethereal solution; it is an oil which is readily oxidised by alkaline permanganate and decomposed by hydriodic acid methyl iodide being formed.The corresponding ethyl ester is a yellow oil. The nitroimine also yields a series of AT-scyl derivatives when the sodium salt is treated with acyl chlorides in hot anhydrous alcohol ; the ucetyl 6enxo92 and 6 e n x e ? ~ e s u l ~ ~ ~ o ? z i c compounds were all thus pre- pared and formed oils which are not decomposed by water.. The 0-methyl ester K. J. P. 0.ORGANIC CHEMISTRY. 183 Platinum Phosphorus Halogen Compounds and their Derivatives. 11. ARTHUR ROBENHEIM and WALTER LEVY (Zeit.anorg. Chem. 1905 43 34-47. Compare Abstr. 1904 ii 131).- By the action of organic amines on alkyl phosphite-platochlorides two series of isomeric compounds RNH,PtCI,P(OR') are produced. The stable series probably corresponds with platososmmine chloride and the labile with platosemidiammine chloride. When aniline is gradually added to a solution of ethyl phosphite- platochloride [P(OEr ),,PtCI,] in alcohol or benzene a t O" crystals of the yellow compound PtPC1,,Cl,Hl,O,N first separate whilst from the filtrate silky needles of a colourless compound isomeric with the former separate. The relative proportion of those compounds pro- duced is dependent on the temperature conditions the latter being formed in larger amount the higher the temperature.The yellow compound is the labile form ; a t its melting point 1OSo it is trsns- formed into the white variety which melts a t 147". The transformation isalso effected on exposure a t the ordinary temperature or on rubbing with a glass rod. The yellow form is probably cis-triethyl phosphite- anilineplatochloride [z;PtEg$k] whilst the white compound is probably tram-triethyl phosphite-anilineplatochloride [ $ o E t ) 3 P ~ ' ~ ~ p h ] . The analogous pyridine compounds PtYCI,,C,,H,,O,N wore pre- pared. The two isomerides were crystalline and resembled the corre- sponding aniline compounds. The action of ammonia was different from that of the organic bases. When a current of dry ammonia was passed into a solution of triethyl phosphite-platochloride in benzene voluminous white crystals of the compound [Pt(NH,),P(OEt),],C14 separated. It is a good electrolyte as distinct from the compounds with aniline and pyridine described.With chloroplatinic acid it forms the pkatinichloride [Pt(NH,),P(OEt),]PtC16. The action of ammonia on methyl diphosphite-platochloride is analogous white crystals of the compound [Pt(NH,),( P[OMe],),]Cl being produced. Phenyl diphosphite-~ZatoclZoride [PtCI,(P[OPh],),] separates from alcohol in white crystals and melts at; 155'. The platinum phosphorus bromo-compounds described behave similarly to the corresponding chloro-compounds. Pliospho~us bromide-plntobromide [PtBr,(PBr,)] prepared by the action of phosphorus pentabromide on platinum black forms reddish- brown crystals which by a n excess of phosphorus tribromide are con- verted into dii~hospho?.us bromide-;okctobromicle [ Pt Br,( PEr,),] which is readily acted on by moisture and reacts violently with methyl alcohol to form the ester [PtBr,(P[OMe],),] which melts a t 136". When ethyl alcohol is used instead of methyl alcohol in the latter reaction the reaction proceeds normally triethyl phosphite-plsto- bromide [P(OEt),,PtBr,] being produced.By the action of aniline on the latter compound two isomerides are formed as in the case c;f the action on the corresponding chloro-compound. The compound [PtEr,(OP[OEt],),] melts at 155". A. McK. 0184 ABSTRACTS OF CHEMICBT PAPERS. Primary Arsines. WILLIAM &I. DFHN (timer. Chem. J. 1905 33 101-153. Compare Yalmer and Dehn Abstr. 1902 i 86).- Primary arsines can be readily prepared by the reduction of alkyl- arsonic acids with amalgamated zinc dust and hydrochloric acid.A detailed account is given of the method of preparation of methyl- arsine. 14lethylarsine is soluble in water to the extent of S5 parts per million. On oxidation with nitric acid it is converted into arsenic oxide and methylarsonic acid. When the compound is passed into a neutral or alkaline solution of silver nitrate silver is precipitated and methylarsonic acid is produced. If the gas is led into a solution of bromine in carbon disnlphide arsenic tribromide is formed. The arsine reacts with solution of iodine with formation of methylarsoni(. and hydriodic acids AsH2Me + 61 + 3H,O = AsMeO(OH) + 6HI When methylarsine is treated with dry hydrogen chloride or hydrogen sulphide little or no action takes place.The cornpound is not affected by yellow phosphorus either a t the ordinary temperature or a t 100 '. It is decomposed by aqueous mercuric chloride with forniation of mercurons chloride and mercury ~r~ethylarsonate. When methyl araine is heated with excess of methyl iodide for 8 hours in a sealed tube a t 1 lo' tetramethylarsonium iodide is produced ; with ethyl iodide under similar conditions methyltriethylarsonium iodide is formed. Xagnesiuna ethykursonate MgAsEtO may be prepared in the following manner. A solution of potassium arsenite is treated with ethyl iodide and when the reaction is complete the solution is acidified with dilute hydrochloric acid and filtered. Chlorine is passed into the filtrate the iodine is removed by filtration the solution is rendered alkaline with ammonia treated with a large excess of magnesia mix- ture and left for 24 hours.The liquid is filtered and on evaporation magnesium ethylarsonate separates. When dried at 1 40° magnesium methylarsonate is obtained as a white powder readily soluble in acids but insoluble inalkalis. It is soluble in water a t 22" to the extent of 2.31 parts per 1000 and in 10 per cent. solution of ammonium chloride t o the extent of 2.66 parts per 1000. A t 25" 0.125 gram dissolves in 1 litre of alcohol. The salt usually contains 1H20 which is not com- pletely removed a t 145". When hydrogen sulphide is passed into a solution of magnesium ethylarsonate in hydrochloric acid etiqlarsine disulphide AsEtS is obtained as a viscid yellow oil having a peculiar disagreeable odour ; it has a sp.gr. 1.836 a t 24" is easily soluble ill benzene chloroform or carbon disulphide and insoluble in water alcohol or ether and is dissolved by dilute nitric acid with formatiou of ethylarsonic acid. Tq*irnetlqlarsine sulpl~ide Me,AsS obtained by the action of heat on methy larsine disulphide crystsllises in white tough lustrous needles and melts at 174". Triethylarsine sulphide melts a t 119.5' and reacts with hydrohromic acid with formation of t r iethyliwsine dibromide ant1 hydrogen sulphide. Magnesium metlqllcwsonc~te Forms small white crystals and is soluble i n water to the extent of 2.118 grams per litre at 22" and 3.085 grams at 9 9 O . Silver piienphrsonccte Ag,PhAsO is obtained as a white glisteningORGANIC CHEMISTRY.185 precipitate when silver nitrate is added to an ammoniacal solution of phenylarsonic acid ; it is practically insoluble in water. A series of experiments was carried out with the object of ascertain- ing the best conditions for the preparation of alkylarsonic acids by G. Meyer's reaction (Abstr. 1883 1078). The results showed that a better yield is obtained with potassium arsenite than with the sodium salt that ethyl iodide gives a better result than the bromide and that in the aliphatic series the yields are inversely as the molecular weight of the alkyl haloid employed. Ethjlursine AsH,Et is a liquid which resembles methylarsine boils at 3 6 O has a sp. gr. 1.217 a t 2 2 O is soluble in water to the extent of 126 parts per million a t I go and has an extremely disagreeable pene- trating odour.It combines with oxygen with formation of ethyl- arsine oxide and water is oxidised by concentrated nitric acid t o ethylarsonic acid arsenic oxide and acetic acid and when passed into silver nitrate solution is converted into ethylarsonic acid silver being precipitated. When the arsine is led into concentrated sulphuric acid white crystals are obtained which probably consist of the salt 2AsH,Et,H,SO,. By the action of ethyl iodide on ethylarsine a t 110' tetraethylarsonium iodide is produced. l'rimet?L?/let/,~larsonium iodide forms hard glistening needles softens a t about 300" and shrinks at 320' and is soluble in water chloroform or hot alcohol. h'tAyZtriiso- amylarsoniurn iodide forms compact.crystals does not melt below 250° is soluble in alcohol and sparingly so in chloroform. When ethylarsine is heated with carbon disutphide for 10 hours in a sealed tube a t 120° triethylarsine sulphide is produced together with small quantities of an oil with an irritating odour resembling that of cacodyl. Phenylarsine boils a t 93' under 70 mm. 84' under 50 mm and a t 77" under 33 mm. pressure and is soluble in alcohol ether or carbon disulphide but insoluble in water. When it is treated with bromine a brick-red precipitate is produced which probably consists of the substance AsHPliBr,HBr ; on exposure to the air it becomes liquid and evolves hydrogen bromide and by the action of zinc and hydro- chloric acid is converted into phenylarsine.Phenylarsine decolorises solution of iodine with formation of phenylarsonic acid and ot'her products. When the arsine is heated with excess of ethyl iodide for 6 hours a t 1 20' phenyltriethylarsonium iodide is produced. Phenyl- trimethylarsoiiium iodide can be prepared in a similar manner. Y~~enyllriisoana?lZurso?iiunL iodide forms pcarly-white crystals melts at 163" and is very soluble in chloroform or alcohol but insoluble in benzene or cold water. When phenylarsine was heated with phenyl iodide no arsonium iodide could be obtained. BERTHOLD KONIG (Chem. Zeit. 1905 29 30).-The author suggests a '' cube" formula for benzene in which the six carbon atoms are arranged in six of the corners of a cube in such a manner that each carbon atom is united by one bond to one hydrogen atom by two bonds one to each of the two neigltbouring carbon atoms whilst the fourth bond extends to one of the two remaining corners of the cube which are not occupied by carbon atoms.The three bonds which extend to each of those two corners are supposed to mutually satisfy one another. E. G. Spatial Formula for Benzene.186 ABSTRACTS OF CHEMICAL PAPERS. I n substitution compounds of benzene this formula is trahsformed into a plane hexagonal type. A. 141cK. Hydrolysis of Methyl Benzenesulphonate. ARTHUR PRAE- TORIUS (MonatslA. 1905 26 1-34. Compare Wegscheider Abstr. 1902 ii 493 ; Wegscheider and Furcht Abstr. 1903 i 342).-The hydrolysis of methyl benzenesulphonate with water is a nnimolecular reaction and t,he rate of hydrolysis therefore is proportional to the concentration of the ester.As the hydrolysis constant with 0.05375 N-sulphuric acid K 0*0007175 is little greater than that with water I ! 0.0007015 the hydrolysis in aqueous solution cannot be accelerated by the presence of hydrogen ions. The formula for the alkaline hydrolysis of carboxylic esters is not applicable to sulphonic esters as in the hydrolysis of methyl benzenesulphonate with au alkali the action of the water cannot be neglected; it must be replaced by Wegscheider’s formula (loc. cit.). G. Y. Triphenylmethyl. PAUL JACOBSON (Ber. 1905 38 196-199 Compare Tschitschibabin. This vol. i 125).-!I!he author agrees with Tschitschibabin that Ullmann and Borsum’s hexaphenylethane is most probably benzhydryltetraphenylmethane but is of opinion that Gomberg’s triphenylmethyl should not be represented as hexaphenyl- e t hane but rat her as 4-t~iphenylmetlql- 1 -d~pihenylmet?~yle.rze-c y c10-A~)~- Itexadiene CPh,:C<~IE:i~~>CH*/CPh,.Such a formula accounts for the bimolecular nature of triphenyl- methyl and a t the same time by a rupture a t the dotted line indicates how the compound could readily react as free triphenylmethyl. It also accounts for the transformation of Gomberg’s compound into Ullmann and Borsum’s so-called hexaphenylethane by the wandering of a single hydrogen atom. J. J. S. Condensation of Benzaldehyde with Toluene. ALFRED KLIECL. (Be?. 1905 38 84-87).-Griepentrog found (Abstr. 1886 887) that benzaldehyde and toluene condense together in the presence of zinc chloride but was unable t o obtain a crystalline product.Benzrtlde- hyde does not condense with benzene in presence of concentrated sulphuric acid but toluene condenses slowly in the cold. After removal of unaltered benzaldehyde and toluene the product is extracted with ether and finally distilled by means of superheated steam. Phenyl- di-p-tolylmetlhane crystallises from methyl alcohol and melts a t 54-54.5O. Crystallisation only takes place slowly as the compound tends to separate in an oily state and inoculation with a crystal is necessary. P~7enyldi-p-tolylcarbi.nol prepared by the addition of methyl benzoate and magnesium to an ethereal solution of p-bromotoluene separates on cooling its solution in light petroleum in a freezing mixture in large colourless crystals sintering at 75” and melting at 76.5-77-5”.Its solution in glacial acetic acid gives a yellowish-green coloration with concentrated sulphuric acid. Zinc dust and acetic acid reduce it t o pheny ldi-p-to1 ylmethane iden tical with that just described C. H. D.ORGANIC CHEMISTRY. 187 Phenylfluorene. ALFRED KLIEGL (Ber. 1905 38 284-297)- Phenylfluorene YGH4>CHPh is best prepared by distilling triphenyl- carbinol with crystalline phosphoric acid. Phenylfluorenol obtained by Ullmann and von Wurstemberger's method (hbstr 1904 i lEid) crystallises from carbon tetrachloride with +CC14 and melts when free from solvent at 107-107*5'. Bromine at the ordinary temperature (I mol.) converts phenylfluorene dissolved in carbon disulphide into 9-bromo-S-pheny@orene YGH4>CBrPh which crystallises from light petroleum in slender needles and melts a t 99" ; on'treating the bromo- compound with hot methyl alcohol the methyl ether C,,H,,*OMe is obtained in long prisms melting a t 92-5-93"; the ethyl ether C,,H,,*OEt obtained in similar manner crystallises in small prisms and melts a t 113'.Bromophenylfluorene is very stable towards boiling water and alkalis but is converted into phenylfluorenol by heating with hydrated sodium acetate in glacial acetic acid solution. The ctcetyl derivative of phenylfluorenol separates from acetic acid or alcohol in prismatic crystals and melts a t 169-169.5". Hydroxy- diyhenylfluorene ?6H4>>CPh*C6H4-OH prepared by condensing phenylfluorenol with phenol crystallises from 96 per cent. alcohol in needles containing alcohol or from acetic acid and melts a t 189.5-190'; the acetyl derivative C19H,,*C6H4*OAc crystallises from acetic acid or alcohol in slender needles and melts a t 176".DiphenyZJEuorene ether C,,H,,O prepared by adding concentrated sulphuric acid to phenyl- fluorenol dissolved in glacial acetic acid is sparingly soluble in all solvents save chloroform and decomposes between 320 and 360". 9-Cldoro-9-phenyZJuorene Cl,Hl,C1 prepared by the action of phos- phorus pentachloride on phenylfluorenol in benzene solution crystallises from light petroleum melts a t 18-79" and with aniline gives anilino- phenyllfuorene ysH4>CPh.NHPh crystallising from light petroleum or alcohol and melting at 175'. Phen?llbe7Lx~l~uorr.e9ze C,,H, prepared by heating phenylfluorene with benzyl chloride and solid potassium hydroxide for 6 hours a t 930' crystallises from a mixture of glacial acetic acid and light petroleum and melts a t 136-137'.On nitration in cold glacial acetic acid solution phenylfluorene gives rise to 2 -nitro - 9 -phen?Jjuoia?ze N02.yGH4>CHPh which crystallises from glacial acetic acid in leaflets and melts a t 135" ; when the hydro- carbon is added to an excess of nitric acid of sp. gr. 1.59 tetranitro- phenylfiuorene is obtained which melts and decomposes a t about 235'. Z-Nitro-9-phenylfluorene on oxidation with chromic acid in acetic acid solution gives 4-nitro-Z-benco?lZbe72xo~c acid CO,H-C,H,(NO,)*COPh which crystallises from benzene or water melts a t 161.5 -1 62') and gives a methyl ester crystallising in prisms and melting a t 104.5'. 2-ATitro- anthraquinone formed on heating 4-nit ro- 2 -benzoyl benzoic acid Tvi th concentrated sulphuric acid at 1 OOO crystallises from light petroleum C6H4 c6H4 C6H4 C,H C6H4188 ABSTRACTS OF CHEMICAL PAPERS.in mossy aggregates of needles melts a t 180.5-181' and is easily reduced by alkaline stannous chloride solution t o 2-aminoanthraquinone. 4-Arnino-2-benxoylbenxoic acid prepared by the reduction of the corre- sponding nitro-compound with ammoniacal ferrous hydroxide crystal- lises from alcohol in golden-yellow efflorescent prisms with lEtOH and melts a t 195' ; 4-lt,ydroxy-2-benxoylbenzoic acid prepared by means of the diazo-reaction decomposes a t about 220-222' and is resolved by fusion with sodium hydroxide into benzoic and p-hydroxybenzoic acids.W. A. D. Syntheses in the Anthracene Series. 111. 9 8 10 10-Tetra- phenyldihydroanthracene and its Derivatives. ALRIN HALLEH. and ALFRED GUYOT (Compt. rend. 1905 140 283-287. Compare Abstr. 1904 i 660).-When 9-hydroxy-9 10 lo-triphenyldihydro- anthracene is heated in glacial acetic acid solut'ion with phenol aniline dimethyl- or diethyl-aniline condensation takes place and mono-substituted derivatives of 9 9 10 10-tetraphenyldihydroanthra- cene are formed in almost quantitative yield When phenol is em- ployed the addition of a small quantity of sulphuric acid is necessary for the reaction to take place. The general formula of the products is C 6 H 4 < ; ~ ~ > c 6 ~ 4 9 where R represents either OH NB NMe or NEt,.The hydroxy-derivative crystallises in small prisms melting a t about 308'. It is insoluble in alkalis but dissolves very readily in alcoholic potash. The amino-derivative forms small white crystals melting a t 3 20'. When diazotised and treated with P-naphthol a red colouring matter is obtained. When the diazo-compound is boiled with absolute alcohol there is no formation of hIdrocarbon but the ethoxy-derivative is obtained in small white crystals melting at 265". These crystals are only slightly soluble in the ordinary solvents. The dimethylamino- derivative forms small white crystals melting a t 285'. The diethyl- amino-derivative forms colourless needles melting at 2 I. 6". 9 10-Dihydroxy-9 1 0-diphenyldihydroanthracene condenses in a similar manner with dimethyl- and diethyl-anilines.In each case equal quantities of two isomerides are obtained which can be very easily separated by reason of their great difference in solubility. They are evidently the cis- and trans- forms corresponding with Ph C,H,R P h C6H,R v \/ c6H4<g>c6H4 and C,H4<g>C6H4 /\ Ph C,H,R /\ C,H,R Ph H. M. D. 9 10-Diphenylphenanthrene. HEINRICH BILTZ (Ber. 1905 38 203-206. Compare Abstr. 1893 i 718 ; 1897 i 533).-The com- pound melting a t 235' (corr.) which was previously obtained byORGANIC CHEMISTRY. 189 condensing benzene and chloral in the presence of aluminium chloride is identical with Werner and Grob’s 9 10-diphenylphenanthrene (Abstr. 1904 i 864). The same compound is obtained by the action of aluminium chloride on a benzene solution of tetraphenylethylene.The reaction is thus similar to the formation of phenylfluorene from tripheny lmethane. J. J. S. Action of Ammonium Nitrite and Ammonium Nitrate (or of Nascent Nitrogen and Nitrous Oxide) on Aromatic -The action of ammonium nitrite on aniline m-phenylenediamine sodium aminonaphthalenesulphonate dimethylaniline phenol and benzaldehyde respectively and of ammonium nitrate on naphthalene ant hracene phenol re sorcinol aniline 0- t oluidine .p- toluidine ben z- idine m-phenylenediamine p-phenylenediamine diphenylamine di- niethylaniline a- and p-et hylnaphthylamines benzaldehyde and benzoic acid respectively was examined. By the action of ammonium nitrite in aqueous solution a t 60-70’ on phenols nitroso-compounds or their decomposition products are formed.By the action of ammonium nitrite on amines diazo-compounds or their decomposition products are formed. Ammonium nitrate had often an oxidising action in the cases examined; aniline and other ainines were oxidised. I n other cases by the action of ammonium nitrate nitrogen was introduced into certain of the compounds investigated as for example with phenol naphthalene benzaldehy do and benzoic acid oxidation proceed- ing at the same time. Introduction of the Groups *CH,*OH and *CH,* into Primary Aromatic Amines and Preparation of Compounds of an Imidic Character. E. I. ORLOFF (J. Russ. Y l ~ y s . Chem. Soc. 1904 36 1303-1 31 l).-The action of formaldehyde solution on the sodium N *CH ,*OH derivative of formanilide yields a yellow oil C,H,<bH2 2 which decomposes on distillation.When treated with dilute hydro- chloric nitric or sulphuric acid the oil congeals to an orange-coloured buse having the composition [OH*CH,*C6H3<~H ] which is soluble in acids has a high molecular weight and when treated Compounds. WILHELM VAUBEL (Chew. Zeit. 1904,28 1245-1246). A. McK. CH n ’ with sodium nitrite in acid solution gives a &troso-compound PH-CH,. c,H,< When boiled with an alkaline solution of ,@naphthol this nitrosocom- pound is converted into a red nxo-dye ONa*CloH,*N:N*C6H3( CH,-OH),. With mercuric iodide dissolved in potassium iodide mercuric cyanide dissolved in potassium or ammonium cyanide or mercuric chloride an acid solution of the base yields a lellow powdery precipitate which NH ~ C H in the last case has the composition 0 CH,.C6H,< I )*,HgC12.The precipitcbte obtained with gold chloride has the forrnulL’C,H ?NAu. The action of formaldehyde on the sodium derivative of formyl-P-190 ABSTRACTS OF CHEMICAL PAPERS. naphthylamine yields an oil C,,H,< CH2 t which is converted N*CH,*OH' by hydrochloric acid into an orange-coloured pasty mass precipitable from concentrated hydrochloric acid by water as a yellow powder having the composition OH*CH2*C,,H,<~H ,NH . With sodium nitrite an 2 acid solution of this base yields a slightly soluble yzitroso-compound OR* C H 2 * C l O H 5 < ~ ~ which gives a red pigment with alkaline P-naphthol solution. With mercuric salts the base yields insoluble yellow compounds whilst aqueous ferric chloride oxidises the base in acid solution to a brown powder.Auric chloride precipitates a yellow powder which becomes brown on heating. The action of formaldehyde solution on the sodium derivative of NU . CH the anilide of suIphanilic acid yields the base SO,H*C,H,< 1 L The sodium derivative of formanilide reacts also with acet- aldehyde giving the imiize base C6H,< NH(l) I and with acetone CHMe(4)' giving the base C,H,< W 1 ) I C Me,( 4)' \ I Like other iminic bases these give yellow precipitates with merburic chloride mercuric iodide in potassium iodide solution platinic chloride or auric chloride. With nitrous acid) they give the corresponding nitroso-compounds N-NO N-NO C 6 H 4 < ( ) ~ ~ e T. H. P. Replacement of the Aldehyde Oxygen Atom by Two Univalent Hydrocarbon Radicles by means of Grignard's Reaction.FRANZ SACHS and LUDWIG SACHS (Ber. 1905 38 5 1 7-5 2 6) .-piso Pro;mJldirnethylan~iline NMe,* C,H,PrB is formed when p-dimethylaminophenylmethylcarbinol is heated with a n excess of magnesium methyl iodide a t loo" or when 1 mol. of p-dimethylamino- benzaldehyde is added to magnesium and methyl bromide correspond- ing with a t least 2 mols. of magnesium methyl bromide i n absolute ethereal solution the ether distilled off and the residue heated a t 100' for 6-8 hours It is a colourless oil with an aromatic odour boils a t 235.6' (corr.) under 752 mm. pressure is volatile in a current of steam and has a sp. gr. 0.92286 a t lSo/lS' and nD 1.5353 at 18'. The rnethioditle CI,H2,N I crystallises in glistening leaflets melts a t 198' (corr.) and when treated with silver oxide in boiling aqueous solution yields the strongly alkaline ammonium base which crystallises in yellow leaflets and melts a t 93-94'; the ethobronzide crystallises in broad rose-coloured leaflets and melts at 66- 67' ; the hydi-ochloride CllH17N,HCl crystallises in broad glistening leaflets and melts at 155' ; the platinichloride (C,,H,7N)2,H,PtC1 crystidlises in large golden-brown needles blackens a t about 197" and melts and decomposes a t 207-208" (corr.) ; the aurichloride crystallises in long lemon-yellow needles or broad leaflets and melts a t 95'.ORGANIC CHEMISTRY. 191 4-DinaetZ~yZan~ino-1-a-ethyZy/ropyZb~n~e.1ze NMe,*C,€€4dCHEt formed in the same manner from p-dimethylaminobenzaldehyde and magnesium ethyl bromide is a yellow oil which boils at 127-129" under 7 nim at 262.2" (corr.) under 754 mm.pressnre is volatile in a current of steam and has a sp. gr. 0.91425 at 19'/19" and nD 1.5266 at 19'. The methiodide C,,H,,NI crystallises in large silky leaflets and melts at 168-1 69" ; the hydrochloride C,,H,,N,HCl crystallises in large glistening leaflets and melts at 131' ; the pZatinichloride crystallises in yellow needles and melts and decomposes a t 195' (corr.). p-Dimethylaminotriphenylmethane NMe,*C,H;CHPh is prepared in the same manner by the action of y-dimethylaminobenzaldehyde on magnesium phenyl bromide. 4-Biethylamino -1 -a-etiLylpro~yZ6en~e32e NE t2 C6H C H E t prepared in the same manner by the action of p-diethylaminobenzaldehyde on magnesium and ethyl bromide is obtained as an oil which boils a t 140-141' under 7 mm.or a t 2 7 P (corr.) under 760.5 mm. pressure and has a sp. gr. 0.90584 at 21'/21° n 1.5209 a t 21". The hydrochloride forms a strongly hygroscopic syrup ; the platini- chZo&de forms golden prismatic crystals and decomposes a t 179' (corr.) ; She methiodide is an oil. NMe,*C,H,*CH N*NH*CO*NH crystallises in yellow leaflets and melts and decomposes a t 224' (corr.) p-Dime~hyZaniinot~io~enxa?lzide NMe,*C,H;CS*NH2 formed by the action of hydrogen sulphide on p-dirnethylaminobenzonitrile dissolved in alcoholic ammonia crystallises in yellow needles sinters at 170° and melts and decomposes at 209" (corr.). p-Diethylamino- benxyliclenesemicurbazone NEt,*C,E,* CH:N*NH* CO *NH crystallises in glistening yeIlow scales and melts and decomposes a t 214' (corr.).p-Diet~~ykcmi~zobenx y lideneaniline N Et,. C,H; CH NPh crys t allises in large glistening yellow scales and melts at 10S-109°. OSKAR LUTZ (J. pr. CJLem. 1905 [ii] '71 34-38 Compare Abstr. 1994 i 831 ; Giustiniani Abstr. 1892 820 ; Ladenburg and Hertz Abstr. 1897 i 460).-Polemical. 4 4-Diaminoformyl- (acetylj -diphenylamine. PARBWERKE VORN. MEISTER LUCIUS S URUNING (I1.R.-P. 156388).-4 4'-Dinitro- formyldipl~eny~accmine COH-N(C6H,*N0,) prepared by nitrating formyldiphenylamine in concentrated sulphuric acid solution separates from hot formic acid in small crystals and melts at 159". This and the corresponding :wetyl compound are reduced by iron and a small quantity of sulphuric acid the bases formed being extracted with dilute sulphuric acid and precipitated by addition of sodium acetate.The sulphates unlike that of 4 4'-diaminodiphenylamine dissolve readily in water. 4 4'-Bianainoformyldippl~enylami~ae COH*N( C,€14*NH,) separates from alcohol in small crystals and melts at 193' ; 4 4'-diaminoacett~l- diphenykamine melts at 195". The bases yield tetrazonium compounds from which azo-dyes may be prepared. (C,,H21K)2H,PtC1 p-Dimeth~lccnainoben~t~Zidepzesenzicarbzon~ G. Y. Giustiniani's Benzylmalimide. A reply t o Ladenburg and Herz (Abstr. 1904 i 992). G. u. C. H. D.192 ABSTRACTS OF CHEMICAT PAPERS. Stereochemical Studies. I. New Method of Separating Racemic Compounds. EMIL ERLENMEYER jun. aod ALFRED ARNOLD ( A m d e n 1904 337 307-328).-After a risund of the methods a t present in use for separating racemic compounds into their active components Pasteur's use of an active base (or acid) to separate a racemic acid (or base) is discussed. In this case two semi-racemic salts + + and - + are formed which can generally be separated by considerable difference in solubility.Such semiracemic compounds should also be formed in other reactions between a racemic and an active substance for example between hydrocyanic acid and active aldehydes. I n this case the racemic carbon atom is produced in the reaction. Representing the two linkings of the carbonyl group by cc and 6 respectively thus a semiracemic compound is formed which can be separated into its constituents by taking advantage of different solubilities &c.If R is symmetric as in benzaldehyde equal numbers of + and - molecules are produced. If It is asymmetric different numbers of + and - molecules are produced as for example in the reduction of d-benzoin where the carbonyl group becomes reduced only hydrobenzoin and no isohydrobenzoin is formed hence a selective reduction of one only of the links of the group occurs. On applying these views to the separating of racemic bases into their active constituents it was found possible to obtain the + and - forms of isodiphenylhydroxyethylamine by causing it to react with the active aldehyde helicin and separating the two condensation products by their different solubilities. The hydrochloride of the d-base melts a t 22s' and has [a] SO.23O ; the hydrochloride of the I-base has the same melting point and both are more easily soluble in methyl alcohol than the y-salt.I n addition to the tartrates of the d- and I-bases previously described the neutral tartrate of the r-base melting at 212-214' has been isolated. On fractionally evaporating the alcoholic solutions of the r-base and helicin under reduced pressure crystals of the base OH~CHPh*CHPh*N:CH~C,H,*O*CfiH1lOS separate; this is the compound of helicin and the d-base the cor- responding compound of helicin and the I-base being deposit,ed as an amorphous mass from the mother liquor. The derivakive of the d-base crgstallises in colourless needles melting at 189' and has [ . I D - 6-43' whilst the derivative of the I-base melts a t go' is hygroscopic and has [ a ] - 43.6".The active bases were obtained by hydrolysing these compounds with dilute hydrochloric acid. The d-base crystal- lised in needles melting a t 113-1 14' and had [.ID - 109*72' whilst the I-base formed crystals melting at 114' was slightly less soluble than the hbase and had [aID - 108'. The solubility of the r-base in alcohol was only one-third of that of the active bases. K. J. P. 0.ORGANIC CHEMISTRP. 193 New Isomerism of Ethylene Derivatives. EMII ERLENMEYER jun. and ALFRED ARNOLD (Annulen 1904,337 329-353. Compare preceding abstract).