G. Pri e et al. / Journal of Fluorine Chemistry 117 (2002) 35±41
39
100). 19F NMR d (ppm): À115.13, À86.01. Anal. Calcd. for
J
22 Hz), 165. MS (70 eV) m/z: 289 (M , 15), 42
19
ꢀ
(
C H F NO : C, 52.02; H, 4.37. Found: C, 51.80; H, 4.39.
CÀF
(100). F NMR d (ppm): À115.13, À86.01. Anal. Calcd. for
1
4
14
5
2
C H F NO : C, 45.68, H, 5.58. Found: C, 45.55; H,5.55.
1
1
16
5
2
3
.2.7. Ethyl-3-diethylamino-4,4,4-trifluorobut-2-
enoate (1b)
3.2.11. Ethyl-4,4,5,5,5-pentafluoro-3-diisopropylaminopent-
2-enoate (5b)
À1
1
IR (cm ): 2984, 1732, 1617, 1216, 1040. H NMR d
ppm): Z-isomer: 1.16 (6H, t, J 7:0 Hz), 1.30 (3H, t, J
À1
1
(
7
5
IR (cm ): 2984, 1737, 1632, 1273, 1205, 1138, 1038. H
NMR d (ppm): Z-isomer: 1.17 (12H, d, J 6:8 Hz), 1.33
(3H, t, J 7:1 Hz), 3.53 (2H, sept, J 6:7 Hz), 4.21 (2H, q,
J 6:7 Hz), 5.94 (1H, s); E-isomer: 1.17 (12H, d,
J 6:8 Hz), 1.30 (3H, t, J 7:1 Hz), 3.53 (2H, sept,
:1 Hz), 3.16 (4H, q, J 7:0 Hz), 4.18 (2H, q, J 7:1 Hz),
.06 (1H, bs); E-isomer: 1.14 (6H, t, J 7:0 Hz), 1.27 (3H,
t, J 7:1 Hz), 3.11 (4H, q, J 7:0 Hz), 4.09 (2H, q,
13
J 7:1 Hz), 5.37 (1H, bs). C NMR d (ppm): Z-isomer:
1
3
1
1
1.7 (2C), 14.0, 45.0 (2C), 60.2, 99.3 (q, JCÀF 5:5 Hz),
20.9 (q, JCÀF 279 Hz), 145.0 (q, JCÀF 32 Hz). MS
J 6:7 Hz), 4.24 (2H, q, J 6:7 Hz), 6.16 (1H, s)).
C
NMR d (ppm): Z-isomer: 14, 22, 51, 61, 85 (t,
JCÀF 10 Hz), 115 (qt, JCÀF 280, 37 Hz), 119 (tq,
JCÀF 270, 38 Hz), 142 (t, JCÀF 24 Hz), 166. MS
ꢀ
19
(
70 eV) m/z: 239 (M , 22), 166 (100). F NMR d
ppm): Z-isomer: À63.3; E-isomer:À59.8. Anal. Calcd.
(
for C H F NO : C, 50.20; H, 6.74. Found: C; 50.00; H,
ꢀ
19
(70 eV) m/z: 317 (M , 15), 43 (100). F NMR d (ppm):
À117.68, À87.82. Anal. Calcd. for C H F NO : C, 49.21,
1
0
16
3
2
6
.77.
1
3
20
5
2
H, 6.35. Found: C, 49.35; H, 6.38.
3
.2.8. Ethyl-4,4,4-trifluoro-3-diisopropylaminobut-2-
enoate (2b)
3.2.12. Ethyl-4,4,5,5,5-pentafluoro-3-diallyllaminopent-2-
enoate (6b)
À1
1
IR (cm ): 2984, 1737, 1632, 1273, 1205, 1138, 1038. H
NMR d (ppm): Z-isomer: 1.16 (12H, d, J 6:5 Hz), 1.23
À1
1
IR (cm ): 2984, 1737, 1632, 1273, 1205, 1141, 1035. H
NMR d (ppm): Z-isomer: 1.3 (3H, t, J 7:1 Hz), 3.70 (4H,
d, J 6:1 Hz), 4.18 (2H, q, J 7:1 Hz), 5.20 (4H, m), 5.45
(1H, s), 5.65 (2H, m); E-isomer: 1.3 (3H, t, J 7:1 Hz), 3.78
(4H, d, J 6:3 Hz), 4.18 (2H, q, J 7:1 Hz), 5.20 (4H, m),
(
3H, t, J 7:1 Hz), 3.53 (2H, sept, J 6:5 Hz), 4.12 (2H, q,
J 7:1 Hz), 5.53 (1H, s); E-isomer: 1.14 (12H, d,
J 6:5 Hz), 1.22 (3H, t, J 7:1 Hz), 3.45 (2H, sept,
1
3
J 6:5 Hz), 4.09 (2H, q, J 7:1 Hz), 5.58 (1H, s).
