SHORT PAPER
Preparation, Alkylation, and Olefination Reaction of 5-Phosphonomethyl-3-methylisoxazole
2029
1H NMR (300 MHz, CDCl3): d = 2.29 (s, 3H, CH3), 6.08 (s, 1H,
CH), 6.90 (d, 1H, J = 16.5 Hz, CHCH), 7.28 (d, 1H, J = 16.5 Hz,
CHCH), 7.30-7.50 (m, 5H, C6H5).
1H NMR (300 MHz, CDCl3): d = 2.21 (s, 3H, CH3), 3.97 (s, 2H,
CH2), 5.89 (s, 1H, CH), 7.20-7.33 (m, 9H, C6H4 and C6H5), 7.55 (s,
1H, CH).
NOE data: 6.90 (6.08, 3 %; 7.28, 0.5 %; 7.47-7.50, 11.0 %)
13C NMR (75 MHz, CDCl3): d = 11.4, 102.4, 111.1, 111.9, 112.0,
121.4, 143.4, 151.7, 160.1, 167.8.
13C NMR (75 MHz, CDCl3): d = 11.4, 34.6, 102.2, 126.2, 126.6,
127.8, 128.7, 128.8, 130.1, 131.4, 134.0, 134.1, 138.2, 160.2, 170.3.
NOE data: 3.97 (5.89, 8.5 %; 7.20-7.33, 22.5 %; 7.55, 1.7 %).
(E)-5-[2-(2-Furyl)ethenyl]-3-methylisoxazole (3b)
Mp 41°C.
1H NMR (300 MHz, CDCl3): d = 2.27 (s, 3H, CH3), 6.03 (s, 1H,
CH), 6.42 (dd, 1H, J = 3.3, 1.7 Hz, CHCHCH), 6.46 (d, 1H, J = 3.3
Hz, CHCH), 6.78 (d, 1H, J = 16.2 Hz, CHCH), 7.03 (d, 1H, J = 16.2
Hz, CHCH), 7.41 (d, 1H, J = 1.7 Hz, CHCH).
HRMS: m/z Calcd for C19H16ClNO 309.0920, found 309.0898.
(Z)-5-[1-Benzyl-2-(4-chlorophenyl)ethenyl]-3-methylisoxazole
(3f-Z)
1H NMR (300 MHz, CDCl3): d = 2.17 (s, 3H, CH3), 3.82 (s, 2H,
CH2), 5.64 (s, 1H, CH), 6.60 (s, 1H, CH), 7.05-7.08 (m, 2/5 x C6H5),
7.18-7.29 (m, 7H, 3/5 x C6H5 and C6H4).
NOE data: 6.78 (6.03, 3.2 %; 7.03, 0 %; 7.41, 0.1 %).
NOE data: 3.82 (5.64, 2.1 %; 6.60, 10.0 %; 7.20-7.29, 10.1 %).
13C NMR (75 MHz, CDCl3): d = 11.4, 102.4, 111.1, 111.9, 112.0,
121.4, 143.4, 151.7, 160.1, 167.8.
13C NMR (75 MHz, CDCl3): d = 11.4, 42.4, 104.2, 126.7, 128.5,
128.6, 128.8, 128.9, 129.9, 132.7, 133.5, 134.9, 138.1, 159.6, 168.5.
(E)-3-Methyl-5-pent-1-enylisoxazole (3c)
1H NMR (300 MHz, CDCl3): d = 0.92 (t, 3H, J = 7.4 HzCH2CH3),
1.47 (sextet, 2H, J = 7.4 Hz, CH2CH2CH3), 2.13-2.21 (m, 2H,
CHCH2CH2), 2.24 (s, 3H, CH3), 5.88 (s, 1H, CH), 6.23 (dt, 1H, J =
16.1, 1.4 Hz, CHCH), 6.46 (dt, 1H, J = 16.1, 7.0 Hz, CHCHCH2).
References
(1) a) Lang, S. A.; Lin, Y.-i In Comprehensive Heterocyclic
Chemistry; Katritzky, A. R., Ed.; Pergamon: Oxford, 1984; p
12.
NOE data: 6.23 (5.88, 2.4 %; 6.46, 0 %).
