PAPER
Synthesis of Geminal Bisperoxides
2219
1,1-Bis(tert-butylperoxy)cyclooctane (4e)15
Oil.
13C NMR (75.47 MHz): d = 19.7, 22.7, 24.3, 26.8, 44.0, 79.1, 108.9.
Anal. Calcd for C14H30O4: C, 64.08; H, 11.52. Found: C, 64.32; H,
11.18.
1H NMR (300.13 MHz): d = 1.20–2.08 (m, 32 H, CH2, CH3).
13C NMR (75.47 MHz): d = 26.9, 27.3, 31.9, 33.8, 37.5, 78.5, 108.1.
Anal. Calcd for C16H32O4: C, 66.63; H, 11.18. Found: C, 66.80; H,
11.13.
Acknowledgment
This work was financially supported by the Grant from the Presi-
dent of the Russian Federation (Federal Program for the Support of
Leading Scientific Schools, Grant NSh 02121.2003.3).
1,1-Bis(tert-butylperoxy)cyclododecane (4f)12,15
White crystals; mp 66–67 °C (CHCl3) (Lit.12 mp 67–68 °C).
1H NMR (300.13 MHz): d = 1.19–1.78 (m, 40 H, CH2, CH3).
13C NMR (75.47 MHz): d = 19.7, 22.1, 22.6, 26.2, 26.7, 27.6, 29.42,
79.0, 110.8.
References
(1) Antonovskii V. L.; In Organicheskie Perekisnye Initsiatory
(in Russian) (Organic Peroxide Initiators); Khimiya:
Moscow, 1972.
Anal. Calcd for C20H40O4: C, 69.72; H, 11.70. Found: C, 69.35; H,
11.86.
(2) (a) Organic Peroxides, Vol. 1; Swern, D., Ed.; Wiley: New
York, 1970. (b) Organic Peroxides, Vol. 2; Swern, D., Ed.;
Wiley: New York, 1971. (c) Organic Peroxides, Vol. 3;
Swern, D., Ed.; Wiley: New York, 1972.
(3) The Chemistry of Peroxides; Patai, S., Ed.; Wiley: New
York; Interscience Publishers: Chichester, 1983.
(4) Kropf, H. In Houben–Weyl, Methoden der Organischen
Chemie, Vol. E13; Georg Thieme Verlag: Stuttgart, 1988.
(5) Sawaki, Y. In Organic Peroxides; Ando, W., Ed.; Wiley-
VCH: New York, 1992, 450.
1,1-Bis(tert-butylperoxy)-2-nonylcyclododecane (4g)
Oil.
1H NMR (300.13 MHz): d = 0.83 (t, J = 6.5 Hz, 3 H, CH3), 1.26 (s,
18 H, CH3), 1.13–1.76 (m, 37 H, CH, CH2).
13C NMR (75.47 MHz): d = 13.9, 21.9, 22.2, 22.8, 22.9, 23.0, 23.1,
23.3, 23.5, 23.8, 24.0, 24.1, 24.6, 25.4, 25.8, 26.2, 28.5, 29.8, 30.3,
31.2, 36.9, 78.6, 111.0.
Anal. Calcd for C29H58O4: C, 73.99; H, 12.42. Found: C, 73.61; H,
12.30.
(6) Peroxide Chemistry; Adam, W., Ed.; Wiley-VCH: New
York, 2000.
(7) Hamada, Y.; Tokuhara, H.; Masuyama, A.; Nojima, M.;
Kim, H.-S.; Ono, K.; Ogura, N.; Wataya, Y. J. Med. Chem.
2002, 45, 1374.
(8) McCullough, K. J.; Ito, T.; Tokuyasu, T.; Masuyama, A.;
Nojima, M. Tetrahedron Lett. 2001, 42, 5529.
(9) Dickey, F. H.; Rust, F. F.; Vaughan, W. E. J. Am. Chem. Soc.
1949, 71, 1433.
(10) Kharash, M.; Sosnovsky, G. J. Org. Chem. 1958, 23, 1322.
