Ene Reaction of 4-Phenyl-1,2,4-triazoline-3,5-dione
J . Org. Chem., Vol. 64, No. 7, 1999 2199
+
cm-1; 1H NMR δ 7.55-7.28 (m, 5H), 5.09 (s, 1H), 5.02 (s, 1H),
4.64 (d, J ) 2.1 Hz, 1H), 3.73-3.68 (m, 1H), 3.39 (s, 3H), 1.82
(
3
1
M , 3), 231 (100); HRMS calcd for C17
H
23
N
3
O
3
317.1739, found
: C, 64.33; H, 7.30; N,
3.24. Found: C, 64.45; H, 7.29; N, 13.06.
3R*,4S*)-2,5,5-Tr im et h yl-3-(4′-p h en yl-1′,2′,4′-t r ia zoli-
d in e-3′,5′-d ion -1′-yl)-1-h exen -4-ol (3b): IR 3464, 1763, 1694
23 3 3
17.1745. Anal. Calcd for C17H N O
1
3
(s, 3H), 1.80-1.23 (m, 6H), 0.90 (t, J ) 7.1 Hz, 3H); C NMR
δ 152.26 (s), 152.20 (s), 140.17 (s), 131.57 (s), 129.00 (d), 127.96
(d), 125.50 (d), 115.04 (t), 80.74 (d), 60.30 (d), 57.47 (q), 30.09
(t), 27.38 (t), 22.73 (t), 21.33 (q), 13.89 (q); MS (m/z, rel
(
-
1 1
cm ; H NMR δ 8.55 (br, 1H), 7.52-7.28 (m, 5H), 5.21 (s, 1H),
+
5
2
1
(
(
.08 (s, 1H), 4.75 (d, J ) 4.1 Hz, 1H), 3.83 (d, J ) 4.1 Hz, 1H),
.54 (br, 1H), 1.96 (s, 3H), 1.00 (s, 9H); 13C NMR δ 152.34 (s),
50.67 (s), 140.70 (s), 131.20 (s), 129.03 (d), 128.16 (d), 125.52
intensity) 331 (M , 40), 231 (87), 101 (100); HRMS calcd for
C
18
H
25
N
3
O
3
331.1896, found 331.1904.
(3R*,4S*)-2-Met h yl-4-m et h oxy-3-(4′-p h en yl-1′,2′,4′-t r i-
a zolid in e-3′,5′-d ion -1′-yl)-2-octen e (3f): IR 3184, 1770, 1700
d), 118.87 (t), 80.00 (d), 61.62 (d), 35.14 (s), 26.17 (q), 23.30
q); MS (m/z, rel intensity) 318 (M+ + 1, 2), 230 (91), 119 (100);
cm ; H NMR δ 7.88 (br, 1H), 7.55-7.26 (m, 5H), 5.19 (s, 1H),
5.11 (s, 1H), 4.76 (d, J ) 4.5 Hz, 1H), 3.67-3.60 (m, 1H), 3.39
(s, 3H), 1.84 (s, 3H), 1.74-1.68 (m, 1H), 1.57-1.49 (m, 1H),
-1 1
HRMS calcd for C17
23 3 3
H N O 317.1739, found 317.1732.
(
2S*,3S*)-4-Meth yl-3-(4′-ph en yl-1′,2′,4′-tr ia zolidin e-3′,5′-
-
1
1
13
d ion -1′-yl)-4-p en ten -2-ol (2c): IR 3239, 1766, 1696 cm ; H
NMR δ 8.70 (br, 1H), 7.50-7.31 (m, 5H), 5.04 (s, 1H), 5.02 (s,
1.37-1.29 (m, 4H), 0.90 (t, J ) 6.9 Hz, 3H); C NMR δ 152.63
(s), 151.68 (s), 138.70 (s), 131.41 (s), 128.93 (d), 127.97 (d),
125.44 (d), 117.91 (t), 82.60 (d), 61.24 (d), 57.23 (q), 29.68 (t),
27.74 (t), 22.73 (t), 22.05 (q), 13.86 (q); MS (m/z, rel intensity)
1
3
H), 4.34 (d, J ) 6.0 Hz, 1H), 4.25 (qd, J ) 6.1, 6.0 Hz, 1H),
.19 (br, 1H), 1.72 (s, 3H), 1.22 (d, J ) 6.1 Hz, 3H); 13C NMR
+
δ 153.05 (s), 152.85 (s), 193.84 (s), 131.29 (s), 129,07 (d), 128.23
331 (M , 16), 231 (89), 101 (100).
