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CDCl3) d 15.8, 49.4, 51.8, 127.9, 128.3, 128.4, 137.3, 137.8,
138.0, 143.1, 158.4, 159.6; MS (EI, 70 eV) m/z (%): 220 (100)
[M+], 219 (99), 129 (54), 115 (56), 101 (64), 78 (52), 77 (72);
HRMS (EI) calcd for C15H12N2 [M+]: 220.1000, Found:
220.1008; Anal. Calcd for C15H12N2: C, 81.70; H, 5.49; N,
12.72. Found: C, 81.03; H, 5.51; N, 12.73.
58.7, 125.5, 125.6, 126.5, 128.0, 128.0, 129.0, 133.0, 133.0,
134.8, 135.2, 159.6, 160.3, 160.9; MS (EI, 70 eV) m/z (%) 424 (14)
[M+], 368 (36), 367 (50), 353 (36), 311 (55), 85 (100), 57 (55), 55
(36), 41 (45), 18 (91) ; Anal. Calcd for C30H36N2: C, 84.85; H,
8.54; N, 6.60; Found C, 84.91; H, 8.64; N, 6.45.
10,12,15-Tri-tert-butyl-10,13-dihydro-10,13-
ethenodibenzo[a,c]phenazine (15)
1-Propyl-1,4-dihydro-1,4-ethenophenazine (12)
Diamine 18 (251 mg, 2.32 mmol) in MeOH (15 mL) mixed with
bicyclic octadiendione 16b (372 mg, 2.11 mmol) gave
dicyanobarrelene 12 in 90% yield; time of reaction = 10 h;
column chromatography (ethyl acetate : hexanes = 1 : 4). IR
(neat): 3062, 2959, 2932, 2871, 1577, 1460, 1326, 1146, 750
cm21; 1H NMR (400 MHz, CDCl3) d 1.18 (t, J = 7.2 Hz, 3 H), 1.76
(qt, J = 7.2, 4.4 Hz, 2 H), 2.46 (m, 2 H), 4.92 (t, J = 6.4 Hz, 1 H),
6.71 (dd, J = 6.4, 1.6 Hz, 2 H), 6.97 (t, J = 6.4 Hz, 2 H), 7.33 (m, 2
H), 7.82 (m, 1 H), 7.89 (m, 1 H); 13C NMR (100 MHz, CDCl3) d
15.0, 18.4, 31.2, 49.1, 55.7, 127.9, 128.3, 128.4, 137.2, 137.7,
138.0, 141.1, 159.0, 159.7; MS (EI) m/z (%): 248 (100) [M+], 247
(41), 233 (36), 219 (93), 205 (43), 125 (58), 77 (60); HRMS (EI)
Calcd for C17H16N2 [M+]: 248.1313, Found: 248.1318.
Phenanthrene-9,10-diamine 20 (380 mg, 1.83 mmol) in n-BuOH
(15 mL) mixed with bicyclic octadiendione 16c (500 mg, 1.66
mmol) and p-TSA (158 mg, 0.83 mmol) gave dicyanobarrelene 15
as a white crystalline solid (160 mg, 20% yield) (mp 235–236 uC).
IR (CHCl3) 3080, 2960, 2900, 2860, 1475, 1460, 1385, 1360, 1335,
1240, 1180, 1085, 905, 840 cm21; UV (n-hexane) l max (e) = 359.3
(1.2 6 104), 351.4 (5.4 6 103) 342.1 (7.2 6 103), 322.9 (7.0 6 103),
265.2 (2.4 6 104), 257.4 (1.9 6 104), 239.1 (1.8 6 104), 210.1 (1.5
104), 194.0 (2.3 6 104); UV (MeOH) 359.9 (1.1 6 104), 342.6 (7.5 6
103), 323.1 (7.4 6 103), 265.0 (2.7 6 104), 239.9 (2.0 6 104), 209.7
(1.8 6 104).; 1H NMR (400 MHz, CDCl3) d 1.14 (s, 18 H) ppm, 1.20–
1.40 (br, 3 H), 1.63–1.90 (br, 6 H), 5.05 (t, J = 2.1 Hz, 1 H), 6.46 (d, J
= 2.1 Hz, 2 H), 7.66–7.73 (m, 4 H), 8.59–8.61 (m, 2 H), 9.12–9.30
(m, 2 H); 13C NMR (400 MHz,CDCl3) d 25.4, 28.8, 32.8, 35.3, 52.1,
59.8, 122.4, 122.5, 124.8, 124.9, 126.9, 127.1, 127.5, 127.6, 130.2,
130.6, 130.9, 132.4, 161.5, 161.6, 162.7,; MS (EI, 70 eV) m/z (%) 474
(34) [M+], 418 (46), 417 (100), 403 (54), 362 (23), 346 (31), 346 (31),
71 (31), 57 (77), 43 (31), 41 (38), 18 (62); Anal. Calcd for C34H38N2:
C, 86.03; H, 8.07; N, 5.90; Found C, 85.37; H, 8.18; N, 5.84.
1,3,11-Tri-tert-butyl-1,4-dihydro-1,4-ethenophenazine (13)
Diaminobenzene 18 (251 mg, 2.32 mmol) in n-BuOH (15 mL)
mixed with bicyclic octadiendione 16c (500 mg, 1.66 mmol)
and p-TSA (158 mg, 0.83 mmol) gave dicyanobarrelene 13 as a
white crystalline solid (470 mg, 76% yield) (mp 129–130 uC);
time of reaction = 7 d; column chromatography (ethyl
acetate : hexanes = 1 : 4). IR (CHCl3) 2960, 2900, 2860, 1480,
General Procedures for photorearrangement.
