Polyorganofullerenes

A method of preparing a polyorganofullerene derivative of the following formula:

• F(--E).sub.n
• wherein
• F is a fullerene core;
• each of each E, independently, is E.sub.1, E.sub.2, E.sub.3, E.sub.4, E.sub.5 or E.sub.6 ;
• in which
• each E.sub.1, independently, is Y.sub.1,Y.sub.2 -amino, (Y.sub.1,Y.sub.2 -alkyl)-amino, Y.sub.1,Y.sub.2 -ethylenediamino, (dihydroxymethyl)alkylamino, (X.sub.1,X.sub.3 -aryl)amino, or X.sub.1,X.sub.3 -aryloxy;
• each E.sub.2, independently, is Y.sub.1,Y.sub.2 -alkoxy, (Y.sub.1,Y.sub.2 -amino)alkoxy, (Y.sub.1,Y.sub.2,Y.sub.3 -aryl)oxy, (dihydroxyalkyl)aryloxy, (Y.sub.1,Y.sub.2,Y.sub.3 -alkyl)amino, (Y.sub.1 Y.sub.2,Y.sub.3 -aryl)amino, or dihydroxyalkylamino;
• each E.sub.3, independently, is Y.sub.1,Y.sub.2,Y.sub.3 -alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y.sub.1,Y.sub.2,Y.sub.3 -alkyl)thio, (X.sub.1,X.sub.3 -aryl)thio, (Y.sub.1,Y.sub.2 -alkyl)thio, (dihydroxyalkyl)thio, Y.sub.1,Y.sub.2 -dioxoalkyl;
• each E.sub.4, independently, is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X.sub.1,X.sub.2,X.sub.3 -heteroaryl)amino, (X.sub.1 -diarylketone)amino, (X,X.sub.1 -oxoaryl)amino, (X,X.sub.1 -dioxoaryl)amino, (Y.sub.1 -alkyl,Y.sub.2 -alkyldioxoheteroaryl)amino, (Y.sub.1 -alkyl,Y.sub.2 -alkyldioxoaryl)amino, (di(Y.sub.1,Y.sub.2 -methyl)dioxoheteroaryl)amino, (di(Y.sub.1,Y.sub.2 -methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxoheteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, or (X.sub.1,X.sub.2,X.sub.3 -alkylaryl)amino;
• each E.sub.5, independently, is (X.sub.1,X.sub.2,X.sub.3 -heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X.sub.1,X.sub.2,X.sub.3 -oxoheteroaryl)oxy, (X.sub.1,X.sub.2,X.sub.3 -oxoaryl)oxy, (X.sub.1,Y.sub.1 -oxoheteroaryl)oxy, (X.sub.1 -diarylketone)oxy, (X,X.sub.1 -oxoaryl)oxy, (X.sub.1,X.sub.2 -dioxoaryl)oxy, (Y.sub.1,Y.sub.2,diaminodihydroxy)alkyl, (X.sub.1,X.sub.2 -heteroaryl)thio, ((tricarboxylalkyl)ethylenediamino)alkoxy, (X.sub.1,X.sub.2 -oxoaryl)thio, (X.sub.1,X.sub.2 -dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y.sub.1 -alkyl(thiocarbonyl)thio, Y.sub.1,Y.sub.2,-alkyl(thiocarbonyl)thio, Y.sub.1,Y.sub.2,Y.sub.3 -alkyl(thiocarbonyl)thio, (Y.sub.1,Y.sub.2 -aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl).sub.1-20 amino, or (pyranosyl) amino;
• each E.sub.6, independently, is Y.sub.1 -amino, Y.sub.1 -alkoxy, or Y.sub.1 -thio;
• each X, independently, is halide;
• each of X.sub.1, X.sub.2, and X.sub.3, independently, is --Y.sub.1, --O--Y.sub.1, --S--Y.sub.1, --NH--Y.sub.1, --CO--O--Y.sub.1, --O--CO--Y.sub.1, --CO--NH--Y.sub.1, --CO--NY.sub.1 Y.sub.2, --NH--CO--Y.sub.1, --SO.sub.2 --Y.sub.1, --CHY.sub.1 Y.sub.2, or --NY.sub.1 Y.sub.2 ;
• each of Y.sub.1, Y.sub.2, and Y.sub.3 independently, is --B--Z;
• each B, independently, is --R.sub.a --O--[Si(CH.sub.3).sub.2 --O--].sub.1-100, C.sub.1-2000 alkyl, C.sub.6-40 aryl, C.sub.7-60 alkylaryl, C.sub.7-60 arylalkyl, (C.sub.1-30 alkyl ether).sub.1-100, (C.sub.6-40 aryl ether).sub.1-100, (C.sub.7-60 alkylaryl ether).sub.1-100, (C.sub.7-60 arylalkyl ether).sub.1-100, (C.sub.1-30 alkyl thioether).sub.1-100, (C.sub.6-40 aryl thioether).sub.1-100, (C.sub.7-60 alkylaryl thioether).sub.1-100, (C.sub.7-60 arylalkyl thioether).sub.1-100, (C.sub.2-50 alkyl ester).sub.1-100, (C.sub.7-60 aryl ester).sub.1-100, (C.sub.8-70 alkylaryl ester).sub.1-100, (C.sub.8-70 arylalkyl ester).sub.1-100, --R--CO--O--(C.sub.1-30 alkyl ether).sub.1-100, --R--CO--O--(C.sub.6-40 aryl ether).sub.1-100, --R--CO--O--(C.sub.7-60 alkylaryl ether).sub.1-100, --R--CO--O--(C.sub.7-60 arylalkyl ether).sub.1-100, (C.sub.4-50 alkyl urethane).sub.1-100, (C.sub.14-60 aryl urethane).sub.1-100, (C.sub.10-80 alkylaryl urethane).sub.1-100, (C.sub.10-80 arylalkyl urethane).sub.1-100, (C.sub.5-50 