K. Michel, R. Fröhlich, E.-U. Würthwein
[(CH2)2Cq], 57.9 (CH3CHCH), 65.7 (CHN), 114.2, 118.4 (CHarom.), 2-methylbutyrate (6f) (0.66 mL, 5.00 mmol). The crude product
FULL PAPER
131.7, 155.9 (ipso-C), 170.1 (C=O) ppm. IR (film): ν = 2928 (vs), was purified by column chromatography. Yellow oil, 0.41 g
˜
2855 (vs), 1751 (s), 1585 (m), 1514 (vs), 1464 (vs), 1454 (vs), 1379 (1.47 mmol; 74%), Rf (TLC) = 0.47 (pentane/TBME = 1:2), dr(GC)
1
3
(vs), 1362 (s), 1296 (s), 1248 (s), 1207 (m), 1180 (s), 1148 (s), 1128 = 2.0:7.8:17.6:67.6. H NMR (400 MHz, CDCl3): δ = 0.97 (t, J =
3
(s), 1113 (m), 1101 (m), 1080 (m), 1055 (m), 1034 (s), 1007 (m), 970 7.5 Hz, 3 H, CH3CH2), 1.34 (s, 3 H, CH3Cq), 1.40 (d, J = 5.2 Hz,
(m), 949 (m), 928 (m), 901 (w), 868 (s), 831 (s), 804 (m), 764 (m),
752 (w), 735 (m), 721 (m), 598 (m), 523 (m), 478 (s), 465 (vs), 451
3 H, CH3CH), 1.73 (q, 3J = 7.4 Hz, 2 H, CH2), 2.82 (dd, 3J1 = 7.8,
3J2 = 2.3 Hz, 1 H, CH3CHCH), 2.92 (dq, J1 = 5.2, J2 = 2.3 Hz,
3
3
(vs), 442 (vs), 432 (vs), 415 (m), 407 (m) cm–1. ESI-EM [M + 1 H, CH3CH), 3.27 (d, 3J = 7.7 Hz, 1 H, CqCH), 3.78 (s, 3 H,
Na]+ calcd. 324.1570; found 324.1575. C18H23NO3 (301.38 g/mol):
calcd. C 71.73, H 7.69, N 4.65; found C 71.54, H 7.76, N 4.61.
OCH3), 6.85–6.92 (m, 2 H, CHarom.), 7.49–7.58 (m, 2 H, CHarom.)
ppm. 13C NMR (100 MHz, CDCl3): δ = 8.8 (CH3CH2), 15.1
(CH3Cq), 17.2 (CH3CH), 28.7 (CH2), 52.2 (CH3CH), 55.4 (OCH3),
56.9 (Cq), 58.1 (CH3CHCH), 63.2 (CqCH), 114.3, 118.2 (CHarom.),
2-(4-Methoxy-phenyl)-3-(3-propyloxiranyl)-2-azaspiro[3.5]nonan-1-
one (7m): From (4-methoxyphenyl)[1-(3-propyloxiranyl)methyl-
idene]amine (1h) (0.66 g, 3.00 mmol), LDA (7.80 mmol) and methyl
cyclohexanecarboxylate (6c) (1.08 mL, 7.50 mmol). The crude
product was purified by column chromatography. Pale yellow oil,
0.62 g (1.86 mmol; 62%), Rf (TLC) = 0.45 (pentane/TBME = 2:1),
131.4, 156.0 (ipso-C), 169.8 (C=O) ppm. IR (film): ν = 2963 (vs),
˜
2932 (vs), 2874 (vs), 2856 (vs), 1746 (vs), 1585 (w), 1514 (vs), 1462
(vs), 1377 (vs), 1298 (s), 1246 (vs), 1178 (m), 1146 (m), 1109 (m),
1078 (m), 1059 (m), 1032 (m), 1003 (m), 949 (m), 893 (w), 864 (m),
833 (s), 762 (m), 725 (m), 592 (w), 476 (vs), 463 (vs), 455 (vs), 442
(vs), 434 (vs), 415 (m), 405 (m) cm–1. ESI-EM [M + Na]+ calcd.
298.1414; found 298.1414. C16H21NO3 (275.34 g/mol): calcd. C
69.79, H 7.69, N 5.09; found C 69.63, H 7.68, N 4.78.
