S. Tsutsui et al.
Bull. Chem. Soc. Jpn., 75, No. 12 (2002) 2665
ture was stirred at 0 °C for 10 min and warmed to room tempera-
ture. Workup similar to that for 1a gave 6a (0.666 g, 3.11 mmol,
47%). 6a: yellow crystals; mp 98 °C; 1H NMR (C6D6) δ 0.03 (s,
9H), 6.29 (s, 1H), 6.51 (s, 1H); 13C NMR (C6D6) δ −2.00, 134.76,
142.36, 143.36, 151.81, 178.26, 188.17; 29Si NMR (C6D6) δ
−3.51; UV (hexane) λmax/nm (ε) 262 (14200), 309 (342), 480
(30); IR (KBr) ν/cm−1 1664, 1637 (CwO); HRMS m/z Found:
214.0217, Calcd for C9H11ClO2Si, 214.0217; Anal. Found: C,
50.04; H, 5.35%, Calcd for C9H11ClO2Si: C, 50.34; H, 5.16%.
Photoreaction of 1a in the Presence of Acetone. A hexane
(4 mL) solution of 1a (19.3 mg, 7.07 × 10−5 mol) and acetone
(60.1 mg, 1.03 mmol) in a Pyrex tube (φ 10 mm) was irradiated (λ
> 350 nm) for 10 min to give adduct 10a (22.5 mg, 6.82 × 10−5
deposited at the Cambridge Crystallographic Data Center, 12
Union Road, Cambridge CB2 1EZ, UK and copies can be ob-
tained on request, free of charge, by quoting the publication cita-
tion and the deposition numbers 192721 and 192722.
References
1
Reviews for photoreaction of organosilicon chemistry. a)
M. G. Steinmetz, Chem. Rev., 95, 1527 (1995). b) M. Kira and T.
Miyazawa, in “The Chemistry of Organic Silicon Compounds,” ed
by Z. Rappoport and Y. Apeloig, John Wiley & Sons, New York
(1998), Vol. 2, Chapter 22, pp. 1311–1377.
2
1029.
3
(1991).
4
K. Sakamoto, J. Abe, and H. Sakurai, Chem. Lett., 1992,
K. Sakamoto and H. Sakurai, J. Am. Chem. Soc., 113, 1466
H. Sakurai, J. Abe, and K. Sakamoto, J. Photochem.
1
mol, 96%). 10a: H NMR (C6D6) δ 0.06 (s, 9H), 0.43 (s, 6H),
1.79 (s, 6H), 5.0 (brs, 1H), 6.72 (s, 1H); 13C NMR (C6D6) δ 0.39,
0.95, 28.99, 84.13, 116.30, 121.79, 127.39, 128.31, 140.64,
144.58, 150.63; 29Si NMR (C6D6) δ 19.07, 23.41; HRMS m/z
Found: 330.0845, Calcd for C14H23ClO3Si3, 330.0874.
PhotoBiol. A: Chem., 65, 111 (1992).
Reviews for quinones. a) “The Chemistry of the
Photoreaction of 1b in the Presence of Acetone. A hexane
(4 mL) solution of 1b (27 mg, 8.5 × 10−5 mol) and acetone
(105 mg, 1.8 mmol) in a Pyrex tube (φ 10 mm) was irradiated (λ
> 350 nm) for 45 min to give adduct 10b (27 mg, 7.2 × 10−5 mol,
85%). 10b: 1H NMR (C6D6) δ 0.05 (s, 9H), 0.43 (s, 6H), 1.80 (s,
6H), 5.1 (brs, 1H), 6.87 (s, 1H); 13C NMR (C6D6) δ 0.17, 1.24,
29.44, 84.42, 113.06, 119.49, 129.16, 142.29, 145.71, 151.64; 29Si
NMR (C6D6) δ 19.12, 23.38; HRMS m/z Found: 374.0364, Calcd
for C14H23BrO3Si2, 374.0369.
5
Quinonoid Compounds Part 1 and Part 2,” ed by S. Patai, John
Wiley & Sons, Bristol (1974). b) “The Chemistry of the
Quinonoid Compounds Part 1 and Part 2,” ed by S. Patai and Z.
Rappoport, John Wiley & Sons, New York (1988), Vol. 2.
6
Some silyl-substituted 1,4-benzoquinones have been re-
ported. See: a) H. Bock and H. Alt, Angew. Chem., Int. Ed. Engl.,
6, 941 (1967). b) G. D. Cooper, B. Williams, and C. P. Lape, J.
Org. Chem., 26, 4171 (1961). c) H. Hashimoto, Yakugaku Zasshi,
87, 535 (1967). d) N. S. Vasileiskaya, L. V. Gorbunova, O. N.
Mamysheva, and G. N. Bortnikov, Izv. Akad. Nauk SSSR, Ser.
