Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1992-06-22
1993-09-21
Cintins, Marianne M.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
560256, 549389, C07D30792
Patent
active
052471004
DESCRIPTION:
BRIEF SUMMARY
This invention relates to a process for the production of sclareolide from sclareol.
8.alpha., 12-oxido-13,14,15,16-tetranorlabdane (Ambroxan.RTM.) is an extremely valuable amber fragrance which is found in ambergris, a metabolism secretion of the sperm whale (Ullmann's Encyklopadie der Technischen Chemie, Vol. 20, page 283, Verlag Chemie Weinheim, 1981). Synthetically, Ambroxan.RTM. can be prepared from sclareol by two-stage oxidation in accordance with U.S. Pat. No. 3,050,532 and subsequent reduction of the sclareolide formed. During the two-stage oxidation process, sclareol (1) is first oxidized with potassium permanganate under alkaline reaction conditions to form the hydroxyketone (2). The hydroxyketone formed is converted without isolation into the enolether (3) by reaction with glacial acetic acid and is subsequently oxidized either with potassium manganate or with chromic acid. The oxidation product obtained, a mixture of sclareolide and acetoxy acid, is saponified and completely cyclized to sclareolide (4). However, the disadvantage of this process lies in the long reaction time of the second oxidation stage. According to the Examples of U.S. Pat. No. 3,050,532, it is about 19.5 hours. ##STR2##
In addition, it is known from DE 36 10 063 that sclareol can be oxidized with hydrogen peroxide in the presence of acids, for example p-toluenesulfonic acid, to form a hydroperoxide from which Ambroxan.RTM. can be prepared with a redox system, for example FeSO.sub.4 /Cu(OAc).sub.2. In this process, too, a long reaction time, namely 7 days, is required for the oxidation stage.
Accordingly, the problem addressed by the present invention was to provide a process for the production of sclareolide which would not require long reaction times. The reduction in the reaction time would be accompanied by at least as good yields of sclareolide as can be obtained with the process known from U.S. Pat. No. 3,050,532.
It has surprisingly been found that the reaction times can be considerably reduced if, in a first stage, sclareol is oxidatively degraded either with hypochlorite salts in the presence of ruthenium compounds or, as in U.S. Pat. No. 3,050,532, with potassium permanganate and, in a second stage, the hydroxyketone obtained is oxidized with peracids and/or salts thereof to sclareolide.
Accordingly, the present invention relates to a two-stage process for the production of sclareolide from sclareol, characterized in that, in a first stage, sclareol is oxidatively degraded to the hydroxyketone 2 and/or the enolether 3 either with hypochlorite salts in the presence of ruthenium compounds or in known manner with potassium permanganate and, in a second stage, the hydroxyketone 2 and/or the enolether 3 is oxidized to sclareolide with peracids and/or peracid salts.
In the process according to the invention, sclareol can be oxidatively degraded to the hydroxyketone 2 and/or the enolether 3 with alkali metal and/or alkaline earth metal hypochlorites, for example sodium and/or calcium hypochlorite, in the presence of ruthenium salts, for example ruthenium dioxide and/or ruthenium trichloride, at temperatures of 0.degree. to 40.degree. C. It can be useful to carry out the reaction in the presence of phase transfer catalysts, for example ammonium compounds, such as tetrabutyl ammonium chloride. Sclareol is dissolved in solvents inert under the reaction conditions, for example methylene chloride and/or cyclohexane, preferably with 0.1 to 10 mol-% and, more preferably, with 0.5 to 3 mol-% ruthenium compounds and preferably with 0 to 20 mol-% and, more preferably, with 0 to 10 mol-% phase transfer catalysts (all mol-% are based on sclareol). To these solutions are added aqueous solutions preferably containing 400 to 1,000 mol-% and, more preferably, 600 to 800 mol-% hypochlorite salts and preferably 0 to 500 mol-% and, more preferably, 100 to 500 mol-% alkali metal hydroxides, such as sodium and/or potassium hydroxide, based on the quantity of sclareol used. On completion of the reaction, acids, for example formic acid, acetic
REFERENCES:
patent: 3050532 (1962-08-01), Schumacher et al.
patent: 3096346 (1963-07-01), Giles et al.
Cambie et al., Aust. J. Chem., 43(7), 1151-62 (1990).
Bruns Klaus
Gerke Thomas
Cintins Marianne M.
Henkel Kommanditgesellschaft auf Aktien
Jaeschke Wayne C.
Millson Jr. Henry E.
Peabody John
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