P. A. Troshin et al.
FULL PAPER
(d, J = 35.0 Hz, 1 F), –144.56 (m, 7.25 F), –146.94 (d, J = 28.5 Hz,
0.5 F), –147.4 (t, J = 30.5 Hz, 0.5 F), –151.77 (t, J = 29.8 Hz, 0.5
F), –154.35 (dt, J = 27.2, 7.1 Hz, 0.25 F), –156.63 (dd, J = 28.2,
7.5 Hz, 0.25 F), –157.70 (m, 0.5 F) ppm. 13C NMR spectrum
(150 MHz, CDCl3) consisted of numerous badly overlapped peaks
because of the atropoisomerism discussed in the text. UV/Vis (tolu-
(CF), 89.82 (CF), 91.39 (CF), 92.03 (CF), 125.3, 127.72, 128.23,
129.04, 130.54, 130.91, 131.02, 131.7, 131.77, 137.88, 146.8, 146.88,
148.26, 150.8, 156, 156.09, 156.17, 163.79, 164.19, 165.1 ppm. UV/
Vis (toluene, ε/–1 cm–1): λ = 335 (27.2ϫ103), 396 (29.6ϫ103), 438
(12.0ϫ103), 571 (5.3ϫ103), 613 (7.8ϫ103), 662 (10.7ϫ103) nm.
MS (MALDI TOF): m/z = 2430 [M+], 1955 {M – C(COOMe)-
ene, ε/–1 cm–1):
λ =
332 (27.1ϫ103), 363 (23.0ϫ103), 396 [COO(CH ) NHC(O)OtBu] }+. FTIR (KBr pellet): ν = 555 (w),
˜
2 3 2
(18.7ϫ103), 443 (10.0ϫ103), 606 (3.8ϫ103), 661 (4.2ϫ103) nm.
MS (MALDI TOF): m/z = 1570 [M+].
668 (w), 781 (w), 815 (m), 861 (m), 970 (m), 1034 (m), 1076 (s),
1119 (vs), 1147 (s), 1168 (s), 1218 (s), 1252 (s), 1275 (s), 1368 (m),
1393 (m), 1436 (w), 1455 (m), 1462 (m), 1506 (m), 1520 (m), 1538
(m), 1698 (m), 1713 (m), 1746 (m), 2869 (w), 2933 (m), 2975 (m)
cm–1.
T1: Yield: 25–46% (80–160 mg). 1H NMR (600 MHz, CDCl3): δ =
1.67 (s, 54 H) 4.06 (s, 9 H) ppm. 19F NMR (282 MHz, CDCl3), δ
= –137.05 (s, 3 F), –144.56 (s, 6 F), –144.78 (s, 6 F) ppm. 13C NMR
(150 MHz, CDCl3): δ = 27.96 (tBu), 31.6 [C(COOtBu)2COOMe],
53.61 (OMe), 71.87 (cage sp3 C), 85.75 (Me3CO), 85.89 (CF), 87.23
(CF), 89.89 (CF), 90.48 (CF), 91.41 (CF), 92.07 (CF), 125.31,
128.24, 129.05, 130.94, 131.76, 146.85, 147.46, 148.42, 150.99,
162.83, 163.24, 165.14 ppm. UV/Vis (toluene, ε/–1 cm–1): λ = 338
(23.8ϫ103), 397 (27.5ϫ103), 438 (10.9ϫ103), 565 (4.0ϫ103), 617
(7.9ϫ103), 661 (11.6ϫ103) nm. MS (MALDI TOF): m/z = 1824
1
T5: Yield: 93% (48 mg). H NMR (600 MHz, DCOOD): δ = 2.88
(m, 12 H, CH2), 2.95 (m, 12 H, CH2), 3.86 (m, 12 H, CH2), 4.84
(m, 9 H, COOMe), 5.24 (br. s., 6 H, NH) ppm. 13C NMR spectrum
was not obtained due to low solubility of this compound in organic
solvents including organic acids and its insufficient stability in
aqueous media. 19F NMR (282 MHz, DCOOD): δ = –76.06
(CF3COO–, 18 F), –136.14 (m, 3 F), –143.32 (m, 6 F), –143.96 (m,
[M+]. FTIR (KBr pellet): ν = 473 (w), 562 (w), 668 (w), 729 (w),
6
F) ppm. UV/Vis (AcOH/water, 1:1; ε/–1cm–1):
λ = 338
˜
(22.1ϫ103), 369 (19.2ϫ103), 393 (20.1ϫ103), 436 (9.4ϫ103), 606
(4.7ϫ103), 665 (7.4ϫ103). MS (ESI): m/z = 1831 [M + H]+, 916
816 (w), 836 (w), 842 (w), 1078 (s), 1120 (vs), 1147 (vs), 1252 (s),
1295 (s), 1372 (m), 1396 (w), 1436 (w), 1462 (w), 1739 (s), 2334
(vw), 2359 (w), 2981 (w) cm–1.
