4-ethynylphenol

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

Procedure: A solution of 382 mg of p-[(trimethylsilyl)ethynyl]-phenol (prepared according to Example 10) in 15 ml of a 1:1 mixture of methanol and 1N aqueous potassium hydroxide solution was stirred at room temperature for 45 minutes in a round flask under argon gasification. Methanol was subsequently removed on a rotary evaporator and the residue, after the addition of 30 ml of 1N hydrochloric acid, was extracted three times with 30 ml of diethyl ether each time. The organic phases were washed twice with 30 ml of water each time and once with 30 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. There were obtained 207 mg (88%) of p-ethynylphenol as a colourless oil (decomposing rapidly in the pure state) which was taken up immediately in 50 ml of diethyl ether and treated with 436 mg of trans-4-pentylcyclohexanecarboxylic acid, 454 mg of N,N'-dicyclohexylcarbodiimide and 24.4 mg of 4-(dimethylamino)pyridine. This mixture was stirred at room temperature for 18 hours and subsequently filtered. The filtrate was treated with 50 ml of water and extracted three times with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of water and with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.4 bar) of the residue (847 mg) on silica gel with 3% ethyl acetate petroleum ether gave 277 mg (46%) of trans-4-pentylcyclohexanecarboxylic acid p-ethynylphenyl ester as colourless crystals (purity 98.5%) which were recrystallized further from methanol (purity 99.1%); m.p. (C-N) 50.6° C., cl.p. (N-I) 78.5° C. Methanol was subsequently removed on a rotary evaporator the residue, after the addition of 30 ml of 1N hydrochloric acid was extracted three times with 30 ml of diethyl ether each time The organic phases were washed twice with 30 ml of water each time once with 30 ml of saturated sodium chloride solution, dried over magnesium sulphate concentrated

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

Procedure: The conventional preparation process of hydroxyphenyl-acetylene has been reported, for example, in Izv. Akad. Nauk SSSR Se. r. Khim 1964(11), 2073-4. In the process, 4-hydroxyacetophenone is chlorinated with phosphorus pentachloride, reacted in liquid ammonia in the presence of metallic sodium and ammonium chloride, and successively treated with water to obtain 4-hydroxyphenylacetylene in 46% yield.

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

Procedure: In 40 ml of pyridine was dissolved poly(p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd., weight average molecular weight: 11,000) and to the solution was added 1.28 g of di-tert-butyl dicarbonate at a room temperature with stirring. The solution was reacted at a room temperature for 3 hours and poured into a solution of one liter of ion-exchanged water and 20 g of concentrated hydrochloric acid. The powder thus-deposited was collected by filtration, washed with water and dried to obtain p-hydroxystyrene/p-(tert-butoxycarbonyloxy)-styrene (60/40) copolymer. The Mw of the resin was 12,000 and the molecular weight distribution (Mw/Mn) thereof was 1.1. The solution was reacted at a room temperature for 3 hours The powder thus-deposited was collected by filtration washed with water dried

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 320 g of propylene glycol monomethyl ether acetate (PGMEA) was dissolved 70 g of poly(p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd.) with heating and the solution was subjected to dehydration by distillation under a reduce pressure and cooled to 20° C. To the solution were added 0.35 g of pyridinium p-toluenesulfonate and 22.4 g of 2-cyclohexylethanol. Then, 17.5 g of tert-butyl vinyl ether was gradually added to the solution, followed by reacting at 20° C. for 5 hours. To the reaction mixture were added 0.28 g of triethylamine and 320 ml of ethyl acetate and the mixture was washed three times with each 150 ml of distilled water. The solvent was distilled off to concentrate, the resulting oily substance was dissolved in 100 ml of acetone and the solution was gradually poured into 2 liters of distilled water. The powder thus-deposited was collected by filtration and dried to obtain 54 g of the desired compound. The Mw of the resin was 12,000 and the molecular weight distribution (Mw/Mn) thereof was 1.1. with heating the solution was subjected to dehydration by distillation under a reduce pressure To the solution were added 0.35 g of pyridinium p-toluenesulfonate and 22.4 g of 2-cyclohexylethanol Then, 17.5 g of tert-butyl vinyl ether was gradually added to the solution To the reaction mixture were added 0.28 g of triethylamine and 320 ml of ethyl acetate the mixture was washed three times with each 150 ml of distilled water The solvent was distilled off to concentrate the resulting oily substance was dissolved in 100 ml of acetone the solution was gradually poured into 2 liters of distilled water The powder thus-deposited was collected by filtration dried

