Epoxycyclohexenedione derivatives

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

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549546, A61K 31335, C07D30302

Patent

active

055654894

DESCRIPTION:

BRIEF SUMMARY
This application is a 371 of PCT/JP94/01542 dated Sep. 20, 1994.


TECHNICAL FIELD

The present invention relates to an epoxycyclohexenedione derivative having antimicrobial activity and antitumor activity or a pharmaceutically acceptable salt thereof.


BACKGROUND ART

Ras oncogene undergoes point mutation in many tumor tissues in humans and is detected as an activated form capable of transforming normal cells. It is essential for the expression of transforming activity of the ras oncogene product that the 12th, 13th or 61st amino acid should undergo point mutation and, additionally, the cysteine residue at the C terminal region should be farnesylated for the membrane association of the ras oncogene product. The reaction is catalyzed by farnesyltransferase (hereinafter referred to as "FTase"). Accordingly, an FTase inhibitor is expected to inhibit the function of the ras oncogene product and thereby to have antitumor activity.
Compounds represented by the following formulae are known as expoxycyclohexene derivatives having FTase inhibitory activity. ##STR3##
Manumycin [Proc. Natl. Acad. Sci. USA, 90, 2281 (1993)]. It is reported that IC50 against FTase of yeast origin is 5 .mu.mol when ras protein of yeast origin is used as a substrate. ##STR4##
Manumycin derivatives (compounds IVa, IVb, and IVc) [Proc. Natl. Acad. Sci. USA, 90, 2281 ( 1993 ); Tetrahedron Letters, (1973); J. Antibiotics, 40, 1530 and 1549 (1987); Japanese Patent Application No. 2-120640, published as unexamined Laid-Open application No. 221377/1992 (U.S. Pat. No. 5,106,868). It is reported that the activity of these compounds can be detected, and that the activity is not numerically described.
An epoxycyclohexenedione derivative represented by the following formula is known, but FTase inhibitory activity of the compound is not reported: ##STR5## Askamycin derivative [J.Am. Chem. Soc., 101, 3402 (1979)]. ##STR6##
LL-C10037 a derivative [J. Am. Chem. Soc., 111., 7932 (1989), J. Org. Chem., 59, 3518 (1994)].


DISCLOSURE OF THE INVENTION

The present invention relates to an epoxycyclohexenedione derivative represented by formula (I): ##STR7## wherein R is a straight-chain or branched alkanoyl group having 10 to 25 carbon atoms, a straight-chain alkenoyl group having 10 to 25 carbon atoms, or a group represented by formula (A): ##STR8## wherein n is an integer of 1 to 4; or a pharmaceutically acceptable salt thereof.
Hereinafter the compound represented by formula (I) is referred to as Compound I. The same applies to the compounds of other formula numbers.
In the definition of each group in Compound I; the straight-chain or branched alkanoyl group having 10 to 25 carbon atoms includes lauroyl, myristoyl, palmitoyl, stearoyl, 3,7,11-trimethyllauroyl, and 3,7,11,15-tetramethylpalmitoyl; the straight-chain alkenoyl group having 10 to 25 carbon atoms includes palmitoleoyl, linoleoyl, and linolenoyl; and the group represented by formula (A) means geranoyl, farnesoyl, geranylgeranoyl or geranylfarnesoyl.
The pharmaceutically acceptable salts of Compound I include pharmaceutically acceptable acid addition salts, for instance, inorganic acid salts such as hydrochloride, sulfate and phosphate; and organic acid salts such as acetate, maleate, fumarate, tartrate and citrate.
The process for producing Compound I is explained below. Compound I can be prepared by the following steps: acylation of 2-amino-4-methoxyphenol (Step 1), oxidation to quinone ( Step 2 ), and epoxidation ( Step 3 ) as illustrated by the following reaction scheme. ##STR9## wherein R has the same meaning as defined above. Step 1:
Compound II can be obtained by reacting 2-amino-4-methoxyphenol with 1 to 2 equivalents of an acyl halide, an acyl anhydride or a mixed acid anhydride having a desired acyl group in the presence of an appropriate base, such as pyridine, N,N-dimethylaniline and N,N-diethylaniline, in a solvent, such as dimethylformamide, dimethylsulfoxide, chloroform, dichloromethane and toluene, or in a solvent such as an appropriate base. The reaction temperature is 0.degree

REFERENCES:
patent: 5106868 (1992-04-01), Nakano et al.
Hara et al., PNAS USA, vol. 90 (1993) 2281-85.
Zeeck et al., J. Antibiotics, vol. 40, No. 11 (1987) 1530-40.
Thierickle et al., J. Antibiotics, vol. 40, No. 11 (1987) 1549-54.
Kakinuma et al., J. Am. Chem. Soc., vol. 101, No. 12 (1979) 3402-04.
Gould et al., J. Am. Chem. Soc., vol. 111, No. 20 (1989) 7932-38.
Wipf et al., J. Org. Chem., vol. 59, No. 13 (1994) 3518-19.
Shen et al., Biochemistry, vol. 30, No. 37 (1991) 8936-44.
Schroder et al., Tetrahedron Lett., No. 50 (1973) 4995-98.

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