0 Rg Anic C H Ern Is T

View Article Online / Journal Homepage / Table of Contents for this issue 473 0 rg anic C h ern ist rg, isaHexane and a New Dodecane. LATHAMCLARKE and R. NOHRISSHREVE (Amer. Chem. S., 1906, 35, 513-519).-iso- Hexane (ethylisobutyl) can be prepared in a yield of 57 per cent. of the theoretical by the reduction of methylisobutylcarbinol. Methyl isobutyl ketone, prepared by boiling ethyl isopropylacetoacetate for six hours with 10 per cent. potassium hydroxide, boils at 119' under 765 mm. pressure. Methylisobutylcarbinol can be obtained by mixing an ethereal solution of the ketone with water and gradually adding sodium ; a small quantity of naethylisobutylpincccone, CH,PrP*CMe(0H) *CMe(OH)*CH,Pr@, is produced simultaneously its a viscous, oily liquid which has a fishy odour, boils at 245', and is soluble in alcohol, ether, ethyl acetate, acetone, benzene, or glacial acetic acid, and insoluble in water. On reducing this pinacone with hydrogen iodide, methylisobietylcarbinyl iodide, CHMe,*CH,*CHMeI, is obtained as n colourless, oily liquid which boils and partially decomposes at 158-160', and is soluble in the usual organic solvents, but insoluble in water. The formation of this iodide is attended by the production of a small quantity of a dodecane (dirnethyldiisobutylethane), CH,PrP*CHMe.CHRIIe.CH2Pr@,which forms R colourless, oily liquid with a faint odour, boils at 208-210', and is soluble in light petroleum, and slightly so in alcohol. E. G. Hexamethylethane. LOUISHENRY (Con@. rend., 1906, 142, 1075 -1076).--Hexamet/~y Zethane (@y y-tetr~metAyZb~cta?ze), Published on 01 January 1906. Downloaded 28/10/2014 17:37:31. CRle,*CMe,, is an accessory product in the synthesis of pinacolyl alcohol by the interaction of acetaldehyde and magnesium tert.-butyl bromide. It crystallises from ether in barbed lamellae, has a piquant, penetrating odour, melts at 103--104','and boils at 106-10i' under 765 mm. pressure. T. A. H. Composition of Light Petroleum. LUIGIBALBIANO and VINCENZOPAOLINI (Gaxxetta, 1906, 36,i, 251 --236. Compare Abstr., 1902, ii, 109).-Fourteen kilos. of American petroleum gave 3.5 grams of mercurous acetate when treated with mercuric acetate, whilst acetone and propaldehyde were found in the solution. These may have been formed by oxidation of P-methyl-4p-pentylene. T. H, P. New Constituents of Coal Tar. FELIX B. AHRENS (Chem. Cent?.., 1906, i, 510-511 ; from Ye&. Ges. Beut. LVuturforsch. Aerxte, 1904, ii, 137-138. Compare Abstr., 1903, i, 515 ; 1904, i, 615 ; 1905, i, 232)-In a fraction from the benzene receiver which boiled at 20--30°, butylene and a compound which contained sulphur and resembled carbon disulphide, but was not identical with it, have VOL. XC. i. k /I View Article Online 474 ABSTRACTS OF CHEMICAL PAPERS. been found. Amylene was isolated from a fraction boiling at 30-40'. 2 :3-Dimethylpyridine has been obtained from a commercial sample of ap-picoline; it boiled at 162-163' and yielded a picrate which melted at 183O and was almost insoluble in alcohol or water. E. W. W. Decomposition of Bromoform under the Influence of Light and Air. NICOLAASSCHOORL and L. M. VAN DEN BERG (Chem. Centr., 1906, i, 441-442 ; from Pharm. WeekbEad, 43, 2-8. Compare this vol., i, 57).-When a current of air is passed through boiling bromoform in sunlight, bromine, bydrogen bromide, and carbon tetrabromide are produced. The primary reactions have already teen investigated in the case of chloroform and iodoform. By the action of light in the presence of oxygen, carbon monoxide is oxidised to the dioxide, hydrogen bromide forms water and bromine, and by the action of the latter on bromoform, carbon tetrabromide and hydrogen bromine are obtained. When bromoform, together with a small quantity of oxygen, is exposed to sunlight in sealed tubes, the action appears to result in the formation of carbon monoxide (1 mol.), bromine (1 rnol.), and hydrogen bromide (1 mol.) ; when a large quantity of oxygen is present, carbon dioxide (2 mols.), water (1 mol.), and bromine (3 mols.) are formed. Carbon oxybromide is an intermediate product. When bromoform is exposed to sunlight in tubes from which the air has been almost completely removed, carbon monoxide and hydrogen bromide are obtained in the proportion of 13.7 to 47 l/lO-equivalents ; this result is con- sistent with the hypothesis that the bromoform is decomposed into carbon dibromide and hydrogen bromide, and that the former is decomposed by the water in the wash-bottles, forming carbon monoxide Published on 01 January 1906. Downloaded 28/10/2014 17:37:31. and hydrogen bromide. In addition to these products, 12 l/l0-equivalents of bromine are also liberated. The liberation of bromine must be assumed to result from the intermediate formation of some other carbon hydrogen bromine compound, possibly of symmetrical tetra- bromoethane, CHBr,,CHBr,, and the decrease of sp. gr. of the contents of the tube from 2.882 to 2.872 at 19' may be an indication of this change. The presence of carbon tetrabromide could not be detected in this case. E. W. W. Comparison of the Decomposition of Chloroform, Bromo- form, and Iodoform under the Influence of Light NICOLAAS SCHOORLand L. M. VAN DEN BERQ(Chem. Centr., 1906, i, 442 ; from Phurm. Teekblud, 43, 8-10. Compare preceding abstract).