chlorides, and determination of the platinum therein; the formation of the secondary amines was also proved by Liebermann's colour reaction. V. H. V.

11

Etherification by Double Decomposition. New Ethereal Salts of Nitrous Acid. By G. BERTONI (Chem. Centr., 1887, 35— 36; compare Abstracts, 1886, 217 and 975).-Tertiary amyl nitrite, CHO·ÑO, is prepared by shaking together at the ordinary temperature tertiary amyl alcohol (3 mols.) with glyceryl trinitrite (1 mol.), and occasionally adding a lump of ice. The liquid separates into two layers, the upper of which is the ethereal salt. This is washed with very dilute aqueous soda, then with water, finally dried over fused calcium nitrate, and fractionally distilled. It is a mobile, slightly yellow, pleasant smelling liquid, boiling at 92-93°, sp. gr. at 0° 09033, very slightly soluble in water, easily soluble in amyl alcohol, ether, chloroform, benzene, &c., decomposed by methyl and ethyl alcohol with formation of methyl and ethyl nitrites. When inspired, it does not give the same symptoms as ordinary amyl nitrite. It is violently decomposed by strong sulphuric acid, and reduced by ammonium sulphide and hydrogen sulphide, with separation of sulphur; it is saponified by alkalis.

2

a-Propylene dinitrite, ON O.CH, CHMe O.NO, is prepared in the same way as the preceding compound by heating a mixture of a-propylene glycol and glyceryl trinitrite on the water-bath. It is a yellowish, very mobile liquid, of suffocating odour, boiling at 108-110°, sp. gr. at 0° = 1144, insoluble in water, soluble in ether, chloroform, benzene, &c., slowly decomposed by water, quickly by methyl and ethyl alcohol, it is dissolved by cold and decomposed by hot acetic acid; dilute sulphuric acid decomposes it. When exposed to sunlight in a closed vessel, it explodes violently.

Secondary octyl nitrite, Č ̧HO·NO, is prepared by treating secondary octyl alcohol (3 mols.) with glyceryl trinitrite (1 mol.) at the ordinary temperature, and proceeding as above. It is a dark yellow, mobile liquid, boiling at 165-166°, sp. gr. at 0° 0.881, insoluble in water, soluble in the alcohols, and decomposed by the lower members, also soluble in ether, chloroform, benzene, &c. When acted on by acids, it is decomposed in the same way as the preceding compounds.

=

The author finds that the physiological actions of these nitrites and also of allyl nitrite (Abstr., 1886, 218) is not different from that of other ethereal nitrites. The poisonous properties of these nitrites increase on the one hand with the percentage of NO2, and on the other with their decomposibility; they stand in the following order: a-propylene, allyl, tertiary amyl, secondary octyl nitrite.

G. H. M.

Phosphoplatinous Chloride. By E. РOMEY (Compt. rend., 104, 364).-Phosphoplatinous chloride dissolves readily in propyl alcohol, with subsequent development of heat and evolution of hydrogen chloride. On adding water to the liquid, a yellow, crystalline precipitate of the compound P(C,H,O),PtCl, is obtained. It can be recrystallised from alcohol. C. H. B.

Formose. By O. LOEW (Ber., 20, 141-144).-The author discusses the properties of formose and its analogy with levulose, and considers it to be a sugar (compare Tollens, Ber., 19, 2134).

Reaction for Fruit-sugar. By T. SELIWANOFF (Ber., 20, 181182). A cold aqueous solution of cane-sugar (2 parts) and resorcinol (1 part) is treated with concentrated hydrochloric acid and quickly warmed. The mixture becomes red, and deposits on cooling an abundant dark precipitate. The latter is amorphous, and is soluble in alcohol. Fruit-sugar and raffinose give the reaction. Dextrose, galactose, maltose, milk-sugar, and inosite gave no coloration.

Levulinic acid gives Baeyer's aldehyde reaction with phenol. adding an alkali to the alcoholic solution of the red condensation product, it becomes first blue, then green, and finally yellowish-grey. When an alcoholic solution of levulinic acid and resorcinol is treated with fuming hydrochloric acid, and water added, the solution gives a white, resinous precipitate, analogous to those obtained by Michael (Abstr., 1884, 597) by the condensation of aldehydes with resorcinol. It becomes red when exposed to air. Quinones and pyruvic acid give the same reaction (compare also Chem. Zeit., 9, 231).

N. H. M.

Inosite. By MACQUENNE (Compt. rend., 104, 297-299).-Inosite heated at 170° for several hours with 15 times its weight of hydriodic acid of sp. gr. 1-85, yields a small quantity of benzene, together with triidophenol, a result which confirms the constitution previously attributed to inosite (this vol., p. 355). Zinc powder yields no definite products, and sodium amalgam exerts no reducing action.

