72 J . Org. Chem., Vol. 66, No. 1, 2001
Kohmoto et al.
8.2, 1H), 6.51 (t, J ) 7.7, 1H), 5.45 (sept, J ) 6.9, 1H), 1.87
(appeared as a broad peak, 6H); 13C NMR (100 MHz, CDCl3):
δ 174.4 (s), 171.0 (s), 133.2 (s), 132.2 (s), 130.7 (s), 130.1 (s),
129.3 (d), 128.5 (d), 128.3 (d), 128.3 (s), 128.3 (d), 128.0 (s),
128.3 (d), 128.3 (s), 128.3 (d), 128.0 (s), 127.2 (d), 126.9 (d),
126.2 (d), 125.7 (d),125.4 (d), 125.0 (d), 123.2 (d), 123.0 (d),
49.4 (d), 20.6 (q); MS (EI, m/z) 417 (M+, 47), 303 (5), 246 (9),
2H), 6.85 (td, J ) 7.5, 1.4 Hz, 2H), 6.81 (br dd, J ) 7.5, 1.4
Hz, 2H), 6.31 (br d, J ) 7.5 Hz, 2H), 6.28 (br d, J ) 10.0 Hz,
2H), 5.63 (ddd, J ) 10.0, 2.3, 1.5 Hz, 2H), 4.94 (s, 2H), 3.75
(br dd, J ) 2.3, 1.5 Hz, 2H); 13C NMR (22.4 MHz, CDCl3) δ
179.4 (s), 136.0 (s), 133.0 (s), 128.9 (d), 128.8 (d), 128.4 (d),
128.3 (d), 128.1 (d), 127.8 (d), 127.7 (d), 127.6 (d), 126.6 (s),
123.1 (d), 58.7 (s), 44.3 (d), 43.2 (t); MS (FAB) 416 (MH+). Anal.
Calcd for C29H21NO2: C, 83.83; H, 5.09; N, 3.37. Found; C,
83.54; H, 5.03, N, 3.32.
205 (100), 177 (41), 155 (73), 127(89). Anal. Calcd for C29H23
-
NO2: C, 83.43; H, 5.55; N, 3.35. Found; C, 83.45; H, 5.31; N,
3.43.
Da ta for [2 + 2] p h otocycloa d d u ct (3d ): colorless crys-
9-An t h r yl-N -(n a p h t h y lc a r b on yl)-N -b e n zy lc a r b ox -
a m id e (7b): yellow crystals; mp 166-171 °C (n-hexane/ethyl
acetate); UV λmax (ꢀ) (CH3CN) 398.0 (4100), 380.0 (4500), 323.5
(5500), 262.5 (37 300)IR (KBr) 1655 cm-1 (CdO); 1H NMR (400
MHz, CDCl3) δ 7.89 (d, J ) 7.1, 2H), 7.71 (br d, J ) 7.2, 2H),
7.56-7.21 (m, 11H), 7.11 (t, J ) 7.0, 1H), 6.90 (d, J ) 7.8,
1H), 6.79 (dd, J ) 7.1, 1.0, 1H), 6.73 (td, J ) 7.7, 1.2, 1H),
6.63 (d, J ) 7.8, 1H), 6.37 (dd, J ) 8.0, 7.3, 1H), 5.65 (s, 2H);
13CNMR (100 MHz, CDCl3) δ 173.4 (s), 172.2 (s), 137.1 (s),
132.5 (s), 131.9 (s), 130.1 (d), 129.8 (s), 129.6 (s), 128.7 (d),
128.6 (d), 128.5 (d), 128.3 (d), 128.1 (s), 128.02 (s), 127.98 (d),
127.1 (d), 126.9 (d), 126.1 (d), 125.3 (d), 124.92 (d), 124.86 (d),
124.3 (d), 123.0 (d), 122.8 (d), 48.1 (t); MS (EI, m/z) 465 (M+,
57), 303 (6), 260 (6), 205 (94), 177 (50), 155 (90), 127 (97), 91
(100), 57(51). Anal. Calcd for C33H23NO2: C, 85.14; H, 4.98;
N, 3.01. Found; C, 85.11; H, 4.98; N 3.11.
