Nov-Dec 2008
An Efficient Synthesis of 5-Benzoyloxazolines by Regio- and Stereo-controlled
1769
16923, 1652, 1527, 1346, 1240, 1064, 962, 751, 692 cm-1; H
nmr (deuteriochloroform): ꢀ 5.6 (d, 1H, J = 7.1 Hz), 5.8 (d, 1H, J
= 7.1 Hz), 7.5 (dd, 2H, J = 7.5, 7.7 Hz), 7.56-7.63 (m, 4H), 7.72
(d, 1H, J = 7.8 Hz), 7.75 (d, 1H, J = 7.7 Hz), 8.0 (dd, 2H, J =
1.3, 8.5 Hz), 8.1 (d, 2H, J = 7.1 Hz), 8.23-8.27 (m, 2H); 13C nmr
(CDCl3): ꢀ 74.0, 88.1, 128.6, 128.7,128.73, 128.82, 128.8,
128.9, 129.1, 129.5, 133.2, 134.1, 139.2, 148.0, 173.0, 195.0;
Anal. Calcd. for C22H16N2O4 (372.11): C, 70.98; H, 4.34; N,
7.52. found: 71.31; H, 4.26; N, 7.50.
144.0, 148.2, 166.0, 195.0; Anal. Calcd. for C24H18N2O4
)
398.13(: C, 72.30; H, 4.51; N, 7.01. found: C, 72.50; H, 4.47; N,
7.20.
1
trans--5-Benzoyl-4-(3-nitrophenyl)-2-((E)-2-phenylethenyl)
-2-oxazoline (4h). Yellow solid, mp 117-119 °C; ir (potassium
bromide): 3062, 2958, 2931, 1667, 1025, 1529, 1350, 1228, 975,
1
755, 666 cm-1; H nmr (deuteriochloroform): ꢀ 5.6 (d, 1H, J =
6.8 Hz), 5.7 (d, 1H, J = 6.8 Hz), 7.3 (d, 1H, J = 15.9 Hz), 7.4 (m,
2H), 7.5 (m, 5H), 7.56 (dd, 1H, J = 7.2, 7.8 Hz), 7.6 (dd, 1H, J =
7.2, 7.6 Hz), 7.66 (d, 1H, J = 15.9 Hz), 7.7 (d, 1H, J = 7.6 Hz),
trans-2-Benzoyl-1,3-di-(3-nitrobenzoyl)aziridine (2f).
White solid, mp 132-134 °C; ir (potassium bromide): 3089,
7.75 (d, 2H, J = 7.8 Hz), 7.8 (d, 1H, J = 8.2 Hz), 8.3 (s, 1H); 13
C
1
2925, 1701, 1672, 1527, 1348, 1224, 721, 682 cm-1; H nmr
nmr (deuteriochloroform): ꢀ 75.0, 79.0, 120.0, 121.0, 123.0,
126.0, 126.6, 128.6, 128.7, 128.8, 129.5, 133.0, 133.2, 134.0,
135.2, 137.0, 144.0, 148.2, 167.0, 198.0; Anal. Calcd. for
C24H18N2O4 ) 398.13(: C, 72.30, H; 4.51; N, 7.01. found: C,
72.15; H, 4.37; N, 7.25.
(deuteriochloroform): ꢀ 4.2 (d, 1H, J = 2.6 Hz), 4.6 (d, 1H, J =
2.6 Hz), 7.5 (dd, 2H, J = 7.87, 8.01 Hz), 7.6 (m, 3H), 7.89 (d,
2H, J = 7.7 Hz), 7.9 (dd, 1H, J = 8.1, 0.8 Hz), 8.2 (m, 1H), 8.3-
8.4 (m, 3H), 8.8 (dd, 1H, J = 1.8, 1.9 Hz); 13C nmr (deuterio-
chloroform): ꢀ 47.0, 49.0, 118.1, 123.2, 125.8, 126.1,126.9,
128.1, 128.7, 128.9, 129.5, 132.2, 133.1,135.2, 135.9, 137.2,
147.2, 148.1, 172.5, 197.1; Anal. Calcd. for C22H15N3O6 (417.1):
C, 63.33; H, 3.63; N, 10.06. found: C, 63.5; H, 3.51; N, 9.93.
trans-5-Benzoyl-2,4-di-(3-nitrophenyl)-2-oxazoline (4f).