[M + 2H]2+. FTIR (KBr pellet): ν = 483 (m), 604 (m), 659 (m),
˜
T2: Yield: 54% (160 mg). 1H NMR (600 MHz, CDCl3): δ = 4.06
(s, 27 H, OMe) ppm. 19F NMR (282 MHz, CDCl3), δ = –137.14
(s, 3 F), –144.58 (s, 12 F) ppm. 13C NMR (150 MHz, CDCl3): δ =
29.68 [C(COOMe)3], 54.3 (OMe), 70.99 (cage sp3 C), 85.69 (CF),
87.23 (CF), 89.72 (CF), 90.39 (CF), 91.3 (CF), 91.99 (CF), 125.26,
128.19, 129, 130.96, 131.71, 135.45, 135.58, 137.84, 146.8, 146.94,
148.3, 150.62, 162.54, 164.13 ppm. UV/Vis (toluene, ε/–1 cm–1): λ
= 335 (24.2 103), 397 (26.8ϫ103), 438 (11.3ϫ103), 567 (4.2ϫ103),
611 (7.7ϫ103), 661 (12.5ϫ103) nm. MS (MALDI TOF): m/z =
723 (m), 760 (m), 801 (s), 839 (s), 890 (s), 1062 (vs), 1124 (vs), 1203
(vs), 1270 (s), 1688 (m), 1732 (m), 1736 (m), 2949 (s), 3108 (s) cm–1.
Synthesis of T6 and T7: Precursor compound M1 or D1
(0.02 mmol) was dissolved in toluene together with a large excess
of 2 (0.06 mmol). Afterwards, a solution of DBU (0.014 mmol) in
toluene (10 mL) was added dropwise. At the end of the addition,
the reaction mixture attained an emerald-green colour characteris-
tic for trannulenes. Chromatography separation on silica using tol-
uene/EtOAc mixtures as the eluent yielded trannulenes T6 and T7.
Further workup was done analogously to procedure reported for
T1 and T2 above.
1572 [M+]. FTIR (KBr pellet): ν = 465 (vw), 540 (vw), 562 (w),
˜
584 (w), 658 (w), 671 (w), 688 (w), 732 (w), 764 (vw), 814 (m), 861
(vw), 935 (w), 946 (w), 968 (w), 1008 (w), 1026 (m), 1034 (m), 1056
(m), 1078 (vs), 1119 (vs), 1147 (s), 1168 (m), 1184 (m), 1244 (s),
1281 (vs), 1363 (vw), 1400 (w), 1437 (m), 1459 (m), 1630 (w), 1748
(vs), 2957 (w) cm–1.
