112 Report of Schimmel § Co. 1921. 



for further condensations, especially of the dimethylq/dohexenone : either — and that 

 will be the most common case — an unsaturated keto-alcohol is formed, or a saturated 

 diketone (IV) will result. The formation of this diketone need only be considered with 

 respect to a secondary reaction (once observed) in which the bis-1 : 3-methylc^cfohexenone 

 (b. p. 200 to 205°, [12 mm.]) yields two different disemicarbazones, viz., of the diketone 

 (m. p. 246°) and of the keto-alcohol (m. p. 215°). 



Since the ketones studied by Ruzicka comprise all the types of the l:2-q/cZohexenones 

 with substitutes in the 1, 2 and 3 positions relative to the carbonyl, the polymerisation 

 which he describes may be assumed to represent a general phenomenon in this group. 



The polymerisation was effected by means of sodamide and proceeded all the more 

 smoothly, the more amide was used in the reaction. We further mention the following 

 compounds prepared by Ruzicka: — Dihydro-bis-1 : S-methylcyoXohexenone (b. p. about 200°, 

 13 mm.; acetate, m. p. 220°); Ms-isophorone, b. p. 203 to 205° (17 mm.), or 140° (*/« mm.), 

 semicarbazone, m. p. 215°, acetate, b. p. about 200° {12 mm.); bis-carvone (V), b. p. 225° 

 (12 mm.), semicarbazone, m. p. 194 to 195°, with evolution of gas, acetate b. p. about 

 225° (11 mm.). 



As regards piperitone, see page 23 of this Report. 



Phenols and Phenol Ethers. 



Some phenols including carvacrol and thymol can, as is well known, be extracted 

 from their alkaline solutions by means of ether 1 ). Stormer and Kippe 2 ) proved that 

 the sodium-compounds of carvacrol can so be extracted by ether from a 30 to 40 per cent, 

 caustic-soda solution, but that thymol under the same condition passes almost entirely 

 into the ether as pure phenol (without sodium). D. C. L. Sherk 3 ) has conducted further 

 experiments in this direction and has found that both carvacrol and thymol dissolved 

 in 5 per cent, caustic soda, when shaken with ether, pass into this solvent without any 

 combination with sodium taking place. Of thymol up to 99.89 per cent, are extracted from 

 the alkaline solution by means of ether; in the case of heptane, carbon tetrachloride, carbon 

 disulphide and benzene the extraction was only partial, amounting to 30 to 68 per cent. 

 How carvacrol behaves under the same conditions is not stated in the paper. 



By the method, recommended by F. Weehuizen for the preparation of phenyl- 

 urethanes*) (application of a petroleum-fraction boiling between 170 and 200° as solvent) 



D. C. L. Sherk 5 ), starting with about 2 to 5 g. of material, obtained 71 per cent, of thymol- 

 phenylurethane (m.p. 106.5 to 107°); 86 per cent, of carvacrolphenylurethane (m.p. 138°; 

 the m. p. of 140° which E. Gildemeister 6 ) determined was not reached by Sherk); 

 84 per cent, of thymohydroquinone-di-phenylurethane (m. p. 232 to 233°); 43 per cent, 

 of thymol-«-naphthylurethane (m.p. 156 to 157°); 35.9 per cent, of carvacrol-«-naphthyl- 

 urethane (m. p. 119°); and a small yield of thymohydroquinone-mono-«-naphthylurethane 

 (m. p. 147 to 148°). fhe preparation of m. p. 287 to 288°, which C. Neuberg and 



E. Hirschberg 7 ) had obtained by heating a-naphthyHsocyanate and carvacrol, was, as 

 Sherk shows, not a carvacrol-a-naphthylurethane, but probably a decomposition-product 

 of a-naphthylisocyanate. Sherk further prepared by the method of Schotten-Baumann (with 

 sodium hydroxide and benzoylchloride) dibenzoylthymohydroquinone (m.p. 141 to 142°). 



!) Berl. Berichte 32 (1899), 1517. — 2 ) Ibid. 36 (1903), 3992. — 3 ) Americ. Journ. Pharm. 93 (1921), 8. — 

 *) Report 1919, 130. — B ) Americ. Journ. Pharm. 93 (1921), 115. — 6 ) Arch, der Pharm. 233 (1895), 188. 

 Cf. Gildemeister and Hoffmann, The Volatile Oils, 2 nd ed., vol. I, p. 474. — 7 ) Report April 1911, 172. 