Yellow solid, mp 106-108 °C; ir (potassium bromide): 3071,
2925, 1693, 1662, 1531, 1350, 750, 707, 682 cm-1; 1H nmr
(deuteriochloroform): ꢀ 5.75 (d, 1H, J = 7.2 Hz), 5.8 (d, 1H, J =
7.2 Hz), 7.5-7.7 (m, 3H), 7.7 (m, 3H), 8.0 (dd, 2H, J = 1.35, 8.5
Hz), 8.2 (m, 2H), 8.4 (dd, 2H, J = 2.0, 8.1 Hz), 8.9 (dd, 1H, J =
1.7, 1.8 Hz); 13C nmr (deuteriochloroform): ꢀ 74.2, 83.2, 117.1,
124.1, 125.5, 126.1,126.8, 128.1, 128.6, 128.9, 129.4, 132.4,
133.1, 135.2, 136.9, 137.4,147.2, 149.1, 172.5, 197.1; Anal.
Calcd. for C22H15N3O6 (417.1): C, 63.33; H, 3.63; N, 10.06.
found: C, 63.50; H, 3.72; N, 9.87.
trans-1-(2-Chlorobenzoyl)-2-benzoyl-3-phenylaziridine (2i).
White solid, mp 139-140 °C; ir (potassium bromide): 3060, 2901,
1
1688, 1649, 1595, 1488, 1265, 1070, 760, 707, 695 cm-1; H nmr
(deuteriochloroform): ꢀ 4.1 (d, 1H, J = 2.4 Hz), 4.4 (d, 1H, J = 2.4
Hz), 7.3 (d, 2H, J = 8.1 Hz), 7.4-7.45 (m, 7H), 7.6 (dd, 1H, J = 1.0,
7.4 Hz), 7.9 (d, 2H, J = 8.1), 8.0 (d, 2H, J = 8.7 Hz); 13C nmr
(deuteriochloroform): ꢀ 48.0, 49.2, 126.9, 128.7, 128.9, 129.2,
129.25, 129.35, 129.4, 130.2, 132.6, 134.5, 135.8, 136.5,
139.2,175.3, 191.9; Anal. Calcd. for C22H16ClNO2 (361.09): C,
73.08; H, 4.47; N, 3.87. found: C, 73.10; H, 4.35; N, 3.65.
trans-5-Benzoyl-2-(2-chlorophenyl)-4-phenyl-2-oxazoline
(4i). Yellow solid, mp 125-127 °C,: ir (potassium bromide):
3060, 2900, 1690, 1649, 1595, 1489, 1448, 1250, 1072, 968,
763, 707, 690 cm-1; 1H nmr (deuteriochloroform): ꢀ 5.5 (d, 1H, J
= 6.6 Hz), 5.77 (d, 1H, J = 6.6 Hz), 7.3 (d, 2H, J = 6.9 Hz), 7.35
(d, 1H, J = 6.2 Hz), 7.4 (d, 2H, J = 7.15 Hz), 7.47 (d, 2H, J = 8.5
Hz), 7.5 (dd, 2H, J = 6.7, 7.8 Hz), 7.6 (dd, 1H, J = 7.2, 7.4 Hz),
7.9 (d, 2H, J = 7.2), 8.0 (d, 2H, J = 6.8); 13C nmr (deuterio-
chloroform): ꢀ 74.2, 87.2, 125.8, 127.4, 128.7, 129.2, 29.3,
129.4, 129.5, 130.5, 134.4, 134.6, 138.6, 141.2, 163.4, 194.6;
Anal. Calcd. for C22H16ClNO2 (361.09): C, 73.08; H, 4.47: N,
3.87. found: C,73.12; H, 4.40; N, 3.77.
trans-2-Benzoyl-1-(2-furyl)-3-phenylaziridine (2g). White
solid, mp 119-122 °C; ir (potassium bromide): 3050, 2992,
1
1675, 1576, 1532, 1470, 1760, 756, 692 cm-1; H nmr (deuterio-
chloroform): ꢀ 4.1 (d, 1H, J = 2.2 Hz), 4.2 (d, 1H, J = 2.2 Hz),
7.1 (dd, 1H, J = 3.6, 4.2 Hz), 7.2 (d, 1H, J = 4.2 Hz), 7.3 (m,
5H), 7.5 (m, 3H), 7.52 (d, 1H, J = 3.6 Hz), 7.9 (d, 2H, J = 7.8
Hz); 13C nmr (deuteriochloroform): ꢀ 45.8, 48.8, 111.6,113.5,
127.1, 128.0, 128.3, 128.6, 133.2, 136.5, 136.9 138.3, 146.2,
147.5, 169.1, 194.5; Anal. Calcd. for C20H15NO3 (317.11): C,
75.75; H, 4.77; N, 4.41. found: C, 75.48; H, 4.51; N, 4.60.
trans-5-Benzoyl-2-(2-furyl)-4-phenyl-2-oxazoline (4g).
