2074 J . Org. Chem., Vol. 61, No. 6, 1996
Ramon et al.
Et3B/O2 In itia tin g System . A 1 M solution of triethylbo-
rane in hexane (1 mL) was added dropwise, directly in a
solution of peroxyketal (10 mmol) and iodide or bromide (in
the case of 3n ) precursor (10 mmol) in benzene (15 mL). The
reaction was monitored by GC by following the disappearance
of the peroxyketal. If peroxyketal remained after the addition
of 1 mL of triethylborane/hexane solution, the same portion
of initiator was added to the medium until the complete
disappearance of the peroxy derivative. The solvent was
evaporated under vacuum and the epoxide was isolated by
bulb-to-bulb distillation under reduced pressure.
1.14 (t, J ) 6.9 Hz, 3H). 13C NMR δ 170.0, 168.5, 62.8, 60.8,
61.7, 61.6, 58.7, 58.3, 37.7, 32.5, 14.3, 14.1, 13.8, 13.5, -2.3,
-2.5. Anal. Calcd for C8H13IO3: C, 33.81; H, 4.58; I, 44.72.
Found: C, 34.04; H, 4.85; I, 45.05.
Meth yl 4,5-ep oxy-4,5-d im eth ylh exa n oa te (3j): bp0.01
)
45 °C; 1H NMR δ 3.60 (s, 3H), 2.37 (t, J ) 8.5 Hz, 2H), 2.10-
1.69 (m, 2H), 1.25, 1.24 and 1.23 (s, 9H). 13C NMR δ 173.4,
63.4, 62.4, 51.5, 30.1, 29.8, 21.2, 20.7, 18.3. Anal. Calcd for
C9H16O3: C, 62.77; H, 9.36. Found: C, 62.37; H, 9.31.
4,5-ep oxy-4,5-d im eth ylh exa n en itr ile (3k ): bp0.2 ) 70 °C;
1H NMR δ 2.30 (t, J ) 8 Hz, 2H), 1.96-1.62 (m, 2H), 1.16,
1.15 and 1.14 (s, 9H). 13C NMR δ 119.4, 62.6, 62.5, 30.2, 21.0,
20.9, 18.0, 13.3. Anal. Calcd for C8H13NO3: C, 69.03; H, 9.41;
N, 10.07. Found: C, 69.31; H, 9.49; N, 10.33.
Products 3b, 3c, 3d , 3g, 3h , and 4a were previously
5
prepared by our group.4,
Eth yl 2,3-ep oxy-2-n on ylbu ta n oa te (3a ): bp0.1 ) 100 °C;
1H NMR δ 4.22-4.00 (m, 2H), 3.16 (q, J ) 5.4 Hz) and 2.97
(q, J ) 5.4 Hz, 1H), 2.18-0.80 (m, 25H); 13C NMR δ 171.0,
61.2, 61.1, 61.0, 58.3, 58.0, 35.9, 33.1, 31.8, 29.6, 29.4, 29.3,
29.2, 27.4, 25.1, 24.7, 22.6, 14.2, 14.0, 13.9, 13.8, 13.7, 13.5.
Anal. Calcd for C15H28O3: C, 70.27; H, 11.01. Found: C,
70.10; H, 11.14.
2,3-Ep oxy-5,5,6,6,7,7,8,8,9,9,10,10,10-tr id eca flu or o-2,3-
d im eth yld eca n e (3l): bp0.3 ) 70 °C; 1H NMR δ 2.33-1.81
(m, 2H), 1.15-0.9 (m, 9H). 13C NMR δ 133.1-110.8, 62.3, 59.7,
36.0 (t, J ) 20.8 Hz), 20.8, 20.5, 19.8. Anal. Calcd for
C12H11F13O: C, 34.47; H, 2.65; F, 59.06. Found: C, 34.67; H,
2.67; F, 59.73.
