H. Ikeda, F. Tanaka, T. Miyashi, K. Akiyama, S. Tero-Kubota
FULL PAPER
ing abbreviations: s, singlet; d, doublet; t, triplet; q, quadruplet; m, rex test tube (diameter 2.5 cm) was degassed with five
1
Ϫ2
multiplet; br., broad; J, coupling constants (Hz). H NMR product
freezeϪpumpϪthaw cycles (Ϫ196 °C/10 Torr/0 °C) and then se-
Ϫ2
analyses were performed with the use of 1,1,2,2- or 1,1,1,2-tetra-
aled at 10 Torr. The sample solution was irradiated through a
chloroethane as internal standards for integration. 13C NMR spec- cutoff filter (λ Ͼ 400 nm) with a 2-kW Xe lamp at 20 Ϯ 1 °C for
tra were obtained at 50 MHz with a Varian Gemini 2000 or at 120 h. After evaporation in vacuo, column chromatography fol-
1
00 MHz with a JEOL GX-400 spectrometer. Mass spectroscopy
lowed by recrystallization from hexane gave 109 mg (0.415 mmol,
23% yield) of 7, 168 mg (0.639 mmol, 36%) of 8, and 13.2 mg
(0.0472 mmol, 3%) of 23. A similar photoreaction of 6 (105 mg,
(MS) was performed with a JEOL JMS-HX110 or a Hitachi M-
2500 mass spectrometer with electron or chemical ionization. The
ox
red
redox potentials (E
p
and E
p
in V vs. SCE) were measured by
0.4 mmol) and TPPBF
4 3
(23.8 mg, 0.06 mmol) in CH CN (20 mL)
cyclic voltammetry with a Yanaco P-1000 voltammetric analyzer
or a PS-07 TOHO polarization unit in acetonitrile and dichloro-
methane containing Et NClO (0.1 ) and nBu NBF (0.1 ),
4 4 4 4
for 2 h gave 57.9 mg (0.221 mmol, 55%) of 10.
Compound 7: Yellow plates (n-hexane). M.p. 106Ϫ107 °C. IR
Ϫ1
(
(
(
(
(
KBr): ν˜ ϭ 2968, 1668, 1595, 1454, 1272, 993, 947, 758 cm . MS
EI, 70 eV): m/z (%) ϭ 263 (20) [M ϩ 1], 262 (100) [M ], 261
10), 247 (18), 244 (32), 229 (13), 220 (16), 219 (16), 207 (15), 206
respectively, as supporting electrolytes (Pt electrode, scan rate 100
mV/s). Since all of the substrates gave irreversible waves, their
ϩ
ϩ
ox
ox
E
p
1/2 values were estimated as E Ϫ 0.03 V, a one-electron oxidation
ϩ
16), 195 (13), 194 (33) [M Ϫ (CH
3
)
2
CϭCϭCH
2
], 171 (16), 166
), 77 (50) [Ph ]. H NMR (400 MHz,
): δ ϭ 1.06 (s, 3 H), 1.25 (s, 3 H), 3.97 (s, 1 H), 5.28 (d, J ϭ
.6 Hz, 1 H), 6.33 (d, J ϭ 1.6 Hz, 1 H), 6.96Ϫ6.99 (dd ϩ m, J ϭ
process being assumed. Fluorescence spectra were recorded on a
Hitachi F-4010 fluorescence spectrophotometer. Steady-state pho-
tolysis was carried out at 20 Ϯ 1 °C with an Ushio 2-kW Xe short
arc lamp with an aqueous IR filter and a Toshiba cutoff filter L-
ϩ
ϩ
1
7 7
11), 165 (64), 91 (19, C H
CDCl
3
1
7
1
7
3
1
1
.8, 1.8 Hz, 2 H), 7.13Ϫ7.19 (m, 4 H), 7.35 (ddd, J ϭ 7.8, 7.8,
.6 Hz, 1 H), 7.45 (ddd, J ϭ 7.8, 7.8, 1.4 Hz, 1 H), 8.20 (dd, J ϭ
.8, 1.4 Hz, 1 H) ppm. C NMR (100 MHz, CDCH ): δ ϭ 25.73,
3
0.54, 41.22, 58.57, 121.41, 126.66, 127.15, 127.79, 128.00 (2 C),
29.14 (2 C), 130.09, 131.69, 134.12, 141.05, 145.15, 150.00,
88.35 ppm.
