New methods for O-tosylation of the natural Cinchona alkaloids have been discovered as a biphasic processes with Bu 3N as a catalyst. The optimized excess of tosyl chlo ride, necessary for transformation of each of the four alkaloids into O-tosyl derivative, decreases in the following order: quinine, quinidine, cinchonidine and cinchon ine. The same decreasing order has been noticed for the hydrolysis rate of the appropriate tosylates to 9-epibases. Difficult conversion of O-tosylcinchonine in the hydrolytic medium of aqueous tartaric acid gives 9-epicinchonine together with parallel formation of cinchonicine en ol tosylate. The latter product is obtained as the main when both cinchonine and cinchonidine tosylates react in the presence of salicylic acid under controlled microwave heating. On the basis of X-ray structure of the new alkene product, the stereoselective syn -E2 quinuclidine ring opening process, competing to the SN2 hydrolysis is postulated for this transformation.