Beilstein J. Org. Chem. 2011, 7, 278–289.
(CH3), 19.9 (CH2), 32.6 (CH2), 38.0 (CH2), 53.1 (CH), 122.9 (ESI–): m/z (%) = 771 (100) [M − H]−. Anal. Calcd for
(CHar), 124.5 (CHar), 143.3 (Cq), 146.6 (Cq), 158.6 (C=O). C36H24F12N4O2 (772.6): C, 55.97; H, 3.13; N, 7.25. Found: C,
Anal. Calcd for C34H28N4O2 (460.6): C, 73.01; H, 7.88; N, 55.58; H, 2.85; N, 7.04.
12.16. Found: C, 73.25; H, 7.95; N, 12.04.
11,12-Bis{N’-[3,5-(bistrifluoromethyl)phenyl]thiourei-
11,12-Bis(N’-phenylureidomethyl)-9,10-dihydro-9,10-eth- domethyl}-9,10-dihydro-9,10-ethenoanthracene (1i):
enoanthracene (1f): Prepared from dibenzobarrelene 1d Prepared from dibenzobarrelene 1d (0.13 g, 0.50 mmol)
(131 mg, 0.50 mmol) according to GP1 and collected by according to GP1 and obtained by recrystallization from
filtration and obtained as a white powder (179 mg, 0.36 mmol, CH2Cl2/hexane as a white solid (0.34 g, 0.43 mmol, 86%),
72%), mp 309–312 °C (dec.). 1H NMR [400 MHz, (CD3)2SO]: mp > 300 °C. 1H NMR [600 MHz, (CD3)2CO]: δ 4.66 (d,
δ 4.07 (d, J = 5 Hz, 4H, CH2), 5.15 (s, 2H, CH), 6.37 (t, J = J = 4 Hz, 4H, CH2), 5.36 (s, 2H, CH), 6.92 (m, 4H, CHar),
5 Hz, 2H, NH), 6.90–6.93 (m, 6H, CHar), 7.20–7.41 (m, 12H, 7.30–7.32 (m, 4H, CHar), 7.73 (m, 4H, CHar overlapped
CHar), 8.29 (s, 2H, NH). 13C NMR [100 MHz, (CD3)2SO]: with NH), 8.25–8.26 (m, 4H, CHar), 9.57 (br s, 2H, NH).
δ 37.9 (CH2), 53.3 (CH), 118.3 (CHar), 121.5 (CHar), 123.0 13C NMR [150 MHz, (CD3)2CO]: δ = 43.4 (CH2), 54.2 (CH),
(CHar), 124.6 (CHar), 129.0 (CHar), 140.8 (Cq), 143.5 (Cq), 117.9 (CHar), 121.5 (CHar), 123.6 (CHar), 125.3 (CHar),
146.5 (Cq), 155.8 (C=O). MS (EI): m/z = 500 [M+]. Anal. Calcd 127.0 (CHar), 132.0 (CHar), 142.4 (Cq), 144.1 (Cq), 146.8 (Cq),
for C34H28N4O2 (500.6): C, 76.78; H, 5.64; N, 11.19. Found: C, 182.4 (C=O). UV (MeCN): λmax (log ε) = 230 (4.49), 246
76.68; H, 5.67; N, 11.12.
(4.59), 272 (4.46), 280 (4.47). MS (ESI): m/z (%) = 803 (100)
[M − H]−. Anal. Calcd for C36H24F12N4S2 (804.7): C, 53.73; H,
11,12-Bis[N’-(4-n-butylphenyl)ureidomethyl]-9,10-dihydro- 3.01; N, 6.96; S, 7.97. Found: C, 53.58; H, 2.79; N, 6.84; S,
9,10-ethenoanthracene (1g): Prepared from dibenzobarrelene 7.97.