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 30 g of poly(p-hydroxystyrene) (VP8000) produced by Nippon Soda Co., Ltd. was dissolved in 120 mL of dimethylsulfoxide (DMSO), and 2.21 g of 1-chloromethylnaphthalene, 34.51 g of potassium carbonate and 0.56 g of sodium iodide were added thereto. The mixture was stirred at 70° C. for 4 hours, and the reaction solution was returned to room temperature. Thereafter, 100 mL of ethyl acetate and 100 mL of distilled water were added thereto, and 130 g of an aqueous 23% acetic acid solution was little by little added to the reaction solution while stirring the reaction solution in ice water. The reaction solution was transferred to a separating funnel, and 100 mL of ethyl acetate and 100 mL of distilled water were further added. After stirring, the aqueous layer was removed, and the organic layer was washed with 200 mL of distilled water five times. The organic layer was then concentrated and dissolved in 120 g of tetrahydrofuran (THF). Thereto, 26.53 g of triethylamine was added, and the reaction solution was cooled to 0° C. Furthermore, 23.43 g of the 3-chloro-3-benzyloxypropionitrile solution above was added dropwise, and the reaction solution was returned to room temperature and then stirred for 4 hours. After adding 200 ml of distilled water to the reaction solution, THF was removed by an evaporator, and 200 mL of ethyl acetate was added to the residue. The reaction solution was transferred to a separating funnel, and the aqueous layer was removed. The organic layer was washed with 200 ml of distilled water three times, concentrated to about 150 mL by an evaporator and added dropwise in 2 L of hexane. A part of the obtained precipitate was sampled for NMR measurement, and the remaining was dissolved in 75 g of PGMEA. From the obtained solution, the low boiling point solvent was removed by an evaporator to obtain 105.2 g of a PGMEA solution (29.6 mass %) of Resin (P-22). was returned to room temperature by little added to the reaction solution The reaction solution was transferred to a separating funnel After stirring the aqueous layer was removed the organic layer was washed with 200 mL of distilled water five times The organic layer was then concentrated dissolved in 120 g of tetrahydrofuran (THF) Thereto, 26.53 g of triethylamine was added the reaction solution was cooled to 0° C Furthermore, 23.43 g of the 3-chloro-3-benzyloxypropionitrile solution above was added dropwise was returned to room temperature stirred for 4 hours After adding 200 ml of distilled water to the reaction solution, THF was removed by an evaporator, and 200 mL of ethyl acetate was added to the residue The reaction solution was transferred to a separating funnel the aqueous layer was removed The organic layer was washed with 200 ml of distilled water three times concentrated to about 150 mL by an evaporator added dropwise in 2 L of hexane A part of the obtained precipitate was sampled for NMR measurement the remaining was dissolved in 75 g of PGMEA From the obtained solution, the low boiling point solvent was removed by an evaporator

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 30 g of poly(p-hydroxystyrene) (VP8000) produced by Nippon Soda Co., Ltd. was dissolved in 120 mL of dimethylsulfoxide (DMSO), and 9.36 g of (1-ethyl)cyclopentyl bromoacetate, 9.70 g of Compound (p-9) above, 34.51 g of potassium carbonate and 0.89 g of sodium iodide were added thereto. The mixture was stirred at 70° C. for 4 hours, and the reaction solution was returned to room temperature. Thereafter, 100 mL of ethyl acetate and 100 mL of distilled water were added thereto, and 130 g of an aqueous 23 mass % acetic acid solution was little by little added to the reaction solution while stirring the reaction solution in ice water. The reaction solution was transferred to a separating funnel, and 100 mL of ethyl acetate and 100 mL of distilled water were further added. After stirring, the aqueous layer was removed, and the organic layer was washed with 200 mL of distilled water five times. The organic layer was then concentrated to about 150 mL and added dropwise in 2 L of hexane. A part of the obtained precipitate was sampled for NMR measurement, and the remaining was dissolved in 70 g of PGMEA. From the obtained solution, the low boiling point solvent was removed by an evaporator to obtain 102.1 g of a PGMEA solution (34.6 mass %) of Resin (P-9). was returned to room temperature by little added to the reaction solution The reaction solution was transferred to a separating funnel After stirring the aqueous layer was removed the organic layer was washed with 200 mL of distilled water five times The organic layer was then concentrated to about 150 mL added dropwise in 2 L of hexane A part of the obtained precipitate was sampled for NMR measurement the remaining was dissolved in 70 g of PGMEA From the obtained solution, the low boiling point solvent was removed by an evaporator

