2090
U. Wittmann et al.
PAPER
2-Fluoro-1-heptylprop-2-enyl [(4-Nitrobenzoyl)amino](phen-
yl)acetate (3j)
Starting from 2-fluorodec-1-en-3-ol (1c, 0.87 g, 5.0 mmol), 3j was
obtained as a white solid; yield: 930 mg (41%); mp 107 °C.
CH), 5.77 (d, J = 6.9 Hz, 0.5 H, 12-CH), 5.81 (d, J = 7.0 Hz, 0.5 H,
12-CH), 7.79 (d, J = 9.1 Hz, 2 H, 20-CH), 7.03 (d, J = 7.2 Hz, 0.5
H, NH), 7.07 (d, J = 6.9 Hz, 0.5 H, NH), 7.30–7.39 (m, 3 H, 15-, 16-
CH), 7.41–7.47 (m, 2 H, 14-CH), 7.79 (d, J = 9.0 Hz, 2 H, 19-CH).
1H NMR: d = 0.86 (t, J = 7.2 Hz, 3 H, 10-CH3), 1.04–1.20 (m, 4 H,
5-, 6-CH2), 1.21–1.40 (m, 6 H, 7-, 8-, 9-CH2), 1.62 and 1.77 (2 m, 2
H, 4-CH2), 4.14 (dd, J = 3.5 Hz, J = 48.5 Hz, 0.5 H, trans-1-CH2),
4.54 (dd, J = 3.4 Hz, J = 17.1 Hz, 0.5 H, cis-1-CH2), 4.62 (dd,
J = 3.3 Hz, J = 52.0 Hz, 0.5 H, trans-1-CH2), 4.77 (dd, J = 3.3 Hz,
J = 16.5 Hz, 0.5 H, cis-1-CH2), 5.32 (m, 1 H, 3-CH), 5.76 (d, J = 6.8
Hz, 0.5 H, 12-CH), 5.79 (d, J = 6.9 Hz, 0.5 H, 12-CH), 7.28–7.46
(m, 6 H, 14-, 15-, 16-CH, NH), 7.97 (m, 2 H, 20-CH), 8.26 (m, 2 H,
19-CH).
13C NMR: d = 14.0, 22.5, 22.6, 24.1, 24.8, 28.8, 28.9, 29.0, 29.1,
30.8, 31.1, 31.5, 31.6, 57.1, 57.3, 73.0 (J = 32.8 Hz), 73.1 (J = 32.3
Hz), 92.3 (J = 17.2 Hz), 93.1 (J = 16.2 Hz), 123.8, 127.3, 127.4,
128.4, 128.9, 129.1, 135.5, 135.9, 139.1, 149.8, 161.7 (J = 260.7
Hz), 161.9 (J = 261.0 Hz), 164.5, 164.6, 169.7, 169.9.
13C NMR: d = 14.0, 22.5, 22.6, 24.4, 24.8, 28.9, 29.0, 29.1, 30.9,
31.2, 31.5, 31.7, 55.4, 56.8, 57.0, 72.6 (J = 32.4 Hz), 72.7 (J = 34.4
Hz), 92.0 (J = 17.0 Hz), 92.8 (J = 19.0 Hz), 113.8, 125.9, 127.3,
127.4, 128.6, 128.9, 129.0, 136.3, 136.7, 161.9 (J = 259.1 Hz),
162.1 (J = 260.5 Hz), 162.5, 166.0, 166.1, 170.1, 170.3.
19F NMR: d = –111.2 (J = 15.0 Hz, J = 15.0 Hz, J = 53.0 Hz),
–110.5 (ddd, J = 11.9 Hz, J = 17.4 Hz, J = 47.6 Hz).
MS: m/z (%) = 441 (1) [M+], 306 (1) [M+ – C8H7O2], 268 (1) [M+ –
C10H18FO], 267 (4) [M+ – C10H19FO], 240 (28) [268 – CO], 135
(100) [C8H7O2 ], 107 (7) [C7H7O+], 105 (8) [C7H7N+], 104 (3)
+
[C7H4O+], 77 (12) [C6H5 ], 72 (3) [C4H5F+], 51 (4) [C4H3 ].
+
+
Oxazol-5(4H)-ones 5a–l; General Procedure
To a soln/suspension of the ester 3a–l (1.0 mmol) in MeCN (1.5
mL) were added CCl4 (0.34 mL, 542 mg, 3.52 mmol), Et3N (0.38
mL, 274 mg, 2.72 mmol) and Ph3P (524 mg, 2.0 mmol). After stir-
ring at r.t. overnight, the mixture was purified by column filtration
(silica gel; cyclohexane–EtOAc, 4:1 to 20:1). The products were
stored under argon or used directly for further reactions.
