Method for the catalytic production of hydrocodone and...

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

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C546S044000, C546S046000

Reexamination Certificate

active

07323565

ABSTRACT:
A method for the catalytic conversion of codeine, morphine or analogs thereof into hydrocodone, hydromorphone or analogs thereof utilizing a transition metal complex of a tertiary phosphine halide as catalyst.

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William S. Knowles, K. Ryoji Noyori, and Barry Sharpless; Information for the Public, the 2001 Nobel Prize in Chemistry: Mirror Image Catalysis;Kungl Vetenskapsakademien, The Royal Swedish Academy of Sciences; Apr. 8, 2002.
Bernard Demerseman, Ronan Le Lagadec, Benedicte Guilbert, Corinne Renouard, Pascale Crochet, and Pierre H. Dixneuf; Chelating and Hemilabile Properties of β- and γ- Keto Phosphines: (η6- Arene) ruthenium (II) Derivatives from γ- Keto Phosphines and synthesis and Reactivity of Bis (η2-keto phosphine-P,O) ruthenium (II) Complexes;Advance ACS Abstracts, Organometallics Vo. 13, No. 6, May 1, 1994.
Manuel M. Baizer, Kurt S. Ellner, and Athanasios Loter; The Rearrangement of Codeine to Dihydrocodeinone;Journal of the American Pharmaceutical Association, vol. XL, p. 580-582; Nov. 1951.
Annika Rimland, Goran Bergson, Ulf Obenius, Stefan Sjoberg, and Bengt Langstrom;Synthesis of N-[Methyl-11C] Hydromorphone by Using Multivariate Strategies for Optimization of Radiochemical Yields; Appl. Radiat. Isol., vol. 38, No. 8, p. 651-654; 1987.
Katada, Masa; Yakugaku Zasshi, Morphine bases. III. Conversion of Phenylpseudocodeine,Journal of the Pharmaceutical Society of Japan; vol. 62, p. 347-355; Nippon Yakugakkai, Japan, 1942. This Article is relevant since it discloses that codeine was arranged to dihydrocodeinone in 50-79% yields using 10% Palladium black as catalyst, 6% Hydrochloric acid as medium, a temperature of 50-80oC and a current of hydrogen. But the reference is not involved in our claims on isomerization of codeine and morphine by a transition metal complex of a tertiary phosphine halid, [M(PR3)nXm]p. (Abstract is provided in English).
Nippon Yakugakkai; Electrolytic Reduction of Morphine and Codine;Journal of the Pharmaceutical Society of Japan; vol. 56, p. 44-52; Nippon Yakugakkai, Japan, 1936.This Article is relevant since it discloses electronic reduction of codeine and morphine to dihydrocodeine and dihydromorphine, respectively. But the reference is not involved in our claims on isomerization of codeine and morphine by a transition metal complex of a tertiary phosphine halid, [M(PR3)nXm]p. (Abstract is provided in English).
C. Mannich and H. Lowenheim; Archiv der Pharmazie;Arch. Pharm.; vol. 258, p. 295-316; 1920. This Article is relevant since it discloses reduction of codeinnone to dihydrocodeinone in the presence of Pd and hydrogen. But the reference is not involved in our claims on isomerization of codeine and morphine by a transition metal complex of a tertiary phosphine halid, [M(PR3)nXm]p. (Abstract is provided in English).
PCT International Search Report dated Jul. 12, 2004; International Application No. PCT/US03/35462; Applicant: Mallinckrodt, Inc.; International Filing Date Nov. 5, 2003.
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Rapoport, Henry; Naumann, Robert; Bissell, Eugene; and Bonner, Robert.The Preparation of some Dihydro Ketones in the Morphine Series by Oppenauer Oxidation; Oppenauer Oxidation in Morphine Series, pp. 1103-1107, Chemical Laboratory of the University of California, May 12, 1950, (Printed in Berkeley, California U.S.A.).
S.G. Davies et al.; Synthesis of 10(s)-Methyl-codeine & 20(s)-methyl-morphine; J. Chimie, 1980, p. 369-375.
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J. Am. Pharm. Assoc., 1950, 40, p. 480.
S.G. Davies et al.; Palladium Catalyzed elaboration of Codeine & Morphine; J. Chem. Soc., Perkin Trans., 2001, 1, (12), p. 1413-1420.

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