-Experi- ments on the action of light alone on chloroform, bromoform, and iodoform have shown that whilst chloroform is not affected, iodoform is partially decomposed in consequence of the presence of traces of air, and bromoform is decomposed spontaneously, probably forming carbon dibromide and hydrogen bromide. By the action of air in the absence of sunlight at higher temperatures, iodoform becomes violet in a quarter of an hour, and the separation of iodine is dis- tinctly visible in an hour; bromoform becomes acid and slightly yellow View Article Online ORGANIC CHEMISTRY. 475 in an hour, and gives a precipitate with silver nitrate, whilst chloroform does not give any reaction with silver nitrate after four hours. E. W. W. Decomposition of Iodoform dissolved in Chloroform by Diffused Daylight and by Radium Rays. WILLEMP. JORtSSEN and WILHELME. RINGER(C1m-n. Centr., 1906, i, 442; from Chem. Week- blud, 2, 799-802. Compare preceding abstracts).-When a solution of iodoform in chloroform is exposed to diffused sunlight in the presence of oxygen, it appears to be completely decomposed. A solution of iodoform in carbon disulphide covered with water does not show any change for some time, and then decomposes only very slowly. A solution of iodoform in chloroform frozen by means of liquid air is not affected by bright daylight so long as it remains solid. By the action of 5 mg. of radium bromide on 50 C.C. of a 1 per cent. solution of iodoform in chloroform at 25", 75.3 per cent. of the iodine was liberated, whilst in a similar solution which was not exposed to the action of radium bromide only 18.8 per cent. of the iodine was found in a free state. The colour of the iodine solution formed by the action of the radium bromide was not so dark as that of similar solutions obtained by the action of daylight. E. W. W. Abnormality in Melting Points of Amides derived from Aliphatic Sulphonic Acids, MAURICEDUQUET (Bull. Acnd. roy. Belg., 19 06, 87-1 20).-is0 Propanesulphonic chloride, CHMe,*SO,Cl, prepared from phosphorus pentachlor ide and the corresponding alkali sulphonate, boils at 79" under 18 mm. pressure. Its solution in ether on treatment with dry ammonia yields the corresponding sulphonamide, which crystallises from ether on addition of light petroleum and melts at 60". is0 Pro~cLnesulphonnn~l~~ecrystallises from a mixture of Published on 01 January 1906. Downloaded 28/10/2014 17:37:31. alcohol and water in colourless, pearly leaflets and melts at 84' isoPropunesu~l~on-a-na~)l~tl~~lu?,zidecrystallises from a mixture of alcohol and water in slender needles and melts at 134". Butane- sulphonic chloride is a mobile, highly-refractive liquid, and boils at 96-97' under 18 mm. pressure. Butaneszclphonamide crystallises from a mixture of ether and light petroloum in silkyleaflets and melts at 45". The corresponding anilide melts between -10' and -15' and the a-ncq.&thyZamide iii colourless spangles melting at 60.5". n/rethasaesuI~hon-a-nuphthyZamidecrystallises in slender, silky needles and melts at 125-1 26'. _Ft~~ccieesulpho?~-a-nc~phthylanzideforms long, colourless prisms and melts at 6 6". Propunesulphon-a-naphthylawtide melts at 84O. isoButanesulphon-a-naphthylanaidecrystallises in colourless spangles and melts at 107'. isoPentanesulphon-a-nuphth?jlamide forms colourless, pearly spangles and melts at 90-91'. The melting points of the series of amides, anilides, and a-naphthylamides described in this and the former paper (Abstr., 1902, i, 428) decrease irregularly as each series is ascended; further, whilst the melting-point curve of the amides of the iso-acids is below that of the amides of the normal acids, the reverse is true of the curves for the anilides and a-naphthylamides of the iso- and normal acids. Similar examples of the fall in melting point as the series are ascended are shown kk2 View Article Online 476 ABSTRACTS OF CHEMICAL PAPERS. by the aromatic sulphonamides (Abstr., 1900, i, 147) and the halogen and other derivatives of these described by Chattaway (Trans., 1905, 87, 145). Determinations of the molecular weights of the lower members of the series of compounds now described indicate that in dilute solutions they are not polymerised, but it is not certain that their high melting points are not the result of polymerisation in the solid state.

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