Fullerene derivatives

Details Fullerene derivatives Fullerene derivatives

2000-04-03

2002-04-30

Gerstl, Robert (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C568S817000

Reexamination Certificate

active

06380434

ABSTRACT:

BACKGROUND
Since the discovery of fullerenes, a number of their poly-substituted derivatives have been reported. For example, polyalkylfullerene derivatives can be prepared by reacting fullerenes with organic alkyl lithium or alkyl Grignard reagents and then with alkyl halides, or directly with organic radicals. See Wudl, et al., ACS Symp. Ser. 1992, 481, 161 and Krusic, et al., Science 1991, 254, 1183. On the other hand, enones react with fullerenes to afford polycycloalkylfullerene derivatives. See Wilson, et al., J. Am. Chem. Soc. 1993, 115, 8495. As another example, polyalkylaminofullerene derivatives is synthesized by reacting fullerenes with alkyl amine. See Hirsch, et al., Angew. Chem. Int. Ed. Engl. 1991, 30, 1309. Some of the above-mentioned reactions, however, suffer from low yields and ion reaction time.
SUMMARY
An aspect of this invention relates to a fullerene derivative of the following formula:
F(—E)
n
(—R
1
)
p
(—R
2
)
q
F is a fullerene core. E is E
1
, E
2
, or E
3
. E
1
is Y
1
,Y
2
-amino, (Y
1
,Y
2
-alkyl)-amino, Y
1
,Y
2
ethylenediamino, (dihydroxymethyl)alkylamino, (X
1
,X
3
-aryl)amino, or X
1
,X
3
-aryloxy. E
2
is Y
1
,Y
2
-alkoxy, (Y
1
,Y
2
-amino)alkoxy, (Y
1
,Y
2
,Y
3
-aryl)oxy, (dihydroxyallkyl)-aryloxy, (Y
1
,Y
2
,Y
3
-alkyl)amino, (Y
1
,Y
2
,Y
3
-aryl)amino, dihydroxyalkylamino, Y
1
,Y
2
,Y
3
-alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y
1
,Y
2
,Y
3
alkyl)thio, (X
1
,X
3
-aryl)thio, (Y
1
,Y
2
-alkyl)thio, (dihydroxyalkyl)thio, Y
1
,Y
2
-dioxoakyl, or tri-(Y
1
,Y
2
,Y
3
-methylaminocarboxyethyl)methylamino. E
3
is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X
1
,X
2
,X
3
-heteroaryl)amino, (X
1
-diarylketone)amino, (X,X
1
-oxoaryl)amino, (X,X
1
-dioxoaryl)amino, (Y
1
-alkyl,Y
2
-alkyldioxoheteroaryl)amino, (Y
1
-alkyl,Y
2
-alkyldioxoaryl)amino, (di(Y
1
,Y
2
-methyl)dioxoheteroaryl)amino, (di(Y
1
,Y
2
-methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxo-heteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, (X
1
,X
2
,X
3
-alkylaryl)amino, (X
1
,X
2
,X
3
heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X
1
,X
2
,X
3
-oxoheteroaryl)oxy, (X
1
,X
2
,X
3
-oxoaryl)oxy, (X
1
,Y
1
-oxoheteroaryl)oxy, (X
1
-diarylketone)oxy, (X,X
1
oxoaryl)oxy, (X
1
,X
2
-dioxoaryl)oxy, (Y
1
,Y
2
,di-aminodihydroxy)alkyl, (X
1
,X
2
-heteroaryl)thio, ((tricarboxylalkyl)ethylene-diamino)alkoxy, (X
1
,X
2
-oxoaryl)thio, (X
1
,X
2
-dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y
1
-alkyl(thiocarbonyl)thio, Y
1
,Y
2
-alkyl(thiocarbonyl)thio, Y
