L. Cointeaux et al. / Il Farmaco 57 (2002) 457–462
461
1.85 (qt, 2H, J=7.3 Hz), 1.58–1.39 (m, 2H), 1.27 (s,
3H), 1.13 (d, 1H, J=8.4 Hz), 0.82 (s, 3H). 13C NMR
(CDCl3): l 147.7, 116.3, 45.8, 40.9, 38.0, 35.9, 33.8,
32.6, 31.7, 31.3, 26.4, 25.7, 21.2. [h]D= −22.1 (c 1.49,
CH2Cl2).
2H), 1.38 (s, 6H), 1.28 (s, 3H), 1.12 (d, 1H, J=8.5 Hz),
0.81 (s, 3H). 13C NMR (CDCl3): l 147.3, 116.1, 104.2,
74.5, 48.8, 45.6, 40.7, 37.8, 33.1, 31.5, 31.1, 26.2, 25.4,
22.6, 21.0. [h]D= −1.9 (c 1.53, CHCl3).
3.1.3. Hydroperoxides 5b–k
Hydroperoxides 5b–k were synthesized following the
Dussault method [8] from, respectively perketals 4b–k.
3.1.2. Preparation of perketals 4a–k
Perketals 4a–k were synthesized following the Dus-
sault procedure [8] from corresponding bromides 3a–k.
1
3.1.3.1. Heptyl hydroperoxide (5b). H NMR (C6D6): l
1
3.1.2.1. 2-Methoxyprop-2-yl-hex-1-yl-peroxide (4a). H
8.10 (bs, 1H), 3.95 (t, 2H, J=6.2 Hz), 1.75–1.05 (m,
10H), 0.96 (t, 3H, J=7.7 Hz). 13C NMR (C6D6): l
76.8, 32.0, 29.4, 27.9, 26.2, 22.9, 14.2.
NMR (CDCl3): l 3.94 (t, 2H, J=6.7 Hz), 3.24 (s, 3H),
1.65–1.4 (m, 2H), 1.32 (s, 6H), 1.3–1.1 (m, 6H), 0.82 (t,
3H, J=6.3 Hz). 13C NMR (CDCl3): l 104.4, 74.9, 48.9,
31.6, 27.7, 25.7, 22.6, 13.8.
3.1.3.2. Octyl hydroperoxide (5c). Spectral data were
identical to those previously reported [11].
3.1.2.2. 2-Methoxyprop-2-yl-hept-1-yl-peroxide (4b).
Spectral data were identical to those previously re-
ported [7].
3.1.3.3. Decyl hydroperoxide (5d), dodecyl hydroperoxide
(5e), hexadecyl hydroperoxide (5f). Spectral data were
identical to those previously reported [8].
1
3.1.2.3. 2-Methoxyprop-2-yl-oct-1-yl-peroxide (4c). H
NMR (CDCl3): l 3.93 (t, 2H, J=6.6 Hz), 3.29 (s, 3H),
1.7–1.4 (m, 2H), 1.31 (s, 6H), 1.25–1.1 (m, 10H), 0.81
(t, 3H, J=6.7 Hz). 13C NMR (CDCl3): l 104.1, 74.7,
48.6, 31.6, 29.2, 29.0, 27.7, 25.9, 22.4, 13.7.
3.1.3.4. Octadecyl hydroperoxide (5g). 1H NMR
(CDCl3): l 7.08 (bs, 1H), 3.95 (t, 2H, J=6.6 Hz),
1.70–1.05 (m, 32H), 0.97 (t, 3H, J=5.5 Hz). 13C NMR
(CDCl3): l 76.7, 32.3, 30.1, 29.8, 28.0, 26.3, 23.0, 14.3.
3.1.2.4. 2-Methoxyprop-2-yl-dec-1-yl-peroxide (4d), 2-
1
methoxyprop-2-yl-dodec-1-yl-peroxide
(4e),
2-
3.1.3.5. 3-Phenoxypropyl hydroperoxide (5h). H NMR
methoxyprop-2-yl-hexadec-1-yl-peroxide (4f). Spectral
data were identical to those previously reported [8].
