Molecules 2010, 15
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4-Methylpentane-2,2-dihydroperoxide (2d) [32]. H-NMR (200 MHz, CDCl3): 9.54 (br s, 2H), 1.80
(m, 1H), 1.62 (d, J = 7 Hz, 2H), 1.42 (s, 3H), 0.98 (d, J = 7 Hz, 6H); FABMS: m/z 173 [M+Na]+.
Cyclohexane-1,1-dihydroperoxide (2e) [37]. 1H-NMR (200 MHz, CDCl3): 9.70 (br s, 2H), 1.93–1.70
(m, 4H), 1.67–1.39 (m, 6H); FABMS: m/z 171 [M+Na]+.
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Methy-phenyl-1,1-dihydroperoxide (2h) [33]. H-NMR (200 MHz, CDCl3): 9.16 (br s, 2H),
7.50–7.43 (m, 2H), 7.38–7.26 (m, 3H), 1.69 (s, 3H); FABMS: m/z 193 [M+Na]+.
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Phenylmethylene-1,1-dihydroperoxide (2l) [33]. H-NMR (200 MHz, CDCl3): 9.57 (br s, 2H),
7.42–7.28 (m, 5H), 6.24 (s, 1H); FABMS: m/z 179 [M+Na]+.
(4-Methylphenyl)methylene-1,1-dihydroperoxide (2m) [41]. 1H-NMR (200 MHz, CDCl3): 9.71 (br s,
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2H), 7.30 (d, J = 8 Hz, 2H), 7.15 (d, J = 8 Hz, 2H), 6.28 (s,1H), 2.32 (s, 3H); C-NMR (50 MHz,
CDCl3): 139.5, 129.4, 129.0, 126.7, 109.8, 21.1; FABMS: m/z 193 [M+Na]+.
(4-Chlorophenyl)methylene-1,1-dihydroperoxide (2n) [32]. 1H-NMR (200 MHz, CDCl3): 9.94 (br s,
2H), 7.85–7.34 (m, 4H), 6.26 (s, 1H); 13C-NMR (50 MHz, CDCl3): 139.6, 129.4, 129.0, 126.8, 10.02;
FABMS: m/z 213 [M+Na]+.
(4-Cyanophenyl)methylene-1,1-dihydroperoxide (2p). White solid; m.p. 107–110 ºC; IR (KBr): 3,414,
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2,916, 2,235, 1,611, 1,405, 1,333, 1,243, 1,199, 1,122, 1,083, 977, 824 cm-1; H-NMR (200 MHz,
CDCl3): 10.08 (s, 2H), 8.04–7.78 (m, 4H), 7.24 (s, 1H); 13C-NMR (50 MHz, CDCl3): 139.3, 129.4,
128.0, 126.1, 117.0, 112.1; FABMS: m/z 204 [M+Na]+; Anal. Calcd for C8H7NO4: C, 53.04; H, 3.86;
N, 7.73. Found: C, 53.15; H, 3.98; N, 7.78.
Octane-1,1-hydroxyhydroperoxide (4q) [42]. Colorless oil; IR (KBr): 3,374, 3,028, 2,931, 2,863,
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1,496, 1,454, 1,357, 1,242, 1,078, 1,030, 924, 748, 699 cm-1; H-NMR (200 MHz, CDCl3): 8.20 (br
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s, 1H), 7.00 (br s, 1H), 4.90 (t, J = 7 Hz, 1H), 2.10–0.70 (m, 15H); C-NMR (50 MHz, CDCl3):
101.2, 32.6, 30.0, 28.5, 24.0, 20.1, 14.0; FABMS: m/z 185 [M+Na]+.
3-Phenylpropane-1,1-hydroxyhydroperoxide (4r) [42]. Colorless oil; IR (KBr): 3384, 3062, 3027,
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2902, 2861, 1496, 1457, 1376, 1242, 1079, 1031, 923, 747, 700 cm-1; H NMR (200 MHz, CDCl3):
9.78 (br s, 1H), 8.65 (br s, 1H), 7.60–7.00 (m, 5H), 5.10 (t, J = 7 Hz, 1H), 2.60 (t, J = 8 Hz, 2H),
2.15–1.60 (m, 2H); 13C NMR (50 MHz, CDCl3): 141.5, 127.5, 125.0, 100.0, 32.2, 28.5; FABMS: m/z
191 [M+Na]+.
4. Conclusions
In summary, a new efficient homogeneous catalyst SrCl2·6H2O has been shown to promote the
synthesis of gem-dihydroperoxides from aliphatic and aromatic ketones and aldehydes using aqueous
H2O2 (30%) in acetonitrile at room temperature. The attractive features of this new approach are the
readily available and non-expensive catalyst, high yields of the products, mild reaction conditions and
the operational simplicity of the procedure.