triethylphosphane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 73 g (0.5 moles) of 2-bromoethylmethyl ether (a reagent available from Tokyo Chemical Industry Co., Ltd.) was added dropwise in 236 g (0.5 moles) of a 25% toluene solution of triethylphosphine (HISHICOLIN (registered trademark) P-2, a trade name of Nippon Chemical Industrial Co., Ltd.), and the mixture was allowed to react at 70 to 80° C. for 6 hours. After completion of the reaction, hexane was added for crystallization, thereby obtaining 125 g (percent yield: 97%) of a crystal of triethyl(2-methoxyethyl) phosphonium bromide. 33 g (0.3 moles) of sodium borofluoride (a reagent available from Kanto Chemical Co., Inc.) was added to 77 g (0.3 moles) of this triethyl (2-methoxyethyl)phosphonium bromide, and the mixture was allowed to react in an aqueous system. Subsequently, the reaction mixture was stirred for aging at room temperature for 3 hours. After completion of stirring, a product was completely dehydrated at 100° C. and at a degree of vacuum of 0.5 kPa, to which was further added 100 mL of dry methylene chloride, and a precipitate was filtered. This filtrate was concentrated and dried in vacuo at 100° C. and at a degree of vacuum of 0.5 kPa for 5 hours. Confirmation of the thus obtained product was carried out by means of 1H-NMR, 13C-NMR, 31P-NMR and 19F-NMR. A yield of the product (colorless transparent liquid) was 60 g (percent yield: 76%), and it was confirmed by 31P-NMR that its purity was 98% or more. to react at 70 to 80° C. for 6 hours was added for crystallization

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 77 g (0.5 moles) of 1-bromopentane (a reagent available from Tokyo Chemical Industry Co., Ltd.) was added dropwise in 236 g (0.5 moles) of a 25% toluene solution of triethylphosphine (HISHICOLIN (registered trademark) P-2, a trade name of Nippon Chemical Industrial Co., Ltd.), and the mixture was allowed to react at 70 to 80° C. for 6 hours. After completion of the reaction, hexane was added for crystallization, thereby obtaining 113 g (percent yield: 84%) of a crystal of triethylpentylphosphonium bromide. 27 g (0.3 moles) of sodium dicyanamide (a reagent available from Wako Pure Chemical Industries, Ltd.) was added to 81 g (0.3 moles) of this triethylpentylphosphonium bromide, and the mixture was allowed to react in an aqueous system. Subsequently, the reaction mixture was stirred for aging at room temperature for 3 hours. After completion of stirring, a product was extracted with dichloromethane and passed through a silica gel column for purification. The solvent was distilled off, and the residue was dried in vacuo at 100° C. and at a degree of vacuum of 0.5 kPa for 5 hours. Confirmation of the thus obtained product was carried out by means of 1H-NMR, 13C-NMR and 31P-NMR. A yield of the product (pale yellow transparent liquid) was 77 g (percent yield: 69%), and it was confirmed by 31P-NMR that its purity was 98% or more. to react at 70 to 80° C. for 6 hours was added for crystallization

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 62 g (0.5 moles) of bromomethylmethyl ether (a reagent available from Tokyo Chemical Industry Co., Ltd.) was added dropwise in 236 g (0.5 moles) of a 25% toluene solution of triethylphosphine (HISHICOLIN (registered trademark) P-2, a trade name of Nippon Chemical Industrial Co., Ltd.), and the mixture was allowed to react at 70 to 80° C. for 6 hours. After completion of the reaction, hexane was added for crystallization, thereby obtaining 97 g (percent yield: 80%) of a crystal of triethyl(methoxymethyl)phosphonium bromide. 86 g (0.3 moles) of lithium bis(trifluoromethylsulfonyl)imide (a reagent available from Kanto Chemical Co., Inc.) was added to 73 g (0.3 moles) of this triethyl(methoxymethyl)phosphonium bromide, and the mixture was allowed to react in an aqueous system. Subsequently, the reaction mixture was stirred for aging at room temperature for 3 hours. After completion of stirring, a lower layer (product) was separated. The separated product was washed with pure water four times and then washed with hexane four times. After completion of washing, the product was dried in vacuo at 100° C. and at a degree of vacuum of 0.5 kPa for 5 hours. Confirmation of the obtained product was carried out by means of 1H-NMR, 13C-NMR, 31P-NMR and 19F-NMR. A yield of the product (colorless transparent liquid) was 104 g (percent yield: 78%), and it was confirmed by 3P-NMR that its purity was 98% or more. to react at 70 to 80° C. for 6 hours was added for crystallization

