2,2-[60]Fullerenoalkanoyl Chlorides
oil. IR (neat) 2977, 2923, 1722, 1495, 1455, 1392, 1368, 1256,
1718, 1637, 1494, 1428, 1252, 1185, 1119, 1078, 870, 734, 698,
525 cm-1; 1H NMR (THF-d8/CS2 ) 1:1 (v/v)) δ 4.28 (s, 2H), 7.29-
7.44 (m, 3H), 7.67-7.69 (m, 2H); 13C NMR (THF-d8/CS2 ) 1:1
(v/v)) δ 35.63, 51.61, 77.41, 127.93, 129.50, 129.90, 137.79, 138.92,
139.06, 141.40, 141.76, 142.84, 142.88, 142.93, 143.55, 143.62,
143.73, 143.76, 143.81, 143.93, 144.36, 144.60, 144.87, 145.21,
145.25, 145.33, 145.47, 145.63, 145.82, 145.87, 146.09, 146.34,
147.66, 149.12, 167.46; MALDI-TOF-MASS (dithranol) for [M]+
C69H8O2 calcd 868.0524, found 868.1671.
1
1142, 979, 960, 847, 744, 699 cm-1; H NMR (CDCl3) δ 1.37 (s,
9H), 2.16 (s, 3H), 2.87-2.94 (m, 1H), 3.10-3.18 (m, 1H), 3.32-
3.37 (m, 1H), 7.19-7.29 (m, 6H, overlapped with internal CHCl3);
13C NMR (CDCl3) δ 14.02, 27.88, 37.19, 49.69, 81.28, 126.62,
128.32, 129.00, 138.25, 170.81.
tert-Butyl [60]Fullerenoacetate (3a). tert-Butyl (dimethylsul-
fanylidene)acetate (7a) was prepared from tert-butyl bromoacetate
(5a) according to the procedure in the literature.6b-e To a toluene
solution (200 mL) of [60]fullerene (200 mg, 0.28 mmol) was added
a toluene solution (5 mL) of 7a (40 mg, 0.23 mmol) at room
temperature. After being stirred at room temperature for 18 h, the
reaction mixture was concentrated under reduced pressure. The
resultant residue was subjected to preparative thin-layer chroma-
tography developed with hexane/toluene (1:1 (v/v)) to afford 3a
as a brown solid (101 mg, 0.12 mmol, 53%) and unreacted [60]-
[60]Fullerenoacetyl Chloride (1a). A solution of 2a (50 mg,
0.064 mmol) and thiony chloride (5.0 mL, 67 mmol) in CH2Cl2/
dioxane (1:1 v/v, 40 mL) was refluxed for 5 h to afford a black
precipitate. The precipitate was collected by filtration (ADVAN-
TEC, filter paper 5A) and washed with CH2Cl2/dioxane (1:1 v/v,
100 mL). The residual solid was dissolved in CS2 (20 mL), and
the insoluble mass was filtered off (ADVANTEC, filter paper 5A).
The filtrate was concentrated to dryness to afford 1a as a black
fullerene (53 mg). IR (KBr) 2973, 2923, 1730, 1366, 526 cm-1
;
1H NMR (CDCl3/CS2 ) 1:1 (v/v)) δ 1.78 (s, 9H), 4.70 (s, 1H);
13C NMR (CDCl3/CS2 ) 1:1 (v/v)) δ 28.05, 40.29, 70.80, 83.26,
136.03, 140.28, 140.68, 140.92, 141.81, 141.87, 142.00, 142.22,
142.59, 142.74, 142.78, 142.87, 143.06, 143.49, 143.72, 144.14,
144.37, 144.42, 144.55, 144.83, 144.89, 144.97, 144.99, 145.41,
145.70, 148.25, 164.52; MALDI-TOF-MASS (dithranol) for [M]+
C66H10O2 calcd 834.0681, found 834.1663.
