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A.C. Razus et al. / Tetrahedron 64 (2008) 1792e1797
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(4.11), 542 (2.86) nm. H NMR (300 MHz, CDCl3): d 1.47
131.76 (Cq), 132.81 (C-20), 133.51 (Cq), 134.13 (C-4), 135.16
(C-6), 136.01 (Cq), 138.11 (Cq), 140.14 (C-2), 140.54 (Cq),
144.37 (Cq), 146.21 (Cq), 148.99 (Cq) ppm. ESI-MS (positive
mode): m/z (%)¼353.1 (100) [Mþ1]. Elemental Analysis
Calcd for C27H28 [352 g/mol]: C 91.99%, H 8.01%; Found:
C 91.90, H 8.00%. IR (solid): nmax 3093w, 3059w, 2957s,
2924s, 2869s, 1566s, 1422s, 1369m, 1326w, 1247w, 1206w,
1076m, 1020m, 866w, 749m (cmꢁ1).
(t, 3H, CH2CH3, J¼7.1 Hz), 2.72 (s, 3H, 6-Me), 2.97 (s, 6H,
40-Me, 80-Me), 4.4 (q, 2H, CH2CH3, J¼7.2 Hz), 7.21 (dd,
1H, 5-H, J¼9.1, 1.1 Hz), 7.25 (s, 2H, 50-H, 70-H), 7.29 (d,
2H, 10-H, 30-H, J¼3.9 Hz), 7.33 (dd, 1H, 7-H, J¼9.1,
1.2 Hz), 7.76 (t, 1H, 20-H, J¼3.9 Hz), 8.45 (s, 1H, 2-H),
8.53 (d, 1H, 8-H, J¼10.2 Hz) ppm. 13C NMR (75.47 MHz,
CDCl3): d 15.01 (CH3CH2), 25.67 (Me-40, Me-80), 28.35
(Me-6), 60.23 (CH2CH3), 116.37 (Cq), 116.77 (C-10, C-30),
128.59 (C-50, C-70), 129.49 (C-5), 129.56 (C-7), 133.77
(C-20), 135.16 (Cq), 136.57 (C-2), 136.65 (C-8), 138.08
(C-4), 139.38 (Cq), 139.62 (Cq), 140.74 (Cq), 144.25 (Cq),
145.82 (Cq), 152.75 (Cq), 165.81 (CO) ppm. ESI-MS (positive
mode): m/z (%)¼369 (60) [Mþ1], 320 (100). Elemental Ana-
lysis Calcd for C26H24O2 [368 g/mol]: C 84.75%, H 6.56%;
Found: C 84.72%, H 6.57%. IR (solid): nmax 3095s, 3064s,
2918s, 2851s, 1690 (nC]O), 1565m, 1511w, 1431s, 1382m,
1202w, 1152w, 1102w, 1070m, 1038m, 858w, 816w, 765w,
733w (cmꢁ1).
