2022 Bull. Chem. Soc. Jpn., 75, No. 9 (2002)
Dynamic Behavior of Anthroyloxyl Radicals
125.2, 125.7, 128.5, 128.7, 129.2, 130.0, 130.37, 130.43, 131.0,
131.9, 132.7, 134.3, 141.3, 142.6, 159.4, 166.6; Found: C, 83.90;
H, 4.27; N, 3.50%; Calcd for C28H17NO2: C, 84.19; H, 4.29; N,
3.51%.
silica-gel column chromatography (ethyl acetate/hexane (1:5))
followed by crystallization from ethanol (1.4 g, 72%); mp 171–
172 °C; UV (CH3CN) λmax 301 nm (ε 4600), 366 (7700), 386
(6800); 1H NMR (CDCl3) δ 6.33 (t, 1H, J = 8 Hz), 6.91 (d, 1H, J
10 Hz), 7.45–7.71 (m, 6H), 8.08 (d, 2H, J = 8 Hz), 8.61–8.66 (m,
3H); 13C NMR (CDCl3) δ 105.0, 121.1, 122.7, 124.5, 125.3,
127.5, 128.1, 129.2, 130.1, 131.0, 134.0, 134.8, 139.0, 156.9,
164.8; Found: C, 76.06; H,4.27; N, 4.45%. Calcd for C20H13NO3:
C, 76.18; H, 4.16; N, 4.44%.
1-(1-Anthroyloxy)-2-pyridone (1APy) and 1-(2-Anthroyl-
oxy)-2-pyridone (2APy). 1-(1-Anthroyloxy)-2-pyridone and 1-
(2-anthroyloxy)-2-pyridone were similarly prepared by dehydra-
tion from the corresponding anthroic acid and 2-hydroxypyridine
N-oxide with DCC in the presence of DAMP in dichloromethane
(78 and 82%, respectively).
1APy: mp 186–187 °C; UV (CH3CN) λmax 387 nm (ε 6200);
1H NMR (CDCl3) δ 6.29 (t, 1H, J = 8 Hz), 6.85 (d, 1H, J = 10
Hz), 7.41–7.59 (m, 5H), 7.99–8.08 (m, 2H), 8.31 (d, 2H J = 8
Hz), 8.50 (s, 1H), 8.62 (d, 1H, J = 10 Hz), 9.53 (s, 1H); 13C NMR
(CDCl3) δ 162.8, 157.0, 138.9, 135.7, 135.3, 132.5, 132.3, 131.1,
130.9, 128.5, 127.8, 127.3, 127.0, 125.9, 125.8, 124.3, 122.9,
122.5, 121.2, 104.6; Found: C, 76.08; H,4.22; N, 4.29%. Calcd
for C20H13NO3: C, 76.18; H, 4.16; N, 4.44%.
N-(1-Anthroyloxy)-9-fluorenylideneamine (1AFA) and N-
(2-Anthroyloxy)-9-fluorenylideneamine (2AFA).
N-(1-An-
throyloxy)-9-fluorenylideneamine and N-(2-anthroyloxy)-9-fluo-
renylideneamine were similarly prepared by dehydration from the
corresponding anthroic acid and 9-fluorenone oxime with DCC in
the presence of DMAP in dichloromethane (83 and 76%, respec-
tively).
1AFA: mp 156–157 °C (EtOH); UV (CH3CN) λmax 301 nm
(ε 13900), 384 (7500); UV (PhH) λmax 304 nm (ε 13200), 387
1
(7500); H NMR (CDCl3) δ 7.16–7.64 (m, 9H), 8.00–8.11 (m,
3H), 8.21–8.34 (m, 3H), 8.51 (s, 1H), 9.52 (s, 1H); 13C NMR
(CDCl3) δ 120.2, 120.4, 123.6, 123.7, 125.3, 126.0, 126.3, 126.4,
127.3, 127.8, 128.4, 128.5, 128.6, 129.1, 130.1, 130.4, 131.7,
131.8, 132.6, 132.8, 134.5, 134.6, 141.2, 142.7, 158.9, 164.9;
Found: C, 84.10, H, 4.27, N 3.50%. Calcd for C28H17NO2: C,
84.19; H, 4.29; N, 3.51%.
2AFA: mp 184–185 °C (EtOH); UV (CH3CN) λmax 302 nm
(ε 26100), 383 (4600); UV (PhH) λmax 302 nm (ε 25700), 384
1
(5700); H NMR (CDCl3) δ 7.42–7.67 (m, 10H), 7.75–8.16 (m,
3H), 8.39 (d, 1H, J = 8 Hz), 8.47 (s, 1H), 8.62 (s, 1H), 8.93 (s,
1H); 13C NMR (CDCl3) δ 120.5, 120.9, 124.0, 124.2, 126.5,
126.8, 127.3, 128.6, 128.9, 129.0, 129.4, 129.5, 130.4, 130.6,
132.2, 132.6, 133.1, 133.5, 133.8, 141.6, 143.2, 159.5, 164.8;
Found: C, 84.03; H, 4.41; N, 3.44%. Calcd for C28H17NO2: C,
84.19; H, 4.29; N, 3.51%.
2APy: mp 213–214 °C; UV (CH3CN) λmax 387 nm (ε 3000);
1H NMR (DMSO-d6): δ 6.39 (t, 1H, J = 8 Hz), 6.70 (d, 1H, J =
10 Hz), 7.54–7.68 (m, 3H), 7.98 (d, 1H, J = 8 Hz), 8.13–8.31 (m,
4H), 8.72 (s, 1H), 8.99 (s, 1H), 9.09 (s, 1H); 13C NMR (DMSO-d6)
δ 162.9, 156.4, 140.6, 137.4, 133.9, 133.3, 132.4, 131.8, 129.6,
128.6, 128.3, 127.5, 126.6, 123.2, 122.3, 121.6, 105.2; Found: C,
75.98; H, 4.21; N, 4.31%. Calcd for C20H13NO3: C, 76.18; H,
4.16; N, 4.44%.
