Allyl Phenyl Ether

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A few crystals of diphenyl are added to a suspension, cooled to 5°-10° C and held under a nitrogen atmosphere, of 2.4 g (0.35 g-atoms) of finely cut lithium wire in 40 ml of absolute tetrahydrofuran. 2 ml of a solution of 9.4 g (70 mmol) of allyl phenyl ether in 10 ml of absolute ether are then added. After a greenish coloration sets in, the rest of the solution is added dropwise at -15° C. After completion of the addition, the mixture is stirred for 30 minutes at 0° C. The resulting allyl lithium solution is decanted off from excess lithium and transferred to a dropping funnel. This solution is added dropwise to a solution, cooled to -60° C and maintained under nitrogen, of 4.48 g (20 mmol) of 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid ethyl ester in 40 ml of absolute ether. After completion of the addition, the mixture is left to warm to room temperature, poured on to ice-water and extracted with three portions of hexane. The combined hexane extracts are washed neutral with three portions of water, dried over sodium sulphate and evaporated. By fractional distillation of the residue there are obtained 3.75 g (85%) of 2-ethyl-3,6,6-trimethyl-1-[but-3-enoyl]-2-cyclohexene; boiling point 57°-58° C/0.04 mm Hg; nD 20 = 1.4865. A few crystals of diphenyl are added to a suspension cooled to 5°-10° C After a greenish coloration sets in, the rest of the solution is added dropwise at -15° C After completion of the addition The resulting allyl lithium solution is decanted off from excess lithium transferred to a dropping funnel This solution is added dropwise to a solution cooled to -60° C After completion of the addition the mixture is left to warm to room temperature extracted with three portions of hexane The combined hexane extracts are washed neutral with three portions of water dried over sodium sulphate evaporated By fractional distillation of the residue there

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of bis(1,5-cyclooctadiene)iridium tetrafluoroborate [Ir(cod)2]+BF4− (0.01 mmol) and toluene (1.0 ml) was treated with phenol (1 mmol) and allyl acetate (5 mmol) with stirring at 100° C. The reaction mixtures after 5 hours and after 15 hours of the reaction were analyzed by gas chromatography. In the reaction mixture after 5 hours, phenyl allyl ether was formed in a yield of 21% with a conversion from phenol of 23%. In the reaction mixture after 15 hours, phenyl allyl ether was formed in a yield of 51% with a conversion from phenol of 51%. In the reaction mixture after 5 hours

反应条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of methyl 2-bromobenzoate (0.206 g, 0.96 mmol) in acetonitrile (3 ml) were added allyl phenyl ether (0.65 ml, 1.09 mmol), tri-o-tolylphosphine (0.014 g, 0.045 mmol), palladium acetate (0.006 g, 0.027 mmol) and triethylamine (0.16 ml, 1.15 mmol), and the mixture was stirred at 100° C. for 4 hr. The reaction mixture was filtered through celite, and ethyl acetate was added to the filtrate. The mixture was washed with water, and the organic layer was dried over sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate) to give methyl 2-(3-phenoxypropenyl)benzoate (0.037 g, 0.14 mmol, yield 15%). The reaction mixture was filtered through celite, and ethyl acetate was added to the filtrate The mixture was washed with water the organic layer was dried over sodium sulfate The solvent was evaporated under reduced pressure the obtained residue was purified by silica gel column chromatography (hexane:ethyl acetate)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of compound 2 (9.0 g, 0.034 mol) and phenyl allyl ether (6.98 ml, 0.051 mol) in 200 ml of toluene is refluxed for 48 hours, cooled and evaporated under vacuum. The semisolid that remained (7.30 g, 54%) is crystallized from ether and recrystallized from ethyl acetate to give tan crystals. Yield: 2.4 g (18%); m.p. 176°-178° C. (Found: C, 74.96; H, 6.41; N, 10.40. C25H25N3O2 requires: C, 75.16; H, 6.31; N, 10.52). is refluxed for 48 hours cooled evaporated under vacuum is crystallized from ether recrystallized from ethyl acetate to give tan crystals

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A mixture of compound 2 (9.0 g, 0.034 mol) and phenyl allyl ether (6.98 ml, 0.051 mol) in 200 ml of toluene is refluxed for 48 hours, cooled and evaporated under vacuum. The semisolid that remained (7.30 g, 54%) is crystallized from ether and recrystallized from ethyl acetate to give tan crystals. Yield: 2.4 g (18%); m.p. 176°-178° C. (Found: C, 74.96; H, 6.41; N, 10.40. C25H25N3O2 requires: C, 75.16; H, 6.31; N, 10.52). is refluxed for 48 hours cooled evaporated under vacuum is crystallized from ether recrystallized from ethyl acetate to give tan crystals

