3
4
FVP of N-(2-allyloxybenzylidene)-2-methylbenzenamine 6a.
FVP of 6a (0.325 g, 1.3 mmol, Tf 650 ◦C, Ti 120 ◦C, P 0.02 Torr,
t 20 min) gave three products. These were purified by dry-flash
chromatography (hexane-ethyl acetate eluent) to give, first, 2-(2-
1.4), 7.83–7.71 (4H, m), 7.46 (1H, ddd, J 7.3 and 6.6, J 1.6),
3
4
3
4
7.26 (1H, dd, J 8.2, J 1.1) and 7.07 (2H, td, J 8.0, J 1.3); dC
159.69 (quat), 158.46 (quat), 141.93 (quat), 134.91 (quat), 132.21,
131.53, 129.64, 129.52, 129.36, 127.77 (quat), 127.69, 124.02,
122.98, 122.47, 121.72 (quat), 119.22 and 118.63. All spectra
were consistent with reported data.3b The second component was
unreacted o-aminobenzophenone (0.035 g, 12%) identified by
comparison with an authentic sample. A trace of 2-allylphenol 7
was also detected (data as above).10
◦
hydroxyphenyl)indole 13a (0.095 g, 35%) mp 168–169 C, (lit.,19
167 ◦C) mixed mp 167–169 ◦C; dH 9.31 (1H, br s) and 7.71–6.85
(10H, m); dC 151.92 (quat), 136.27 (quat), 134.85 (quat), 128.71,
128.14, 122.01, 121.33, 120.26, 119.94, 118.93 (quat), 116.46,
110.90 and 99.88 (one quaternary carbon not apparent); m/z 209
(M+, 100%), 180 (47), 152 (16) and 77 (37). The second component
was 2-allylphenol 7 (0.009 g, 5%) from its 1H NMR spectrum; dH
7.13–7.05 (2H, m), 6.90–6.74 (2H, m), 5.92 (1H, m), 4.96–5.13 (3H,
m) and 3.39 (2H, m), consistent with literature data.10 The third
component was 2-[(o-tolylimino)methyl]phenol 9a (0.020 g, 7%);
dH 13.53 (1H, br s), 8.57 (1H, s), 7.47–6.93 (8H, m) and 2.40 (3H,
s); dC 162.11, 161.06 (quat), 147.30 (quat), 133.00, 132.19 (quat),
132.06, 130.57, 126.90, 126.74, 119.19 (quat), 118.93, 117.60,
117.09 and 18.10; m/z 211 (M+, 58), 118 (100), 91 (82), 65 (64)
and 39 (57). Spectra were identical with the authentic sample made
using the procedure described above.
FVP of N-(2-allyloxybenzylidene)-2-phenylthiobenzenamine 6d.
FVP of 6d (0.540 g, 1.6 mmol, Tf 650 ◦C, Ti 150–155 ◦C, P 0.013
Torr, t 15 min) gave three significant products. These were purified
by dry-flash chromatography (hexane-ethyl acetate eluant) to give,
first, biphenyl (0.005 g, 2%); dH 7.64–7.62 (4H, m), 7.55–7.46 (4H,
m) and 7.38–7.30 (2H, m); dC 141.67 (quat), 129.16, 127.66 and
127.45; m/z 154 (M+, 100%) and 77 (34). The NMR spectra were
consistent with literature data.10 The second component was 2-(2-
hydroxyphenyl)benzothiazole 20d (0.300 g, 84%) mp 130–133 ◦C
(lit.,20 132–135 ◦C); dH 12.51 (1H, br s), 7.94–7.92 (1H, m), 7.74–
7.72 (1H, m) and 7.56–6.97 (7H, m); dC 169.19 (quat), 157.76
(quat), 151.64 (quat) 132.58, 132.40 (quat), 128.24, 126.51, 125.37,
121.99, 121.34, 119.35, 117.69 and 116.60 (quat); m/z 227 (M+,
100%), 201 (86), 167 (29), 109 (25), 65 (50) and 39 (66). Spectra
were consistent with literature data.20 The third component was
2-allylphenol 7 (0.019 g, 9%); dH 7.14–7.06 (2H, m), 6.93–6.72
(2H, m), 6.08–5.94 (1H, m), 5.18–5.01 (2H, m) and 3.41 (2H,
m); dC 153.82 (quat), 136.34, 130.21, 127.63, 125.31 (quat),
120.59, 116.13, 115.54 and 34.82 (spectra consistent with literature
data10). A trace of 2-[(2-phenylthio)phenylimino]methylphenol 9d
was detected by comparison with an authentic sample (made as
described above).
FVP of N-(2-allyloxybenzylidene)-2-benzylbenzenamine 6b.
FVP of 6b (0.408 g, 1.2 mmol, Tf 650 ◦C, Ti 120–130 ◦C, P 0.009
Torr, t 20 min) gave four products. These were purified by dry-
flash chromatography (hexane-ether eluent) to give, first, fluorene
3
(0.005 g, 2%); dH 7.75–7.51 (2H, d, J 6.6), 7.58–7.45 (2H, m),
7.38–7.24 (4H, m), 3.83 (2H, s); m/z 166 (M+, 100%) and 83 (38).
