Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1994-10-17
1996-06-11
Evans, Joseph E.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
562467, C07D30792
Patent
active
055257283
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/EP93/00874 filed Apr. 8, 1993.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a process for the production of sclareolide from sclareol and/or abienol.
A full definition of the trivial names and abbreviations used in the following in conjunction with the accompanying numbers in round brackets is given in the Example section which shows the associated IUPAC name and the corresponding structural formula.
2. Statement of the Related Art
Ambroxan (7) is a valuable ambergris fragrance which is found in a metabolic secretion of the sperm whale (cf. Ullmanns Enzyklopadie der technischen Chemic, Vol. 20, pages 283, Weinheim 1981). In view of limited natural resources, the increasing demand for ambroxan has led in recent years to the development of processes by which ambroxan can be synthetically obtained from inexpensive raw materials. Sclareolide (6) in particular has proved to be an important ambroxan precursor so that the concern of many research groups has been to develop processes by which sclareolide can be synthesized from natural raw materials, more particularly sclareol (1).
According to U.S. Pat. No. 3,050,532, sclareol is first oxidized with potassium permanganate under alkaline reaction conditions to form the hydroxyketone (3) which, without further isolation, is converted with glacial acetic acid into the enolethers (4). The enolether is then oxidized either with potassium permanganate or with chromic acid. The oxidation product obtained is saponified and then cyclized to form sclareolide (6). Unfortunately, this process is attended by the disadvantage that the oxidation step is carried out with potassium permanganate which is ecologically unsafe, i.e. toxic. In addition, the MnO.sub.2 (magnesium dioxide) formed therefrom is very difficult to filter off in the working-up phase.
Finally, German patent application DE 39 42 358 describes a process in which sclareol is first oxidatively degraded with hypochlorite salts in the presence of ruthenium salts to form the hydroxyketone (3) and/or the enolether (4), the intermediate product thus obtained and isolated is oxidized with peracids and/or peracid salts and, after saponification and acidic ring closure, is converted into sclareolide. This process gives sclareolide in a yield of around 65%, based on sclareol.
Accordingly, in view of the key position of ambroxan in the field of fragrances, there is a general need to develop improved syntheses. This demand extends in particular to improvements in individual process steps and to the development of alternative syntheses for the production of important intermediate products or precursors of ambroxan. Accordingly, the problem addressed by the present invention was to create better access to sclareolide starting out from sclareol and structurally closely related compounds.
DESCRIPTION OF THE INVENTION
According to the invention, the solution to this problem characterized in that sclareol (1) and abienol (2) is first reacted with 10.5 to 25 times the molar quantity of an oxidizing agent in aqueous medium in the absence of an organic solvent and in the presence of a ruthenium catalyst and an emulsifier to form a crude product which, thereafter, is either converted in the presence of a base into the salt of 8.alpha.-hydroxy-11-carboxy-12,13,14,15,16-pentanorlabdane, hereinafter referred to as the hydroxy acid (5), and the hydroxy acid (5) is cyclized in acidic medium to form sclareolide or is subjected to an after-reaction at elevated temperature and subsequently distilled, the after-reaction optionally taking place in situ during the distillation phase.
Accordingly, the present invention relates to a process for the production of sclareolide in which sclareol and/or abienol is reacted with 10.5 to 25 times the molar quantity--based on sclareol and/or abienol--of an oxidizing agent in aqueous medium in the absence of an organic solvent and in the presence of a ruthenium catalyst and an emulsifier to form a crude product which, thereafter, is e
REFERENCES:
patent: 3050532 (1962-08-01), Schumacher et al.
patent: 4503240 (1985-03-01), Staiger et al.
patent: 5212078 (1993-05-01), Farbood et al.
patent: 5247100 (1993-09-01), Gerke et al.
patent: 5290955 (1994-03-01), Asanuma et al.
Ullmanns Enzyklopadie der technischen Chemie, vol. 20, p. 283, Weinheim 1981.
Gerke Thomas
Schneider Markus
Stalberg Theo
Drach John E.
Evans Joseph E.
Henkel Kommanditgesellschaft auf Aktien
Jaeschke Wayne C.
Millson Jr. Henry E.
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