NY SCIENTIFIC RESEARCH. Sey ei Ba A2S 
Be shove: t room “temperature, ‘But becomes colourless at 0°. oe crystals are more 
“unstable than the inactive product. They react readily with benzylamine, piperidine, 
with alcoholic alkali to form nitrosopinene, and with aniline. The benzylamine 
"derivative melts at 144 to 145°; [¢]p about 92° in 2.5. per cent. acetone solution. 
The piperidide melts at 84°; fal abouts 50°. / 
The active nitrosochloride readily reacts with es to’ form acne. pinene: — 
be p. 155 to 159°, [a]) about 53.75° (in 4 per cent. alcoholic solution), np 1.470. The 
_ maximum rotation observed with natural a-pinene is, according to ee. + 51 52°"). 
_ d-«-Pinene yielded an inactive hydrochloride, m. p. 118°. 
The poor yields of pinene nitrosochloride (about 50 per cent.) are, according to 
E Schorger, due not alone to the formation of readily soluble active nitrosochloride, 
but. also to side reactions. The disappearance of the blue colour and the precipitation 
of crystals is accompanied by an evolution of gas which, by the usual reagents, proved — 
to be nitrogen. Lynn was unsuccessful in trying to obtain well- defined bodies from 
_ the -mother liquors. of the Prepaiaiow of the nitrosochloride. | 
ve 
. <Fwo publications by Aschan?) on the De ae of pinene and the additive power 
of unsaturated compounds show that little was hitherto known about the former subject. 
 He- investigated the action of chlorine in. carefully dried solvents at. temperatures — 
between — 15° and zero. The results were in no accord with the earlier statements. 
The action of the halogen passed off in a complex way. The first fractions of the 
- product yielded abundant quantities of solid pinene hydrochloride. From the higher 
fractions, the only body which could be isolated : was a pinene dichloride (Il) (?), which 
is possibly formed by rearrangement of a primarily-formed normal dichloro addition — 
p Product a It presented det in shape of EG NLS sc ORNDIE bi- -pyramidic tabular 
CE: , ; 
es; £2 HOCH, Cee: CH, : 
RR ee te SCN ek CICA one -CHCL 
+ aE so eli a EG ean BNC BSS 
as ; LHC pC. 1 Plead ee ye egE eo te: c(CH 
ey | CH feces Mer cenage ly | 
iy. Normal dichloro addition product ay Pinene dichloride 
~ -_of a@-pinene. formed by. Tearrangement of (I).. 
x “crystals, m. p. 173 to 174°; ‘bs p. about 130° (10 mm.). In addition, a liquid Hidhidride cs 
eee ‘to be formed; b. p. 120 to dpe (10 mm.) which, however, could not be 
_ obtained in the pure ‘stake: Both chlorides were not attacked by boiling with aniline. 
_ Preliminary experiments showed that on further chlorination of pinene hydro- 
_ chloride in chloroform or carbon tetrachloride up to four hydrogen atoms may readily 
_be substitutéd by chlorine yielding white crystalline ‘products of the m. p. 135°, | 
150 to 152°, -and 130°, The analytical data lay between CratigCh, and CrofhisCla; 
a dichloride could not be isolated. 
| 5 Further experiments of Aschan demonstrated that the action of pinene on various 
‘ terpene hydrochlorides, especially at higher, temperature, regularly passes off in -this 
_ manner that hydrogen chloride is split off from the hydrochlorides with: formation of 
ordinary pinene hydrochloride bonny! chloride). This reaction was observed in the 
rs 
oe ') Comp. Gildemeister and éseainckha: The Volatile Oils, 294. ed., vol. I. p. 293. — 2%) Ofversigt af Finska 
| Vetenskaps-Societetens Worhandlingar #7 (May 4, 1915); 58 (Dec. 20,-1915); Chem. Zentralbl. 1918, I]. 952, 953. 
