The Reactions of Morphine and Codeine

The removal of the alcoholic hydroxyl by reaction of the corresponding toluene sulfonate with lithium aluminum hydride has been described Codeine tosylate (CCCXXXVIII) thus leads to A -deoxycodeine (381) and dihydrocodeine to dihydrodeoxycodeine (382). The former reduction may be contrasted with that of a-chlorocodide (CCCXXXIX), which leads to A -deoxycodeine with the same reagent (383). This is in 

The reduction of codeinone to codeine has been achieved in high yield with sodium borohydride (384), while it has been claimed that dihydro-codeinone gives mainly dihydroisocodeine under the conditions of the Meerwein-Ponndorf reduction (385). This is to be compared to the unreactivity of dihydroisocodeine to the Oppenauer oxidation with potassium -butoxide and benzophenone (386). Obviously the steric requirements are not the same for these two reagent systems. 

The interesting observations have been made by Perrine and Small (387) that the Wolff-Kishner reduction of dihydrocodeinone leads to A -dihydrodeoxycodeine (CCCXL) while ethyl mercaptan in concentrated hydrochloric acid leads to dihydrothebainone (CCCXLI) apparently via its 5-thioethyi derivative. 

The generalization has previously been made (Vol. II, p. 180) that 8,14 morphine derivatives are always reduced catalytically to the natural series (C14 hydrogen trans to the benzene ring)  

Rapoport and Lavigne (388) have incorrectly claimed that there are several exceptions to this generalization. Of the two cases they mention, one (A -thebainonemethine) is morphine alkaloid in name only The molecule is in reality a simple phenanthrene derivative and the course of its hydrogenation is irrelevant. In the other purported 

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