19F NMR: d = –111.3 (J = 15.1 Hz, J = 15.1 Hz, J = 47.6 Hz),
–110.6 (J = 12.9 Hz, J = 16.7 Hz, J = 49.5 Hz).
MS: m/z (%) = 456 (0) [M+], 341 (1), 325 (1) [M+ – C6H13NO2], 256
(16) [M+ – C11H17FO2], 255 (55) [M+ – C11H18FO2], 206 (1)
+
+
[C12H11FO2 ], 156 (10) [C10H18F+], 150 (100) [C7H4NO3 ] 136 (4)
[156 – HF], 134 (14) [C8H8NO+], 120 (19) [C7H6NO+], 105 (26)
4-(2-Fluoroprop-2-enyl)-4-methyl-2-phenyloxazol-5(4H)-one
(5a)
[C7H7N+], 104 (52) [C7H4O+], 72 (88) [C4H5F+], 55 (91) [C4H7 ].
+
Starting from 3a (126 mg, 0.50 mmol), 5a was obtained as a light
yellow oil; yield: 117 mg (100%).
1H NMR: d = 1.48 (s, 3 H, 6-CH3), 2.72 (m, 2 H, 3-CH2), 4.28 (dd,
J = 3.0 Hz, J = 48.9 Hz, 1 H, 5-CH2), 4.52 (dd, J = 3.0 Hz, J = 17.0
Hz, 1 H, 5-CH2), 7.38 (m, 2 H, 10-CH), 7.48 (m, 1 H, 11-CH), 7.90
(m, 2 H, 9-CH).
13C NMR: d = 23.7, 40.8 (J = 26.7 Hz), 67.8 (J = 2.5 Hz), 94.1
(J = 17.8 Hz), 125.8, 128.0, 128.7, 132.7, 160.5, 161.0 (J = 256.9
Hz), 179.5.
19F NMR: d = –93.7 (J = 15.3 Hz, J = 24.8 Hz, J = 49.6 Hz).
2-Fluoro-1-heptylprop-2-enyl (Phenyl){[4-(trifluoromethyl)-
benzoyl]amino}acetate (3k)
Starting from 2-fluorodec-1-en-3-ol (1c, 0.87 g, 5.0 mmol), 3k was
obtained as a white solid; yield: 1.67 g (70%); mp 115 °C.
1H NMR: d = 0.86 (t, J = 7.2 Hz, 3 H, 10-CH3), 1.05–1.15 (m, 4 H,
5-, 6-CH2), 1.20–1.35 (m, 6 H, 7-, 8-, 9-CH2), 1.62 and 1.76 (2 m, 2
H, 4-CH2), 4.12 (dd, J = 3.4 Hz, J = 48.5 Hz, 0.5 H, trans-1-CH2),
4.54 (dd, J = 3.4 Hz, J = 17.1 Hz, 0.5 H, cis-1-CH2), 4.63 (dd,
J = 3.3 Hz, J = 48.2 Hz, 0.5 H, trans-1-CH2), 4.77 (dd, J = 3.3 Hz,
J = 16.8 Hz, 0.5 H, cis-1-CH2), 5.32 (m, 1 H, 3-CH), 5.76 (d, J = 6.7
Hz, 0.5 H, 12-CH), 5.80 (d, J = 6.9 Hz, 0.5 H, 12-CH), 7.21 (d,
J = 6.3 Hz, 0.5 H, NH), 7.26 (d, J = 7.1 Hz, 0.5 H, NH), 7.34–7.47
(m, 5 H, 14-, 15-, 16-CH), 7.69 (d, J = 8.1 Hz, 2 H, 19-CH), 8.26 (d,
J = 8.0 Hz, 2 H, 20-CH).
MS: m/z (%) = 233 (4) [M+], 188 (1) [M+ – C2H2F], 174 (21) [M+ –
+
C3H4F], 147 (3) [C8H5O2N+], 105 (100) [C7H5O+], 77 (38) [C6H5 ],
+
+
59 (1), 51 (16) [C4H3 ], 39 (6) [C3H3 ].
13C NMR: d = 14.0, 22.6, 22.6, 24.4, 24.8, 28.8, 28.9, 29.0, 29.1,
30.8, 31.1, 31.6, 31.7, 57.0, 57.1, 72.9 (J = 32.6 Hz), 73.0 (J = 31.4
Hz), 92.2 (J = 15.9 Hz), 93.2 (J = 17.5 Hz), 123.6 (J = 273.1 Hz),
125.6, 125.7, 127.3, 127.4, 127.6, 128.0, 128.8, 129.1, 133.5
(J = 33.1 Hz), 135.8, 136.1, 136.8, 161.7 (J = 260.5 Hz), 161.8
(J = 261.0 Hz), 165.2, 165.3, 169.9, 170.0.