C
1
3
NMR d (ppm): Z-isomer: 14.0, 21.4 (4C), 49.9 (2C), 60.5,
21.1 (q, J
5.65 (2H, m), 5.70 (1H, s)). C NMR d (ppm): 14.8, 55, 60,
1
280 Hz), 109.1 (q, J
5:5 Hz), 143.5
106 (t, J
5 Hz), 115 (qt, J
220, 40 Hz), 119, 122
CÀF
CÀF
CÀF
CÀF
ꢀ
(
(
q, JCÀF 33 Hz), 165.2. MS (70 eV) m/z: 267 (M , 2), 43
(tq, JCÀF 230, 39 Hz), 146 (t, JCÀF 25 Hz), 165. MS
1
9
ꢀ
19
100). F NMR d (ppm): Z-isomer: À64.2; E-isomer:
(70 eV) m/z: 313 (M , 2), 41 (100). F NMR d (ppm):
À115.1, À85.9. Anal. Calcd. for C H F NO : C, 49.84; H,
À60.2. Anal. Calcd. for C H F NO : C, 53.92; H, 7.54.
1
2
20
3
2
13 16
5
2
Found: C, 53.70; H, 7.57.
5.15. Found: C, 50.04; H, 5.13.
3
.2.9. Ethyl-4,4,4-trifluoro-3-morpholinobut-2-enoate (3b)
3.2.13. (E)-Ethyl-4,4,4-trifluoro-3-aminobut-2-enoate
(7b)/(E)-ethyl-4,4,5,5,5-pentafluoro-3-aminopent-2-
enoate (8b)
In this case, water was added to the mixture at the end of
the reaction, the organic phase was dried over magnesium
sulfate and diethyl ether was evaporated and 90% yields of
7b and 8b were obtained.
À1
1
IR (cm ): 2990, 2875, 1730, 1625, 1037. H NMR d
ppm): Z-isomer: 1.21 (3H, t, J 7:1 Hz), 2.89 (4H, m),
.69 (4H, m), 4.15 (2H, q, J 7:1 Hz), 5.21 (1H, s); E-
isomer: 1.20 (3H, t, J 7:1 Hz), 3.21 (4H, m), 3.67 (4H, m),
(
3
13
4
.08 (2H, q, J 7:1 Hz), 5.32 (1H, s). C NMR d (ppm): Z-
isomer: 14.0, 50.0 (2C), 60.9, 66.2 (2C), 104.8 (q
J 5:8 Hz), 120.7 (q, JCÀF 278 Hz), 146.8 (q,
,
ꢀ
JCÀF 32:5 Hz), 165. MS (70 eV) m/z: 253 (M , 55),
3.2.14. (E)-Ethyl-4,4,4-trifluoro-3-aminobut-2-enoate (7b)
1
1
9
2
06 (100). F NMR d (ppm): Z-isomer: À63.7; E-isomer:
H NMR d (ppm): 1.3 (3H, t, J 7:1 Hz), 4.18 (2H, q,
1
3
À59.5. Anal. Calcd. for C H F NO C, 47.43; H, 5.57.
J 7:1 Hz), 5.13 (1H, s), 6.25 (2H, bs). C NMR d (ppm):
15, 60, 89 (q, JCÀF 5 Hz), 120 (q, JCÀF 220 Hz), 147 (q,
1
0
14
3
3
Found: C, 47.57; H, 5.54.
ꢀ
J
25 Hz), 168. MS (70 eV) m/z: 183 (M , 13), 68
19
CÀF
(100).
3.2.10. Ethyl-4,4,5,5,5-pentafluoro-3-diethylaminopent-2-
enoate (4b)
F NMR d (ppm): À70. Anal. Calcd. for
2
C H F NO :C, 39.35; H, 4.40. Found: C, 39.46; H, 4.41.
6
8
3
À1
1
IR (cm ): 2984, 1737, 1632, 1273, 1205, 1140, 1040. H
NMR d (ppm): Z-isomer: 1.05 (6H, t, J 7 Hz), 1.30 (3H, t,
J 7:1 Hz), 3.13 (4H, q, J 7 Hz), 4.18 (2H, q,
J 7:1 Hz), 5.38 (1H, s); E-isomer: 1.10 (6H, t,
J 7:1 Hz), 1.30 (3H, t, J 7:1 Hz), 3.24 (4H, q,
3.2.15. (E)-Ethyl-4,4,5,5,5-pentafluoro-3-aminopent-2-
enoate (8b)
1
H NMR d (ppm): 1.3 (3H, t, J 7:1 Hz), 4.20 (2H, q,
1
3
J 7:1 Hz), 5.36 (1H, s), 6.20 (2H, bs). C NMR d (ppm):
15, 60, 88 (t, JCÀF 5 Hz), 118 (qt, JCÀF 220, 40 Hz),
125 (tq, JCÀF 230, 30 Hz), 147 (t, JCÀF 25 Hz), 170.
1
3
J 7:1 Hz), 4.18 (2H, q, J 7:1 Hz), 5.67 (1H, s).
C
NMR d (ppm): E-isomer: 14, 15, 47, 61, 105, 115 (qt,
JCÀF 260, 37 Hz), 119 (tq, JCÀF 280, 3 Hz), 146 (t,
ꢀ
19
MS (70 eV) m/z: 233 (M , 26), 68 (100). F NMR d (ppm):