1470, 1390, 1360, 1305, 1240, 1180, 960, 920, 885, 845 cm21
;
Unless stated otherwise, photoreactants were placed in Pyrex tubes
and dissolved either in deuterated benzene (for direct irradiation)
or in deuterated acetone (for sensitized irradiation). The resulting
mixtures were degassed either by sonication or by bubbling argon
gas (1 (h) and then irradiated with 350 nm light until the reaction
was complete. Solvents were removed under reduced pressure and
purification of crude products was performed by column
chromatography using ethyl acetate : hexanes as eluant. Unless
specified otherwise, relative yields of photoproducts were deter-
mined by 1H NMR integrations of the mixture.
UV (n-hexane) l max (e) = 330.4(6.0 6 103), 316.1 (7.1 6 103)
255.2 (7.3 6 103), 234.1 (8.7 6 103), 215.6 (2.7 6 104); UV
(MeOH) 321.2 (9.2 6 103), 236.8 (1.2 6 104), 215.6 (3.6 6 104);
1H NMR (400 MHz, CDCl3) d 1.11 (s, 18 H), 1.15–1.30 (br, 3 H),
1.55–1.75 (br, 6 H), 4.90 (t, J = 2.1 Hz, 1 H), 6.38 (d, J = 2.1 Hz, 2
H), 7.52–7.55 (m, 2 H), 7.80–7.86 (m, 2 H); 13C NMR (400
MHz,CDCl3) d 25.3, 28.7, 32.7, 35.2, 51.6, 59.1, 127.7, 127.7,
127.9, 128.7, 129.6, 136.7, 137.1, 160.3, 161.1, 161.7; MS (EI, 75
eV) m/z (%) 374 [M+], 318 (40), 317 (72), 304 (19), 303 (68), 261
(56), 248 (21), 247 (24), 86 (19), 84 (28), 59 (33), 57 (36), 43
(100), 41 (28), 29 (19); Anal. Calcd for C26H34N2: C, 83.37; H,
9.15; N, 7.48; Found C, 83.41; H, 9.24; N, 7.57.
Irradiation of 8.
Irradiation of 8 (10 mg) in C6D6 (2 mL) with 350 nm light for 4 h
1
afforded a 23 : 20 : 21 : 36 mixture (determined by H-NMR) of
1,3,13-Tri-tert-butyl-1,4-dihydro-1,4-ethenobenzo[b]phenazine
photoproducts 32, 33, 34, and 35, respectively. The crude mixture
was separated in a column (ethyl acetate : hexanes = 1 : 6) to
obtain 35 (3.2 mg), and non-separable mixture of 32, 33, and 34.
(14)
Diaminonaphthalene 19 (366.75 mg, 2.32 mmol) in n-BuOH
(15 mL) mixed with bicyclic octadiendione 16c (500 mg, 1.66
mmol) and p-TSA (158 mg, 0.83 mmol) gave dicyanobarrelene
14 as a white crystalline solid (450 mg, 64% yield) (mp 256–257
uC). IR (CHCl3) 3080, 3050, 2960, 2900, 2860, 1640, 1600, 1560,
1475, 1460, 1395, 1365, 1320, 1240, 1190, 1080, 1010, 960, 920,
885, 840 cm21; UV (n-hexane) l max (e) = 365.3(6.5 6 103),
280.1 (2.1 6 104) 257.5 (3.0 6 104), 238.7 (2.5 6 104), 201.6
(1.1 6 104); UV (MeOH) 368.0 (2.1 6 104), 350.7 (1.8 6 104),
284.2 (5.1 6 104), 258.8 (8. 5 6 104), 237.4 (8.6 6 104); 1H
NMR (400 MHz, CDCl3) d 1.13 (s, 18 H), 1.21–1.33 (br, 3 H),
1.53–1.80 (br, 6 H), 4.89 (t, J = 1.8 Hz, 1 H), 6.37 (d, J = 1.8 Hz, 2
H), 7.44–7.46 (m, 2 H), 7.97–7.99 (m, 2 H), 8.30 (s, 1 H), 8.36 (s,
1 H); 13C NMR (400 MHz, CDCl3) d 25.4, 28.8, 32.7, 35.3, 51.4,
1-Methyl-2a,2b,6b,6c-Tetrahydrocyclopropa[3,4]pentaleno[1,2-
b]pyrazine-4,5-dicarbonitrile (35)
IR (neat): 3058, 2922, 2854, 2236, 1732, 1626, 1539, 1371, 1332,
972, 836, 809 cm21; 1H NMR (400 MHz, CDCl3) d 1.76 (d, J = 0.8
Hz, 3 H), 3.09 (ddd, J = 2.4, 6.0, 7.2 Hz, 1 H), 3.22 (dd, J = 6.0,
7.2 Hz, 1 H), 3.67 (ddd, J = 6.0, 6.0, 6.0 Hz, 1 H), 3.90 (d, J = 6.0
Hz, 1 H), 5.21 (m, 1 H); 13C NMR (100 MHz, CDCl3) d 13.2, 36.2,
41.9, 49.5, 56.3, 113.6, 113.8, 121.7, 129.2, 131.6, 143.9, 157.8,
162.6. MS (EI, 70 eV) m/z (%): 220 (57) [M+], 219 (100), 206 (31),
71 (8), 63 (7), 57 (19), 55 (10); HRMS(EI) calcd for C13H8N4 [M+]:
220.0749, Found: 220.0770.
This journal is ß The Royal Society of Chemistry 2013
RSC Adv., 2013, 3, 1165–1178 | 1175