3
9 (λ Ͼ 360 nm) for direct irradiation, or Y-43 (λ Ͼ 400 nm) for
TPPBF - and CA-sensitization. The ethereal solvents were dried
and distilled from LiAlH . Acetonitrile was dried and distilled from
and then LiAlH . Benzene and dichloromethane were dried
and distilled from LiAlH . The deuterated solvents used for the
4
1
3
4
P
2
O
5
4
4
kinetic study, [D
6
]DCB (99.6% deuterated) and [D
4
]DMSO
˚
(99.6%), were dried over 4 A molecular sieves and treated with
Compound 8: Pale yellow plates (n-hexane). M.p. 112.5Ϫ113 °C. IR
Ϫ1
K
2
CO
3
before use. Merck silica gel 60 (230Ϫ400 mesh) was used
(KBr): ν˜ ϭ 1647, 1599, 1458, 1338, 773, 700, 709 cm . MS (El,
ϩ
ϩ
for column chromatography.
70 eV): m/z (%) ϭ 263 (20) [M ϩ 1], 262 (100) [M ], 248 (12),
ϩ
ϩ
2
2
47 (61) [M Ϫ CH
3
], 232 (15), 229 (17), 219 (20) [M Ϫ COCH
3
],
):
Preparation of 5 and 6: The two isomeric methylenecyclopropanes
1
04 (12), 203 (14), 202 (13), 159 (27). H NMR (400 MHz, CDCl
3
5
and 6 were prepared in 8 and 30% yields, respectively, through a
δ ϭ 1.74 (q, J ϭ 2.0 Hz, 3 H), 1.82 (s, 3 H), 2.07 (q, J ϭ 2.0 Hz,
[
2ϩ2] cycloaddition between 3-methylbuta-1,2-diene (1,1-dimeth-
3
8
H), 6.96 (ddd, J ϭ 8.0, 1.6, 0.8 Hz, 1 H), 7.13Ϫ7.40 (m, 7 H),
[
26]
[27]
[7]
ylallene) and diphenylketene, by known procedures.
1
3
.21 (ddd, J ϭ 8.0, 1.6, 0.8 Hz, 1 H) ppm. C NMR (100 MHz,
): δ ϭ 11.7, 18.2, 27.1, 48.9, 126.3, 126.5, 126.7, 127.4 (2 C),
10.5 °C). IR (KBr): ν˜ ϭ 1744, 1651 cm (ref. 1739 cm ). MS 128.6 (2 C), 128.7, 129.5, 131.0, 132.0, 144.1, 150.8, 157.8,
[7]
Compound 5: Pale yellow cubes (n-hexane). M.p. 108Ϫ109 °C (ref.
1
(
CDCl
3
Ϫ1
[7]
Ϫ1
ϩ
ϩ
3
70 eV): m/z (%) ϭ 262 (100) [M ], 247 (31) [M Ϫ CH ], 219 (100) 184.3 ppm.
1
[
247 Ϫ CO], 165 (6). H NMR (200 MHz, CDCl
H), 5.12 (d, J ϭ 1.1 Hz, 1 H), 5.88 (d, J ϭ 1.1 Hz, 1 H), 7.20Ϫ7.44
m, 10 H) ppm. 13C NMR (50 MHz, CDCl
): δ ϭ 27.17 (2 C),
7.48, 77.95, 110.74 (2 C), 126.65 (2 C), 127.83 (4 C), 128.22 (4 C),
40.64, 162.38, 202.82 ppm.
3
): δ ϭ 1.29 (s, 6
Compound 23: Colorless needles (n-hexane). M.p. 118.5Ϫ119.5 °C.
Ϫ1
IR (KBr): ν˜ ϭ 2982, 1759, 1300, 1211, 991, 763, 708 cm . MS
(
4
1
3
ϩ
ϩ
ϩ
(
9
CH
EI, 70 eV): m/z (%) ϭ 278 (16) [M ], 105 (16) [C
8
H
9
or PhCO ],
CO], 77 (16) [Ph ], 68 (65) [(CH CϭCϭ
], 67 (12). H NMR (400 MHz, CDCl ): δ ϭ 1.21 (s, 6 H),
ϩ
ϩ
6 (100) [M Ϫ Ph
2
3 2
)
ϩ
1
2
3
[
7]
13
Compound 6: Colorless plates (EtOH). M.p. 150Ϫ150.5 °C (ref.