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Lithium wire (2.1 g, 303 mmol) in small pieces in 26 ml of dry tetrahydrofuran containing a trace of naphthalene under argon was cooled to -15° and was treated with 3.32 g (24.8 mmol) of allyl phenyl ether in 14 ml of tetrahydrofuran containing a trace of naphthalene, with rapid stirring for 45 minutes. After an additional 1.25 hours at room temperature, 14.7 ml (ca. 6.6 mmol) of the allyllithium solution was added at -15° over 2 minutes to 635 mg (3.3 mmol) of copper iodide in 10 ml of tetrahydrofuran under argon with rapid stirring. After 5 minutes, the dark solution was of lithium diallylcuprate cooled to -78° and 245 mg (3.0 mmol) of cyclopentenone in 2 ml of tetrahydrofuran was added over 2 minutes. After 40 minutes at -78°, 1 ml of tetramethylethylenediamine was added followed 5 minutes later by 3.0 g (15.5 mmol) of 1-iodo-2-pentyne in 10 ml of hexamethylphosphoramide. After 2 additional hours at -78°, 1 ml of methanol was added and the mixture was poured into aqueous ammonium chloride-ammonium hydroxide-ether. After rapidly stirring for 15 minutes, the organic phase was separated and washed successively with aqueous sodium hydroxide, aqueous hydrochloric acid, aqueous sodium thiosulfate, and aqueous sodium chloride. After drying over potassium carbonate, the solvent was removed under reduced pressure and the resulting oil was chromatographed on silica gel using chloroform-hexane to afford 325 mg of 2-pentynyl, 3-allylcyclopentanone (57%). After an additional 1.25 hours at room temperature After 5 minutes cooled to -78° After 40 minutes at -78° After rapidly stirring for 15 minutes the organic phase was separated washed successively with aqueous sodium hydroxide, aqueous hydrochloric acid, aqueous sodium thiosulfate, and aqueous sodium chloride After drying over potassium carbonate the solvent was removed under reduced pressure the resulting oil was chromatographed on silica gel

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 40 g of allyloxybenzene in 50 ml of acetic acid are added dropwise 78.4 g of phenyliodosotoluene sulfonate in 100 ml of acetic acid and the mixture is stirred at room temperature for 2 hours. The reaction mixture is poured into 1l of dioxane, the precipitate of (allyloxyphenyl)-phenyliodonium toluenesulfonate obtained is washed with ether and dried. Conversion into bis-fluorosulfonylimide is carried out by mixing 15 g of (allyloxyphenyl)-phenyliodonium toluenesulfonate and 7 g of KN(SO2F)2 in 150 ml of water at 0° C. The salt is extracted with 2×50 ml of dichloromethane and the solvent is evaporated. The residual salt (consisting of (allyloxyphenyl)-phenyliodonium bis-fluorosulfonylimide) is diluted with 60 ml of THF and is introduced into a three-neck flask provided with a cooler, a mechanical stirrer and a neutral gas inlet (Argon), said flask containing 8.5 g of a copolymer of dimethylsiloxane and (hydrogeno)(methyl)-siloxane (HMS 301 25% SiH, Mw 1900 sold by Gelest Inc., Tullytown, Pa., U.S.A.) in solution in 60 ml of THF and 90 mg of chloroplatinic acid H2PtCl6. The mixture was heated under reflux for 2 hours. 1 g of 1-hexene was thereafter added and the reaction was continued for 1 hour. A sampling enables to confirm the complete disappearance of IR bands of the SiH bond which confirms hydrosilylation between the allyl groups of (allyloxyphenyl)-phenyliodonium bis-fluorosulfonylimide and groups SiH of the copolymer of dimethylsiloxane and (hydrogeno)(methyl)-siloxane. The polymer thus obtained which contains ionic pendant groups is precipitated in methanol and purified by means of three operations of dissolution (THF)/precipitation (methanol and ether).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 40 g of allyloxybenzene in 50 ml of acetic acid are added dropwise 78.4 g of phenyliodosotoluene sulfonate in 100 ml of acetic acid and the mixture is stirred at room temperature for 2 hours. The reaction mixture is poured into 1l of dioxane, the precipitate of (allyloxyphenyl)-phenyliodonium toluenesulfonate obtained is washed with ether and dried. Conversion into bis-fluorosulfonylimide is carried out by mixing 15 g of (allyloxyphenyl)-phenyliodonium toluenesulfonate and 7 g of KN(SO2F)2 in 150 ml of water at 0° C. The salt is extracted with 2×50 ml of dichloromethane and the solvent is evaporated. The residual salt (consisting of (allyloxyphenyl)-phenyliodonium bis-fluorosulfonylimide) is diluted with 60 ml of THF and is introduced into a three-neck flask provided with a cooler, a mechanical stirrer and a neutral gas inlet (Argon), said flask containing 8.5 g of a copolymer of dimethylsiloxane and (hydrogeno)(methyl)-siloxane (HMS 301 25% SiH, Mw 1900 sold by Gelest Inc., Tullytown, Pa., U.S.A.) in solution in 60 ml of THF and 90 mg of chloroplatinic acid H2PtCl6. The mixture was heated under reflux for 2 hours. 1 g of 1-hexene was thereafter added and the reaction was continued for 1 hour. A sampling enables to confirm the complete disappearance of IR bands of the SiH bond which confirms hydrosilylation between the allyl groups of (allyloxyphenyl)-phenyliodonium bis-fluorosulfonylimide and groups SiH of the copolymer of dimethylsiloxane and (hydrogeno)(methyl)-siloxane. The polymer thus obtained which contains ionic pendant groups is precipitated in methanol and purified by means of three operations of dissolution (THF)/precipitation (methanol and ether).

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The procedure for preparing the copolymer in Example 1 was repeated except that potassium itaconate and o-allylphenol were used in place of potassium methacrylate and 4-allyl-2-methoxyphenol, respectively to obtain a copolymer of stearyl methacrylate, potassium itaconate and O-allyl phenol. The procedure for preparing the copolymer in Example 1