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G. Bianchini et al. / Tetrahedron 62 (2006) 12326–12333
4.4.9. 7-Hydroxy-2-heptanone 13. 1H NMR (CDCl3)
d 1.33–1.40 (m, 2H), 1.54–1.62 (m, 4H), 2.14 (s, 3H), 2.19
(br, 1H), 2.45 (m, 2H), 3.63 (m, 2H). 13C NMR (CDCl3)
d 23.35, 25.20, 29.80, 32.29, 43.52, 62.35, 209.32. GC–
MS m/z (%): 101 (60), 83 (16), 59 (84), 43 (100).
that the sensitive part of the EPR cavity (1 cm length) was
always full; no variations were observed in the density of
samples. All the experimental spectra were fitted by the
6/9/91 DOS version of the SIM14S simulation program.
4.4.10. 1,10-Dimethyl-1,10-bi(cyclohexyl) 14. 1H NMR
(CDCl3) d 1.64–1.55 (m, 8H), 1.47–1.07 (m, 12H), 0.81 (s,
6H). 13C NMR (CDCl3) d 38.10, 30.34, 26.61, 20.34,
16.61. GC–MS m/z (%): 97 (100), 69 (20), 55 (75), 43 (25).
Acknowledgements
Italian MIUR (PRIN-COFIN 2003) is acknowledged for
financial support. Prof. Roberto Scotti (University of
Milano-Bicocca, Milano, Italy) is acknowledged for helpful
discussion about EPR investigation.
4.4.11. 1,2-Dimethylcyclopentanol 15.29 1H NMR (CDCl3)
d 1.98–1.50 (m, 6H), 1.87 (br s, 1H), 1.21–1.14 (m, 1H), 1.11
(s, 3H), 0.84 (d, J¼7 Hz, 3H). 13C NMR (CDCl3) d 81.00,
44.62, 39.98, 31.75, 22.78, 20.48, 15.36. GC–MS m/z (%):
114 (5), 99 (12), 85 (30), 71 (100), 43 (60).
References and notes
1. (a) Herrmann, W. A.; Fischer, R. W.; Marz, D. W. Chem. Rev.
1997, 97, 3197–3246; (b) Beattie, I. R.; Jones, P. J. Inorg.
Chem. 1979, 18, 2318–2319.
4.4.12. 1,5-Dimethyl-6-oxabicyclo[3.1.0]hexane 16.34 1H
NMR (CDCl3) d 1.81–1.73 (m, 2H), 1.70–1.65 (m, 2H),
1.38–1.22 (m, 2H), 1.22 (s, 6H). 13C NMR (CDCl3)
d 62.97, 35.41, 17.01, 16.84. GC–MS m/z (%): 112 (60),
97 (80), 71 (50), 69 (49), 43 (100).
2. As selected examples of recent applications concerning the use
ꢁ
of MTO in organic synthesis see: (a) Johansson, M.; Linden,
A. A.; Backvall, J.-E. J. Organomet. Chem. 2005, 690, 3614–
€
3619; (b) Soldaini, G.; Cardona, F.; Goti, A. Tetrahedron
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Fabrizi, G.; Goggiamani, A. Tetrahedron Lett. 2003, 44,
8991–8994; (d) Abu-Omar, M. M.; Owens, G. S.; Durazzo,
A. Catalytic Olefin Epoxidation and Dihydroxylation with
Hydrogen Peroxide in Common Ionic Liquids: Comparative
Kinetics and Mechanistic Study; ACS Symposium Series 856
(Ionic Liquids as Green Solvents); American Chemical
Society: Washington, DC, 2003; pp 277–288; (e) Espenson,
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C. C.; Lopes, A. D. Appl. Organomet. Chem. 2001, 15, 43–50.
3. (a) Shul’pin, G. B. C. R. Chim. 2003, 6, 163–178; (b) Nizova,
G. V.; Bolm, C.; Ceccarelli, S.; Pavan, C.; Shul’pin, G. B. Adv.
Synth. Catal. 2002, 344, 899–905.
4.4.13. 2,3-Dimethylcyclopentanone 17. 1H NMR (CDCl3)
d 2.23–1.75 (m, 5H), 1.38–1.29 (m, 1H), 0.93 (d, J¼7.1 Hz,
3H), 0.90 (d, J¼6.9 Hz, 3H). 13C NMR (CDCl3) d 218.04,
47.05, 39.25, 35.38, 28.66, 16.74, 11.22. GC–MS m/z (%):
112 (50), 97 (22), 81 (75), 69 (100), 55 (82).
