Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1995-08-25
1997-06-10
Richter, Johann
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549433, 549545, 558 44, 558 46, 558270, 558276, 558482, C07D30102
Patent
active
056377380
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT GB94/00307 filed Feb. 26, 1994.
This invention relates to chemical processes, and in particular to processes for making (1S,2R)-1,2-epoxy-1,2,3,4-tetrahydronaphthalene having the Formula (I): ##STR4## and the enantiomer thereof having the Formula (IA): ##STR5##
Compounds of Formulae (I) and (IA) are useful as intermediates for the synthesis of biologically active compounds, for example pharmaceutical compounds. As epoxides they are capable of undergoing a variety of reactions enabling preparation of a wide range of further products.
According to the present invention there is provided a process for the preparation of (1S,2R)-1,2-epoxy-1,2,3,4-tetrahydronaphthalene having the Formula (I) which comprises the steps of cis-(1R,2S)-1,2-dihydroxy-1,2,3,4-tetrahydronaphthalene having the Formula (V): ##STR6## (b) reacting the dihydroxy compound of Formula (V) with a sulphonyl halide of formula R.sup.1 SO.sub.2 Z wherein R.sup.1 is methyl, ethyl, trifluoromethyl, phenyl or p-tolyl, and Z is fluorine, chlorine, bromine or iodine to give a bis-sulphonyl ester of Formula (X): ##STR7## and (c) treating the bis-sulphonyl ester (X) with an alkali metal carbonate or alkali metal hydroxide to give the compound of Formula (I).
The hydrogenation Step (a) of the present process may be carried out by standard procedures for example by reacting a solution of compound (II) with hydrogen in the presence of a metal catalyst. The metal catalyst may be any hydrogenation catalyst such as those comprising Raney nickel, platinum, palladium, ruthenium or rhodium which may be used as a finely divided free metal or metal oxide or as a metal or metal oxide carried on a support selected from charcoal, alumina or silica. The metal catalyst is preferably supported on charcoal, more preferably is from 0.5 to 10% platinum or palladium on charcoal and especially 10% palladium on charcoal. Conveniently the compound (II) may be dissolved or dispersed in a liquid medium such as a lower alcohol, preferably methanol or ethanol for the hydrogenation reaction. The reaction may be performed at a temperature from 0.degree. C. to 100.degree. C. and is preferably performed at temperatures from 20.degree. C. to 25.degree. C. The product (V) may be recovered by filtering off the catalyst and evaporating the filtrate. The product may be purified by conventional methods such as recrystallisation.
In step (b) the sulphonyl halide is preferably reacted with the dihydroxy compound (V) in the presence of a tertiary amine as an acid acceptor. Examples of tertiary amines include triethylamine, pyridine and dimethylaniline. The reaction is preferably conducted in an inert solvent at a temperature from -30.degree. C. to 10.degree. C. preferably at from -20.degree. C. to 5.degree. C. and especially at from 0.degree. to 5.degree. C. Examples of suitable solvents include ethers such as diethylether or tetrahydrofuran, hydrocarbons such as benzene, toluene or xylene and halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane. At the end of the reaction the tertiary amine hydrohalide formed may be removed by filtration and the bis-sulphonyl ester may be recovered by evaporation of the filtrate, and further purified by conventional means such as recrystallisation. Preferred sulphonyl halides are selected from methane-, trifluoromethane- and p-toluenesulphonyl chlorides.
In stage (c), the alkali metal carbonate may be, for example sodium or potassium carbonate. The alkali metal hydroxide may be sodium or potassium hydroxide. The reaction may be performed in water or a mixture of water and a lower alcohol preferably methanol or ethanol and may be carried out at a temperature of from -70.degree. C. to 100.degree. C. preferably from -20.degree. C. to 70.degree. C. and more preferably from 0.degree. C. to 40.degree. C. Alternatively stage (c) may be carried out in a mixture of water and immiscible organic solvent preferably a halogenated alkane such as dichloromethane, chloroform or carbon tetrachloride, a hydrocarbon suc
REFERENCES:
patent: 4082773 (1978-04-01), Hauck
Becker et al., J. Am. Chem. Soc. (1979), 101 (19) pp. 5679-5687.
White, et al: "Photolysis of cis-1, 2-dihydroxyindancarbonate and cis-1, 2-dihydroxy-1,2,3,4-tetrahydronaphthalene carbonate", Chemical Abstracts, vol. 110, No. 25, issued 1989, Jun. 19, p. 631, col. 2, No. 231 476r; & J. Heterocycl. Chem. 1988, 25(6), 1781--3.
Blacker Andrew J.
Boyd Derek R.
Brown Stephen M.
Sheldrake Gary N.
Richter Johann
Stockton Laura L.
Zeneca Limited
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