4198
A. Zhou et al. / Tetrahedron 62 (2006) 4188–4200
K1
1
Anal. Calcd for C H N O : C, 70.24; H, 6.87; N, 10.69.
660, 1625, 1521, 1437, 1326, 1242, 1065, 814, 786 cm
.
4.1.20. N-Phenyl-2-(3,4,4,6-tetramethyl-[1,3]oxazinan-2-
ylidene)-acetamide (15a). Mp 164–166 8C. H NMR
1
2
3 27 3 3
Found: C, 70.03; H, 7.06; N, 10.62.
(300 MHz, CDCl ): d 8.82 (s, 1H), 7.54–6.95 (m, 5H),
3
4
.42 (m, 1H), 4.10 (s, 1H), 2.70 (s, 3H), 1.90–1.70 (m, 2H),
1
3
0
zolidin-2-ylidene)-malonamide (10c). Mp 195–196 8C.
1.51 (d, JZ6.2 Hz, 3H), 1.32 (s, 3H), 1.25 (s, 3H). C NMR
CDCl ): d 161.3, 154.3, 128.7, 125.4, 118.7, 119.1, 71.3,
67.6, 55.4, 46.7, 28.6, 26.9, 22.4, 17.2.
4
.1.14. N,N -Bis-(4-nitrophenyl)-2-(3,4,4-trimethyloxa-
(
3
1
H NMR (300 MHz, CDCl ): d 10.58 (s, 2H), 8.19–7.87
3
1
m, 8H), 4.66 (s, 2H), 3.08 (s, 3H), 1.54 (s, 6H). C NMR
3
(
(
7
1
CDCl ): d 169.8, 166.6, 149.7, 147.4, 125.6, 119.4, 78.7,
3
4.1.21. N-p-Nitrophenyl-2-(3,4,4,6-tetramethyl-[1,3]-
oxazinan-2-ylidene)-acetamide (15b). Mp 194–196 8C.
8.5, 64.5, 30.2, 23.6. IR (KBr): 3581, 3238, 2968, 1697,
625, 1575, 1507, 1335, 1257, 1118, 1056, 867, 761 cm
K1
1
.
H NMR (300 MHz, CDCl
m, 4H), 4.45 (m, 1H), 4.12 (s, 1H), 2.74 (s, 3H), 1.99–1.82
): d 9.14 (s, 1H), 8.16–7.62
3
(
0
oxazinan-2-ylidene)-malonamide (11a). Mp 166–168 8C.
(m, 2H), 1.56 (d, JZ6.2 Hz, 3H), 1.35 (s, 3H), 1.32 (s, 3H).
4
.1.15. N,N -Bis-(4-tolyl)-2-(3,4,4,6-tetramethyl-[1,3]-
13
C NMR (CDCl ): d 165.0, 157.5, 132.5, 125.2, 119.6,
117.9, 72.5, 69.7, 55.6, 47.5, 30.5, 27.8, 26.7, 20.6. IR
3
1
H NMR (300 MHz, CDCl ): d 10.03 (s, 2H), 7.40–7.08 (m,
3
(
1
neat): 3587, 3191, 2974, 1703, 1625, 1538, 1502, 1335,
257, 1112, 1056, 861, 761 cm
8
1
3
1
H), 4.57–4.45 (m, 1H), 3.11 (s, 3H), 2.29 (s, 6H), 2.04–
.91 (m, 2H), 1.55 (d, JZ5.2 Hz, 3H), 1.48 (s, 3H), 1.47 (s,
K1
.
1
H). C NMR (CDCl ): d 169.6, 166.3, 137.0, 132.1, 129.2,
3
3
4
4
1
1
.1.22. 3,3,4,10,10-Pentamethyl-6,8-diphenyl-1-oxa-
,6,8-triazaspiro[4,5]decane-7,9-dione (17a). Mp 147–
20.3, 88.5, 70.9, 57.7, 45.1, 35.5, 27.5, 27.2, 20.7, 20.0. IR
(
5
KBr): 3435, 2927, 1638, 1507, 1313, 1245, 1052, 821, 728,
05 cm
1
48 8C. H NMR (300 MHz, CDCl ): d 7.16–7.44 (m,
K1
.
