(E)-1-bromo-6,6-dimethylhept-2-en-4-yne

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

Procedure: (E,E)-2-(6,6-dimethyl-2-hepten-4-ynyl)-3-[3-[2-[3-(3-thienyl)phenyl]ethenyl]phenyl]propionic acid methyl ester, (E)-2-(6,6-dimethyl-2-hepten-4-ynyl)-3-[3-[4-(3-thienyl)-2-thienylmethoxy]phenyl]propionic acid methyl ester, (E)-2-(6,6-dimethyl-2,4-heptadiynyl)-3-[3-[2-[3-(3-thienyl)phenyl]ethenyl]phenyl]propionic acid methyl ester, (E)-2-(6,6-dimethyl-2-hepten-4-ynyl)-7-[3-(3-thienyl)phenoxy]heptanoic acid methyl ester and (E,E)-2-(6,6-dimethyl-2-hexen-4-ynyl)-8-[3-(3-thienyl)phenyl]-7-octenoic acid methyl ester are obtained by carrying out the same reactions as in Referential Example 4 except that 6,6-dimethyl-2,4-heptadiynyl bromide and/or (E)-3-[3-[2-[3-(3-bromomethylphenyl)ethenyl]phenyl]thiophene, 2-(3-bromomethylphenoxymethyl)-4-(3-thienyl)thiophene, 3-[3-(5-iodopentanoxy)phenyl]thiophene or (E)-3-[3-(6-iodo-1-hexenyl)phenyl]thiophene are used, respectively, in place of (E)-6,6-dimethyl-2-hepten-4-ynyl bromide and/or 3-[3-(3-bromomethylphenoxymethyl)phenyl]thiophene which are the raw material compounds used in the above reaction. used in the above reaction

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

Procedure: 4.05 ml of malonic acid dimethyl ester is dissolved in 40 ml of dimethylformamide, 1.29 g of 60% oily sodium hydride and 6.5 g of (E)-6,6-dimethyl-2-hepten-4-ynyl bromide (containing about 5% Z-form) are added gradually, and the mixture is stirred at that temperature for 1 hour. Saturated saline and ethyl ether are added to the reaction solution to form two liquid phases, the ether layer is taken, washed with saturated saline and dried over anhydrous magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue is purified by silica gel column chromatography [Wako gel C-200, 400 g; hexane/ethyl acetate=19/1→9/1] to obtain 6.26 g of (E)-6,6-dimethyl-2-hepten-4-ynylmalonic acid dimethyl ester as colorless oil. to form two liquid phases washed with saturated saline dried over anhydrous magnesium sulfate the solvent is distilled off under reduced pressure The residue is purified by silica gel column chromatography [Wako gel C-200, 400 g; hexane/ethyl acetate=19/1→9/1]

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

Procedure: 3.34 g of diethylphosphonoacetic acid ethyl ester is dissolved in 40 ml of ethanol, 594 mg of 60% oily sodium hydride is added under ice cooling and stirring, and ethanol solution (10 ml) of 600 mg of (E)-6,6-dimethyl-2-hepten-4-ynyl bromide is added dropwise, and the mixture is stirred for 5 hours. The reaction solution is neutralized with 1N hydrochloric acid and then concentrated under reduced pressure, the residue is dissolved in a mixture of water with ethyl acetate, the organic layer is taken and post-treated in a conventional manner, and the product is purified by silica gel column chromatography [Wako gel C-200, 140 g; hexane/ethyl acetate=3/1→1/1] to obtain 686 mg of (E)-diethylphosphono-(6,6-dimethyl-2-hepten-4-ynyl)acetic acid ethyl ester as colorless oil. the mixture is stirred for 5 hours concentrated under reduced pressure the residue is dissolved in a mixture of water with ethyl acetate post-treated in a conventional manner the product is purified by silica gel column chromatography [Wako gel C-200, 140 g; hexane/ethyl acetate=3/1→1/1]

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

Procedure: Compound of Example 53 was obtained by performing the same reaction as in Example 52 except that 2-[2-[3-(3-thienyl)phenoxy]ethoxy]ethylamine and (E)-6,6-dimethyl-2-hepten-4-ynyl bromide were used instead of the starting compounds, 5-[3-(3-thienyl)phenoxy]pentylamine and (E)-6-methoxy-6-methyl-2-hepten-4-ynyl bromide, which were used in the above-mentioned reaction. were used in the above-mentioned reaction

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

Procedure: 5 g of 1-(Hydroxymethyl)naphthalin are in THF are treated at room temperature with 900 mg of 80% NaH (dissolved in mineral oil) and stirred until the evolution of gas ceases (ca. 1 hr.). A solution of 6.36 g of (E)-1-bromo-6,6-di-methyl-2-hepten-4-ine in DMF are added dropwise and the reaction mixture stirred overnight at room temperature. the reaction mixture stirred overnight at room temperature