The Journal of Organic Chemistry
Article
the ε-H a doublet among α-Br products. The crude product was then
purified by flash chromatography with silica gel eluting with 10:1
hexane/ethyl acetate or 20:1 hexane/chloroform so that a yield of the
mixture could be determined.
grant (No. 99-50413) from NSF, Professor Christopher J.
Nichols for providing thoughtful suggestions during the
development of the project, and Professor Dean J. Tantillo
(University of California, Davis) for generously permitting use
of computational resources by M.W.L. Special thanks are given
to Professor Thomas R. R. Pettus (University of California,
Santa Barbara) for extensive kind help in compiling, preparing,
writing, and editing of this manuscript.
2-Bromo-3,4-dimethylphenol (α-Br 1): pale yellow solid; 1H NMR
(300 MHz; CDCl3) δ 6.99 (d, J = 8.2 Hz, 1H), 6.79 (d, J = 10.6 Hz,
1H), 5.47 (s, 1H), 2.36 (s, 3H), 2.26 (s, 3H).
2-Bromo-4,5-dimethylphenol (ε-Br 1): pale yellow solid; 1H NMR
(300 MHz; CDCl3) δ 7.20 (s, 1H), 6.82 (s, 1H), 5.25 (s, 1H), 2.18 (s,
3H), 2.17 (s, 3H).
4-Bromo-2,3-dihydro-1H-inden-5-ol (α-Br 4): pale yellow solid; 1H
NMR (300 MHz; CDCl3) δ 7.03 (d, J = 7.6, 1H), 6.80 (d, J = 7.6,
1H), 5.74 (s, 1H), 1.92 (m, 4H), 2.11 (m, 2H).
REFERENCES
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NMR (300 MHz; CDCl3) δ 7.28 (s, 1H), 6.89 (s, 1H), 5.35 (s, 1H),
2.83 (m, 4H), 2.18 (m, 2H).
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1-Bromo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-2-ol (α-Br 5):
1
pale yellow solid; H NMR (300 MHz; CDCl3) δ 6.94 (d, J = 7.6,
1H), 6.76 (d, J = 8.2, 1H), 5.51 (s, 1H), 2.70−2.67 (m, 4H), 1.80−
1.59 (m, 6H).
3-Bromo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-2-ol (ε-Br 5):
1
pale yellow solid; H NMR (300 MHz; CDCl3) δ 7.16 (s, 1H), 6.78
(s, 1H), 5.27 (s, 1H), 2.70−2.67 (m, 4H), 1.80−1.59 (m, 6H).
1-Bromo-5,6,7,8-tetrahydronaphthalen-2-ol (α-Br 6): white crys-
talline solid; 1H NMR (300 MHz; CDCl3) δ 6.95 (d, J = 8.2, 1H), 6.82
(d, J = 8.2, 1H), 5.52 (s, 1H), 2.72 (m, 4H), 1.75 (m, 4H).
3-Bromo-5,6,7,8-tetrahydronaphthalen-2-ol (ε-Br 6): white crys-
1
talline solid; H NMR (300 MHz; CDCl3) δ 7.16 (s, 1H), 6.74 (s,
1H), 5.80 (s, 1H), 2.72 (m, 4H), 1.75 (m, 4H).
Computational Methods. Quantum mechanical calculations were
performed with GAUSSIAN03.17 All calculations (optimizations,
frequencies, and NICS) were performed in the gas phase using the
B3LYP/6-31G(d) level of theory.18−22 NMR single-point calculations
for the NICS values utilized the default GIAO method.23−27
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
1H NMR spectra and all data emerging from quantum
mechanical calculations (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
Present Address
§Physical Science Department, Butte College, Oroville, CA
95965.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This work was supported in part by a Research Corporation
Cottrell College Science Award (No. 7720), a California State
University Program for Education and Research in Biotechnol-
ogy (CSUPERB) Faculty−Student Collaborative Research
Seed Grant, CSUPERB Faculty−Student Collaborative Re-
search: Development Grant, and start-up funds provided by the
College of Natural Sciences of California State University,
Chico. The above funding supported J.Z. and her under-
graduate student co-workers during completion of the reported
research. We thankProfessor David B. Ball for obtaining the
departmental high-field NMR spectrometer through a CCLI
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