and 14g (0.046 g, 29%) after HPLC (toluene flow rate 2.0 mL
minϪ1; 1 : 1 mixture of reactant : product at t = 7.6 min. and
t = 7.9 min respectively). UV-vis (DCM): 373 (sh) nm, 468.
1H NMR (CDCl3, 300 MHz): δ 1.22 (t, 6 H, J 7 Hz), 4.14
(s, 5 H), 4.24 (q, 4 H, J 7 Hz), 4.27 (m, 2 H), 4.44 (m, 2 H), 4.45
(s, 1 H), 5.20 (s, 2 H), 6.66 (d, 1H, J 16 Hz), 6.87 (d, 1 H, J 16
Hz), 7.29 (d, 2 H, J 8 Hz), 7.40 (d, 2 H, J 8 Hz). 13C NMR
(CDCl3, 75 MHz): δ 13.9, 59.0, 62.5, 66.9, 67.9, 69.2, 69.3,
125.2, 126.2, 128.2, 129.3, 133.5, 138.7, 164.2, 164.3. MS(ES):
m/z 504.1218 (Mϩ) calc. 504.3616 for C27H28O6Fe.
(4.7 ml minϪ1) gave fractions eluting at 8.9 min, 4.0 min and
3.8 min. Concentration of these fractions in vacuo provided 4a
(2.0 mg, 34%), 4b (<1.0 mg) and 4c (trace).
1
4a: H NMR: δ 3.78 (s, 6 H), 3.79 (s, 6 H), 5.29 (d, 2 H,
J 4 Hz), 5.31 (d, 2 H, J 4 Hz), 6.46 (m, 4 H), 6.49 (m, 2 H). 19
F
NMR (CDCl3): δ Ϫ158.4 (td, 1 F, J 21, 11 Hz), Ϫ156.8 (td, 1 F,
J 23, 11 Hz), Ϫ154.1 (dt, 1F, J 28, 7 Hz), Ϫ147.7 (d, 1 F, J 28
Hz), Ϫ145.5 (d, 1 F), Ϫ145.0 (s, 1 F), Ϫ143.1 (s, 2 F), Ϫ142.2
(s, 1 F), Ϫ139.9 (d, 1 F, J 26 Hz), Ϫ139.5 (dt, 1 F, J 27, 4 Hz),
Ϫ137.4 (s, 1 F), Ϫ136.1 (s, 1 F), Ϫ135.6 (s, 1 F), Ϫ135.1 (s, 1 F),
Ϫ131.2 (d, 1 F, J 17 Hz), Ϫ107.2 (s, 1 F). MS(EI): m/z 1043
[C60F17]ϩ.
Compound 15h
4b: 1H NMR: δ 3.77 (s, 6 H), 3.78 (s, 6 H), 3.79 (s, 6 H), 3.81
(s, 6 H), 5.24 (m, 3 H), 5.26 (m, 3 H), 5.28 (m, 1 H), 5.30
(m, 1 H), 6.44 (m, 2 H), 6.48 (m, 4 H), 6.50 (m, 4 H), 6.52
(m, 2 H). 19F NMR (CDCl3): δ Ϫ156.9 (bt, 1 F), Ϫ153.3 (d, 1 F,
J 26 Hz), Ϫ150.5 (d, 1 F, J 26 Hz), Ϫ146.2 (m, 1 F), Ϫ145.9 (d,
1 F, J 30 Hz), Ϫ144.2 (s, 1 F), Ϫ143.2 (s, 2 F), Ϫ142.9 (s, 1 F),
Ϫ141.7 (s, 1 F), Ϫ141.5 (s, 1 F), Ϫ139.6 (d, 1 F, J 30 Hz),
Ϫ139.3 (d, 1 F, J 30 Hz), Ϫ137.0 (s, 1 F), Ϫ135.0 (s, 1 F),
Ϫ123.4 (s, 1 F). MS(EI): m/z 1024 [C60F16]ϩ.
Using 14h (0.180 g, 0.455 mmol), sodium hydride (0.011 g,
0.452 mmol) and ethyl chloroformate (43 µL, 0.452 mmol) gave
15h (0.051 g, 24%; 34% based on recovered starting material)
and 14h (0.093 g, 52%) after flash column chromatography
[silica gel, DCM : petroleum spirit (1 : 1).