(C6D6): l 9.01–8.08 (bs, 1H), 7.10 (t, 2H, J=8.0 Hz),
6.81 (dt, 3H, J=8.1, 1.2 Hz), 3.94 (dt, 2H, J=6.2, 1.75
Hz), 3.68 (t, 2H, J=6.2 Hz), 1.83 (qt, 2H, J=6.2 Hz).
13C NMR (C6D6): l 159.2, 129.7, 121.1, 114.9, 73.6,
64.7, 28.0.
3.1.2.5. 2-Methoxyprop-2-yl octadec-1-yl-peroxide (4g).
1H NMR (CDCl3): l 3.95 (t, 2H, J=6.4 Hz), 3.30 (s,
3H), 1.75–1.5 (m, 2H), 1.38 (s, 6H), 1.3–1.2 (m, 30H),
0.87 (t, 3H, J=6.1 Hz). 13C NMR (CDCl3): l 94.1,
75.2, 49.1, 31.9, 29.4, 27.8, 26.1, 22.7, 14.1.
3.1.3.6. 2-Phenylethyl hydroperoxide (5i). 1H NMR
(C6D6): l 9.45 (bs, 1H), 7.42–7.07 (m, 5H), 4.20 (t, 2H,
J=6.9 Hz), 2.96 (t, 2H, J=6.9 Hz). 13C NMR (C6D6):
l 138.6, 129.2, 128.6, 126.5, 77.4, 34.4.
3.1.2.6. 2-Methoxyprop-2-yl-3-phenoxyprop-1-yl-per-
oxide (4h). Spectral data were identical to those pre-
viously reported [7].
3.1.3.7. 3-Cyanopropyl hydroperoxide (5j). 1H NMR
(CDCl3): l 9.2 (bs, 1H), 3.66 (t, 2H, J=5.7 Hz), 1.76
(t, 2H, J=7.3 Hz), 1.41 (qt, 2H, J=5.7 Hz). 13C NMR
(CDCl3): l 119.6, 74.0, 23.8, 13.5.
3.1.2.7. 2-Methoxyprop-2-yl-2-phenyleth-1-yl-peroxide
(4i). Spectral data were identical to those previously
reported [7].
3.1.3.8. 3-[(1S)-6,6-dimethyl-bicyclo[3.1.1]hept-2-en-2-
yl]-propyl-hydroperoxide (5k). H NMR (C6D6): l 7.87
1
3.1.2.8. 2-Methoxyprop-2-yl-3-cyano-prop-1-yl-pero-
xide (4j). Spectral data were identical to those previ-
ously reported [7].
(bs, 1H), 5.23–5.11 (m, 1H), 3.83 (t, 2H, J=6.4 Hz),
2.29 (dt, 1H, J=8.4, 5.7 Hz), 2.23–2.12 (m, 2H),
2.09–1.84 (m, 4H), 1.71–1.45 (m, 2H), 1.23 (s, 3H),
1.18 (d, 1H, J=8.4 Hz), 0.86 (s, 3H). 13C NMR
(C6D6): l 148.0, 116.7, 76.8, 46.1, 41.3, 38.1, 33.4, 32.0,
31.6, 26.5, 25.7, 21.5.
3.1.2.9. 2-Methoxyprop-2-yl-3-[(1S)-6,6-dimethyl-bicy-
clo[3.1.1]hept-2-en-2-yl]-prop-1-yl-peroxide (4k). 1H
NMR (CDCl3): l 5.27–5.10 (m, 1H), 3.99 (t, 2H,
J=6.6 Hz), 3.30 (s, 3H), 2.33 (dt, 1H, J=8.5, 5.7 Hz),
2.26–2.14 (m, 2H), 2.14–1.88 (m, 4H), 1.82–1.51 (m,
Hydroperoxides 5l–m were obtained following litera-
ture [8].