-ln substances of the type CR,R,:CR,R which can exist in two geometric isomerides transformation of the labile into the stable form can undoubtedly occur directly by a simple revolution of the linking between the carbon atoms and without any addition t o the ethylene linkage.It can be shown that in this revolution there are two intermediate positions in which the attractive forces causing the revolution are in equilibrium ; these two positions must therefore have the same stability. Further i t can be shown that these two positions bear to one another the relation of object to image if the four groups R,,R R,,R are supposed to occupy the four angles of a tetrahedra. Applying these considerations to the isomer ism of the cinnamic acids it is suggested that allocinnamic acid which crystallises in hemihedric forms is a racemic compound of the two stereoisomerides. Possibly Liebermann's isocinnamic acid is one of these isomerides whilst Erlenmeyer's isocinnamic acid is the geometric isoniericle of ordinary cinnamic acid.It is doubtful whether these stereoisomerides would be optically active but their asymmetry would have an effect when they were combined with an asymmetric substance. Such an example appears to exist in the compounds of isodiphenylhydroxyethylamine and cinnam- aldehyde. Since isomeric compounds appear to be formed from cinnamaldehyde and hippuric acid it is possible that the aldehyde is itself composite. Cinnamaldehyde and I-isodiphenyl hydroxyethylamine yield two isomeric dextrorotatory compounds whilst the d-base yields another pair of lzvorotatory compounds five modifications with the inactive form altogether existing. r-isoDiphenylhydroxyethylamine and cinnamaldehyde when mixed in mol. proportions in alcoholic solution yield a precipitate of the compound OH*CHPh*CHPh*N:CH*CH:CHPh which forms colourless crystals melting and decomposing a t 185'; it is decomposed into its constituents by dilute sulphuric acid.The I-base gives a similar substance representing 50 per cent. of the material used; it is sparingly soluble melts and decomposes at 190° and is dextrorotatory ; from the mother liquor an isomeric substance is obtained which forms pale yellow crystals melting a t 131' and having [a],+52*56' in alcoholic solution. The d-base yields a similar pair of substances of similar properties but Isevorotatory [a] - 52-12' in alcoholic solution. The solubility of the three substances of higher melting point in 100 parts of alcohol are compound from r-base (m.p. lSSO) 0.12 part compound from cl-base (m. p. 190') 0,174 part and compound from I-base (m. p. 190') 0.178 part. Derivatives of Bacemic and O11ticdly Acthe isoDilJJ~enyll~ydroxy1- etlq?arnine.-The beiizyliclene conzpouwl of the cl-base prepared from the components in alcoholic solution crystallises in colourless needles melting a t 137' and having [a],+55*53' in alcohol solution; the benzylidene compound of the 1-base melted at 137' and had [ a ] - 56.00'. The compound from snlicylaldehyde and the r-base forms pale yellow crystals melting a t 113'. The anisaldehyde cornpound of the194 ABSTRACTS OF CHEMICAL PAPERS. r-base crystallises in colourless needles melting a t 145" the vanillin com- pound forms yellow cubical crystals melting at 148' the piperonal con2- pound colourless needles melting a t 131' and the p-nitrobenzaldehyde compound yellow needles melting a t 132'.Ethyl acetoacetate con- denses with the r-base forming yellow rhombic crystals melting at 145"; the similar conzpouncl from pyruvic acid and the r-base forms crystals melting and decomposing a t 152" ; the analogous compound with the d-base is insoluble melts a t 161' and has [.IL + 88.82' in alcoholic solution whilst the dcrivative of the I-base which melts at 161' has - 87.71'. The cccetyl derivative of the r-base crystallises in colourless needles melting at 152' and yields a hydrochloride melting at 193"; no diacetyl derivative could be obtained. The d-acetyl derivative melts at 159' has [.ID + 12-74' and forms a hydrochloride melting at 196-1 97".- 12.80'. The r-benxogl derivative prepared by the action of benzoyl chloride in benzene solution crystallises in needles melting at 223' ; the d-benxo$ derivative forms needles melting a t 215' and having [a] + 29.02' in methyl-alcoholic solution and the I-6enzoyZ derivative melting a t 214-215O [a] - 29.00'. The r-dibenaoyl derivative pre- pared by boiling the base with benzoyl chloride is a powder melting a t 187" and is identical with the compound obtained from diphenyl- hydroxyethylamine a fact which shows that the latter changes partly into the iso-compound on benzoylnting. The hydrochloride of the r-base yields with potassium cyanate the compound OH*CH~h.CHPh*NH.CO.NH which separates from acetone in crystals containing acetone and melts when dry a t 157".K. J. 9. 0. The 1-acetyl derivative has [ Action of Phosphorus Pentachloride on Tertiary Cyclic Amines. Synthesis of Dyes and Formation of Phosphorus. PAUL LEMOULT (Compt. ?*end. 1905 140 248-250. Compare Abstr. 1904 i 380 806 807; this vol. i 48)-Phosphorus pentachloride yields a deep blue coloration with dimethylaniline (compare Michler and Walden Abstr. 1882 175) which disappears on boiling methyl chloride being evolved ; if however the temperature is maintained a t 80" to loo" there is no evolution of gas and the solid product which is deeply coloured consists of ( 1) tetramethyldiaminodiphenylmethane ; (2) hexamethyltriaminotriphenylmethane the leuco-base of hexamethyl- violet ; (3) the compound PO(C,H,*NMe,) not yet described but which gives with alcohol the compound PO(C,H,*NMe,j,,EtOH obtained by Michaelis and von Soden (Abstr.1885 1134) ; and (4) an orange-yellow substance containing free phosphorus. Colouring matters were also obtained when methylethylaniline dimethyl-o- toluidine benzylmethylaniline or diphenylmethylamine replace the dimethylamine in the above reaction but dimethyl-p-toluidine diethyl- aniline or benzylethylaniline do not give coloured products with phosphorus pentachloride. These facts show that only those tertiary cyclic amines in which t'he para-position of the aryl radicle is free and which contain at least one methyl group are capable of giving synthetical dyes with phosphorus pentachloride. N. A. W.ORGANIC CHEMISTRY. 195 Phenylcarbimide as a Reagent for Determining the Con- stitution of Tautomeric Compounds.A BTHUR MICHAEL (Bey. 1905 38 22-49. Compare Dieckmann Hoppe and Stein this vol. i 135).-The author has studied the action of phenylcarbimide on compounds showing enol-keto- tautomerism and their sodium deriva- tives with a view to determining the influence of bhe more or less acid character of the compounds concerned on the course of the reartion. I n the case of sodium derivatives phenylcarbimide forms an additive product whenever the nature of the parent compound is such that the sodium is '(more fully neutralised " in the additive product than in the original compound (Abstr. 1900 i 321 ; 1904 ii 164). When this is not the case polymerisation to triphenyl isocyanurate (Hofmann Ber. 1870 8 268) takes place often accompanied by secondary decompositions.Thus sodium ethoxide and the sodium derivatives of ethyl a-formyl- propionate formylcamphor and ethyl formylphenylacetate only cauce polymerisation of the phenylcarbimide phenylnrethane being also formed under certain conditions. Phenylcarbimide reacts with the sodium or copper derivative of ethyl acetoacetate in ether a t the ordinary temperatnre to form a C-additive conapozcnd ONa*CIMe:C(CO,Et)*CO*NI€Ph. Acids set free the hydroxylic compound crystallising from alcohol in large prisms and melting a t 57" (compare Dieckmann Abstr. 1900 i 482). The senzicarbaxone melts a t 152-154' and is converted into a compound melting a t 210-320° by crystallisation from water. Potassium hydroxide hydrolyses it to the nionoanilide of malonic acid.Ethyl sodiomalonate and phenylcarbimide react vigorously in ether to form a C-conapountl Cl,H170,N crystsliising from alcohol in long white prismatic needles and melting a t 126". The sodium salt is hydrolysed by water and dissolves only in an excess of sodium hydroxide. Ethyl sodiobenzoylacetate yields an additive compound C18H1704N crystallising in white prismatic needles melting a t 145-146' but previously softening. This compound is neutral but dissolves in alkali hydroxides on heating and acids then precipitate the white labile enolic form which dissolves readily in alkaline solutions but passes gradually into the stable ketonic form (compare Wislicenus Abstr. 1S99 i 60; Rnhemann and Watson Trans. 1904 85 456). Sodiodiacetylmethane yields an additive C O W L ~ O U ? ~ ~ C,,H,,O,N crpstallising from water in prismatic needles melting a t 1 18-120".It dissolves readily in alkali carbonates and is reprecipitated by acids. Alkali hydr- oxide decomposes it forming acetoacetanilide. Ethyl sodioforinylacetate yields an enolic aclclit ice compound OH*CH:C(CO,Et)*CO*NHPh crystallising from alcohol in white prisms melting at 62-53'. The sodium salt C,,H120,NNa,2€120 forms white crystds moderately soluble in water. The phenyl- hydrazone forms white prisms melting a t 136-1 37". In the reaction between ethyl sodioethylmalonate and phenyl- carbimide one carbethoxy-group is eliminated and a compound The enolic form has no tendency to ketonise.196 ABSTRACTS OF CHEMICAL PAPERS. C25H2104N3 is formed crystallising from benzene in rounded groups of small prisms melting a t 141-142" and behaving as a weak mono- basic acid.The siluer salt forms white prismatic needles. The same compound is obtained from ethyl ethylacetoacetate and phenyl- carbimide. The product from ethyl sodiomethylnialonate nielts a t 19s- 2 00". Sodionitromethane and phenylcarbimide react together only slowly forming nitroacetanilide NO,*CH,* CO*NHPh crystallising froin water in bright yellow feathery leaflets melting at 138-1 39" and dissolving readily in alcohol ether chloroform or benzene together with nit?.onzaZo?aaniZide NO,*CH(CO-NHPh) crystallising from alcohol in pale yellow leaflets melting a t 141-142". Potassium nitroform does not react with phenylcarbimide. The conclusion drawn by Goldschmidt and Meissler (Abstr.1890 499) that only enolic compounds form additive products on heating with phenylcarbimide is not justified. Acetophenone ethyl malonate ethyl ethylmalonate and ethyl oxaloacetate do not react with phenyl. carbimide a t 100O. Ethyl ethylacetoacetate reacts a t lSO" forming an oil boiling at 190-210° under 17 mm. pressure. In the series of compounds next examined the reaction takes place more readily with increasing acidity of the compound employed. An accumulation of ketonic groups hinders the reaction even when an enolic group is present. Ethyl acetoacetate diacetylmethane and ethyl benzoylacetate yield the same additive products as their sodium derivatives. Dibenzoyl- methane reacts with phenylcarbimide in ethereal solution a t the ordinary temperature the product melting a t 195-1 96" or 205-207' according to the time of heating (compare Wislicenus Zoc.cit.). Ethyl a-formylpropionate reacts readily to form the compound CHO C Me( C02Et)* CO NHPh cry stallising from benzene in colourless glistening prismatic needles melting a t 11 7-1 19". It is insoluble in alkali hydroxides but is slowly decomposed by them forming a-formyl- propionanilide C,,H,,O,N melting a t 82-87". Semicarbazide acetate reacts with it to form a crystalline compound of unknown constitution melting a t 231-232'. Both ethyl a- and P-formylphenylncetat es react readily with phenyl- carbimide the products melting at 59" and 116" respectively. This result is contrary to the statement of W. Wislicenus (Abstr. 1896 i 552) and is being further investigated.Nitroethane and nitromethane do not react below 240° great decomposition then taking place. Dibenzoylacetylmethnne and its enolic isonieride do not yield additive products with phenylcarbimide. The former yields a compouibd melting a t 1 18-122" and not containing nitrogen. Enolic benzoyl- diacetylmethnne yields n coqiound containing nitrogen which is being further investignted. Phloroglucinol and phenylcarbimide react in cold ethereal solution to form a compound C,7H,,0,N crystallising from alcohol or benzene in white prismatic needles melting at 190-192" and isomeric with the componnd obtained by Goldschmidt and Meissler (Abstr. 1890 499). C. H. D.ORGANIC CHEMISTRY. 197 Thymomenthol [Hexahydrothymol] and its Derivatives. L ~ ~ o N BRUNEL (Compt.rend. 1905 140 252-253)-Hexahgdro- thymol (for which the author suggests the name thymomenthol to recall its origin and its close relationship to menthol) is more con- veniently prepared by the direct hydrogenation of thymol in the presence of reduced nickel a t 160" than a t 180-185O (compare Abstr. 1904 i lSS) the amount of acetone formed (compare Sabatier and Senderens Abstr. 1903 i 454) being much less a t the lower tempera- ture. Pure thymomenthol is a syrupy colourless liquid with a strong odonr of mint has n sp. gr. 0.913 a t 0" melts between - 5" and 0" boils a t 215.5" under atmospheric pressure is insoluble in water readily soluble in alcohol ether or acetic acid volatilises rapidly at the ordinary temperature and is converted into tetrahydrocymene (thymomenthene) by the action of phosphoric oxide or potassium hydrogen sulphate ; the new hydrocarbon closely resembles menthene having a sp.gr. 0.823 a t O3 and boiling a t 167-1684 whilst the corresponding values for menthene are Oms266 and 167.4'. The esters of thymomenthol are readily prepared by heating the alcohol with excess of the acid anhydride or by heating molecular proportions of the alcohol and acid anhydride with pyridine or by the action of the acid anhydride on the sodium derivative of the alcohol; they yield on hydrolysis ,8-thymomenthol which is a stereoisomeride of the original o r a-compound and crystallises in long colourless needles melting a t 2So and boiling a t 217" under atmospheric pressure is readily soluble in alcohol ether acetone light petroleum or acetic acid insoluble in water and is much less volatile than the a-isomeride.,8- Thymomenthy? hydyogen succinnte CO,H* C,H,* GO,* C,,H, crystal- lises in thin colourless odourless needles melting at SO" soluble in alcohol and in warm light petrolenin. P-Thjnzomentkyl Ihydyogen pldmlnte CO,H*C,H,:CO,.C,,H, crystallises in large colourless odourless prisms melting at lgS" readily soluble in alcohol or chloro- form. 31. A. W. Nitrosophenol Dyes. 111. HERMAN DECKER and BORIS SoLoNrNA (Bey. 1905 38 64-68 ; 720. Compare Abstr. 1902 i 767 ; 1903 i 83S).-When crude nitric acid is added to a solution of thymol methyl ether in acetic acid a dark blue uncrystallisable solution of an oxonium salt is obtained (compare Kehrmann Abstr. 1902 i 767). On reducing at 0' with stannous chloride and hydrochloric acid and decomposing the stannochloride formed dit4 ymolylnmine dimethyl ether NH(C,H,MePr*OMe) is obtained melting a t 88.5-89" after crystal- lisiition from alcohol.The hgchocldoride forms white needles com- mencing to melt a t 140" ; the hydriodide forms white needles melting indistinctly a t 136'. Ferric chloride oxidises the ether in alcoholic solution to t h y m o p ino.lzethymoZglinzicle metlql ether 0 C,H,MePr :N* C,H,MePr* OMe crystallising from methyl alcohol in red needles and melting at 66-67". Stannous chloride reduces it quantitatively to dithymolyl- antine methgl ether. The same red indophenol ether may be prepared by the action of nitroso-sulphuric acid on thymol and methylation of the product by means of methyl sulphnte.VOL. LXXXVIII. i. P198 ABSTRACTS OF CHEMICAL PAPERS. Thymol 9%-butyl ether and nitric acid react in acetic acid solution to form an oxonium dinitrate containing the complex C,H;O*C,,H,,*N :C oH,,:O( C,HJ *NO the other NO group being prohably attached to the nitrogen atom. The salt forms bronze crystals melting a t 6 6 O and is more stable than the ethyl derivative obtained by Kehrmann. Dit7qntol&mine dibutyl ether C,sH,303N forms bright yellow crystals melting a t 69.5"; the hyclrochlovide forms white needles and melts a t 107". Thymoquinone- th,ynzoZgZinzide n- butgZ ether C',,H,,O,N crystallises in red prisms and melts a t 55'. The same colour-reactions (forination of blue oxonium salt and red indophenol ether) were observed in the case of thymol isopropyl ether and p-xylenol ethyl and inethyl ethers.C. H. D. Myristicin. I . ENRICO RIMINI (Gaxxetta 1904,34 ii 281-300). -In order to ascertain whether Angeli's method of detecting the presence of an allyl group by the action of nitrous acid is of general applicability the author has tested it on a number of compounds. It is found that nitrous acid reacts with all compounds containing an allyl group as a side-chain but with much greater difficulty than with those having a propenyl side group. The reaction can however be employed to distinguish allyl compounds from propenyl compounds since the nitrosites obtained yield in. the former case nitro-oximes. and in the latter peroxides of dioximes. From the behaviour of myristicin and isornyristicin towards nitrous acid and towards mercuric acetate it is concluded that the former contains an allyl side-chain and the latter a gropenyl side-chain.MethyZchavicoZ a-witrosite OMe* C,H,*C,H,,N,O prepared by the action of nitrous acid on methylchavicol in light petroleum solution forms a pale lemon-yellow powder melting and decomposing a t 147'. On boiling with absolute alcohol in a reflux apparatus until dissolved it passes into meth ylchavicol p-nitrosite OMe*C,H,*CH,* C(NOH)*CH,*NO which is deposited from benzene in white crystals melting a t 112'. p-Methoxyphen?lZnitroacetorLe OMe*C,H,*CH,*CO*CH,*NO obtained by boiling the preceding compound with dilute sulphuric acid crystallises from alcohol in shining white scales melting a t 89O. On oxidation with dilute alkaline permanganate solution it yields anisic and homoanisic acids.On gentle reduction with stannous chloride and hydrochloric acid in alcoholic solntion it gives p-methoxyphenpl- am inoacetone hydrochloride ORle°CGH,* CH,*CO* CH,*NH,,HCl which crystallises from alcohol in shining white laminz melting and decom- posing a t 198-199". crystallises from alcohol in orange-yellow needles decomposing at 148'. The corresponding picrate C,,Hl@,N,OH* C,H,(NO,) prepared by the xction of ammonia on p-methoxyphenylaminoacetoneORGANIC CHEMISTRY. 199 hydrochloride is deposited from aqueous alcohol as a white crystalline powder melting and decomposing at about 150'. Hethyleuyeno2 a-nityosite C,H3(0Me),*C3H,,N,03 which is only obtainable with dificulty forms a lemon-yellow powder melting and decomposing a t 130'.When boiled with alcohol a syrupy p-nitrosite is formed and this with dilute sulphuric acid gives climethoxgphenyl- nitroacetone C,H,(OlWe),~CH,*CO*CH,*NO which crystallises from alcohol in plates melting at 103'. On treatment with hydroxylainine in presence of sodium carbonate and hydroxide this does not give the nitroxime expected but di~~ethoxybenxylToxai,zic acid C6H3( Ohle),*CH,*CO *NH-OH which separates from alcohol in mammillary aggregates melting and decomposing a t 1 3 7 O and gives a violet coloration with ferric chloride and a bottle-green precipitate with copper acetate. When reduced dimethoxyphenylnitroacetone yields dirnethoxy - p7~e~ylaminoacetone the picrate of which separates from alcohol in crystals melting and decomposing a t 153'. ApioZe a-nitrosite CH,:O,:C,H(OMe),*C,H,,N,O prepared only with great difficulty and in small yield is a lemon-yellow powder which melts and decomposes a t about 138" and is insoluble in all ordinary solvents.Bill-upiole a-nitrosite melts and decomposes at 139'. Myristicirt a-nitrosite C H,:O, C6H,( OMe) *C,H,,N,O formed to- gether with a large proportion of resin fi40m myristicin and nitrous acid is a yellow powder melting and decomposing a t 130'. The p-nitrosite could only be obtained as a syrup which when treated with dilute sulphuric acid yields metho<xymethylenedioxyphenylnitro- acetone CH,:O,:C,H,(OMe)*CH,*CO*CH,.NO crystallising from alcohol in shining scales melting a t 132-133O. On reduction the foregoing compound yields methozymet~~pZe~zediox?/- phenyluminoacetone the picrute of which separates from alcohol in crystals melting and evolving gas at 182'.C,H3(OMe),*CH,*C0~CH2*NH2,C,H,(N02),*OH CH, O,:C,H,(OMe) CH,. CO *CH2*NH2,C,H,07N3 Diisonityosoisomyristicin peroxide prepared by the action of nitrous acid on isomyristicin is deposited from alcohol i n shining yellow crystals melting a t 103'. Reduction by means of zinc dust and acetic acid in alcoholic solution yields di- isoitilyosoisomg~istici?~ CH :O, C,H,( OMe) C( NOH) CMe NOH which separates from aqueous alcohol in white crystals melting a t 136'. The mercuric acetate compound of n-tpristicin CR,:0,:C,H2(0Me)*C,H~(OH)*Hg*OAc prepared together with a non-crystalline isomeyide by treating a benzene solution of myristicin (1 mol.) with a saturated aqueous solution of mercuric acetate (1 rnol.) crystallises from benzene in white mammillary masses melting a t I l l 0 .Treatment of an aqueous solution of this compound (1 rnol.) with saturated potassium chloride (1 rnol.) solution yields the compound C,,H,,O,ClHg separating from alcohol in white crystals melting at 137". Di~~ydroxyisomyristicin CH,:O C,H,( OMe) C,H,( OH) obtained by P 2200 ABSTRACTS OF CHEMICAL PAPERS. the prolonged action of a saturated aqueous solution of mercuric acetate (4 mols.) on a benzene solution of isomyristicin (1 mol.) with subsequent reduction by means of zinc and potassium hydroxide solution crystallises from ether in mammillary masses melting at isoiMyl.ist,icii~pici.ate CH2:0,:C,H,(OMe) C3H,,C,H307N crystallises from alcohol in red needles melting at S6".The ready formation of such a compound is characteristic of all propenyl compounds especially those containing a methylenedioxy-group (compare Bruni and Tornani Abstr. 1904 i 875). 11 4-1 15". T. H. P. Condensation of Nitromalonaldehyde with Benzyl Methyl Ketone. HENRY B. HILL and WILLIAM J. HALE (Amer. Chem. J. 1905 33 1-21).-When benzyl methyl ketone reacts with the sodium derivative of nitromalonaldehyde 5-nitro-2-hydroxydiphenyl is produced which melts a t 125-1 26' (corr.) (compare Borsche Abstr. 1900 i 594); its sodium derivative crystallises with 3$H,O. The methyl ether of 5-nitro-2-hydroxydiphenyl crystallises in colourless needles and melts at 95.8' (corr.) ; the ethyl ether melts a t 110.6O (corr.) and the 6enxoyZ derivative forms small white irregular prisms and melts a t 99.3' (corr).5-Amino-2-hydroxydiphenyl melts a t 199' (corr.) diphenylquinone melts a t 112-113' (corr,) and 3 5-dinitro-2-hydroxydiphenyl melts a t 207-208° (corr.) (compare Borsche Abstr. 1900 i 24). The sodium derivative of 3 5-dinitro-2-hydroxydiphenyl crystallises with 2H,O ; the methyl ether crystallises in colourless leaflets and melts at 114-1 15' (corr.) When 3 5-dinitro-2-hydroxydiphenyl is reduced with tin and hydrochloric acid the hydrochloride of 3 5-diamino- 2-hydroxydiphenyl is produced which forms colourless crystals ; on treating this compound with potassium carbonate a yellow flocculent precipitate of the base is obtained which becomes reddish-brown when dry and is soluble in alcohol or glacial acetic acid.On oxidising the methyl ether of 5-nitro-2-hydroxydiphenyl with a solution of chromium trioxide in glacial acetic acid the methyl ether of 5-nitrosalicylic acid is produced together with benzoic acid. The methyl ether of 3 5-dinitro-2-hydroxydiphenyl is oxidised by chromic acid with considerable difficulty small quantities of the methyl ether of 3 5-dinitrosalicylic acid being produced. When either 5-nitro-2-hydroxydiphenyl or 3 5-dinitro-2-hydroxy- diphenyl is boiled with nitric acid of sp. gr. 1.40 carbon dioxide is evolved and p-nitrobenzoic acid is produced. By the action of nitric acid of sp. gr. 1.40 on the methyl ether of 3 5-dinitro-2-hydroxydipheny1 the methgl ether of 3 5 4'-trinitro- 2-hydroxydiphenyl NO,*C,H,* CGH2(NO,),* OMe is produced which crys- tallises in prisms and melts a t 170-171° (corr.).3 5 4'-Trinitro-2- Jbydroxydiphenyl obtained by hydrolysing the methyl ether with con- centrated hydrochloric acid crystallises in pale yellow prisms melts a t 163-164' (corr.) is readily soluble in benzene ether or chloro- form and fairly so in glacial acetic acid or carbon disulphide and on oxidation with nitric acid yields p-nitrobenzoic acid ; the socZium salt forms orange-red crystals.ORGANIC CHEMISTRY. 201 When 5-nitro-2-hydroxydiphenyl methyl ether is boiled with a mixture of nitric and glacial acetic acids the methyl ether of 5 4'-dinitro- 2-hydroxydiphenyl N0,*C6H4*C6H,(N02)*OMe is produced which crys- tallises in white slender needles and melts a t 222-223" (corr.) ; on hydrolysis with concentrated hydrochloric acid it is converted into 5 4'- dinitro-2-hydroxydiphenyl which crystallises in long slender pale yellow needles melts a t 224-225" (corr.) is readily soluble in alcohol ether chloroform cr glacial acetic acid 2nd moderately so in hot benzene and on oxidation with nitric acid is converted into p-nitro- benzoic acid ; the sodium salt crystallises in orange-red needles.By the action of nitric acid of sp. gr. 1.40 on 5-nitro-2-hydroxy- diphenyl methyl ether the methyl ether of 3 5 4'-trinitro-2-hydroxy- diphenyl is produced together with the nzethyl ethei- of the correspond- ing 5 2' 4'-trinitro-derivative Cf,H,( NO,);C,H,(NO,)*OMe ; the latter compound crystallises in small flattened prisms and melts a t 104-106° (corr.).5 2' 4'-l'rinitro-2-hydroxydiphenyl obtained by hydrolysing the methyl ether with concentrated hydrochloric acid crystallises in small pointed yellow prisms melts a t 152 -153' (corr.) is readily soluble in chloroform and fairly so in glacial acetic acid warm alcohol or warm benzene and on oxidation with nitric acid of sp. gr. 1-40 is converted into 2 4-dinitrobenzoic acid ; the sodium deriva- five crystallises in orange-red needles. A Correction [a-Nitrosoresorcinol Monoethyl Ethers]. FERDINAND HENRICH (J. pr. Chenz. 1905 [ii] 71 56. Compare Abstr. 1904 i 1006).-The author misunderstood Wegscheider's views as t o the nature of the two modifications of a-nitrosoresorcinol monoethyl ether (7'iees.h. deut. NaturJ A r x t e in Zctssel) and now finds them to agree with his own (Zoc.cit.). Oxidation Products of Octohydroanthracene. MARCEL GODCHOT (Conzpt. Tend. 1905 140 250-252).-0ctohydroanthracene (Abstr. 1904 i 987) is readily oxidised by chromic acid to anthra- quinone but when the oxidation is effected in acetic acid solution at the ordinary temperature dih?ldro-oxanthl.unol and hexahydroanthro9ie are obtained. DiT~ydro-oxantTiraizoZ C,H,<C(oH)>C6H6 crystallises from alcohol in large yellow prismatic needles melting at 159" dis- solves readily in hot alcohol benzene toluene or acetic acid is not fluorescent and its solutions give a deep red coloration with alkalis Diucetyldihydro-oxant?wanoE C6H4<c(0Ac)>C,H6 C( OAc) crystallises in large colourless needles melting a t 220° and soluble in hut alcohol benzene or acetic acid the solutions in alcohol or acetic acid exhibit'ing a beautiful blue fluorescence.Hexulqdrourzthrone C,,H,,O crystallises i n hard clear plates melts at 45.5' boils a t 222-225" under 25 nmi. pressure is readily soluble in all the ordinary organic solvents slightly volatile with steam and reduces Fehling's solution or ammoniacal silver nitrate. The semicarbaxone crystallises in small yellow leafy crystals melting a t 250". Dibromohexahydroanthrone CI4Hl4OBrP forms prismatic crystals melting a t 123-1 2 4 O readily soluble xn alcohol carbon bisulphide or ether. E. G. G. Y. CPH) M. A W.202 ABSTRACTS OF CHEMICAL PAPERS. p-Dimethylaminobenzaldehyde. 111. Action of Magnesium Organic Compounds. FRANZ SACIHS and LUDWIG SACHS (Ber.1905 38 511-517. Compare Abstr. 1903 i 37; 1904 i 506).- p-Birnethylanzinophenylmeth~Zcarbinol NI\IIIe,*C,H,*CHMe*OH formed by the action of 1 mol. of p-dimethylaminobenzaldehyde on 1 mol. of magnesium and two mols. of methyl iodide in ethereal solution crys- tallises in lemon-coloured microscopic prismatic pointed leaflets melts at 60*25O is easily soluble in water and the usual organic solvents and dissolves in concentrated sulphuric acid to a yellow solution and in glacial acetic acid to a yellow solution which becomes green when heated; the h?/drOCh~O?'ide is obtained as a white floccu- lent hygroscopic precipitate ; the platinicJdoride forms a brownish- yellow flocculent mass. Attempts to prepare the corresponding styrene by distillation of the carbinol or by conversion into the chloride and heating with pyridine or by treatment with either excess of magnesium methyl iodide or acetic anhydride were unsuccessf id chiefly owing to the formation of decomposition and polymerisation products.p-Dimetlzylan2inopl~enyletlLylcu?.binol NMe,*C,H 9 CHEt* OH formed by the action of p-dimethylaminobenzaldehyde on magnesium etbyl bromide in well-cooled ethereal solution crystallises in needles melts at 46" gradually decomposes at the ordinary temperature and is only slightly soluble in water but easily so in the ordinary organic solvents ; the plcctinichloride forms a yellow oil. When heated under 10 mm. pressure the carbinol yields 4-dimethylamino-1-ha-propenylbenzene (p-dimethylaminophenylpropylene) which distils at 152 -1 54O crystal- lises in microscopic white needles slowly decomposes at the ordinary temperature and dissolves in concentrated sulphuric acid to a golden in hot glacial acetic acid t o a bluish-green solution ; the plati?ticJJoricle crystallises in broad yellow needles and melts at 132".p- D i m e t J q Znnzinophen y 1 be n x y Zcar b in0 1 N Me,* C H CH (0 H ) C H P h prepared by the action of the aldehyde on magnesium and benzyl chloride crystallises in sheaves of white needles melts a t 59-60' has a bitter flavour and forms an oily platinichlos.ide. p-Diriethylamino- stilbene NMe,*C,H,-CH:CHPh is formed on prolonged boiling of the carbinol in alcohol or on heating the carbinol under 10 mm. pressure when the stilbene distils a t 251-252". It crystallises in broad glistening leaflets and melts at 147-148'.The hydrochloride crystal- lises in small whiteleaflets and melts and decomposes at 174-1'75"; the platinichloride crystallises in small colourless needles rapidly becomes rust-coloured and melts and decomposes a t 168' ; the picmte crystallises in brown microscopic needles and melts a t 158" ; the inethiodicle crystallises in yellow leaflets and melts a t 204' (corr. ). p-BimetA ylccminophen y 1-a-naphth ylcarbino I NMe,*C,H,*CH(OH)*CloH7 prepared by the action of the aldehyde on magnesium and a-bromo- naphthalene crystallises in white prisms melts at 97-98' and dissolves in mineral acids to form coloured solutions. The platini- chloride crystallises in hexagonal leaflets which reniain unchanged at 230O.ORGANIC CHEMISTRY.203 s-Diphenylcarbarnide was the only product obtained by the action of phenylcarbimide on the above carbinols. Action of Magnesium Ethyl Iodide on Piperonaldehyde. New Synthesis of isosafrole. EFISIO MAMELI (Gaxxetta 1904 34 ii 409-419).-Besides the work already noticed (Abstr. 1904 i l023) a description is given of the benxoyl derivative of ethylpperonyl- carbinol CH2:02:C6H3* CHEt*OBz which separates from benzene in white crystals melting a t 112". Ethylpiperonyl Ether. EFISIO MAMELT (Atti R. Acead. Lime; 1904 [v] 13 ii 611-614. Compare Abstr. 