M.D. Meijer et al. / Inorganica Chimica Acta 352 (2003) 247ꢃ
/252
249
was purified by column chromatography using toluene/
hexane (1/5 to 1/1, v/v gradient) as eluens, affording 5 as
1
a dark brown solid (0.25 g, 24%). H NMR (CS2/C6D6,
2.9. 1,2-Dihydro-61-ethoxycarbonyl-61-[3?,5?-
bis(phenylsulfidomethyl)benzyloxycarbonyl]-1,2-
methano[60]fullerene (8)
3/1 (v/v)): d 7.59 (s, 2H, ArH), 7.00 (m, 11H, ArH), 4.98
(s, 1H, CH), 3.88 (s, 4H, CH2S). 13C{1H} NMR (CS2/
C6D6, 3/1 (v/v)): d 149.73, 147.54, 145.79, 145.66,
145.41, 145.36, 145.33, 145.32, 144.98, 144.90, 144.70,
144.62, 144.42, 143.97, 143.91, 143.30, 143.27, 143.22,
143.18, 142.90, 142.51, 142.37, 142.32, 141.32, 141.11,
138.80, 138.62, 136.63, 136.48, 133.59, 130.41, 129.84,
A solution of C60 (0.47 g, 0.66 mmol), I2 (0.17 g, 0.66
mmol), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene; 0.20
g, 1.3 mmol) and 7 (0.31 g, 0.66 mmol) in dry toluene
(600 ml) was stirred for 22 h (Scheme 2). Then silica gel
(9 g) was added and all volatiles were removed in vacuo.
Column chromatography using toluene/hexane as eluens
(1/5 to 1/0, v/v gradient) afforded unreacted C60 (0.25 g),
and the crude product, which was washed with Et2O
129.72, 129.08, 126.54 (C60Ã
/
C and aryl C), 75.5 (C60-
sp3), 43.5 (bridgehead-C), 38.8 (CH2SPh).
(3ꢄ25 ml) and dried in vacuo, yielding 8 as a brown
/
solid (0.18 g, 23%, 52% based on reacted C60). 1H NMR
(CS2/C6D6, 3/1 (v/v)): d 7.02 (m, 13H, ArH), 5.12 (s,
2.7. 3,5-Bis(phenylsulfidomethyl)benzyl alcohol (6)
3
2H, OCH2), 4.20 (q, Jꢁ
/
6.9 Hz, 2H, OEt), 3.79 (s, 4H,
7.2 Hz, 3H, OEt). 13C{1H} NMR
3
CH2S), 1.09 (t, Jꢁ
/
A solution of 2 (2.46 g, 7.02 mmol) in dry Et2O (25
ml) was slowly added to a suspension of LiAlH4 (3.03 g,
79.8 mmol) in Et2O (75 ml). The reaction mixture was
stirred for 3 days and carefully quenched with a
saturated NaCl solution (90 ml). The reaction mixture
was filtered, and the organic layer was isolated and
washed with a saturated aqueous NaCl solution (50 ml).
The aqueous layers were combined and were extracted
(CS2/C6D6, 3/1 (v/v)): d 163.1, 163.0 (CO), 145.98,
145.87, 145.85, 145.80, 144.77, 145.45, 145.28, 145.22,
144.52, 143.71, 143.62, 142.85, 142.46, 141.58, 139.97,
139.68, 138.97, 137.21, 136.01, 130.35, 130.25, 129.53,
128.62, 126.92 (C60Ã
/
C and aryl C), 72.3 (C60-sp3), 68.6
(OCH2), 63.7 (OEt), 52.8 (bridgehead-C), 39.3 (CH2S),
14.8 (OEt).
with Et2O (2ꢄ50 ml). The organic fractions were
/
2.10. N-methyl-2-[4?-[chloropalladio]-3?,5?-
bis(phenylsulfidomethyl)phenyl]-3,4-fulleropyrrolidine
(9)
combined, dried over MgSO4 and filtered. All volatiles
were removed in vacuo yielding 6 as a yellow oil (2.33 g,
94%). 1H NMR (CDCl3): d 7.27 (m, 13H, ArH), 4.55 (d,
3Jꢁ
/
6.0 Hz, 2H, OCH2), 4.05 (s, 4H, CH2S), 2.16 (t,
5.9 Hz, 1H, OH). 13C{1H} NMR (CDCl3): d 141.8,
To a solution of 3 (106 mg, 97 mmol) in toluene (100
ml) was added a solution of [Pd(CH3CN)4](BF4)2 (48
mg, 108 mmol) in CH3CN (25 ml). The reaction mixture
was heated at 80 8C for 3 h, after which a solution of
LiCl (60 mg, 1.4 mmol) in MeOH (30 ml) was added.
