March 2005
Photochemistry of 4- and 5- Phenyl Substituted Isoxazoles
281
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[26] Irradiation of 4-4d in methanol was accompanied by signifi-
cant H/D exchange with the solvent.
3-(trifluoromethyl)isoxazole (16) (0.0495 g, 0.232 mmol, 63%
recovery). The band at Rf = 0.57 gave 5-phenyl-2-(trifluo-
romethyl)oxazole (17) ( 0.0031g, 0.015 mmol, 11% yield) as a
1
yellow oil (lit. [48] mp 2-4 ºC); H-NMR (deuteriochloroform):
13
δ 7.44 (S 1H), 7.45 (m, 3H); 7.68 (m, 2H); C-NMR (deuteri-
ochloroform): δ (DEPT 135) 153.9(+), 150.0(0), 122.3(+),
129.9(+), 129.1(+), 126.2(0), 124.9(+), 122.3(+), 115.2(q,
J=270.3Hz) (0); MS mz(%), 213(100), 165(47), 105(36), 89(15),
77(33), 51(17). The band at Rf = 0.23 gave a mixture of (E)- and
(Z)-2-methoxy-2-(trifluoromethyl)-3-benzoylaziridine (18a and
1
18b) (0.0249g, 0.10 mmol, 72.5% yield); H-NMR (deuteri-
ochloroform) δ 2.7 (br. d, J= 9.0 Hz, 1H), 2.8 (br. s, 1H), 3.5(s,
3H), 3.6 (s, 3H), 3.6 (d, J= 9.0 Hz, IH), 3.8 (d, J=8.8 Hz, IH), 7.5
13
(m, 4H), 7.6 (m, 2H), 7.9 (m, 4H);
CNMR (deuteriochloro-
form) δ 190.5, 190.2, 135.1, 134.9, 129.5, 129.4, 129.1, 128.9,
123.2, 73.3, 55.2, 46.4, 43.8; MS m/z (%) 245(1), 213(12),
110(12), 105 (100), 77(38), 69(10).
Preparative-scale Irradiation of 5-Phenyl-3-(trifuloromethyl)-
isoxazole (16) in Acetonitrile.
-2
A solution of 16 (0.0156 g, 7.3 x 10 mmole) in acetonnitrile
[27]
An N-methyl substituted product analogous to 20 was
(5.0 ml) was placed in a quartz tube, sealed with a rubber septum,
purged with nitrogen for 15 minutes, and irradiated for 180 min-
utes. After removal of the solvent at reduced pressure the orange
residual oil (0.014 g) was subjected to column chromatography
(silcia gel). The column was eluted with hexane:dichloromethane,
2:1 (3.0 ml), and hexane:dichloromethane, 1:1 (25.0 ml). Thirteen
fractions (2.0 ml) were collected. Fractions 7-11 were combined
and concentrated to yield 5-phenyl-2-(trifluoromethyl)oxazole
(17) as a yellow oil (0.0094 g, 60% yield).
observed by photolysis of 3-methyl-5-phenylisoxazole in methanol sol-
vent. See reference [23].
[28] See A. Hassner, in Azides and Nitrenes. Reactivity and
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Heterocyclic Compounds, O. Buchardt, ed., John Wiley and Sons, New
York, 1976.
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