编辑: f19970615123fa | 2019-01-24 |
1 H-NMR (CDCl3, 400MHz): δ 6.6-6.8 (s,1H), 6-6.13 (s, 1H), 1.83-1.95 ( s, 3H), 1.17- 1.28 (s, 6H).
7 Mass Spectral data: m/e (relative intensity):
284 (M+ 7),
205 (1),
177 (0.5),
153 (6),
151 (87),
123 (11),
107 (7),
95 (100),
84 (40),
67 (27),
55 (38),
40 (24). Step
2 Methoxy carbonylation of the vinyl triflate: To a solution of Pd(OAc)2 (176mg, 0.8mmol), triphenylphosphine (444mg, 1.7mmol), diisopropylethylamine (Huning'
s base, 4.5ml, 26mmol) and methanol (20mL) in dry DMF( 50ml) under a dry nitrogen atmosphere, was added 2g of the vinyl triflate isolated from the previous reaction. A stream of CO was bubbled through the solution for
20 mins and stirred with a CO balloon for
12 hours. Standard workup with ether and water gave black oil after the removal of solvent. Flash chromatography (silica gel, 12% ether in petroleum ether) gave the product as a pale yellow liquid (1.33g).
1 H-NMR (CDCl3, 400MHz): δ 7.2-7.4 (d, 1H), 6.4-6.65 (d, 1H), 3.66-3.91 (s, 3H), 1.8- 2.1 (d, 3H), 1.25-1.35(s,6H). Mass Spectral data: m/e (relative intensity):
194 (M+ ,95),
179 (17),
162 (20),
151 (68),
135 (48),
134 (75),
124 (23),
107 (78),
91 (100),
79 (28),
77 (26),
65 (30),
52 (16),
43 (28),
39 (33). Step 3: Hydrolysis of ester to acid: The ester obtained in the above step was stirred with 10% LiOH solution in methanol water mixture for 8-12 hours. Methanol was removed under vacuum and added cold water to this mixture and acidified with dilute hydrochloric acid to precipitate the acid. The acid was filtered, dried and s........