The reaction mixture was cooled down to room
temperature, stirred for another 1.5 h and evaporated
3Jꢁ
/
138.2, 136.4, 130.1, 129.1, 128.9, 126.7, 126.5 (aryl C),
65.0 (COH), 39.1 (CH2S). Anal. Calc. for C21H20OS2:
C, 71.55; H, 5.72. Found: C, 71.63; H, 5.78%.
2.8. 1-[3,5-Bis(phenylsulfidomethyl)benzyloxy]-3-
ethoxymalonate (7)
in vacuo. The residue was washed with MeOH (2ꢄ
/
40
ml) and extracted with CS2 (3ꢄ60 ml). The organic
/
fraction was evaporated in vacuo, yielding 9 as dark
brown solid (77 mg, 64%). Due to the poor solubility of
9 in common NMR solvents, no 13C{1H} NMR
To a solution of 6 (1.01 g, 2.87 mmol) in CH2Cl2 (75
ml) was added pyridine (0.24 ml, 2.9 mmol). A solution
of ethyl malonyl chloride (0.40 ml, 3.1 mmol) in CH2Cl2
(10 ml) was slowly added at 0 8C. The reaction mixture
was allowed to warm up to room temperature overnight
and water (50 ml) was added. The organic fraction was
separated, washed with 0.05 M solution of Na2CO3 (50
ml), dried over MgSO4 and evaporated in vacuo,
1
spectrum could be obtained. H NMR (CS2/C6D6, 3/1
(v/v)): d 7.53, 7.16, 7.04 (m, 12H, ArH), 4.73 (d, 2Jꢁ
Hz, 1H, CHN), 4.68 (s, 1H, CHN), 4.15 (s, 4H, CH2S),
/9.6
2
4.08 (d, Jꢁ
/
9.6 Hz, 1H, CHN), 2.64 (s, 3H, NCH3).
Cl]ꢂ).
MALDI-TOF (9-NA): m/zꢁ
/
1202.1 ([Mꢀ
/
1
yielding 7 as an orange oil (1.29 g, 100%). H NMR
(CDCl3): d 7.19 (m, 13H, ArH), 5.07 (s, 2H, OCH2),
2.11. 1,2-Dihydro-61-{4?-(chloropalladio)-3?,5?-
(bisphenylsulfidomethyl)phenyl}-1,2-methano-
[60]fullerene (10)
4.05 (s, 4H, CH2S), 4.19 (q, 3Jꢁ
10.8 Hz, 2H, OEt), 3.39
/
3
(s, 2H, OCCH2CO), 1.25 (t, Jꢁ10.8 Hz, 3H, OEt).
/
13C{1H} NMR (CDCl3): d 165.8 (CO), 137.7, 135.6,
135.4, 129.3, 128.8, 128.4, 126.9, 125.9 (aryl C), 66.1
(OCH2), 61.0 (OEt), 41.0 (COCH2CO), 38.0 (CH2S),
13.6 (OEt). Anal. Calc. for C26H26O4S2: C, 66.92; H,
5.62. Found: C, 67.10; H, 5.62%.
Complex 10 was synthesized in a similar way as 9,
using 5 (99 mg, 94 mmol), [Pd(CH3CN)4](BF4)2 (53 mg,
119 mmol) and LiCl (60 mg, 1.4 mmol), yielding 10 as a
1
brown solid (69 mg, 61%). H NMR (CDCl3): d 7.89,
7.59, 7.40 (m, 12H, ArH), 5.27 (s, 1H, CH), 4.75 (s, 4H,