4.3.4. 2-tert Butyl-6,40,80-trimethyl-[1,60]biazulenyl (3d)
Green crystals, mp 122e124 ꢀC. UVevis (MeOH): lmax
(log 3) 206 (4.33), 243 (4.56), 277 (4.78), 295 (4.92), 347
(4.06), 395 (3.45), 558 (2.58) nm. 1H NMR (300 MHz,
t
CDCl3): d 1.31 (s, 9H, Bu), 2.54 (s, 3H, 6-Me), 2.88 (s, 6H,
40-Me, 80-Me), 6.85 (d, 1H, 5-H, J¼10.2 Hz), 7.03 (d, 1H,
7-H, J¼9.6 Hz), 7.26 (s, 2H, 50-H, 70-H), 7.28 (s, 1H, 3-H),
7.44 (d, 2H, 10-H, 30-H, J¼3.8 Hz), 7.53 (d, 1H, 4-H,
J¼10.1 Hz), 7.76 (t, 1H, 20-H, J¼3.8 Hz), 8.12 (d, 1H, 8-H,
J¼9.9 Hz) ppm. 13C NMR (75.47 MHz, CDCl3): d 24.97
(Me-40, Me-80), 27.79 (Me-6), 32.06 (Me-tBu), 34.90
(Cq-tBu), 114.90 (C-3), 116.12 (C-10, C-30), 124.44 (C-5, C-
7), 130.25 (C-50, C-70), 133.43 (C-20), 133.62, 133.71 (C-8),
134.70 (C-4), 134.71 (Cq), 136.78 (Cq), 137.33 (Cq), 137.75
(Cq), 144.51 (Cq), 147.62 (Cq) ppm. ESI-MS (positive
mode): m/z (%)¼353 (100) [Mþ1]. Elemental Analysis Calcd
for C27H28 [352 g/mol]: C 91.99%, H 8.01%; Found: C
91.93%, H 8.03%. IR (solid): nmax 3095w, 3070w, 3010w,
2953m, 2919m, 2853m, 1563s, 1479m, 1420s, 1314w,
1242w, 1206m, 1069w, 1008w, 862w, 812m, 746s (cmꢁ1).
4.3.7. 40,80-Diphenyl-[1,60]biazulenyl (5a)
Green oil. UVevis (MeOH): lmax (log 3) 202 (4.61), 236
(4.60), 287sh (4.58), 305 (4.63), 435 (4.21), 558 (2.89) nm.
1H NMR (400 MHz, CDCl3): d 7.16 (d, 2H, 10-H, 30-H,
J¼4.0 Hz), 7.21 (t, 1H, 7-H, J¼9.6 Hz), 7.24 (t, 1H, 5-H,
J¼9.6 Hz), 7.43 (d, 1H, 3-H, J¼4.0 Hz), 7.46e7.53 (m, 6H,
300-H, 400-H, 500-H), 7.54 (s, 2H, 50-H, 70-H), 7.60 (t, 1H, 6-
H, J¼9.6 Hz), 7.68e7.71 (m, 5H, 20-H, 200-H, 600-H), 8.14
(d, 1H, 2-H, J¼3.8 Hz), 8.37 (d, 1H, 4-H, J¼9.2 Hz), 8.70
(d, 1H, 8-H, J¼9.6 Hz) ppm. 13C NMR (100.62 MHz,
CDCl3): 117.82 (C-3), 120.08 (C-10, C-30), 123.99 (C-7),
124.42 (C-5), 124.83 (C-6), 127.76 (C-50, C-70), 127.90
(C-400), 128.10 (C-300, C-500), 128.38 (C-20), 129.26 (C-200,
C-600), 134.68 (Cq), 135.84 (C-8), 137.72 (C-4), 138.24
(Cq), 138.56 (C-2), 142.44 (Cq), 144.55 (Cq), 145.00 (Cq),
149.68 (Cq) ppm. ESI-MS (positive mode): m/z (%)¼407
(100%) [Mþ1]. Elemental Analysis Calcd for C32H22
[406 g/mol]: C 94.55%, H 5.45%; Found: C 94.43%, H 5.49%.
IR (solid): nmax 3059w, 3028w, 2958s, 2927s, 2858m, 1560m,
1538m, 1495m, 1459m, 1447m, 1436m, 1418m, 1339w,
1276m, 1126w, 1075w, 1029w, 771m, 743m, 702m (cmꢁ1).
