The Journal of Organic Chemistry
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General Procedures. The cyclic ether of interest was dissolved to
give a 0.6 M solution in either CDCl3 or CD2Cl2, whichever was found
to be more suitable. Next, 2 equiv CBr4 were added with an internal
standard (toluene). Using the appropriate amount of Ph3P given in
Schemes 1 and 2, a 0.6 M solution of Ph3P dissolved in the same
solvent was added dropwise to the stirred mixture for ca. 60 min. The
solution became slightly yellow and then colorless over time.
Sometimes a white precipitate was observed between 10−60 min
after the addition of Ph3P. In some cases it dissolved after ca. 2−4 h
but in others it remained. Aliquots from the reactions of 1 and 6 were
periodically withdrawn and analyzed by NMR and GC-MS. After the
durations listed in Scheme 1 and Scheme 2, the reaction mixtures were
quenched and worked up in the standard manner.
1,3-Dibromo-2,2-dimethylpropane (2): tR 6.49 min; m/z (EI) 230
([M]+, 20), 151 (65), 149 (65), 137 (80), 135 (95), 109 (18), 107
(18), 95 (18), 93 (18), 55 (100).
3-Bromo-2,2-dimethylpropanol (3): tR 5.14 min; m/z (EI) 137
([M − HCHO]+, 12), 135 (12), 109 (3), 107 (3), 86 (14), 69 (5), 56
(100).
(4) (a) Cizmarikova, R.; Heger, J. Chem. Zvesti 1978, 32, 92−99.
(b) Szymanska, E.; Frydenvang, K.; Contreras-Sanz, A.; Pickering, D.
S.; Frola, E.; Serafimoska, Z.; Nielsen, B.; Kastrup, J. S.; Johansen, T.
N. J. Med. Chem. 2011, 54, 7289−7298.
(5) Oae, S.; Itoh, O.; Numata, T.; Yoshimura, T. Bull. Chem. Soc. Jpn.
1983, 56, 270−279.
(6) (a) Zoidis, G.; Benaki, D.; Myrianthopoulos, V.; Naesens, L.; De
Clercq, E.; Mikros, E.; Kolocouris, N. Tetrahedron Lett. 2009, 50,
2671−2675. (b) Zoidis, G.; Kolocouris, N.; Naesens, L.; De Clercq, E.
Bioorg. Med. Chem. 2009, 17, 1534−1541.
(7) Wiley, G. A.; Hershkowitz, R. L.; Rein, B. M.; Chung, B. C. J. Am.
Chem. Soc. 1964, 86, 964−965.
(8) Castro, B. R. Org. React. 1983, 29, 1−162.
(9) (a) Appel, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 801−811.
(b) Downie, I. M.; Holmes, J. B.; Lee, J. B. Chem. Ind. (London) 1966,
22, 900−901. (c) Calzada, J. G.; Hooz, J. Org. Synth. 1974, 54, 63−67.
(d) Baughman, T. W.; Sworen, J. C.; Wagener, K. B. Tetrahedron
2004, 60, 10943−10948. (e) Newman, S. G.; Bryan, C. S.; Perez, D.;
Lautens, M. Synthesis 2011, 342−346. (f) Slagle, J. D.; Huang, T. T. S.;
Franzus, B. J. Org. Chem. 1981, 46, 3526−3530. (g) Appel, R.;
Warning, K. Chem. Ber. 1975, 108, 1437−1441. (h) Appel, R.;
(3-Bromo-2,2-dimethylpropoxy)triphenylphosphonium cation
(4): δH/ppm (400.1 MHz, CD2Cl2) 1.17 (6 H, s), 3.50 (2 H, s),
3
4.15 (2 H, d, JPH 3.9), see the Supporting Information for aromatic
Kleinstuck, R.; Ziehn, K.-D. Chem. Ber. 1971, 104, 2025−2026.
̈
protons; δC/ppm (100.6 MHz, CD2Cl2) 22.9, 30.0 (d 1JCP 47.2), 37.1,
41.2, 76.6 (d 2JCP 8.3), 116.4 (d 1JCP 107), 130.5 (d JCP 13.0), 135.3 (d
JCP 10.0), 135.9 (d JCP 13.0); δP/ppm (162.02 MHz, CD2Cl2) 63.2
(see Figures S7−S11).
(i) Lee, J. B.; Nolan, T. J. Can. J. Chem. 1966, 44, 1331−1334.
(10) (a) Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 3769−
3772. (b) Gosh, A. K.; Wang, Y. J. Am. Chem. Soc. 2000, 122, 11027−
11028. (c) Gibtner, T.; Hampel, F.; Gisselbrecht, J.-P.; Hirsch, A.