Khim., 1972, 2755. e) L. D. Foland, J. O. Karlsson, S. T. Perri, R.
Schwabe, S. L. Xu, S. Patil, and H. W. Moore, J. Am. Chem. Soc.,
111, 975 (1989). f) K. Sakamoto, S. Tsutsui, K. Ebata, C. Kabuto,
and H. Sakurai, Chem. Lett., 2000, 226.
Photoreaction of 1c in the Presence of Acetone.3 A hexane
(10 mL) solution of 1c (45 mg, 1.53 × 10−5 mol) and acetone
(460 mg, 7.93 mmol) in a Pyrex tube (φ 20 mm) was irradiated (λ
> 520 nm) for 60 min to give adduct 10c (33 mg, 9.35 × 10−6
mol, 61%). 10c: 1H NMR (C6D6) δ 0.21 (s, 9H), 0.49 (s, 6H), 1.34
(s, 9H), 1.72 (s, 6H), 4.20 (s, 1H), 6.82 (s, 1H); 13C NMR (C6D6) δ
0.55, 1.43, 30.13, 30.18, 34.50, 83.39, 115.61, 125.70, 139.88,
144.32, 146.50, 151.85; 29Si NMR (C6D6) δ 16.46, 22.11; HRMS
m/z Found: 352.1892, Calcd for C18H32O3Si2, 352.1890.
7
Crystal data for 6a: C9H11ClO2Si; MW = 214.72; mono-
clinic, a = 12.678(1) Å; b = 6.741(0) Å; c = 14.044(1) Å; β =
116.51°; V = 1074.1 Å3; space group P21/c; Z = 4, Dcalcd = 1.33
g/cm3. The final R and RW factors were 0.037 and 0.044 for 1588
reflections with Fo > 3σ(Fo).
X-ray Crystallographic Analysis of 1a.14,15 A suitable sin-
gle crystal of 1a was obtained by recrystallization from hexane.
Crystal data were described above. Data collection were done at
170 K using a Rigaku AFC-5R diffractometer, graphite mono-
chromatized Mo-Kα (λ = 0.71069 Å) radiation. Reflections with
I > 3σ(I) were used in the least-squares refinement. The structure
was solved by RANTAN81 direct method. The non-hydrogen at-
oms were refined anisotropically. Atomic scattering factors were
applied from the literature. The ACOS 2200 computer at Tohoku
University performed all calculations using UNICS ꢀ Package
System.
8
9
B. Rees, Acta Crystallogr, Sect. B, 26, 1304 (1970).
B. Rees, Acta Crystallogr, Sect. B, 26, 1292 (1970).
10 F. von Bolhuis and C. Th. Kiers, Acta Crystallogr, Sect. B,
34, 3697 (1978).
11 Silylene–Lewis base complexes were observed by the sim-
ilar conditions. a) G. R. Gillette, G. H. Noren, and R. West, Orga-
nometallics, 6, 2617 (1987). b) G. R. Gillette, G. H. Noren, and
R. West, Organometallics, 8, 487 (1989). c) M.-A. Pearsall and R.
West, J. Am. Chem. Soc., 110, 7228 (1988). d) W. Ando, K.
Hagiwara, and A. Sekiguchi, Organometallics, 6, 2270 (1987).
e) W. Ando, A. Sekiguchi, K. Hagiwara, A. Sakakibara, and H.
Yoshida. Organometallics, 7, 558 (1988). f) M. Kira, T.
Maruyama, and H. Sakurai, Heteroatom Chem., 5, 305 (1994).
12 N. Takeda, H. Suzuki, N. Tokitoh, R. Okazaki, and S.
Nagase, J. Am. Chem. Soc., 119, 1456 (1997).
α
Observation of -Sila-m-quinonemethide 3 and Their 2-
MeTHF Complex 12 at 77 K in Glass Matrixes by UV-Vis
Spectroscopy. 1 and 3-MP, 2-MeTHF, or 3-MP/2-MeTHF
(100/1) mixed solvent were placed in a sealed tube with a quartz
cell. The solution was irradiated at 77 K and monitored by UV-vis
spectroscopy.
Supporting Information Available. Ordering information is
given on any current masthead page. Tables of atomic coordi-
nates, anisotropic thermal parameters, bond lengths and angles,
and observed and calculated structure factors for compound 1a
and 6a (33 pages) are available. The crystallographic data for two
crystals are deposited as Document No. 75053 at the Office of the
Editor of Bull. Chem. Soc. Jpn. Crystallographic data have been
13 M. S. Gong and H. K. Hall, Jr., Macromolecules, 19, 3011
(1986).
14 “International Tables for X-ray Crystallography,” Kyuoch
Press, Birmingham (1974), Vol. ꢁ, p. 72.
15 T. Sakurai and K. Kobayashi, Rikagaku Kenkyusho
Hokoku, 55, 69 (1979).