Chromic acid oxidises inosite in the cold, with formation of formic acid and evolution of some carbonic anhydride. Potassium permanganate in neutral or alkaline solution oxidises it to carbonic anhydride. The halogens have no action in presence of water in the cold, but bromine and water at 100° yield the brown products previously described (loc. cit.).

Boiling dilute nitric acid has no action on inosite, but the concentrated acid attacks it regularly at 100° with formation of oxalic acid, but if the reaction is conducted in an open dish on a water-bath, no oxalic acid is formed, and if the liquid is evaporated to dryness, it leaves a white residue which dissolves in water with effervescence, forming a solution of tetrahydroxyquinone, CO2(OH), which may be precipitated in the form of the barium compound C.O2(OH)2O,Ba. In presence of air and a slight excess of alkali, tetrahydroxyquinone rapidly alters to dihydroxydiquinone, a very unstable substance which yields with barium salts an eosin-coloured precipitate, CO,Ba.

If the solution of the products of the action of nitric acid is mixed with an excess of sodium carbonate and a small quantity of alcohol, it deposits a greenish-black crystalline powder, which contains the disodium compounds of tetrahydroxyquinone and dihydroxydiquinone. If this mixture is decomposed by hydrochloric acid, and the product recrystallised from boiling alcohol, it yields tetrahydroxyquinone which may be purified by washing with water. When the tetrahydroxyquinone is treated with cold concentrated nitric acid, heat is

developed, nitrogen oxides are evolved, and the hydrated triquinone, CO + 8H2O, described by Nietzki and Benckiser, is obtained as a white crystalline powder; this may be reconverted into tetrahydroxyquinone by suspending it in water, and passing a current of sulphurous anhydride into the liquid. If the triquinone is heated with water it becomes yellow, and if the liquid is evaporated after neutralising with potash, potassium croconate, C,O,K2 + 2H2O, is obtained in beautiful crystals, which are also formed when a current of air is passed into an alkaline solution of tetrahydroxyquinone or rhodizonic acid.

Inosite, in fact, yields the same products of oxidation as those which have been obtained by Nietzki and Benckiser by the oxidation of hexahydroxybenzene, a result which establishes the constitution ascribed to inosite by the author in his previous paper (loc. cit.).

C. H. B. Dry Distillation of Starch with Lime. By V. HORVAT (Chem. Centr., 1887, 38-39).—The substances were used in the proportion of 14. The products found were acetone, mesityl oxide, isophorone, boiling at 207°, and identical with that obtained by heating acetone with lime or soda, and isomeric with the phorone from acetone and hydrochloric acid. The fraction boiling between 128° and 207° consisted of a series of ketones of the formula C,H2O, and that boiling above 207° of still higher condensation products of acetone than isophorone. The latter did not yield adipic acid when oxidised.

G. H. M. True Nature of Nägeli's Starch-cellulose. By A. MAYER (Chem. Centr., 1887, 6).-When starch-granules are treated with saliva or dilute acids, delicate skeletons always remain behind, and from Nägeli's researches have hitherto been considered to consist of cellulose. The starch-granule, therefore, appeared to be composed of an intimate mixture of two substances, cellulose, and a substance which Nägeli called granulose. Mayer now states that these skeletons do not consist of a substance which is contained in intact starchgranules, but are really a conversion product formed by the action of the acids or ferment employed, and are identical with amylodextrin. The use of the terms starch-cellulose and granulose must, therefore, be abandoned, and the homogeneous substance of the starch-granule be simply called starch-substance. G. H. M.

Paragalactin. By E. SCHULZE and E. STEIGER (Ber., 20, 290-294). When finely-powdered seeds of Lupinus luteus, after removal of the fat by ether, are treated with cold, very dilute aqueous potash, both the constituents soluble in water and the albuminoids are removed; the residue is somewhat gelatinous, and contains in a very impure state the substance which the authors term paragalactin. This substance could not be obtained in a state of purity, as no solvent could be found for it which did not cause alteration. seems to form 25 per cent. of the seed, and is probably a carbohydrate of the formula C.H10O5; when heated with dilute acids, it is converted into galactose, no other sugar being formed. It is not dissolved by heating with water under pressure, nor is it converted into a sugar

It

by diastase. By the action of tartaric acid, or of hot 10 per cent. aqueous potash, solutions are obtained from which, on addition of alcohol, white gelatinous substances separate; these, however, would seem to be decomposition products. An acetyl-derivative prepared from the substance obtained by the last method, gave numbers agreeing with the formula C.H,O,Aс ̧, and began to decompose at 225° without previous fusion. A. J. G.

Trimethylpropylammonium Iodide and Hydroxide. By T. LANGELI (Gazzetta, 16, 385-389).-When propylamine and methyl iodide, preferably diluted with alcohol, are heated together, trimethylpropylammonium iodide is formed, together with propylmethylamine and propylamine hydroiodides, thus: 4PrNH, +4MeI = PrMe,NI + NHPrMe, HI + 2NH2Pr‚HI. The first of these salts crystallises in long needles melting at 190°; the corresponding chloride forms a crystalline mass, and the platinochloride, (NMe, Pr)2,PtCl, a yellow crystalline precipitate. Trimethylpropylammmonium hydroxide decomposes on distillation into propylene and trimethylamine, thus: CH2Me CH2 N Me, OH = CH(CH): CH2+ NMes + OH2.

