EXAMPLE 7
Production of 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid ethylester
Preparation:
4.98 g (30 mmole) p-hydroxybenzoic acid ethylester
3.06 g (30 mmole) phenylacetylene
31.26 g (120 mmole) tin tetrachloride
22.24 g (120 mmole) tributylamine
150 ml 1,2-dichlorethane
Method:
Under an argon atmosphere, a solution of 4.98 g (30 mmole) phydroxy-benzoic acid ethylester, 3.06 g (30 mmole) phenylacetylene, 31.26 g (120 mmole) tin tetrachloride and 22.24 (120 mmole) tributylamine in 150 ml 1,2-dichlorethane are heated for 1 h with recycling. Then 60 ml 4 M KOH and 30 ml ethanol are added to the reaction mixture and heated for 1 h with recycling. Following cooling, the solution is acidified with 4 M HCl and extracted twice with 150 ml diethylether each time. The purified organic phases are dried through MgSO4 and the solvent is removed on the rotary evaporator. The remaining residue undergoes absorptive filtering (silica gel, MTBE) and the raw product obtained in this way is cleaned by column chromatography (silica gel, toluene/MTBE=8/1 (v/v)). 2.63 g (9.8 mmole, 33%) 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid-ethylester are obtained.
Yield: 2.63 g (9.8 mmole, 33%) 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid-ethylester.
1H-NMR (400 MHz, CDCl3): δ [ppm]=1.36 (t, 3J=7.1 Hz, 3H, CH3), 4.33 (q, 3J=7.1 Hz, 2H, OCH2), 5.44 (d, 2J=0.9 Hz, 1H, ═CH2), 5.91 (d, 2J=0.9 Hz, 1H, ═CH2), 6.97 (d, 3J=8.5 Hz, 1H, PhH), 7.34 (m, 5H, PhH), 7.89 (d, 4J=2.1 Hz, 1H, PhH), 7.96 (dd, 3J=8.5 Hz, 4J=2.1 Hz, 1H, PhH).
13C-NMR (100 MHz, CDCl3): δ [ppm]=14.3 (CH3), 60.8 (OCH2), 115.8 (CHarom), 117.5 (═CH2), 122.9 (Cqarom), 126.9 (2×CHarom) 127.5 (Cqarom), 128.8 (3×CHarom), 131.3 (CHarom), 132.3 (CHarom), 138.7 (Cqarom), 144.3 (Cqolefin), 157.1 (Cqarom), 166.3 (COOEt).
MS (EI, 70EV): m/z [%]=268 (M+, 98), 267 (100), 253 (35) 239 (32), 225 (13), 223 (24), 194 (6), 165 (20), 152 (12), 115 (5), 111 (6), 104 (7).
http://www.google.com/patents/US6809225
DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO .....FOR BLOG HOME CLICK HERE
Production of 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid ethylester
4.98 g (30 mmole) p-hydroxybenzoic acid ethylester
3.06 g (30 mmole) phenylacetylene
31.26 g (120 mmole) tin tetrachloride
22.24 g (120 mmole) tributylamine
150 ml 1,2-dichlorethane
Method:
Under an argon atmosphere, a solution of 4.98 g (30 mmole) phydroxy-benzoic acid ethylester, 3.06 g (30 mmole) phenylacetylene, 31.26 g (120 mmole) tin tetrachloride and 22.24 (120 mmole) tributylamine in 150 ml 1,2-dichlorethane are heated for 1 h with recycling. Then 60 ml 4 M KOH and 30 ml ethanol are added to the reaction mixture and heated for 1 h with recycling. Following cooling, the solution is acidified with 4 M HCl and extracted twice with 150 ml diethylether each time. The purified organic phases are dried through MgSO4 and the solvent is removed on the rotary evaporator. The remaining residue undergoes absorptive filtering (silica gel, MTBE) and the raw product obtained in this way is cleaned by column chromatography (silica gel, toluene/MTBE=8/1 (v/v)). 2.63 g (9.8 mmole, 33%) 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid-ethylester are obtained.
Yield: 2.63 g (9.8 mmole, 33%) 4-hydroxy-3-(1-phenyl-vinyl)-benzoic acid-ethylester.
1H-NMR (400 MHz, CDCl3): δ [ppm]=1.36 (t, 3J=7.1 Hz, 3H, CH3), 4.33 (q, 3J=7.1 Hz, 2H, OCH2), 5.44 (d, 2J=0.9 Hz, 1H, ═CH2), 5.91 (d, 2J=0.9 Hz, 1H, ═CH2), 6.97 (d, 3J=8.5 Hz, 1H, PhH), 7.34 (m, 5H, PhH), 7.89 (d, 4J=2.1 Hz, 1H, PhH), 7.96 (dd, 3J=8.5 Hz, 4J=2.1 Hz, 1H, PhH).
13C-NMR (100 MHz, CDCl3): δ [ppm]=14.3 (CH3), 60.8 (OCH2), 115.8 (CHarom), 117.5 (═CH2), 122.9 (Cqarom), 126.9 (2×CHarom) 127.5 (Cqarom), 128.8 (3×CHarom), 131.3 (CHarom), 132.3 (CHarom), 138.7 (Cqarom), 144.3 (Cqolefin), 157.1 (Cqarom), 166.3 (COOEt).
MS (EI, 70EV): m/z [%]=268 (M+, 98), 267 (100), 253 (35) 239 (32), 225 (13), 223 (24), 194 (6), 165 (20), 152 (12), 115 (5), 111 (6), 104 (7).
http://www.google.com/patents/US6809225
DRUG APPROVALS BY DR ANTHONY MELVIN CRASTO .....FOR BLOG HOME CLICK HERE
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