3
0H), 3.49 (d, JZ6.8 Hz, 1H), 2.67 (d, JZ6.8 Hz, 1H), 2.64
(
s, 3H), 1.71 (s, 3H), 1.33 (s, 3H), 1.06 (s, 3H), 0.78 (s, 3H).
C NMR (CDCl ): d 174.7, 152.4, 136.2, 135.8, 131.4,
0
1,3]oxazinan-2-ylidene)-malonamide (11b). Mp 205–
4
[
.1.16. N,N -Bis-(4-nitrophenyl)-2-(3,4,4,6-tetramethyl-
13
3
1
2
1
31.3, 131.1, 128.9, 128.4, 127.9, 108.2, 77.7, 59.3, 48.1,
6.3, 26.1, 24.7, 24.6, 19.0. IR (KBr): 2980, 2940, 1710,
1
08 8C. H NMR (300 MHz, CDCl ): d 10.64 (s, 2H),
2
3
8
.16–7.66 (m, 8H), 4.73 (m, 1H), 3.21 (s, 3H), 2.15–2.02
K1
660, 1595, 1490, 1390, 1315, 1180, 1081, 840, 690 cm
.
(
m, 2H), 1.65 (d, JZ5.2 Hz, 3H), 1.56 (s, 3H), 1.55 (s, 3H).
Anal. Calcd for C H O N : C, 70.24; H, 6.87; N, 10.69.
23 27 3 3
Found: C, 70.01; H, 7.24; N, 10.39.
1
3
C NMR (CDCl ): d 170.7, 165.9, 147.4, 145.8, 142.1,
3
1
3
1
7
29.9, 125.1, 124.8, 119.7, 118.8, 82.7, 72.3, 58.8, 44.4,
6.1, 27.5, 27.0, 20.3. IR (KBr): 3412, 3074, 2990, 1720,
650, 1600, 1536, 1491, 1407, 1335, 1257, 1118, 1056, 846,
4.1.23. 3,3,4,10,10-Pentamethyl-6,8-di-p-tolyl-1-oxa-
4,6,8-triazaspiro[4,5]decane-7,9-dione (17b). Mp 165–
1
1
K1
44 cm
.
1
67 8C. H NMR (300 MHz, CDCl ): d 7.26–7.03 (m,
3
0H), 3.48 (d, JZ7.7 Hz, 1H), 2.71 (d, JZ7.7 Hz, 1H), 2.61
4.1.17. N-Phenyl-2-(3,4,4-trimethyloxazolidin-2-yli-
dene)-acetamide (14a). Mp 151–152 8C. H NMR
(s, 3H), 2.35 (s, 6H), 1.68 (s, 3H), 1.32 (s, 3H), 1.06 (s, 3H),
1
1
3
0
.8 (s, 3H). C NMR (CDCl ): d 174.7, 152.5, 137.8, 133.5,
3
(
300 MHz, CDCl ): d 8.26 (s, 1H), 7.55–6.99 (m, 4H),
3
131.1, 130.7, 129.5, 129.3, 128.7, 128, 108.1, 77.6, 59.2,
8.1, 26.3, 26.2, 24.8, 24.7, 21.1, 19.0. IR (KBr): 2985,
1735, 1678, 1507, 1393, 1327, 1189, 1034, 821, 723,
1
3
4
NMR (CDCl ): d 166.0, 161.7, 139.6, 128.6, 122.3, 119.5,
.18 (s, 2H), 4.03 (s, 1H), 2.63 (s, 3H), 1.27 (s, 6H).
C
4
3
K1
7
1
8.6, 70.4, 60.0, 26.5, 22.5. IR (KBr): 3289, 2964, 1757,
532, 1255, 1038, 831, 743, 521 cm . Anal. Calcd for
5
N, 9.98. Found: C, 71.04; H, 7.60; N, 9.77.
