5506
M. Suzuki et al. / Tetrahedron 67 (2011) 5500e5506
assignable to 7. 1H NMR (CD3CN):
d
0.49 (9H, s), 1.02 (9H, s), 1.08
temperature on beamline 4B2 (parallel beam optics) at the PF
synchrotron facility using a wavelength of 1.197040(7) A. The
ꢀ
(9H, s), 1.40 (9H, s), 2.98 (1H, d, J¼3.6 Hz), 6.24 (1H, d, J¼1.9 Hz),
7.06 (1H, d, J¼3.6 Hz), 7.26 (1H, d, J¼1.9 Hz), 8.00 (4H, m). 13C NMR
sample was loaded into a borosilicate glass capillary (2.0 mm di-
ameter) and was used for the diffraction measurement in trans-
mission mode. The powder X-ray diffraction pattern was indexed
using the program DICVOL04.17 The structure solution was carried
out using the simulated annealing method incorporated in the
program DASH.18 The best structure obtained in the structure so-
lution calculation was used as the initial structural model for
Rietveld refinement, which was carried out using the GSAS
program.19
(CDCl3): d 202.0, 200.0, 192.9, 154.5, 153.5, 151.2, 144.6, 143.0, 140.8,
136.7, 135.8, 132.4, 125.2, 124.1, 123.5, 115.6, 63.9, 50.8, 34.4, 34.2,
32.5, 32.1, 29.3, 28.7, 27.4, 26.2. Anal. Calcd for C37H44O4: C, 80.45;
H, 7.97%. Found: C, 80.72; H, 7.88%.
4.2.2. 2,4-Di-tert-butylbenzo[b]naphtho[2,3-d]furan-6,11-dione
(8). 1H NMR (CD3CN):
d 1.51 (9H, s), 1.43 (9H, s), 7.64 (1H, d,
J¼2.1 Hz), 7.84 (2H, m), 8.10 (1H, d, J¼2.1 Hz), 8.18 (2H, m). 13C NMR
(CDCl3):
d 29.96, 31.69, 34.75, 35.26, 117.47, 123.14, 124.27, 124.50,
126.64, 126.81, 132.61, 133.40, 133.72, 133.95, 135.70, 149.53, 153.20,
153.47, 175.25, 181.88. MS (m/z): 360 (Mþ), 344. Anal. Calcd for
C24H24O3: C, 80.00; H, 6.67%. Found: C, 80.26; H, 6.29%.
4.5.1. Crystal data for 6. C37H44O4, P21 (#4), monoclinic,
¼102.5746(1)ꢀ,
Rp¼0.0215,
ꢀ
a¼10.3569(3), b¼16.5705(4), c¼9.7932(4) A,
b
3
ꢀ
V¼1640.39(10) A ,
Z¼2,
Dcalcd¼1.119 g/cm3,
Rwp¼0.0287, CCDC 818653.
4.3. Reaction of ninhydrin with 2,4-di-tert-butylphenol
To a solution of ninhydrin (3.02 g, 17 mmol) in acetic acid
(30 mL) were added 2,4-di-tert-butylphenol (6.97 g, 34 mmol) and
a drop of concd sulfuric acid. The mixture was heated at reflux for
4 h. Aqueous work up, extraction with dichloromethane (300 mL),
and drying over anhydrous Mg2SO4 afforded a reddish solution.
After the solvent was removed under reduced pressure, the
resulting solids were chromatographed on silica gel with benzene
as eluent to give 10 (1.82 g, 20%).
Acknowledgements
This work was supported by Grants-in-Aid for Scientific Re-
search (C) from MEXT (Nos. 21550048 and 21550008). Part of this
work was performed under the approval of the Photon Factory
Program Advisory Committee (Proposal No. 2009G658).
