144 Report of Schimmel $ Co. April 1913. 



Further proof of the last-mentioned assumption is seen by Skita in the fact that 

 dihydro-ionone has, properly speaking, ceased to be an odoriferous body. Tiemann 

 had already expressed the view that the odoriferous character of ionone was due to 

 its «,/9-double bond. According to this view, a dihydro-ionone hydrogenated in its 

 nucleus must be an odoriferous body. As a matter of fact, dihydroq/docitral and 

 acetone, in the presence of tartaric acid, yield a dihydroionone, b. p. 124 to 125° 

 (14 mm.) which possesses a pronounced odour reminding of ionone. Skita recommends 

 that the name dihydro-ionone should be reserved for this body and that the two other 

 dihydro-iones described above should be described respectively as /-ketobutanes-(2) of 

 the trimethyl-(l,l,3)-tetrahydrobenzenes-(2) and -(3). 



In all the above ionone-reductions the keto-group remained intact. 



Pseudoionone yielded a tetrahydro-pseudoionone (b. p. 126 to 127° at 14 mm.), of 

 the following constitution: — 



(CH 3 ) 2 • C : CH • CH 2 • CH 2 • CH 2 ■ CH (CH S ) • CH 2 ■ CH 2 • CO • CH 8 



Phenols and Phenol-ethers. 



In a paper dealing with the conversion of phenol allylethers into C-allylphenols, 

 L. Claisen 1 ) describes a phenol which is probably an isomeride of eugenol. This is 

 C-allylguajacol, which Claisen has prepared from guajacol allylether, C 6 H4(OCH3)(OC 3 H5) 

 (b. p. 116° at 14 mm.; di 50 1,058) by heating it to about 230°. It constitutes a phenol 

 with a pronounced odour of cloves, b. p. 122° at 12 mm., di 5 o 1,071. It differs from 

 eugenol in the m. p. of its phenylurethane (101°, eugenolphenylurethane 95,5°) and of 

 its _p-nitrobenzoate (97°, eugenol-^-nitrobenzoate 81°). With regard to the constitution 

 of C-allyl guajacol it is thought that the position to which the allyl has migrated 

 must be either the para- or the or^o-position. If the former, eugenol would be 

 present. 



Another instance of the conversion of a phenol-O-allylether into C-allylether is 

 afforded in the case of O-allyl salicylate. Many years ago Scichilone described an 

 acid which he thought to be allylsalicylic acid, C6H 4 (OC 3 H 6 )COOH. Singularly enough, 

 this acid took a pronounced violet colour with ferric chloride. In reality, as Claisen 

 has shown, Scichilone was not dealing with allylsalicylic acid but with a mixture of 

 C-allyl and C-propenyl salicylic acids. Scichilone started from methyl salicylate, which 

 he allylated in methylalcohol with potash and allyl iodide. He thus obtained an ester 

 which, before distillation, was no doubt the true O-derivative. But under repeated 

 distillation at ordinary pressure this body became converted into the C-allylated ester, 

 which in addition, when saponified with aqueous potash, became partly transformed 

 into the propenyl derivative. From the potassium-compound of ethyl salicylate with 

 allyl bromide Claisen has obtained pure O-allylethyl salicylate (I) in the form of a 

 colourless oil, b. p. 153° (13 mm.) which did not acquire colour when treated with 

 ferric chloride. Boiling for a brief period with methyl alcoholic potash gave rise to 

 O-allyl salicylate (m. p. 65°). When the O-allylester is subjected to prolonged heating 

 at 230° it gives rise to C-allyl ethylsalicylate (II) (b. p. 142° at 12 mm.) which affords 

 a violet-blue colour with ferric chloride. Free C-allyl salicylic acid melts at 96° and 

 when heated with aqueous caustic potash to 170° is converted into propenyl salicylic 

 acid (III), m. p. 158°. Both acids give pronounced colour reactions with ferric chloride. 



l ) Berl. Berichte 45 (1912), 3157. 