P h otocycloa d d ition of 1 a n d 7. A solution of 1 or 7 (ca.
0.25 mmol) in benzene (10 mL) in a Pyrex test tube (18 mm ×
180 mm) was irradiated with a 400-W high-pressure mercury
lamp (AHH400S) under bubbling argon or oxygen for 4-6.5
h. The reaction tube was cooled in a water bucket. In the case
of photocycloaddition of 1, after the evaporation of the mixture,
the residue was chromatographed on silica gel and further
purified by HPLC with hexanes-ethyl acetate as eluent.
Photocycloaddition of 7 proceeded quantitatively and gave the
pure cycloadduct 8 without purification.
tals; mp 198-200 °C (n-hexane/ethyl acetate); IR (KBr) 1700
1
cm-1 (CdO); H NMR (400 MHz, CDCl3) δ 7.54 (dd, J ) 7.5,
1.4 Hz, 2H), 7.45-7.29 (m, 3H), 7.00 (td, J ) 7.5, 1.4 Hz, 2H),
6.85 (td, J ) 7.5, 1.4 Hz, 2H), 6.81 (br dd, J ) 7.5, 1.4 Hz,
2H), 6.31 (br d, J ) 7.5 Hz, 2H), 6.28 (br d, J ) 10.0 Hz, 2H),
5.63 (ddd, J ) 10.0, 2.3, 1.5 Hz, 2H), 4.94 (s, 2H), 3.75 (br dd,
J ) 2.3, 1.5 Hz, 2H), 1.92 (s, 3H); 13C NMR (22.4 MHz, CDCl3)
δ 179.5 (s), 136.1 (s), 134.6 (s), 133.1 (s), 132.2 (s), 128.8 (d),
128.3 (d), 128.2 (d), 127.72 (d), 127.66 (d), 127.6 (d), 127.4 (d),
127.3 (d), 126.6 (s), 123.8 (d), 123.4 (d), 120.4 (d), 58.9 (s), 58.7
(s), 44.3 (d), 43.6 (d), 43.2 (t), 20.0 (q); HRMS (EI) calcd for
C
30H23NO2 (M+) 429.1729, found 429.1725.
Da ta for [4 + 4] p h otocycloa d d u ct (syn -4a ): white
1
powder, mp 113.5-114.0 °C; IR (KBr) 1705 cm-1 (CdO); H
NMR (270 MHz, CDCl3) δ 6.80-6.70 (m, 6H), 6.66-6.51 (m,
4H), 6.42 (d, J ) 8.3 Hz, 2H), 4.74 (septet, J ) 6.9 Hz, 1H),
4.00 (m, 2H), 1.62 (d, J ) 6.9 Hz, 6H); HRMS (FAB) calcd for
C
25H22NO2 (MH+) 368.1651, found 368.1648.
Da ta for [4 + 4] p h otocycloa d d u ct (syn -4c): white
1
powder, mp 194.8-195.5 °C; IR (KBr) 1710 cm-1 (CdO); H
NMR (270 MHz, CDCl3) δ 7.59-7.51 (m, 2H), 7.46-7.31 (m,
3H), 6.79-6.59 (m, 8H), 6.43 (d, J ) 6.9 Hz, 2H), 6.40 (d, J )
6.9 Hz, 2H), 4.99 (s, 2H), 3.98 (m, 2H); 13C NMR (125 MHz,
CDCl3) δ 177.7 (s), 143.7 (s), 141.2 (s), 139.2 (d), 135.9 (s), 135.5
(d), 128.8 (d), 128.6 (d), 127.2 (d), 125.9 (d), 125.3 (d), 124.4
(d), 123.1 (d); HRMS (FAB) calcd for
416.1651, found 416.1653.
C
29H22NO2 (MH+)
The 1H NMR (400 MHz) monitoring experiment of the
photocycloaddition of 1 (ca. 0.02 mmol) was carried out in an
NMR tube with benzene-d6 (0.5 mL) as a solvent under
bubbling of argon or oxygen without an internal standard.
