82 Report of Schimmel 8 Co. April 1913. 



of menthol in Japan itself is not important (about 1500 lbs.), the principal buyers being 

 the manufacturers of tooth-powders and patent-medicines. The oil is used in large 

 quantities for cheap confectionery and the like. 



We take this opportunity of referring to the detailed account of Japanese peppermint 

 by Naojiro Inouye which is incorporated in our Report of November 1908 (pp. 199 to 233). 



d-Ethyl-n-amylcarbinol, the occurrence of which in Japanese peppermint oil we 

 mentioned in our Report of April 1912, p. 102, has since then been prepared by us 

 synthetically. We started from n-caproic aldehyde prepared by the familiar method. 

 The aldehyde, which was purified from the primarily-produced bisulphite-compound, 

 constitutes a very mobile liquid with a slightly acrid odour, b. p. 35 to 37° (19 to 20 mm.); 

 diso 0,818s 1 ); n D20O 1,42785. We found the m. p. of the semicarbazone to be 114,5 to 

 115,5°, whereas according to P. Bagard 2 ) it is 106°. We reacted upon the caproic 

 aldehyde with magnesium ethyliodide and thus obtained i-ethyl-w-amylcarbinol, of 

 which the properties are set forth in the subjoined table: — 



i-Ethyl-ra-amylcarbinol d-Ethyl-rc-amylcarbinol 



(synthet.) (from peppermint oil) 



B.p. 176 to 177,5° 178,5 to 179,5° 



d 15 o 0,8286 0,8276 to 0,8279 



n D20O 1,42785 1,42755 to 1,42775 



n D150 1,42975 



Mol. Refr. 40,55, calc. f. C 8 H 18 40,67 



Acid phthalate, m. p. 65 to 65,5° 65,5 to 66° 



The acid phthalate of t'-ethyl-n-amylcarbinol, re-dissolved from chloroform, when 

 mixed with the same ester of the natural alcohol, suffered no depression of m. p. 

 Sap. v. 61,1; calc. for C 6 H 4 C0 2 HC0 2 C 8 H 17 60,5. 



From the natural d-ethyl-n-amylcarbinol, we prepared the benzoate. This constituted 

 a somewhat viscous, colourless liquid, with a faint odour; b.p. 126,5° (3 mm.); di 5 o 0,9641; 

 « D + 5°58'; n D20O 1,48905; ester v. 240,8 and 239,6 = 100,5 and 100 p.c. octyl benzoate. 

 The acetate was formed when d-ethyl-n-amylcarbinol was boiled with acetic anhydride 

 and anhydrous sodium acetate. It constitutes a liquid with a peculiar odour, at the 

 same time fruity and reminding of rose oil: b.p. 194 to 194,5°, d X5 o 0,8693, « D — 4° 46', 

 nD2oo 1,41535, ester v. 327,5 and 328,5 = 100,8 and 100,5 p.c. octylacetate. It is a curious 

 fact that the dextrorotatory alcohol yielded a lsevorotatory acetate. The alcohol 

 regenerated from the lsevorotatory acetate, showed almost the same degree of 

 dextrorotation (« D -f 6°20' [+3° 10' in a 50 mm. tube]) as the original (« D -f 6°37'). 



We have also repeated the process (already referred to in our last April Report) 

 of oxidising natural d-ethyl-n-amylcarbinol, and obtained n-caproic acid, b. p. 77,5 to 

 80° (3 mm.), d 15Q 0,9342, acid v. 484,5 = 100,25 p.c. caproic acid. Analysis of the 

 silver-salt: found 48,60 p.c. silver, calc. for C 6 HuAg0 2 48,43 p. c. The amide gave 

 m. p. 100 to 100,5° (from water) which is characteristic of n-caproic amide. 



Two years ago we mentioned in our Reports 3 ) the experiments which have been 

 made by Thorns in the cultivation of Japanese peppermint at Dahlem, near Berlin, and 



x ) According to A. Lieben and G. Janecek [Liebigs Annalen 187 (1877), 131] the density is d 20 o 0,8335; but 

 the estimation of these authors, as they themselves acknowledge, is not quite reliable because the- aldehyde 

 was probably already oxidised in part. — 2 ) Bull. Soc. chim. IV. 1 (1907), 319. — 3 ) Report April 1911, 92; 

 October 1911, 71, 