(11) Nazarova, Z. F.; Bocharova, Y. E.; Batog, A. E.;
Romantsevich, M. K. Zh. Org. Khim. 1966, 2, 259; Chem.
Abstr. 1966, 65, 2116.
(12) Komai, T.; Matsushima, M.; Nakajima, T. Ger. Offen.,
2546743, 1976; Chem. Abstr. 1976, 85, 63706.
(13) Mukaiyama, T.; Miyoshi, N.; Kato, J.; Ohshima, M. Chem.
Lett. 1986, 1385.
(14) Sugihara, Y.; Watanabe, Y.; Kumura, H.; Nakamura, T.;
Suyama, S.; Sawaki, Y. Bull. Chem. Soc. Jpn. 1992, 65, 664.
(15) Matsuyama, K.; Kimura, H. J. Org. Chem. 1993, 58, 1766.
(16) Weygand, C.; Hilgetag, G. Organischen-Chemischen
Experimentierkunst; Johann Ambrosius Barth Verlag:
Leipzig, 1964.
(17) Becker, H. G. O.; Berger, W.; Domschke, G. Organikum;
VEB Deutscher Verlag der Wissenschaften: Berlin, 1964.
(18) Meerwein, H. In Houben–Weyl, Methoden der Organischen
Chemie, Vol. VI/3; Muller, E., Ed.; Georg Thieme Verlag:
Stuttgart, 1965, 199.
2,2-Bis(tert-butylperoxy)adamantane (6)
Oil.
1H NMR (300.13 MHz): d = 1.28 (s, 18 H, CH3), 1.51–2.09 (m, 14
H, CH2).
13C NMR (75.47 MHz): d = 26.7, 27.1, 31.7, 33.7, 37.4, 78.3, 107.9.
Anal. Calcd for C18H32O4: C, 69.19; H, 10.32. Found: C, 69.31; H,
10.30.
1,1-Bis(tert-butylperoxy)nonane (8a)
Oil.
1H NMR (300.13 MHz): d = 0.83 (t, J = 6.5 Hz, 3 H, CH3), 1.15–
1.78 (m, 32 H, CH2, CH3), 4.73 (t, J = 5.9 Hz, 1 H, CH).
13C NMR (75.47 MHz): d = 14.0, 22.6, 24.1, 24.5, 26.4, 29.0, 29.1,
29.3, 31.8, 80.2, 107.6.
Anal. Calcd for C17H36O4: C, 67.06; H, 11.92. Found: C, 67.31; H,
12.15.
5,5-Bis(tert-butylperoxy)nonane (8b)11
Oil.
1H NMR (300.13 MHz): d = 0.84 (t, J = 6.9 Hz, 6 H, CH3), 1.12–
1.82 (m, 30 H, CH2, CH3).
13C NMR (75.47 MHz): d = 14.1, 23.1, 26.8, 29.4, 31.1, 79.0, 110.3.
Anal. Calcd for C17H36O4: C, 67.06; H, 11.92. Found: C, 67.21; H,
11.85.
(19) Terent’ev, A. O.; Kutkin, A. V.; Platonov, M. M.;
Vorontsov, I. I.; Antipin, M. Y.; Ogibin, Y. N.; Nikishin, G.
I. Izv. Akad. Nauk, Ser. Khim. 2004, 650; Russ. Chem. Bull.
Int. Ed., 2004, 681.
(20) Dictionary of Organic Compounds, Vol. 1-7, 5th ed.;
Chapman & Hall: New York / Liverpool / Toronto, 1982–
1988, Suppl. 1–6.
2,2-Bis(tert-butylperoxy)-4-methylpentane (8c)9
Oil.
1H NMR (300.13 MHz): d = 0.93 (d, J = 6.7 Hz, 6 H, CH3), 1.23 (s,
18 H, CH3), 1.38 (s, 3 H, CH3), 1.67 (d, J = 6.2 Hz, 2 H, CH2), 1.75–
1.87 (m, 1 H, CH).
(21) Matsuyama, K.; Kumura, H. J. Org. Chem. 1993, 58, 1766.
Synthesis 2005, No. 13, 2215–2219 © Thieme Stuttgart · New York