1
dr(GC) = 0.5:0.4:9.6:88.5. H NMR (600 MHz, CDCl3): δ = 1.00
3
(t, J = 7.30 Hz, 3 H, CH3CH), 1.40–1.81 (m, 10 H, CH2), 1.82–
3
1.95 (m, 3 H, CH2), 1.96–2.03 (m, 1 H, CH2), 2.88 (dd, J1 = 8.1,
3J2 = 2.0 Hz, 1 H, CqCHCH), 2.89–2.93 (m, 1 H, CH2CH), 3.16
3
3-Ethyl-1-(4-methoxyphenyl)-3-methyl-4-(3-propyloxiranyl)azetidin-
2-one (7p): From (4-methoxyphenyl)-[1-(3-propyloxiranyl)methyl-
idene]amine (1h) (0.66 g, 3.00 mmol), LDA (7.80 mmol) and methyl
2-methylbutyrate (6f) (0.98 mL, 7.50 mmol). The crude product
was purified by column chromatography. Yellow oil, 0.58 g
(1.91 mmol; 64%), Rf (TLC) = 0.35 (pentane/TBME = 2:1), dr(1H
(d, J = 8.1 Hz, 1 H, CqCH), 3.78 (s, 3 H, OCH3), 6.83–6.88 (m 2
H, CHarom.), 7.51–7.56 (m, 2 H, CHarom.) ppm. 13C NMR
(100 MHz, CDCl3): δ = 13.9 (CH3CH2), 19.3, 23.1, 23.4, 25.3, 27.9,
33.1, 33.6 (CH2), 55.4 (OCH3), 56.4 (CH2CH), 56.7 (CqCHCH),
57.4 (Cq), 65.8 (CqCH), 114.2, 118.4 (CHarom.), 131.8, 155.9 (ipso-
C), 170.2 (C=O) ppm. IR (film): ν = 2957 (vs), 2932 (vs), 2856
˜
1
NMR) = 0.05(C):0.42(B):1.00(A). H NMR (600 MHz, CDCl3): δ
(vs), 1751 (s), 1585 (w), 1514 (s), 1462 (vs), 1379 (s), 1362 (s), 1342
(m), 1298 (s), 1248 (s), 1207 (m), 1178 (m), 1148 (m), 1132 (m),
1113 (m), 1082 (m), 1036 (m), 970 (w), 908 (m), 883 (w), 860 (w),
831 (m), 804 (m), 735 (w), 523 (m), 476 (s), 463 (vs), 451 (vs), 442
(vs), 417 (m), 407 (m) cm–1. ESI-EM [M + Na]+ calcd. 352.1889;
found 352.1878. C20H28NO3 (329.43 g/mol): calcd. C 72.92, H 8.26,
N 4.25; found C 72.81, H 8.31, N 4.23.
= 0.96–1.01, 1.10–1.12 (m, 6 H, CH3, A/B/C), 1.34 (s, 3 H, CH3Cq,
A), 1.37 (s, 3 H, CH3Cq, B), 1.39 (s, 3 H, CH3Cq, C), 1.42–1.75
(m, 6 H, CH2, A/B/C), 1.90–1.96 (m, CH3CH2Cq, C), 2.84–2.87
(m, 2 H, CH2CHCH, A), 2.89–2.91 (m, 2 H, CH2CHCH, B), 3.09
(dd, 3J1 = 8.3, 3J2 = 4.4 Hz, 1 H, CHCHCq, C), 3.12–3.16 (m, 1
H, CH2CH), 3.20 (d, 3J = 7.8 Hz, 1 H, CqCH, B), 3.27 (d, 3J =
3
7.6 Hz, 1 H, CqCH, A), 3.47 (d, J = 8.3 Hz, 1 H, CqCH, C), 3.78
1-(4-Methoxy-phenyl)-3-methyl-4-(3-methyloxiranyl)azetidin-2-one
(7n): From (4-methoxyphenyl)[1-(3-methyloxiranyl)methylidene]-
amine (1d) (0.46 g, 2.40 mmol), LDA (7.80 mmol) and methyl pro-
pionate (6d) (0.72 mL, 7.50 mmol). The crude product was purified
by column chromatography. Pale yellow oil, 0.06 g (0.24 mmol;
10 %), Rf (TLC) = 0.35 (pentane/TBME = 1:4), dr(GC) =
(s, 1 H, OCH3, A/B/C), 6.87–6.90 (m, 2 H, CHarom., A/B/C), 7.51–
7.58 (m, 2 H, CHarom., A/B/C) ppm. 13C NMR (150 MHz, CDCl3):
