— 175 — 



chloride melts at 180°. Bornyl-p-toluidine boils at 162° (3 mm.) and 

 congeals into needles, m. p. 33°; the m. p. of the hydrochloride is 214°, 

 with decomposition. Bornyl-m-xylidine, CioHi 7 NH<^ ^>CH 3 , boils at 167° 



CH 3 

 (7 mm.), m. p. 79° (large needles from methylalcohol). By acting upon 

 bornylchloride with m-toluylenediamine the authors were unable to isolate 

 bornyltoluylenediamine; camphene and diamino ditolylamine being produced. 



Menthenols. As mentioned in our previous Report 1 ), Wallach has 

 again insisted upon the necessity of preparing the alicyclic hydrocarbons 

 and alcohols by more than one method when it is desired to determine and 

 check their properties. Regarded from this standpoint a synthesis of 

 d-zl' 2 -m-menthenol-8 and of d-zl 2 ' 8(9) -m-menthadiene, carried out by Haworth, 

 Perkin and Wallach 2 ), is of particular interest. The two bodies had al- 

 ready been obtained synthetically in the inactive state by Perkin and 

 Tattersall 3 ) from hexahydro-m-toluic acid. By altering their experimental 

 conditions Haworth, Perkin and Wallach have been able to prepare a con- 

 siderable quantity of the two inactive compounds, and thus to make pos- 

 sible an exact determination of their properties. But the authors have 

 succeeded in preparing the dextrorotatory forms of the two bodies by 

 another method. They started from d-1 -methyl c?/dohexane-3-one (I), which 

 reacts with zinc and «-bromopropionic ester, forming l-methyl-3-hydroxy- 

 c^cZohexane-3-a-ethylpropionate (II). When heated at normal pressure 

 in a hydrogen atmosphere the free acid decomposes, giving rise to D-l- 

 l-methyl-3-ethylidenec?/cZohexane (III). The nitrosochloride of this hydro- 

 carbon, when gently heated with glacial acetic acid and anhydrous sodium 

 acetate, yields the oxime of d-3-acetyl-l-methyl-J 2 -cycZohexene (IV). The 

 ketone, when treated with an excess of ethereal solution of methyl 

 magnesium iodide, yields d-J 2 -m-menthenol-8 (V) a liquid possessing the 

 following properties: b. p. 206 to 208° (760 mm.), 103 to 105° (22 mm.), 

 d|| 0,923, [«] D + 55,56°, n D 1,4728, m. p. of the phenylurethane 124°. 

 When oxidised with 2% aqueous solution of permanganate of potassium 

 at 0°, a-methyladipic acid is formed. d-J 2,8(9) -menthadiene (VI) was prepared 

 from the alcohol by shaking with 1,5% sulphuric acid: b. p. 181° (736 mm.), 

 dg§ 0,864, [«] D + 64,0°, n D 1,4946. 



i-zl 2 -m-menthenol-8, (prepared according to the method described above, 

 from i-l-methyl-zl 2 -cz/cfohexene-3-carboxylic acid) and i-J 2,8(9) -m-mentha- 

 diene respectively gave the following constants: b. p. 110° (30 mm.), 

 d|f 0,9281, n D 1,4772, m. p. of the phenylurethane 127°, and b. p. 182 to 

 183° (770 mm.), d 2 ^ 0,8624, n D 1,5030. This shows that the properties of 

 the bodies prepared by different methods are practically identical. 



*) Report October 1910, 190. 



2 ) Liebigs Annalen 379 (1911), 131; Journ. chem. Soc. 99 (1911), 118. 



8 ) Journ. chem. Soc. 87 (1905), 1101; Report October 1905, 93. 