1904 i 743).-When kept in an impure state ethylpiperonylca~bi~~ol (Abstr. 1904 i 1023) becomes slowly etherified yielding elhyZpi$eronyZ ethe~ G. Y. T. H. P. 1 (CB,<C). 8. c H c. c HEt eo 0.C- CH YH which crystallises from benzene or alcohol in small white prisms melt- ing at 8 8 O dissolves readily in ether light petroleum chloroform or pyridine and slightly in acetic acid and exhibits norinal cryoscopic behaviour in benzene solution. It does not reduce ammoniacal silver nitrate or Fehling's solution and does not combine with benzoyl chloride or phenylhydrazine. On treatment with concentrated sul- phuric acid the crystals become dark red whilst the liquid assumes an intense blood-red coloration which changes to violet in a few hours. Concentrated nitric acid dissolves the ether. with great energy nitrous fumes being abundantly evolved; on adding water to the mixture a nitro-derivative is precipitated. When heated even under reduced pressure the ether decomposes into water and isosafrole ; this decom- position takes place in two stages like that of the corresponding methyl compound (Zoc.cit.). T. H. P. Reactions of Sodium Benzhydrol. RAYMOND Foss BACON (Anzer. Chem. J. 1905 33 68-97) -The sodium derivative of benzhydrol crystallises in large transparent colourless plates turns green or greenish-blue on exposure to light but becomes colourless again in the dark; it decomposes a t 250" with formation of benzene sodium benzoate diphenylmethane and sometimes tetraphenylethane and tetrapheiiylethylene. When dry air and oxygen are passed over sodium benzhydrol a t the ordinary temperature benzophenone sodium peroxide sodium carbonate and a small quantity of sodium benzoate are produced. The reaction is considered to take place between the dissociated benzhydrol molecules and the active oxygen molecules in accordance with the following scheme CFh, + 2NaOH + 0 -+ CYh,(ONa) + H,02 -+ COPh + Na,O + H,O.The amount of sodium peroxide present a t the end of one experiment W:LS found to be only 21.67 p9r cent. of the amount demanded by the equation this being due to its reduction by the unchanged diphenylmethylene CPh, + Na,O -+ COPh + Na,O. When bromodiphenylmethane is oxidised with potassium perman- ganate in presence of sulphuric acid benzophenone is obtained. If dry oxygen is passed through bromodiphenylmethane at 160-1 70°,204 ADSTRACTS OF CHEMICAL PAPERS. hydrogen bromide is evolved and benzophenone is produced together with a small quantity of tetraphenylethylene.By the action of sodium on an ethereal solution of bromodiphenylmethane tetraphenyletharie and diphenylmethane are formed. Conrad and Iiodgkinson (Abstr. 1877 590) have shown that when sodium reacts with benzyl acetate a t 135" benzyl acetoacetate is not produced but the chief product is benzyl P-phenylpropionnte. It is now found that benzyl ether is also formed in this reaction. The action of sodium on benzyl acetate and benzhydryl acetate in cold ethereal solution has been studied by Shaklee who has found that the main products of the reaction are acetic acid and benzyl alcohol or benzhydrol respectively? a small amount of diacetyl being formed in each case. B e n x y l cccetoacetnte which has been prepared by Shaklee by the action of benzyl alcohol on ethyl acetoacetate a t 160" is a colourless mobile oil which boils a t 162-164" under 16 mm.pressure boils and decomposes at about 270" under the ordinary pressure and gives a blood-red coloration with alcoholic ferric chloride ; its copper derivative melts at 1564 Benshyclryl cccetoacetate prepared in a similar manner crystallises in colourless plates melts a t 56" is very soluble in most organic solvents and gives a deep purple coloration with ferric chloride; the copper derivative melts a t 174-1 76". Experiments have shown that by the action of sodium o r sodium benzyloxide on benzyl acetate a t loo" only traces of benzyl aceto- acetate are produced and that similarly only very small quantities of benzhydryl acetoacetate can be obtained by the action of sodium benz- hydro1 on benzhydryl acetate.PP-Diphenylpropionic acid melts a t 155' instead of 151' as stated by Henderson (Trans. 189 1 59 734). Benxhydrgl /3P-diphenyll- propionate obtained by the action of bromodiphenylmethane on potassium PP-diphenylpropionate a t 150-1 60° crystallises from al- cohol in colourless needles melts a t ll2' and is readily soluble in benzene and sparingly so in ether When ethylacetanilide is heated for a considerable time with sodium benzhydrol in a sealed tube etbylaniline benzhydrol benzhydryl ether PP-diphenylpropionic acid and small quantities of benzophenone and tetrsphenylethsne are formed. If benzhydryl acetate is heated with quicklime in a sealed tube for 6 hours a t 230-250° pp-diphenyl- propionic acid tet raphenylethnne benzhydryl ether benzhydrol and a small amount of benzophenone are produced.By the ihteraction of benzhydryl acetate and sodium benzhydrol in a sealed tube a t 150-1 60° PP-diphenylpropionic acid benzhydryl PP-diphenylpropionate benzhydrol benzhydryl elher tetraphenyl- ethylene and small quantities of benzophenone and tetraphenylethane are formed. When benzhydryl acetate is heated with sodium a t 130-140" /3,L?-diphenylpropionic acid benzhydrol tetraphenylethylene benzophenone and traces of tetraphenylet hane are produced. If sodium benzhydrol and benzhydryl acetate are heated together a t 300-310" in a sealed tube /3/3-diphenylpropionic acid (75 per cent. of the theoretical yield) diphenylmethane benzophenone and a small quantity of benzoic acid are produced.ORGANIC CHEMISTRY.205 Bemdyd?*yZ jbmzate obtained by the action of potassium formate on bromodiphenylmethane is a colourless oil which boils at 159-1 60' under 10 mm. pressure. When this ester is heated with sodium benz- hydro1 for 8 hours in a sealed tube at 300-310° diphenylacetic acid is produced. Benxhydryl isobutyyate is a crystalline substance which melts a t 5 4 O boils at 1S5-1S7° under 15 min. pressure and is soluble in alcohol o r ether. When this compound is heated with sodium benzhydrol in a sealed tube P/3-diphenyl-aa-dimethylpropior1ic acid benzhydrol di- phenylmethane and benzophenone are produced. The results of several experiments shorn that the yield of /3p-diphenyl-aa-dimethylpropionic acid never exceeds 30 per cent. and that diphenylmethnne and benzo- phenone are always obtained owing to the decomposition of a large proportion of the sodium benzhydrol.Nef (Abstr. 1898 i 106) has shated that benzhydryl acetate de- composes a t 300' with formation of acetic acid tetraphenylethylene and tetraphenylethane. On repeating this experiment acetic acid tetraphenylethylene benzophenone and diphenylmethane were ob- tained but tetraphenylethane was not produced. Benzhydryl ethyl ether is decomposed a t 300" into acetaldehyde tetraphenylethane and benzophenone. Fromm and Achert (Abstr. 1903 i 340) have shown that benzyl sulphide decomposes when heated with formation of hydrogen sulphide toluene st il belie t hionessal (t etrapheny 1 t hiophen) and s-tetraphenyl- butane. These results can be explained on the supposition that the benzyl sulphide first undergoes dissociation into hydrogen sulphide ( 1 mol.) and phenylmethylene (2 mols.) This view is supported by the fact that when benzyl chloride is heated with anhydrous potassium oxalate s-tetraphenylbutane is produced.Benxyl. P-phenylpropionute is a colourless oil which boils a t 190-195" under 10 mm. pressure and is rapidly hydrolysed by alcoholic potassium hydroxide at the ordinary temperature. The action of sodium on benzyl acetate has been studied by Conrad and Hodgkinson (Zoc. cit.). On repeating their experiments it was found that the neutral and less volatile products obtained by them after treatment with alcoholic potassium hydroxide must have con- sisted largely of benzyl ether. When a mixture of benzyl isobutyrate and sodium benzyloxide is heated a t 300-310" in a sealed tube benzyl alcohol benzyl ether isobutyric acid benzoic acid and traces of benzaldehyde are obtained but a-benzylisobutyric acid is not produced.It is probable that the substance described by Hodgkinson (Trans. 1875 33 495) as benzyl a-benzylisobutgrate consisted of benzyl ether. E. G. Ketonic Decomposition of the Triphenylcarbinols. OTTO FISCHER and WALTER HEW (Ber. 1905 38 335-339).-Trinitrotri- phenylmetliane is hardly affected by a boiling solution of chromic acid in acetic acid but is decomposed when heated with nitric acid of sp. gr. 1.4 for 3 hours a t 150" giving 4 4'-dinitrobenzophenone ; small quantities of this substance are also formed in the preparation of206 ABSTRACTS OF CHEMICAL PAPERS.trinitrophenylcarbinol by the oxidation of trinitrotriphenylmethaue by the air in presence of alkali. ~ri-p-bronaotrip~enylmet?~c~~2e C19H13Br8 prepared from p-leucaniline by means of the diazo-reaction crystallises from light petroleum in thick colonrless prisms and iiielts a t 112' ; it is oxidised by chromic acid in acetic acid solution to a mixture of 20 per cent. of 4 4'-di- bromobenzophenoiie and 80 per cent. of tri-p-bronzotripl~e?ayZcur~inoZ which crystallises from benzene or light petroleum in thick plates and melts a t 133". Tri-p-cl~Zorotri~?~e?ayZnaet?~~~~~e crystallises from light petroleum in prisms melts a t S7-SSo and on oxidation with chromic acid as in the foregoing case gives mostly ~ricl~Zorotr~~l~e~aylcc~rbi~~oZ which separates from light petroleum containing benzene in thick crystals melting a t 98' ; a little dichlorobenzophenone is formed.~l'l'i-p-ioC17otrip~,enyZn~etl~c~ne forms slightly yellow crystals melts at 131 -1 3 2 O and on oxidation with chroniic acid gives principally tri-p-iodotripl~enyZcur~i?zoZ although some 4 4'-di-iodobenzophenone is formed ; the carbinol crystallises in long yellow prisms and melts at 155'. W. A. D. €-Halogen Derivatives of Amylamine. JULIUS VON BRAUN and A. STEINDORFF (Ber. 1905 38 169-1 79).-Benxoyl-E-phenoxyumyZ- amide NH Bz*[CH,],*OPh,. prepared by warming an alcoholic solution of benzoyl-e-cbloroamylamide with phenol and sodium separates from a mixture of ethyl alcohol and water in glistening leaflets and melts a t 89'. When heated with three times its amount of hydrobromic acid saturated a t Oo for 4 hours a t 150' in a sealed tube it formed e-bronioaniylamine hydrobromide which mas converted into the free base C,HloBr*NH the plutiniclJoricZe of which was analysed.BenxoyEe-6rorrizoumyZurr~ide NH Bz. C5H10Br f orms snow-white crystals and melts a t 59-61'. When an alcoholic solution of benzoyl-6-chloroamylamide is boiled with sodium iodide benxoyl-e-iodonmykc~mide NHBz-C,HIoI is formed ; it crystallises in prisms and melts at 54-45'. c-lodounaykamine prepared by heating its benzoyl derivative with fuming hydriodic acid in a sealed tube a t 150" and then adding alkali readily undergoes transformation when heated into piperidine hydriodide thus NH,*C,H,,I = C5KHlI,HI. Benzogl-eiodoamylamide is more reactive than the corresponding bromo-compound.Whilst the latter reacts with difficulty with secondary bases the former reacts with great readiness even a t the ordinary temperature. BenxoyZpipeyidyZcaduverine NHBZ*[CH~]~*C,NH,~ formed by the action of benzoyl-c-iodoamylamide on piperidine separates from light petroleum in glistening crystals and melts at 74O. It dissolves readily in dilute acids ; its picrate melts at 104'. c-Benxoykamino-n-hexonitrile (benxoyl-c- Zeucine witrile) NHBz*[CH2],*CN prepared by the action of benzoyl-e-iodoamylamide on a solution of potassium cyanide in a mixture of water and alcohol separates fromORGANIC CHEMISTRY. 207 water or dilute alcohol in snow-white glistening leaflets and melts a t 95". When hydrolysed it forms r-leucine NH,*[CK,],*CO,H whilst by reduction and subsequent hydrolysis hexamethylenediamine NH,* [ CH,],*NH is produced.By the action of phosphorus pentachloride on benzoylamino-ehexo- nitrile the irnide chloride CPhCl:N* [CKal5*CN is formed which on elevation of temperature is transformed into a mixture of benzo- nitrile and c-chlorohexonitrile C,K,,Cl*CN. When the latter com- pound is mixed with a solution of pheiiol and sodium in ethyl alcohol E-p~~enoxy~~exonitriZe 0Ph*[CH,],.CN is fozmed as snow-white crystals which melt a t 36'. A. RICK. Reaction between Organic Magnesium Compounds and Unsaturated Compounds. 11. Reactions with Derivatives of Cinnamic Acid. ELMER P. KOHLER and GERTRUDE HERITAGE (Amer. Chern. J. 1905 33 21-35. Compare Abstr. 1904 i 595).- When an ethereal solution of methyl cinnamate is added gradually to a solution of magnesium phenyl bromide a t - 10' and the resulting yellow magnesium compound is decomposed by shaking with finely- crushed ice on dissolving the magnesium salts in hydrochloric acid a t 0" diphenylpropiophenone is produced together with methyl PP-diphenyl- propionate which crystallises in large lustrous prisms and melts at 47'; a number of other substances are simultaneously formed.By the action of benzoyl chloride on the magnesium compound benzoyl- triphenylpropenol is obtained together with a benzoate C23H,,,03 which crystallises in long white silky needles melts at 130-133' and is easily hydrolysed with formation of benzoic acid and methyl diphenyl- propionate. The relative amounts of diphenylpropiophenone and methyl PP-diphenylpropionate produced vary with the temperature.At - lo" the quantity of the ketone obtained rarely exceeds 5 per cent. of the total product whilst at 35" as much as 20 per cent. is formed. I n the case of ethyl cinnamate only a trace of ketone is produced at - lo" and less than 10 per cent. a t 35'. The amyl ester yields only a trace of ketone at 35" and none at - loo. By the action of magnesium methyl iodide on methyl cinnamate dimethylstyrylcarbinol UHPh:CH*CMe,*OH is produced which on oxidation with potassium permanganate is converted into benzoic and hydroxyisobutyric acids. An oily substance C,,H,,O probably the ether O(CMe,*CH:CHPh) amounting to less than 5 per cent. of the total product is also formed which boils a t 128' under 11 mni.pressure combines with bromine and is oxidised by hot alkaline potassium permanganate ; under certain conditions benzylideneacetone is alm produced. By the action of magnesium phenyl bromide on cinnamyl chloride diphen y lpropiophenone cinnamic acid and /3P- diphenylpr opionic acid are obtained together with other compounds. Cinna?nylethylccniZide CHPh :CH*CO*KPhEt obtained by the action of cinnamyl chloride on ethylaniline crystallises in large colourless prisms melts at 74" and is readily soluble in ether alcohol chloroform or carbon disulphide and moderately so in boiling light petroleum. When this substance is treated with magnesium phenyl208 ABSTRACTS OF CHEMICAL PAPERS. bromide /3P-diphenylpropionylethylanilide is produced which is con- verted by bromine into di2~l~es~yZbi.omoprop~onylet~yZan~lide. This compound crystallises in large colourless prisms melts a t 178" is readily soluble in chloroform acetone or boiling alcohol and is hydrolysed by hydrochloric acid with formation of a- bronzo-PP-diphenynyl- pyopionic acid Cf-lPh,*C)HBr*CO,H which melts and decomposes a t about 164" is readily soluble in alcohol or ether and when boiled with alcoholic potassium hydroxide is converted into P-phenylcinnamic acid.An attempt mas made t o prepare a-bromo-PP-diphenylpropionic acid by the direct bromination of diphenylcinnamic acid but it was found that the main product of the reaction was phenylhydrindone. ,8-PhenyZcinnamic acid CPh, CH*CO,H crystallises in colourless needles melts at 142" is readily soluble in alcohol or ether and moderately so in boiling water does not combine with bromine at the ordinary temperature but is oxidised by cold potassium permanganate solution with formation of benzophenone and carbon dioxide.E. G. Reaction between Unsaturated Compounds and Organic Magnesium Compounde. IV. Reactions with Esters of a-Phenylcinnamic Acid. ELMER P. KOHLER and GERTRUDE HERITAGE (Amer. Chen2. J. 1905 33 153-163).-When an ethereal solution of methpl a-phenylcinnamate is treated with magnesium phenyl bromide the covzpound CHPh,*CPh:C(OXgBr)*OMe is produced which crystallises in small lustrous prisms and if left for a day changes into a thick paste. By extracting t'his paste with chloro- form methyl aP,8-tri3,'ILe.nylpropionccte CHPh,*CHPh* CO,Me is obtained which crystallises in hard lustrous plates and melts a t 159'.aPP-~r2pl~enyZ~~ropionic cccicl crystallises in needles melts a t 2 1 lo and is readily soluble in alcohol or ether sparingly. so in light petroleum and insoluble in water. The ethyl ester crystallises in plates and melts at 120'. When the additive compound of methyl a-phenylcinnamate with magnesium phenyl bromide is treated with dry hydrogen chloride methyl triphenylpropionate and magnesium chloride are produced. It reacts with acetyl chloride with formation of the compouncl CHPh,*CPh:C(OAc)*ONe which crystallises from alcohol in plates melts at 75" and on hydrolysis yields acetic acid and methyl triphenyl- propionate. By the action of bromine on the magnesium compound methyl tripizenylbi.o,,to~~op~o~~c~te CHPh2*CPhBr*C0,Me is produced which crystallises in large colourless prisms melts and decomposes at 150-152° and is readily soluble in chloroform or hot acetone and slightly so in alcohol or ether.When this ester is boiled with alcoholic potassium hydroxide i t is converted into triphenylacrylic acid melting at 213'. When methyl a-phenglcinnamate is treated with magnesium o-tolyl bromide an additive conzpound separates in colourless crystals which on decomposition with water yields rnetlhyl o-tolyldiplwaylpropionate C7H7*CHPh*CHPh*C02Me. This ester crystallises in hard lustrous plates melts at 150' and on hydrolysis is converted into o-tolyldi-ORGANIC CHEMISTRY. 209 phmglpropionic acid which crystallises in long needles and melts a t 1 goo.By the action of magnesium a-naphthyl bromide on methyl a-phenyl- cinnamate an additive compound is produced which on decomposition yields methyl p- 1 -ncbpJLthyl -ap-dil3henyZ~o~ionate C,,Hp*CIHPh*CHPh*CO,Me which crystallises in small lustrous pyramids or prisms melts a t 1 TO" and is readily soluble in chloroform ether or light petroleum. Another methyl ester is simultaneously produced which crystallises in large lustrous prisms melts a t 128" and is more soluble in organic solvents than the isomeride melting at 170". These esters are perhaps stereo- isomeric but as they furnish the same acid on hydrolysis it is not possible to prove that they represent two racemic modifications. p-l-~'ap?~thyl-ap-~~ppkenyZ;rropionic acid crystallises in short thick needles and melts a t 171".When methyl a-phenylcinnamate is treated with magnesium methyl iodide Ys-dzphenyl-P-nzethyl - AY- but en-P-ol CHPh CPh* CMe,*OH is produced which crystallises in thin plates or long flat needles molts at 68" is readily soluble in acetone or ether and fa.irly so in light petroleum is oxidised by alkaline pernianganate with formation of benzoic and acetic acids and does not combine with bromine. E. G. Mechanism of the Synthesis of Salicylic Acid. CORNELIS -When sodium phenyl cnrbonate is heated its tension of dissociation becomes equal to the atmosphere a t S5" ; beyond this it increases until the temperature reaches 100" and then diminishes this being due t o the reabsorption of carbon dioxide and the formation of salicylic acid. These observations indicate that sodium phenyl carbonate may be an intermediate product in the production of sodium salicylate by Schmitt's method (Abstr.1885 709 and 982) but that it does not play this r6Ze under the conditions prescribed by Kolbe. It is sug- gested that in Kolbe's process the sodium phenoxide is first converted into the corresponding o-carboxylic acid ONa*C,H,*CO,H and that this then undergoes isomeric traiisformation into sodium aalicylate. Sodium phenoxide o-cctrboxylic acid (0-socloxybenxoic acid) may be obtained as a white crystalline powder by heating sodium phenyl carbonate in closed tubes at 100" for four days. When mixed with sodium phenoxide and heated at 150" in closed tubes it furnishes disodium salicylate and phenol and when heated with methyl iodide it yields methyl salicylate probably as the result of isomeric transforma- tion of the anisole-o-carboxylic acid first formed since the latter when heated during one day at 150" in the presence of small quantities of o-sodoxybenzoic acid is completely converted into methyl salicylate.It is probable that there is also no intermediate formation of carbon- ates in the preparation of carboxylic acids from phloroglucinol (Will Abstr. 1SSt5 906) or resorcinol (Senhofer and Brunner Abstr. lSSl 265) but this inay occur with hydroxyquinoline (Schmitt and Engel- mann Abstr. 1887 738; 1888 66). A. LOBRY DEBRuYNandS. TIJMSTRA (Rec. tl'ctv. chin&. ,1904,23,385-393). T. A. H.210 ABSTRACTS OF CHEMICAL PAPERS. Action of Organo-magnesium Compounds on Phthdic Anhydride.HUGO BAUER ( B e y . 1905 38 240-241. Compare Abstr 1904 41 7).-PhthaZopJtenone C6H4<-C01)0 melting a t 115' is formed by the interaction of magnesium phenyl bromide and phthalic anhydride along with small quantities of a compound melting a t 1 4 6 O probably identical with Zincke's P-dibenzoylbenzene. Further the crude reaction mixture on the addition of dilute sulphuric acid yields a viscid yellow oil soluble in light petroleum with a green fluorescence ; in time the fluorescence disappears and phthalophenone crystallises out. Dibenzyl'hthalide C H 4 < ~ ~ 2 ~ 2 > 0 forms colour- less needles melting a t 203-204'. By the interaction of magnesium p-tolyl bromide and phthalic anhydride a brown resin is formed from which a compound possibly o-ditolztoglbenxene melting a t 189-190° isomeric with di t ol ylpht halide was isolated.ADOLF DAUBE (Bey. 1905 38 206-209). -The ethylidenephthalide was prepared by Gottlieb's method (Abstr. 1899 i 51 1) and hydrolysed to propiophenone-o-carboxylic acid. This acid readily reacts with hydroxylamjne yielding the anhydride of propiophenoneoxime-o-carboxylic acid C 6 H 4%0-0 which crystal- lises from hot water in prisms melting a t 119". Hydrazine converts the acid into 1-ethylphthalazone (Paul Abstr. 1899 i 776) which can be readily alkylated yielding 1 3-dicthyE phthakaxone? CcH4<C0-NEt CEt:y . This melts a t 49-50' and distils a t 307'. Phosphorus oxychloride reacts with ethylphthalazone yielding 4- chloi.o-l-ethy~ht~c6Zaxine C,H,<CC1=N which crystallises from alcohol in needles melting a t 93'. On reduction with tin and hydro- chloric acid it yields etl~yldihydroisoindole C,H,<CH->NH which boils a t 32'7-329'.The chloro-compound readily reacts with sodium alkyloxicles. 4-Methoxy-1-ethylphthakazine melts a t 49O the etJboxy-compound a t 5 3 O and the phenoxy-derivative a t 89'. EtJ~~lphtJ~aZintidine C H < ~ ~ ~ > N H obtained by the reduction of ethylphthalazone with zinc and hydrochloric acid forms colourless crystals melting at 105" and turning red on exposure t o the air. Ethylidenephthalide yields an additive product with nitric peroxide ; when this is crystallised from glacial acetic acid a small amount of 0- nitroethylidenephthalide NO,*CMe:C<C >COY is obtained. It crystallises in yellow needles melting a t 1 2 3 O .Tolylnaphthalimides and Naphthylnaphthalirnides. GUIDO BA~~OELLINI (G'nzxetta 1904 34 ii 454-459).-The author has pre- pared o-tolylnaphthalirnide by the interaction of naphthalic anhydride CPh E. F. A. Ethylidenephthalide. ,.CEC CEt:T;J CHEt 6 4 J. J. 8.ORGANIC CHEMISTRY. 211 and o-toluidine and finds that it crystallises from acetic acid in yellow needles melting a t 217-21s" ; Janbert (Abstr. 1895 i 239) gave 214". m-ToZyZ.lzap~t~~aZimide Cl,H6<~~>N*C,H,&Ie crystallises from alcohol in shining yellow needles melting a t 175-176" and dissolves readily in acetic acid ethyl acetate or chloroform and to a slight extent in ether benzene or carbon disulphide. p-~olylnapl~thnlimide CISHl,O,N crystallises from acetic acid in small yellow needles melting a t 304-305O and dissolves readily in chloroform and slightly in alcohol carbon disulphide benzene or ethyl ace tat e.a-Nal3hthylna;uhthalimide C,,H,<~~>N*Cl,H7 separates from acetic acid as a yellow crystalline powder melting at 214-2 15" and is very soluble in carbon disulphide chloroform or nitrobenzene and slightly so in ether light petroleum ethyl acetate acetone benzene or methyl ethyl or amyl alcohol. P-Napht~yZnap?itha~~i,,tide Cg2HI3O2N crystallises from acetic acid in yellow needles melting a t 291-392" and dissolves readily in chloroform or nitrobenzene less so in methyl ethyl or amyl alcohol benzene ethyl acetate o r acetone and to a slight extent in ether carbon disulphide or light petroleum. T. H. P. The Oxonium Nature of Santonin.EDGAR WEDEKIND and A. KOCH (Bey. 1905 38 421-428).-Santonin and such of its derivatives as contain the carbonyl group intact behave as oxonium compounds and yield salts with acids and donble compounds with certain metallic haloids. Desmotroposantonin and other enolic deri- vatives have no basic properties. Santonin nitrate C~,Hl,O,,HNO forms colourless crystals and decomposes at 145'; it is stable in dry air but is decomposed quanti- tatively into its components by water (compare Andreocci A t t i 22. Accad. Lincei 1896 [v] 5 ii 309). SantonirL antimony pentachloride 2Cl,,H,,O,,SbC1,,HCI prepared by mixing the components slowly in glacial acetic acid solution forms colourless needles and decomposes a t 145'. It dissolves readily in most organic solvents ; water and alcohols decompose it.The rotation in acetone solution is that due to the ssntonin present. The hydrogen chloride in the salt is produced by chlorination of a part of the santonin (compare following abstract). Santonic acid antimony penta- chloride forms stable crystals and decomposes a t 145". Xantonin tin tetrabvomide 2C,,H1803,SnBrq,HBr forms yellow prisms and decomposes a t 12'7O. Oxonium salts of similarly abnormal composition have been described by Rosenheim and Levy (Abstr. 1904 i 1024). Scmtonin f e w i c chloi-ide forms brown crystals and melts and decom- poses at 210" ; the bright yellow plcitinichloride is unstable. It was not found possible to prepare a hydrochloride oxalate or picrate ; the ferro- ferri- aiid cobalti-cyanides mill be described shortly.C. H. D.212 ABSTRACTS OF CHEMICAL PAPERS. The Behaviour of Halogens towards Santonin. EDGAR WEDEKIND and A. KOCH ( R e p . 1905 38 429-435. Compare pre- ceding abstract).-It was not found possible to prepare bromo-substi- tuted derivatives of santonin as described by Klein (Abstr. 1893 i 112). Santonin reacts with bromine in acetic acid or chloroform solution to form a complex oxoniunz bromide C,oH3706Rr3 which contains two atoms of active bromine and one atom as hydrogen bromide and thus has the constitution L It decomposes at 1 0 5 O and slowly loses bromine under the action of light. Xccntonin oxonium iodide C3,,H370613 forms dark olive-green tablets with metallic reflex stable in dry air and decomposes a t 135'. It is less readily decomposed by water than the bromide.The behaviour of chlorine is quite different froin that of bromine only substitubion derivatives being formed. Dichlorosantonin c 5H,,O,C12 prepared from santonin and dr.y chlorine in chloroform solution forms - - long colourless prisms becomes yellow a t 140" and decomposes at 175". Chlorine water reacts with santonin forming chlorosantonin C15H1703Cl which crystallises from dilute alcohol and melts and decom- poses a t 235". Compounds from Lichen. WILEIELM ZOPF (Annalen 1905 338 35-70. Compare Abstr. 1904 i 1020).-Hesse's formula C,sH2,07 for rhizocarpic acid is incorrect the molecular formula Yseudovernia ericetorurn contains atranoric acid pFysodalin ( Hesse's physodic acid) and a bitter material but no furiuracic acid isidic acid or olivetoric acid.The plqsodnliya forms crystals melting a t 201-202° and yields a diacetyl derivative melting a t 15s'. Hesse's lepraric acid could not be found in Lepraria chlorina. Tbe last mentioned crystallises in rhombic plates and is insoluble in alkali hydroxides. Lecanora vccricc yields psoromic acid and I-usnic acid the latter having [a] - 489.2' in chloroform at 17". Catocccrpus ore'ites contains rhizocarpic acid and psoromic acid. Usnecc Sclwccderi contains usnaric acid d-usnic acid (La] + 498.3' in chloroform) and a colourless substance which could not be identified. Hesse's ochro- lecbiaic acid obtained from Oclwolechia pallescens var. payella is identical with variolaric acid ; the former melts a t about 280° the latter at 283". Parrnelia revoluta yields atranoric acid and gryophoric acid.The latter acid is characterised by a very delicate blood-red coloration with bleaching powder. Pnrrnelicc pilosella yields atranoric acid and a crystalline bitter material pilosellic acid ; the latter melts at 241jQ and gives a violet coloration with ferric chloride and a yellow solution with potassium hydroxide and ammonia. From Xtictina gilva stictinin was isolated which crystallises in needles melting a t 160-161' giving a reddish-violet coloration with ferric chloride and a cinnabar- red coloration with concentrated sulphuric acid changing to an C. H. D. being (C13H1003)2' Lepraricc j a v u contains calycin pinastric acid and calyciarin.ORGANIC CHEMISTRY. 213 orange-yellow solution with more acid. Calgciurn hpperellum. Rhizocarpic acid was found in o-Methylaminobenzaldehyde OTTO SCHMIDT (BET.1905 38 200-203. Compare Heller Abstr. 1904 i 160; Bamberger ibid. 422).-The physical constants of Heller's methylanthranil indicate tbat it cannot be n homologue of anthranil but rat.her a mixture of methyl- and dimethyl-o-aminobenzaldehydes. Refractro- metric determinations have shown that the group NmC:C*CO always produces an abnormally high refraction in a compound. K. J. P. 0. Sp. gr. at t. ED. Mn. o-Methylaminobenzaldehyde.. . 1.1092 11 *So/4O 1.62773 43.177 Methyl methylanthranilate . .. 1.1348 12.3 /4 1.58395 48.658 Ethyl aminoacetate . . . ... 1,0358 11.8 14 1.42737 25.55 Acetylanthranil . . . ... 1.2034 7S.3 14 1,56862 43.81 J. J. 8. (Compare Briihl Abstr. 1904 i 92 and 160.) p-Hydroxynaphthaldehyde. MARIO BETTI and CURIO M.MUNDICI ( A t t i R. Accad. Lincei 1904 [v] 13 ii 542-550).- P-Hydroxynaphthaldehydephenylhydrazone and P-hydroxynaphthyl- ideneaniline have already been described (Gattermann and Horlacher Abstr. 1899 i 372). CH N*C,H,* NO crystallises from alcohol in dark red needles showing a metallic green reflex or from benzene in yellowish-red scales or ruby-red plates melting at 222'. P-IIydroxynaphth ylidene-p-.nitroccnili.lze OH* C - 1 2-Na~?