Chem.Eur. J. 2002, 68, 408−432. (d) Mori, M.; Tonogaki, K.;
Kinoshita, A. Org. Synth. 2005, 81, 1−13.
3-Chloro-2,2-dimethylpropanol (5): tR 3.87 min; m/z (EI) 91 ([M
− HCHO]+, 9), 90 (9), 73 (37), 63 (9), 56 (100).
1,4-Dibromobutane (7): 670 μL (596 mg; 8.27 mmol) of oxolane
(6) was dissolved in 15 mL of CHCl3 and 6.12 g (18.45 mmol) of
CBr4 were added. Then 8.29 g (31.61 mmol) of Ph3P dissolved in 5
mL of CHCl3 were added dropwise to the stirred mixture over 60 min.
After stirring for 10 d at room temperature the reaction mixture was
quenched with water, transferred into a separatory funnel and the
organic layer was washed once with water. After drying over MgSO4,
filtration, and rotary-evaporating of the solvent, the crude product was
Kugelrohr-distilled (9 Torr, oven temperature ca. 90 °C) to afford 7 in
a yield of 1.66 g (93%); tR 6.97 min; m/z (EI) 216 (M+, 1), 137 (95),
135 (98), 111 (13), 109 (12), 93 (6), 81 (4), 55 (100).
(11) Harris, D. C. Quantitative Chemical Analysis, 6th ed.; Macmillan:
New York, 2003.
(12) (a) Lerm, M.; Gais, H.-J.; Cheng, K.; Vermeeren, C. J. Am.
Chem. Soc. 2003, 125, 9653−9667. (b) Wolkoff, P. Can. J. Chem. 1975,
53, 1333−1335. (c) Li, X.-Y.; Hu, J.-S. Tetrahedron Lett. 1987, 28,
6317−6320. (d) Godfrey, S. M.; McAuliffe, C. A.; Mushtaq, I.;
Pritchard, R. G.; Sheffield, J. M. J. Chem. Soc., Dalton Trans. 1998,
3815−3818. (e) Jain, D. V. S.; Chopra, R. Indian J. Chem., Sect. A
1982, 21A, 709−711. (f) Markl, G. Chem. Ber. 1962, 95, 3003−3007.
̈
(g) Ramirez, F.; Desai, N. B.; McKelvie, N. J. Am. Chem. Soc. 1962, 84,
1745−1747.
(13) Wan, J.; Zhan, C.-G. Theor. Chim. Acta 1995, 92, 61−65.
(14) Spectroscopic Methods in Organic Chemistry, 2nd ed.; Hesse, M.,
Meier, H., Zeeh, B., Eds.; Thieme: Stuttgart, 2007.
ASSOCIATED CONTENT
* Supporting Information
■
S
(15) (a) Benson, S. W.; Cruickshank, F. R.; Golden, D. M.; Haugen,
G. R.; O’Neal, H. E.; Rodgers, A. S.; Shaw, R.; Walsh, R. Chem. Rev.
1969, 69, 279−324. (b) Thermochemical Kinetics: Methods for the
Estimation of Thermochemical Data and Rate Parameters, 2nd ed.;
Benson, S. W., Ed.; Wiley: New York, 1976.
(16) Verevkin, S. P.; Emel’yanenko, V. N.; Pimerzin, A. A.;
Vishnevskaya, E. E. J. Phys. Chem. A 2011, 115, 1992−2004.
NMR and GC-MS spectra of all new compounds and of known
compounds to use for comparison. This material is available
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Ms. S. Felsinger of the Institute of Organic
Chemistry of the University of Vienna for recording 2-D
NMR spectra.
REFERENCES
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(1) Advanced Organic Chemistry, 5th ed.; Smith, M. B., March, J.,
Eds.; Wiley: New York, 2001; pp 519−521.
(2) (a) Nordvik, T.; Mieusset, J.-L.; Brinker, U. H. Org. Lett. 2004, 6,
715−718. (b) Xu, L.; Brinker, U. H. In Synthetic Organic
Sonochemistry; Luche, J.-L., Ed.; Plenum: New York, 1998; pp 344−
345. (c) Xu, L.; Smith, W. B.; Brinker, U. H. J. Am. Chem. Soc. 1992,
114, 783−784. (d) Mieusset, J.-L.; Brinker, U. H. J. Org. Chem. 2007,
72, 10211−10219.
(3) Nordvik, T.; Brinker, U. H. J. Org. Chem. 2003, 68, 9394−9399.
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dx.doi.org/10.1021/jo302360t | J. Org. Chem. XXXX, XXX, XXX−XXX