13C NMR (75 MHz, CDCl3): d = 11.4, 13.6, 21.8, 34.9, 100.5, 115.9,
138.2, 159.8, 168.4.
b) Baraldi, P. G.; Barco, A.; Benetti, S.; Pollini, G. P.; Simoni,
D. Synthesis 1987, 857.
c) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates
in Organic Synthesis; VCH: New York, 1988.
d) Eicher, T.; Hauptmann, S. The Chemistry of Heterocycles;
Thieme: Stuttgart, 1995.
HRMS: m/z Calcd for C9H13NO 151.0997, found 151.0992.
(E)-3-Methyl-5-(1-methyl-2-phenylethenyl)isoxazole (3d)
Mp 43°C.
1H NMR (300 MHz, CDCl3): d = 2.20 (s, 3H, CH3), 2.30 (s, 3H,
CH3), 6.10 (s, 1H, CH), 7.24-7.38 (m, 6H, CHC6H5).
(2) Maryanoff, B. E.; Reitz, A. B. Chem. Rev. 1989, 89, 863.
(3) Crimmin, M. J.; O’Hanlon, P. J.; Rogers, N. H.; Walker, G. J.
Chem. Soc., Perkin Trans. 1 1989, 2047.
(4) Tsuge, O.; Kanemasa, S.; Suga, H. Chem. Lett. 1987, 323.
(5) Tsuge, O.; Kanemasa, S.; Suga, H.; Nakagawa, N. Bull. Chem.
Soc. Jpn. 1987, 60, 2463.
(6) Mukaiyama, T.; Hoshino, T. J. Am. Chem. Soc. 1960, 82,
5339.
NOE data: 2.20 (6.10, 6.2 %; 7.36-7.38, 6.7 %).
13C NMR (75 MHz, CDCl3): d = 11.5, 15.3, 101.0, 123.8, 127.6,
128.3, 129.4, 130.6, 136.3, 160.1, 171.6.
HRMS: m/z Calcd for C13H13NO 199.0997, found 199.0997.
(7) Kashima, C.; Yamamoto, Y.; Tsuda, Y. Heterocycles 1977, 6,
805.
(E)-3-Methyl-5-[2-phenyl-1-(prop-2-enyl)ethenyl]isoxazole (3e)
1H NMR (300 MHz, CDCl3): d = 2.29 (s, 3H, CH3), 3.32-3.35 (m,
2H, CH2CH), 5.12-5.19 (m, 2H, CHCH2), 5.93-6.04 (m, 1H,
CH2CHCH2), 6.08 (s, 1H, CH), 7.29-7.38 (m, 5H, C6H5), 7.44 (s,
1H, CH).
(8) The diallylated side product has both allyl groups at the 5-
methyl group of 1. The use of phenylselenenyl bromide gave
two kinds of diphenylselenenylated side products. One of
which involved both of the phenylselenenyl groups at the 5-
methyl position, and the other having one phenylselenenyl
group at the 5-methyl position and one at the 4-position of the
isoxazole ring.
(9) Flynn, D. L.; Belliotti, T. R.; Boctor, A. M.; Connor, D. T.;
Kostlan, C. R.; Nies, D. E.; Ortwine, D. F.; Schrier, D. J.;
Sircar, J. C. J. Med. Chem. 1991, 34, 518.
NOE data: 3.32-3.35 (5.93-6.04, 7.1 %; 6.08, 5.6 %; 7.35-7.38, 7.5
%).
13C NMR (75 MHz, CDCl3): d = 11.5, 33.1, 101.5, 116.7, 125.5,
128.0, 128.4, 129.0, 132.1, 135.0, 135.9, 160.1, 170.8.
HRMS: m/z Calcd for C15H15NO 225.1154, found 225.1154.
(E)-5-[1-Benzyl-2-(4-chlorophenyl)ethenyl]-3-methylisoxazole
(3f-E)
Article Identifier:
Mp 68-69°C.
1437-210X,E;1999,0,12,2027,2029,ftx,en;F04499SS.pdf
Synthesis 1999, No. 12, 2027–2029 ISSN 0039-7881 © Thieme Stuttgart · New York