Grignard Keagent on Camphoric and Isocarnphoric Esters. \ 1 



it distilled at 140-142° under 7 mm. pressure, or at 159-160° under 

 20-21 mm. pressure. On analysis the following results were 

 obtained : — 



0-3177 gave 0-8220 COs and 0-2716 H,0. C = 70-56 ; H=9-56. 



0-3126 gave 0-8069 CO^ and 0-2653 H,0. C = 70-35 ; H =9-48. 



CuHjiOg requires C = 70-00 ; H = 10-00 per cent. 



Tlie oxidation of the substance Cj^H^^O-i : — The oil was dissolved 

 in benzene and shaken with an acidic solution of potassium 

 permanganate (5%). On driving off the benzene, an oily 

 substance was obtained, which was fractionated. The portion 

 distilling about 150° under 7 mm. pressure gave a considerable 

 quantity of crystals on cooling. These were recrystallised from 

 alcohol, and the colourless needles thus obtained melted at 

 224-225°, and gave the following results on analysis, showing that 

 the substance is camphoric anhydride : — 



0-1002 gave 0-2424 CO., and 0-0701 HA C = 65-98 ; H=7-82. 

 CioHiiOg requires = 65-90 ; H = 7-74 per cent. 



Tlie action of alcoholic potaslt, on the substance C^^H^iO-i : — The oil 

 was boiled with an excess of alcoholic potash for twenty hours, and 

 after the usual treatment, an oil separated out on acidification. 

 This was extracted with ether, the etherial solution dried over 

 calcium chloride, the ether driven off, and the residue fractionated 

 under a reduced pressure. Camphoric anhydride was again 

 obtained in a considerable quantity. 



These changes can easily be explained if a constitution of 

 methyl 1 :2 :2-trimethyl-3-isobutyryl-c^c?o-pentane-l-carboxylate be 

 given to the substance CHH24O3 as stated in the introductory part, 

 its formation from dimethyl camphorate and magnesium isopropyl 

 iodide being represented as follows: — 