4.4.14. 6-Hydroxyheptan-2-one 18. 1H NMR (CDCl3)
d 3.87 (m, 1H), 3.11 (br s, 1H), 2.49 (t, J¼6.8 Hz, 2H),
2.10 (s, 3H), 1.63 (m, 2H), 1.43 (m, 2H), 1.19 (d,
J¼6.7 Hz, 3H). 13C NMR (CDCl3) d 207.98, 68.22, 43.68,
42.95, 29.12, 28.75, 19.22. GC–MS m/z (%): 101 (58), 83
(14), 59 (80), 43 (100).
4.4.15. 1,10,2,20-Tetramethyl-1,10-bi(cyclopentyl) 19. 1H
NMR (CDCl3) d 1.83–1.72 (m, 2H), 1.65–1.45 (m, 8H),
1.38–1.26 (m, 2H), 1.10–0.99 (m, 2H), 0.92 (s, 6H), 0.89
(d, J¼6.8 Hz, 3H). 13C NMR (CDCl3) d 45.18, 38.42,
38.05, 36.22, 21.14, 15.28, 14.77. GC–MS m/z (%): 97
(100), 69 (22), 55 (73), 43 (58).
4. (a) Schuchardt, U.; Mandelli, D.; Shul’pin, G. B. Tetrahedron
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5. Herrmann, W. A.; Fischer, R. W.; Scherer, W.; Rauch, M. U.
Angew. Chem., Int. Ed. Engl. 1993, 32, 1157–1160.
4.5. EPR analysis
6. (a) Owens, G. S.; Durazzo, A.; Abu-Omar, M. M. Chem.—Eur.
J. 2002, 8, 3053–3059; (b) See Ref. 5.
7. (a) Wu, Y.-D.; Sun, J. J. Org. Chem. 1998, 63, 1752–1753; (b)
The EPR spectra were recorded on samples in powdered
form. Pure MTO and resins were studied as received. Het-
erogeneous catalysts I–V were prepared as previously
described. The H2O2-treated samples were prepared by
suspending the catalyst (1 g) in t-BuOH (30 mL), then
H2O2 (5 equiv) was added and the suspension was main-
tained under stirring for 1 h. At the end, the catalyst was re-
covered by filtration and allowed to dry in air. For all
samples, spectra were recorded at 25 ꢁC on an X-band CW
EPR Bruker EMX spectrometer. The g values were deter-
mined by standardisation with a,a0-diphenyl-b-picryl hydra-
zyl (DPPH), g¼2.0036ꢄ0.0003. The spin concentration,
expressed as spin/g of catalyst, was calculated with
a ꢄ10% accuracy by double integration of the resonance
lines and referring the area under the absorption curve to
that of the standard Bruker weak pitch (1013ꢄ5% spin/
cm); then the weight of sample filling 1 cm length of EPR
cavity was determined. Care was taken in order to ensure
€
Gisdakis, P.; Antonczak, S.; Kostlmeier, S.; Herrmann, W. A.;
Rosch, N. Angew. Chem., Int. Ed. 1998, 37, 2211–2214.
€
8. For selected examples of a butterfly-like transition state in the
oxidation of hydrocarbons with dimethyldioxirane see: (a)
Murray, R. W.; Gu, D. J. Chem. Soc., Perkin Trans. 2 1994,
451–453; (b) Marples, B. A.; Muxworthy, J. P.; Baggaley,
K. H. Tetrahedron Lett. 1991, 32, 533–536.
€
9. (a) Adam, W.; Saha-Moller, C. R.; Weichold, O. J. Org. Chem.
2000, 65, 2897–2899; (b) Wang, T.-J.; Li, D.-C.; Bai, J.-H.;
Huang, M.-Y.; Jiang, Y.-Y. J. Macromol. Sci., Part A: Pure
Appl. Chem. 1998, A35, 531–538; (c) Neumann, R.; Wang,
T.-J. Chem. Commun. 1997, 1915–1916.
10. For general considerations on the heterogenation of active spe-
cies on polymeric supports see: Thomas, J. M.; Thomas, W. J.
Principles and Practice of Heterogeneous Catalysis; VCH:
New York, NY, 1997.