Met h yl 4,5-ep oxy-4-(et h oxyca r b on yl)-2-m et h ylh ex-
a n oa te (3e): bp0.1 ) 90 °C; 1H NMR δ 4.10-3.91 (m, 2H), 3.46
(s, 3H), 3.05 (q, J ) 5.4 Hz) and 2.99 (q, J ) 5.4 Hz, 1H), 2.62-
1.34 (m, 3H), 1.15 (d, J ) 5.4 Hz) and 1.14 (d, J ) 5.4 Hz,
6H), 1.08 (t, J ) 6.8 Hz) and 1.00 (t, J ) 6.8 Hz, 3H). 13C
NMR δ 176.0, 175.8, 170.7, 170.5, 61.4, 61.3, 59.3, 58.3, 57.7,
51.6, 51.5, 36.1, 36.0, 30.7, 30.4, 17.3, 16.9, 14.1, 13.9, 13.4,
13.3. Anal. Calcd for C11H18O5: C, 57.39; H, 7.83. Found:
C, 57.30; H, 7.71.
2,3-Ep oxy-6,6,6-tr iflu or o-2,3-d im eth ylh exa n e (3m ): bp1
) 50 °C; 1H NMR δ 2.05-1.73 (m, 2H), 1.59-1.32 (m, 2H),
1.02-0.85 (m, 9H). 13C NMR δ 126.5 (q, J ) 275.8 Hz), 62.3,
62.1, 29.5 (q, J ) 29.1 Hz), 26.7, 20.5, 20.1, 17.7. Anal. Calcd
for C8H13F3O: C, 52.74; H, 7.19; F, 31.28. Found: C, 52.47;
H, 7.27; F, 30.50.
5,5,5-Tr ich lor o-2,3-ep oxy-2,3-d im eth ylp en ta n e (3n ): bp1
) 60 °C; 1H NMR 2.81-2.62 (m, 2H), 1.28 (s, 3H), 1.00 (s, 3H),
0.95 (s, 3H). 13C NMR 96.0, 62.5, 61.8, 58.4, 21.6, 21.4, 19.4.
Anal. Calcd for C8H13Cl3O: C, 41.50; H, 5.66; Cl, 45.93.
Found: C, 41.22; H, 5.39; Cl, 46.25.
Eth yl 2,3-ep oxy-2-(3-oxobu tyl)bu ta n oa te (3f): bp0.1
)
85 °C; 1H NMR δ 4.07-3.89 (m, 2H), 3.08 (q, J ) 5.5 Hz) and
2.89 (q, J ) 5.5Hz, 1H), 2.49-2.37 (m, 2H), 2.20-2.00 and
1.86-1.55 (m, 2H), 1.95 (s, 3H), 1.15 (d, J ) 5.5 Hz, 3H), 1.09
(t, J ) 7.1 Hz, 3H). 13C NMR δ 206.9, 170.5, 62.0, 59.9, 61.4,
61.3, 58.9, 58.6, 38.9, 38.2, 29.6, 26.7, 21.2, 14.1, 13.9, 13.5,
13.4. Anal. Calcd for C10H16O4: C, 59.97; H, 8.07. Found:
C, 59.87; H, 7.97.
Ack n ow led gm en t. The authors acknowledge Akzo
Nobel for a fellowship to one of us (F.R.), Dr. A. J . De
J ongh, Dr. P. Hope, Dr. J . Meijer (Akzo Nobel Deventer),
and Dr. L. Vertommen (Akzo Nobel Ahrnem) for very
fruitful discussions during the course of this study, and
Dr. D. Colombani for preliminary experiments.
Eth yl 2,3-ep oxy-2-(2-iod oeth yl)bu ta n oa te (3i): bp0.01
)
100 °C; 1H NMR δ 4.15-3.96 (m, 2H), 3.26-2.98 (m, 3H),
2.61-2.46 and 2.09-1.95 (m, 2H), 1.24 (d, J ) 5.4 Hz, 3H),
J O951783N