5.46 (s, 1 H), 6.26 (s, 1 H), 7.27Ϫ7.49 (m, 10 H) ppm. C NMR
47 °C). IR (KBr): ν˜ ϭ 1724, 1663 cm (ref. 1720 cm ). MS (100 MHz, CDCl
): δ ϭ 2.49 (2 C), 48.21, 92.63, 119.08, 126.75 (4
], 219 (8) C), 127.77 (2 C), 128.06 (4 C), 140.21 (2 C), 147.08, 169.90 ppm.
]. H NMR (200 MHz,
): δ ϭ 1.80 (s, 3 H), 2.15 (s, 3 H), 3.33 (br. s, 2 H), 7.15Ϫ7.45
m, 10 H) ppm. 13C NMR (50 MHz, CDCl
): δ ϭ 21.46, 21.59,
7.06, 70.20, 126.67 (2 C), 126.98 (4 C), 128.54 (4 C), 138.19,
42.79 (2 C), 145.83, 199.00 ppm.
Ϫ1
[7]
Ϫ1
1
3
ϩ
ϩ
(70 eV): m/z (%) ϭ 262 (80) [M ], 247 (10) [M Ϫ CH
3
ϩ
1
[M
Ϫ CO], 180 (100) [Ph
2 2
CϭCϭCH
Compound 10: Pale yellow powder (n-hexane). M.p. 56 °C. IR
CDCl
3
Ϫ1
(
KBr): ν˜ ϭ 1665, 1622, 1593, 1454, 1300, 1288, 1227, 708 cm
.
(
3
ϩ
ϩ
MS (El, 70 eV): m/z (%) ϭ 263 (20) [M ϩ 1], 262 (100) [M ], 261
8), 247 (18), 229 (8), 221 (5), 220 (9), 219 (8), 207 (10), 206 (11),
3
1
(
1
ϩ
95 (9), 194 (14) [M Ϫ (CH
3
)
2
CϭCϭCH
). 1H NMR (200 MHz, CDCl
3
2
], 178 (6), 171 (9), 165
ϩ
General Procedure for TPPBF
4
- or CA-Sensitized Photoreactions:
(24), 115 (5), 91 (6, C
7
H
7
): δ ϭ
A solution (6 mL) containing 5 or 6 (0.06 mmol) and TPPBF
4
1.68 (s, 3 H), 2.17 (s, 3 H), 3.00 (dd, J ϭ 13.7, 7.4 Hz, 1 H), 3.11
(0.018 mmol) or CA (0.06 mmol) in a Pyrex test tube (diameter (dd, J ϭ 13.7, 5.1 Hz, 1 H), 4.13 (dd, J ϭ 7.4, 5.1 Hz, 1 H), 6.96
1
.5 cm) was degassed by five freezeϪpumpϪthawϪcycles (Ϫ196
(dd, J ϭ 6.4, 2.0 Hz, 1 H), 7.11 (AAЈBBЈC, J ϭ 7.5, 2.0 Hz, 2 H),
7.20Ϫ7.42 (m, 5 H), 8.18 (dd, J ϭ 6.8, 2.4 Hz, 1 H) ppm. C NMR
Ϫ2
Ϫ2
13
°C/10 Torr/ambient temperature) and was then sealed at 10
3
Torr. The sample solution was irradiated through a cutoff filter (λ (50 MHz, CDCl ): δ ϭ 22.69, 23.17, 37.12, 46.07, 126.71, 127.10,
Ͼ 400 nm) with a 2-kW Xe lamp at 20 Ϯ 1 °C. For CA, the sample
solution, which contained a slight suspension of CA, was irradiated
similarly, after precipitation of CA by standing for 5 min. After
evaporation in vacuo, the product yields were determined by H
NMR spectroscopy.
127.85, 128.41 (2 C ϩ1 C), 128.48 (2 C), 128.83, 132.83, 134.99,
143.66, 145.41, 146.97, 189.97 ppm.
Isolation of 9: A CH
.3 mmol) and CA (80.4 mg, 0.33 mmol) in a Pyrex test tube (diam-
eter 3.0 cm) was degassed with five freezeϪpumpϪthaw cycles
2 2
Cl solution (30 mL) containing 6 (78.7 mg,
1
0
Ϫ2
Ϫ2
Isolation of 7, 8, and 10: A CH
2
Cl
2
solution (18 mL) containing 5
4
(71.4 mg, 0.183 mmol) in a Py-
(Ϫ196 °C/10 Torr/ambient temperature) and then sealed at 10
Torr. After precipitation of CA by standing for 5 min, the sample
(472 mg, 1.80 mmol) and TPPBF
1506
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1500Ϫ1508