alkyl urea).sub.1-100, (C.sub.14-60 aryl urea).sub.1-100, (C.sub.10-80 alkylaryl urea).sub.1-100, (C.sub.10-80 arylalkyl urea).sub.1-100, (C.sub.2-50 alkyl amide).sub.1-100, (C.sub.7-60 aryl amide).sub.1-100, (C.sub.8-70 alkylaryl amide).sub.1-100, (C.sub.8-70 arylalkyl amide).sub.1-100, (C.sub.3-30 alkyl anhydride).sub.1-100, (C.sub.8-50 aryl anhydride).sub.1-100, (C.sub.9-60 alkylaryl anhydride).sub.1-100, (C.sub.9-60 arylalkyl anhydride).sub.1-100, (C.sub.2-30 alkyl carbonate).sub.1-100, (C.sub.7-50 aryl carbonate).sub.1-100, (C.sub.8-60 alkylaryl carbonate).sub.1-100, (C.sub.8-60 arylalkyl carbonate).sub.1-100, --R.sub.1 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.1-30 alkyl ether, C.sub.6-40 aryl ether, C.sub.7-60 alkylaryl ether, or C.sub.7-60 arylalkyl ether).sub.1-100, --R.sub.1 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.2-50 alkyl ester, C.sub.7-60 aryl ester, C.sub.8-70 alkylaryl ester, or C.sub.8-70 arylalkyl ester).sub.1-100, --R.sub.1 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.1-30 alkyl ether, C.sub.6-40 aryl ether, C.sub.7-60 alkylaryl ether, or C.sub.7-60 arylalkyl ether).sub.1-100 --CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--, --R.sub.1 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.2-50 alkyl ester, C.sub.7-60 aryl ester, C.sub.8-70 alkylaryl ester, or C.sub.8-70 arylalkyl ester).sub.1-100 --R.sub.3 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--, --R.sub.1 --NH--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.1-30 alkyl ether, C.sub.6-40 aryl ether, C.sub.7-60 alkylaryl ether, or C.sub.7-60 arylalkyl ether).sub.1-100, --R.sub.1 --NH--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--(C.sub.2-50 alkyl ester, C.sub.7-60 aryl ester, C.sub.8-70 alkylaryl ester, or C.sub.8-70 arylalkyl ester).sub.1-100, --R.sub.1 --NH--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.1-30 alkyl ether, C.sub.6-40 aryl ether, C.sub.7-60 alkylaryl ether, or C.sub.7-60 arylalkyl ether).sub.1-100 --CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--, --R.sub.1 --NH--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--(C.sub.2-50 alkyl ester, C.sub.7-60 aryl ester, C.sub.8-70 alkylaryl ester, or C.sub.8-70 arylalkyl ester).sub.1-100 --R.sub.3 O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--O--, --R.sub.1 --O--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--NH--(C.sub.2-50 alkyl amide, C.sub.7-60 aryl amide, C.sub.8-70 alkylaryl amide, or C.sub.8-70 arylalkyl amide).sub.1-100, or --R.sub.1 --NH--CO--NH--(R.sub.2 or Ar--R.sub.2 --Ar)--NH--CO--NH--(C.sub.2-50 alkyl amide, C.sub.7-60 aryl amide, C.sub.8-70 alkylaryl amide, or C.sub.8-70 arylalkyl amide).sub.1-100 ;
• each Z, independently, is --C--D--, wherein each C, independently, is independently --R--, --R--Ar--, --Ar--R--, or --Ar--;
• and each D, independently, is --H, --OH, --SH, --NH.sub.2, --NHOH, --SO.sub.3 H, --OSO.sub.3 H, --COOH, --CONH.sub.2, --CO--NH--NH.sub.2, --CH(NH.sub.2)--COOH, --P(OH).sub.3, --PO(OH).sub.2, --O--PO(OH).sub.2, --O--PO(OH)--O--PO(OH).sub.2, --O--PO(O.sup.-)--O--CH.sub.2 CH.sub.2 NH.sub.3.sup.+, -glycoside, --OCH.sub.3, --O--CH.sub.2 --(CHOH).sub.4 --CH.sub.2 OH, --O--CH.sub.2 --(CHOH).sub.2 --CH.sub.2 OH, --C.sub.6 H.sub.3 (OH).sub.2, --NH.sup.3+, --N.sup.+ H.sub.2 R.sub.b, --N.sup.+ HR.sub.b R.sub.c, or N.sup.+ HR.sub.b R.sub.c R.sub.d ;
• wherein each of R, R.sub.1, R.sub.2, R.sub.3, R.sub.a, R.sub.b, R.sub.c and R.sub.d, independently, is C.sub.1-30 alkyl and each Ar, independently, is aryl;
• and n is 1-30;
• said method comprising:
• contacting a polynitrofullerene or polycyclosulfated fullerene intermediate with a nucleophilic agent to produce a corresponding polyorganofullerene derivative covered by the formula recited above.