1H NMR (CDCl3, 500 MHz): δ 1.20 (t, 6 H, J 7.2 Hz), 4.21
(q, 4 H, J 7.2 Hz), 4.48 (s, 1 H), 5.64 (s, 2 H), 7.51 (m, 2 H),
7.57 (m, 2 H), 7.74 (m, 2 H), 7.83 (dd, 1 H, J 8.4, 0.9 Hz), 8.17
(d, 1 H, J 7.7 Hz), 8.26 (m, 3 H). 13C NMR (CDCl3, 125.76
MHz): δ 13.8, 59.0, 62.5, 66.5, 119.5, 120.4, 120.6, 120.7, 123.8,
126.6, 126.7, 127.2, 128.1, 128.3, 128.4, 128.8, 129.1, 129.7,
130.7, 131.0, 131.8, 132.6, 133.0, 134.6, 163.8, 164.0. MS(EI):
m/z 468 [M]ϩ.
Compound 4c
Reagent quantities were DBU (0.6 mg, 3.67 µmol), C60F18
(3.0 mg, 2.82 µmol) and 3 (2.2 mg, 4.52 µmol). HPLC (4.7 ml
minϪ1) gave a single fraction eluting at 3.8 min. Concentration
of this fraction in vacuo provided 4c (2.0 mg, 32%).
1H NMR: δ 3.78 (bs, 36 H), 5.42 (bd, 6 H, J 11.0 Hz), 5.46
(bd, 6 H, J 11.0 Hz), 6.58 (bs, 6 H), 6.49 (bs, 12 H). 19F NMR
(CDCl3): δ Ϫ144.0 (6 F), Ϫ143.8 (6 F), Ϫ135.9 (3 F). MS(EI):
m/z 1005 [C60F15]ϩ.
Compound 22
Using 21 (0.152 g, 0.31 mmol), sodium hydride (0.010 g,
0.40 mmol) and ethyl chloroformate (44 µL, 0.46 mmol) pro-
vided 22 (0.052 g, 30%; 83% based on recovered starting
material) and 21 (0.097 g, 64%) after HPLC eluting toluene
(flow rate 2.0 mL minϪ1; 1 : 2 mixture of 22 : 21 at t = 7.3 min.
and t = 7.9 min respectively). UV/vis (DCM, ε): 304 (7430) nm,
317 (6123), 332 (6252), 415 (sh, 9203), 440 (19507), 469 (23727).
1H NMR (CDCl3, 500 MHz): δ 1.29 (t, 6 H, J 7.2 Hz), 4.48
(q, 4 H, J 7.2 Hz), 4.50 (s, 1 H), 5.29 (s, 2 H), 7.41 (d, 2 H,
J 7.9 Hz), 7.51 (m, 2 H), 7.62 (dd, 1 H, J 7.5, 0.7), 7.66 (d, 2 H,
J 7.9 Hz), 7.72 (d, 1 H, J 8.0 Hz), 7.73 (d, 1 H, J 8.1 Hz), 7.76
(d, 1 H, J 7.9 Hz), 8.18 (d, 1 H, J 7.9 Hz), 8.22 (dd, 1 H, J 7.7,
1.0 Hz), 8.23 (dd, 1 H, J 7.8, 1.0 Hz), 8.27 (dd, 1 H, J 7.7,
1.0 Hz), 8.29 (dd, 1 H, J 8.2, 1.0 Hz). 13C NMR (CDCl3, 125.76
MHz): δ 13.9, 59.0, 62.6, 67.5, 88.7, 94.9, 119.7, 120.7, 120.8,
121.0, 126.1, 126.6, 126.7, 127.3, 128.1, 128.3 (2 C), 128.5,
128.6, 129.9, 130.7, 131.0, 131.1, 131.6, 131.7, 131.8 (2 C),
132.0, 134.6, 135.0, 163.7, 163.8. MALDI-TOF: m/z 569 [M]ϩ.