19 cm . Anal. Calcd for C H N O : C, 71.27; H, 7.36;
25 31 3 3
K1
C H O N : C, 68.31; H, 7.31; N, 11.38. Found: C, 68.48;
1
4 18 2 2
H, 7.11; N, 11.24.
4
4
.1.24. 2,4,10,10-Tetramethyl-6,8-bis-(4-phenyl)-1-oxa-
,6,8-triazaspiro[4,5]decane-7,9-dione (17c). Compound
4
.1.18. N-p-Tolyl-2-(3,4,4-trimethyloxazolidin-2-yli-
17c consists of two diastereomers. They are (2R,5R)/
(2S,5S)-2,4,10,10-tetramethyl-6,8-(4-nitrophenyl)-1-oxa-
3,6,8-triazospiro[4,5]decane-7,9-dione (17c).
1
dene)-acetamide (14b). Mp 160–162 8C. H NMR
300 MHz, CDCl ): d 8.19 (s, 1H), 7.42–7.07 (m, 4H),
(
3
4
6
1
2
.17 (s, 2H), 4.02 (s, 1H), 2.62 (s, 3H), 2.29 (s, 3H), 1.26 (s,
H). C NMR (CDCl ): d 166.0, 161.6, 137.0, 131.8, 129.1,
1
3
1
Mp 129–133 8C. H NMR (300 MHz, CDCl ): d 7.45–7.14
(m, 10H), 4.11(m, 1H), 3.02 (m, 1H), 2.76 (s, 3H), 2.58 (m,
1H), 1.69 (s, 3H), 1.33 (s, 3H), 0.46 (d, JZ6.0 Hz, 3H). C
3
3
19.7, 78.5, 70.4, 60.0, 26.6, 22.5, 20.7. IR (KBr): 3295,
976, 1760, 1523, 1253, 1041, 821, 731, 510 cm . Anal.
K1
13
Calcd for C H N O : C, 69.24; H, 7.69; N, 10.77. Found:
1
C, 69.10; H, 7.93; N, 10.53.
NMR (CDCl ): d 176.3, 154.1, 137.2, 133.8, 132.5, 132.2,
129.9, 129.7, 129.5, 129.1, 108.1, 76.1, 60.7, 49.1, 34.5,
5
20
2
2
3
2
6
6.0, 19.7, 18.5. Anal. Calcd for C H O N : C, 69.67; H,
22 25 3 3
.59; N, 11.08. Found: C, 69.53; H, 6.77; N, 11.21.
4
.1.19. N-p-Nitrophenyl-2-(3,4,4-trimethyloxazolidin-2-
ylidene)-acetamide (14c). Mp 190–193 8C. H NMR
1
(
300 MHz, CDCl ): d 8.58 (s, 1H), 8.16–7.70 (m, 4H),
3
4.1.25. (2S,5R)/(2R,5S)-2,4,10,10-Tetramethyl-6,8-(4-
nitrophenyl)-1-oxa-3,6,8-triazospiro[4,5]decane-7,9-
1
3
4
NMR (CDCl ): d 168.9, 162.4, 146.2, 142.2, 125.1, 118.3,
.24 (s, 2H), 4.07 (s, 1H), 2.68 (s, 3H), 1.32 (s, 6H).
C
1
dione (17c). Mp 129–133 8C. H NMR (300 MHz, CDCl ):
3
3
8
1
7
0.4, 70.3, 56.1, 26.7, 22.8. IR (neat): 3567, 3198, 2982,
709, 1633, 1537, 1515, 1324, 1237, 1131, 1061, 911, 864,
d 7.45–7.14 (m, 10H), 3.30 (m, 1H), 3.02 (m, 2H), 2.76 (s,
3H), 2.70 (m, 1H), 1.69 (s, 3H), 1.33 (s, 3H), 1.12 (d, JZ
K1
13
6.2 Hz, 3H). C NMR (CDCl ): d 176.3, 154.2, 139.3,
57 cm
.
3