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 30 g of poly(p-hydroxystyrene) (VP2500) produced by Nippon Soda Co., Ltd. was dissolved in 150 mL of DMSO, and 4.41 g of 1-chloromethylnaphthalene, 34.51 g of potassium carbonate and 0.56 g of sodium iodide were added thereto. The mixture was stirred at 70° C. for 4 hours, and the reaction solution was returned to room temperature. Subsequently, 6.65 g of α-chlorobenzyl methyl ether was added dropwise thereto and after stirring at room temperature for 3 hours, 3.40 g of butanesultone was added dropwise. The reaction solution was further stirred at room temperature for 4 hours, and 100 mL of ethyl acetate and 100 mL of distilled water were added thereto. Thereafter, 130 g of an aqueous 21 mass % ammonium chloride solution was little by little added to the reaction solution while stirring the reaction solution in ice water. The reaction solution was transferred to a separating funnel, and 100 mL of ethyl acetate and 100 mL of distilled water were further added. After stirring, the aqueous layer was removed, and the organic layer was washed with 200 mL of distilled water five times. The organic layer was then concentrated to about 150 mL and added dropwise in 2 L of hexane. The obtained precipitate was dissolved in a methanol:THF mixed solution, and 7.50 g of triphenylsulfonium bromide was added thereto. The mixture was stirred at room temperature for 2 hours, and the reaction solution was concentrated under reduced pressure, diluted with 300 mL of ethyl acetate, and washed with 300 mL of distilled water five times. The organic layer was concentrated and dissolved in 70 g of PGMEA, and the low boiling point solvent was then removed by an evaporator to obtain 108.2 g of a PGMEA solution (32.5 mass %) of Resin (P-7). was returned to room temperature after stirring at room temperature for 3 hours The reaction solution was further stirred at room temperature for 4 hours by little added to the reaction solution The reaction solution was transferred to a separating funnel After stirring the aqueous layer was removed the organic layer was washed with 200 mL of distilled water five times The organic layer was then concentrated to about 150 mL added dropwise in 2 L of hexane The obtained precipitate was dissolved in a methanol THF mixed solution, and 7.50 g of triphenylsulfonium bromide was added The mixture was stirred at room temperature for 2 hours the reaction solution was concentrated under reduced pressure diluted with 300 mL of ethyl acetate washed with 300 mL of distilled water five times The organic layer was concentrated dissolved in 70 g of PGMEA the low boiling point solvent was then removed by an evaporator

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 30 g of poly(p-hydroxystyrene) (VP8000) produced by Nippon Soda Co., Ltd. was dissolved in 120 mL of dimethylsulfoxide (DMSO), and 3.04 g of 4-chloromethylbiphenyl, 34.51 g of potassium carbonate and 0.56 g of sodium iodide were added thereto. The mixture was stirred at 70° C. for 4 hours, and the reaction solution was returned to room temperature. Subsequently, 8.21 g of α-chlorobenzyl methyl ether was added dropwise thereto and after stirring at room temperature for 4 hours, 100 mL of ethyl acetate and 100 mL of distilled water were added thereto. Thereafter, 130 g of an aqueous 21 mass % ammonium chloride solution was little by little added to the reaction solution while stirring the reaction solution in ice water. The reaction solution was transferred to a separating funnel, and 100 mL of ethyl acetate and 100 mL of distilled water were further added. After stirring, the aqueous layer was removed, and the organic layer was washed with 200 mL of distilled water five times. The organic layer was then concentrated to about 150 mL and added dropwise in 2 L of hexane. A part of the obtained precipitate was sampled for NMR measurement, and the remaining was dissolved in 70 g of PGMEA. From the obtained solution, the low boiling point solvent was removed by an evaporator to obtain 100.1 g of a PGMEA solution (33.8 mass %) of Resin (P-4). was returned to room temperature after stirring at room temperature for 4 hours by little added to the reaction solution The reaction solution was transferred to a separating funnel After stirring the aqueous layer was removed the organic layer was washed with 200 mL of distilled water five times The organic layer was then concentrated to about 150 mL added dropwise in 2 L of hexane A part of the obtained precipitate was sampled for NMR measurement the remaining was dissolved in 70 g of PGMEA From the obtained solution, the low boiling point solvent was removed by an evaporator

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

Procedure: In 40 ml of pyridine was dissolved poly(p-hydroxystyrene) (VP-8000, manufactured by Nippon Soda Co., Ltd., weight average molecular weight: 1,1000) and to the solution was added 1.28 g of di-tert-butyl dicarbonate at a room temperature with stirring. The solution was reacted at a room temperature for 3 hours and poured into a solution of one liter of ion exchange water and 20 g of concentrated hydrochloric acid. The powder thus-deposited was collected by filtration, washed with water and dried to obtain 2.1 g of p-hydroxystyrene/p-(tert-butoxycarbonyloxy)-styrene (60/40) copolymer. The solution was reacted at a room temperature for 3 hours The powder thus-deposited was collected by filtration washed with water dried

