7-iodohept-1-ene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate was separately prepared from 1-iodo-4,4,5,5,5-pentafluoropentane, diethyl malonate and 1-iodo-6-heptene. A solution of this compound (4.55 g, 13.21 mmol), (3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochroman (2.5 g, 7.342 mmol) and benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (302 mg, 0.367 mmol) in dichloromethane (60 ml) was heated under reflux for 6 hours. After the reaction was completed, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30) to give ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate (3.46 g, Yield 72%) as an oil. under reflux for 6 hours the solvent was distilled off the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate was separately prepared from 1-iodo-4,4,5,5,5-pentafluoropentane, diethyl malonate and 1-iodo-6-heptene. A solution of this compound (4.55 g, 13.21 mmol), (3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochroman (2.5 g, 7.342 mmol) and benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (302 mg, 0.367 mmol) in dichloromethane (60 ml) was heated under reflux for 6 hours. After the reaction was completed, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30) to give ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate (3.46 g, Yield 72%) as an oil. under reflux for 6 hours the solvent was distilled off the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate was separately prepared from 1-iodo-4,4,5,5,5-pentafluoropentane, diethyl malonate and 1-iodo-6-heptene. A solution of this compound (4.55 g, 13.21 mmol), (3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochroman (2.5 g, 7.342 mmol) and benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (302 mg, 0.367 mmol) in dichloromethane (60 ml) was heated under reflux for 6 hours. After the reaction was completed, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30) to give ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate (3.46 g, Yield 72%) as an oil. under reflux for 6 hours the solvent was distilled off the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dimethylmalonate(8.16 ml, 71.4 mmol) was dissolved in anhydrous DMSO(60 ml), 60% sodium hydride(1.29 g, 53.55 mmol) was added thereto at 0° C., and the resulting mixture was stirred for 30 minutes at room temperature. To the reaction mixture was added 7-iodohept-1-ene(8.0 g, 35.70 mmol), which was then stirred under heating at 60˜70° C. for 4 hours. The temperature was lowered to 0° C. and water was added. The mixture thus obtained was extracted with ethyl acetate, washed with water and saturated saline solution in order, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (eluent:n-hexane/ethyl acetate=40/1, v/v) to give 7.1 g(Yield 87.1%) of the pure title compound as a colorless oil. was then stirred under heating at 60˜70° C. for 4 hours was lowered to 0° C. The mixture thus obtained was extracted with ethyl acetate washed with water and saturated saline solution in order dried over anhydrous magnesium sulfate concentrated under reduced pressure The residue was purified by column chromatography (eluent

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Starting with the ethyl 2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)-8-nonenoate prepared from diethyl malonate, 7-iodo-1-heptene and 1-iodo-3,3,4,4,5,5,6,6,6-nonafluorohexane as in Example 9 and the allyl compound prepared in Example 21, the same procedure as shown in Example 21 was repeated to give 10-[(3RS,4RS)-3-ethyl-7-hydroxy-3-(4-hydroxyphenyl)chroman-4-yl]-2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)decanoic acid.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Starting with the ethyl 2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)-8-nonenoate prepared from diethyl malonate, 7-iodo-1-heptene and 1-iodo-3,3,4,4,5,5,6,6,6-nonafluorohexane as in Example 9 and the allyl compound prepared in Example 13, the same procedure as shown in Example 13 was repeated to give 10-[(3RS,4RS)-3-ethyl-7-hydroxy-3-(4-hydroxyphenyl)thiochroman-4-yl]-2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)decanoic acid.

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (60%, 5.78 g, 144.59 mmol) was added to anhydrous tetrahydrofuran (250 ml) and cooled to 0° C. To this mixture, diethyl malonate (25.09 g, 156.64 mmol) was slowly added dropwise, followed by stirring for 1 hour at room temperature. 7-Iodo-1-heptene (27 g, 120.49 mmol) dissolved in anhydrous tetrahydrofuran (50 ml) was then slowly added dropwise to the mixture, followed by stirring for 12 hours at room temperature. Water was added to the reaction mixture, which was then extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/40) to give diethyl 2-(6-heptenyl)malonate (25.8 g, Yield 84%). was then slowly added dropwise to the mixture by stirring for 12 hours at room temperature was then extracted twice with ethyl acetate The combined organic layers were washed with water and saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/40)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The diethyl 2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)-malonate prepared in Step 1 of Example 2 (1.2 g, 3.0 mmol) was slowly added dropwise to a suspension of 60% sodium hydride (288 mg, 12 mmol) in anhydrous dimethyl sulfoxide (20 ml) at 0° C., followed by stirring for 1 hour at room temperature. After 7-iodohept-1-ene (795 mg, 2.5 mmol) was slowly added dropwise, the reaction mixture was stirred for 12 hours at room temperature. Water was added to the reaction mixture, which was then extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/40) to give diethyl 2-(6-heptenyl)-2-(3,3,4,4,5,5,6,6,6-nonafluorohexyl)malonate (1.08 g, Yield 73%). the reaction mixture was stirred for 12 hours at room temperature was then extracted twice with ethyl acetate The combined organic layers were washed with water and saturated aqueous sodium chloride dried over anhydrous magnesium sulfate After distilling off the solvent the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/40)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Ethyl 2-(4,4,5,5,5-pentafluoropentyl)-8-nonenoate was separately prepared from 1-iodo-4,4,5,5,5-pentafluoropentane, diethyl malonate and 1-iodo-6-heptene. A solution of this compound (4.55 g, 13.21 mmol), (3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methyl-4-(2-propenyl)thiochroman (2.5 g, 7.342 mmol) and benzylidene-bis(tricyclohexylphosphine)dichlororuthenium (302 mg, 0.367 mmol) in dichloromethane (60 ml) was heated under reflux for 6 hours. After the reaction was completed, the solvent was distilled off and the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30) to give ethyl 10-[(3R,4R)-7-methoxy-3-(4-methoxyphenyl)-3-methylthiochroman-4-yl]-2-(4,4,5,5,5-pentafluoropentyl)-8-decenoate (3.46 g, Yield 72%) as an oil. under reflux for 6 hours the solvent was distilled off the resulting residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/30)