~t?iacournarincarboxylic m i d CloH6<o- -°CH:y* co Co,H prepared by the condensation of P-hydroxynaphthaldehyde and malonic acid in presence of acetic acid crystallises from alcohol in scales or in yellow silky needles melting and decomposing at 233'; the alcoholic solution exhibits vivid yellowish-blue fluorescence! and is faintly alkaline to litmus.The action of dry hydrogen chloride on P-hydroxynaphthaldehyde in methyl alcoholic solution yields a hydrochloride of dinaphtha- xantliydrole C H / A \ O * C l separating as a green crystalline mass which dissolves in acetic acid giving an intensely brown coloration and is decomposed by water even in the cold ; at 1 1 5 O it forms drops and a t 216-21S0 it melts and decomposes. When treated with methyl alcohol in the cold it yields the corresponding methyll deriva- tive OMe*CH<clOHF>O C H which crystallises from methyl alcohol in pale yellow strongly refracting prisms mslting a t 178'. Cold ethyl alcohol yields (1) the ethyl derivative C23Hi802 which crystallises from alcohol in colourless silky needles melting at 1 4 9 O and reddening slightly in the a i r ; it has the normal molecular weight in freezing benzene and forms a bright red picrate melting at 241'; (2) di- nnphthnxnntheiie CH,<CIOHG>O C H which is obtained in larger yield by C H 'C 10 J%' 10 F 10 6 Q VOL.LXXXVIII i.214 ABSTRACTS OF CHEMICAL PAPERS. the action of hot ethyl alcohol on the hydrochloride and crystallises from benzene in shining colourless needles melting a t 203-204'. T. H. P. The 3-Met hyl-6-a1 kylcyclo hexanones and the Corresponding Phenols Homologues of Mentbone and Menthol. ALBIN HALLER (Conzpt. Tend. 1905 140 127-130).-When the sodium derivative of 3-methylcycZohexanone prepared by the action of sodamide on the ketone is treated with an alkyl iodide the corre- sponding 3-methyl-6-alkylcyclohexanone is obtained (compare Abstr.1904 i 600). E y the prolonged action of methyl iodide on the sodium derivative of 3-methylcyclohexanone a mixture of the di- tri- tetra- and penta-meth$cycldiexanones is formed. 3-illethyl-6-ethyZ- cyclohexanone C,H,,O boils at 83-84" under 18 mm. pressure has a sp. gr. 0.9016 at 15'/4' and [a]= + 8'32' and yields a semicarbnzons melting a t 1 5 2-1 54'. 3-Metl~yl- 6-propylcy clohexanone C,,H,,O boils a t 97-98" under 1s mm. pressure has a sp. gr. 0,8994 a t 15"/4O and [aID + 3'21' ; its sernicas.baxone melts a t 154-156'. 3-Methyl- 6-aZZyZcyclohexlanone C,,H,,O boils at 98-99' under 18 mm. pres- sure has a sp. gr. 0.9233 at 15'/4' and [a],+ 18'2'; its senzi- carbazone melts at 146-1 48".3-Met~~yZclialZyZcyclohexccnone C13H200 boils a t 130-132' under 20 mm. pressure has a sp. gr. 0.9365 a t 1P/4' and [aID+62'2'; its semicarbazone melts at 141-143'. 3-~~ethyl-6-isobutyZcyclohexunone C,,H,,O boils a t 93-95" under I 1 mm. pressure bas a sp. gr. 0.9950 a t 15'/4" and [ The 3-methyl-6-alkylcycZohexanones on reduction with sodium in absolute alcohol yield the corresponding phenols which have an odour similar to that of menthol boil a t R slightly higher temperatrirs than the ketone from which they are derived and form condensation products with benzaldehyde which are oxidised by potassium per- manganate to form the a-methyl-6-alkyladipic acid and benzoic acid according to the equation CH,<CH~-CO>C:CHPh + 0 = CO,H CHMe CH,* CH CHR* CO,H + PhC0,H.3-MethyZ-6-ethyZcyclohexanoZ C,HI8O boils a t 85-47' under 1 1 mm. pressure ; 3-ntethyZ-6-p~opyZcyclohexnnol C,,H2,0 distils a t 102-104° under 15 mm. pressure. 3-llleth~Z-6-aZl~lcyclohexunol C,,H,,O boils a t 98-1 00" under 10 mm. pressure. 3-MetlqZ-6-isobutyl- cyclohexmol CllH2,0 cry stallises from light petroleum in thin needles melting at 68- 69O ; a liquid stereoisomeride boils a t 110-1 12' under 16 mm. pressure. + 0'24' ; its seinicarbazone melts a t 171-1 73'. CH *CHMe M. A. W. Condensation of Imines with Aldehydes a n d Ketones. CHARLES MAPER (ZuZZ. Xoc cliim. 1905 [iii] 33 157-162. Compare Abstr. 1904 i 832).-When molecular solutions of acetophenone and benzylidenenniline in alcohol are mixed anilinobenzylacetophenone COPh*CH,*CHPh*NHPh is formed (Tambor and Wildi Abstr.1898 i 313) ; from this by the action of sulphuric acid benzylidenesceto- phenone is produced. With benzylidene p-tolnidine p-ioZuidinobenx$- acetophenoyte COPh*CH,*CHPh*NIH*C,H,Me is obtained; this separatesORGANIC CHEMISTRY. 2 13 from alcohol in small colourless needles and melts at 172'. P-Naphtliyt- aminobenxylaoetophenone COPh*CH CHPh*NH*C,,H obtained by the interaction of acetophenone and benzylidene-P-naphthylamine dis- solved in alcohol in presence of sodium methoxide crystallises from boiling benzene in small needles melts a t 199O and is slightly soluble in cold alcohol more so on warming. P-Anilino-p-phenyldiethyl ketone NHPh*CHPh*CH,*COEt obtained by the interaction of methyl ethyl ketone with benzylideneaniline crystallises from alcohol in small colourless needles melts a t 121° and is slightly soluble in cold alcohol more so on warming.The solution in sulphuric acid furnishes on addition of excess of water benzylidene- methyl ethyl ketone CHPh:CH*COEt (Harries and Muller Abstr. 1902 i 295 j instead of the quinoline derivative expected (compare Simon and ConduchB Abstr. 1904 i 521). /3-Anilino-/3-phertyZethyJ propyl ketone NHPh*CHPh*CH,*COPra forms small needles and melts at 88". p-A?zilino-P-p~enyZethyl hexyl ketone NHPh* CHPh*CH,*CO* C6Hl3 forms colourless needles melts a t 92-93' and is converted by sulphuric acid into benxylidenemethyl hexyl ketone CHPh:CH*CO*C,H, whioh forms colourless needles melting a t 34O. P-Anilino-/I-phenyl- ethyl heptyl ketone NHPh*CHPh*CH,*CO*C7H15 crystallises in needles melts a t 93-94' is slightly soluble in alcohol readily so in ether and with sulphuric acid yields ben,xylidenemethyl heptyl ketone which crystal- lises from light petroleum in needles and from methyl alcohol in scales melts at 52' and is soluble in ether.p-Aniliizo-/3-phenylethyZ nonyl ketone forms small needles melts at 96' and furnishes benzylidene- methyl nonyl ketone. Reactions between Organic Magnesium Compounds and Unsaturated Compounds. 111. Reactions with Compounds containing Bromine. ELMER P. KOHLER and RUTH M. JOHNSTIN (Amer. Chem. J. 1905 33 35-45 Compare Abstr. 1904 i 595 and this vol. i 207 208).-When an ethereal solution of ethyl a-bromo- cinnamate is added gradually to a solution of magnesium phenyl bromide and the resulting yellow precipitate is decomposed with ice- water bromodiphenylpropiophenone (Kohler Abstr.1904 i 596) is produced together with benzoic acid and /I-phenylcinnamic acid. By the action of magnesium methyl iodide on ethyl a-bromo- cinnamate an oily product is obtained which does not contain an ester and is slowly decomposed by boiling alcoholic potassium hydroxide with formation of potassium bromide potassium benzoate and a gum. When the oil is oxidised with dilute potassium permanganate acetone benzoic acid and probably hydroxyisobutyric acid are obtained whence it is concluded that the chief product of the reaction is a tertiary alcohol CHPh CBr* C Xe,*OH. When a-bromobenzylideneacetophenone is treated with magnesium phenyl bromide and the product decomposed with ice-water a nearly theoretical yield of a-bromo-/3/3-diphenylpropiophenone is produced.P~enylbenxy lideizecccet ophenone CPh, CH COPh obtained by the action of boiling alcoholic potassium hydroxide on bromodiphenylpropio- phenone crystallises in large lemon-yellow prisms melts at 92" is T. A. H. 2 22 16 ABSTRACTS OF CHEMICAL PAPERS. readily soluble in alcohol or ether and slightly so in light petroleum and on oxidation with dilute potassium permanganate is converted into benzophenone and benzoic acid. By the action of magnesium phenyl bromide ,on stilbene bromide diphenyl is produced. Magnesium phenyl bromide reacts with ethyl dibromophenylpropionate with formation of diphenylpropiophenone and ethyl diphenylpropionate. When benzylideneacetophenone bromide is slowly added to a solution of magnesium phenyl bromide a t a low temperature bromodiphenyl- propiophenone and diphen ylpropiophenone are produced but if the reaction is carried out a t 35' the products consist of diphenyl and diphenylpropiophenons. By the action of magnesium naphthyl bromide on benzylidene- acetophenone bromide naphthylphenyl$wopiophenone is obtained which crystallises in needles melts at lalo and is readily soluble in ether or alcohol.When a-bromodiphenylpropiophenone is treated with a n ethereal solution of magnesium phenyl bromide diphenylpropiophenone and diphenyl are produced. If however the mixture is treated with benzoyl chloride before the addition of water benzopltriphenylpropenol is obtained. E. G. Pinacone-Pinacolin Rearrangement.SALOMON 3'. ACREE (Amer. Chena. J. 1905 33 180-195. Compare Abstr. 1904 i 742 747).- When dihydroxydiphenyldihydrophenanthrene is heated with acetyl 76H4'(?0 is produced which melts C,H,-CPh,' chloride diphenylphenanthrone a t 19So and is not easily oxidised by chromic acid (compare Werner and Grob Abstr. 1904 i S65). When this substance is heated with alcoholic potassium hydroxide a t 150-190' for 6 hours an acid pro- bably CHPh,*C,H,*C,H,*CO,H is formed which melts at 180-190". By the action of magnesium phenyl bromide on acenaphthenequinone dihydroxydip~enyll~~~ydrouce~aap~~t7~ene C H < (?Ph*oH is obtained lo ' CPh-OH' which crystallises from alcohol or glacial acetic acid melts a t 154O and when heated with acetyl chloride remains unchanged.When s-diphenyldi-p-tolylpinacone (Acree Abstr. 1904 i 743) is heated with acetyl chloride for 10 hours a substance is produced which is probably identical with the P-di-p- t ol y Id i phen ylpinacolin described by Thorner and Zincke (Abstr. 1878 i 223). By the action of magnesium phenyl bromide on ethyl oxalate P-benzopinacolin is not produced but benzopinacone only is obtained (compare Dilthey and Last Abstr. 1904 i 667). Tetraphenyltetramethylene glycol (Dilthey and Last Zoc. cit.) melts at 206O. When ethyl succinate is treated with a boiling ethereal solution of magnesium phenyl bromide a substame probably tetra- >0 is formed,which crystallises phenyl t etramethylene oxide from alcohol melts a t 163-165' and slowly decolorises solution of bromine QH,*CPh CH,*CPh,ORGANIC CHEMISTRY.217 By the action of magnesium ethyl iodide on benzoin up-diphenyl- butylene ap-glycol OH.CPhEt*CHPh*OH is produced which melts at 115-116' and is only very slowly attacked by bromine. Diphenyl-m-tolylcarbinol (Bistrzycki and Gyr Abstr. 1904 i 498) boils at 255' under 26 mm. pressure and melts a t 65". E. G. Behaviour of Tetrabromo-o-benzoquinone towards Ketones and Aldehydes. C. LORING JACKSON and F. W. RUSSE (Bey. 1905 38 419-421. Compare Abstr. 1904 i 254).-Tetrabromo-o-benzo- quinone does not combine with ketones and aldehydes to form compounds similar to those obtained from alcohols but is converted by them into a mixture of hexabrorno-o-quinocatechol ether C,Br,O, C,Br,O hexabromodihydroxycatechol ether C,Br,O,:C,Br,( OH)2 and heptu- bromo-o-puinocatechol ILemiether OH*C,Br,0*C6Br,0,,l~C6Hg. The last compound crystallises from benzene in large flat yellow prisms which lose benzene on exposure to air.It dissolves in ether chloroform or nitrobenzene without decomposition ; the alcoholic solution decomposes on warming and deposits hexabromo-o-quinocatechol ether. The hexabromo-compound is best prepared from tetrabromo:o-benzoquinone and acetone in the presence of benzene at the ordinary temperature the reaction being completed in two weeks. When an excess of acetone is employed and the benzene is omitted the two first-named compounds are chiefly obtained. Some bromoacetone is also produced and when acetophenone is employed w-bromoacetophenone is obtained C. H. D. Action of Potassium Iodide on Bromanil and Chloranil.HENRY A. TORREY and W. H. HUNTER (Bey. 1905 38 555-556)- When heated with potassium iodide in acetone solution bromanil forms dibromodi-iodo-p-benxopuinone C,O,Br,I which crystallises in reddish- brown prisms or golden plates commences to sublime a t about 240° melts at about 255O is easily soluble in benzene toluene hot acetone or ethyl acetate but only slightly so in alcohol ether or light petroleum; it dissolves in hot aqueous sodium hydroxide to a purple solution and is easily reduced to the colourless quinol. With sodium phenoxide in aqueous solution the quinone forms a phenoxy-derivative with diphenylamine in light petroleum solution an additive compound C602Br212,NE€Ph which separates in dark red crystals and with o- toluidine a similar additive compound.The action of powdered potassium iodide on chloranil partly dissolved in acetone leads to the formation of a green substance which contains potassium and wheii treated with water yields a yellow insoluble compound and a purple solution. Under the same conditions bromsnil yields a similar derivative. G Y. 2-Nitro-3 6 - dihydroxy - p - benzoquinone - 5 - sulghonic Acid. RUDOLF NIETZKI and ALFRED KUMANN (Ber. 1905 38 453-454)' -Potassium 3 ; 6-dichloroquinol-2 ; 5-disulphonate prepared by the218 ABSTRACTS OF CHEMICAL PSPERS. action of potassium sulphite on chloranil reacts on warming with potassium nitrite to form potassium 2-nitro-3 6-di?~ydroxy-p-benxo- quinone-5-suZphonate NO,*C,O,(OK),*SO,K which crystallises from water in yellow needles.The acid may be regarded as nitranilic acid in which one nitro-group is replaced by a sulpho-group. Silver nitrate precipitates a yellow crystalline potassium silver salt C,O,NSKAg,. Btannous chloride reduces the potassium salt yielding 2-amino-3 6- di~yclroxyq2ii?.Lol-ti-su~?honic acid ?hydrochloride NH,*C,( OH),*SO,H,HCl which forms colourless crystals becoming brown on exposure to air. It was not found possible to break down the ring by oxidation. C. H. D. Dissociation of Phenoquinone and Quinhydrone. HENRY A. TORREY and H HARDENBERGH (Amer. Chew. J. 1905 33 167-179. Compare Biltris Abstr. 1899 i 199).-As a preliminary to the study of the dissociation of phenoquinone the molecular weights in benzene solution of its dissociation products phenol and quinone were deter- mined.Determinations of the molecular weight of phenol by the ebuIlioscopic method gave results which show that this substance is somewhat polymerised a t the boiling point of benzene and deter- minations by the cryoscopic method confirmed the conclusions of Beckmann (Abstr. 1889 ll) Auwers (Abstr. 1894 ii 133) and others that phenol is polymerised even a t low concentrations and that the polymerisation increases with the concentration. The average value obtained for the molecular weight of quinone by the boiling point method was 116 and by the freezing poiat method 105. The results of the cryoscopic determinations agree with those obtained by Auwers (Zoc. cit.) and show that the molecular weight of quinone is not affected by the concentration. Determinations of the molecular weight of phenoquinone by both methods have shown that this substance is highly dissociated in ben- zene solution; Biltris (Zoc c i t .) has found that this is also the case in ethereal solution. When phenol is added to a saturated solution of phenoquinone a considerable quantity of phenoquinone separates showing that phenol and quinone are the dissociation products. The action of these dissociation products on dissolved phenoquinone was studied by both ebullioscopic and cryoscopic methods. The results of these experiments are tabulated and show that by the addition of one of the dissociation products to the dissociated phenoquinone solution a re-association takes place. A determination of the molecular weight of quinhydrone in benzene solution has shown that the substance is completely dissociated into quinone and quinol as Riltris (loc.cit.) has shown is the case in ethereal solution. If quinhydrone is dissolved in warm chloroform and the solution is slowly cooled quinol separates a t about 35'. As in the case of phsnoquinone quinhydrone may be precipitated from its solution by the addition of one of its dissociation products. The yellow colour of solutions of phenoquinone and quinhydrone in various organic solvents shows that in general both substances are dissociated. E. G.ORGANIC CHEMISTRY. 219 &c-m-Xylenol a n d Tetramethyldiphenoquinone. KARL AUWERS and TH VON MARKOVITS (Ber. 1905 38 226-23'7).- 3 5 3' 5'-5?etrametl~yldiphenoquinolze-4 4' C,,H,Me,O is best pre- pared by oxidising uic-m-xylenol dissolved in glacial acetic acid with chromic anhydride. Within 15-20 minutes the quinone separates in glistening needles ; crystallised from lritrobenzene or xylene it separ- ates in dark red needles and melts when fairly quickly heated at 210'.The quinone is also obtained when other oxidising agents w e employed as for example ferric salts but the chromic anhydride method gives the best results. Hyciroxylamine and phenylhydrazine act as reducing agents ; the quinone is best reduced by the action of zinc-dust on the suspension in boiling acetic acid. The quinol 3 5 3' 5'-tetrametTbyZ-4 4'-diphenoZ C,,H,Me,(OH) so obtained crystallises in colourless glass glistening needles and flat prisms melt- at 220-221' ; the dicccetate separates from acetic acid in long needles melting at 174-175".The diphenol is very easily reoxidised to the quinone especially in alkaline solution a puinhydrone being formed as an intermediate product ; this crystallises in dark steel-blue plates melting at' 201'. 2-Chloro-3 5 3' 5'-tetrcmethyl-4 4'-dihydroxy- dzphenyl OH*C,HClMe,* C,H,Me,*OH prepared by the action of concentrated hydrochloric acid on the quinone cry stallises in needles melting a t 203'. It is shown that only those phenols in which both the ortho- positions relative t o the hydroxyl group are occupied and both the meta- and para-positions are free undergo easy oxidation to di- yhenoquinone derivatives in this manner. Further the analogy bet ween tetramethyldiphenoquinone and coerulignone (te tramethoxydi- phenoquinone) is pointed out (compare Liebermann Abstr.1873,1033; Hofmann Abstr. 1878 417 and Herzig and Pollak Abstr. 1904 i 808 876). E. F. A. Alizarin Dimethyl Ether. CARL GRAEBE (Ber. 1905 38 152-153. Compare Abstr. 1902 i 42).-'J!he action of methyl sulphate on deoxyalizarin in alkaline solution leads to the formation which crystal- CH,* F:C(Oi\te)* s*OMe C0-C CH--CH of the dimethyl ether C,H,< lises in golden needles melts at 150° is easily soluble in alcohol dis- Eolves in concentrated sulphuric acid to a reddish-yellow solution and is oxidised by sodium chromate and glacial acetic acid to alixurin dimethyl ether Cl6Hl2q4. This crystallises in golden needles melts a t 215O is easily soluble in benzene or chloroform and moderately so in hot alcohol and dissolves in concentrated sulphuric acid t o a red solution.I t is identical with the dimethyl ether obtained from 1-nitro-2-methoxyanthraquinone (Farbwerke vorm. Meister; Lucius & Bruning). G. Y. Action of Alcoholic Potassium Hydroxide on Phenanthra- quinone. RICHARD MEYER and OSKAR SPENCLER (Bey. 1905 38 440-450).-1n the preparation of diphenic acid by the action of alcoholic potassium hydroxide on phenanthraquinone a yellow sub-220 ABSTRACTS OF CHEMICAL PAPERS. stance is first obtained and is converted into diphenic acid by prolonged boiling. The alcohol takes part in the reaction the yellow compound not being obtained in aqueous or methyl alcoholic solution. The same compound is obtained by heating phensn thraquinone and glycollic acid in methyl alcoholic solution C,,H80 + C,H,03 = C16H803 -+ 2H20.It is the lactone of 1 O-h~ydro~~~~~enant~~~yZ-9-glyoxylic acid which crystallises from organ& solvents in orange needles and melts and decomposes a t 220-221'. It dissolves in alkalis t o yellow solu- tions from which it is reprecipitated by acids. The bariunz salt C16H804Ba forms pale yellow felted needles. The phenylhydraxone forms reddish-yellow needles and melts and decomposes at 254'. Zinc dust reduces the lactone in alkaline solution to diphenylene- d ih ydrof wan >CH2 which crystallises from dilute acetic C,H;C-0 acid in long flat needles and melts at 152'. When fused the lactone evolves carbon monoxide and carbon dioxide \!,H,*g.CH forming a mixture of the compounds 7GH4* f*cO's 7sH4 and C,H,'C*CO*C C6H4 C.H. D. F,H4*s* CO* fj*Q6H4 C,H,*C-O-C* C6H4' A Synthesis of Menthone and Menthol. ALBIN HALLER and CAMILLE MARTINE (C'ompt. rend. 1905 140 130-1 32).-3-Methyl-6- isopropylcyclohexanone prepared by the action of isopropyl iodide on the sodium derivative of optically active 3-methylcydohexanone (this vol. i 214) boils a t 207-209° has a sp. gr. 0.9008 to 0,9017 a t 17" and [.ID +. 12'56' to 8'52' and is a mixture of d- and I-menthone yielding an oxime a semicarbazone and a condensation product with benzaldehyde which are respectively identical with the corresponding derivatives of menthone ; on reduction with sodium in absolute alcohol it is converted into menthol m. D. 42-43' which combines with phthalic acid to form a menthyl hyirogen phthalate melting a t 120'.M. A. W. Cinnamylidenecamphor a n d its Reduction Products. HANS RUPE and GUNNAR PRISELL (Btr. 1905 38 104-122).-Cinnamyl- was described by Haller YO C8H14<G CH*C H CIIPh' idenecam phor (Abstr. 1891 1498) as an uncrystallisnble oil but when prepared from sodium camphor and cinnamaldehyde in toluene suspension it may be obtained in a solid form and then crystallises fiom alcohol in yellow amber-like rhombic crystals [a b c = 0-84856 1 1.86321 insoluble in water dissolving readily in ether benzene or chloroform. It melts at 88-89' and boils at 227-228-5' under 11 mm. pressure and at 159O in the vacuum of the cathode light ; [a] was found to be + 269.74' in benzene and + 296.11' in chloroform. Sodium amalgam reduces cinnamylideuecamphor in methyl alcoholicORGANIC CHEMISTRY.221 co solution to y-phenyZpropyZca;n~r~ol. C8Hk6H. CH,. CH,.CH,Ph' ing at 200' under 11 mm. pressure and dissolving readily in organic solvents. It has a sp. gr. 1.0064 a t 2O0/4" ; n 1.5242 ; [a] + 66.53' in chloroform. Potassium permanganate oxidises it to benzoic and camphoric acids. It does not yield additive products with bromine or hydrogen bromide. On heating cinnaniylidenecarnphor with a cold saturated solution of hydrogen bromide in glacial acetic acid at loo' an oily product is obtained consisting of a mixture of a bromo-acid and a brominated hydrocarbon. Zinc dust and acetic acid reduce it. The reduction product contains 1.'r~en~Zbutadien?lltri,meth?lZcyclopentune C,H,Rlle,* CH CH.CH:CHPh a colourless uncrystallisable oil boiling at 180' under 10 mm.pressure and having a sp. gr. 0.9995 at 20'/4' n 1.54089 and [ a ] + 3.86". The second reductioii product is phenylbuten~l- or phnyZ- butadienyl-trimethy/lcyclopentenecurBoxyZic acid which boils at 236-23s' under 1 2 mm. pressure and has a sp. gr. 1.0007 at 2Oo/4O and n 1,52901. Zinc dust and acetic acid reduce ciiinamylidenecamphor and the product may be separated by crystallisation from alcohol followed by fractional distillation of the uncrystallisable portion into four fractions the first two of which yield on crystallisation geometrically isomeric forms of dipphenylpropylenedicanaphoy CHPh CH-CH C H*C,H,Me,*CO,H c,Hl,<yo F-CH,*CH:CHPh C H ''<C*CH,*CH:CHPh. yo F*C H,* C H CHPh C H P~:CH*CH,.~->C CS%< c 0 co l4 trans-.cis-. The trans-modiJication crystallises from alcohol in white leaflets melts at lSS' dissolves readily in ether benzene or chloroform and has [ a ] + 40.63'. The cis-mod$crctio.n crystallises in microscopic leaflets melts at 152O dissolves readily in organic solvents and has [a]= +30.22'. Both forms react with bromine in chloroform solution to form a dibromo-derivative CS,H,,O,Br a yellow crystal- line powder melting at 1 1 8 O which yields the trans-compound on reduction. Both the cis- and trans-compounds combine with hydrogen bromide in glacial acetic acid solution yielding a mixture of an a-hyhobronzide C,,H,,O,Br melting a t 168O and a P-hydrobromide melting at 215' and dissolving more readily in organic solvents than the a-isomeride.Zinc dust and acetic acid reduce the a-hydrobromide to trans-di- y-p~~enyZpro~yZd~c~7~2pr~or C3sH5002 which crystallises from alcohol in small cubes and melts at 162". I n similar manner the P-hydro- bromide yields on reduction cis-di-y-pphenyZpropyZd~c~~~pr~or which separates from alcohol as a white crystalline powder and melts a t 205'. Both isomerides are stable towards potassium permanganate bromine and hydrogen bromide. The third fraction from the reduction of cinnamylidenecamphor is222 ABSTRACTS OF CHEMICAL PAPERS. an uncrystallisable oil. The last fraction contains a compound C35H4603 which crystallises from alcohol in white silky needles and melts at 250'. C. H. D. Transformation of Carvone and Eucairvone into Carvacrol and the Velocity of this Transformation. T.M. M. DORMAAR (Rec. trav. c?~im. 1904 23 394-400).-The meaanrements were made by heating solutions of the ketones in acetic acid with phosphoric oxide at 205" and observing the changes in specific gravity which took place. I n the case of carvone an attempt was made to use the change of specific rotation as a criterion of the progress of transformation but this method was abandoned owing to the production of a small amount of colouring matter which interfered with the accuracy of the readings. The reaction in both cases was uiiimolecular ; the mean value of k in the case of the carvone transformation was 0-038 and for that of eucarvone 0.019. T. A. H. Oximes of Pulegone. FRIEDRICH W. SEMMLER (Ber. 1905 38 146-148. Compare Beckinann and Pleissner Abstr.1891 936 ; Wallach Abstr. 1896 i 309 ; Harries and Roeder Abstr. 1900 i 102).-YuZegone dioxirrae CHMe<CH~*C(NoH)>CH*CMe2*NH*OH CH,-CH is obtained when the alcoholic-ethGesl solution of the product of the action of hydroxylamine according to Beckmann's method on pulegone is extracted with a small quantity of concentrated aqueous sodium hydroxide and carbon dioxide passed through the alkaline extract. It melts at 118" and is reduced by sodium and alcohol to 3 8-dianzino- menthane C H M e < ~ ~ ~ ~ ~ ~ ! > C H * C ~ ~ e ~ * N ~ ~ which boils a t 118-121° under 10 nim. pressure and has a sp. gr. 0.956 a t 20° and nD 1.489 ; the thiocarbanaide derivative Cz,H,,N,SZ melts a t 157". The action of nitrous acid on the sulphate of the base in aqueous solu= tion leads to the formation of the glycol C,,H,,O which boils at 146-148" under 10 mm.pressure an? is converted by the action of dilute sulphuric acid into isopulegol. When distilled the hydrochloride of 3 8-diaminornenthane yields hydrocarbons and a base (9 q H M e * C H ~ * ~ H * ~ H CH - CH,* CH* C Me which boils a t 65" uncle;- 15 mk. preesur;! and forms an insoluble picrate melting a t 130". G. Y. Camphene Camphenylone isoBorneo1 and Camphor. Lours BOUVEAULT and GUSTAVE BLANC (Compt. rmd. 1905 140 93--95).- Methylcamphenylol obtained by Wagner Moycho and Zienkowski by the action of magnesium methyl iodide on camphenylone (Abstr. 1904 i 435) behaves as a tertiary alcohol on boiling withpyruvic acid (com- pare Bouveault Abstr. 1904 i 465) the main product of the reaction being camphene which reacts with the pyruvic acid to form isobornyl pyruvate boiling at 133-134' under 11 mm.pressure and yielding aORGANIC CHEMISTRY 223 semicarbazone melting a t 214' or 821' according to the rate of heating. isoBorneo1 on the contrary behaves as a primary or secondary alcohol when heated with pyrnvic acid forming a pyruvate the semicarbazone of which is identical with the one already described. 31. A. W. Green Colour of Kajeput ;Oil. H C. PRINSEN GEERLIGS (Chem. Centr. 1905 1 95 ; from Chenz. TPeekblad 1904 1 931-934).-The green colour of the oil is due to the presence of copper this being dissolved by the butyric and valeric acids and the esters of these which are contained in the oil. This was shown by experiments with the purified oil from which the acids and esters had been completely removed.This purified oil after addition of water and either ethyl formate acetate propionate butyrate valerate lactate citrate oxalate or cinnamate and a small quantity of the corresponding acid was treated with copper shavings. The butyrate and valerate mixtures were the only ones which developed a green colour the copper dissolving in the aqueous layer in all the other cases. Valerian oil also dissolves copper and as in the case of kajeput oil the green colour cannot be removed by shaking ont with water. H. M. D. Peppermint Oil from Java. P. VAN DER WIELEN (Chem. Centr. 1905 1 95 ; from Plmvn. TVeekblnd 1904 41 1081-1084).- Examination of an essential oil obtained from Mentha javanica gave the following data.It was light green in colour had a bitter taste and an odour resembling peppermint. Sp. gr. = 0.9214 at 15'; uD + 4'40' at 20' in a 100 mm. tube. It dissolved in one and a half times its volume of 70 per cent. alcohol. After cooling to -60° it became entirely liquid again a t - 15". It contained a considerable amount of pulegone but little or no merithol or menthone. H. M. D. Varieties of Caoutchouc. Weber's Dinitrocaoutchouc. CARL D. HARRIES (Ber. 1905 38 S7-90. Compare Abstr. 1902 i 811 ; 1903 i 189 642 ; 1904 i 757 1038; Weber Abstr. 1908 i 552 ; 1903 ii 762).-The properties of Weber's compound of caout- chouc with nitric peroxide vary with the time during which the reagent is allowed to act. When rapidly prepared in benzene solution the product is a yellow sandy powder decomposing a t about go' insoluble in benzene alcohol ethyl acetate chloroform or carbon disulphide but dissolving in nitrobenzene aniline pyridine or quinoline on warm- ing. When the product is allowed to remain 20 hours before filtering it becomes soluble in ethyl acetate or acetone and decomposes at 157-160'.Its properties resemble those of Weber's compound but the composition differs from the formula C,,H,,O,N assigned by him and approaches that of the author's nitrosite C,oH,,07N,. C. H. D. Caoutchouc Nitrosite and its Use for the Analysis of Crude Caoutchoucs and Caoutchouc Products. I. PAUL ALEXANDER (Bey. 1905 38 181-184).-According to Weber (Abstr. 1902 i 552) a compound C,,,H,,O,N is formed when a mixture of224 ABSTRACTS OF CHEMICAL PAPERS.nitrogen peroxide and oxygen is passed into caoutchouc solutions. The author in amplification of earlier work (compare Abstr. 1904 i 905) has now examined a considerable number of samples of caoutchouc from various sources according to Weber's method but the products obtained did not possess the composition C,,H,,0,N2. The figures for the analyses made agreed better for those of Harries' nitrosite " c '' than for Weber's compound. African Copals. CH. COFFIGNIER (Bull. Xoc. chim. 1905 [ iii] 33 169 -176).