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United States Patent (19) 11 Patent Number: 5,348,975 Chandraratna 45 Date of Patent: Sep

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United States Patent (19) 11 Patent Number: 5,348,975 Chandraratna 45 Date of Patent: Sep US005348975A United States Patent (19) 11 Patent Number: 5,348,975 Chandraratna 45 Date of Patent: Sep. 20, 1994 54) 7-CHROMANYLESTERS OF PHENOLS AND OTHER PUBLICATIONS BENZOCACDS HAVING RETNOD-LIKE A General Synthesis of Terminal and Internal Arylalk ACTIVITY ynes by the Palladium-Catalyzed Reaction of Alkynyl 75 Inventor: Roshantha A. S. Chandraratna, El zinc Reagents with Aryl Halides by Anthony O. King Toro, Calif. and Ei-ichi Negishi, J. Org. Chem. 43 No. 2, 1978 p. 358. (73) Assignee: Allergan, Inc., Irvine, Calif. Conversion of Methyl Ketones into Terminal Acety lenes and (E)-Tri-substituted Olefins of Terpenoid Ori (21) Appl. No.: 143,682 (List continued on next page.) (22) Filed: Oct. 27, 1993 Primary Examiner-Nicky Chan Related U.S. Application Data Attorney, Agent, or Firm-Gabor L. Szekeres; Robert J. Baran; Martin A. Voet 62 Division of Ser. No. 918,538, Jul. 22, 1992, which is a division of Ser. No. 676,152, Mar. 26, 1991, Pat. No. (57) ABSTRACT 5,134,159. Retinoid like activity is exhibited by compounds of the (51) Int. Cli..................... A61K 31/35; C07D 311/04 formula (52) U.S. C. .................................... 514/456; 549/410; 549/370; 549/347; 514/452; 514/450 58 Field of Search ....................... 514/456, 452, 450; 549/410, 370, 347 (56) References Cited U.S. PATENT DOCUMENTS 4,096,341 6/1978 Frazer . 4,326,055 4/1982 Loeliger . 4,391,731 7/1983 Boller et al. 4,695,649 9/1987 Magami et al. wherein the R1-R6 groups are independently H or 4,723,028 2/1988 Shudo . straight chain or branched chain lower alkyl or cycloal 4,739,098 4/1988 Chandraratna . 4,740,519 4/1988 Shroot et al. kyl of 1 to 6 carbons; Xsymbolizes an ester or thioester 4,810,804 3/1989 Chandraratna . linkage, Y is lower branched chain alkyl having 2 to 6 4,826,969 5/1989 Maignan et al. carbons, cycloalkyl having 3 to 6 carbons or is (CH2) 4,855,320 8/1989 Chatterjee et al. where n is an integer between 0 to 6 or is an alkenyl 4,895,868 1/1990 Chandraratna . group of 2 to 6 carbons, and having 1 or 2 double bonds, 4,980,369 12/1990 Chandraratna . or an alkynyl group of 2 to 6 carbons; and Z is H, OH, 4,992,468 2/1991 Chandraratna . OR', OCOR', -COOH or a pharmaceutically accept 5,006,550 4/1991 Chandraratna . able salt COOR8, COONR9R10, -CH2OH, CH2OR11, 5,013,744 5/1991 Chandraratna . CH2OCOR11, CHO, CHOR12), CHOR13O, -COR', 5,015,658 5/1991 Chandraratna . CR'(OR12)2, or CR'OR13O; where R' is an alky, cyclo (List continued on next page.) alkyl or alkenyl group containing 1-5 carbons, R8 is an alkyl group of 1-10 carbons, or a cycloalkyl group of FOREIGN PATENT DOCUMENTS 5-10 carbons, or R8 is phenyl or lower alkylphenyl, R9 0130795 1/1985 European Pat. Off. and R10 independently or hydrogen, an alkyl group of 176034A 4/1986 European Pat. Off. 1-10 carbons, or a cycloalkyl group of 5-10 carbons or 0272921 6/1988 European Pat. Off. phenyl or lower alkyl phenyl, R11 is lower alkyl, and 0284288 9/1988 European Pat. Off. R13 is a divalent alkyl radical of 2-5 carbons. 0350846 7/1989 European Pat. Off. 3708060 9/1987 Fed. Rep. of Germany . 18 Claims, No Drawings 5,348,975 Page 2 U.S. PATENT DOCUMENTS CRC Press In, 1990, pp. 334-335, 354. 5,023,341 6/1991 Chandraratna . Synthesis of 2,2'-Diacyl-1,1'-biaryls. Regiocontrolled 5,037,825 8/1991 Klaus et al. Protection of... by Mervic, et al., J. Org. Chem, No. 5,045,551 9/1991 Chandraratna . 45, pp. 4720-4725, 1980. 5,053,523 10/1991 Chandratatna. 5,068,252 11/1991 Chandraratna . A Dopamine Receptor Model and Its Application in the 5,089,509 2/1992 Chandraratna . Design of a New Class of Rigid Pyrrolo2,3-glisoquino 5,130,335 7/1992 Chandraratna . line Antipsychotics, Gary L. Olson, et al. American 5,134,159 7/1992 Chandraratna . Chemical Society, 1981, vol. 24, No. 9, pp. 1026-1031. 5,162,546 11/1992 Chandraratna . 6.2.3 Conformatioinal Restriction, Williams, et al., Drug 5,175,185 12/1992 Chandraratna . Discovery and Development, 1987 The Humans Press, pp. 5,183,827 2/1993 Chandraratna . 54-55. 5,202,471 4/1993 Chandraratna . 5,231,113 7/1993 Chandraratna . V. Retinoid Structure-Biological Activity Relation 5,234,926 8/1993 Chandraratna . ships, Chemistry and Biology of Synthetic Retinoids, 5,248,777 9/1993 Chandraratna . pp. 324-356 (1982). 5,264,456 11/1993 Chandraratna . Davis et al. J. Organomettalic Chem 387 (1990) 381-390. 5,264,578 11/1993 Chandraratna . Effects of 13-Cis-Retinoic Acid, All-Trans-Retinoic 5,272,156 12/1993 Chandraratna ..................... 