(
(
d), 125.70 (d), 116.01 (t), 66.30 (d), 65.90 (d), 21.11 (q), 20.83
(3S*,4S*)-2,5,5-Tr im eth yl-4-m eth oxy-3-(4′-ph en yl-1′,2′,4′-
tr ia zolid in e-3′,5′-d ion -1′-yl)-1-h exen e (2g): IR 3226, 1770,
+
q); MS (m/z, rel intensity) 275 (M , 2), 231 (100); HRMS calcd
-
1 1
for C14
H
17
N
3
O
3
275.1270, found 275.1254. Anal. Calcd for
: C, 61.08; H, 6.22; N, 15.26. Found: C, 61.07; H,
.29; N, 15.24.
2S*,3R*)-4-Meth yl-3-(4′-ph en yl-1′,2′,4′-tr iazolidin e-3′,5′-
1703 cm ; H NMR δ 8.31 (br, 1H), 7.54-7.30 (m, 5H), 5.14
14 17 3 3
C H N O
(s, 1H), 5.09 (s, 1H), 4.89 (d, J ) 1.0 Hz, 1H), 3.58 (s, 3H),
1
3
6
3.39 (d, J ) 1.0 Hz, 1H), 1.85 (s, 3H), 0.99 (s, 9H); C NMR δ
151.85 (s), 150.58 (s), 141.64 (s), 131.45 (s), 128.81 (d), 127.76
(d), 125.36 (d), 114.08 (t), 88.98 (d), 62.50 (q), 56.84 (d), 36.32
(
-
1 1
d ion -1′-yl)-4-p en ten -2-ol (3c): IR 3440, 1766, 1697 cm ; H
NMR δ 8.62 (br, 1H), 7.50-7.34 (m, 5H), 5.15 (s, 1H), 5.12 (s,
+
(s), 26.36 (q), 21.56 (q); MS (m/z, rel intensity) 331 (M , 8),
1
)
1
H), 4.40-4.30 (m, 2H), 2.60 (br, 1H), 1.86 (s, 3H), 1.26 (d, J
231 (41), 101 (100); HRMS calcd for C18 331.1896,
H
25
N
3
O
3
1
3
5.9 Hz, 3H); C NMR δ 152.68 (s), 151.71 (s), 139.03 (s),
found 331.1884. Anal. Calcd for C18H N O : C, 65.23; H, 7.30;
25 3 3
31.11 (s), 129.14 (d), 128.36 (d), 125.25 (d), 117.70 (t), 67.74
N, 12.68. Found: C, 65.32; H, 7.64; N, 12.69.
(
d), 65.87 (d), 21.87 (q), 20.15 (q); MS (m/z, rel intensity) 275
(3R*,4S*)-2,5,5-Tr im eth yl-4-m eth oxy-3-(4′-ph en yl-1′,2′,4′-
tr ia zolid in e-3′,5′-d ion -1′-yl)-1-h exen e (3g): IR 3121, 1768,
+
(M , 2), 231 (100).
-
1 1
(
3S*,4S*)-2-Meth yl-3-(4′-ph en yl-1′,2′,4′-tr ia zolidin e-3′,5′-
1698 cm ; H NMR δ 7.55-7.30 (m, 5H), 5.24 (s, 1H), 5.07 (s,
d ion -1′-yl)-1,6-h ep ta d ien -4-ol (2d ): IR 3462, 1768, 1697
1H), 4.74 (d, J ) 5.5 Hz, 1H), 3.45 (s, 3H), 3.34 (d, J ) 5.5 Hz,
-
1
1
13
cm ; H NMR δ 8.15 (br, 1H), 7.55-7.30 (m, 5H), 5.87-5.73
m, 1H), 5.20 (s, 1H), 5.16-5.15 (m, 1H), 5.12 (s, 2H), 4.53 (d,
1H), 1.89 (s, 3H), 0.98 (s, 9H); C NMR δ 152.74 (s), 150.98
(
(s), 140.88 (s), 131.34 (s), 129.02 (d), 128.12 (d), 125.39 (d),
117.44 (t), 90.63 (d), 62.19 (q), 60.79 (d), 36.46 (s), 26.77 (q),
J ) 4.1 Hz, 1H), 4.23-4.16 (m, 1H), 2.64 (br, 1H), 2.44-2.22
1
3
+
(
(
m, 2H), 1.76 (s, 3H); C NMR δ 152.94 (s), 152.74 (s), 139.63
23.46 (q); MS (m/z, rel intensity) 331 (M , 4), 230 (3), 101 (100).
