Alkaloids dihydrocodeinone

Rice, K.C. (1980) Synthetic Opium Alkaloids and Derivatives. A Short Total Synthesis of (ib)-Dihydrothebainone, ( )-Dihydrocodeinone, and ( )-Nordihydrocodemone as an Approach to a Practical Synthesis of Morphine, Codeine, and Congeners. Journal of Organic Chemistry, 45, 3135-3137. 

Hong, C.Y, Kado, N., Overman, L.E. (1993) Asymmetric Synthesis of Either Enantiomer of Opium Alkaloids and Morphinans. Total Synthesis of (—)- and (-f)-Dihydrocodeinone and (—)- and (-F)-Morphine. Journal of the American Chemical Society, 115, 11028-11029. 

Aminoalkylation, mainly carried out on alkylkclones (441-445, Fig. 166), is largely used and mentioned among the classical synthetic methods in alkaloid chemistry (sec pp. 361 and 363 in Ref. 2). In a few cases, for example with dihydrocodeinone, the reaction is uncontrollable and proceeds up to deamination, followed by dimerization of the vinyl-ketone produced. ... 

The alkaloid contents of transformed and non-transformed calli were analyzed by an ELISA and an HPLC. The crude extract can be immediately subjected to the ELISA analysis as described above (sections 3.1, 3.4) using morphine-specific monoclonal antibody [145]. The morphine-specific antibody used has a high affinity for morphine, codeine, ethylmorphine, dihydromorphine, and dihydrocodeine, less reactivity with dihydromorphinone, dihydrocodeinone, and norcodeine, but almost no reactivity with naloxone and naltrexone [145]. 

In fact this sequence of reactions gave a base [xLvm] as final product, showing that C-13 is the point of attachment of the side-chain in dihydrocodeinone, and therefore in the morphine alkaloids generally [68]. 

Hydrocodone, 4,5-Epoxy-3-methoxy- 17-methvt-morphinan-6-one dihydrocodeinone Bekadid Dicodid. C,H31NOj mol wt 299.36. C 72.21%, H 7-07%, N 4.68%, O [6,03%. Prepn by hydrogenation of codeinone Mannich, Lowenheim, Arch. Pharm. 258, 295 (1920) by oxidation of dihydrocodeine, Ger. pat. 415,097 (1925 to E. Merck), Frdl. 15, 1518 (1925-1927) by catalytic rearrangement of codeine Ger. pet. 623,821. Industrial prepn from dihydrocodeine Pfister. Tishler, U.S. pal, 2,715,626 (1955 to Merck Co-)-Toxicity data Eddy, Reid, J. Pharmacol. Exp. Ther. 52,468 (1934). Review Small. Lutz. "Chemistry of the Opium Alkaloids, Suppl. No. 103, Public Health Reports, Washington (1932). 

Synthetic work on morphine and morphinandienone alkaloids continues unabated. Amurine " and O-methylflavinantine have been obtained by the benzyne reaction of appropriate benzyl isoquinoline precursors. A review concerning new synthetic derivatives of dihydrocodeinone is not readily available.Codeine has been prepared in 98% yield from morphine using... 

Rice KC (1980) Synthetic opium-alkaloids and derivatives - a short total synthesis of (-1-/—)-dihydrothebainone, (+/—)-dihydrocodeinone, and (-f/—)-nordihydrocodeinone as an approach to a practical synthesis of morphine, codeine, and congeners. J Org Chem... 

Hong CY, Kado N, Overman LE (1993) Asymmetric-synthesis of either enantiomer of opium-alkaloids and morphinans - total synthesis of (—)-dihydrocodeinone and (-1-)-dihydrocodeinone and (—)-morphine and (+)-morphine. J Am Chem Soc 115 11028-11029 Mulzer J, Dumer G, Trauner D (1996) Formal total synthesis of (—)-morphine by cuprate conjugate addition. Angew Chem hit Ed 35 2830-2832... 

As dihydrocodeinone has been converted to morphine before, this hydrogenation concludes the formal synthesis of this important alkaloid. The completion of the synthetic route included the conversion of the tertiary amine into the corresponding carbamate before the C7-C8 unsaturation... 

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