Patent ID: 6297207
Filing Date: 2001-10-02
Classification: A61K,C11D

Abstract:
A singlet oxygen generator having the formula: ##STR50##wherein P is a photosensitizer unit having the formula: ##STR51##or the formula: ##STR52##wherein M is a photoactive metal or non-metal having a valence greater than or equal to 3 which is selected from the group consisting of silicon, phosphorous, palladium, platinum, lead, germanium, tin, and mixtures thereof; rings A, B, C, and D are aromatic rings, wherein each of said rings A, B, C, and D are each independently:i) a benzene ring unit having the formula: ##STR53##ii) a 2,3-naphthylene ring unit having the formula: ##STR54##iii) a 1,2-naphthylene ring unit having the formula: ##STR55##iv) an anthracene ring unit having the formula: ##STR56##v) an phenanthrene ring unit having the formula: ##STR57##wherein each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 unit is independently selected from the group consisting of:a) hydrogen;b) halogen;c) hydroxy;d) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;e) halogen substituted C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;f) polyhydroxyl substituted C.sub.3 -C.sub.22 alkyl;g) C.sub.1 -C.sub.22 alkoxy;h) branched alkoxy having the formula: ##STR58##wherein Z is hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkoxy, --CO.sub.2 H, --OCH.sub.2 CO.sub.2 H, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, --PO.sub.3.sup.2- M, OPO.sub.3.sup.2- M, or mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance;x is 0 or 1, each y independently has the value from 0 to 6, each z independently has the value from 0 to 100;i) substituted aryl, unsubstituted aryl, or mixtures thereof;j) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof;k) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;l) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof;m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof;n) C.sub.1 -C.sub.22 thioalkyl, C.sub.3 -C.sub.22 branched thioalkyl, or mixtures thereof;o) an ester of the formula --CO.sub.2 R.sup.9 wherein R.sup.9 isi) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;ii) halogen substituted C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;iii) polyhydroxyl substituted C.sub.3 -C.sub.22 alkylene;iv) C.sub.3 -C.sub.22 glycol;v) C.sub.1 -C.sub.22 alkoxy;vi) C.sub.3 -C.sub.22 branched alkoxy;vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof;ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof;xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof;p) an alkyleneamino unit of the formula: ##STR59##wherein R.sup.10 and R.sup.11 are C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;R.sup.12 is:i) hydrogen;ii) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;A is nitrogen or oxygen; X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or 1, u is from 0 to 22;q) an amino unit of the formula:--NR.sup.17 R.sup.18wherein R.sup.17 and R.sup.18 are C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;r) an alkylethyleneoxy unit of the formula:--(A).sub.v (CH.sub.2).sub.y (OCH.sub.2 CH.sub.2).sub.x Zwherein Z is:i) hydrogen;ii) hydroxyl;iii) --CO.sub.2 H;iv) --SO.sub.3.sup.- M.sup.+ ;v) --OSO.sub.3.sup.- M.sup.+ ;vi) C.sub.1 -C.sub.6 alkoxy;vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;ix) alkyleneamino; or mixtures thereof;A is nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12;s) substituted siloxy of the formula:--OSiR.sup.19 R.sup.20 R.sup.21wherein each R.sup.19, R.sup.20, and R.sup.21 is independentlyi) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:--(A).sub.v --(CH.sub.2).sub.y (OCH.sub.2 CH.sub.2).sub.x Zwherein Z is:a) hydrogen;b) hydroxyl;c) --CO.sub.2 H;d) --SO.sub.3.sup.- M.sup.+ ;e) --OSO.sub.3.sup.- M.sup.+ ;f) C.sub.1 -C.sub.6 alkoxy;g) substituted aryl, unsubstituted aryl, or mixtures thereof;h) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;i) alkyleneamino; or mixtures thereof;A is nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12;and mixtures thereof;R is an axial moiety which mediates the solubility or substantivity of the singlet oxygen generator wherein R is selected from:a) hydrogen;b) halogen;c) hydroxy;d) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;e) halogen substituted C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;f) polyhydroxyl substituted C.sub.3 -C.sub.22 alkyl;g) C.sub.1 -C.sub.22 alkoxy;h) branched alkoxy having the formula: ##STR60##wherein Z is hydrogen, hydroxyl, C.sub.1 -C.sub.30 alkyl, C.sub.1 -C.sub.30 alkoxy, --CO.sub.2 H, --OCH.sub.2 CO.sub.2 H, --SO.sub.3.sup.