The 1H NMR spectrum was consistent with literature data.10 The
second was 3-phenylindole 14b (0.100 g, 42%), mp 84–87 ◦C (lit.,6
85–87 ◦C); dH 8.17 (1H, br s), 8.01 (1H, m), 7.74–7.69 (2H, m)
and 7.53–7.24 (8H, m); dC 136.47 (quat), 135.41 (quat), 128.64,
127.33, 125.84, 125.54 (quat), 122.24, 121.69, 120.16, 119.65,
118.07 (quat) and 111.30; m/z 193 (M+, 100%), 165 (46), 139
(10), 96 (20) and 43 (7). The NMR spectra were consistent with
literature data.6 The third component was 2-(2-hydroxyphenyl)-3-
phenylindole 13b (0.070 g, 20%); (Found: M+, 285.1156. C20H15NO
requires M 285.1154. Anal. Calcd for C20H15NO: C, 84.2; H,
5.3; N, 4.9. Found: C, 84.0; H, 5.2; N, 5.0.); dH (360 MHz)
FVP of N-(2-allyloxybenzylidene)-2-phenoxybenzenamine 6e.
FVP of 6e (0.480 g, 1.46 mmol, Tf 650 ◦C, Ti 130–140 ◦C, P
0.01 Torr, t 25 min) gave three products. These were separated
by dry-flash chromatography (hexane-diethyl ether eluent) to give,
first,◦2-(2-hydroxyphenyl)benzoxazole 13e (0.110 g, 36%) mp 121–
◦
124 C (lit.,21 125–126 C); dH 11.49 (1H, s), 8.03–7.98 (1H, m),
3
8.43 (1H, br s), 7.86 (1H, d J 8.0), 7.51–7.48 (3H, m), 7.46–
7.73–7.69 (1H, m), 7.61–7.54 (1H, m), 7.48–7.32 (3H, m), 7.15–
7.10 (1H, m) and 7.04–6.96 (1H, m); dC 162.77 (quat), 158.62
(quat), 148.99 (quat), 139.89 (quat), 133.38, 126.97, 125.21, 124.83,
119.39, 119.09, 117.27, 110.47 and 110.42; m/z 211 (M+, 100%),
183 (39), 154 (19), 92 (24) and 63 (33). The NMR spectra were
consistent with literature data.21 The second component was 2-
phenylbenzoxazole 21e (0.040 g, 14%); dH 8.28–8.22 (2H, m),
7.79–7.74 (1H, m), 7.60–7.47 (4H, m) and 7.38–7.31 (2H, m);
dC 162.89 (quat), 150.59 (quat), 141.93 (quat), 131.39, 128.77,
127.48, 126.99 (quat), 124.98, 124.44, 119.94 and 110.46. The
NMR spectra were consistent with literature data.10 The third
component was 2-allylphenol 7 (0.012 g, 6%) (data as above).10
7.39 (3H, m), 7.36–7.29 (3H, m), 7.27–7.24 (1H, m), 7.03–6.98
(1H, m), 6.95–6.92 (1H, m) and 5.42 (1H, m); dC 153.45 (quat),
136.79 (quat), 134.40 (quat), 130.93, 130.60, 130.22 (quat), 129.56,
129.31, 128.89 (quat), 127.28, 123.52, 121.31, 121.12, 120.12,
119.42 (quat), 116.88, 116.36 (quat) and 111.52; m/z 285 (M+). The
fourth component was 2-(2-hydroxyphenyl)indole 13a (0.030 g,
12%); dH 9.43 (1H, br s), 7.73–7.65 (2H, m) and 7.50–6.86 (8H,
m); dC 151.80 (quat), 136.08 (quat), 134.72 (quat), 128.58, 128.04,
121.87, 121.15, 120.18, 119.84, 118.82 (quat), 116.45, 110.90 and
99.61 (one quaternary carbon not apparent); m/z 209 (M+, 100%),
180 (74), 152 (44) and 77 (48) (data consistent with those reported
above).
FVP
of
[2-(2-allyloxybenzylideneamino)phenyl](phenyl)
FVP of N-(2-allyloxybenzylidene)-N¢-methyl-N¢-phenylben-
methanone 6c. FVP of 6c (0.504 g, 1.5 mmol, Tf 650 ◦C,
Ti 155–160 ◦C, P 0.023 Torr, t 25 min) gave a complex pyrolysate
from which three products were identified. These were purified
by dry-flash chromatography (hexane-ether eluent) to give, first,
6-(2-hydroxyphenyl)phenanthridine 19 (0.140 g, 35%); dH (360
zene-1,2-diamine 6f. FVP of 6f (0.50 g, 1.46 mmol, Tf 650 C,
◦
Ti 150 ◦C, P 0.01 Torr, t 180 min) gave a yellow liquid which
was separated by dry flash chromatography using hexane-ethyl
acetate as eluants. The products were 2-(2-hydroxyphenyl)-1-
◦
phenylbenzimidazole 22 (0.13 g, 32%) m.p. 116–119 C (lit.,22
MHz) 8.76 (1H, d, J 8.3), 8.65 (1H, dd, J 8.1, J 1.5), 8.56
(1H, dd, J 8.4), 8.16 (1H, m), 7.95 (1H, ddd, J 8.3 and 7.1, J
119 ◦C); dH 13.56 (1H, br. s), 7.82 (1H, m), 7.67–7.57 (3H, m),
3
3
4
3
3
4
7.45–7.08 (7H, m), 6.86 (1H, m) and 6.54 (1H, m) (consistent
This journal is The Royal Society of Chemistry 2012
Org. Biomol. Chem., 2012, 10, 623–630 | 629
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