1
solid (51 mg, 0.064 mmol, quant.). IR (KBr) 1780, 520 cm-1; H
NMR (CDCl3/CS2 ) 1:1 (v/v)) δ 5.23 (s, 1H); 13C NMR (THF-
d8/CS2 ) 1:1 (v/v)) δ 40.79, 72.63, 137.45, 141.79, 142.09, 143.07,
143.14, 143.26, 143.54, 143.80, 143.93, 144.00, 144.30, 144.74,
144.99, 145.28, 145.47, 145.56, 145.65, 145.73, 146.02, 146.12,
146.15, 146.19, 146.36, 146.79, 147.67, 150.08, 167.30; MALDI-
TOF-MASS (dithranol) for [M]+ C62HClO calcd 795.9716, found
795.9085.
tert-Butyl 2,2-[60]Fullereno-3-phenylpropionate (3c). To a
CH2Cl2 solution (12 mL) of 5c (252 mg, 1.0 mmol) was added
trimethyloxonium tetrafluoroborate (148 mg, 1.0 mmol) at room
temperature. After being stirred at room temperature for 24 h, the
resultant CH2Cl2 solution of [1-(tert-butoxycarbonyl)-2-phenylethyl]-
dimethylsulfonium tetrafluoroborate (6c-BF4) (0.083 M) was used
for the following reaction without further purification.
2,2-[60]Fullereno-3-phenylpropionyl Chloride (1c). A solution
of 2c (50 mg, 0.057 mmol) and thiony chloride (4.5 mL, 60 mmol)
in CH2Cl2/dioxane (1:1 v/v, 40 mL) was refluxed for 5 h. The
reaction mixture was concentrated under reduced pressure, and the
resultant residue was triturated with hexane, collected by filtration
(ADVANTEC, filter paper 5A), and washed with hexane (50 mL).
The residual solid was dissolved in CS2 (20 mL), and the insoluble
mass was filtered off (ADVANTEC, filter paper 5A). The filtrate
was concentrated to dryness to afford 1c as a black solid (47.6 mg,
0.053 mmol, 93%). IR (KBr) 2923, 1794, 1509, 1427, 1184, 912,
To a toluene solution (72 mL) of [60]fullerene (72 mg, 0.10
mmol) were successively added a CH2Cl2 solution of 6c-BF4 (0.083
M, 1.8 mL, 0.15 mmol) and a toluene solution (0.56 mL) of 1,8-
diazabicyclo[5.4.0]undec-7-ene (25.8 mg, 0.17 mmol) at room
temperature. After being stirred at room temperature for 18 h, the
reaction mixture was subjected to silica gel plug filtration (toluene),
and the filtrate was concentrated under reduced pressure. The
resultant residue was subjected to preparative thin-layer chroma-
tography developed with CS2 to afford 3c as a brown solid (43.9
mg, 0.047 mmol, 47%) and unreacted [60]fullerene (33.0 mg, 46%).
IR (KBr) 2972, 2924, 1726, 1453, 1427, 1366, 1184, 1153, 1130,
1
878, 736, 694, 654, 524 cm-1; H NMR (CDCl3) δ 4.37 (s, 2H),
7.36-7.47 (m, 3H), 7.63-7.65 (m, 2H); 13C NMR (CDCl3/CS2 )
1:1 (v/v)) δ 34.75, 58.03, 75.36, 127.99, 128.98, 129.20, 134.77,
137.64, 138.32, 140.98, 141.18, 141.79, 141.98, 142.04, 142.12,
142.84, 142.95, 143.00, 143.16, 143.54, 143.73, 144.46, 144.56,
144.60, 144.67, 144.72, 144.76, 144.80, 145.04, 145.14, 145.19,
145.22, 145.75, 166.41; MALDI-TOF-MASS (dithranol) for [M]+
C69H7ClO calcd 886.0185, found 886.2068.
