126 



(b. p. 176,5° [corr.]; d^ 0,9235; d-^ 0,9119; n D160 1,458), but little 

 ketone and m-xylene. The phenyl ure thane melts at 96°, the acetic 

 ester boils at 198° (corr.). By the action of molten zinc chloride 

 the alcohol is converted into a hydrocarbon which appears to be 

 identical with a hydrocarbon which the authors have previously x ) obtained 

 from dimethyl - 1,3 - cyclohexanol - 3 , viz., dimethyl - 1,3 - cyclohexene - 4, 

 b. p. 124 ; d^ 0,8210; n D 1,451. On oxidation with chromic acid 

 mixture or abstraction of hydrogen over copper, there is formed 

 from the alcohol, dimethyl- 1, 3 -cyclohexanone-4 (b. p. 176,5° [coir.]; 



0° 16° 



d^ 0,9210; d-^o 0,9124; n Di6° I >446)> whose semicarbazone melts 

 at 190° with decomposition. 1,4,2-xylenol yields, in addition to 90 /o 

 alcohol, io°/ ketone without formation of xylene. Dimethyl- 1,4-cyclo- 

 hexanol-2 (b. p. 178,5° [corr.]; d^ 0,9218; d 1 ^ 0,9073; n D160 1,455) 

 yields a phenyl urethane of the m. p. 115°. Dimethyl- 1,4 -cyclo- 

 hexanone-2 boils at 176° (corr.); its semicarbazone melts at 155° 

 with decomposition. 



Aldehydes. 



G. Darzens and P. Lefebure 2 ) have applied Darzens' synthesis 

 of glycide esters to cyclohexanones, and produced by decomposition 

 of the corresponding glycidic acids the relative hexahydrobenz- 

 aldehydes. If to a mixture of equal molecules cyclohexanone and 

 monochloracetic ester at 0°, 1 mol. dry sodium ethylate is slowly 

 added, the mixture left standing first of all at ordinary temperature 

 for 48 hours, then for 6 hours on a water bath, and the condensation- 

 product dissolved in water, there is obtained in a yield of 65 °/ , the 

 glycide ester of cyclohexylacetic acid of the formula 



CH 



CH, 



-CH 



>C — CH- 

 -CH/ \ Q / 







-COOC 2 H, 



CH 2 - 





The ester boils at 128 to 129° (17 mm. pressure), has a faint skatol- 

 like odour, and can be very readily saponified. In order to produce 

 hexahydrobenzaldehyde, the free acid is slowly distilled in vacuo (30 mm. 

 pressure), when it is split up into aldehyde and carbon dioxide. The 

 aldehyde boils at atmospheric pressure between 155 and 157°, at 

 20 mm. between 75 and 78°. It has a very strong odour of valeric 

 aldehyde; its semicarbazone melts at 173 to 174°. From o-methyl- 

 cyclohexanone is formed in an analogous manner o - methylhexa- 

 hydrobenzaldehyde, a body not yet known; b. p. 61 to 62° 



*) Ibidem 141 (1905), 21. 



2 ) Compt. rend. 142 (1906), 714. 



