143 



help of Grignard's reaction, and by making use of his own well- 

 known method of building up ketones from unsaturated hydrocarbons x ) : 



CH 2 -CH 2 .CH 2 v 

 I >CO 



ch 2 .ch 2 .ch/ 



suberone 



CH 2 -CH 2 «CH ^v 



I /CCHg 



CH^CH^CH,/ 



methylsuberene 



CH 2 .CH -CO x 

 I ' >CCH 3 



ch 2 .ch 2 .ch/ 



methylsuberenone 



.OH 



CH Q 



CH Q 



CH 2 .CH 2 .CH 2 / X C1 

 methylsuberene nitrosochloride 



CH 2 .CH 2 .CO v 



I )CHCH 3 



CH 2 .CH 2 .CH 2 / 



methylsuberone 



CH 2 .CH 2 .CH 2X 



CH 2 .CH 2 .CH 2 / 

 methylsuberol 



NOH 



CH 2 .CH 2 .C 



By the action of methylmagnesium iodide on suberone, and by 

 decomposition of the double compound formed with sulphuric acid, 

 methylsuberol is obtained, which by heating with bisulphate in a 

 current of hydrogen passes over easily with loss of water into 

 A 1 - methylsuberene (A 1 - methyl - I - cycloheptene), C 8 H 14 ; d 0,824 ; 

 b. p. 137,5 to ^S^ ; n Di9,5 14581. Wallach indicates for this 

 hydrocarbon the two following possible formulae: — 



I. II. 



C H • C H ' CH 



1 



CH • CH, • CH„ 



C-CH q 



CH • CH„ • CH 



CH • CH • CH, 



>C = CH 9 



Now the hydrocarbon (formula II) previously 2 ) produced by 

 Wallach from suberene acetic acid, agrees on the whole in its 

 physical properties with the one mentioned above, but from a 

 chemical point of view the two show a totally different behaviour, 

 and for this reason formula I no doubt belongs to methylsuberene. 

 As, in view of the method of production, another isomerisation was 

 not impossible, the correctness of the formula was also tested by an 

 oxydative degradation of the hydrocarbon. The hydrocarbon, as 

 might be expected from formula I, was oxidised to £-acetylcaproic 

 acid, CH 3 .CO.CH 2 .CH 2 .CH 2 .CH 2 .CH 2 -COOH, and the 

 degradation of the keto acid to normal pimelic acid with hypo- 

 bromite was also carried out easily. 



The nitrosate and the nitrosochloride of the hydrocarbon w r ere 

 obtained in a good yield, 70 and 65 to (>y°/ respectively; both 



x ) Comp. Reports April 1903, 92; April 1904, 124; October 1904, 128. 

 *) Liebi^s Annalen 314 (1900), 158. 



