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M. Abarbri et al.
PAPER
Anal. Calcd for C 11 H12 O2: C, 74.98; H, 6.86. Found: C, 75.10; H,
6.84.
(Z)-3-Benzyloct-2-enoic Acid (3l)
IR: 3469, 3414, 2958, 2931, 1692, 1635, 1602, 1190 cm–1.
1H NMR (200 MHz, CDCl3): = 0.85 (3 H, t, J = 6.4 Hz), 1.23
1.25 (4 H, m), 1.37 1.48 (2 H, m), 2.08 (2 H, t, J = 7.4 Hz), 4.06 (2
H, s), 5.82 (1 H, s), 7.24 7.27 (5 H, m), 11 (1 H, s).
13C NMR (50 MHz, CDCl3): = 13.9, 22.4, 27.2, 31.3, 37.3, 37.5,
115.9, 126.3, 128.4, 128.9, 138.6, 164.9, 172.
MS (70 eV): m/z (%) = 232 (M+, 63), 176 (17), 158 (83), 131 (45),
130 (35), 129 (64), 128 (35), 127 (12), 117 (45), 115 (51), 92 (13),
91 (91), 77 (16), 65 (30), 55 (19), 43 (18), 41 (32), 39 (25), 29 (31),
28 (100), 27 (20).
(Z)-3-Benzylbut-2-enoic Acid (3g)
Mp: 72 °C.
IR (KBr): 3029, 2671, 2592, 1683, 1635, 1601, 1192 cm–1.
1H NMR (200 MHz, CDCl3): = 1.80 (3 H, d, J = 1.3 Hz), 4.03 (2
H, s), 5.8 (1 H, br q, J = 1.3 Hz), 7.23 (5 H, br s), 10.65 (1 H, s).
13C NMR (50 MHz, CDCl3): = 25, 39.2, 116.8, 126.6, 128.7 (2
C),129.1 (2 C), 138.7, 161.1, 172.3.
MS (70 eV): m/z (%) = 176 (M+, 69), 158 (65), 131 (70), 129 (73),
116 (28), 115 (97), 92 (12), 91 (100), 89 (23), 77 (31), 65 (65), 51
(51), 45 (29), 41 (21), 39 (87), 29 (13), 27 (29), 18 (32), 17 (24).
(E)-3-Phenylbut-2-enoic Acid (3m)
Mp: 91 92 °C.
IR (KBr): 3450, 2933, 1675, 1620, 1595, 868 cm–1.
1H NMR (200 MHz, CDCl3): = 2.61 (3 H, d, J = 4.5 Hz), 6.20 (1
H, q, J = 4.5 Hz), 7.35 7.57 (5 H, m), 11.3 (1 H, br s).
13C NMR (50 MHz, CDCl3): = 18.3, 116.5, 126.4 (2 C), 128.6 (2
C), 129.3, 142, 158.5, 172.6.
MS (70 eV): m/z (%) = 162 (M+, 81), 161 (74), 145 (55), 116 (54),
115 (100), 105 (18), 78 (30), 77 (28), 65 (15), 51 (12), 39 (30), 28
(14).
Anal. Calcd for C11 H12O2: C, 74.98; H, 6.86. Found: C, 74.88; H,
6.89.
(Z)-3,7-Dimethyloct-2,6-dienoic Acid (3h)
IR: 3300, 2967, 2920, 1690, 1636, 1181 cm–1.
1H NMR (200 MHz, CDCl3): = 1.55 (3 H, s), 1.62 (3 H, s), 1.85
(3 H, s), 2.11 (2 H, m), 2.58 (2 H, t, J = 7 Hz), 5.05 (1 H, t, J = 6.8
Hz), 5.59 (1 H, s), 10.23 (1 H, s).
13C NMR (50 MHz, CDCl3): = 17.6, 25, 25.7, 27, 33.8, 116.1,
123.7, 132.5, 163.4, 172.1.
(E)-3,4-Diphenylbut-2-enoic Acid (3n)
Mp: 138 139 °C.
IR (KBr): 3080, 1683, 1612, 1598 cm–1.
1H NMR (200 MHz, CDCl3): = 4.52 (2 H, s), 6.27 (1 H, s), 7.05
7.55 (10 H, m), 11.5 (1 H, s).
MS (70 eV): m/z (%) = 168 (M+, 5), 123 (14), 100 (19), 69 (100), 67
(11), 41 (95), 39 (32), 29 (12), 27 (22).
Anal. Calcd for C10H16O2: C, 71.39; H, 9.59. Found: C, 71.42; H,
9.57.
(Z)-3-Methylnon-2-en-4-ynoic Acid (3i)
13C NMR (50 MHz, CDCl3): = 36.5, 118, 126.1, 127, 128.4,
128.5, 128.6, 129.3, 138.3, 140.6, 160.2, 172.1.