Transient absorption spectra were measured on excitation
at 355 nm (Continuum SL I-10, 6 ns fwhm, 20 mJ per pulse
at 5 Hz repetition) with a detection system (Tokyo instru-
ments) composed of a multichannel diode array (Princeton
IRY-512G: 18 ns gate width) with a SPEX 270M monochro-
mator (resolution: 0.3 nm/channel). Decay profiles measured
by a photomultiplier (Hamamatsu Photonics SR928) were
analyzed by the Marquardt nonlinear least-squares fitting
method.
Da ta for [2 + 2] p h otocycloa d d u ct (3a ): colorless crys-
tals; 190-191 °C (n-hexane/ethyl acetate); IR (KBr) 1700 cm-1
(CdO); 1H NMR (270 MHz, CDCl3) δ 7.02 (td, J ) 7.3, 1.4 Hz,
2H), 6.91 (td, J ) 7.3, 1.4 Hz, 2H), 6.83 (dd, J ) 7.3, 1.4 Hz,
2H), 6.44 (br d, J ) 7.3 Hz, 2H), 6.30 (br d, J ) 9.9 Hz, 2H),
5.67 (ddd, J ) 9.9, 2.5, 1.5 Hz, 2H), 4.67 (sept, J ) 6.9 Hz,
1H), 3.79 (br dd, J ) 2.5, 1.5 Hz, 2H), 1.60 (d, J ) 6.9 Hz,
6H); 13C NMR (22.4 MHz, CDCl3) δ 179.8 (s), 133.1 (s), 128.3
(d), 127.7 (d), 127.6 (d), 126.9 (s), 123.2 (d), 58.3 (s), 44.5 (d),
19.3 (q); HRMS (FAB) calcd for C25H22NO2 (MH+) 368.1651,
found 368.1649. Anal. Calcd for C25H21NO2: C, 81.72; H, 5.76;
N, 3.81. Found; C, 81.45; H, 5.60, N, 3.73.
1
Da ta for [4 + 4] p h otocycloa d d u ct (a n ti-4a ): H NMR
(500 MHz, CDCl3) δ 7.20-7.10 (m, 6H), 6.88 (d, J ) 6.9 Hz,
2H), 6.12 (ddd, J ) 8.2, 4.7, 2.5 Hz, 2H), 5.83 (d, J ) 8.2 Hz,
2H), 4.77 (sept, J ) 6.9 Hz, 1H), 4.05 (m, 2H), 1.68 (d, J ) 6.9
Hz, 3H), 1.62 (d, J ) 6.9 Hz, 3H); HRMS (FAB) calcd for
C
25H22NO2 (MH+) 368.1651, found 368.1655.
Da ta for [4 + 4] p h otocycloa d d u ct (a n ti-4c): colorless
1
crystals; mp 144.0-144.2 °C; IR (KBr) 1710 cm-1 (CdO); H
NMR (500 MHz, CDCl3) δ 7.57 (m, 2H), 7.45-7.35 (m, 3H),
7.13 (m, 4H), 7.08-7.02 (m, 2H), 6.72 (d, J ) 7.4 Hz, 2H), 6.12
(ddd, J ) 8.2, 4.7, 2.5 Hz, 2H), 5.82 (d, J ) 8.2 Hz, 2H), 5.06
(dd, J ) 13.9 Hz, 1H), 4.97 (d, J ) 13.9 Hz, 1H), 4.02 (m, 2H);
13C NMR (22.4 MHz, CDCl3) δ 177.9 (s), 144.3 (s), 142.1 (s),
138.3 (d), 135.9 (s), 134.0 (d), 128.9 (d), 128.7 (d), 128.2 (d),
126.7 (d), 126.6 (d), 126.0 (d), 123.5 (d), 63.8 (s), 47.7 (d), 43.1
(t); HRMS (FAB) calcd for C29H22NO2 (MH+) 416.1651, found
416.1649.