s), 133.19 (d), 131.29 (s), 129.03 (d), 128.17 (d), 125.62 (d),
(3S*,4S*)-4-Acet oxy-2-m et h yl-3-(4′-p h en yl-1′,2′,4′-t r i-
a zolid in e-3′,5′-d ion -1′-yl)-1-octen e (2h ): IR 3216, 1776,
1
19.21 (t), 115.99 (t), 69.59 (d), 63.22 (d), 38.97 (t), 21.18 (q);
+
-1 1
MS (m/z, rel intensity) 301 (M , 2), 231 (44), 41(100); HRMS
calcd for C16 301.1426, found 301.1418. Anal. Calcd
for C16 : C, 13.94; H, 63.70; N, 6.36. Found: C, 13.92;
H, 63.70; N, 6.42.
3R*,4S*)-2-Meth yl-3-(4′-ph en yl-1′,2′,4′-tr iazolidin e-3′,5′-
d ion -1′-yl)-1,6-h ep ta d ien -4-ol (3d ): IR 3440, 1765, 1657
1716, 1696 cm ; H NMR δ 7.85 (br, 1H), 7.50-7.30 (m, 5H),
5.28-5.20 (m, 1H), 5.08 (s, 2H), 4.60 (d, J ) 8.2 Hz, 1H), 2.07
(s, 3H), 1.81 (s, 3H), 1.65-1.57 (m, 2H), 1.34-1.27 (m, 4H),
0.88 (t, J ) 6.5 Hz, 3H); 13C NMR δ 171.54 (s), 153.58 (s),
153.45 (s), 138.76 (s), 131.23 (s), 128.98 (d), 128.12 (d), 125.39
(d), 117.20 (t), 71.52 (d), 62.91 (d), 31.22 (t), 27.25 (t), 22.23
(t), 21.43 (q), 20.90 (q), 13.79 (q); MS (m/z, rel intensity) 359
19 3 3
H N O
H N O
19 3 3
(
-
1 1
cm ; H NMR δ 8.05 (br, 1H), 7.55-7.30 (m, 5H), 5.87-5.72
+
(m, 1H), 5.24 (s, 1H), 5.22 (s, 1H), 5.20 (s, 1H), 5.16 (s, 1H),
(M , 4), 299 (19), 230 (39), 119 (100); HRMS calcd for
4
2
1
.53 (d, J ) 4.3 Hz, 1H), 4.24-4.17 (m, 1H), 2.42-2.24 (m,
H), 1.90 (s, 3H); 13C NMR δ 152.65 (s), 151.53 (s), 138.84 (s),
33.55 (d), 131.14 (s), 129.10 (d), 128.28 (d), 125.59 (d), 119.01
C
C
19
H
H
25
N
N
3
O
O
4
359.1845, found 359.1842. Anal. Calcd for
: C, 63.49; H, 7.01; N, 11.69. Found: C, 63.42; H,
19
25
3
4
7.06; N, 11.62.
(
t), 118.14 (t), 71.01 (d), 64.00 (d), 38.49 (t), 21.81 (q); MS (m/
(3R*,4S*)-4-Acet oxy-2-m et h yl-3-(4′-p h en yl-1′,2′,4′-t r i-
a zolid in e-3′,5′-d ion -1′-yl)-1-octen e (3h ): IR 3145, 1776,
+
z, rel intensity) 301 (M , 11), 231 (100).
1S*,2S*)-3-Meth yl-1-p h en yl-2-(4′-p h en yl-1′,2′,4′-tr ia zo-
lid in e-3′,5′-d ion -1′-yl)-3-bu ten -1-ol (2e): IR 3440, 1766, 1697
-1 1
(
1712, 1696 cm ; H NMR δ 7.51-7.33 (m, 5H), 5.46-5.38 (m,
1H), 5.15 (s, 1H), 5.13 (s, 1H), 4.68 (d, J ) 6.8 Hz, 1H), 2.04
(s, 3H), 1.83 (s, 3H), 1.68-1.50 (m, 2H), 1.45-1.20 (m, 4H),
0.86 (t, J ) 7.0 Hz, 3H); 13C NMR δ 170.77 (s), 153.40 (s),
152.39 (s), 138.39 (s), 131.17 (s), 129.06 (d), 128.22 (d), 125.50
(d), 117.02 (t), 71.60 (d), 62.35 (d), 31.19 (t), 27.25 (t), 22.40
(t), 21.60 (q), 20.96 (q), 13.84 (q); MS (m/z, rel intensity) 359
-
1 1
cm ; H NMR δ 7.45-7.25 (m, 10H), 5.28 (d, J ) 5.5 Hz, 1H),
5
3
1
.17 (s, 1H), 5.27 (s, 1H), 4.81 (d, J ) 5.5 Hz, 1H), 1.76 (s,
13
H); C NMR (100 MHz, DMSO-d
6
) δ 153.51 (s), 152.56 (s),
41.99 (s), 139.48 (s), 131.97 (s), 128.66 (d), 127.89 (d), 127.53
(d), 127.34 (d), 127.14 (d), 125.80 (d), 116.19 (t), 70.92 (d), 66.41
+
+
(
d), 21.45 (q); MS (m/z, rel intensity) 337 (M , 4), 320 (46),
(M , 5), 299 (41), 230 (100).