-Three West African resins known commercially as Kissel Cameroon and Accra copals are described. Kissel copal melts a t l l O o has a sp. gr. 1,066 a t 2 7 O acid number 70.4 Kottstorfer number 117.8 and is soluble in excess of boiling alcohol t o the extent of 50 per cent.Cameroon copal melts a t 150° has a sp. gr. 1.052 a t 27' acid number 159.7 Kottstorfer number 70.0 and is soluble to the extent of 45 per cent. in excess of boiling alcohol. Accra copnl melts a t 120° has a sp. gr. 1.033 a t 27' acid number 97.8 Kattstorfer number 140 and is soluble in excess of boiling alcohol to the extent of 90 per cent. The solubilities of the three copals in twelve different solvents are tabulated in the original. A. McK. T. A. H. Decomposition Products of a Derivative of Artemisin (1 4Dimethyl-P-naphthol and Propionic Acid). PASQUALE BERTOLO (Gaxxetta 1904 34 ii 322-326. Compare Abstr. 1902 i 814 and 1904 i 177).-When fused with potassium hydroxide the product of the reduction of artemisin by stannous chloride and hydro- chloric acid yields 1 4-dimethyl-P-naphthol (Zoc. cit.) and propionic acid.It hence behaves quite like the desmotroposantonins but does not like the latter yield santonous acids on reduction with zinc dust and acetic acid. When however this reduction product of artemisin is subjected to reduction by Ladenburg's method it yields a substance which is probably the corresponding acid and is to be further inves- tigated. Artemisin hence contains the same fundamental nucleus as santonin united to a propionic acid residue. T. H. P. [Theory of Dyeing.] WILHELII BILTZ (Ber. 1905,38 184-187). Researches in the Furan Series. R. MARQUIS (Ann. Chinz. Phys. 1905 [viii] 4 196-288).-The paper is mainly a re'sumb of work already published (compare Abstr. 1900 i 798; 1901 i 222 ; 1902 i 302 483 ; 1903 i 49 370 644 ; 1904 i 82).The aldehyde obtained by the action of water on nitrosuccinaldehyde monoacetin (Abstr. 1902 i 483) has been identified as maleic dialdehyde and the following derivatives prepared (1) a diphenylhydraxone melting at 236-237' by Maquenne's metallic block method and yielding on crystallising in scales of tH*CH:N*rPh CH*CH:N*NPh ' oxidation the tetraxone a magnificent red colour with a green reflex and melting a t 174-175'; -Polemical. A reply to Zacharias (this vol. i 75). A. McK.ORGANIC CHEMISTRY. 225 decomposing a t 220° and yielding a C H*C H :NOH CK*CH:NOH ' (2) the dioxhze I I dibenxoyl derivative melting a t 165'. M. A. W. Beckmann's Rearrangement in Oximes of Ketone-alcohols of the Benzoin Type.ALFRED WERNER and TH. DETSL'HEFF (Bey. 1905 38 69-S4. Compare Werner and Piguet this vol. i 66).-1n the preparation of a-benzoinoxime by Goldschmid and Polanovska's method (Abstr. 1887 492) the p-oxime is simultaneously produced and a method for the separation of the oximes is described. Acetyl.a-6enxoinoxi./ne 0 Ac-XCPh *CHPh*OH separates from warm alcohol in colourless granular crystals and melts a t 118'. Ace@-,& benxoinoxirne forms long fl3t prisms and melts a t 111'. Chromic acid oxidises the P-compound in acetic acid solution at 40-50' t o acetyl-y- benziloxime thus confirming the configurations already assigned (Zoc. cit.). Phenylcarbimide combines with both oximes in ethereal solution with development of heat. The a-compound separates from warm ether in white crystals and melts a t 124'; the P-compound crystal- lises from dilute alcohol in feathery groups of silky needles and melts at 120'.I n the preparation of u-fnroinoxime (Macnair Abstr. 1 S90 1245) P-furoinoxime is produced a t the same time and separates from ether in slightly yellow groups of crystals melting a t 102'. Furoin is much more readily converted into the oximes than benzoin. The Beckmann rearrangement of the f uroinoxiines proceeds with difficulty when phosphorus pentachloride is used more readily with benzenesulphonic chloride. I n both cases a rearrangement of the second type occurs the a-oxime yielding a nitrile and the p-oxime a carbylamine. Pyromucic acid was obtained on hydrolysing the nitrile with dilute sulphuric acid.Acetyl-afuroinoxime C,2Hl ,O,N separates from benzene in granular crystals and me1 ts a t 11 3' ; acetyl-P-furoinoxime forms groups of needles and melts a t 108'. The acetyl group is removed on warming with alcohol. Phenylcarbimide combines with the furoinoximes the a-compound C17H140,N forming colourless star-shaped crystals melting at 56' and becoming dark in air; the /3-compound forms needles melting at 120". Benzofuroin COPh*CH(OH).C,OH reacts with hydroxylamine in alkaline solution t o form a mixture of a-benxoficroiizoxii?ae crgstal- lising from alcohol in small prisms melting a t 160' and P-benxofuroin- oxime which crystallises with difficulty but forms transparent crystals containing ether which break up at 35" and then melt at 90". With benzenesulphonic chloride the a-oxiine yields benzaldehyde and furfuronitrile ; the p-oxime yields .L carbylamine.This determines the following configuration for the oximes The a-compound is not attacked. OIE.CHP1.1. *C,OH OH*CHPh* *C,OH N*OH * AcetyZ-a-benxof~ici.oi~zoxii)ze C1,,H1,O,N crys tallises froiii benzene and a. 0H.N ; P.226 ABSTRACTS OF CHEMICAL PAPERS. melts a t 115'; acetyZ-P-ficyoinoxime forms needles and melts a t 9 6'. The compomd of phenylcarbimide with a-benzofuroinoxime C,,H lii04N2,* forms an uncrystallisable syrup ; the /3-corrCpound crystal- lises from dilute alcohol and melts a t 138'. I n each pair of oximes here studied the a-isomeride in which the hydroxyl and CHR*OH groups occupy the &-position has a higher melting point and is less soluble than the /3-oxime.C. H. D. Derivatives of Dihydroisobenzofuran. ALFRED GUYOT and J. CATEL (Conzpt. rend. 1905 140 254-256. Compare Haller and Guyot Abstr. 1904 i 660).-MethyIphthalate or methyl o-benzoyl- benzoate react with magnesium phenyl bromide t o give 2-hydroxy- 1 1 2-triphenyl-1 2-dihyclroisobenxoficran C6H4<Cph -CPh oH>O melt- ing a t 1 1 8 O and the same compound is obtained by the condensation of magnesium phenyl bromide with diphenylphthalide according to the equation C6H4<:E!>0 + MgPhBr = C6H4<GF$i&>0 -3 The authors find that diphenylphthalid; is formed as an intermediate compound in the first reactions methyl phthalate yielding first benz- oylbenzoic acid and then diphenylphthalide by the action of a small quantity of magnesium phenyl bromide whilst methyl benzoylbenzoate yields dipheiiylphthalide and o-dibenzoylben zene under similar con- ditions. 2-Hydroxy-1 1 2-triphenyl-1 2-dihydroisobeazofuran con- denses readily with phenols or aromatic amines t o give derivatives of the type C,H4<-CPh2--)0 where R = *NMe *NH *OH &c.the compounds with dimethylaniline phenol and aniline melting a t 177" 1 6 7 O and 200' respectively and is reduced by sodium amalgam in alcoholic solution yielding 0- benxiLydryltriplierlc~rbino1 CPh(C,H,R) melting a t 150'. M. A . W. 9-Phenylxanthen. RICHARD MEYER (Bey. 1905 38 450-453. Compare Meyer and Saul Abstr. 1893 i 471 ; Ullmann and Engi Abstr. 1904 i 682).-9-Phenylxanthen prepared by distilling fluoran with zinc dust melts a t 138-139" and that prepared by reducing phenylxanthydrol at 144- 1 4 5 O .The two products resemble one another in all respects except the melting point. C. H. D. Dibromo-additive Compounds of the Cinchona Alkaloids. A. CHRTSTENEEN (J. pr. Chem. 1905 [ii] 71 1-29. Compare Abstr. 1904 i 184 ; Comstock and Iioenigs Abstr. 1892 1010).--Two isomeric cinchonidine dibromides are foimed by adding bromine to t,he alkaloid in hydrogen bromide and glacial acetic acid solution ; a-cin-ORGANIC CHEMISTRY. 22'7 chonidine dibromide crystallises out as the hydrobromide ; the p-iso- meride is precipitated from the mother liquor as the insoluble nitrate. a-Cinchonidine di bromide crystallises in large thin rhombic often hexagonal leaflets blackens a t about 2003 melts a t about 225O is optically inactive and evolves only traces of hydrogen bromide when boiled with alcohol.crystallises in rosettes or sheaves of long prismatic needles (Abstr. 1901 i 481) ; the hydrobromide C,SH2,0N2Brz,2HBr,2H,0 forms a yellow powder consisting OF microscopic prisms ; the perbromide C,,H220N,Br.2 2HBr,Br2 crystallises in yellow quadrat'ic leaflets ; the suZphc6te (C,,H,,0N2Brz)z,H2S04,3H20 crystallises in long needles o r prisms is almost insoluble in cold water but dissolves easily in dilute sulphuric acid with formation of an acid snlpliate. When treated with concentrated sulphuric acid a-cinchonidice dibromide forms a sulphonic acid which crystallises in long thin needles evolvc s hydrogen bromide when boiled with alcoholic potassium hydroxide and forms an insoluble nitrate C 9H210N,Br,~S03H,HN03,H20./3-Cinchonidinedibromide crystalllses in long prisms blackens a t about 200' melts a t about 210° has [ a ] - 135' in 2.15 per cent. solution in a mixture of chloroform and alcohol and when boiled in 90 per cent. alcohol is partly converted into bromscinchonidine. The nitrate C19H2,0N,Brz,2HN03,H,0 crystallises in microscopic rhombic plates or from boiling water in short prisms (compare Abstr. 1904 i 520); the hydrobronzide C1,1~,,0N,Br,,2HBr,3H,0 crystallises in long white sharp needles ; the perbvomide Cl,H,,0N2Br2 2H Br Br4,H20 (?) crys- tallises in prisms and is reduced with aq'xeous sulphurous acid to P-cinchonidine d2 bromide ; the szdpliate crystallises in needles and a t 100-105° is partly converted into the snlphonic acid ; the insoluble acid sulphate C19H2,0NzBr2,2HzS0 formed when an excess of sulphuric acid is added to the sclution of the P-dibromide in dilute sulphuric acid crystallises in thin colour- less hexagonal rhombic leaflets. The sulphonnic m i d formed by the action of concentrated sulphuric acid does not form an insoluble nitrate or hydrobromide.Both cinchonidine dibromides yield the same dibromocinchonidine and bromocinchonidine (Abstr. 1904 i 520). Comstock and Koenigs' a- and P-cinchonine dibromides (Abstr. 1587 281) are formed by the action of bromine on the alkaloid in hydrogen bromide and glacial acetic acid solution ; the hydrobromide of the a-isomeride crys- tallises from the reaction solution whilst the P-isomeride is precipi- tated on addition of ammonia to the mother liquors a-Cinchonine dibromide crystallises in tufts of small leaflets and has [aID + 179.4' in 2.05 per cent.solution in a mixture of chloroform and alcohol. The nitrate C,9H,20N,Brz,2HN0,,H,0 crystallises in feathery aggregates of needles and is only slightly soluble in cold water; the hydro bromide C19Hz20N2Br 2HBr crystallises in long prismatic needles or pointed prisms ; the perbromide CIl9H2,0N2Br2,2HBr,Br2! formed by the action of an excess of bromine on the a-dibromide in hydrogen The nitrate C,,H,,ON,Br,,2HNO3,2H20 (C~9H2,ON,Br,)2,H2s0~,7H,O (I) - - bromide a.nd glacial acetic acid solution crystallises in microscopic-228 ABSTRACTS OF CHEMICAL PAPERS. yellow needles; the sulphate is only slightly soluble in water but easily soluble in an excess of dilute sulphuric acid.P-Cinchonine dibromide forms a granular partly crystalline powder has [.ID +107.5' in 1 per cent. solution in a mixture of chloro- form and alcohol and when boiled with alcohol is partly converted into bromocinchonine. The nitrate C,,H,,0NzBr2,2HN03,H20 crys- tallises in long thin plates ; the hydrobromide Ci9H2201V2Br2 2HBr forms small crystals resembling octahedra ; the sulphate resembles the a-salt. Both cinchonine dibromides when treated with alcoholic potassium hydroxide yield the same bromocinchonine. Action of Methyl Iodide on the isoNitroso-compounds of Cinchotoxine and Quinotoxine. GEORC ROHDE and G. SCHWAB (Be?.. 1905 38 306-320. Compare von Miller and Rohde Abstr. 1901 i 95).-isoilii't~*osonzeth~/Zcinchonine G.Y. obtained by the action of amyl nitrite and shdium e<hoxide" on methyl- cinchonine dissolved in absolute alcohol crystallises from ethyl acetate in colourlese prisms melts at 158-159' and is beet purified through the hgdrocldoride C2,,H2402N,Cl which separates from alcohol on adding chloroform in crystals containing the latter and melts and decomposes a t about 230'. isoNitrosomethyZcirzcho.ltine hydviodide C2,H,,02N31 resembles the hydrochloride in separating with chloroform of crystallisation and melts and decomposes at about lS0". isoNitrosomethylcinchonine methiodide C6H4->C*C( N* OH) *CO* CMe<CH(C CH,--CH CH ) .CH~>NMe,lfeI N G ~ ~ * ~ ~ separates from methyl alcohol in slightly red crystals and melts and decomposes between 2 2 8 O and 335'.isoNitrosocinchotoxine hydriodide C,,H,,O,N,T prepared from isonitrosocinchotoxine melts at 8 5 O subsequently solidifies and then melts and decomposes a t 2 1 0 O . The methiodide C,,H,,O,N,,MeI described by von Miller and Rohde (Zoc. cit.) is really identical with the isonitrosomethylcinchonine methiodide just described ; this would explain the abnormal properties it was supposed to possess. The action of methyl iodide on iso- nitrosocinchotoxine thus gives rise to the methiodide and hydriodide of isonitroeomethylcinchonine and to isonitrosocinchotoxine hydriodide. isoil'itrosoquinotoxine hydriodide C,oH,,O,N,I prepared by adding the requisite quantity of sodium acetate to a solution of the dihydriodide melts a t 102-105° and after solidification a t 217". iso- Nitrosomethylquinine prepared by the action of amyl nitrite on methylquinine is identical with isonitrosomethylquinotoxine (Zoc.cit.) ; it separates from benzene in wedge-shaped crystals containing benzene and melting a t 69-71' but when free from benzene it melts at 156'. The liydriodide C2iH,60,N,T of isonitrosomethylquinotoxine crystal- lises from alcohol and melts a t 207'; the methiodide C,,H,,O,N,I crystallises from alcohol in slender needles or in nodules and melts and decomposes at about 163'. The action of methyl iodide on isonitroso-ORGANIC CHEMISTRY. 229 quinotoxine dissolved in chloroform gives {gonitrosomethylquinotoxine methiodide and ~sonitrosomethy~quinotoxine hydriodide. W. A. D. Harmine and Harmaline. OTTO FISCHER and CHRISTJAN BUCK (Ber.1905 38 329-335. Compare Abstr. 1901 i 405).-When harminic acid is heated with concentrated hydrochloric acid for several hours a t 190-200° it loses only one carboxyl group and gives apo- harrninecarboxylic mid which crystallises from hot water in slender needles or small plates and is both acid and basic in its properties ; the hydrochloride C,H,O,N HCl platinichloride and aurichloi.ide are well defined substances. When heated at 330' the acid loses carbon dioxide and gives apoharmine ; towards reducing agents for example hydriodic acid or sodium in boiling ainyl alcohol the acid is very stable. i~eti~ylapolbccrrninecarboxylic acid C oHlo02N2 prepared either by methylating apoharminecarboxylic acid or by heating methylharminic acid with concentrated hydrochloric acid at 190' for 2 hours gives a hydrocldoride C,,Hl,O,N,,HC1,H,O crystallising in colourless plates and a hydmhdide Cl,H,oO,N,,HI crystallising in needles.Xtroapo- hurminecarboxylic mid C,H,O,N prepared by direct nitration crystallises from water in nearly colourless prisms and begins to decompose a t about 190'. Nitroapoharmine nitrate C,H70,N,,HN0 +H,O crystallises in reddish-yellow nodular aggregates. On methylation nitroapoharmine gives nitromethylapoharrrzine C9H902N3 which crystal- lises from dilute methyl alcohol and decomposes a t about 225'; the hydriodide C,H,O,N,,HI forms yellow leaflets the aurichloride melts a t 174' and the platanichloride with 2H,O decomposes a t 240-245'. Nitroapoharmine is not changed when boiled with chromic acid in acetic acid solution; on reduction with tin and hydrochloric acid it gives arninoapolbarmine which was isolated as the platinichloride CsH,,N,PtCl ; this crystallises in golden-yellow prisms and decomposes at 270'.Bihydroapohurmine picrate CSH1002,C,H307N3 is a crystalline salt which is of service in purifying the base. When concentrated sulphuric acid is added to harmine dissolved in acetic anhydride a harmine-N-sulphonic acid C,,H,,O,N,S is obtained which crystallises in slender needles and is decomposed by boiling dilute hydrochloric acid giving sulphur dioxide and harrnine hydro- chloride. W. A. D. Chloro-derivatives of Strychnine. GAETANO MINUNNI and F. FERRULLI (Gaxxetta 1904 34 ii 364-373).-The following derivatives of the tetrachlorostrychnine obtained by Minunni and Ortoleva (Abstr.1900 i 309) have been prepared. The hydrochloride C21H180,N2Cl,,2H,0 separates from acetic acid solution in white acicular crystals which are only slightly soluble in the ordinary solvents and begin to lose hydrogen chloride a t loo' although at 260' they are still unmelted. The free base ( + H,O) melts and decomposes a t 165-1 70". The phenylhydraxone C,IH180N2C14:N2HPh VOL. LxxxvlII. i. r230 AUS1'1-tBCTS OF CHEM ICAL PAPEHS separates from alcohol in minute yellow crystals which do not melt at 260' and are soluble in alcohol benzene or ethyl acetate and to a slight ext'ent in ether. The acetyl derivative C,lH,70,N,C1,Ac which is very readily soluble in ethyl acetate and to a less extent in alcohol or benzene begins to turn brown at about 140" and melts without decomposing at 180-1 9 7".The benzoy? derivative C,lH,,O,N,C1,Bz separates from ether in crystals which turn brown a t about 150" blacken a t 220° and do not melt a t 260"; it dissolves slightly in alcohol and readily in ethyl acetate benzene or acetic acid. Another benxoyl derivative (with H,O) was also prepared which separates from alcohol in pale yellow crystals softening a t 130' and melting and decomposing at 150-155"; it is soluble in ether alcohol acetic acid and ethyl acetate. The action of excess of acetyl chloride on tetrachloro- strychnine in pyridine solution yields diucetyZtrichZorostryc?~nine C,~H,,O,N,Cl,Ac which separates from ether or alcohol in white acicular crystals melting and decomposing a t 185' and dissolving in ethyl acetate or acetic acid.is deposited from alcohol in microscopic crystals which turn brown at about 1'70" do not melt a t 260° and dissolve readily in acetic acid or ethyl acetate and to a slight extent in ether or benzene. ~etracr7~lorodinitrostr?lchizine (321 HI ,O,N,C1 (NO,) 2 T. H. P. Action of Chlorine on Brucine in Glacial Acetic Acid Solution. GAETANO MINUNNI and R. CIUSA (Gaxxetta 1904 34 ii 361-363).-By passing chlorine into a solution of brucine hydrate in glacial acetic acid hexachlorobrucine hydrochloride C,3H,o0,N2C1,,HC1 is obtained as a white crystalline powder turning red in the light and dissolving in alcohol ethyl acetate ammonia or potassium hydroxide solution or in concentrated sulphuric acid with evolution of hydrogen chloride. The buse is a white powder which is turned yellow by light and is soluble in ether benzene alcohol ethyl acetate or chloroform.Both the base and its hydrochloride turn brown at about 120" blacken a t about 20@' and are still unmelted at 260'. They are not attacked by concentrated nitric acid. The hydrochlorides of tetrachlorostrychnine and hexachlorobrucine are non-poisonous and quite innocuous to dogs. By G. CORONEDI. T. H. P. 8-Aminoparaxanfhine and its Derivatives. C. F. BOEHRINGER (PT SOHNE (D.R.-P. 156901. Compare following abstract).-8-Chloro- paraxanthine reacts with ammonia a t 150-155' in alcoholic solution to form %aminoparaxanthine C7H70,N,-NH which blackens at 350' without melting. The sodium salt forms colourless needles. 8-Methyl- c6minoparaxanthine sinters at 350' and melts and decomposes at 3'70'.8-0imethyZamino~arc~x~ntr7Lz'ne forms long needles and melts at 225' ; the crystalline sodium salt dissolves readily in water. 8-Anilino- paraxanthine melts and decomposes a t about 340'. C. H. D. 8-Aminotheophylline and its Alkyl and Aryl Derivatives. C. P. BOEHRINGER & SOHNE (D.R.-P. i56900).-8-ChlorotheophyllineORGANIC CHEMISTRY. 231 reacts with ammonia or amines on heating in alcoholic solution a t 150" although less readily than 8-chlorocaffeine. 8- AmirLot?~eo;l,~yZZine E t & F e l B T E > C * B H forms needles and becomes brown at 310" slowly melting and decomposing. 8-Anil- i?aotl~eopI~$Zisze crystallises from alcohol in colourless needles and melts a t 320O. 8-Dinaeth~lnirzino€~eo~)~~y~Z~ne forms long needles and melts a t about 330" t o a colourless liquid.All these derivatives form salts with both acids and hases. L. A. TSCHUGAEFF and N. A. SCHLOESTNGER (J. Izuss. Phys. Chem Soc. 1904 36 1 258-1 268).-A close connection exists between haemoglobin and chlorophyll since both contain a pyrrole nucleus and both are capable of yielding haemopyrrole under certain conditions. From the work of Kuster (Abstr. 1900 i 68 ; 1901 i 58 and 298; 1902 i 845) it seems probable that haemopyrrole is 3-methyl-4-propylpyrrole. I n an attempt to synthesise the latter compound the author has prepared the follow ing pyrrole derivatives. 2-Methyl-5-isopropylpyrrole (see Tiemann and Semmler dbstr. 1897 i 247) resembles hzmopyrrole in yielding a mercury compound (C,H1,N),Hg,4HgC12 but differs from it in its other reactions.The interaction of ethyl sodiopropylmalonate and ethyl a-bromo- propionate yields the ester C0,Et*CHMe*CPr(C02Et)2 which boils at 276-282" and is a viscous liquid with the characteristic odour of polycarboxylic esters. Hydrolysis of this ester by means of sodium hydroxide yields a-methyl-P-prop?llsuccinic acid C02H*CH Me* CH Pr CO,H which crystallises from water in long needles melting a t 156-151" and is readily soluble in alcohol ether and most other organic solvents ; when gently heated it sublimes. The silver salt of this acid C,H,,(CO,Ag) forms a heavy curdy precipitate and the ammonium salt a micro-crystalline precipitate soluble in water ; the sodium potassiunz uranium lead copper and iron salts were prepared.On heating the ammonium salt for some time at its melting point and sub- sequently distilling under diminished pressure i t yields the cor- responding in&& NH<Eg:xE which boils at 167-168' under 20 mm. pressure and sets to a crystalline mass melting a t 51-53O. The transformation of this imide into 3-methyl-4-propylpyrrole is attended with difficulty the reaction being possibly brought about to some slight extent by heating the imide with phosphorus trisulphide or pentasulphide. T. H. P. Ethyl 1-Gamphyl-2 5-dimethylpyrrole-3 4-dicarboxylate and its Derivatives. CARL BULOW (Ber. 1905 38 189-193. Compare Knorr and Bulow Abstr. 1884 138l).-Ethyl diacetylsuccinat e readily condenses with an acetic acid solution of camphylamine y i el din g e@d 1 - cccviphyl- 2 ; 5 -dime t A plpywole- 3 4 - dicccr bowy la te C.H. D. Attempt to Synthesise Hemopyrrole. r 2232 ABSTRACTS OF CHEMICAL PAPERS. which crystallises in large glistening plates melting at 78". It dissolves in most organic solvents is odourless and tasteless and on hydrolysis with aqueous alcoholic potash yields the potassizrm salt from which the acid may be obtained by addition of acetic acid. The acid melts and decomposes a t 2 0 4 O and on titration with standard potassium hydroxide in presence of phenolphthalein behaves as a monobasic acid. It dissolves readily in alcohol or acetic acid but is reprecipitated on the addition of water and is only sparingly soluble in benzene. The ammonium salt crystallises in colourless slender needles is readily soluble in hob water and its solution yields pre- cipit,ates with solutions of calcic ferric or cupric chlorides and with silver nitrate.When heated at 204-2210' the acid is decomposed yielding l-cum- phyl-2 5-dirnethylpyrrole in the form of a viscid yellow oil which dis- solves readily in most solvents. I t s alcoholic solution when warmed with ferric chloride solution is turned an intense orange-yellow colour and a pine shaving dipped in the solution gives a violet-red coloration with concentrated hydrochloric acid. J. J. S. 4-Methylpyridine. FELIX l3. AHRENS (Ber. 1905 38 155-159). -The high boiling fraction of commercial '' P-picoline " was added to the calculated amount of 30 per cent. alcoholic hydrochloric acid when 2 6-dimethylpyridine hydrochloride separated whilst from the filtrate the double salt of mercuric chloride and 4-methylpyridine was pre- pared.3-Methylpyridine is as chemically active as the corresponding 1 -compound. 4 4'-Dinaetl~yZdiz)~l.idyl prepared by the action of sodium on 4-methylpyridin0 was identified by conversion into its various salts. The aurichloi*ide does not melt sharply ; the platinicldoride begins to decompose a t 250'; the mercuric?doride melts a t lS5' whilst the picrute melts and decomposes a t 194". 4-AlZyZpyidine mercukldoride prepared from the product obtained by interaction of 4-methylpyridine and paraldehyde crystallises in needles and melts a t 150'. The hydrochloride forms transparent crys- tals and melts and decomposes a t 247". The base is a colourless liquid and boils at 200-202'; its platinichloride melts and decom- poses a t 206'; its nurichloride melts and decomposes at 174O whilst its picrate melts and decomposes a t 169-1 70".4-Allylpyridine W A S reduced by sodium ethoxide the reduction pro- duct converted into its nitroso-derivative from which 4-coniine hydro- chloride was prepared. 4-Coniine is a colourless liquid and boils at 178-1 80'. Its platinichloride and hydrochloride were analysed. A. McK. 4-Stilbazole. CONRAD FRIEDL~NDER (Ber. 1905 38 159-160. Compare preceding abstract).-4-XtiZbazole prepared by the condensa- tion of 4-methylpyridine and benzaldehyde separates from alcohol in glistening leaflets and melts at 127'. Its hydrochloride forms yellowish-green needles and melts at 204' ; the hydrobromide forms brownish-red needles and melts at 174' ; the picrate melts a t 213' ; the Iqdrogen taytmte melts at 164-165" ; the zirzcochloride formsORGANIC CHEMISTRY.233 yellow needles which soften at about 230' and melt a t 250"; the auri- chloride forms red needles and melts at 205" ; the platinichloiide melts at 310' ; the bromine udditive compozcnd C,,H,,NBr2 melts indefinitely a t 228-230'. A. BIcK. 4-Pyrophthalone. ERICH DURING (Bey. 1905 38 161-1 64. Compare preceding abstracts ; Eibner Abstr. 1901 i 348 61 1 ; Huber Abstr. 1903 i 576).-4-Pyropl~thulone prepared by the condensatio; Gf 4-methylpyridine and phthalic anhy- dride by zinc chloride separates from a mixture of ethyl alcohol and glacial acetic acid in glistening orange-coloured needles which begin to decompose at 250'.The hydrochloride forms red needles; the mercuric chloride double sult forms orange-red needles which decompose a t about 271'; the platinicldoride begins to decompose a t 260'. The sodium salt is crimson. Xtilbaxyl alcol~ol OH*CH2*C6H,-CH:CH*C5NH4 prepared by the reduction of 4-pyrophthalone in glacial acetic acid solution by zinc dust forms the ?qdroclzloride which is bright yellow and begins to decompose a t 210' ; the hydrobromide decomposes a t 230' ; the nitrate melts a t 160-1 65' ; the aurichloride decomposes a t 165-1 67' ; the plutinichloride melts and decomposes at 185'. Tetrachloro-4-p yrophthnlone CO<O>C UH*C,NH prepared from 4-methylpyridine and tetrachlorophthalic anhydride forms a dark green powder. A. McK. C6C4 Reduction Products of 4'-Methyl-4-stilbazole.4 - ~ T r i c h l o r o - hydroxg propylpyridine. ERICH DURING (Rer. 1905 38 164-1 67. Compare preceding abstracts).-4'-MethyZ-4-stilbtcxoZe C,H,Me~CH:CH*C,N€I prepared by the condensation of 4-methyl- pyridine with y- tolualdehyde separates from alcohol in white crystals which soften at 80' and melt a t 101-102°. Its hydro- chloride melts a t 120"; its hydrobromide melts a t 176-177' ; its mewurichloride softens at 195' and begins to melt a t 208'; its nurichloride melts and decomposes at 191' ; its platinic?doride melts and decomposes a t 193'. When reduced by hydriodic acid and red phosphorus 4'-methyl-4-stil- bazole forms 4'-methyldihydro-4-stilba,zoZe C,H,BXe*CH,*CH,.C,NH a colourless liquid which boils a t 220' under 80 mm.pressure; the hydrochloride softens a t 135' and begins to melt a t 140'; the hydro- bromide melts at 149-150'; the hydqsiodide softens at 132' and melts a t 138'; the mercurichioride melts indefinitely a t 110'; the aurichloride melts a t 155' ; the pkutinichloride melts and decomposes at 194'. 4'-Melhyl-4-stilbccxoZine C,H,Me*CH,.CH,*C,NH, prepared by the reduction of 4'-methyl-4-stilbazole by sodium ethoxide is a colourless liquid which boils a t 215' ; its platinichloride melts and decomposes at 205'. CC1 CH (0 H ) CH C,NH 4-W- T?.ic?~loro-P-hydroxyps.opylpyri~ine,234 ABSTRACTS OF CHEMICAL PAPERS. prepared from 4-methylpyridine and chloral forms glistening plates and melts a t 160'; its pkatiiziciilaride inelts and decomposes a t 198'. A. MoK. Pyridine-2 3 4-tricarboxylic Acid.ALFRED KIRPAL (Monutsh. 1905 28 53-64).-The adydride of pyridine-2 3 4-tricarboxylic. acid is formed when the tricarboxylic acid is warmed with acetic anhydride a t 30--40° ; it melts a t 170' and when heated on the water-bath with acetic anhydride yields cinchomeronic anhydride which is also formed when the tricarboxvlic acid is boiled with acetic abhydride by the formula I -* The tricarboxylic anhydride"is therefore to be represented >0 and Meyer's anhydride chloride CH'CK - jE*CO N-C(CO,H\*C*CO \ A CH:CH--#*CO (Abstr. 1901 i 750) by I - >O. The 3-methyl ester N - C(COCl)*C*CO I H:CH-?CozH (compare Wegscheider Abstr. 1902 i 618) is N = C(C0,H) -C* C0,Me formed biwarmingithe anhydride with methyl alcohol ; it crystallises in glistening plates melts a t 170° and when heated with methyl- alcoholic hydrogen chloride yields the trimethyl ester which melts a t 102' (m.p. 97" Meyer loc. cit.). The action of aqueous ammonia on the 3-methyl ester leads to the formation of the ammonium salt of the monamic acid NH,*CO*C,NH,( CO,NH,) which crystallises in colourless flat needles loses 1H20 a t loo' and melts and decomposes a t 1 5 0 O . The ccnzic acid C8H605N2 crystallises in colour- less prisms melts at lSO' and when heated above its melting point yields cinchomeronimine. The dimethyl ester melts at 183' (Rint Abstr. 1897 i 485 gives m. p. 166") and yields traces of the trimethyl ester on prolonged boiling with methyl-alcoholic hydro- chloric acid in agreement with the constitution \ Y / Contrary to expectation the diethyl ester of pyridine-2 3 4-tricarb- oxylic acid yields diethyl cinchonieronate when heated a t 150-160' or with alcoholic hydrochloric acid under pressure which points to the constitution N < ~ ~ ~ ~ ~ ~ 2 ~ ] > C * C 0 E t .When warmed in a reflux apparatus with methyl iodide and aqueous sodium carbonate pyridine-2 3 4-tricarboxylic acid yields the betaine ~ H/C( C O P ) .c >c*co2H I (?) co \C:H=NMe--O which crystallises in small colourless prisms becomes brown a t 1 SO" melts and decomposes a t 220° and when boiled with water yields ayophyllenic acid. 0. Y. Action of Ally1 Iodide on Tetrahydroquinoline. EDGAR WEDEKIND (Bey. 1905 38 436-440).-The compound described by Wedekind and Oechelen (Abstr. 