4-[(2Z)-2-Fluorohex-2-enyl]-4-methyl-2-phenyloxazol-5(4H)-
one (5b)
Starting from 3b (156 mg, 0.53 mmol), 5b was obtained as a light
yellow oil; yield: 146 mg (100%).
1H NMR: d = 0.75 (t, J = 7.4 Hz, 3 H, 8-CH3), 1.24 (ps sext, J = 7.4
Hz, 2 H, 7-CH2), 1.55 (s, 3 H, 9-CH3), 1.94 (m, 2 H, 6-CH2), 2.71
(m, 2 H, 3-CH2), 4.64 (dt, J = 7.6 Hz, J = 37.0 Hz, 1 H, 5-CH), 7.44
(m, 2 H, 13-CH), 7.56 (m, 1 H, 14-CH), 7.98 (m, 2 H, 12-CH).
13C NMR: d = 13.3, 22.3, 23.6, 25.4 (J = 3.8 Hz), 41.3 (J = 28.0
Hz), 68.2 (J = 2.6 Hz), 110.0 (J = 14.0 Hz), 126.0, 127.9, 128.7,
132.6, 154.2 (J = 251.8 Hz), 167.0, 179.8.
19F NMR: d = –111.4 (J = 15.9 Hz, J = 16.2 Hz, J = 47.7 Hz),
–110.7 (J = 13.6 Hz, J = 18.1 Hz, J = 48.0 Hz), –63.5.
MS: m/z (%) = 480 (1) [M+], 460 (1) [M+ – HF], 374 (2) [460 –
C6H13], 306 (1) [M+ – C10H18FO and M+ – C8H4F3O], 278 (26)
[306 – CO], 173 (100) [C10H19FO+ and C8H4F3O], 145 (57)
[C7H4F3 ], 105 (8) [C7H5O+], 104 (30) [C7H4O+], 77 (33) [C6H5 ],
+
+
19F NMR: d = –108.6 (J = 15.3 Hz, J = 24.8 Hz, J = 38.2 Hz).
72 (18) [C4H5F+], 51 (4) [C4H3 ].
+
MS: m/z (%) = 275 (1) [M+], 188 (1) [M+ – C5H8F], 175 (24) [M+ +
H – C6H10F], 174 (25) [M+ – C6H10F], 105 (100) [C7H5O+], 77 (37)
2-Fluoro-1-heptylprop-2-enyl [4-Methoxybenzoyl)amino]-
(phenyl)acetate (3l)
Starting from 2-fluorodec-1-en-3-ol (1c, 0.87 g, 5.0 mmol), 3l was
+
[C6H5 ], 59 (5), 51 (7), 42 (4).
obtained as a white solid; yield: 1.72 g (78%); mp 93 °C.
4-[(2Z)-2-Fluorodec-2-enyl]-4-methyl-2-phenyloxazol-5(4H)-
one (5c)
Starting from 3c (175 mg, 0.50 mmol), 5c was obtained as a light
1H NMR: d = 0.86 (t, J = 7.2 Hz, 3 H, 10-CH3), 1.04–1.18 (m, 4 H,
5-, 6-CH2), 1.21–1.40 (m, 6 H, 7-, 8-, 9-CH2), 1.62 and 1.77 (2 m, 2
H, 4-CH2), 3.83 (s, 3 H, 22-CH3), 4.12 (dd, J = 3.5 Hz, J = 48.4 Hz,
0.5 H, trans-1-CH2), 4.52 (dd, J = 3.5 Hz, J = 17.1 Hz, 0.5 H, cis-1-
CH2), 4.61 (dd, J = 3.3 Hz, J = 48.0 Hz, 0.5 H, trans-1-CH2), 4.75
(dd, J = 3.4 Hz, J = 16.6 Hz, 0.5 H, cis-1-CH2), 5.31 (m, 1 H, 3-
yellow oil; yield: 164 mg (100%).
1H NMR: d = 0.84 (t, J = 7.2 Hz, 3 H, 12-CH3), 1.08–1.27 (m, 10 H,
7-, 8-, 9-, 10-, 11-CH2), 1.55 (s, 3 H, 13-CH3), 1.95 (m, 2 H, 6-CH2),
2.60–2.90 (m, 2 H, 3-CH2), 4.62 (dt, J = 7.6 Hz, J = 37.2 Hz, 1 H,
Synthesis 2006, No. 13, 2085–2096 © Thieme Stuttgart · New York