- M.sup.+, --OSO.sub.3.sup.- M.sup.+, PO.sub.3.sup.2- M, --OPO.sub.3.sup.2- M, or mixtures thereof; M is a water soluble cation in sufficient amount to satisfy charge balance; x is 0 or 1, each y independently has the value from 0 to 6, each z independently has the value from 0 to 100;i) substituted aryl, unsubstituted aryl, or mixtures thereof;j) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof;k) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;l) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof;m) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof;n) C.sub.1 -C.sub.22 thioalkyl, C.sub.3 -C.sub.22 branched thioalkyl, or mixtures thereof;o) a carboxylate of the formula: ##STR61##wherein R.sup.9 is:i) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;ii) halogen substituted C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;iii) polyhydroxyl substituted C.sub.3 -C.sub.22 alkylene;iv) C.sub.3 -C.sub.22 glycol;v) C.sub.1 -C.sub.22 alkoxy;vi) C.sub.3 -C.sub.22 branched alkoxy;vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof;ix) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;x) substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or mixtures thereof;xi) substituted alkyleneoxyaryl, unsubstituted alkyleneoxyaryl, or mixtures thereof;p) an alkyleneamino unit of the formula: ##STR62##wherein R.sup.10 and R.sup.11 are C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;R.sup.12 is:i) hydrogen;ii) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;A is nitrogen or oxygen; X is chlorine, bromine, iodine, or other water soluble anion, v is 0 or 1, u is from 0 to 22;q) an amino unit of the formula:--NR.sup.17 R.sup.18wherein R.sup.17 and R.sup.18 are C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;r) an alkylethyleneoxy unit of the formula:--(A).sub.v --(CH.sub.2).sub.y (OCH.sub.2 CH.sub.2).sub.x Zwherein Z is:i) hydrogen;ii) hydroxyl;iii) --CO.sub.2 H;iv) --SO.sub.3.sup.- M.sup.+ ;v) --OSO.sub.3.sup.- M.sup.+ ;vi) C.sub.1 -C.sub.6 alkoxy;vii) substituted aryl, unsubstituted aryl, or mixtures thereof;viii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;ix) alkyleneamino; or mixtures thereof;A is nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12;s) substituted siloxy of the formula:--OSiR.sup.19 R.sup.20 R.sup.21wherein each R.sup.19, R.sup.20, and R.sup.21 is independentlyi) C.sub.1 -C.sub.22 alkyl, C.sub.3 -C.sub.22 branched alkyl, C.sub.2 -C.sub.22 alkenyl, C.sub.3 -C.sub.22 branched alkenyl, or mixtures thereof;ii) substituted aryl, unsubstituted aryl, or mixtures thereof;iii) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;iv) an alkylethyleneoxy unit of the formula:--(A).sub.v --(CH.sub.2).sub.y (OCH.sub.2 CH.sub.2).sub.x Z;wherein Z is:a) hydrogen;b) hydroxyl;c) --CO.sub.2 H;d) --SO.sub.3.sup.- M.sup.+ ;e) --OSO.sub.3.sup.- M.sup.+ ;f) C.sub.1 -C.sub.6 alkoxy;g) substituted aryl, unsubstituted aryl, or mixtures thereof;h) substituted aryloxy, unsubstituted aryloxy, or mixtures thereof;i) alkyleneamino; or mixtures thereof;A is nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12;and mixtures thereof; and D is a unit which increases the efficiency of singlet oxygen production, said unit having the formula--L.sup.1 --Eor--L.sup.1 --B--[L.sup.2 --E].sub.mwherein E is an aromatic unit, provided said E aromatic unit:a) absorbs ultra violet radiation at a wavelength of from about 200 nm to about 400 nm;b) has an extinction coefficient of at least about 100; andc) has a fluorescence spectrum which overlaps the absorption band of said photosensitizer unit;B is a branching unit; and L.sup.1 and L.sup.2 are linking units, provided said linking units when taken together with said B unit comprise a total of at least 20 continuous covalent bonds from said P unit to said E units; m is from 2 to 4.