1903 i 116) as l-allyltetrahydro- quinoline hydriodide does not contain allyl and is really tetrahydro- yuinoline hydriodide being formed by the following reaction C9H10N.C3H5 + C2H5T = C9Hl,:N~i,I + C,Hti + C,H2,ORGANIC CHEMISTRY.235 the allyl group being expelled from the tertiary base l)y the action of ethyl iodide. The reaction between allyl iodide and tetrahydro- quinoline proceeds differently in the presence or absence of alcohol ; in the first case addition taking place to form 1-allyltetrahydro- quinoline hydriodide ancl in the second hydrogen iodide being formed which combines with unaltered tetrahydroquinoline to form the hydriodide allyltetrahydroquinoline remaining as the free base. A repetition of the reaction between ethylene iodide and ethyl tetrahydroisoquinolino-%acetate (Wedekind Abstr. 1904 i 96) has shown that the principal product is the hydriodide of the ester C28H3804N2T melting a t 153-154'.It was not found possible to obtain again the iodide melting at 16s-169". C. H. D. 7-Aminoquinaldine [7-Amino-2-methylquinoline]. E. ALBER (J. pr. Chern. 1905 [iil 71 39-54. Compare Doebner and Miller Abstr. 1884 1373 ; Gerdeisen Abstr. 1889 520).-The action of nitric acid of sp. gr. 1.49 on benzylacetone at -18' leads to the formation of a mixture of p - and o-nitrobenzylacetones. p-ilritro- benzylmetone N0,*C,H4*CH,*CH2*C01SIe crystallises in long white needles melts a t 42" boils a t 204" under 13 mm. pressure and is identical with Wortsmann's product (Inaug. Diss. Basel 1903) obtained by hydrolysis of ethyl p-ni t robenzylacetonedicarboxylate.The phenyZhyclra.xone of p-nitrobenzylacetone forms yellow crystals melts a t 1 0 3 O and decomposes on exposure to light more slowly in the dark. op-Dinityobenxylacetone is formed by the action of nitric acid of sp. gr. 1.52 on the mononitro-compounds in concentrated sulphuric acid or on benzylacetone in fuming sulphuric acid a t - 18". It crystallises in small colourless rhombic leaflets in long p.risms or in large plates melts at 58-59' and when warmed m t h aqueous potassium hydroxide forms a dark red solution. A reduction of the dinitro-compound with stannous chloride and concentrated hydrochloric acid leads to the formation of '7-amino- 2-methpZquinoZine which crystallises in long slender colourless needles melts a t 14S0 is easily volatile in a cnrrent of steam forms 3 violet-blue fluorescent solution in ether which shows a green fluor- escence when poured into water and when diazotised and '' coupled " with P-naphthol in alkaline solution forms a dark red dye.The hycho- chZoride crystallises in microscopic yellow needles and dissolves in water to a solution with intensely green fluorescence ; the tin dou6Ze salt crystallises in leaflets and dyes tannated cotton-wool yellow ; these salts give the pine-wood pyrrole reaction. The 6enzoyZ deriva- tive C,7Hl,0N,,H,0 crystallises in small white needles loses H20 a t loo" melts a t 172-173' and forms a fluorescent blue solution in dilute hydrochloric acid. The ncetyl derivative Cl2Hl3ON2 crystal- lises in long yellow needles melts a t 192" is easily soluble in alcohol but only slightly so in benzene or petroleum dissolves in dilute acids t o blue fluorescent solutions and gives the pine-mood reaction.The picrate C1,HloN,,C,H,O7N crystallises in long yellow needles ancl melts a t 2 13-2 14'. The properties described show the author's 7-amino-4-meth~l-236 ABSTRACTS OF CHEMICAL PAPERS. quinoline t o be isomeric and not identical with Doebner and Miller's base (Zoc. cit.) obtained by reduction of 7-nitro-2-methylquinoline. G. Y. a-Naphthoyltetrahydroquinoline. JULIUS VON RRAUN (Ber. 1905 38 1'79-181 ).-a-Naphthoyl chloride prepared by the action of phosphorus pentachloride on a-naphthoic acid is a transparent liquid and boils at 1'72-173' under 15 mm. pressure. l-a-iVaphtho?/Z- tetraJz,ydroqzciwoZine C H < ~ ~ * c 1 ~ ~ ~ > C H 2 prepared by shaking a- naph thoyl chloride with an alkili hydrogide and tetrahydroquinoline forms colourless crystals and melts at 115'.When the amide is gradually heated a t 160" with phosphorus pentachloride the acid chloride C,,H7 CC1 N C,H,* C3H6Cl first formed is transformed into naphtlLoyZ-o-y-c?doropropyZanilide C,,H7* CO*NH* C,H,* C,H,CI which forms red crystals and melts a t 133'. Constitution of a-Naphthindole. ROBERT PSCHORR and E. KUHTZ (Ber. 1905 38 217-219).-a-Nnphthindole is easily prepared in a manner analogous to Hinsberg's preparation of P-naphthindole (Abstr. 1888,372) by distillation of a-naphthoxindole with zinc dust and is iden- tical with Schlieper's naphthindole (Abstr. 1887 153 963). To settle whether the nitrogen ring is attached to the naphthalene ring a t tohe 1 2 or 1 8 position an attempt was made to condense l-amino-2-ethoxy- naphthalene and 1-aminonaphthalene-8-sulphonic acid (in which the 2 and 8 positions respectively are already occupied) with glyoxal sodium' bisulphite by Hinsberg's method.Only in the latter compound sub- stituted in the 8 position was a naphthindole derivative a-rzapl~th- indoZedisulp?Lonic acid obtained which on heating with zinc dust was converted into naDhthindole this therefore has the constitution A. McK. E. F. A. 2 2-Dinaphtha - 1 1 - imine [aa - Di - p - naphthacarbazole]. VICTOR VESELY (Ber. 1905 38 136-139. Compare Nietzki and Goll Abstr. 1886 245 ; Meissenheimer and Witte Abstr. 1904 i 1 9 3). -2-Cldoro- 1 -nitroiecc;ul~tJ~alene CloHG02NCl prepared from 1-nitro-P-naphthylamine byVot6cek and ZeniSek's method (Abstr.1900 i 19) crystallises in yellow needles melts at 95.5" distils without de- composition above 360° and is reduced by zinc dust in glacial acetic acid solution to 2-chloro-a-naphthylamine (Cleve Abstr. 1887 961). 2-Bromo-l-nitronaphthnlene obtained in the same manner crystallises in slender yellow needles melts at 102-103° and distils without de- composition above 360'. When boiled with copper powder in nitrobenzene solution 2-iodo-l- nitronaphthalene (Meldola Trans. 1885 47 521) yields 1 l-dinitro- 2 2-dinaphthyZ C20H1504N2 which crystallises in colourless scales commences to blacken at 265" melts a t 276' and is reduced by zinc dust in glacial acetic acid solution to 2 2-dinaphtha-1 1-imine,ORGANIC CHEMISTRY.237 This is identical with Nietzki and Goll’s dinaphthacarbazole (Zoc. cit.). The constitution of the two bases obtained- by these authors from 1 1-hydrazonaphthalene must be C,H4<CH=CH cH= C,>C,H4 C(NH,):?-F]:C(NH,) for naphthidine. G. Y. Syntheses in the Anthracene Series and New Dyes. OSCAR BALLY (Bey. 1905 38 194-196).-When P-aminoanthra- quinone is condensed with glycerol as in the ordinary Skraup’s syn- thesis the product is not Graebe’s anthraquinolinequinone (Annalen 1880 201 349) but benxanthronequinoline C20Hl10N which crystal- lises from toluene in needles melting a t 251’. The same compound is also formed when anthraquinonequinoline is condensed with glycerol and is represented by the formula Anthranol or anthraqiiinone readily condenses with glycerol yield- Compounds of ing benxanthrone itself C17Hlo0 which melts at 170’.this type when fused with alkali yield dyes. J. 3 . S. Aelactones [Alkylideneoxazolones] and their Transforma- tions. EMIL ERLENMEYER jun. (Annulen 1904 337 265-271. Compare Abstr. 1902 i 595 ; this vol. i 13l).-Although a-amino- acids and their mono-alkyl derivatives readily yield dimolecular anhy- drides hippuric acid is not capable of such a reaction but its alkyl- idene derivatives R*CH:C(NHBz)*CO,H on the other hand give internal anhydrides. Since these anhydrides are converted by ammonia into amides R*CH:C(NHBz)*CO*NH which lose water and yield compounds possessing the characters of acid imides and having it seems likely that the the probable formula CHPh:C< anhydrides are formed from the tautomeric hippuric acids and consequently are represented by the formula N=CPh CO-hH ’ R*CH:C[NPh:C(OH)].CO.NH N=yPh (30.0 * CHPh:C< The name “ azlactone ” [alkylideneoxazolone] is given to such anhy- drides of the general form R*CH:C< I a formula which N=CR co.0 accounts for their formation from a-acylamino-acids only and their yellow colour.The latter depends not only on the ring but also on the nature and position of the substituting groups. K. J. P. 0.238 ABSTRACTS OF CHEMICAL PAPERS. Aelactones [Alkylideneoxazolones] from Cinnamaldehyde or Cuminaldehyde and Hippuric Acid. Em ERLENmYER jun. and 0. MATTER (AnnuZen 1904 337 271-282. Compare preceding abstract).-On heating cinnamaldehyde hippuric acid and sodium acetate with acetic anhydride at looo the aslactone [2-phenyl-4-cin- is obtained as orange- rnccmyZideneoxc~soZone] CHPh CH* CH C< yellow needles melting a t 1 5 2 O which can only be purified by conver- sion into cinnamylidenehippuric acid CHPh C'H*CH C( NHBz) -CO,H by warming with aqueous sodium hydroxide ; it crystallises in yellow needles melting and decomposing at 238O and is reconverted into the azlactone by heating with acetic anhydride. After prolonged heating with hydrochloric acid under pressure at 120° the acid is decomposed into carbon dioxide benzoic acid naphthalene and a-naphthoic acid.The intermediate unsaturated ketonic acid CHPh:CH*CH,-CO*CO,H could not be isolated. The ethyl ester of cinnamylidenehippuric acid prepared by dissolving the acid in alcoholic sodium hydroxide crystal- lises in colourless needles melting a t 132".Cuminaldehyde and hippuric acid yield the axlactone C2yhenyl- which crystallises 4-cumylideneoxccsolorze] CGH4PraaCH:C< in yellow needles melting a t 12 1'. C,H,Prp* CH C (NHBz) - CO,H is obtained as colourless needles melting at 201' by dissolving the azlactone in sodium hydroxide ; the methyl ester forms crystals melting at 128' and the ethyl ester colourless needles melting at 164'. The amide prepared by treating the azlactone with ammonia crystallises in colourless needles melting a t 170'. When warmed with sodium N=yPh co.0 N=yPh coo0 Cuinylidenehippwic ucid " N=yPh coo0 which crys- hydroxide it yields the intide C6H4Pr@*CH:C< tallises in yellow needles melting at 245'.If the azlactone is boiled for 3 to 4 hours with sodium hydroxide (3 mols.) the sodium salt of p-isopropylphenyZpyruvic mid CGH,Pr~*~H2*CO*C0,H is obtained ; the free ucid crystallises in leaflets melting a t 78" decomposes in the air,:and gives a green coloration with ferric chloride. The keto-acid condenses with benzaldehvde in the Dresence of concentrated hydro- chloric acid yielding the oxylactoize C,H,Pr~*CH<CHPh*~' which c0-CO' crystallises in colourless leaflets melting at 2 1 2 O and giving a green coloration with ferric chloride. Azlactones [Alkylideneoxazolones] from Furfuraldehyde or Salicylaldehyde and Hippuric Acid. EMIL ERLENMEYER jun. and WERNER STADLIN (Annulen 1904 33'7 283-293. Compare preceding :abstracts).-Furfuraldehyde and hippuric acid yield the axluctone [ 2 -phen y Z- 4~urficrylideneoxc~sol~ne~~ C40H,* CH C< which crystallises in golden-yellow needles melting at 171" ; by warm- ing with dilute sodium hydroxide it is converted into furfurylidene- K.J. P. 0. N=yPh (20.0 'ORGANIC CHEMISTRY. 239 hippuric C L C ~ ~ C1,0H3*~H:~(NIII;z)*C0,H ; the latter. crystallises in leaflets melting a t 210". The methyl ester is foriued when the azlactone is warmed with a methyl-alcoholic solution of potassium hydroxide and crystallises in leaflets melting a t 141° and the ethyl ester in colonrless needles melting at 132-133". The amide is pre- pared by the action of ammonia on the azlactone and forms pale N=y P h CO-NH ' yellow needles melting a t 184".prepared by warming the amide with sodium hydroxide solution is an intensely yellow insoluble substance decomposing at 34 lo. The piperidide C,OH CH C( N HBz) *GO. C,NH, is obtained by warming the azlactone with alcoholic piperidine solution as colourless needles melting a t 162-163'. The interaction of salicylaldehyde and hippuric acid has been previously studied by Plochl Wolfrum and Kebuffat (Be?.. 1885 18 11 83) who isolated two substances one a yellow substance C,2H2r0,N2 or Cl6HI3O4N which is now shown to be the axlccctoiie [%phe?z?/Z- 4-o-ucetoxy beizx~Zicle?zeoxuxolonel The imide C,OH,*CH:C< the other substance is the colourless be?zxo~il~~minocopi~,zccriiz which was thought to be benzoyliminocoumarin. These two substances are formed from the normal primary product benxoykc~minocoumaric acid OH.C6H,*CH:C(NHBz)*C~~H which then loses water in two different ways possibly from the two stereoisomeric forms.The substance which is formed from the coumarone by the action of sodium hydroxide is not salicylglycidic acid but o-hydroxy~hen?llp~rzcvic acid which immediately condenses to oxycoumarin C,I'I,<. The azlactone is prepared by heating hippuric acid salicylaldehyde and sodium acetate with acetic anhydride on the water-bath and is contained in the first alcoholic extracts of the product whilst the benzoylnminocoumarin is found in the last extiaacts; it crystallises in palo yellow leaflets melting a t 137-138" and is con- verted by heating with 10 per cent. sodium hydroxide into benzoyl- arninocoumarin and benzoylaminocoumaric acid OH.CGH,*CH:C(NHBz)~C102H ; the latter forms colourless crystals iiielting a t 185'.Benzoylaruino- coumarin crystallises in needles melting a t 172?-173' and is insoluble in sodium carbonate solution. When either the adactone or benzoyl- aminocoumarin is boiled with sodium hydroxide the oxycoumarin is obtained as needles melting a t 152" which give a green coloration with ferric chloride. It yields a pTLenyZhydraxone C15H1203Nd which crystallises in yellow plates melting a t 173-174" and also condenses with o-phenylenediamine giving the conzpozcnd C15HlnON2 which crystallises in colourless needles melting at 230'. Ylie azlac toile could not be converted into an ester. 0-70 CH,*CO240 ABSTRACTS OF CHEMICAL PAPERS. Attempts to obtain isomerides of tyrosine from benz oylamino- coumaric acid were not successful. K.J. P. 0. Azlactonea [Alkylideneoxazolones] formed in the Con- densation of .m-Hydroxybenzaldehyde or Anisaldehyde with Hippuric Acid. EMIL ERLENMEYER jun. and FRITZ WITTENBERG (Aiznalen 190.1 33'7 294-301. Compare preceding abstracts).- The acetylaxlactone [2-pJ~en~l-4-m-oceto.r,ybenzylideneoxazolone] OAC*C~H,*CH:C<~~. N z C P h t is prepared from m-hydroxybenzaldehyde and hippuric acid and forms crystals melting at 145"; when treated with sodium hydroxide the m-hyc2roxy6enxylidenel~i~puric mid 0 H* C,H;C H C( NH Bz)*CO H is obtained as crystals melting at 204'; the etlbyl ester crystallises in needles melting at 118' ; the pipes.idl.de which is prepared by heating the azlactone with alcoholic piperidine crystallises in colourless needles melting at 201'.The corresponding p-methoxy-compound OMe*CGH,*CH:C<CO.d N-CPh is prepared from anisaldehyde and hippuric acid and crystallises in yellow needles melting at 156.5' ; when warmed with sodium hydroxide p-methoxybenxyliclenehi~puric acid ONe*C,H,*CH:C(NHBz)*CO,H is formed as colourless needles melting and decomposing at 225'; the methyl ester prepared from the azlactone and methyl alcoholic sodiim hydroxide forms colourless leaflets melting at 153' and the anzide prepared from the azlactone and ammonia colourless crystals - - Nr?Ph prepared CO NH The ifizide OXe*C,H,*CH C< melting at 1 €4'7'. from the amide by the action of sodium hydroxide crystallises in yellow needles melting at 283". Onle*C,H,*CH:C(NHBz)*CO*C,~H,o prepared from the azlactone and alcoholic piperidine crystallises in colourless leaflets melting at 173'.p-MethoxgplAenylpyruvic acid OMe*C6H;CH,*CO*C0,H is obtained by boiling the azlactone for several hours with a slight excess of 10 per cent. sodium hydroxide and crystallises in prisms melting at 186"; it gives a green coloration with ferric chloride and decomposes on keeping. Its phefiylhydraxoize C,,H,,O,N crystallises in colourless leaflets melting at 154'. I n the presence of concentrated hydrochloric acid the keto-acid condenses with benzaldehyde forming the a-oxylnctone The piperidide which crystallises in prisms with 1 mol. of alcohol melting at 180'. K. J. P. 0. Condensation of Pyruvic Acid with Hippuric Acid. EMIL ERLENMEYER jun.and E. ARBENZ (Awmalen 1904 337 302-306. Compare preceding abstracts).-The condensation of pyruvic acid with hippuric acid was first investigated by Hoffmann (Ber. 1886 19,ORGANIC CHEMISTRY. 241 2555) who obtained a compound which is now shown to be the ; it forms colourless crystals carboxylic acid CO,H*CMe:C< N=yPh co.0 melting at 157". By a1 kali hydroxides the acid CO,H-CMe C( NHBz) CO,H is probably formed but on setting it free from its salts is immediately reconverted into the azktctone. When the azlactone is boiled with barium carbonate the barium salt' C,,H,O,NBa,2HO is formed. When treated with dilute sulphuric acid the azlnctone undergoes the characteristic decomposition ammonia benzoic acid and methyl- oxalacetic acid being produced ; the latter hawever decomposes into carbon dioxide and methylpyruvic acid which was identified by means of a characteristic barium salt and its phenylhydrazone and in addition by its conversion into scatolecarboxylic acid and scatole.K. J. P. 0. Methylstion of Dibenzenesulphonebenzidine. OSCAR HINS- BERG (Bey. 1905 38 554. Compare Abstr. 1893 i 168 ; Willstatter and Kalb Abstr. 1904 i 1050).-Dibenzenesulphonedimethylbenz- idine prepared by heating dibenzenesulphonebenzidine with methyl iodide methyl alcohol and aqueous sodium hydroxide under pressure at looo melts at 189-190". When the reaction takes place in an open vessel the methylation is not complete; the melting point 179-180" previously observed was that of a mixture so obtained. G . Y. Action of Secondary Aromatic Axnines on Dinitro- phenylpyridinium Chloride.THEODOR ZINCKE and W. WURKER (Anncden 1905 338 107-141).-1t has been shown that primary aromatic bases such as aniline interact with dinitropyridinium chloride yielding besides dinitroaniline a red salt of a univalent base for which either the formula NPh:CH*CH:CH*CH:CH*NHPh or was suggested. Konig imagines that the substance is desmotropic and can be represented by either formula. Similar compounds have now been obtained by the action of methylaniline on the pyridinium chloride which is decomposed by alkali hydroxides giving the aldehyde NMePh*CH:CH*CH:CH*CHO and methylaniline. The original salt must therefore have the formula NMePh*CH:CH*CH:CH*CH:NMePhCI. The methylaniline group can easily he replaced by an oxime or hydr- azone group or by aniline or p-chloroaniline.These reactions are all in favour of the open chain formula. Dinitrophenylpyridinium chloride is heated in alcoholic solution with methylaniline and the product poured into dilute hydrochloric acid ; the compound NMePh * CH CH-CH CH* CH:NMePhCl crystallises with 1hH,O from water and with HCI and 3MeOH from methyl- alcoholic hydrochloric acid and melts and decomposes a t 1 16-1 18' ; it forms a colourless solution in concentrated sulphuric acid bnt yields a red sulphate I t s acetic acid solution gives a brownish-red242 ABSTRACTS OF CHEiMICAL PAPERS. precipitate with potassium dichromate and its alcoholic solution with potassium tri-iodide a periodide which crystallises in violet needles melting and decomposing a t 170-1 72".Methylpbromoaniline (which is a yellow oil boiling a t 136-13s" under 1 2 min. pressure) and the pyridinium salt react giving the coitzpouvd C,H,Br *NMe* C1H:CH-CH CH*CH:NClMe*C,H,Br which crystallises in red leaflets or needles sintering at 200" and melting and decomposing a t 205-208"; it dissolves without colour in con- centrated sulphuric acid ; on dilution the sulphate is precipitated as red flocks. The platinichloride (C,,H,,Rr,N~),PtCl i s a brick-red crystalline powder sintering at 1 70° melting and decomposing a t 187". When the methylaniline compouiid is boiled with 20 per cent. methyl- alcoholic sodium carbonate solution and the product acidified with acetic acid the compound NMePh*CH:CH*CH:CH*CHO is obtained as yellow needles melting and decomposing at 78-SOo; it is soluble in dilute acids but rapidly decomposed by them with the formation of methylaniline ; it reduces an ammoniacal silver solution.It yields an oxime and a phenylhydraxoize which are also formed directly from the original methylaniline compound. It reacts with primary and secondary arylamines and with ruethylaniline regenerates the original material. It forms double salts and a crystalline plntiizichloride (C,,H,,ON),PtCl which is a reddish-brown powder melting and decomposing at 157-160". The picrate forms pale brown needles melting and decomposing a t The aldehyde C,H,Br*Nl\le*CH:CH*CH:CH.CHO obtained in a similar manner to the compound just described crystallisesin yellow plates or flattened needles melting and decomposing at 11 6- 117" ; its salts are unstable and the platinichloride (C,,H,,ONBr),,PtCl is a pale brown unstable powder.The oximecrystallises in pale yellow needles melting and decomposing at 115-1 17" and is insoluble in alkali hydroxides but is dissolved and decomposed by acids ; its solution in concentrated sulphuric acid has a blood-red coloration. The phenylhydrazone crystallises in pale yellow leaflets readily decomposed by acids. The compound NMePh*CH:CH*CH:CH*CH:NHPhCl is prepared by treating the aldehyde with aniline and hydrochloric acid and crystallises in ruby-red needles melting and decomposing a t 159-161" ; the salt is converted into the base by alkalis. The compound NMePh* CH C H*CH CH* CH :NHCl* C,H,Cl is prepared from the aldehyde and p-chloroaniline and crystallises in red leaflets melting and decomposing a t 115-1 18' ; when boiled with hydrochloric acid it is converted into chloro~r~enyl23yridini~~ chloride.The free base C,,HI7N,Cl is very stable and crystallises in needles which are dark brown by reflected and pale yellow by transmitted light ; it melts and decomposes a t 127". The aldehyde C,,H1,ON when treated with methyl-p-bromoaniline and hydrochloric acid yields the salt NMePh*CH:CH*CH:CH*CH:NMeC1.C,H,Br which forms a dark red crystalline powder sintering and then melting and decomposing a t 144'. The compound C,H,Br.N~~e.CH:CH*CH:CH*CI~:NMePhCl is 142-144'.ORGANIC CHEMISTRY. 243 formed from the aldehyde C,,H,,ONBr and methylaniline and is a purplish-red crystalline powder melting and decomposing a t 11 1-1 12".Cinnamaldehyde and methylaniline yield an unstable compound CHPh:CH*CH:NMePhCl which forms a mercuricldoride crystallisiag in orange-red needles melting and decomposing a t 167-169" and a plcctinichloricle which forms yellow crystals. The methylaniline compound is decomposed by aniline and p-chloro- aniline both methylaniline groups being replaced by aniline groups. The oxinw N HPh*CH:CH*CH:CH.CH:NOH and the pl~e?a?/lh?/draxone NHPh*CH:UH*CH:CH*CH:N HPh of the diaiiilide which was pre- viously described have now been preparecl ; the former crystallises in yellow needles melting and decomposing a t 146" and the latter in yellow leaflets melting and decomposing a t 135". K. J. P. 0. Malachite-green and Crystal-violet. RUDOLF LAMBRECHT and HUGO WEIL (Bey.1905 38 270-2S2. Compare Abstr. 1904 i S 7 7 ). - Tetranzethyld ianainotriphen ylcccrbothiol SH*CPh (C,H,*NMe,) obtained by passing hydrogen sulphide into a cold alcoholic solution of malachite-green containing acetic acid crystallises from a mixture of benzene and alcohol as a colourless powder and melts a t 153'; the analogous cornpound SH*C(C,H4*NMe,) obtained from crystal-violet melts at 159". The same substances are obtained by using ammonium sulphide or sodium polysulphides instead of hydrogen sulphide. Tetrarnetlzylclictminothiobenxoplenone C,,H,,N,S is obtained from the mother liquors of the carbothiol of crystal-violet and crystallises from alcohol in steel-blue needles melting at 202". The carbothiols are not decomposed when heated with benzene and sodium hydroxide or metallic sodium but are reduced on boiling with alcohol through which hydrogen sulphide is passed to form leuco-malachite-green and leuco- crystal-violet.When the carbothiol of malachite-green is heated with dilute acetic acid it is rapidly decomposed giving hydrogen sulphide and a solution of the quinonoid salt of the malachite-green base; on the other hand an excess of dilute mineral acids under similar conditions only slowly eliminates hydrogen sulphide from the carbothiols although the theoretical quantity of a dilute mineral acid brings about the loss of hydrogen sulphide a t 50". The nature of the following salts illustrates the gradual production of colour from triphenylcarbinol bases. Colou.rless Salts.-The stannichloride of tetranzet?~?/Zdi~na.inotr~~~e?ayl- carbothiol C,,H2GN,S,2HC1,SnCI,BH,0 is obtained by dissolving the carbothiol in ice-cold hydrochlorlc acid and adding stannic chloride.The analogous derivcctive C,,H,,N,S,3 HC1,l +SnCI,,l &H,O of crystal- violet is also colourless. Orange-coloured Sci1ts.-The salt NMe,CKC,H,:CPh- C,H,*NMe,,HCl,SnCl 2$H,O is obtained in orange-red crystals by warming tetramethyldiarnino- triphenylcarbinol with 30 per cent. hydrochloric acid and then adding stannic chloride. The analogous salt NMe,Cl C H,:C ( C,jH,-NMe2,HC1) 2SnCI4,2 H,O was obtained from the crystal-violet base.244 ABSTRACTS OF CHEMICAL PAPERS. Green Siclts.-Under special conditions the diacid salt NMe,Cl C,H, C( C,H,*NMe,) *C,H,*N Me2 HCl,ZnCl 3 H,O derived from the crystal-violet base can be obtained in bright green crystals ; it corresponds with the ordinary green salt NMe,Cl:C,H,:CPh*C,H,*NMe2 of the malachite-green base.W. A. D. Replacement of the Hydroxyl Group by the Hydraaine Group. HARTWIG FRANZEN (Ber. 1905 38 266-270).-Two new methods of preparing hydrazines are described. a- or P-Naphthyl.. hydrazine is formed on heating a- or /3-naphthol hydrazine sulphate and hydrazine hydrate together with a little alcohol in a sealed tube for S hours a t 100'. Hydrazine a- or /3-hydroxynaphthoate when heated a t 140-150' loses water and carbon dioxide forming a- or P-naphthylhydrazine. 2 3-Na~ht?~yZenedihydra~ine C,,H,(NH*NH,) prepared from 2 3-dioxynaphthalene by the former method crystallises in colourless minute needles melting and decomposing at 155-156' which reduce Fehling's and ammoniacal silver solutions on warming ; the hydro- chloride forms a snow-white crystalline mass without a sharp melting point.Benxy Zidene-2 3-naphth ylenedihydraxone C ,H,( NH*N CHPh) crystallises from benzene in yellow needles which melt and decompose at 2 0 5 O . 1 3 - D ibenxylideneamino-2-phen yl-2 3-naphthccdihydroglyoxaline C1oHG<N(N N(N:CHPh)>CHPh CHPh) prepared by the interaction of the hydrazine with excess of benzaldehyde crystallises from xylene in yellow needles melting and decomposing a t 227-22s'. E. E. A. Nitroso- and Azo-derivatives of SPyrazolones. A.UGUST MICHAELIS (Ber. 1905 38 154-155).-Substitution in all three pyrazolones is readily effected in the 4-position.Halogen derivatives are formed bv the action of chlorine or of bromine on solutions of .! 3-pyrazolones in glacial acetic acid or chloroform. NH-(?o prepared CMe:C*NO 4-Nitroso-l-p?~enyl-5-methyl-3-pyrccxolone NPh< by the action of sodium nitrite on a solution of 1-phenyl-&methyl- 3-pyrazolone in glacial acetic acid separates from ethyl acetats in green needles and melts indefinitely at 159'. formed by the action of NH-YO CMe:C*N :NPh' The mo-compound NPh< diazobenzene chloride on an alkaline solution of 1 -phenyl-5-methyl- 3-pyrazolone forms gold-coloured leaflets and melts at 99-100'. By the action of phosphorus oxychloride it is converted into the 3-chloro- pyraxole NPh< I A. McK. N=xx1 CMe:C*N:NPh' Amino-derivatives of Pyrimidine. SIEGMUND GABRIEL (Ber.1905 38 149. Compare Abstr. 1902 i 59 ; Traube,. this vol. i lOl).-As Traube states 2 4 5 6-tetraminopyrimidine to be only a di-acid base the author has repeated the preparation and analysis ofORGANIC CHEMISTRY. 245 the hydrochloride and confirms his former statement that the compo- sition is C,HsN,,3HCl. G. P. Thio-derivatives of Pyrimidine. FARBENFABRIKEN VORK FRIEDR. BAYER 6 Co. (D.K.-P. 156055).-Thiocarbamide and its monoalkyl derivatives react with the sodium or potassium derivative of ethyl cyanoacetate to form pyrimidine compounds of the formula NR<C Co-CH2>C:NH (a H) N which are readily converted into derivatives OF hypoxanthine. The compound from ethyl cyanoacetate and thio- carbamide forms colourless crystals and dissolves readily in hot water and in dilute acids or alkalis. The preparation of compounds from methylthiocarbamide and allythiocarbamide is also described.C. H. D. Reduction of a-Dibenzylideneacetonehydroxylamineoxime. GAETANO MINUNNI and R. CIUSA (Gaxxetta 1904 34 ii 373-376. Compare Minunni Abstr. 1900 i 237 ; Minunni and Cxrta-Satta Abstr. 1900 i 237).-Reduction of a-dibenzylideneacetonehydroxyl- amineoxime with sodium and amyl alcohol yields a base C17HlSN2 which is either a Dvrazoline derivative of the structure L . l CH,-FHPh CHPh CH* CH<NH-N ? or a hydrazoethane compound having the formula CHP h CH*CH<Egg2Ph)>NH. The Ii,ycZroc?i,lo~ide of the base is very hygroscopic; the plutini- chloride C,7H,,N,,H,PtCI forms a yellow crystalline powder readily soluble in water or alcohol.The benxoyl derivative CI7Hl7N2Bz crystallises from alcohol in white needles melting at 209-2 10'. T. H. P. Bensiminazoles and their Decomposition. OTTO FISCIIER (Ber. 1905 38 320-328. Compare Abstr. 1904 i 195)-[With 0. VEIEL.]-~ -Methylbenziminazole is best prepared by boiling methyl- o-phenylenediamine obtained by reducing o-nitromethylaniline with crystalline formic acid ; it crystallises from light petroleum in white prisms melts at 61° and gives a hydrochloride C,H,N,Cl crystallising from alcohol in needles ; the platinichloride C1,,H,,N,PtC1,,2H,0 forms reddish-yellow prisms and the picrate melts at 244'. 1 3 -Bibenxylbenximinaxole Iydyochloride C,,H,,N,Cl obtained by heating benziminazole with benzyl chloride for several hours a t loo' crystallises from alcohol ; the platirzichloricle melts a t 21 6" the uurichloride a t 155' and the picrate a t 208'.1 3-Dibenxyl- benxirninnxoZe-2-ol C,,H,,ON obtained by adding potassium hydroxide to a solution of the hydrochloride crystallises from light petroleum in colourless nodules melts a t 11 3-1 14* and when heated with con- centrated alcoholic potassium hydroxide is resolved into formic acid and s-dibenxyl-o-phenylenediarnine The latter separates from light petroleum in thick crystals melts a t 71" and gives a hydrochloride C,oH,,N,C1 melting a t 149' ; it combines with salicylaldehyde to VOL. LXXXVIII. i. s246 ABSTRACTS OF CHEMICAL PAPERS. form 2-o-hydroxypiienyl-1 3-dibenzylhyd~obenzinainccxoZe which crys- tallises from alcohol in white needles melts at 136O and is resolved by acids into its constituents. When s-dibenzyl-o-phenylenediamine is heated with acetic acid and a little acetic anhydride 1 3-dibenxyl- 2-methylbenximinaxoZe-2-01 c! H <N(C7HT)>CMe*OH is obtained crystallising from alcohol in white needles and melting at 1 5 3 O ; the plntinichloride C4,H,,N,PtC1 forms yellow leaflets.On oxidation with ferric chloride in alcoholic solution the diamine is converted into ~-tetrccbenxyldiami.nophenu;xoniu~~a chloride C40H,6N,Cl,,BH20. [With J. G. Mouso~.]