1
,Y
2
,Y
3
-alkyl(thiocarbonyl)thio, (Y
1
,Y
2
-aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl)
1-100
amino, (pyranosyl)amino, (Y
1
-aminoaryl)
1-100
amino, (amino(sulfoaryl))
1-100
amino, peptidyl, thymidinyl, uridinyl, guanosinyl, adenosinyl, cholesteryl, or biotinylallcoxy. X is halide. Each of X
1
, X
2
, and X
3
, independently, is —Y
1
, —O—Y
1
, —S—Y
1
, —NH—Y
1
, —CO—O—Y
1
, —O—CO—Y
1
, —CO—NH—Y
1
, —CO—NY
1
Y
2
, —NH—CO—Y
1
, —SO
2
—Y
1
, —CHY
1
Y
2
, or —NY
1
Y
2
. Each of Y
1
, Y
2
, and Y
3
, independently, is —Z or —B—Z. B is —R
a
—O—[Si(CH
3
)
2
—O—]
1-100
, C
2-100
alkyl, C
6-40
aryl, C
7-2000
alkylaryl, C
7-2000
arylalkyl, (C
1-30
alkyl ether)
1-100
, (C
6-40
aryl ether)
1-100
, (C
7-2000
alkylaryl ether)
1-100
, (C
7-2000
arylalky ether)
1-100
, (C
1-30
alkyl thioether)
1-100
, (C
6-40
aryl thioether)
1-100
, (C
7-2000
alkylaryl thioether)
1-100
, (C
7-2000
arylalkyl thioether)
1-100
, (C
2-50
alkyl ester)
1-100
, (C
7-2000
aryl ester)
1-100
, (C
8-2000
alkylaryl ester)
1-100
, (C
8-2000
arylalkyl ester)
1-100
, —R
a=l —CO—O—(C
1-30
alkyl ether)
1-100
, —R
a
—CO—O—(C
6-40
aryl ether)
1-100
, —R
a
—CO—O—(C
7-2000
alkylaryl ether)
1-100
, —R
a
—CO—O (C
7-2000
arylalkyl ether)
1-100
, (C
4-50
alkyl urethane)
1-100
, (C
14-60
aryl urethane)
1-100
, (C
10-2000
alkylaryl urethane)
1-100
, (C
10-2000
arylalkyl urethane)
1-100
, (C
5-50
alkyl urea)
1-100
, (C
14-60
aryl urea)
1-100
, (C
10-2000
alkylaryl urea)
1-100
, (C
10-2000
arylalkyl urea)
1-100
, (C
2-50
alkyl amide)
1-100
, (C
7-60
aryl amide)
1-100
, (C
8-2000
alkayl amide)
1-100
, (C
8-2000
arylalkyl amide)
1-100
, (C
3-30
alkyl anhydride)
1-100
, (C
8-50
aryl anhydride)
1-100
, (C
9-2000
alkylaryl anhydride)
1-100
, (C
9-2000
arylalkyl anhydride)
1-100
, (C
2-30
alkyl carbonate)
1-100
, (C
7-50
aryl carbonate)
1-100
, (C
8-2000
alkylaryl carbonate)
1-100
, (C
8-2000
arylalkyl carbonate)
1-100
, —R
a
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
1-30
alkyl ether, C
6-40
aryl ether, C
7-2000
alkylaryl ether, or C
7-2000
arylalkyl ethel )
1-100
, —R
a
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
2-50
alkyl ester, C
7-60
aryl ester, C
8-2000
alkylaryl ester, or C
8-2000
arylalkyl ester)
1-100
, —R
a
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
1-30
alkyl ether, C
6-40
aryl ether, C
7-2000
alkylaryl ether, or C
7-2000
arylalkyl ether)
1-100
—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—, —R
a
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
2-50
alkyl ester, C
7-60
aryl ester, C
8-2000
alkylaryl ester, or C
8-2000
arylalkyl ester)
1-100
—R
c
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—, —R
a
—NH—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
1-30
alkyl ether, C
6-40
aryl ether, C