V. H. V. Salts of Diisobutylamine and Triisobutylamine. By H. MALBOT (Compt. rend., 104, 366-369).-Diisobutyl hydrochloride, N(C,H,),H,HCl, is easily obtained in a state of purity, and forms plates or leaflets with a greasy lustre, the transparence and aggregation of the crystals depending on the nature of the solvent. It is somewhat easily soluble in alcohol and in water, slightly soluble in isobutyl alcohol, and only very slightly soluble in ether. It sublimes somewhat rapidly at 240°, and if maintained for some time at 262° it melts partially, and sublimes completely with slight blackening and evolution of isobutylamine. If heated rapidly to a temperature somewhat higher than its melting point, it melts easily without sensible decomposition.

Diisobutyl platinochloride, 2N(C,H,),H,H,PtCl, is obtained in long, dark-red channelled prisms by mixing a concentrated solution of platinic chloride with a saturated solution of diisobutylamine hydre. chloride and allowing the liquid to stand.

The hydro

Triisobutylamine platinochloride, 2N(C,H,),,H,PtCl. chloride is first prepared by the action of concentrated hydrochloric acid on the amine, but combination takes place very slowly. The liquid is then evaporated to a syrup, taken up with a little ethyl alcohol, and mixed with concentrated platinic chloride solution. A precipitate of small orange prisms forms immediately, and if the liquid is filtered after 24 hours it gradually deposits large, ruby-coloured crystals with very brilliant facets.

The differences in crystalline form between the platinochloride of diisobutylamine and triisobutylamine are so well marked that the two compounds can readily be separated mechanically after they have been crystallised together from a mixture. C. H. B.

Isobutaldehyde and its Polymeric Modification. By G. A. BARBAGLIA (Gazzetta, 16, 430-437).-Isobutaldehyde is readily polymerised by adding to it a small quantity of iodine, the mixture being

kept cool. The rapidity of the conversion is dependent on the quantity of iodine, the lowering of the temperature, and the purity of the aldehyde; a slight variation in the conditions makes a considerable difference in the time required for the change. Even under the most favourable conditions, however, the conversion is never complete. It is difficult to explain the peculiar function of the iodine, and the author classifies the phenomenon among the so-called "catalytic changes." As regards its nature, the trimolecular or polymeric modification of the isobutaldehyde differs from the simpler or monomolecular form, in that the latter is characterised by its susceptibility to chemical change as evidenced by its oxidisability, its combination with ammonia and the alkaline hydrogen sulphites, and its conversion into the isothiobutaldehyde and isobutyric acid, whereas the former is unaltered by oxidising agents, as also by ammonia and the alkaline bisulphites, and is not readily altered by sulphur.

The polymeric modification crystallises in glistening prisms melting at 59.5° with partial sublimation, it boils at 195.2° (at 752 mm.) with but slight alteration. If heated for some time in a sealed tube at 150°, it is partially reconverted into isobutaldehyde.

Isobutaldehyde, even of a high degree of purity, becomes polymerised spontaneously after a time.

V. H. V.

Action of Sulphur on Aldehydes. By G. A. BARBAGLIA (Gazzetta, 16, 426-430).-In the course of the preparation of thiovaleraldehyde from sulphur and valeraldehyde (Abstr., 1881, 34), the author observed the formation of a substance which crystallises in slender prisms, melts at 945°, and is insoluble in water, very soluble in alcohol and ether. More recent analytical results indicate that this compound is a trithiovaleraldehyde, C,H&S,; this might be formed as follows: CH10S + 2S2 = C2H ̧Š1 + 2H,S; the compound having the structural formula

CH2 CH CH⚫CH.CHS.

If this interpretation were correct, hydrogen sulphide would be evolved in the second phase of the reaction, that between thiovaleraldehyde and sulphur; this was found to occur when the two were heated at bont 200° in sealed tubes for several days, but the product did not yield trithiovaleraldehyde in the crystalline state, and the analytical results were unsatisfactory.

V. H. V.

Compounds of Aldehydes and Ketones with Mercaptans. By H. FASBENDER (Ber., 20, 460-465).-Ethylene mercaptan combines with pyruvic acid and aldehydes with evolution of heat; at first an additive product is formed, which is decomposed by water into its constituents. If hydrogen chloride is passed into an equimolecular mixture of benzaldehyde and ethylene mercaptan, benzylidene ethylene bisulphide is obtained which melts at 29°; it is insoluble in water, soluble in alcohol and ether. When treated with bromine in chloroform solution, it is converted to diethylene tetrasulphide, CH, S.S.CH, CH2'S SCH2 ">