Grignard Reagent on Carnpbori« andlsocamphoric Esters. 3 



Japanese camphor according to the processes given by F. Wreden 

 (Annalen, 1872, 163, 323) and W. A. Noyes (Amer. Chem. 

 Jom-n., 1894, 16, 307), was converted into the neutral methyl ester 

 by means of dimethyl sulphate, according to the patent method of 

 J. D. Riedel (D.R.P., 189840 [1906] and 196152 [1908]). 



Dimethyl fl-camphorate thus prepared boils at 147-150° under 

 10 mm. pressure, or at 162-164° under 29 mm. pressure, while 

 Riedel gives its boiling point as 145-147° under 20 mm. pressure. 

 The sample was, therefore, analysed and proved to be free from 

 impurities. 



0-2213 gave 0-5101 CO, and 0-1739 H,,0. C = 62-87 ; H = 8-78. 

 Ci,,H.,oO, requires C =63-10 ; H = 8-85 per cent. 



The reaction between dimethyl camphorate and magnesium 

 phenyl bromide was carried out in precisely the same manner as in 

 the case of diethyl phthalate (loc. cit.). An etherial solution of 

 the ester was added to magnesium phenyl bromide in the propor- 

 tion of 1 to 4 molecules, and the product, obtained by decomposing 

 the resulting solution with ice and dilute sulphuric acid, was 

 subjected to steam distillation to remove the excess of bromoben- 

 zene and diphenyl, formed as a by-product. The residual oil soon 

 solidified, and the solidified mass was finely pulverised and dried 

 in a vacuum over sulphuric acid. In order to remove the oil still 

 adhering, the yellowish powder thus obtained was rubbed in a 

 mortar with a small quantity of alcohol which was then well 

 sucked, and the product recrystallised from hot alcohol. Small 

 colourless needle-shaped crystals with a melting point of 154-155°- 

 were thus obtained. They are easily soluble in ether, benzene, 

 carbon bisulphide, acetone, chloroform, and hot alcohol, and 

 difficultly soluble in cold alcohol, and petroleum ether. On 