White solid, mp 111-113 °C; ir (potassium bromide): 5075,
2925, 1675, 1525, 1230, 757, 694 cm-1; 1H nmr (deuteriochloro-
form): ꢀ 5.6 (d, 1H, J = 7.0 Hz), 5.8 (d, 1H, J = 7.0 Hz), 7.15 (d,
1H, J = 4.3 Hz), 7.18 (dd, 1H, J = 3.6, 4.3 Hz), 7.6 (m, 5H), 7.7
(dd, 1H, J = 7.4, 8.1 Hz), 7.8 (d, 1H , J = 3.6 Hz), 8.0 (d, 2H, J =
7.4 Hz), 8.27(d, 2H, J = 8.6 Hz); 13C nmr (deuteriochloroform):
ꢀ 75.8, 85.8, 112.1, 115.5, 127.2, 128.4, 128.6, 128.9, 132.2,
134.5, 136.9 137.3, 147.2, 147.4, 160.1, 196.5; Anal. Calcd. for
C20H15NO3 (317.11): C, 75.75; H, 4.77; N, 4.41. found: C, 75.55;
H, 4.62; N, 4.50.
N-((R)-2-Chloro-1,3-diphenyl-1-oxo-propan-2-yl)acetamide
(3a). White solid, mp 88-91°C; ir (potassium bromide): 3286,
1
3085, 2950, 1685, 1637, 1520, 1355, 757, 696 cm-1; H nmr
(deuteriochloroform): ꢀ 2.1 (s, 3H), 5.4 (d, 1H, J = 7.0 Hz), 6.2
(dd, 1H, J = 7.0, 8.8 Hz), 6.5 (d, 1H, J = 8.8 Hz), 7.8 (m, 3H),
7.5-7.6 (m, 5H), 8.1 (d, 2H, J = 7.2 Hz); 13C nmr (deuterio-
chloroform): ꢀ = 24.1, 128.7, 128.8, 129.2, 129.4, 130.1, 131.6,
132.1 133.2, 136.8, 138.0, 170.0, 195.0; Anal. Calcd. for
C17H16ClNO2 (301.77): C, 67.70; H, 5.30; N, 4.60. found: C,
67.50; H, 5.50; N, 4.71.
Acknowledgments. We are thankful to Research Council of
University of Guilan for the partial support of this work.
trans-2-Benzoyl-1-cinnamoyl-3-(3-nitrophenyl)aziridine
(2h). White solid, mp 138-140 °C; ir (potassium bromide): 3062,
2958, 2931, 1667, 1025,1529, 1350, 1228, 975, 755, 666 cm-1;
1H nmr (deuteriochloroform): ꢀ 4.1 (d, 1H, J = 2.1 Hz), 4.3 (d,
1H, J = 2.1 Hz), 6.5 (d, 1H, J = 15.9 Hz), 7.4 (m, 2H), 7.5 (m,
5H), 7.64 (dd, 1H, J = 7.1, 7.8 Hz), 7.7 (dd, 1H, J = 7.2, 7.7 Hz),
7.8 (d, 1H, J = 15.9 Hz), 7.85 (d, 1H , J = 7.6 Hz), 8.0 (d, 2H, J =
7.6 Hz), 8.2 (d, 1H, J = 8.1 Hz), 8.3 (s, 1H); 13C nmr
(deuteriochloroform): ꢀ 44.0, 48.0, 119.0, 119.3, 123, 126, 12.4,
128.7, 128.8, 128.9, 129.5, 133, 133.2, 134.0, 135.2, 136.4,
REFERENCES AND NOTES
[1a] Gant, T. G.; Meyers, A. I. Tetrahedron 1994, 50, 2297; [b]
Andreasch, R. Monatsh. Chem. 1884, 5, 33.
[2a] Bonini, B. F.; Capito, E.; Franchini, M.; Fochi, M.; Ricci, A.;
Zwanenburg, B. Tetrahedron: Asymmetry 2006, 17, 3135; [b] Zhang, X.;
Lin, W.; Gong, L.; Mi, A.; Cui, X.; Jiang, Y.; Choi, M. C. K.; Chan A.
S. C. Tetrahedron Lett. 2002, 43, 1535; [c] Chai, Z.; Liu, X.-Y.; Wu, X.-
Y.; Zhao, G. Tetrahedron: Asymmetry 2006, 17, 2442.
[3a] Meyer, F.; Laaziri, A.; Papini, A. M.; Uziel, J.; Juge S.