1
838, 754, 696, 525 cm-1; H NMR (CDCl3) δ 1.44 (s, 9H), 4.20
(s, 2H), 7.33-7.44 (m, 3H), 7.63-7.65 (m, 2H); 13C NMR (CDCl3/
CS2 ) 1:1 (v/v)) δ 27.83, 35.17, 50.68, 76.28, 83.41, 127.28,
128.67, 129.22, 136.60, 137.79, 138.02, 140.72, 141.01, 141.98,
142.03, 142.11, 142.77, 142.85, 142.94, 142.98, 143.03, 143.09,
143.56, 143.77, 144.13, 144.47, 144.53, 144.61, 144.68, 144.72,
145.05, 145.10, 145.15, 145.41, 146.52, 147.90, 165.46; MALDI-
TOF-MASS (dithranol) for [M]+ C73H16O2 calcd 924.1150, found
924.3105.
[60]Fullerenoacetic Acid (2a). A toluene solution (150 mL) of
3a (214 mg, 0.26 mmol) and p-TsOH‚H2O (88 mg, 0.52 mmol)
was refluxed for 8 h to afford a suspension. The brown solid thus
precipitated was collected by filtration (ADVANTEC, filter paper
5A) and washed successively with toluene (100 mL) and water
(30 mL). The residual solid was dissolved in CH2Cl2/dioxane (1:1
(v/v), 30 mL), and the insoluble mass was filtered off (ADVAN-
TEC, filter paper 5A). The filtrate was concentrated to dryness to
afford 2 as a brown solid (145 mg, 0.19 mmol, 72%). IR (KBr)
3420, 1700, 520 cm-1; 1H NMR (THF-d8/CS2 ) 1:1 (v/v)) δ 5.18
(s, 1H); 13C NMR (THF-d8/CS2 ) 1:1 (v/v)) δ 40.32, 72.10, 136.99,
141.37, 141.65, 142.61, 142.70, 142.81, 143.09, 143.36, 143.49,
143.56, 143.65, 143.87, 144.30, 144.55, 144.85, 145.04, 145.12,
145.20, 145.27, 145.43, 145.59, 145.67, 145.72, 145.75, 145.89,
146.32, 147.14, 149.56, 166.80; MALDI-TOF-MASS (dithranol)
for [M]+ C62H2O2 calcd 778.0055, found 778.1925.
General Procedure for the Condensation of the 2,2-[60]-
Fullerenoalkanoyl Chlorides 1 with the Amines 8. To a suspen-
sion of 1 (0.0188 mmol) in pyridine (15 mL) was added the amine
or ammonium salt 8 (0.0188 mmol) at room temperature, and
mixture was stirred at room temperature for 12 h. The reaction
mixture was concentrated under reduced pressure, and residual
pyridine was azeotropically removed with toluene (30 mL). The
resultant residue was subjected to preparative thin-layer chroma-
tography developed with CS2/CH2Cl2 to afford the corresponding
amide 9 as a brown solid.
General Procedure for the Condensation of the 2,2-[60]-
Fullerenoalkanoyl Chlorides 1 with the Alcohols 10. To a
bromobenzene solution (15 mL) of 1 (0.0188 mmol) were added
the alcohol 10 (0.15 mmol) and 4-(dimethylamino)pyridine (2.4-
4.8 mg, 0.0197-0.0395 mmol) at room temperature. The mixture
was stirred for 3-12 h and concentrated under reduced pressure.
The resultant residue was subjected to preparative thin-layer
chromatography developed with CS2/CH2Cl2 to afford the corre-
sponding ester 11 as a brown solid.
Supporting Information Available: Synthetic procedures and
characterization data for the new compounds 1b, 1d, 2b, 2d, 3b,
3d, 5b, 5d, 9a‚a-j, 9c‚a, 9c‚b, 9c‚d, 11a‚a-o, 11c‚b, 11c‚e, and
11c‚f and 1H and 13C NMR spectra of 1a-d, 2a-d, 3a-d, 5b-d,
9a‚a, 9c‚a, 11a‚b, and 11c‚b. This material is available free of
2,2-[60]Fullereno-3-phenylpropionic Acid (2c). The title com-
pound was synthesized from 3c through a procedure similar to that
for the preparation of 2a (71% yield). IR (KBr) 3435, 2918, 2848,
JO052399L
J. Org. Chem, Vol. 71, No. 4, 2006 1639