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In 120 ml of butyl acetate was dissolved 32.4 g (0.2 mol) of p-acetoxystyrene. Three 0.033 g portions of azobisisobutyronitrile (AIBN) were added at an interval of 2.5 hours to the solution with stirring at 80° C. in a nitrogen stream and stirring was thereafter continued for 5 hours, whereby polymerization reaction was conducted. The resultant reaction mixture was poured into 1,200 ml of hexane to precipitate a white resin. The resin obtained was dried and then dissolved in 150 ml of methanol. Thereto was added an aqueous solution prepared by dissolving 7.7 g (0.19 mol) of sodium hydroxide in 50 ml of water. This mixture was heated with refluxing for 3 hours to hydrolyze the resin. Thereafter, the reaction mixture was diluted with 200 ml of water and neutralized with hydrochloric acid to precipitate a white resin. This resin was taken out by filtration, washed with water, dried, and then dissolved in 200 ml of tetrahydrofuran to give a solution, which was added dropwise to 5 L of ultrapure water with vigorous agitation to conduct reprecipitation. This reprecipitation operation was repeated three times. The resin thus obtained was dried in a vacuum dryer at 120° C. for 12 hours to obtain poly(p-hydroxystyrene) as alkali-soluble resin R-1. stirring whereby polymerization reaction The resultant reaction mixture to precipitate a white resin The resin obtained was dried dissolved in 150 ml of methanol Thereto was added an aqueous solution prepared This mixture was heated with refluxing for 3 hours to precipitate a white resin This resin was taken out by filtration washed with water dried dissolved in 200 ml of tetrahydrofuran to give a solution, which reprecipitation The resin thus obtained was dried in a vacuum dryer at 120° C. for 12 hours

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

Procedure: 32.4 g (0.2 mol) of p-acetoxystyrene was dissolved in 120 ml of butyl acetate and thereto, 0.033 g of azobisisobutyronitrile (AIBN) was added at 80° C. while stirring in a nitrogen stream 3 times every 2.5 hours. The stirring was further continued for 5 hours to perform the polymerization reaction. The reaction solution was charged into 1,200 ml of hexane and white resin was precipitated. The resin obtained was dried and then dissolved in 150 ml of methanol and thereto, an aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide/50 ml of water was added. The mixed solution was heated under reflux for 3 hours to perform the hydrolysis, then diluted by adding 200 ml of water, and neutralized with hydrochloric acid to precipitate white resin. This resin was separated by filtration, washed with water, and dried. The resulting resin was dissolved in 200 ml of tetrahydrofuran. The resulting solution was added dropwise to 5 L of ultrapure water while vigorously stirring to reprecipitate the resin. This reprecipitation operation was repeated 3 times and the resin obtained was dried in a vacuum dryer at 120° C. for 12 hours to obtain poly(p-hydoxystyrene) Alkali-Soluble Resin R-1. The stirring was further continued for 5 hours the polymerization reaction was precipitated The resin obtained was dried dissolved in 150 ml of methanol The mixed solution was heated under reflux for 3 hours the hydrolysis diluted to precipitate white resin This resin was separated by filtration washed with water dried The resulting resin was dissolved in 200 ml of tetrahydrofuran The resulting solution was added dropwise to 5 L of ultrapure water while vigorously stirring the resin obtained was dried in a vacuum dryer at 120° C. for 12 hours

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

Procedure: In 250 mL of ethyl acetate, 50.0 g of poly(p-hydroxystyrene) (from Nippon Soda Co., Ltd.; weight average molecular weight (Mw) is about 15,000 and distribution (Mw/Mn) thereof about 1.05) was dissolved, then14.8 g of di-tert-butyl dicarbonate and 11.0 g of pyridine were added and reacted at room temperature for 4 hours. Said reaction solution was then concentrated under reduced pressure, followed by dissolving in 250 mL of acetone, then poured into 3 L of water for precipitation. The thus deposited crystal was filtered off and dried under reduced pressure to obtain 50.8 g of poly(p-hydroxystyrene/p-tert-butoxycarbonyloxystyrene) as a white powder crystal. The thus obtained crystal was named polymer A2. A composition ratio of p-hydroxystyrene unit and p-tert-butoxycarbonyloxystyrene unit in polymer A2 was found to be about 85:15 from the measurement results by 13CNMR. Weight average molecular weight (Mw) of polymer A2 was about 16,500 and distribution (Mw/Mn) thereof was about 1.05 from the measurement results by gel permeation chromatography using polystyrene as a standard. about 1.05) was dissolved reacted at room temperature for 4 hours reaction solution was then concentrated under reduced pressure by dissolving in 250 mL of acetone poured into 3 L of water for precipitation The thus deposited crystal was filtered off dried under reduced pressure