References and notes
4.3.1. 2,4,12,14-Tetra-tert-butyl-6H-dibenzo[b.f]benzofuro[3,2-d]ox-
ocin-6-one (10). Mp 216e217 ꢀC. IR (Nujol): 1732, 1248 cmꢁ1 1H
.
1. (a) Diradicals; Borden, W. T., Ed.; Wiley: New York, NY, 1982; (b) Rajca, A. Chem.
Rev. 1994, 94, 871; (c) Adam, W.; van Barneld, C.; Emmert, O.; Harrer, H. M.;
Kita, F.; Kumar, A. S.; Maas, W.; Nau, W. M.; Reddy, S. H. K.; Wirz, J. Pure Appl.
Chem. 1997, 69, 735.
2. Kiyohara, S.; Ishizuka, K.; Wakabayashi, H.; Miyamae, H.; Kanazumi, M.; Kato,
T.; Kobayashi, K. Tetrahedron Lett. 2007, 48, 6877.
NMR (CDCl3):
d
6.61 (1H, d, J¼1.8 Hz), 6.80 (1H, q, J¼1.5 Hz), 6.87
(1H, d, J¼3.1 Hz), 7.28 (1H, J¼1.8 Hz), 7.89 (4H, m). MS (m/z): 536
(Mþ). Anal. Calcd for C37H44O3 :C, 82.78; H, 8.18%. Found: C, 82.26;
H, 8.04%.
3. (a) Hashimoto, S.; Sakuma, N,; Wakabayashi, H.; Miyamae, H.; Kobayashi, K.
Chem. Lett. 2008, 37, 696; (b) Das, S.; Frohlich, R.; Pramanik, A. A. Org. Lett.
2006, 8, 4263; (c) Na, J. E.; Lee, K. Y.; Seo, J.; Kim, J. N. Tetrahedron Lett. 2005,
46, 4505.
4. (a) Tsuge, O.; Watanabe, H.; Kanemasa, S. Chem. Lett. 1984, 1415; (b) Dean, F. M.;
Herbin, G. A.; Matkin, D. A.; Price, A. W.; Robinson, M. L. J. Chem. Soc. Perkin
Trans. 1 1980, 1986; (c) Bennett, D. J.; Dean, F. M.; Herbin, G. A.; Matkin, D. A.;
Price, A. W.; Robinson, M. L. J. Chem. Soc., Perkin Trans. 1 1980, 1978; (d) Feringa,
B.; Wynberg, H. Tetrahedron Lett 1977, 447; (e) Katoh, T.; Ohmori, O.; Iwasaki,
K.; Inoue, M. Tetrahedron 2002, 58, 1289.
5. Tashiro, M.; Yoshiya, H.; Fukata, G. J. Org. Chem. 1981, 46, 3784.
6. Frimer, A. A.; Marks, V.; Sprecher, M.; Gilinsky-Sharon, P. J. Org. Chem. 1994, 59,
1831 and references cited there.
7. (a) Taub, D.; Kuo, C. H.; Slates, H. L.; Wender, N. L. Tetrahedron 1963, 19, 1; (b)
Hewgill, F. R.; Raston, C. L.; Skelton, B. W.; Webb, R. J.; White, A. H. Aust. J. Chem.
1983, 36, 1603.
8. (a) Matsuura, T.; Ogura, K. J. Am. Chem. Soc. 1967, 89, 3846; (b) Matsuura, T.;
Meng, J.-B.; Ito, Y.; Irie, M.; Fukuyama, K. Tetrahedron 1987, 43, 2451.
9. (a) Schaffner, K.; Demuth, M. In Rearrangements in Ground and Excited States;
de Mayo, P., Ed.; Academic: New York, NY, 1980; Vol. 3, pp 281e348; (b)
Schultz, A. G. Pure Appl. Chem. 1988, 60, 981; (c) Schuster, D. I. Acc. Chem. Res.
1978, 11, 65.