Photolyses of AFAs and APys. A solution of a radical pre-
cursor in acetonitrile or benzene was irradiated with 300-nm light
(Rayonet RPR-3000 lamps) or 365-nm light (Riko 400-W high-
pressure mercury lamp with a CuSO4 solution filter), and the prod-
ucts were analyzed qualitatively and quantitatively by HPLC.
Quantum Yield Measurements. The quantum yields were
determined by irradiating solutions of AFAs in acetonitrile and
benzene with 302- or 365-nm light from a Bunkokeiki SM-5 su-
per-monochro-irradiator equipped with a 300-W xenon lamp.
Consumption of AFAs was monitored by HPLC, and the amount
of light quanta was determined by potassium tris(oxalato)fer-
rate(ꢁ) actinometry.30
N-(9-Anthroyloxy)diphenylmethanimine (9ADPM) and N-
(9-Anthroyloxy)isopropylideneamine (9AIPA). N-(9-Anthro-
yloxy)diphenylmethanimine and N-(9-anthroyloxy)isopropylide-
neamine were similarly prepared by dehydration from 9-anthroic
acid and benzophenone and acetone oximes, respectively, with
DCC in the presence of DMAP in dichloromethane (51 and 46%,
respectively).
1
9ADPM: mp 151–152 °C (EtOH); H NMR (CDCl3) δ 8.45
(s, 1H), 8.05–7.90 (m, 4H), 7.72–7.68 (m, 2H), 7.49–7.26 (m,
12H); 13C NMR (CDCl3) δ 124.5, 124.8, 126.4, 127.6, 127.9,
128.2, 128.3, 128.6, 129.0, 129.2, 130.3, 130.5, 131.9, 134.0,
166.2, 166.5; Found: C, 83.51; H, 4.81; N, 3.46%. Calcd for
C28H19NO2: C, 83.77; H, 4.77; N, 3.49%.
9AIPA: mp 170 °C (EtOH); 1H NMR (CDCl3) δ 1.97 (s, 3H),
2.18 (s, 3H), 7.45–7.59 (m, 4H), 8.02 (d, 2H, J = 8 Hz); 8.15 (d,
2H, J = 8 Hz), 8.54 (s, 1H); 13C NMR (CDCl3) δ 16.8, 21.6,
124.5, 125.0, 125.6, 126.6, 128.0, 128.3, 129.1, 130.3, 164.8,
166.5; Found: C, 77.90; H, 5.52; N, 4.97%. Calcd for C18H15NO2:
C, 77.96; H, 5.45; N, 5.05%.
Fluorescence Measurements. Fluorescence quantum yields
were determined by using anthracene as a standard (φf = 0.27 in
ethanol).31 Fluorescence lifetimes were measured by a single pho-
ton counting technique (Horiba NAES 110 time-resolved fluoro-
photometer).
N-(p-Methoxybenzoyloxy)diphenylmethanimine (MeOB-
Laser-Flash Photolyses. Laser-flash photolyses were per-
formed by using an excimer laser (Lambda Physik LPX-100, Xe-
Cl, 308 nm, 10-ns fwhm, 70 mJ/pulse) and a pulsed xenon arc
(Ushio UXL-159, 150 W) as a monitoring light source. The de-
tails of the apparatus for laser-flash photolysis have been de-
scribed elsewhere.32 The temperature of each sample cell was
controlled with a thermostated cell holder and a circulating water
bath (Haake F3-K). An excimer laser-pumped dye laser (Lambda
Physik FL3002) was used to obtain 360- (10-ns fwhm, 7–8 mJ/
pulse) and 444-nm laser pulses (10-ns fwhm, 12–13 mJ/pulse)
with DMQ and Coumarin 120 dyes, respectively. In two-color la-
ser photolyses, 580-nm laser pulses were supplied from an exci-
mer laser (Lambda Physik Lextra, XeCl, 308 nm)-pumped dye la-
ser (Lambda Physik Scanmate; dye: Rhodamine 6G, 10-ns fwhm,
DPM). N-(p-Methoxybenzoyloxy)diphenylmethanimine
was
prepared from p-methoxybenzoyl chloride and benzophenone
oxime in pyridine. MeOBDPM was crystallized from ethanol; mp
1
153–154.5 °C; H NMR (CDCl3) δ 3.81 (s, 3H), 6.82–6.85 (m,
2H), 7.36–7.77 (m, 12H); 13C NMR (CDCl3) δ 55.4, 113.7, 121.0,
128.2, 128.3, 128.5, 128.8, 129.0, 129.5, 130.8, 131.4, 131.6,
132.9, 134.7, 163.4, 163.5, 165.0; Found: C, 76.06; H, 5.13; N,
4.19%. Calcd for C21H17NO3: C, 76.12; H, 5.17; N, 4.23%.
1-(9-Anthroyloxy)-2-pyridone (9APy). 1-(9-Anthroyloxy)-
2-pyridone was prepared by dehydration from 9-anthroic acid
(1.38 g, 6.22 mmol) and 2-hydroxypyridine N-oxide (0.83 g, 7.46
mmol) with DCC (2.55 g, 12.4 mmol) in the presence of DMAP
(76 mg, 0.62 mmol) in dichloromethane; 9APy was purified by