-~-~romobenx~m~naxoZe C7H5N2Br prepared by heating 4-bromo-1 2-diaminobenzene with formic acid crystallises from yater in colourless needles melts at 137O and gives a crystalline plutinichloride and nurichloride ; when heated with an excess of methyl iodide it is converted into 5- bronao-1 3-dimethylbenximinccxolium iodide C,H,,N,BrI which is easily decomposed by cold aqueous sodium hydroxide giving 5-brOmO- 1 3-dimethylbenxinairzcczoZe-2-oZ C,H,,ON,Br ; the latter crystallises from light petroleum in white needles melts a t 103O and is hydrolysed by boiling aqueous sodium hydroxide to 4-bromo-o-phenyZsnedimetliyldiunaine ; this crystallises from dilute alcohol in needles and melts a t 78'. 5-&omo- 1 2 3-trimethylbenximinuxoZi~~ iodide obtained by heat- ing 5-bromo-2-methylbenziminazole mi th methyl iodide crystallises from dilute alcohol in thick yellow prisms and is with difficulty transformed by hot aqueous potassium hydroxide into 5-bromo- 1 2 3-tr~met~~y~benx~rnincc~ole-2-0~ C,H,Br<NMe>CMe*OH NMe which forms white needles and melts at 173'.5-Chloro-l 2 3-trimethylbenximirzccxolium iodide C,,H,,N,ClI pre- pared by the action of methyl iodide on 5-chloro-2-methylbenzimin- azole is however converted into the corresponding carbinol by gently warming it with aqueous sodium hydroxide; the product crystallises from alcohol in colourless prisms and melts a t 152-153'. W. A. D. W,H7) C,oH,,ON,C4 Synthesis of Derivatives of Ketoquinazoline. BRONISLAW VON PAWLEWSKI (Ber. 1905 38 130-131).-4-Keto-2-tl~ion-3-phenyl- 1 2 3 4-tetrahydrop.ui?aaxol~ne C 6 H 4 < i g g i h is formed when a molecular mixture of anthranilic acid and phenylthiocarbamide is heated at 160-166O. It crystallises from alcohol in small irregular nacreous leaflets. melts a t 304-306'. and when treated with alkaline hydrogen peroxide solution is converted into 2 4-diketo-3-phenyl- Co-yPh which is formed NH CO 1 2 3 ; 4-tetrahydropuinaxoline C,H,< also when a molecular mixture of anthranilic acid and phenylcarbamide is heated a t 160-180" and finally a t 200".It crystallises in long colourless flat prisms and needles from glacial acetic acid in largeORGANIC CHEMISTRY. 247 leaflets melts at 215-277" and dissolves in aqueous alkalis to solutions which after dilution with water have a violet fluorescence. G Y. Quinoxaline and Benziminazole Compounds from 4-Nitro- 2-aminodiphenylamine. ARNOLD REISSERT and G. GOLL (Ber. 1905 38 90-104).-4-Nitro-2-arninodiphenylamine (Nietzki and Almenriider Abstr. 189 6 i 164) combines with potassium cyanide and formaldehyde in dilute alcoholic solution to form 5-nitro-2-aniZino- p?Len?JgZycine NHPh*C,H,(NO,)*NH* CH,*CO,H which melts at 96" after repeated precipitation from sodium carbonate solution by hydro- chloric acid.It dissolves readily in alcohol acetic acid or acetone sparingly in ether or benzene but is partially dehydrated on heating so cannot be recrystallised. On heating with concentrated sulphuric acid water is removed and 6-?~itro-2-keto-l-phenylletrahydroquinoxaZine NO,* C,H,<GFiX;' is formed ; this crystallises from glacial acetic acid in bright yellow needles when Slowly cooled or in darker yellow tablets when rapidly cooled and melts at 230.5' after drying a t 100' in a vacuum. It dissolves in Concentrated acids to colourless solutions and is not decomposed on boiling.It is insoluble in benzene or ether but dissolves readily in hot acetone. The same compound is obtained on heating nitroaminodipheiiylamine with bromoacetic acid and sodium acetate. Hydrogen chloride and stannous chloride reduce the acetic acid solution to 6-acnzi.i~o-2-keto - 1 -pheny Ztet~cchydroquinoxaline C14Hl ,ON which crystallises from alcohol in small colourless needles melting a t 158" and becoming yellow in the air. It is insoluble in alkalis and dissolves readily in acetone or glacial acetic acid very sparingly in ether or benzene. Ferric chloride oxidises the hydrochloride an intense blue coloration rapidly becoming brown heing produced. The diacetyl derivative N H A C * C H < ~ ~ ~ bo crystallises from dilute acetic acid in star-shaped groups of colourless lancet-like leaflets and melts at; 128 -1 31".Nitroaminodiphenylamine combines with ethyl oxalate (compare Meyer and Seeliger Abstr. 1897 i 45) on boiling t o form 6-nityo- N==C* OH 3-ltydro~y- 2 - ke t 0- I -phenyldiIq d roquin OXCL 1 ine crystallising from ethyl oxalate or nitrobenzene in microscopic colour- less needles remaining unaltered a t 330". Most organic solvents dissolve only traces. On boiling with a solution of sodium sulphicle 6-anzino-3-l~ydroxy-2-keto-l-p~~n~Zd~~~~dro~~i?~oxaZ~ne CI4Hi1O2N3 is formed and crystallises in slender yellowish-white needles not melting a t 330'. It dissolves readilv in acids or alkalis and is readilv oxidised. NAc CH N 0 C,H,<w h. bo .I .I The szcZplmte forms a colourless sparingly soluble precipitate. NAc*FO NPh-CO The diacetyl derivative NHAc*C,H,< s 2248 ABSTRACTS OF CHEMICAL PAPERS.forms small colourless crystals infusible a t 300° and dissolves readily in alkalis thus suggesting the third of the above formulz. I n the condensation of nitroaminodiphenylamine with ethyl oxalate etlq I 5 -nitro - 1 -pheny Zbenximinaxo Ze- 2 - carboxy Zat e No~*C,H3<Nph~C'co,Et -N is also produced which crystallises from alcohol in colourless tabular leaflets and melts a t 150.5'. It dissolves readily in chloroform or hot acetic acid acetone or ethyl oxalate sparingly in ether or benzene. The carboxylic acid forms a colourless uncrystallieable powder dissolv- ing readily in alcohol acetic acid or acetone sparingly in ether or benzene and does not melt a t 300'.Concentrated hydrochloric acid decomposes the ester a t 1 50° Forming 5-~~itro-l-pl~e~2~Zbe~zxii'lLinaxOle No,*C,H,<Nph>CH -N which forms colourless crystals and melts a t 159.5' and dissolves readily in acids. Stannous chloride reduces it to 5-antino-1 -~?~en?lZbenxinzinccxoZe C13H11N3 separating from benzene in colourless crystals and melting a t 130-1 31'. The sta~tnocldo~ide C,,H,,N,,ZHCl,SnCl fornis colourless needles. The cccetpl derivative C,,H130N forms small colourless crystals melting a t 170.5" and yields a crystalline lug&-och Zoride. C. H. D. Amino-derivatives of Phenyldiphenylenemethane and the Corresponding Carbinol. ALFRED GUYOT and M. GRANDERYE (BUZZ. Xoc. cl~im. 1905 [iii] 33 198-205. Compare Abstr.1901 i 569 ; 1903 i 748 and Ullmann and Wurstemberger Abstr. 1904 i 154).- as-Tetramethyldiaminophenyldiphenglenemethane produced together with the o-hydroxy-leuco-base of malachite-green (Fischer Abstr. 1 SS1 587) by diazotising the o-amino-leuco-base of malachite-green in sulphuric acid and then heating a t looo melts at 158" (compare Abstr. 1903 i 748). similarly prepared from Noelting's bis; (Abstr. 1 S9 1 727 and 1892 187) having the constitution CH(C,H;N~~e2),.C,H,Me.NH by diazotisation forms small white crystals. melts at 1 4 2 O and is slightly soluble in alcohol and ether more so in benzene. On oxida- tion it furnishes a dull violet dye. Tetrametl~yldiaminopl~enyZ-m-nitro- diphenyZenen%ethane similarly prepared from a nitro-base which mill be described in a future paper crystallises in slender brilliant orange- yellow needles melts at 170' resembles the foregoing in solubility and gives a blue dye on oxidation.~etranaetl~~Zdiaminopl~en~~pl~enyZene~a~l~t~~yZe~~eiaethc~ne similarly pre- pared from the 6ase NMe,*C,H,*CH< I to be described in future paper forms slender white needles melts at 225-226' and is soluble in benzene and scarcely so in alcohol and ether. C H *NMe C,,H,*NH T. A. H.ORGANIC CHEMISTRY. 249 Desmotropic Compounds. HEINRICH GOLDSCHMIDT (Zed. iZ!ektrochena. 1905,11,5-7).-Dimroth (this vol. i 98) from his experi- ments on the velocity of the conversion of methyl 5-hydroxy-1-phenyl- 1 2 3-triazole-4-carboxylate into its ketonic form has drawn the con- clusion that the reaction only affects the non-dissociated molecules and does not take place between the ions.Owing to the fact that the non- dissociated molecules are in equilibrium with the ions however the product of the concentrations of the ions is proportional to the con- centration of the non-dissociated molecules a d the velocity of re- action which Dimroth has shown to be proportional to the latter is therefore proportional to the former. Hence the experiments cannot decide whether the change is ionic or not. T. E. 12 2-Diamino-4 4-oxalotoluidide.] FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D. R.-P. 156 177).-rn-Tolylenediamine combines with oxalic acid a t 100-225° to form 2 2'-diccnziizo-4 4'-oxalotoluidide C,O,(NH*CsH,Me*NIi,) which separates as an amorphous yellow powder melting a t lSr3-280° according to the mode of precipitation.It is insoluble in water and dissolves sparingly in hot alcohol to a yellow solution with slight green fluorescence. Azo- dyes may be prepared from the tetrazonium compound. On fusing cliarnino-oxalotoluidide with sulphur a t 80-140° hydrogen sulphide is evolved and the reaction then ceases but on heat- ing further condensation takes place a t 170" and a new conzpozcizd is obtained which dyes a fast yellow shade in a sodium sulphide bath. C. H. D. Formation of Heterocyclic Compounds from Hydraeine Derivatives. XVIII. Action of Ammonia on Tetrabromo- beneylideneaeine. ROBERT STOLL~ (J. pi.. Chent. 1905 [ii] 71 30-33. Compare Abstr. 1903 i 721; 1904 i 102 200 453 626 627 694-697 ; this vol. i 94-97).-The action of ammonia on a cooled solution of tetrabromobenzylideneazine in carbon tetrachloride leads to the formation of a benzylidene derivative of 3 6-diphenyl- 1 4-dihydrotetrazine and benzylideneazine./CPh:N \N CPh/ \ The beotx@idene derivative NL CHPh -N is formed also when 3 6-diphenyl-1 4dihydrotetrazine is shaken with benzaldehyde and dilute sulphuric acid. It crystallises in needles melts a t 207" is soluble in alcohol 01- carbon tetrachloride but not in water and yields the dihydrotetrazine when a current of steam is passed through a suspen- sion of it in dilute sulphuric acid. G. Y. Action of Dicyanodiamide on the Primary Aromatic Amine Hydrochlorides. AUGUSTE LUMIERE LOUIS LUMI~RE and E. PERRIN (Bull. Soc. cltim. 1905 [iii] 33 205-207).-The authors find that in the preparation of phenyldiguanides by the action of di- cyanodiamide (cyanoguanidine) on aniline hydrochloride it is unneces- sary to heat the reagents dissolved in alcohol in closed vessels since250 ABSTRACTE OF CHEMICAL PAPERS the reaction takes place when the two reagents are fused together over an oil-bath (compare Smolka and Friedrich Abstr.1888 830). p-H~~roxyphenyldiguanide hydrochloride NH,*C(NH)*NH* C(NH*C,H,*OH):NH,HCl similarly prepared melts a t 203-204' ; the picwte melts at 200-201°. p-Anisyldigzcanide hydrochloride melts at 221-222' and the picrate at The o- and p-phenetyldiguanide hydrochlorides melt respectively at 183-184' and 209-ZlO" and the corresponding picrates a t 161-162" and 182-1 83" respectively. The diguanide derived from antipyrine yields a picrate melting and decomposing a t 137-138'.These hydro- chlorides on treatment with silver oxide furnish the diguanides which are strongly alkaline substances very soluble in water. T. A. H. 1 9 3 -1 9 5". [o-lxydroxyazo-derivatives of a-Naph thylamine. 1 BADISCHE ANILIN & SODA-FABRIK (D.R.-P. 156440).-Whilst it is not possible to subs ti tut e hydroxyl for the sulpho-group in diazobenzene-o-sulphonic acid and its homologues by means of alkaline compounds the reaction takes place readily in the case of the di- and poly-sulphonic acids of a-naphtliylamine. The diazo-compounds of a-naphthylamine-2 4- and -2 5-disulphonic acids or of a-nsphthylamine-2 4 6- or -2 4 7-tri- sulphonic acids react in the cold with alkali or alkaline earth acetates or carbonates or with alkali nitrites the sulpho-group being replaced by hydroxyl. The diazohydroxy-compounds thus obtained do not combine readily but yield stable brown or violet dyes with P-naphthol.Subsequent treatment with chromium salts produces fast dark blue or black shades C. H D. Limits of Coupling of Diaxobenzene with Aniline. LEO VIGNON (Compt. rend. 1905 140 91-93. Compare Abstr. 1004 i 637 1065) .-Diazobenzene chloride does not condense with amino- azobenzene either in aqueous or alcoholic solution but aniline con- denses readily with diazoaminoazobenzene at 0' to form the toll-apound NPh:N*C,H,*N:N*NHPh which crystallises from alcohol melts at; 11 2" and on prolonged heating at 40" with aniline and aniline hydro- chloride breaks down into aminoazobenzene (compare however Nietzki and Diesterweg Abstr.1883 1080). Anilinebisdiazobenz- ene NH(N:NPh) prepared by the action of aniline on nitroso- acetanilide (Pechmann and Frobenins Abstr. 1894 i 283) when heated with aniline and aniline hydrochloride also yields aminoazo- benzene which appears to represent the limit of combination of diazo- benzene with aniline (compare Abstr. 1904 i 701). Attempts to prepare anilinebisdiazobenzene by the action of diazobenzene chloride on diazoaminobenzene or on aniline were unsuccessful. M. A. W. [Azo-dyes from Alphylsulphonaminonaphthol Derivatives.] GADISCHE ANILEN- st SODA-FABRIK (D.R.-P. 156157).-Eenzsnesul- phonic chloride reacts with 8-amino-a-naphthol-4-sulphonic acid in alkaline solution t o form 8-benxenesuZ~~hon~iriino-a-nic~l~tl~ol-4-suZp~~on~acid which is sparingly soluble.The quantity present may be deter- mined by titration with a nitrophenyldiazonium salt in acetic acidORGANIC CHEMISTRY. 251 solution. The acid combines with diazotised picrarnic acid in slightly alkaline solution to form a crystalline azo-compound which may be filtered washed with sodium chloride solution and dried. The dye dissolves in water to a violet solution becoming red on the addition of alkalis. It yields fast bluish-black shades on subsequent treat- ment with chromium salts. Similar compounds are obtained from 0- or p-t oluenesulp honic chloride. C. H. D. [Azo-dyes from Nitro-m-diamines.] BADISCHE ANILIN- & SODA- FABRIK (D.R.-P. 156352).-The diazosulphonic acids of the benzene and naphthalene series such as the diazo-compounds of p-toluidine- o-sulphonic p-chloroaniline-m-sulphonic or /3-naphthylamine-8-sulphonic acicl combine with nitrated nz-diamines to form monoazo-dyes which yield fast yellow or orange lakes with metallic salts. C. H. D. Protective Action of Salt on Solutions of Proteids. W ILHELM BILTZ (Zed. Elektrochem. 1 9 04 10 9 3 7-9 3 8). -Precipitated and well-washed hydrated ferric oxide or zirconium dioxide was shaken with solutions containing albumin and the quantity of albumin remain- ing in solution determined. A comparison of the results obtained with solutions containing salt and with dialysed solutions showed that the latter lost more albumin than the former. It is probable that a maximum protective action would be found a t a certain concentration of salt since a large exsess of it precipitates albumin. The observations give an explanation of the fact that circulating blood does not coagulate. T. E. Action of Pepsin on Albumin Precipitated by Heat in Pre- sence of Acid. F. DISDIER (J. Pharm. Chim. 1905 [vi] 21 5-14).- The amount of acetic tartaric and oxalic acids in one per cent. solu- tions required for the precipitation of 100 grams of white of egg are 45 57 and 48 C.C. respectively numbers which are directly propor- tional to the equivalent weights of the acids. This rule also holds with nitric butyric and citric acids. Using the most favourable proportions of hydrochloric acid for the digestion by pepsin of albumin precipitated by acid and for dissolved albumin the author finds that whilst the rates of digestion are equal with an acidity of 0.2 per cent. with an acidity of 0.1 per cent 9 grams of precipitated albumin require 3 hours the same weight of dissolved material requiring 12 hours for digestion. The difference in the acidity necessary for digestion is not due to acid combined with the precipitated albumin. G. D. L. Oxidation of Proteids with Calcium Permanganate. 11. Oxidation of Gelatin. FRIEDRICH KUTSCHEH. and M ARTIK SCIIENCK (Ber. 1905 38 455-459. Compare Abstr. 1904 i 955).-The crystalline product obtained in the oxidation of gelatin with calcium permanganate and formerly described as oxaluramide proves to be oxamide. The filtrate contains guanidine in quantity corresponding with the arginine in the original material (compare also Loew Abstr. 1885 823). C. H. D.252 ABSTRACTS OF CHEMICAL PAPERS Hydrolytic Cleavage of Proto-albumose. PHOEBUS A. LEVENE (Proc. Amer. Pl~ysiol. Soc. 1904 xii-xiii ; Amer. J. Physiol. 13)- Mixed with the hexone bases obtained from proto-albumose a new material C12H220,N was obtained. The copper and silver salts were prepared and analysed ; further investigation is in progress. W. D. H. Haloid Acid Salts of Peptones. KALLE & Co. (D.R..-P. 156399). -The irritant compounds produced in the action of lialoid acids on peptones may .be removed by washing the products with an alkali carbonate solution until neutral. The pure peptone salts yield non- irritant double salts with metallic haloids. C. H. D. Protagon. E. R. POSNER and WILLIAM J. GIES (Proc. Arner. Physiol. Xoc. 1904 xxxv ; Arner. J. Physiol. 13).-Further facts in favour of the view that protagon is not a chemical unit. W. D. H. Absorptiometric Estimation of the Amount of Nitric Oxide combined by Unit Weight of Methaemoglobin. GUSTAV VON H~FNER and B. REINBOLD (Clzern. Centr. 1905 i 374 ; from Arch. Anat. Physiol. physiol. Abth. 1904 391-395).-Meth~emoglobin solutions take a purplish-red colour with nitric oxide (Hufner and Otto) ; Hiifner and Kulz state that the spectroscopic appearances of such a solution are the same as those of a solution obtained by passing a stream of nitric oxide through a solution of carboxyhzmoglobin. It is now shown that the volume of nitric oxide per gram of pigment is almost twice as great as that of carbon monoxide united to each gram of hzrnoglobin. W. D. H. Haemochromogen and Carbon Monoxide. GUSTAV VON HUFNER and WILLIAM K~STER (Chem. Centr. 1905 i 373-374; from Arch. Anat. Physiol. physiol. Abth. 1904 387-390).-H~emochromogen was prepared from aceto-hEemin by reduction with potassium hydro- sulphide ; this combines with carbon monoxide like haernoalobin in thiproportion of 1 molecule of the gas per atom.of iron. W. D. H. Spectroscopic Characters of Hematoporphyrin. ARTHUH. SCHULZ (Chena. Centr. 1905 i 373 ; from Arch. Anat. Physiol.,physiol. Abtlt 1904 271-286).-Hzmatoporphyrin prepared by Nencki and Zaleski’s methods dissolved in alcohol shows five spectroscopic bands ; the positions and relative intensities of these are described as also are the changes which occur in them with different concentrations or on the addition of such reagents as acids alkalis and zinc chloride. W. D. H,

ISSN:0368-1769    

DOI:10.1039/CA9058800165

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

172 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Gases Dissolved in Minerals. K. H~TTNER (Zeit. acnorg. Chern. 1905 43 8-13).-The gases evolved on heating separately a large number of different minerals in a porcelain tube a t 800-850° in an atmosphere of carbon dioxide were collected in a Schiff’s nitrometer containing a 50 per cent. solution of potassium hydroxide and analysed. The percentages of oxygen carbon monoxide hydrogen and nitrogen respectively in the various mixtures are tabulated. The rare gases obtained in certain cases were not further investigated. The carbon monoxide found was not formed as Gautier supposes by the reduction of carbon dioxide by ferrous compounds but by the reduction of carbon dioxide by hydrogen nor was it present in solution in the original minerals.The hydrogen found was probably also not present in the original minerals. Hydrogen and carbon monoxide are formed when minerals which contain water are heated in a current of carbon dioxide. Hydrogen is produced by the action of reducing agents such as ferrous and man- ganous compounds on water vapour. A. McK.MINERALOGICAL CHEMISTRY. 173 [Graphite from Moravia. Nigrine (3) from Bohemia.] FRANTI~EK KovL6 (Zed. Kryst. Min. 1904 39 399 ; from Zeit. chem. Ind. Prccg. 1902 6 pp.).-Graphite from Tresni in Moravia I light grey scaly ; 11 dark grey finely scaly ; 111 blackish-grey compact. Water Water C. Ash. (at 150”). (comb.). Total. I. 58.07 38-45 1.08 2-40 100*00 11. 49.04 46-33 1 *96 2.67 100~00 IIT. 33.63 62-40 1.77 2.20 100*00 Nigrine (2) occurring in orthoclase at Polanka near Chrudim in Bohemia gave TiO,.SiO,. Fe,O,. FeO. MgO. Total. Sp. gr. 70.05 0.76 28.30 0.62 0.12 99.86 4.48 L. J. S. Composition of Fiedlerite. AUGUST B. DE SCHULTEN (Compt. rend. 1905 140 315-316).-The mineral fiedlerite fonnd in 188’7 as crystals in the ancient lead slags of Laurion in Greece has not hitherto been analysed. Analysis of colourless crystals gave the following results PbO. PB. c1. H,O. Total. Sp. gr. 29.02 5 1.01 17.48 2.33 99.84 5.88 The formula Pb0,2PbC12,H,0 shows the relation of fiedlerite to laurionite (Pb0,PbC1,,H20) and penfieldite (Pb0,2PbC12) which are associated minerals in the Laurion slags. Fiedlerite when heated decrepitates becomes opaque and loses its water at 150’. It is readily attacked by cold water the transparent crystals soon becoming opaque.L. J. S. Salts from the Region of Lake Chad. H. COURTET (Campt. rend. 1905 140 316-318).-The African desert in the neighbour- hood of Lake Chad abounds in surface efflorescences of alkali salts. The salts noticed are thenardite (“,SO,) sodium chloride and trona ( 3Na,0,4C02,5H,0). L. J. S. New Mineral from the Asbestos Mines of the LanternaValley. LUIGI BRUGNATELLI (Chem. Centr. 1904 ii 1754; from Rend. R. Inst. Lornbardo Xci. Lett. 35 869-874).-The new mineral has been found accompanying a form of peridotite closely approximating to dunite. It occurs in the form of aggregates of small prisms imbedded in the latter or of a white earthy substance covering the asbestos mineral. Analysis gave MgO. co,.H,O. 41.34 22.37 36.29174 ABSTRACTS OF CHEMICAL PAPERS corresponding with the formula MgCO3,Mg(OH),,3H,O ; sp. gr. at 16’ 2.028 hardness 2-3; it appears to be monoclinic. The name ccrtinite has been given to it. H. M. I). Triplite from a New Swedish Locality. IVAR NORDENSKJ~LD (Zeit. Kryst. Min. 1904 39 390; from Geol. For. Forb. Stockholm 1902 24 412-414).-Triplite occurs in the quartz of a pegmatite- vein which is worked for felspar near the lake Lilln Elgsjon in the parish Krokek Government of Linkoping. It is brown in colour and has the usual characters of triplite ; analysis gave P,05. F. MnO. FeO. Fe203. MgO. CaO. A1203. 32.05 8.72 35-23 18.43 2.38 4.46 2.10 0.37 Na,O. SiO,. HzO. Total (less 0 for F). 0.31 0.18 0.10 100*66 L. J. S. Artificial Production of Hopeite.AUGUST B. DE SCHULTEN (Bull. SOC. franp. &tin. 1904 27 100- 103).-8mall crystals of hopeite (Zn,P,0,,4H20) are obtained by mixing solutions of zinc sulphate and disodium hydrogen phosphate and by other methods. Larger crystals suitable for the determination of the crystallographic and optical constants were obtained by the following method zinc phosphate precipitated from solutions of zinc sulphate (45 grams ZnS0,,7H20 in 0.5 litre) and disodium hydrogen phosphate (37 grams HNa2P0,,12H,0 in 0.5 litre) is dissolved in a slight excess of sulphuric acid the solution heated on a water-bath and ammonia solution (3 100) added drop by drop ; at the end of eight days brilliant and limpid crystals 4.4 mm. in length were formed. The crystals are orthorhombic and have the characters of the natural mineral; sp.gr. 3.109. L. J S. Artiflcial Production of Barium- and Strontium-haidinger- ite. AUGUST B. DE SCHULTEN (Bull. SOC. franp Min. 1904 27 104-109).-Crystals of the compounds H.BaAsO,,H,O and HSrAs0,,H20 were obtained by a method similar t o that described in the preceding abstract. The crystals of both are orthorhombic and isomorphous with the mineral haidingerite (HCaAsO,,H,O) (compare Abstr. 1904 ii 492). L. J. S. Artificial Production of Barium- Lead- and Strontium- monetite and of Arsenated Monetites. AUGUST B. DE SCHULTEN (Bull. SOC. f r a y . Min. 1904 27 109-123).-By the methods described in the preceding abstracts crystals of the following com- pounds isomorphous with the triclinic monetite (HCaPO,) were obtained each of which is described crystallographically HBaPO (orthorhom bic) HPbPO (monoclinic) HSrPO (orthorhom bic) HSrAsO (triclinic) and HPbAsO (monoclinic).I;. J. 8.MINERALOGICAL CHEMISTRY. 175 Artificial Production of Hureaulite and Cadmium-hureau- lite. AUGUST B. DE SCHULTEN (BUZZ. Soc. f r a y . M k . 1904 27 123-1 29).-Monocliiiic crystals of hureaulite (HzMn3.P2O8,4H,0) and of the corresponding cadmium compound were obtained by the method described in the preceding abstracts. L. J S. Artificial Production by a Wet Method of Anhydrous Chromates of Barium Lead and Strontium. AUGUST B. DE SCHULTEN (BUZZ. SOC. frunp Mi?%. 1904 27 129-1 37).-Crystals 1.2 mm. in length of crocoite (PbCrO,) were obtained by adding a solution of potassium dichromate drop by drop to a warm solution of lead nitrate with concentrated nitric acid.Crystals of barium chromate (BaCrO,) which are orthorhombic and isomorphous with barytes were obtained in a similar manner. Strontium chromate being more soluble than the corresponding lead and barium chromates is more difficult to obtain in measurable crystals which are monoclinic and isomorphous with crocoite ;*the following method was successful ammonia was added drop by drop for a period of thirty days to a warm solution of strontium nitrate and potassium dichromate. L. J. S. Formation of Oceanic Salt Deposits. XXXIX. Tempera- tures of Transformation below 25". JACOBUS H. VAN'T HOFF and WILHELM MEYERHOFFER (Sitxungsber. X. A h d . rl'iss. Bedin 1904 1418-1 421. Compare Abstr.1904 ii 492)-The temperature at which Glauber's salt is transformed into thenardite is normally 3 2 * 4 O but in presence of other salts the temperature is lower. Thus in presence of sodium chloride the transformation occurs a t 17.9' in presence of sodium chloride + glaserite a t 1 6 * 3 O in presence of sodium chloride + blodite a t 15*3O in presence of sodium chloride + glnserite + blodite at 13.7'. Other components besides thenardite that dis- appear as the temperature falls are magnesium sulphate hexahydrate at 13O kieserite at 1 8 O leonite at 18" and blodite at 4.5'. J. C. P. Origin of Sodalite in Syenites. STANISLAUS J. THUGUTT (Centr. Min. 1905 86-S9).-The sodalite of sodalite-syenites has been con- sidered by some authors to be of primary and by others of secondary origin.It is pointed out that both sodalite and ultramarine (which is proved to be present in both blue and white sodalite) have been artificially prepared only by fusion atid that various attempts to obtain them by a wet method have been unsuccessful; further sodalite is readily decomposed by water and aqueous solutions (Abstr. 1895 ii 358). These facts are taken t o prove that sodalite is always an original mineral of igneous origin. L. J. S. [Meerschaum and Jarosite.] FRANTI~EK KovAli (Zeit. Krpst. Min. 1904 39 400; from Frogs*. d. c'echosl. Handels. akad. Prag. 1903 13 pp.).-A finely fibrous to compact pale yellow mineral occurring in crevices in a felspar- hornblende-rock in western Moravia,176 ABSTRACTS OF CHEMICAL PAPERS mas shown on analysis to have the composition of meerschaum (H*Mg,Si,O,o) 3320 SiO,.MgO. CnO. MnO. A1,03. Fe,Oa. (comb.).* CO,. Total 57.77 25.03 0.87 0.64 2'74 1-24 11.74 trace 100'00 * 5-49 per cent. of hygroscopic water deducted. Jarosite as an ochre-yellow encrustation on harnatite from Sichotin in Moravia gave Fe,O,. 81,0,. CnO. K,O. Na,O. SO,. H,O. Insol. Total. 51-05 0.40 0.46 7.50 0'28 29-40 10'88 10.88 100.57 L. J. S. Titanolivine from Val Malenco Lombardy. LUIGI BRUGNA- TELLI (Zeit. Kvyst. Min. 1904 39 209-219).-Nodules and veins of titanolivine occur with olivine antigorite magnetite &c. in the serpentine-schists at several spots in the neighbourhood of Chiesa. It is a deep cherry-red in colour and resembles garnet in appearance ; sp. gr. 3.20-3-26. The optical characters of the material point to monoclinic symmetry as previously suggested for the mineral by Lacroix.It is sometimes twinned and is frequently regularly inter- grown with olivine. The mineral offers more resistance to weathering than does the associated olivine but the products of decomposition namely antigorite and a colourless diopside are the same for both. Analysis by G. Anelli gave SiO,. TiO,. MgO. FeO. MnO. Fe,O,. F. H,O. Total. 36'86 4.75 45'50 10.05 trace 1-08 trace 1.57 99'84 The ratios (Si,Ti)O R"O H,O = 1.06 2 0.14 are almost identical with those obtained by Damour for the mineral from the Tyrol and Switzerland. Titan- olivine thus appears t o be a distinct mineral species and to be related to olivine as clinohumite is to humite. Water is given off only a t a high temperature.L. J. S. [Hornblende from Bohemia.] By HEINRICH I;. BARV~R (Zeit. Kyyst. Misz. 1904 39 398; from Abh. biihm. Akad. 1902 No. 22).- In a paper on the chemical relations of some rocks from Eule the following analysis is given of a hornblende which was isolated from the granite of Zampach near Eule SiO,. TiO,. A120,. Fe20,. FeO. MnO. CaO. 44-16 trace 8-54 8.17 14-23 0.48 1045 MgO. (hygros.). (ignition). Total. Sp. gr. 10.39 0.58 1 -59 99'51 3'19 H20 H,O L. J. S. [Chrysocolla from Western Australia.] EDWARD S. SIMPSON (Rep. Dep. Mines JV. Aqcstr. for 1903 1904 p. 143).-A supposed occurrence of turquoise with copper and gold ores has been reportedMINERALOGICAL CHEMISTRY. 177 from the Murchison district. Although of a brilliant colour like turquoise the mineral is shown by the following analysis to be chrysocolla and not turquoise H,O H,O (ig- SiO,.CuO. FeO. MgO. A1,0,. P,O,. at 100". nition). Total. 39'90 43-36 0-65 trace nil nil 9'36 7.42 100.69 The report includes various other mineralogical notes and analyseg L. J. 8. of gypsum diatomite clay and chalk. [Alteration Product of Topaz.] A. KREJfif (Zed. Kryst. Min. 1904 39 399; from Xitx.-bey. k. bohm. Ges. Wiss. 1902 No. xxxv 7 pp.),-The minerals beryl tourmaline andalusite and topaz from Yisek in Bohemia are described. The alteration product of the topaz is proved by the following analysis by F. KO& to be compact muscovite. SiO,. F. Fe,O,. A1,0,. RlnO. CaO. MgO. K20. Na,O. H,O. Total. Sp. gr. 47.71 0.17 2'87 33%1 1.10 trace 1-04 8.12 0'84 5.11 10057 2.45 L.J. S. [Naegite a New Mineral,] TSUNASHIR~ WADA (Minerals of Japan T6ky6 1904).-This book contains a description of all the mineral species found in Japan with notes on their modes of occurrence and localities and is an extension of the paper by K. Jimb6 (Abstr. 1900 ii 87). Numerous analyses which have hitherto not appeared in a European language are quoted and a new species naegite is described. The new mineral is found with fergusonite in the alluvial tin washings a t NaGgi near Takayama in the province Mino as green to brown spheroidal aggregates wit'h indistinct crystals on the surface The crystals are tabular or prismatic in habit and appear to be tetragonal with the pyramid angle (111) (111) about 56g which is near that of zircon.Under the microscope the mineral is grass- green and transparent and is sometimes optically birefringent but more often isotropic. Hardness '74 ; sp. gr. 4.09. It is pronouncedly radioactive. SiO,. UO,. Tho,. Ta,O,. Nb,O,. CeO,. Fe,O,. CaO. MgO. H,O. Total 34.89 28.27 16.50 7.00 4'10 1.59 1-60 1.71 0.57 3.12 99'35 The mineral is thus mainly a silicate of uranium and thorium and is considered to be isomorphous with zircon and thorite [but it is to be noted that the composition deviates very considerably from that of an orthosilicate]. Beckelite a Calcium Cero-lanthano-didymo-silicate. J ~ Z E F MOROZEWICZ (BUZZ. Acccd. Sci. Cyracovie 1905 annee 1904 485-492).- The new mineral occurs as an accessory constituent of a dyke-rock com- posed of nephelite albite zgirite and magnetj te which is associated with the mariupolite (Abstr.1902 ii 668) and elsolite-syenites of the Mariupol district on the Sea of Azov Russia. The wax-yellow grains Analysis by T. Tamura gave L. J. S. vor LXXXVTII. ii 13178 ABSTRACTS OF CHEMICAL PAPERS. and octahedral or rhombic-dodecahedra1 crystals which measure up to 8 cm. across resemble pyrochlore in general appearance and physical characters but have a cubic instead of an octahedral cleavage. Sp. gr. 4.15 ; hardness 5. The mineral is readily decomposed by acids with separation of silica. Chemically it is quite distinct from pyrochlore containing no niobium titanium or fluorine. Analysis gave SiO,. A1,0,. Fe,O,. ZrO,. Y203,Er,03. Ce,O,. La203. Di,O,. 17.13 0'30 trace 2-50 2.80 28'10 13.60 18.00 Mn,O,. CaO. MgO. K,O. Na,O. ignition. Total. 0.07 15.46 trace 0.39 0.78 0'99 100-13 Loss on The formula is Ca3(Ce,La,Di,Y),(Si,Zr)3015 which written as Ca,R,Si,O,,,R,O shows a relation to garnet with rare earths in place of alumina and an analogy to calcium alumino-silicate. L. J. S. Orbicular Gabbro from California. ANDREW C. LAWSON (BUZZ. Dept. Geol. Univ. California 1904 3 383-396) .-A petrological description is given of the various facies of an outcrop of gabbro at Dehesa San Diego Co. The normal type is a coarse-grained horn- blende-gabbro with olivine and hypersthene. The spheroids of the orbicular type measure about 6 cm. across and consist of a core of felspar surrounded by concentric shells of radially crystallised olivine and felspar. Analysis of the spheroids gave the results under I (by J. W. Howson) and of the felspar (anorthite) isolated from them the results under I1 (by W. T. Schaller) SiO,. A120,. FeO. XgO. CaO. Na,O. K20. Total. 40'08 22'86 11-96 12'40 11'41 1-26 0.38 100% 44-39 36.55 trace nil 18.67 0'83 - 100.44 1,. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9058805172