MS (70 eV): m/z (%) = 238 (M+, 100), 221 (17), 220 (46), 193 (56),
192 (74), 91 (50), 178 (26), 147 (21), 115 (72), 91 (47), 77 (31), 65
(27), 51 (23), 39 (18).
IR: 3350, 2957, 2931, 2873, 2215, 1682, 1610, 1195 cm–1.
1H NMR (200 MHz, CDCl3): = 0.89 (3 H, t, J = 7.2 Hz), 1.21 (2
H, m), 1.56 1.71 (2 H, m), 2.13 (3 H, s), 2.46 (2 H, t, J = 7.3 Hz),
5.95 (1 H, s), 11 (1 H, s).
13C NMR (50 MHz, CDCl3): = 13.8, 21.5, 22.2, 29, 33.4, 105.8,
110.6, 119, 156.5, 165.1.
Anal. Calcd for C16H14O2: C, 80.65; H, 5.92. Found: C, 80.42; H,
5.90.
MS (70 eV): m/z (%) = 166 (M+, 34), 138 (28), 109 (87), 96 (33), 95
(83), 53 (100), 51 (10), 41(23), 29 (18), 27 (37).
(Z)-3-Phenyl-3-(p-tolyl)propenoic Acid (3o)
Mp: 174 °C.
(Z)-3-Methyl-5-trimethylsilylpent-2-en-4-ynoic Acid (3j)
IR (KBr): 3448, 1700, 1612, 1595, 1209, 860 cm–1.
1H NMR (200 MHz, CDCl3): = 2.37 (3 H, s), 6.26 (1 H, s), 7.05
7.45 (9 H, m), 10.15 (1 H, s).
13C NMR (50 MHz, CDCl3): = 21.4, 116.2, 128.3, 128.5, 128.6,
129.4, 129.6, 135.4, 138.5, 141.2, 159.2, 171.4.
MS (70 eV): m/z (%) = 238 (M+, 100), 237 (44), 193 (25), 179 (17),
IR: 3326, 2957, 2149, 1695, 1612 cm–1.
1H NMR (200 MHz, CDCl3): = 0.23 (9 H, s), 2.13 (3 H, s), 5.98
(1 H, s), 10.55 (1 H, s).
13C NMR (50 MHz, CDCl3):
154.2, 169.7.
= 0.4, 25.3, 109.9, 117.4, 125.1,
MS (70 eV): m/z (%) = 182 (M+, 2), 168 (11), 167 (76), 149 (13),
101 (17), 99 (100), 75 (66), 45 (25), 43 (13).
178 (43), 165 (16), 115 (18), 77 (8), 51 (9), 39 (8).
Anal. Calcd for C16H14O2: C, 80.65; H, 5.92. Found: C, 80.55; H,
5.94.
Anal. Calcd for C9H14O2Si: C, 59.30; H, 7.74. Found: C, 59.27; H,
7.72.
(Z)-3-Methylhex-2,5-dienoic Acid (3p)
(E)-3-Methyloct-2-enoic Acid (3k)
(Z)-3-iodobut-2-enoic acid (Z)-2a (2.12 g, 10 mmol) diluted in ben-
zene (20 mL) was added dropwise to a benzene soln of allyltributyl-
tin (4.3 g, 13 mmol). Pd(PPh3)4 (577 mg, 0.5 mmol) was added at
the end of the addition. The mixture was stirred for 3 h at 80 °C and
then hydrolysed with a sat. soln of KF (25 mL) and acetone (25 mL)
after cooling. After vigorous stirring for 2 h, the reaction mixture
was filtered, washed with NH4Cl soln and extracted with Et2O. The
organic layer was then treated with 1N NaOH soln and washed with
Et2O, the aq layer was acidified with 1N HCl soln and extracted
with Et2O. The etheral soln was dried over MgSO4. The solvent was
removed and crude 3p was purified using column chromatography
IR: 3039, 2959, 2931, 2867, 1682, 1637, 1169 cm–1.
1H NMR (200 MHz, CDCl3): = 0.8 (3 H, t, J = 6.4 Hz), 1.03 1.24
(4 H, m), 1.28 1.4 (2 H, m), 2.16 (3 H, d, J = 1.5 Hz), 2.35 (2 H, t,
J = 7 Hz), 5.69 (1 H, br q, J = 1.5 Hz), 11 (1 H, s).
13C NMR (50 MHz, CDCl3): = 13.7, 18.7, 22.3, 26.9, 31.2, 41,
114.8, 163.6, 172.6.
MS (70 eV): m/z (%) = 156 (M+, 5), 141 (13), 139 (95), 113 (26),
100 (56), 97 (11), 96 (40), 95 (36), 82 (27), 81 (21), 71 (11), 69 (22),
67 (29), 59 (11), 57 (18), 56 (17), 55 (45), 45 (14), 43 (50), 41 (100),
39 (75), 29 (81), 28 (12), 27 (67).
Synthesis 2002, No. 4, 543–551 ISSN 0039-7881 © Thieme Stuttgart · New York