Fluorinated flavone acetic acid

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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549403, 546196, 544151, 514320, 5142335, A61K 3135, C07D31130

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active

052389545

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

The present invention is directed toward novel fluorinated flavone acetic acids (FAA) suitable for use as antitumor agents. The fluorinated FAA compounds are more effective than their unfluorinated counterparts. For example B. Derwinko and L-Y. Yang, "The Activity of flavone acetic acid (NSC 347512) on human colon cancer cells in vitro" Invest. New Drugs, 4:289-93 (1986) disclose that FAA (4-oxo-2-phenyl-4H-1-benzopyran-8-acetic acid) had "relatively poor cytotoxic effects and because the therapeutic range of FAA is so narrow, we conclude that this agent will not be a valuable contribution to the antitumor arsenal at least for colon cancer." Meanwhile, the fluorinated FAA of the present invention has shown curative activity in murine pancreatic carcinoma models and against solid tumors. In particular, they have been shown to exhibit activity against human tumor cell lines and an FAA resistant cell line.


INFORMATION DISCLOSURE

U.S. Pat. Nos. 4,783,533 and 4,602,034 disclose FAA compounds chemically called (4-oxo-4H-(1)-benzopyran-8-yl)alconic acids their salts and derivatives as well as methods for their preparation and use in the control of tumors. European Patent Application 0278176 discloses various flavone acetic acid analogs described as xanthenone-4-acetic acid. The synthesis and antitumor effect of substituted 4-oxo-4H-1-benzopyrans are described in Eur. J. Med. Chem., 20, 5, p. 393-402 (1985) which was authored by the same inventors of 4,783,533 and 4,602,034.
FAA compounds, particularly a diethylaminoethyl ester derivative are discussed in Drugs of the Future, Vol. 12, 2, p. 123-25 (1987). An article in Cancer Research, 48, 5878-82 (Oct. 15, 1988) entitled "Phase I and Clinical Pharmacology Study of Intravenous Flavone Acetic Acid" by Weiss, et al. describes the basic antitumor effects of FAA and results when administered to patients. FAA is reported to have murine tumor activity in animals although no objective tumor response was observed in humans tested. The article also reports the toxicity problems associated with FAA such as acute hypotension and generalized fatigue and asthemia.


SUMMARY OF THE INVENTION

In one aspect the subject invention is a compound according to Formula I wherein R.sub.1 is CHO, CN, CO.sub.2 M, CO.sub.2 R.sub.3 or CONR.sub.3 R.sub.4 where M is hydrogen or a pharmaceutically acceptable salt such as Li, Na, K, Ca or other acceptable counter-ion for carboxylic acids, R.sub.3 and R.sub.4 are independently hydrogen, C.sub.1 -C.sub.12 alkyl or heterosubstituted alkyl, C.sub.3 -C.sub.10 cycloalkyl or heterosubstituted cycloalkyl, C.sub.6 -C.sub.12 aryl, alkylaryl or are joined to form a C.sub.3 -C.sub.10 cycloalkyl or heterosubstituted cycloalkyl; R.sub.2 is hydrogen, fluorine, methyl, CF.sub.3, phenyl or substituted phenyl. The fluorinated phenyl ring can be fluorinated at any of the C2 to C6 positions and n is 1 to 5, inclusive. Preferably, R.sub.1 is CO.sub.2 M and R.sub.2 is hydrogen.
Typical fluorinated phenyl rings can include 3-fluorophenyl, 2,3,4,5-tetrafluorophenyl, pentafluorophenyl, 3,4-difluorophenyl, 2-fluorophenyl, 4-fluorophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, 3,4,5-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, 2,3-difluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2,5-difluorophenyl or 2,4-difluorophenyl. Preferred compounds include 4-oxo-2-(3-fluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(pentafluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(3,4-difluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(2-fluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(4-fluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(2,6-difluorophenyl)-4H-1-benzopyran-8-acetic acid, or 4-oxo-2-(3,5-difluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(3,4-difluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(pentafluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(3,4,5-trifluorophenyl)-4H-1-benzopyran-8-acetic acid, 4-oxo-2-(2,3,5,6-tetrafluorophenyl)-4H- 1-benzopyran-8-acetic acid, 4-oxo-2-(2,3-difluorophenyl)-4H

REFERENCES:
patent: 4602034 (1986-07-01), Briet et al.
patent: 4783533 (1988-11-01), Briet et al.
patent: 5116954 (1992-05-01), Briet et al.
Atassi, G., et al., "Synthesis and Antitumor Activity of Some 8-Substituted-4-oxo-4H-1-benzopyrans," Eur. J. Med. Chem. 20(5):393-402 (1985).
Zee-Cheng, R. K-Y. and C. C. Cheng, "Flavoneacetic Acid," Drugs of the Future 12(2):123-125 (1987).
Weiss, R. B., et al., "Phase I and Clinical Pharmacology Study of Intravenous Flavone Acetic Acid (NSC 347512).sup.1," Cancer Research 48:5878-5882 (1988).

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