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of α,α'-dichloro-o-xylene (15.0 g, 86.0 mmol) in toluene (200 ml) was added triethylphosphine (6.3 ml, 43.0 mmol) under argon gas. The reaction mixture was stirred for several days at room temperature under argon after which time the triethylphosphonium chloride salt had crystallized out of solution. The crystals were filtered and washed with toluene (3×50 mL) and pentane (3×50 mL) and dried: 1H NMR (CDCl3) δ1.15-1.26 (dt, 9), 2.58-2.69 (m, 6H), 4.39-4.44 (d, 2H), 4.87 (s, 2H) , 7.31-7.34 (dd, 2H) , 7.43-7.46 (dd, 1H), 7.50-7.54 (m, 1H). had crystallized out of solution The crystals were filtered washed with toluene (3×50 mL) and pentane (3×50 mL) dried

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl thiocyanate (55 g, 0.209 mole) was dissolved in acetone (200 ml) under an argon atmosphere. Water (7.6 g, 0.42 mole) was added and the reaction cooled to 0° C. Triethylphosphine (24.7 g, 0.209 mole) was added dropwise over a period of 1 hour and the reaction was then allowed to warm to room temperature with stirring. The solution was concentrated, solvents removed, and the resulting oil purified by chromatography on silica. The fractions containing the thiol were combined, the solvents removed to yield a white powder which was recrystallized from methanol/water and dried to yield 43.3 g of the desired product. NMR confirmed the identity of the product. to warm to room temperature The solution was concentrated solvents removed the resulting oil purified by chromatography on silica The fractions containing the thiol the solvents removed to yield a white powder which was recrystallized from methanol/water dried

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenylthiocyanate (55 g, 0.209 mole) was dissolved in acetone (200 ml) under an argon atmosphere. Water (7.6 g, 0.42 mole) was added and the reaction cooled to 0° C. Triethylphosphine (24.7 g, 0.209 mole) was added dropwise over a period of 1 hour and the reaction was then allowed to warm to room temperature with stirring. The solution was concentrated, solvents removed, and the resulting oil purified by chromatography on silica The fractions containing the thiol were combined and the solvents removed to yield a white powder Recrystallization from methanol/water yielded, upon drying, 43.3 g of the title compound. The NMR spectrum confirmed the identity of the product. to warm to room temperature The solution was concentrated solvents removed the resulting oil purified by chromatography on silica The fractions containing the thiol the solvents removed to yield a white powder Recrystallization from methanol/water yielded upon drying

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of α,α'-dichloro-o-xylene (15.0 g, 86.0 mmol) in toluene (200 ml) was added triethylphosphine (6.3 ml, 43.0 mmol) under argon gas. The reaction mixture was stirred for several days at room temperature under argon after which time the triethylphosphonium chloride salt had crystallized out of solution. The crystals were filtered and washed with toluene (3×50 mL) and pentane (3×50 mL) and dried: 1H NMR (CDCl3) δ 1.15-1.26 (dt, 9H), 2.58-2.69 (m, 6H), 4.39-4.44 (d, 2H), 4.87 (s, 2H), 7.31-7.34 (dd, 2H), 7.43-7.46 (dd, 1H), 7.50-7.54 (m, 1H). had crystallized out of solution The crystals were filtered washed with toluene (3×50 mL) and pentane (3×50 mL) dried

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of α,α'-dichloro-o-xylene (15.0 g, 86.0 mmol) in toluene (200 ml) was added triethylphosphine (6.3 ml, 43.0 mmol) under argon gas. The reaction mixture was stirred for several days at room temperature under argon after which time the triethylphosphonium chloride salt had crystallized out of solution. The crystals were filtered and washed with toluene (3×50 mL) and pentane (3×50 mL) and dried: 1H NMR (CDCl3) δ 1.15-1.26 (dt, 9H), 2.58-2.69 (m, 6H), 4.39-4.44 (d, 2H), 4.87 (s, 2H), 7.31-7.34 (dd, 2H), 7.43-7.46 (dd, 1H), 7.50-7.54 (m, 1H). had crystallized out of solution The crystals were filtered washed with toluene (3×50 mL) and pentane (3×50 mL) dried

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenylthiocyanate (55 g, 0.209 mole) was dissolved in acetone (200 ml) under an argon atmosphere. Water (7.6 g, 0.42 mole) was added and the reaction cooled to 0° C. Triethylphosphine (24.7 g, 0.209 mole) was added dropwise over a period of 1 hour and the reaction was then allowed to warm to room temperature with stirring. The solution was concentrated, solvents removed, and the resulting oil purified by chromatography on silica. The fractions containing the thiol were combined and the solvents removed to yield a white powder. Recrystallization from methanol/water yielded, upon drying, 43.3 g of the title compound. The NMR spectrum confirmed the identity of the product. to warm to room temperature The solution was concentrated solvents removed the resulting oil purified by chromatography on silica The fractions containing the thiol the solvents removed to yield a white powder Recrystallization from methanol/water yielded upon drying