出版商:RSC    

年代:1905

数据来源: RSC

摘要:

178 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. The Power of Human Blood to Decompose Hydrogen Peroxide. HERMANN SILBERGLEIT and MAX MOSSE (Chem. Centr. 1905 i 268-269 ; from Beitr. klin. Med. Feestscluift 1904).-The same amount of hydrogen peroxide is decomposed in the same time by the same amount of blood from healthy people with the normal amount of hsemoglobin and corpuscles. The catalytic power of the blood runs parallel with the number of corpuscles. W. D. H. Peptic and Tryptic Digestion of Proteids. 11. D. LAWROFF (Zeit. plysiol. Chem. 1905 43 447-463).-The proIonged action ofPHYSIOLOGICAL CHEMISTRY. 179 0.5 per cent. hydrochloric acid leads to the formation only more slowly of the same products as those formed during peptic digestion. The experiments were mainly performed with gelatin and hsmoglo bin.W. D. H. Pancreas and Glycolysis. -RICHARD CLAUS and GUSTAV EMBDEN (Beitr. chem. Physiol. Puth. 1905 6 214-231. Compare Cohnheim Abstr. 1903 ii 788 ; 1904 ii 675).-Polemical mainly against Cohnheim’s view that the pancreas exercises power in promoting gly colysis in muscle. Cohnheim’s results are not confirmed. W. D. H. Physiology of Mollusca. I. LAFAYETTE B. MENDEL and HAROLD C. BRADLEY (Amer. J. Physiol. 1905 13 17-29).-Digestion in Xycotypus is effected by the salivary glands and the hepato-pancreas. The former histologically resemble those of higher animals ; their secretion contains mucin and a proteolytic enzyme which normally acts in the cold and in solutions which are neutral or arnphoteric; it closely resembles trypsin.The liver or hepato-pancreas contains an amylase invertase and lipase. Digestion occurs in the stomach and in the hepatic ducts ; absorption occurs in the same situations. W. D. H. Movements of the Alimentary Canal after Section of Nerves. W. B. CANNON (Proc. Anzer. Plqsiol. SOC. 1904 xxii ; Anzer. J. Physiol. 13).-X-Ray observations were made on the movements of the food mixed with bismuth subnitrate. After vagu ssection there is stasis in the esophagus and the advance from the stomach is a little slowed but almost normal. Stomach and intestinal movements also continue after cutting the splanchnics. The stomach movements are inhibited by distress in both conditions. The difference in the rate of discharge of carbohydrates and proteids was also preserved in both con- ditions.W. D. €1. Carbohydrate Combustion in the Animal Organism. JULIUS STOKLASA (Bey. 1905 38 664-670. Compare Stoklasa and Czerny’ Abstr. 1903 ii 320 and 1904 i 275).-It is shown that the crude enzymes obtained from previously frozen muscles possess practically no activity as compared with the enzymes separated from the same parts when fresh and unfrozen. Special experiments were made to show that the fermentative action is not due to bacteria as suggested by Cohnheim (this vol. ii 675). Experiments which will be described later in detail have shown that in the decomposition in presence of air of carbohydrates by the enzymes of muscle extract in addition to lactic acid alcohol and carbon dioxide there are formed acetic acid a little formic acid and hydrogen. A hypothetical scheme of the degradation of dextrose by the enzymes in question is appended.W. A. D. Physiological Economy in Nutrition. RUSSELL H. CHITTEXDEN (published in book form 1904 1-478 New York).-A fuli account of experiments carried out on the author’s own person on that of his 13-2180 ABSTRACTS OF CHEMlCAL PAPERS. colleagues and students and on soldiers and athletes. Each experi- ment lasted for many months. The diet taken the excreta the body weight the general health tests of strength and of mental sharpness are the points mainly considered. The general conclusion reached is that the proteid intake may be reduced to one-half or one-third of the usually accepted standard not only without harm but with great advantage ; equilibrium is maintained health improves bodily and mental vigourincresse.Modern diet is condemned as not merely uselessly excessive but positively harmful. The importance of the question and of the results attained can hardly be exaggerated. W. D. H. Gelatin as a Sublstitute for Proteid in Food. J. Ii. MURLIN (Proc. Anzer. Physiol. Soc. 1904 xxix-xxx ; Amel.. J. Physiol. 13). - I n dogs it is a matter of indifference how much of the proteid-nitrogen is replaced by gelatin-nitrogen up to one-half of the starvation require- ment. Even if two-thirds is replaced equilibrium is maintained provided the carbohydrate amounts t o one-half t o two-thirds of the calorific requirement. Corresponding results were obtained in man. W. D. I€. Proteid Synthesis in the Animal Body.VALDEMAR HENRIQUES and C. HANSEN (Zeit. physiol. Chem. 1905 43 417-446).-From experiments on rats i t was found that the products of decomposition of casein formed by acids will not maintain the body in nitrogenous equilibrium even if given in large quantities but that if the products are obtained by means of proteolysis by trypsin and erepsin nitro- genous equilibrium is maintained or nitrogen may even increase. The same is true for the products of tryptic digestion which are not precipitable by phosphotungstic acid (monoamino-acids) and for t,hose products which are soluble in warm 96 per cent. alcohol. The products which are insoluble in alcohol do not possess this property. W. L). H. Influence of Carbohydrate Diet on the Composition of the Child. FRANZ STEINITZ and RICHARD WEIGERT (Beitr.chem. Physiol. Path. 1905 6 206-213).-An opportunity arose of making analyses of four infants who had died from malnutrition due t o a n excess of carbohydrate in the food. The analyses bring out a low percentage of water and salts and a high percentage of fat. W. D. H. Effect of Blood on the Kidney. TORALD SOLLMANN (Proc. Arner. Physiol. Soc. 1904 xxxi ; Amer. J. Physiol. 13).-Viscid solutions of egg-white and gum acacia markedly decrease vein and ureter flow and kidney volume. Dilute defibrinated blood produces the same effect several days after excision If freshly excised kidneys are used the vein-flow is increased; the dilator effect is also produced by blood saturated with carbon monoxide by blood laked a t 63O and by serum ; it is destroyed by coagulating the proteids. The effects however vary with different kidneys and different samples of blood.Hydro-PHYSIOLOGICAL CHEMISTRY. 181 cysnic acid is also a dilator ; SO also is adrenaline under certain con- ditions. W. D. H. Effects of Isotonic Solutions on the Kidney. TORALD SOLLNANN (Proc. Anzer. Plu~lsiol. Xoc. 1904 xxx ; Amer. J. Plqsiol. 13)-Excised kidneys were perfused with solutions isotonic with 1 per cent. sodium chloride solution. Cane sugar and dextrose cause very slight changes. Alcohol and urea diminish the vein and ureter flow and the kidney volume; they penetrate the cells. f n regard to cations barium calcium and hydrogen produce the same effect ; magnesium increases both flows; potassium and ammonium have little or no effect.I n regard to anions sulphate and citrate increase and hydroxide carbon- ate and hydrogen carbonate lessen the flow. All these effects are removable by subsequent perf usion with sodium chloride. Locke’s solution (minus the sugar) causes a slight increase of ureter flow without changes in the venous flow or kidney volume. These effects can be produced several days after excision. W. D. H. Rate of Absorption from Intra-muscular Tissue. S. J. MELTZER and JOHN AUER (Proc. Anzer. Pl~ysioZ. Xoc. 1904 xxxii-xxxiii ; Amer. J. PI~ysioZ. 13).-Absorpt;ion from the intra-muscular tissue is incom- parably more rapid and efficient than from the subcutaneons tissue. W. D. H. Alcohol in Animal Organs. MAURICE NICLOUX (Zeit. physiol. Chern. 1905 43 476. Compare Abstr.1904 ii 595).-Landsberg (Abstr. 1904 ii 499) has confirmed in the main the author’s previous results by his method The present communication relates to some details in technique. W. D. H. Physiology of Glycogen. WERA ADAMOFF (Zeit. Biol. 1905 46 281-301).-Chickens just out of the shell contain little or no glyco- gen. Four days later the glycogen begins to increase. New-born rabbits yield 4.36 grams of sugar from glycogen per kilo. of body weight; this amount is small compared to that in well-fed adult dogs. The human liver from later fcetal periods contains glycogen but not more than is obtainable from an adult animal in a state of inanition. A bundance of glycogen is therefore not n characteristic of embryonic tissues. The energy of growth and amount of glycogen are not related.W D. H. Lactic Acids in the Animal Organism. G. MORIYA (Zeit. physiol. Chem. 1905 43 397-401).-The statement is generally made on the authority of W. Miiller (Arrzrrzalen 1857 103,152) and of Gscheidlen (PJlUger’s Archiv 1874 8 178) that the lactic acid ob- tained from the brain is not sarcolactic acid but fermentation lactic acid. This however is incorrect; the acid present is sarcolactic or d-lactic acid as in other organs. It was identified not only in the brain of several kinds of animals but also in lymph glands kidneys thymus spleen pancreas and thyroid. W. D. H.182 ABSTRACTS OF CHEMlCAL PAPERS. Para-lactic Acid. ARTHUR R. MANDEL (Proc. Amer. Physiol. Xoc. 1904 xvi; Amer. J. Physiol. 13).-After producing phloridzin diabetes in a fasting dog poisoned with phosphorus the urine reaction changes from ammoniacal to acid (Lusk).It seemed possible that lactic acid which is produced in phosphorus poisoning and is probably the cause of the excess of ammonia in the urine might be derived as a cleavage product of sugar which originates from proteid. If this is so no lactic acid should be formed in diabetes even although phosphorus poisoning is present. This is the case ; the blood and urine of a fast- ing dog poisoned with phosphorus contained lactic acid ; this disappears when diabetes is induced by phloridzin. Ingestion of fermentation lactic acid in diabetes leads to a slight reduction of proteid metabolism and therefore of sugar output. 11 synthesis of a small quantity of lactic acid into sugar also seems to occur.W. D. H. Origin of Creatinine. WALDEMAR KOCH (Proc. Amw. Physiol. Xoc. 1904 xix; Amer. J. Physiol. 13)-The relation of the methyl groups of lecithin to that of creatinine suggested feeding experiments with lecithin added to a creatine-free diet ; the amount of lecithin given varied from 0.5 to 7 grams a day but the amount of creatinine only varied slightly. Excess of lecithin is probably stored for it does not appear in the faxes. Another factor (proteid katabolisrn) is involved in supplying most of the nitrogen of the creatinine molecule. W. D. H. The Source of Substances containing Sulphur in Animals. JULIUS WOHLGEMUTH (Zeit. physiol. Chem. 1905 43 469-475).- Cystin is regarded as a source of the gaseous products hydrogen sul- phide methyl mercaptan and ethyl sulphide as it is also of taurine and of sulphates non-oxidised sulphur and sulphites.The seat of formation is probably the intestine. W. D. €€. Histological Changes in Wool-fibre by the Prolonged Action of Water. Chemical Nature of the Wax of Corpses. NAZARENO TARUGI (Gaxxetta 1904 34 ii 469-4’74).-Tbe author has examined the woollen sock of a drowned man who had remained under water for more than 22 months. The boot had prevented the swell- ing of the foot which had taken up the shape of the boot. The total absence of any part of the sock outside the boot showed that the con- tinuous action of the water had completely destroyed the woollen tissue by slow oxidation processes and mechanical action. The part of the sock inside the boot had been kept intact by a substance which bad filtered into the wool and which the author finds to consist mainly of palmitic acid.This acid is formed by the slow oxidation of the fatty substance of the foot. T. H. P. Staining Reactions of Animal Cells. MAX MOSSE (Chenz. Centy. 1905 i 386 ; from Salkowski’s Festschrift 1904).-The paper mainly treats of histological methods and especially of the different solu- bilities and staining reactions of nuclein and paranuclein (nucleoli),PHYSIOLOGICAL CHEMISTRY. 183 Acid dyes are stated to colour the nuclein and ammoniacal dyes the paranuclein best. Absolute alcohol and then mercuric chloride are the best indifferent fixatives. W.D. H. Reversal of Ciliary Movement in Metazoa. G. H.PARKER (Amer. J. Physiol. 1905 13 1-16).-The reversal of the effective stroke in the cilia of protozoa is well known.It is rarer in metazoa. The present experiments were mads in the labial cilia of the anemone Metp*idium rnarginutum. The majority of the substances tried produce no effect. Reversal is not produced by changes in osmotic pressure nor by anions but by potassium-ions. The reversal observed with crab meat juice depends on organic compounds of potassium ; if the extractives are removed crab meat has no effect. Irreversible cilia are probably not symmetrical in that they consist of a supporting elastic element on one side of which is contractile material. W. D. H. Eck’s Fistula in Dogs. PHILIP B. HAWK (Proc. Amer. PhysioE. ~ o c . 1904 xiv ; Amer. S. Physiol. 13).-This operation was success- fully performed in two dogs who lived for 59 and 30 days respectively.The liver function was much impaired. The dogs lost greatly in body weight and exhibited ataxy and cataleptic attacks while they lived. Feeding with sodium carbamate or injection of this salt into the blood stream of normal dogs did not produce these symptoms. W. D. H. Iron in Mother’s Milk. WILLIAM CAMERER (Zeit. Biol. 1905 46 371).-As an addition to former data fresh analyses are given of a specimen of human milk from the third to the twelfth days of lactation. I n one analysis 100 C.C. of milk contained 21 mg. of Fe203 and 100 grams of ash contained 66.4 rng. In a second analysis the numbers were 0.13 and 50.2 respectively. W. D. H. Formation of Acids by Enzymes. J. E. HINKINS (Anzer.Chem. S. 1905 33 164-167).-A series of experiments has been made to determine the action of diastase and pancreatin on solutions of triacetyldextrose in presence of peptone. The results show that in each case the solutions gradually become acid. A study was also made of the combined effect of bacteria and enzymes on the solution. It was found that when the liquids containing diastase or pancreatin were treated with cultures of bacteria taken from ths mouths of persons having severe tooth erosion and were kept at 3 7 O a larger amount of acid was produced than in the absence of the bacteria. It is shown that solutions rendered acid by the action of enzymes readily dissolve cements employed for tooth fillings. It is concluded that the abnormal increase in the acidity of the saliva of persons suffering from tooth erosion is probably due to the action of enzymes on certain constituents of the saliva.E. G. Normal Urine. OTTO FOLIN (Amer. J. Physiol. 1905 13 45-65 66-1 15).-The tables giving the composition of normal184 ABSTRACTS OF CHEMlCAL PAPERS. urine in most text-books are derived from the old analyses of Parkes and thus date from a time before the introduction of the Kjeldahl method and before the importance of the estimation of total nitrogen was recognised. Bunge calls attention to the fact that in the voluminous literature on the urine there is still no record of the complete analysis of any one concrete sample of a normal 24 hours’ urine. Hopkins points out the importance of the urinary analysis being considered in relation to the diet.The first of the present papers aims at re- pairing this gap in statistics the second deals with the laws governing the composition of normal urine. Complete analyses are presented of thirty urines from six normal persons all kept for seven days on a uniform diet; the urine in each case was analysed for the last five days only of the period. The diet contained 119 grams of proteid 148 of fat and 225 of carbohydrate that is it approximates to the old Voit standard. The estimahions made mere of total nitrogen urea ammonia creatinine uric acid chlorides phosphates total sulphur sulphates of both kinds ‘‘ neutral sulphur,” indican total acidity and mineral acidity. The final averages for the 24 hours’ urine are as follows Volume of urine ...Total nitrogen ... Urea ... ... ... Urea nitrogen . . Ammonia nitrogen ... Creatinine ... ... Creatinine nitrogen ... Uric acid ... ... Uric acid nitrogen I -. Undetermined nitrogen ... ... 1430 C.C. ... ... 16 grams. ... ... 29.8 ... ... 13.9 ... ... 0.7 9 7 ... ... 1.56 ... ... 0.58 ... ... 0.37 ... ... 0.12 ... ... 0.60 The following are the results in percentages of total nitrogen urea 87.5 ; ammonia 4.3 ; urea and ammonia 91.8 ; creatinine 3-6 ; uric acid 0.8 ; undetermined 3.75. The results regarding non-nitrogenous constituents are Total sulphur as SO ... ... Inorganic SO .. ... ... Ethereal SO3 ... ... ... ‘‘ Neutral ” SO,. . ... -.. Acidity ... ... ... ... Mineral acidity . . ... ... Organic acidity . . ... ... Total phosphates.. . ... ...Chlorine ... ... ... ... Indican (Fehling’s solution = 100) 3‘31 grams. 2.92 0.22 0.17 617 C.C. of N/10 solution. 304 9 313 9 9 3.87 grams P,O,. 6.1 grams 77 The average weight of the people investigated mas 63.4 kilos. The numbers correspond very well to what has hitherto been con- sidered normal. The question next arises what should be considered normal’? The foregoing can only be considered normal on the basis of Voit’s normal diet.PHYSIOLOGICAL CHEMISTRY. 185 But there are races of mankind who take a very different diet and yet are normal There are individuals like vegetarians and those who for various reasons have reduced their diet particularly so far as proteid is concerned much below the Voit standard; they remain normal but their urine has a very different composition.The urine of one such person gave total nitrogen 4 to 8 grams ; urea nitrogen 62 to 80 ; ammonia nitrogen 4.2 t o 11.7 ; creatinine nitrogen 5.5 to 11.1 ; uric acid nitrogen 1.2 t o 2.4; undetermined 4.8 to 14.6 per cent of total nitrogen. The wide variations were due to temporary changes in the diet but the low urea value and the higher values of the other nitrogenous constituents would more accurately represent the usual condition on the subject’s usual diet. What is particularly noticeable in such persons is the comparatively low value of the urea nitrogen and the first law laid down is that the distribution of the nitrogen depends on the absolute amount of total nitrogen present. There are similar differences in the distribution of the sulphur and a similar rule is laid down.The amount of creatinine is specially interesting ; on a nitrogen-rich diet i t only accounts for 3.6 per cent. of the nitrogen whereas on a diet poor in nitrogen the urea nitrogen may sink to 62 per cent. and the creatinine nitrogen rise to 11 per cent. of the total. The absolute quantity of creatinine excreted in the same person on both diets is the same; there are individualdifferences between different people ; corpulent people excrete less than thin people. Creatinine excretion is an index of one kind of proteid metabolism and demands further study. Burinn and Schur reached a very similar con- clusion regarding endogenous purine. The conclusion drawn from the present work regarding uric acid is that the excretion of this substance in reduced proteid metabolism is diminished but not nearly in pro- portion to the total nitrogen hence the percentage of uric acid nitrogen is increased. A clear line of division between endogenous and exogenous purine as postulated by Burian and Schur was not wholly confirmed in the present work.With regard to ammonia the following general conclusion is drawn a pronounced reduction of the total nitrogen is accompanied by a relative rise in ammonia nitrogen provided the food is not such as to yield an alkaline ash ; and further the absolute quantity of undetermined nitrogen increases under the influence of a diet poor in nitrogen but there is a relative increase. The only nitrogenous substance which suffers a relative as well as an absolute decrease with nitrogen-poor food is urea ; the percentage of urea-nitrogen in normal human urine as well as in nearly all pathological urine is often reduced to 60 per cent.of the total. A further reduction is probably abnormal although that is still unsettled. Urinary indican is an approximate measure of intestinal putrefac- tion; the ethereal sulphates are not so being only partly produced in this way ; they represent a form of sulphur metabolism which becomes more prominent when the food contains but little proteid ; the neutral sulphur is not at all due to processes similar to those which give rise to indican but is in the main independent of the total sulphur and of katabolised proteid. Accurate sulphur determinations are how- ever at present beset with errors of technique.The volume of urine depends directly on the amount of water taken186 ABSTRACTS OF CHEMlCAL PAPERS. in ; variations not due to variations of intake are related to the reci- procal action of the skin. Provided the chloride intake is constant the chlorine elimination varies with the volume of the urine. The phosphates in clear acid urine are all monobasic ; the acidity is ordinarily greater than the acidity of all the phosphates the excess being due to free organic acicls ; the mineral acidity decreases and often is a minus quantity on a proteid-poor diet. The organic acids do not diminish so much. W. D. H. Urine of the Coyote. ROBERT E. SWAIN (Amer. J. Physiol. 1905 13 30-34).-Kynurenic acid has hitherto been found only in dog’s urine; i t is absent even i u the fox and wolf. It is however present in the urine of the coyote an animal closely related to the dog and inhabiting the arid districts of N.W.America. The total nitrogen is 36.4 grams per litre most of which is present as urea. The amount of kynurenic acid is 0.4 gram per litre. A crystalline deposit found in the urine was analysed and the formula assigned to it. Jaff e’s urocanic acid has the formula C12H120,N,,4H,0. Further investigation of this new material is promised. C12H904N4,4H20 W. D. H. Acidity of Urine. HEINRICH DRESER (Beitr. chenz. physiol. path. 1905 6 178-190).-What is termed the intensity of acidity is regarded as an important factor in the therapeutic action of urinary disinfectants such as camphoric and salicylic acids. I n acid human urine the acidity obtained by titration with alkali is often twice or thrice as great as that reckoned from the amount of acid phosphate.The urinary acidity cannot therefore depend on a mixture of primary and secondary alkali phosphates W. D. H. Elimination of Creatinine. LAFAYETTE B. MENDEL and OLIVER E. CLOSSON (Proc. Amer. Pluysiol. Xoc. 1904 xix-xx ; Amer. J. Physiol. 13).-Data on this question are meagre and conflicting. There is a noteworthy excretion of this substance in vegetarians and those on a low proteid diet. On a creatine-free diet there is a tendency t o parallelism between total nitrogen output and the excretion of creatinine. W. D. H. Urea in Human Urine. WILLIAM CAMERER (Zeit. Biol. 1905 Compare Abstr. 1903 ii 688).-A critical analysis 46 322-370.of methods and results. W. D. H. Bence-Jones Proteid. LUGWIG L~NDEMANN (Chem. Centr. 1905 i 269-270; from Arch. klin. Ned. 81 114-118).-A case in which this proteid occurred in the urine is described. Its characters resemble those described by others in the main. It is regarded as an albumose. W. D. H. Behaviour of p-Dimethylsminobenzaldehyde in Animal Metabolism. MAX JAFFE (Zeit. physiol. Chem. 1905 43 374-396). -p-Dimethylaminobenzaldehyde dissolved in hydrochloric acid is aPHYSIOLOGICAL CHEMISTRY. 187 reagent which gives a red colour with normal urine; this reaction is increased in certain pathological cases mainly of abdominal disease. What substance in urine gives the colour is uncertain. If the drug itself is given t o rabbits it is excreted mainly in combination with glycuronic acid but among other substances found also in the urine are p-dimethylarninobenzoic acid and p-methylaminobenzoic acid.W. D. H. Pigments originating from Scatole and the Scatoxyl Question. CH. PORCHER and CH. HERVIEUX (J. Pharnz. Chinz. 1905 [ vi] 21 55-65. Compare Abstr. 1904 [ ii] 577).-The chromogen appearing in the urine after administration of scatole on a milk diet is in the authors' opinion a derivative of a scatoxyl probably C,H,< >GO. It is not as supposed by Maillard indirubin. The colour due to scatole differs from those due to indole in its insolubility in chloroform and further it is withdrawn by dilute alkali from the amyl alcohol solution being reproduced on acidification. CHMe NH G. D. L. Diabetes Mellitus.GRAHAM LUSK and ARTHUR R. MANDEL (J. Arner. Mecl. ASSOC. July 1904; Deut. ArcJ~iv. klin. Med. 1904 81 472-492).-A rapidly fatal case of diabetes is recorded. There was low acidosis and a trace of albumin in the urine; on a meat diet the dextrose nitrogen ratio was 3.65 1. This is the same as in phloridzin diabetes in dogs and was unaltered by fat digestion or fat metabolism. The sugar was derived from proteid alone. There was complete intolerance for carbohydrates ; 85 per cent. of starch and SO per cent. of Izevulose given being excreted as sugar in the urine. Withdrawal of carbohydrate food had no effect on urinary nitrogen. Urea elimination was normal. The significance of the 3.65 1 ratio in a meat diet is very great. It indicatis a rapidly fatal result.W. D. H. Experimental Diabetes. FRANK P. UNDERHILL (Pvoc. Arner. Physiol. SOC. 1904 xxxvi ; Amer. J. P?Aysiol. 13).-Piperidine causes diabetes and hyperglyczmia if painted on the pancreas intraperito- neally or intravascularly injected. This substance and a number of others including narcotics various alkaloids and possibly adrenaline appear to have no particular influence on the pancreas but probably act on the respiratory centre producing dyspnea and thus a diabetic condition secondarily. W. D. H. Soaps in Certain Pathological Conditions. OSKAR KLOTZ (Proc. Arner. Physiol. Xoc. 1904 xxi-xxii ; Amer. J. Physiol. 13).- I n certain calcareous deposits the centre is composed of calcium salts ; the periphery contains potassium sodium and ammonium soaps. As degeneration continues these are converted into calcium soaps and finally into calcium phosphate and carbonate.Soaps may also be demonstrated in pus and a calcium soap is formed during fat necrosis. W. D. H.188 ABSTRACTS OF CHEMlCAL PAPERS. Behaviour of Guanine in the Rabbit. ALFRED SCHITTENHELM and ERNST BENDIX (Zeit. physiol. Chem. 1905 43 365-373).-Intra- venous or subcutaneous injection of guanine dissolved in sodium hydroxide leads in rabbits to a great increase of purine substances especially uric acid in the urine. W. D. H. Action of Urotropin and Allied Compounds. ARTHUR NICOLAIER (Chem. Centr. 1905 i 283-284 ; from Arch. klin. Med. 81 181-223).-The use of urotropin and a number of similar compounds in the treatment of bacterial invasion of the urinary passages is attributed t o the fact that in decomposition these substances yield formaldehyde. Urotropin methylenecitrate yields by heating much more formaldehyde than urotropin but has no stronger effect on the urine than urotropin itself. This compound owes its therapeutic effect only to the urobropin it contains. Formaldehyde is also a solvent of uric acid. W. D. H. Ricin. TIXOMAS B. OSBORNE and LAFAYETTE B. MENDEL (Proc. Amer. Pl~piol. SOC. 1‘304 xxxii ; Amer. J. l’hpiol. 13).-The castor- bean proteids were fractionated by neutral salts into portions with great and slight toxicity and ricin was prepared in rz pure form-. The toxic preparations sediment red corpuscles ; this property is lost when the proteid is heated to coagulation point Pure ricin can be kept for months without deterioration. After administration toxic symptoms do not occur until after a latent period of 15 hours. The toxicity is enormously diminished if ricin is given by the alimentary canal. ” W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9058805178

出版商:RSC    

年代:1905

数据来源: RSC