Compound 7
This was prepared according to an earlier method.6b
13C NMR (CDCl3, 125 MHz): δ 14.0 (s, –CO2CH2CH3), 53.4
[s, –C(CO2Et)3], 63.8 (s, –CO2CH2CH3), 71.0 (bs, C), 85.5
(m, C–F), 87.4 (m, C–F), 89.6 (t, J 238, 26 Hz; C–F), 90.3
(t, J 240, 26 Hz; C–F), 91.6 (t, J 238, 26 Hz; C–F), 92.3
(m, C–F) (all sp3 fullerenyl); 130.9 3 [m, C], 131.7 [s, C], 135.0
[s, C], 135.1 [s, C], 146.8 [s, C], 147.2 [s, C], 148.2 [bs, C], 150.9
[s, C], 163.1 [bs, C], (all sp2 fullerenyl) 163.8 [s, –C᎐O].
᎐
Compound 16a
Reagent quantities were DBU (1.28 mg, 8.46 µmol), C60F18
(9.0 mg, 8.46 µmol) and 15a (2.87 mg, 8.46 µmol). HPLC
(2.0 mL minϪ1) gave a single fraction at 7.8 min. Concentration
of the toluene solution gave the product 16a as a green solid
(6.9 mg, 41%). UV/vis (DCM): 338 nm, 397, 438, 612, 667.
1H NMR (CDCl3, 500 MHz, 338 K): δ 1.28 (t, 18 H,
J 7.2 Hz), 4.53 (q, 12 H, J 7.2 Hz), 5.27 (s, 6 H), 7.54 (d, 6 H,
J 8.7 Hz), 8.21 (d, 6 H, J 8.7 Hz). 19F NMR: δ Ϫ142.4 (6 F),
Ϫ142.3 (6 F), Ϫ135.1 (3 F). MALDI-TOF (Ϫve ion mode):
m/z 1005 [C60F15]Ϫ.
Preparation of trannulenes
In all of these preparations, DBU was added to C60F18 and
malonate in toluene at room temperature and stirred for a fur-
ther 10 min, the product being then filtered and processed.
Emerald green solutions were obtained except where indicated.
Compound 2
Compound 16b
Reagent quantities were DBU (0.52 mg, 3.39 µmol), C60F18
(3 mg, 2.82 µmol) and 1 (1.77 mg, 4.23 µmol). HPLC (2.0 mL
minϪ1) gave a single fraction at 8.0 min. Concentration of the
toluene solution gave the product as a green solid (4.1 mg,
78%).
Reagent quantities were DBU (0.58 mg, 3.67 µmol), C60F18
(3.0 mg, 2.82 µmol) and 15b (1.60 mg, 4.51 µmol). HPLC
(4.7 mL minϪ1) gave a single fraction at 3.3 min. Concentration
of the toluene solution gave the product 16b as a green solid
(2.4 mg, 34%). UV/vis (DCM): 280 nm, 397, 612, 667.
1H NMR (CDCl3, 500 MHz): δ 5.45 (d, 6 H, J 12 Hz), 5.49
(d, 6 H, J 12 Hz)], 7.43 (m, 30 H). 19F NMR: δ Ϫ143.24 (s, 6 F),
Ϫ144.00 (s, 6 F), Ϫ136.9 (s, 3 F). MALDI-TOF (Ϫve ion
mode): 1005 [C60F15]Ϫ.
1H NMR (CDCl3, 500 MHz, 298 K): δ 1.48 (t, 18 H,
J 7.2 Hz), 3.86 (bs, 18 H), 4.46 (bq, 12 H, J 7.2 Hz), 5.45
(bs, 6 H), 6.58 (bs, 3 H), 6.64 (bs, 6 H). 19F NMR: δ Ϫ142.6,
Ϫ142.3, Ϫ134.5. MALDI-TOF (Ϫve ion mode): 1005 [C60F15]Ϫ.
Compounds 4a/4b
Compound 16c
Reagent quantities were DBU (0.4 mg, 2.82 µmol), C60F18
(3.0 mg, 2.82 µmol) and 3 (1.37 mg, 2.82 µmol). The solution
changed colour from lemon yellow to olive green. HPLC
Reagent quantities were DBU (1.67 mg, 11.0 µmol), C60F18
(9.0 mg, 8.46 µmol) and 15c (5.5 mg, 13.53 µmol). HPLC
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 3 1 9 – 3 2 9
327