2
3
1
31 (100); HRMS calcd for C19
37.1418. Anal. Calcd for C19
2.45. Found: C, 67.12; H, 5.93; N, 12.12.
1S*,2R*)-3-Meth yl-1-p h en yl-2-(4′-p h en yl-1′,2′,4′-tr ia zo-
lid in e-3′,5′-d ion -1′-yl)-3-bu ten -1-ol (3e): IR 3477, 1769, 1692
H
19
N
3
O
3
337.1426, found
(3S*,4S*)-4-Acetoxy-2,5,5-tr im eth yl-3-(4′-p h en yl-1′,2′,4′-
tr ia zolid in e-3′,5′-d ion -1′-yl)-1-h exen e (2i): IR 3232, 1768,
19 3 3
H N O : C, 67.64; H, 5.68; N,
-
1 1
1745, 1705 cm ; H NMR δ 8.38 (br, 1H), 7.50-7.28 (m, 5H),
(
5.20 (d, J ) 3.9 Hz, 1H), 5.15 (s, 1H), 5.04 (s, 1H), 4.95 (d, J
1
3
) 3.9 Hz, 1H), 1.99 (s, 3H), 1.76 (s, 3H), 0.97 (s, 9H); C NMR
δ 170.49 (s), 152.96 (s), 152.14 (s), 140.17 (s), 131.25 (s), 128.99
(d), 128.16 (d), 125.44 (d), 115.90 (t), 77.27 (d), 58.56 (d), 35.31
-
1
1
cm ; H NMR (CD
3
OD) δ 7.48-7.42 (m, 2H), 7.42-7.30 (m,
H), 7.05-6.95 (m, 2H), 5.40 (s, 1H), 5.28 (s, 1H), 5.16 (d, J )
.8 Hz, 1H), 4.75 (d, J ) 9.8 Hz, 1H), 1.94 (s, 3H); 13C NMR-
) δ 151.43 (s), 151.25 (s), 142.32 (s), 140.21
s), 131.42 (s), 128.53 (d), 127.61 (d), 127.54 (d), 127.36 (d),
27.05 (d), 125.65 (d), 116.14 (t), 70.54 (d), 64.92 (d), 20.75
6
9
(s), 26.36 (q), 21.65 (q), 20.67 (q); MS (m/z, rel intensity) 359
+
(100 MHz, DMSO-d
6
(M , 8), 299 (37), 230 (100); HRMS calcd for C19
H
25
N
3
O
4
(
1
359.1845, found 359.1846. Anal. Calcd for C19
25 3 4
H N O : C,
63.49; H, 7.01; N, 11.69. Found: C, 63.30; H, 7.09; N, 11.69.
(3R*,4S*)-4-Acetoxy-2,5,5-tr im eth yl-3-(4′-p h en yl-1′,2′,4′-
tr ia zolid in e-3′,5′-d ion -1′-yl)-1-h exen e (3i): IR 3168, 1768,
+
(
2
q); MS (FAB, m/z, rel intensity) 338 [(M + 1) , 37], 320 (78),
30 (85), 178 (100).
3S*,4S*)-2-Met h yl-4-m et h oxy-3-(4′-p h en yl-1′,2′,4′-t r i-
a zolid in e-3′,5′-d ion -1′-yl)-2-octen e (2f): IR 3200, 1771, 1704
-
1 1
(
1711, 1688 cm ; H NMR δ 7.53-7.30 (m, 5H), 5.16 (s, 1H),
5.08 (s, 1H), 5.06 (d, J ) 5.5 Hz, 1H), 4.93 (d, J ) 5.5 Hz, 1H),