177 — 



pared from American turpentine oil was made to react with sodium 

 methylate. The reaction mixture contained, besides nitrosopinene, the 

 new body CnHi 9 N0 2 which, when dissolved from ligroin, melted at 102° 

 and was optically inactive. The presence of a methoxyl group was proved 

 by determination according to Zeisel and that of an oximido group by its 

 solubility in soda liquor and hydrochloric acid, as well as by the pre- 

 paration of a phenylurethane (m. p. 102°, from ligroin). A urethane of 

 the same m. p. may also be obtained by acting with phenyl isocyanate 

 upon nitrosopinene, but the two are not identical, because the m. p. 

 of the mixture is considerably depressed. If the compound CnHi 9 N0 2 

 is left in a closed vessel at ordinary temperature with alcoholic hydro- 

 chloric acid solution, i-hydrochloro-carvoxime (m. p. 125,5°) is formed. 

 The process of reaction of sodium methylate upon pinene nitroso- 

 chloride may be expressed as follows: — 



CH CH CH 



H 2 C 

 HC 



C(CH.3)2 



CH 2 H 2 C 

 CH-N-O-HC 



(CH 3 ) 2 ( 



> 



CH 2 H 2 C 

 2 Mol. 



CH HC 



/ NcH 2 



C(CHs)J 



<^ JcrNOH 





c — c 



NO 



1 ( 



:i — ( 







C — OCH 3 



CH3 CH3 CH3 



The new body must, from the above, be regarded as methoxyhydro- 

 isonitrosopinene. 



In the same paper the authors 1 ) discuss the detection of «-pinene 

 by means of its nitrolbenzylamine. The m. p. of this compound is always 

 given as 122 to 123°. This was also observed to be the case with a 

 pinene nitrolbenzylamine prepared by Deussen and Philipp from American 

 turpentine oil, but more careful examination revealed the existence in 

 the molten mass of solid particles which did not melt below 135 to 140°. 

 Fractional crystallisation of the base from ethyl acetate enabled the authors 

 to isolate the high melting body: m. p. 148 to 149° (without decomposition), 

 Md + 96,7° (in ethyl acetate). Whether the new body represents an active 

 nitrolbenzylamine could not as yet be determined. 



In conclusion the authors show 2 ) that pinene nitrolbenzylamine con- 

 tains an oximido-group, because it reacts with phenyl isocyanate, forming 

 a phenylurethane, m. p. 189,5 to 190°. 



When an aqueous sodium nitrite solution is allowed to act upon a 

 strongly cooled solution of the hydrochloride or sulphate of o-hydroxylamino 



x ) Liebigs Annalen 374 (1910), 116. 

 2 ) Ibidem 119. 



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