4.3.5. N-(4080-Dimethyl-[1,60]biazulenyl-3-yl)-N-methyl-
formamide (4b)
Green crystals, mp 140e142 ꢀC. UVevis (MeOH): lmax
(log 3) 245 (4.42), 284 (4.53), 314 (4.38), 424 (3.97); 559
(2.70) nm. 1H NMR (300 MHz, CDCl3): d 2.17 (s, 3H,
COCH3), 2.78 (s, 6H, 40-Me, 80-Me), 6.88 (t, 1H, 5-H or 7-
H, J¼9.6 Hz), 6.91 (t, 1H, 7-H or 5-H, J¼9.5 Hz), 7.25
(s, 2H, 50-H, 70-H), 7.27 (d, 2H, 10-H, 30-H, J¼4.0 Hz), 7.39
(t, 1H, 6-H, J¼9.7 Hz), 7.58 (t, 1H, 20-H, J¼3.9 Hz), 7.94
(d, 1H, 4-H, J¼10.1 Hz), 8.29 (s, 1H, 2-H), 8.28 (d, 1H, 8-
H, J¼9.1 Hz) ppm. 13C NMR (75.47 MHz, CDCl3): d 25.65
(Me-40, Me-80), 30.08 (COCH3), 116.58 (C-10, C-30), 122.48
(C-5 or 7), 124.28 (C-7 or 5), 128.62 (Cq), 128.88 (C-50,
C-70), 132.23 (C-20), 132.51 (C-2), 133.55 (Cq), 133.63
(C-8), 134.10 (Cq), 136.99 (C-4), 139.62 (C-6), 145.65 (Cq),
155.34 (Cq), 155.55 (Cq), 168.79 (Cq) ppm. ESI-MS (positive
mode): m/z (%)¼340 (100) [Mþ1]. Elemental Analysis Calcd
for C24H21NO [339 g/mol]: C 84.92%, H 6.24%, N 4.13%;
Found: C 84.85%, H 6.28% N 4.15%. IR (solid): nmax
2958s, 2927s, 2872m, 2858s, 1729 (nC]O), 1567w, 1461m,
1380w, 1270m, 1170w, 1122m, 1072m, 1039w, 960w, 868w,
739w, 704w (cmꢁ1).
4.3.8. 4,6,8-Trimethyl-40,80-diphenyl-[1,60]biazulenyl (5b)
Green crystals, mp 184e185 ꢀC. UVevis (MeOH): lmax
(log 3) 202 (4.40), 244 (4.43), 287sh (4.41), 300 (4.53), 441
(3.82), 555 (2.80) nm. 1H NMR (400 MHz, CDCl3): d 1.42 (s,
6H, 40-Me, 60-Me), 2.58 (s, 3H, 8-Me), 2.62 (s, 3H, 6-Me),
2.87 (s, 3H, 4-Me), 6.99 (s, 1H, 7-H), 7.04 (s, 1H, 5-H), 7.15
(d, 2H, 10-H, 30-H, J¼3.98 Hz), 7.32 (d, 1H, 3-H, J¼4.12 Hz),
7.37 (s, 2H, 50-H, 70-H), 7.37e7.48 (m, 6H, 300-H, 400-H, 500-H),
7.62e7.65 (m, 4H, 200-H, 600-H), 7.67 (d, 1H, 2-H, J¼4.12 Hz),
7.70 (t, 1H, 20-H, J¼4.23 Hz) ppm. 13C NMR (100.62 MHz,
CDCl3): 25.88 (Me-40, Me-80), 28.79 (Me-4), 29.73 (Me-6),
30.66 (Me-8), 115.43 (CH), 120.25 (CH), 125.87 (CH),
127.89 (CH), 128.12 (CH), 128.35 (CH), 128.93 (CH), 129.56
(CH), 129.73 (Cq), 131.86 (Cq), 134.79 (CH), 136.95 (CH),
137.09 (Cq), 137.38 (Cq), 138.06 (Cq), 144.77 (Cq), 146.50
4.3.6. 6,40,80-Trimethyl-[1,60]biazulenyl-3-carboxylic
acid ethyl ester (4c)
Green crystals, mp 134e135 ꢀC. UVevis (MeOH): lmax
(log 3) 206 (4.36), 242 (4.50), 286 (4.60), 309 (4.57), 397