10. (a) Lind, H.; Winkler, T.; Loeliger, H. J. Polym. Sci. Part C, 1976, 57, 225; (b)
Zimmerman, H. E.; Keese, R.; Nasielski, J.; Sweton, J. S. J. Am. Chem. Soc. 1966,
88, 4895.
4.4. Single-crystal X-ray crystallography
X-ray crystallographic data were collected at cryogenic tem-
perature (ꢁ50 ꢀC) for 6 and at ambient temperature for others on
a Rigaku-RAPID imaging plate two-dimensional area detector using
ꢀ
graphite monochromatized Mo K
a
radiation(
l
¼0.71073 A). All
crystallographic calculations were performed using Crystal-
Structure crystallographic software.16 Crystal data have been sub-
mitted to CCDC, which can be obtained free of charge at
4.4.1. Crystal data for 5. C37H44O4, P-21/c (#14), a¼9.4641(9),
3
ꢀ
ꢀ
ꢀ
b¼24.3590(20), c¼14.6422(11) A,
b
¼104.825(3) , V¼3263.2(5) A ,
Z¼4, Dcalcd¼1.125 g/cm3, R1¼0.1241, wR2¼0.3521, CCDC 813921.
Crystal data for (6)(CH3CN): C39H47O4N, P-1 (#2), a¼9.7554(5),
¼85.6750(15)ꢀ,
ꢀ
b¼12.5742(5), c¼14.6696(8) A,
a
b
¼77.3860(15)ꢀ,
3
g
¼82.0220(14) , V¼1737.13(14) A , Z¼2, Dcalcd¼1.135 g/cm3, R1¼0.0467,
ꢀ
ꢀ
wR2¼0.1520, CCDC 813922. Crystal data for 8. C24H24O3, Pnma (#62),
3
ꢀ
ꢀ
a¼15.1070(13), b¼7.1473(5), c¼18.1696(14) A, V¼1961.9(3) A , Z¼4,
11. The NMR analysis could not reveal if acetonitrile molecules were retained in the
amorphous region where the reactions took place. It would be reasonable to
assume that the solvate has been lost in such a region.
12. Paul, I. C.; Curtin, D. Y. Acc. Chem. Res. 1973, 6, 217.
13. Rietveld, H. M. J. Appl. Crystallogr. 1969, 2, 65.
Dcalcd¼1.220 g/cm3, R1¼0.1231, wR2¼0.1924. CCDC 813923.Crystal
data for (10)2(benzene)3: C46H53O3, P-1 (#2), a¼9.57324(5),
¼66.0570(9)ꢀ,
ꢀ
b¼15.2267(7), c¼15.2332(7) A,
a
b
¼77.3180(15)ꢀ,
3
ꢀ
14. Roussey, J.-C.; Laude, B. C. R. Acad. Sci. Ser. C, 1979, 288, 225.
15. Das, S.; Frohlich, R.; Pramanik, A. Synlett 2006, 207.
g
¼84.2820(16)ꢀ, V¼1979.83(16) A , Z¼2, Dcalcd¼1.097 g/cm3,
R1¼0.1097, wR2¼0.2720, CCDC 813924.
16. CrystalStructure, Ver.3. 7; Rigaku Corporation: Tokyo, 2005.
17. (a) Boultif, A.; Louer, D. J. Appl. Crystallogr. 1991, 24, 987; (b) Boultif, A.; Louer, D.
J. Appl. Crystallogr. 2004, 37, 724.
18. David, W. I. F.; Shankland, K.; van de Streek, J.; Pidcock, E.; Motherwell, W. D. S.;
Cole, J. C. J. Appl. Crystallogr. 2006, 39, 910.
4.5. Powder X-ray diffraction
The synchrotron X-ray powder diffraction data for the poly-
crystalline sample of the desolvated 6 were recorded at ambient
19. Larson, A. C.; Von Dreele, R. B. GSAS, Los Alamos Laboratory Report No. LA-UR-
86-748, 1987, p 19.