Journal of the Chemical Society 1908/I. [antikvár]

JOURNAL op THE CHEMICAL SOCIETY. '. I J- ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. PART I. Organic Chemistry. The Development of Organic Chemistry in the Last Forty Years. Carl Geaebe (Ber., 1907, 40, 4638—4644).—A lecture delivered before the German Chemical Society. W. H. G. Fractional Distillation of Higher Normal Paraffins from Lignite in the Vacuum of the Cathode Light. Feiedrtch Krafft {Ber., 1907, 40, 4779—4784).—An examination of a Saxon paraffin wax of a complicated character. The apparatus used consists essentially of a small flask for distillation provided with a long neck in which the thermometer bulb can be immers.^d in the liquid or vapour at will; for details, the original should be consulted. The first fractionation of 450 grams resulted in the collection of five fractions, and each fraction was carefully redistilled. After repeated fractionation, the following eighteen hydrocarbons were isolated and their molecular weights by the boiling-point method determined. B. p., 0 ram. M. p. D liquid. C1SH40 Nonadeoane 109-0° 31-8—32-0° — C2„H42 Icosane 117-5 36-3—36-6 0-7775 C2iH44 Heneioosane 125-5 39-9—402 0-7778 C52H45 Docosane 130-5 44-0—44-5 0 7776 CogHis Tricosane 138-0 47-2—47-5 0-7799 C!4H5o Tetraoosane 145-5 50-7—51-3 0 77.31 C25H52 Pentacosane 152-5 53-8—54 0-7785 CajHsi He.xacosane 160 56-8—57 0-7787 CjiHje Heptaoosane 167 about 59-4 0-7789 CjsHss Octacosane 173-5 „ 61-6 0-7792 CjgHeo Nonacosane 179 63-6-6Í-1 0-7797 C30H62 Triacontane 186 65-6 0 7797 C31H54 Hentriacontane 193-5 68-4 0-7799 C32H88 Dotriacontane 201 69-8 0-7798 CajHgg Tritriaeontane 208 71-8 0'7801 CsjHjo Tetratriacontane 215 about 73 0-7806 C3bH,2 Pentatriacontane 222 „ 74 0 7813 CaoH,^ Hexatriaoontane about 230 „ 76 0-7819 VOL. XCIV. i, ^ 2 ABSTRACTS OF CHEMICAL PAPERS. There is a series of still higher homologues present in this paraffin, b. p. 250—29070 mm., and a portion boiling above 300°, the hydrocarbons of which must contain at least fifty carbon atoms. W. R. Electro-Syntheses [with Ethylene and Acetylene]. Sima M. Losanitsch {Ber., 1907, 40, 4656—4666).—See this vol., ii, 32. Isomeric Change of isoButyl Alcohol BflFected by Nitrous Acid. Louis Henry {Gompt. rend., 1907, 145, 899—902).—The isomeric change which certain aliphatic amines undergo when their salts are treated with metallic nitrites has been examined in the cases of n-propylamine (Meyer and Forster, Abstr., 1876, 543) and |8;8-dimethylpropylamine (Tissier, Abstr., 1891, 998; Freund and Lenze, Abstr., 1891, 1172); in the first case, a mixture of n- and iso-propyl alcohols is obtained containing 58% of the secondary alcohol, whilst in the second case the tertiary alcohol, dimethylethylcarbinol, is the sole product of the reaction. The author has extended the investigation to the intermediate homologue, isobutylamine, and finds that on treatment with sodium nitrite in a slightly acid solution it is converted into a mixture of isobutyl alcohol and trimethylcarbinol, of which 75% is the tertiary alcohol. These three amines contain respectively the groupings: -CH^-CH^-NH^, >CH-CH2-NH2, and )0-0H2-NH2, and the results show that when they are converted into alcohols by the action of nitrous acid they suffer a partial or complete isomeric change, whereby the resulting alcohol has the hydroxyl attached to that carbon atom which in bhe original compound was associated with the least number of hydrogen atoms. M. A. W. Action of Magnesium Organic Compounds on Tiglic Aldehyde. Paul Abelmann {Ber., 1907, 40, 4589—4590).— ^.y-pentene-P-ol, CHMelCMe-CHMe-OH, obtained from magnesium methyl bromide and tiglic aldehyde, is a colourless liquid, b. p. 139—141°. Its acetate, OgHi^Oj, has b. p. 153—155°. h-Methyl-^^-hexene-y-ol, CHMelCMe-CHEt-OH, obtained from magnesium ethyl bromide and tiglic aldehyde, has b. p. 154—155°/ 80 mm. Its acetate, CgHjgO,, has b. p. 167—170°. yq-Dimethyl-\^-octene-h-ol, CHMe:CMe-OH(OH)-CH2-Cn2-CHMe2, obtained from magnesium isoamyl bromide and tiglic aldehyde, has b. p. 202—204°. A. McK. Esterification of Phosphoric Acid by G-lycerol. Georges Pruniee {Bull. Soc. chim., 1907, [iv], 1, 1046—1048).—The rate of esterification of phosphoric acid by glycerol has been investigated under varying conditions of concentration, temperature (110°, 130°, or 150°), and pressure, and the nature of the products determined. The results show that care must be taken to eliminate water as it is formed, and this may be accomplished by heating the reaction mixture under reduced pressure or by exposing a comparatively large evaporating surface.