514/314 Acid, and Acitretin on the Proliferation, Lipid Synthe OTHER PUBLICATIONS sis and Keratin Expression of Cultured Human Sebo gin by Ei-ichi, Anthony O. King and William L. Klima, cytes. In Vitro, C. C. Zouboulis, The Journal of Investi J. Org. Chem. 45 No. 12, 1980. p. 2526. gative Dermatology, vol. 96, No. 5, May 1991, pp. Sporn et al. in J. Amer. Acad. Derm. 15:756-764 (1986). 792-797. A Convenient Synthesis of Ethynylarenes and Die Organ maintenance of human sebaceuous glands: in thynylarenes by S. Takahashi, Y. Kuroyama, K. vitro effects of 13-cis retinoic acid and testosterone, Sonogashira, N. Hagihara, Synthesis 1980 pp. 627-630. John Ridden, et al., Journal of Cell Science, vol. 95, Shudo et al. in Chem. Phar. Bull. 33:404–407 (1985). 1990, pp. 125-136. Kagechika et al. in J. Med. Chem. 31:2182-2192 (1988). Characterization of Human Sebaceous Cells In Vitro, Chemistry and Biology of Synthetic Retinoids by Mar Thomas I. Doran, et al., The Journal of Investigative cia I. Dawson and William H. Okamura, published by Dermatology, vol. 96, No. 3, Mar. 1991. 5,348,975 1. 2 7-CHROMANYLESTERS OF PHENOLS AND CR'(OR12)2, or CR'OR13O; where R is an alkyl, cyclo BENZOIC ACDS HAVING RETNOED-LKE alkyl or alkenyl group containing 1-5 carbons, R8 is an ACTIVITY alkyl group of 1-10 carbons, or a cycloalkyl group of 5-10 carbons, or Rs is phenyl or lower alkylphenyl, R9 CROSS-REFERENCE TO RELATED and R10 independently are hydrogen, an alkyl group of APPLICATION 1-10 carbons, or a cycloalkyl group of 5-10 carbons or The present application is a divisional of application phenyl or lower alkyl phenyl, R11 is lower alkyl, R12 is Ser. No. 07/918,538 filed on Jul. 22, 1992, which was a lower alkyl, R13 is divalent alkyl radical of 2-5 carbons. divisional of application Ser. No. 07/676,152, filed on 10 In a second aspect, this invention relates to the use of Mar. 26, 1991, issued as U.S. Pat. No. 5,134,159. the compounds of Formula 1 for treating dermatoses, BACKGROUND such as acne, Darier's disease, psoriasis, icthyosis, ec This invention relates to novel compounds having Zema, atopic dermatitis and epithelial cancers. These retinoid-like activity. More specifically, the invention 15 compounds are also useful in the treatment of arthritic relates to compounds having a substituted chroman diseases and other immunological disorders (e.g. lupus portion and a substituted phenyl portion linked to the 7-position of the chroman nucleus through an ester or erythematosus), in promoting wound healing, in treat thioester group. ing dry eye syndrome and in reversing and preventing 20 the effects of sun damage to skin. RELATED ART This invention also relates to a pharmaceutical formu Carboxylic acid derivatives useful for inhibiting the lation comprising a compound of Formula 1 in admix degeneration of cartilage of the general formula 4-(2- ture with a pharmaceutically acceptable excipient. (4,4-dimethyl-6-X)-2-methylvinyl)benzoic acid where X is tetrahydroquinolinyl, chromanyl or thiochromanyl 25 In another aspect, this invention relates to the process are disclosed in European Patent Application 0133795 for making a compound of Formula 1 which process published Jan. 9, 1985. European Patent Application comprises reacting compounds of Formula 2 with com 176034A published Apr. 2, 1986 discloses tetrahydro pounds of Formula 3, naphthalene compounds having an ethynylbenzoic acid group. U.S. Pat. No. 4,739,098 discloses compounds of 30 retinoid-like activity where three olefinic units from the Formula 2 acid-containing moiety of retinoid acid are replaced by an ethynylphenyl functionality. The publication by Sporn et. al. in J. Anner. Acad. Derm. 15:756-764 (1986) discloses the compound 4 35 A' (5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-2-naph thoylamino) benzoic acid as a retinoid-like agent. Fur Formula 3 ther compounds of background interest to the present invention are disclosed by Shudo et al. in Chem. Phar. Bull. 33:404-407 (1985). A patent application of the present inventor, assigned to the same assignee as this application, describes com pounds having a substituted chroman portion and a substituted phenyl portion linked to the 6-position of the where R1-R6, Y and Z are defined as above in connec chroman nucleus through an ester or thioester group. 45 tion with Formula 1, and wherein one of A and B' is an SUMMARY OF THE INVENTION OH or SH group, and the other is a carboxylic acid (COOH) or an appropriate derivative (such as an acid This invention covers compounds of Formula 1 chloride) suitable for forming an ester with a hydroxyl R 50 or thiol group, and where the reaction is conducted R R2 s Formula 1 under conditions suitable for forming an ester or thioes ter bond between the chroman ring of the compound of Formula 2 and the phenyl ring of the compound of ic Y-Z Formula 3.
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