1
T6: Yield: 68% (22.5 mg). H NMR (600 MHz, CDCl3): δ = 1.69
(s, 18 H, tBu), 3.85 (s, 3 H, OMe), 4.05 (s, 18 H, OMe) ppm. 19F
NMR (282 MHz, CDCl3), δ = –137.05 (s, 1 F), –137.14 (s, 2 F),
–144.51 (s, 2 F), –144.59 (m, 6 F), –144.64 (m, 4 F) ppm. 13C NMR
(200 MHz, CDCl3): δ = 28.03 (tBu), 29.44 [C(COOR)3], 29.70
[C(COOR)3], 53.37 (OMe), 54.26 (OMe), 86.17 (Me3CO), 87.35
(CF), 128.63, 128.96, 131.72, 131.75, 135.21, 135.77, 141.06,
146.47, 146.59, 146.67, 146.79, 146.93, 146.96, 147.23, 147.86,
148.18, 148.2, 148.25, 148.28, 148.31, 150.63, 150.66, 150.69,
150.75, 150.86, 150.89, 162.87 (C=O), 164.15 (C=O), 164.2 (C=O)
ppm. UV/Vis (toluene, ε/–1 cm–1): λ = 334 (23.0ϫ103), 396
(24.3ϫ103), 441 (9.1ϫ103), 565 (3.6ϫ103), 617 (6.6ϫ103), 660
(9.5ϫ103). MS (MALDI TOF): m/z = 1656 [M+]. FTIR (KBr pel-
Synthesis of T4 and T5: Trannulene T4 was synthesized from
C60F18 (200 mg, 0.19 mmol) and C–H acid 5 (1360 mg, 2.85 mmol)
in accordance with the procedure described above for the prepara-
tion of T1 and T2. Isolation and purification of T4 was performed
by using silica gel column chromatography (Acros organics, 40–
60 µ, 60 Å) and mixtures of toluene and ethyl acetate in variable
ratios as eluent (volume concentration of EtOAc was gradually in-
creased from 5 and 65%). T4 was obtained as a dark-green solid
after concentration of the eluate, washing the residue with hexane
and drying in air.
let): ν = 466 (w), 674 (w), 736 (m), 816 (m), 974 (m), 1029 (s), 1076
˜
(vs), 1118 (vs), 1143 (s), 1247 (s), 1278 (s), 1436 (m), 1747 (s), 2851
For preparation of trannulene T5, precursor T4 (50 mg) was first
dissolved in neat trifluoroacetic acid (5 mL). Afterwards, this solu-
tion was stirred at room temperature for 5 min and then concen-
trated to dryness in vacuo. The residue was washed with dichloro-
methane and dried in air. Trannulene T5 was obtained as a hygro-
scopic green solid highly soluble in water.
(s), 2924 (s), 2957 (s) cm–1.
T7: Yield: 75% (26 mg). 1H NMR (600 MHz, CDCl3): δ = 1.64 (s,
18 H, tBu), 1.67 (s, 18 H, tBu), 3.99 (s, 6 H, OMe), 4.04 (s, 9 H,
OMe) ppm. 19F NMR (282 MHz, CDCl3), δ = –137.06 (s, 2 F),
–137.13 (s, 1 F), –144.54 (m, 4 F), –144.61 (s, 2 F), –144.69 (m, 6
F) ppm. 13C NMR (200 MHz, CDCl3): δ = 25.42 (tBu), 25.45
T4: Yield: 31% (142 mg). 1H NMR (600 MHz, CDCl3): δ = 1.50
(s, 18 H, tBu), 1.52 (s, 36 H, tBu), 1.75 (m, 12 H, CH2), 2.09 (m, (tBu), 27.17 [C(COOR)3], 29.06 [C(COOR)3], 51.1 (OMe), 51.66
12 H, CH2), 3.33 (m, 12 H, CH2), 4.59 (m, 9 H, COOMe), 5.07 (OMe), 83.45 (Me3CO), 87.35 (CF), 89.86 (CF), 90.33 (CF), 91.42
(br. s., 6 H, NH) ppm. 19F NMR (282 MHz, CDCl3), δ = –136.27
(CF), 130.97, 131.7, 131.79, 146.37, 146.61, 146.87, 147.25, 147.41,
(s, 3 F), –143.58 (m, 12 F) ppm. 13C NMR (150 MHz, CDCl3): δ 147.89, 148.15, 148.57, 150.71, 150.89, 162.85 (C=O), 164.16
= 28.45 (tBu), 29.01 (CH2-CH2-CH2), 33.87 [C(COOR)2COOMe], (C=O), 165.1 (C=O) ppm. UV/Vis (toluene, ε/–1 cm–1): λ = 334
37.3 (CH2NHBoc), 53.48 (OMe), 54.32 (OMe), 65.64 (COO-CH2- (22.2 103), 396 (23.5ϫ103), 441 (8.4ϫ103), 565 (3.0ϫ103), 617
), 79.47 [C(CH3)3], 79.51 [C(CH3)3], 83.36 (CF), 85.68 (CF), 87.23
(4.9ϫ103), 660 (8.8ϫ103). MS (MALDI TOF): m/z = 1740 [M+].
1044
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Eur. J. Org. Chem. 2010, 1037–1045