Da ta for 1,8-ep id ioxid e (5a ): colorless crystals; mp 168.5-
169.0 °C (n-hexane/ethyl acetate); IR (KBr) 1705 cm-1 (CdO);
1H NMR (270 MHz, CDCl3) δ 7.32-7.24 (m, 4H), 7.22-7.12
(m, 2H), 7.05-6.95 (m, 2H), 6.20 (dd, J ) 9.6, 6.5 Hz, 2H),
5.65 (d, J ) 9.6 Hz, 2H), 5.45 (d, J ) 6.5 Hz, 2H), 4.89 (sept,
J ) 6.9 Hz, 1H), 1.76 (d, J ) 6.9 Hz, 3H), 1.75 (d, J ) 6.9 Hz,
3H); 13C NMR (22.4 MHz, CDCl3) δ 178.3 (s), 137.4 (s), 135.1
(s), 133.4 (d), 130.3 (d), 128.6 (d), 128.3 (d), 127.2 (d), 123.5
(d), 77.5 (d), 60.4 (s), 45.3 (d), 20.2 (q), 19.0 (q); HRMS (FAB)
calcd for C25H22NO4 (MH+) 400.1533, found 400.1541. Anal.
Calcd for C25H21NO4: C, 75.17; H, 5.30; N, 3.51. Found; C,
75.42; H, 5.33, N, 3.49.
Da ta for 1,8-ep id ioxid e (5b): white powder; mp 160.0-
161.0 °C; IR (KBr) 1710 cm-1 (CdO); 1H NMR (270 MHz,
CDCl3) δ 7.44-7.38 (m, 1H), 7.35-7.24 (m, 4H), 7.22-7.14 (m,
1H), 7.05-6.96 (m, 2H), 6.16 (dd, J ) 9.6, 6.8 Hz, 1H), 5.92
(d, J ) 9.6 Hz, 1H), 5.69 (d, J ) 9.6 Hz, 1H), 5.48 (d, J ) 9.6
Hz, 1H), 5.40 (d, J ) 6.8 Hz, 1H), 4.89 (sept, J ) 6.9 Hz, 1H),
1.76 (d, J ) 6.9 Hz, 3H), 1.76 (s, 3H), 1.75 (d, J ) 6.9 Hz, 3H);
13C NMR (22.4 MHz, CDCl3) δ 178.6 (s), 138.3 (s), 137.8 (s),
136.2 (s), 135.6 (s), 133.6 (d), 133.3 (d), 130.8 (d), 130.3 (d),
Da ta for [2 + 2] p h otocycloa d d u ct (3b): amorphous, IR
1
(KBr) 1705 cm-1 (CdO); H NMR (270 MHz, CDCl3) δ 7.12-
6.76 (m, 6H), 6.46-6.38 (m, 2H), 6.26 (br d, J ) 10.0 Hz, 1H),
5.66 (dm, J ) 10.0 Hz, 1H), 5.53 (br m, 1H), 4.66 (sept, J )
6.9 Hz, 1H), 3.74 (br m, 2H), 1.94 (s, 3H), 1.60 (d, J ) 6.9 Hz,
6H); 13C NMR (22.4 MHz, CDCl3) δ 179.8 (s), 134.6 (s), 133.1
(s), 132.1 (s), 128.14 (d), 128.08 (d), 128.0 (d), 127.4 (d), 127.3
(d), 127.2 (d), 123.7 (d), 123.4 (d), 120.4 (d), 58.3 (s), 58.1 (s),
44.4 (d), 44.3 (d), 43.7 (d), 20.0 (q), 19.3 (q); HRMS (FAB) calcd
for C26H24NO2 (MH+) 382.1808, found 382.1805.
Da ta for [2 + 2] p h otocycloa d d u ct (3c): colorless
crystals; mp 196.5-197.5 °C (n-hexane/ethyl acetate); IR (KBr)
1700 cm-1 (CdO); 1H NMR (270 MHz, CDCl3) δ 7.54 (dd, J )
7.5, 1.4 Hz, 2H), 7.45-7.29 (m, 3H), 7.00 (td, J ) 7.5, 1.4 Hz,