— 144 — 



can then be readily converted with sodium methylate into methyl- 

 suberane methyloxime, which corresponds to the formula 



CH 2 — CH 2 — C(NOH) v / OCH 8 



I ^ C' 



CH 2 — CH 2 CH/ ^CHg 



As in the reaction the acid radical (N0 3 or CI) is substituted by 

 OCH 3 , it is not a question of a simple oxime. The 7 -ring system, 

 therefore, with entirely analogous changes shows a smaller inclination 

 to the formation of an ethylenic linking in the ring than the 6 -ring 

 system. If by means of tertiary bases (dimethylaniline) I mol. hydro- 

 chloric acid is split off from methyl suberene nitrosochloride, the oxime 

 of methyl suberenone is obtained. The ketone regenerated in the 

 usual manner from the semicarbazone (m. p. 162 to 163 ) has the 

 following properties: d 0,9695; n D2i° 14867; b. p. 200 to 205 . By 

 reducing methylsuberenone in alcoholic solution with sodium, an 

 alcohol was obtained (though only in a small yield, owing to an 

 abundant formation of pinacone) which was oxidised with chromic acid 

 to methyl-i-cycloheptanone-2 (methylsuberone) , which, however, for 

 the present could only be detected in the form of its semicarbazone 

 of the m. p. 129 to 13 1°. 



Several years ago already 1 ) Wallach has, as the first synthetic 

 methene hydrocarbon 2 ), built up methene suberene (methene cyclo- 

 heptamethylene) from suberone; it should only be noted that in his 

 recent investigations on the subject 3 ), he condensed suberone and 

 bromoacetic ester with magnesium instead of zinc, and with the addition 

 of iodine. A comparison of methene suberene with the linking-isomeric 

 methylsuberene snowed, as already stated, a decided analogy of the 

 physical constants; only the totally different chemical behaviour proved 

 the difference in their constitution. Methene suberene, contrary to 

 /?-phellandrene, showed no tendency to autoxidation. According to 

 Wallach the pronounced oxidability of /J-phellandrene is not due 

 to the ethylene linking adjacent to the methene, for sabinene, which 

 contains one methene group has an equally indifferent behaviour as 

 methene suberene. The glycol : 



CH 2 -CH 2 -CH 2X 



i >c(oh)ch 2 (oh) 



ch 2 .ch 2 .ch/ 



produced from it by oxidation with 1 per cent, potassium permanganate 

 solution, melts at 50 to 51 , and when brought in contact with dilute 





x ) Liebig's Annalen 314 (1900), 147; Report April 1901, 61. 



2 ) Liebig's Annalen 343 (1905), 28; Report April 1906, 114. 



3 ) Liebig's Annalen 345 (1906), 146. 