7-2000
alkylaryl ether, or C
7-2000
arylalkyl ether)
1-100
, —R
a
—NH—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
2-50
alkyl ester, C
7-60
aryl ester, C
8-2000
alkylaryl ester, or C
8-2000
arylalkyl ester)
1-100
, —R
a
—NH—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
1-30
alkyl ether, C
6-40
aryl ether, C
7-2000
alkylaryl ether, or C
7-2000
arylalkyl ether)
1-100
—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—, —R
a
—NH—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—(C
2-50
alkyl ester, C
7-60
aryl ester, C
8-2000
alkylaryl ester, or C
8-2000
arylalkyl ester)
1-100
—R
c
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—O—, —R
a
—O—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—H—(C
2-50
alkyl amide, C
7-60
aryl amide C
8-2000
alkylaryl amide, or C
8-2000
arylalkyl amide)
1-100
, —R
a
—NH—CO—NH—(R
b
or Ar—R
b
—Ar)—NH—CO—NH—(C
2-50
alkyl amide, C
7-60
aryl amide, C
8-2000
alkylaryl amide, or C
8-2000
arylalkyl amide)
1-100
. Each Z, independently, is —G—D, wherein G is —R
a
—, —R
a
—Ar—, —Ar—R
a
—, or —Ar—. D is —H, —OH, —SH, —NH
2
, —NHOH, —SO
3
H, —OSO
3
H, —CO
2
H, —CONH
2
, —CONHNH
2
, —CH(NH
2
)—CO
2
H, —NH—CH
2
—CO
2
H, —P(OH)
3
, —PO(OH)
2
, —O—PO(OH)
2
, —O—PO(OH)—O—PO(OH)
2
,—O—PO(O
31
)—O—CH
2
CH
2
NH
3
+
, —O—PO(O
−
)—O—CH
2
CH
2
—N
+
(CH
3
)
3
, -glycoside, -oligosaccharide, —CO-glycoside, —CO-oligosaccharide, —OCH
3
, —OCH
2
(CHOH)
4
—CH
2
OH, —OCH
2
(CHOH)
2
—CH
2
OH, —CO—OCH
2
(CHOH)
4
—CH
2
OH, —C
6
H
3
(OH)
2
, —N(CH
2
CO
2
H)
2
, —CO—N(CH
2
CO
2
H)
2
, —CO—NH—C(CH
2
CH
2
CO
2
H)
3
, —CO—NH—C(CH
2
CH
2
OH)
3
, —[CH
2
—CH(CO
2
R
a
)]
1-100
—H, —NH
3
+
, —N
+
H
2
R
a
, —N
+
HR
a
R
b
, or —N
+
R
a
R
b
R
c
. Each of R
a
, R
b
, and R
c
, independently, is C
1-20
alkyl and Ar is aryl. R
1
is —OH or —NH
2
. R
2
is —O— (an epoxide formed by joining 2 fullerene carbon atoms and an oxygen atom). n is 1-30; p is 1-20; and q is 0-10. Note that when R
1
is —NH
2
, q is 0.
Another aspect of this invention relates to a method preparing a fullerene derivative of the formula F(—E)
n
(—R
1
)
p
(—R
2
)
q
. The method includes the steps of obtaining a polynitrofullerene or polycyclosulfated fullerene intermediate (see Examples 1 and 2); contacting the intermediate with a nucleophilic agent to produce a fullerene derivative of the formula F(—E)
n
(see Examples 3-26), and contacting the resulting fullerene derivative with a hydroxylating or an aminating agent to produce a fullerene derivative of the formula F(—E)
n
(—R
1
)
p
(—R
2
)
q
, wherein each of F, E, R
1
, R
2
, p, q, and n has been defined above (see Examples 28 and 29).
By the term “alkyl” is meant a straight chain that contains 1-30 carbon atoms, or a branche

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