147 



Alcohols. 



B orneol. The isomerisations occurring when phosphorus or hydrogen 

 halogenides act on secondary hydroaromatic alcohols or glycols, have 

 been explained by Kondakow and his collaborators in earlier works 

 thus, that during the first phase of the reaction a complete or partial 

 racemisation and geometric isomerisation takes place. There are further 

 formed independent haloid derivatives of different stability, which probably 

 depends upon the stereochemical position of the halogen and the 

 hydrogen atoms. The unstable isomerides among these secondary ones 

 are readily converted into tertiary haloid anhydrides, and that either 

 on account of an atomic migration, or by the abstraction of the 

 hydrohalogen, and its reattachment at another place. In some hydro- 

 aromatic alcohols a rearrangement of the carbon nucleus may then take 

 place. But with regard to the behaviour of the alcohols, their esters 

 and ethers, towards the hydrohalogen acids, with reference to the formation 

 of isomerides, nothing is as yet known. Kondakow and Schindel- 

 meiser 1 ) examined in this respect the behaviour of the 1-bornylacetate 

 of the m. p. 29° and the rotatory power Mpigo — 43,63°, frozen out from 

 the oil of Abies sibirica, which yielded on saponification a 1-borneol of 

 the m. p. 203 to 204° and the rotation Md20° — 3°, l 6°- When treated 

 with glacial acetic and hydrochloric acids (for 3 hours at 125°), a 

 pure pinene hydrochloride of the m. p. 124° was formed. After re- 

 crystallisation from alcohol, it was stable towards alcoholic solution of 

 silver nitrate; heating with water to 120° only split off 25% of the 

 (total?) chlorine. After this treatment the hydrochloride showed the 

 melting point 118 to 1 2 1 °, possibly due to the presence of camphene. 

 In every case the hydrochloride was inactive. A fresh proof had 

 therefore been given of the identity of bornyl chloride with pinene 

 hydrochloride. The authors summarise in tabulated form the rotatory 

 values of pinene (d- and 1-) and the corresponding halogenhydrates, 

 as ascertained by previous investigators. In the same manner they 

 treated a fenchyl acetate obtained from 1-fenchyl alcohol of the m. p. 

 above 45° and the rotation M D — 15° 22', by heating with acetic an- 

 hydride to 155 to 160°. The acetate, whose constants were as follows: 

 d 20 o 0,972; [a] D _ 63°24 / ; n D 1,4565; b. p. 91 to 91,5° (12 mm. 

 pressure) or [a] D — 6i°io' and b. p. as above respectively, when 

 heated with glacial acetic and hydrochloric acids to ioo°, was not 

 completely converted into the chloride; the product had d2o° 0,952; 

 n D 1,4758; [a] D o; b. p. 68 to 74° (11 mm. pressure), and reacted with 

 silver nitrate. When this chloride was treated with alcoholic potash, 

 little inactive fenchene of the b. p. 145 to 166° was formed; the bulk 

 remained unchanged, but probably owing to admixtures (possibly fenchyl 



3 ) Journ. f. prakt. Chem. II. 75 (1907), 529. 