δ = 8.9, 8.9, 9.3 (CH3CH2Cq, A/B/C), 13.9, 13.9, 13.9 (CH3CH2,
A/B/C), 15.2 (CH3Cq, A/B/C), 19.2, 19.2, 19.2, 20.3, 24.8, 25.2,
28.7, 30.6, 33.6 (CH2, A/B/C), 55.4, 55.5 (OCH3, A/B/C), 56.0
(CH2CH, B/C), 56.2 (CH2CH, A), 56.5, 56.6, 56.8 (CH, Cq, B/C),
56.9 (Cq, A), 57.0 (CH2CHCH, A), 63.4 (CqCH, A), 63.9 (CqCH,
1
28(A):23(B):3:3:1. H NMR (400 MHz, CDCl3): δ = 1.34–1.41 (m,
12 H, CH3CHCHCHN, CH3CHC=O, A/B), 2.83–2.87 (m, 2 H,
CH3CHCHCHN, A/B), 2.93–3.01 (m, 2 H, CH3CHCHCHN, A/
1 C), 66.5 (CqCH, B), 114.3, 114.3, 118.3, 118.4, 118.4 (CHarom.
,
A/B/C), 131.5, 131.7, 156.0, 156.0 (ipso-C, A/B/C), 169.9, 170.0
B), 3.15–3.21 (m, 1 H, CHC=O, B), 3.28 (dd, 3J1 = 7.5, 3J2
=
(C=O, A/B/C) ppm. IR (film): ν = 3476 (w), 3080 (w), 2964 (vs),
˜
2.5 Hz, 1 H, CHN, B), 3.45–3.52 (m, 1 H, CHC=O, A), 3.57–3.60
(m, 1 H, CHN, A), 3.78 (s, 6 H, OCH3, A/B), 6.81–6.92 (m, 4 H,
CHarom., A/B), 7.46–7.56 (m, 4 H, CHarom., A/B) ppm. 13C NMR
(100 MHz, CDCl3): δ = 9.6 (CH3CHC=O, A), 12.8 (CH3CHC=O,
B), 17.1 (CH3CHCHCHN, A/B), 46.3 (CHC=O, A), 47.1
(CHC=O, B), 52.0, 52.1 (CH3CHCHCHN, A/B), 55.4 (OCH3, A/
B ) , 5 7 . 8 ( C H N, A ) , 5 7 . 9 ( C H 3 C H C H C H N, A ) , 5 9 . 0
(CH3CHCHCHN, B), 61.8 (CHN, B), 114.3, 114.3, 118.2, 118.3
(CHarom., A/B), 131.4, 131.5, 156.0 (ipso-C, A/B), 166.8, 167.1
2934 (vs), 2876 (s), 2837 (m), 1877 (vw), 1746 (vs), 1612 (w), 1585
(w), 1514 (vs), 1462 (vs), 1445 (s), 1393 (vs), 1369 (s), 1339 (m),
1298 (s), 1246 (vs), 1180 (s), 1146 (s), 1109 (s), 1084 (m), 1034 (s),
1005 (w), 934 (w), 907 (m), 833 (vs), 810 (m), 787 (w), 773 (w), 731
(w), 594 (w), 525 (m), 478 (vs), 457 (vs), 440 (vs), 417 (m), 411
(m) cm–1. ESI-EM [M + Na]+ calcd. 326.1727; found 326.1736.
C18H25NO3 (303.40 g/mol): calcd. C 71.26, H 8.31, N 4.62; found
C 71.22, H 8.62, N 4.56.
1-(2-Benzylphenyl)-3-ethyl-3-methyl-4-(3-propyloxiranyl)azetidin-2-
one (7q): From (2-benzylphenyl)[1-(3-propyloxiranyl)methylidene]-
amine (1g) (0.84 g, 3.00 mmol), LDA (7.80 mmol) and methyl 2-
methylbutyrate (6f) (0.98 mL, 7.50 mmol). The crude product was
purified by column chromatography. Yellow solid, 1.00 g
(2.75 mmol; 92%), m.p. 63 °C, Rf (TLC) = 0.42 (pentane/TBME =
3:1), dr(1H NMR) = 0.01:0.09(C):0.18(B):1.00(A). 1H NMR
(600 MHz, CDCl3): δ = 0.88–0.94 (m, 6 H, CH3, A), 0.97–1.01 (m,
6 H, CH3, B/C), 1.10–1.11 (m, 3 H, CH3Cq, A/B/C), 1.24–1.61 (m,
6 H, CH2, A/B/C), 1.97 (dd, 3J1 = 7.5, 3J2 = 2.3 Hz, 1 H,
(C=O, A/B) ppm. IR (film): ν = 2961 (vs), 2934 (vs), 2872 (vs),
˜
2853 (vs), 1757 (w), 1585 (vw), 1514 (m), 1462 (vs), 1377 (s), 1298
(m), 1248 (m), 1180 (w), 1151 (w), 1030 (w), 943 (vw), 866 (vw),
831 (w), 800 (vw), 721 (w), 471 (vs), 461 (vs), 451 (vs), 444 (vs),
434 (vs), 413 (s) cm–1. ESI-EM [M + Na]+ calcd. 270.1101; found
270.1099. C14H17NO3 (247.29 g/mol): calcd. C 68.00, H 6.93, N
5.66; found C 67.70, H 6.96, N 5.39.
3-Ethyl-1-(4-methoxyphenyl)-3-methyl-4-(3-methyloxiranyl)azetidin-
2-one (7o): From (4-methoxyphenyl)-[1-(3-methyloxiranyl)methyl-
idene]amine (1d) (0.38 g, 2.00 mmol), LDA (5.20 mmol) and methyl CH2CHCH, A), 2.10 (dd, 3J1 = 7.7, 3J2 = 2.3 Hz, 1 H, CH2CHCH,
5662
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Eur. J. Org. Chem. 2009, 5653–5665