1d (0.12 g, 0.45 mmol) according to GP1, collected by filtration
and dried in vacuo. White amorphous solid, yield 0.21 g General procedure for the synthetic photolysis in solution
(0.34 mmol, 76%), mp > 320 °C. 1H NMR [400 MHz, (GP2): Solutions of the substrate (10−3–10−2 mol/l) were
(CD3)2SO]: δ 0.89 (t, J = 7 Hz, 6H, CH3), 1.26–1.55 (m, 8H, placed in a Duran flask (acetone) or quartz test tube (other
CH2CH2CH3), 2.47–2.50 (m, 4H, PhCH2CH2, partly over- solvents), and argon gas was bubbled carefully through the
lapped with the solvent signal), 3.97 (d, J = 6 Hz, 4H, solution for at least 20 min. The solution was irradiated for
C=CCH2), 5.14 (s, 2H, CH), 6.06 (t, J = 6 Hz, 2H, NH), 4–15 h with stirring until the starting material was fully
6.90–6.92 (m, 4H, CHar), 7.03–7.05 (m, 4H, CHar), 7.25–7.29 converted as determined by TLC or 1H NMR spectroscopic
(m, 8H, CHar), 8.42 (s, 2H, NH). 13C NMR [100 MHz, analysis. After evaporation of the solvent in vacuo, the
(CD3)2SO]: δ 14.2 (CH3), 22.1 (CH2), 33.7 (CH2), 34.5 (CH2), photolysate was analyzed by 1H NMR spectroscopy. In prepara-
37.9 (CH2), 53.3 (CH), 118.4 (CHar), 123.0 (CHar), 124.6 tive experiments, the photoproduct was isolated by recrystal-
(CHar), 128.8 (CHar), 135.3 (CHar), 138.4 (Cq), 143.5 (Cq), lization or column chromatography.
146.5 (Cq), 155.9 (C=O). MS (EI): m/z (%) = 613 [M+]. Anal.
Calcd for C40H44N4O2 (612.8): C, 78.40; H, 7.24; N, 9.14. 4b,8b-Dihydro-8c,8e-bis{N’-[3,5-bis(trifluoromethyl)phe-
Found: C, 78.12; H, 7.25; N, 9.09.
nyl]ureidomethyl}dibenzo[a,f]cyclopropa[c,d]pentalene
(2h): Prepared by irradiation of 1h (48.0 mg, 0.06 mmol) in
11,12-Bis{N’-[3,5-bis(trifluoromethyl)phenyl]ureido- acetone solution according to GP2 and obtained as white crys-
methyl}-9,10-dihydro-9,10-ethenoanthracene (1h): Prepared tals (29.0 mg, 0.04 mmol, 60%), mp 246–247 °C. 1H NMR
from dibenzobarrelene 1d (0.13 g, 0.50 mmol) according to [600 MHz, (CD3)2CO]: δ 3.22 (s, 1H, CH), 3.78 (dd, J = 15, 6
GP1. After filtration of the precipitate, the product was purified Hz, 1H, CH2), 3.82 (dd, J = 15, 6 Hz, 1H, CH2), 3.94 (dd, J =
by recrystallization from CH2Cl2/hexane and obtained as a 15, 6 Hz, 1H, CH2), 4.44 (dd, J = 15, 6 Hz, 1H, CH2), 4.63 (s,
white solid (0.33 g, 0.41 mmol, 82%), mp > 300 °C. 1H NMR 1H, CH), 6.42 (t, J = 5 Hz, 1H, NH), 6.53 (t, J = 5 Hz, 1H, NH),
[400 MHz, (CD3)2CO]: δ 4.18 (d, J = 4 Hz, 4H, CH2), 5.25 (s, 6.99–7.05 (m, 4H, CHar), 7.21–7.25 (m, 3H, CHar), 7.36–7.38
2H, CH), 6.43 (br s, 2H, NH), 6.86 (m, 4H, CHar), 7.27 (m, 4H, (m, 1H, CHar), 7.49 (s, 2H, CHar), 8.09 (s, 2H, CHar), 8.13 (s,
CHar), 7.51 (s, 2H, CHar), 8.03 (br s, 4H, CHar), 8.64 (br s, 2H, 2H, CHar), 8.75 (s, 1H, NH), 8.81 (s, 1H, NH). 13C NMR [150
NH). 13C NMR [100 MHz, (CD3)2CO]: δ 38.3 (CH2), 53.3 MHz, (CD3)2CO]: δ 41.3 (CH2), 41.4 (CH2), 46.7 (CH), 53.3
(CH), 113.9 (CHar), 117.7 (CHar), 122.4 (CHar), 123.0 (CHar), (Cq), 58.8 (Cq), 67.4 (CH), 115.6 (CHar), 115.6 (CHar), 115.6
124.6 (CHar), 125.1 (CHar), 130.7 (CHar), 131.1 (CHar), 142.7 (CHar), 115.7 (CHar), 119.3 (CHar), 119.3 (CHar), 123.4 (CHar),
(Cq), 143.4 (Cq), 146.4 (Cq), 155.4 (C=O). UV (MeCN): λmax 123.4 (CHar), 124.5 (CHar), 124.6 (Cq), 125.8 (CHar), 126.3
(log ε) = 229 (4.49), 246 (4.86), 272 (4.01), 280 (4.13). MS (Cq), 126.4 (CHar), 126.6 (CHar), 128.1 (CHar), 128.2 (CHar),
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