1-bromododecane

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

実験手順: 2,4,6-Trihydroxybenzaldehyde (250 mg, 1.45 mmol), 1-bromododecane (2.15 g, 8.63 mmol), K2CO3 (600 mg, 4.34 mmol) and KI (40 mg, 0.24 mmol) were mixed in DMF (10 ml), followed by stirring at 70° C. for 20 hours. The resulting reaction product was cooled to 20° C., and chloroform (50 ml) was added thereto to separate into an organic phase and an aqueous phase. Only the organic phase was washed with salt water (100 ml) two times, and then dried using Na2SO4. The resulting crude product was purified by column chromatography (silica gel, hexane/CH2Cl2=1:1) to obtain yellow oily 2,4,6-tridecyloxybenzaldehyde (1a) (460 mg, yield: 48%). It was confirmed by 1H NMR quantitative analysis that 1a is 2,4,6-tridodecyloxybenzaldehyde. The resulting reaction product was cooled to 20° C. to separate into an organic phase Only the organic phase was washed with salt water (100 ml) two times dried The resulting crude product was purified by column chromatography (silica gel, hexane/CH2Cl2=1:1)

反応条件: temp:55.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 47 g pyrrolidine, 149.5 g 1-bromododecane and 83 g potassium carbonate were added to 560 mL acetone. The reaction mixture was heated at 55° C. for 24 hr, then filtered. Solvent was removed from the filtrate, yielding 92 g N-dodecylpyrrolidine. 80 g N-dodecylpyrrolidine and 52.6 g 1-bromo-3-chloropropane were dissolved in 133 mL methanol and the reaction mixture was heated at 65° C. for 18 hr. After cooling to room temperature, methanol was removed under reduced pressure. The residue was poured into 2 L diethylether with stirring and the mixture was allowed to stand for another 6 hr. The white precipitate thus formed was filtered and was dried at 40° C. under a vacuum for 24 hr yielding 85 g (3-chloropropyl)dodecylpyrrolidinium bromide as a white solid. filtered Solvent was removed from the filtrate

反応条件: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The ground polymer of Example 23 (5 g) was placed in a 500 mL 3-necked round-bottomed flask and suspended in 100 mL deionized water and the suspension was stirred with a mechanical stirrer. To this swollen gel, a solution of 15 g 1-bromodecane in 100 mL ethanol was added and the reaction mixture was stirred for 10 minutes. 2 g 50% aqueous sodium hydroxide was then added and the reaction mixture was stirred at room temperature for 40 minutes followed by heating to 75° C. Subsequently, an additional 4 g 50% NaOH was added in a 1 g batch at an interval of 1.5 hr (the base addition maintained a pH between 10 to 12). The reaction mixture was allowed to stir at 75° C. for a total period of 20 hr. After cooling to 30° C., 2 mL concentrated HCl was added and the mixture was stirred for 30 minutes. The polymer was filtered off and washed with 500 mL deionized water and 500 mL methanol. The filtered polymer particles were slurried in methanol (400 mL), stirred for 40 minutes and reisolated by filtration. This process was then repeated. The polymer was suspended in 500 mL 2M NaCl solution and the suspension was stirred for 40 minutes. The polymer was filtered off and this NaCl treatment was repeated two more times. The fitered polymer cake was washed with 500 mL deionized water and suspended in 500 mL deionized water. After stirring the suspension for 30 minutes, the polymer was filtered off and resuspended in 500 mL deionized water. The resulting suspension was stirred for 30 minutes. 1 mL concentrated HCl was added to the suspension, which was then stirred for 35 minutes. The pH of the suspension was found to be 2.2. The polymer was then filtered off and dried at 60° C. in a forced air oven, yielding 13.3 g of the alkylated polymer as a pale white solid. The polymer was ground and passed through a 140 mesh sieve. the reaction mixture was stirred for 10 minutes the reaction mixture was stirred at room temperature for 40 minutes the base addition maintained a pH between 10 to 12) to stir at 75° C. for a total period of 20 hr After cooling to 30° C. the mixture was stirred for 30 minutes The polymer was filtered off washed with 500 mL stirred for 40 minutes reisolated by filtration the suspension was stirred for 40 minutes The polymer was filtered off The fitered polymer cake was washed with 500 mL After stirring the suspension for 30 minutes the polymer was filtered off The resulting suspension was stirred for 30 minutes 1 mL concentrated HCl was added to the suspension, which was then stirred for 35 minutes The polymer was then filtered off dried at 60° C. in a forced air oven

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a 2 L Morton flask was added diallylmethylamine (100 g), 1-bromododecane (249 g), and tetrahydrofuran (750 mL). The mixture was heated to 65° C. for 44 h, and then allowed to cool to room temperature. The solvent was removed by rotary vacuum evaporation to leave two layers. Diethylether (500 mL) was added and the mixture was stirred for 1 hr. The mixture was allowed to settle and the top layer was decanted and discarded. Additional diethylether (500 mL) was added. The mixture was stirred for 24 h, and the top layer was again decanted and discarded. The remaining oil was dried in a vacuum oven at 65° C. for 4 days to yield 67 g of product. to cool to room temperature The solvent was removed by rotary vacuum evaporation to leave two layers the top layer was decanted Additional diethylether (500 mL) was added The mixture was stirred for 24 h the top layer was again decanted The remaining oil was dried in a vacuum oven at 65° C. for 4 days

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

実験手順: Isopropylideneglycerol (solketal, 26.4 g, 0.20 mol) in 60 mL of toluene was added dropwise to a solution of powered KOH (22.4 g, 0.04 mol) in 150 mL of toluene. The resulting mixture was refluxed for 4 h. 1-Bromododecane (50 g, 0.20 mol) in 40 mL of toluene was then added dropwise, and the solution was refluxed for 10 h. After cooling, the reaction mixture was diluted with 200 mL of ice-water and extracted with diethyl ether (3×100 mL). The ether layers were dried over magnesium sulfate, and the solvent was removed in vacuo. The residue was dissolved in 60 mL of diethyl ether and 260 mL of MeOH. Concentrated HCl (60 mL) was added, and the solution refluxed for 16 h. After cooling, ice-water (150 mL) was addecl, and the layers separated. The aqueous layer was extracted with diethyl ether (2×75 mL). The combined organic fractions were then dried over sodium sulfate, filtered, and concentrated in vacuo. The solid residue was recrystallized from MeOH to give 37 g (0.14 mol, 71%) of a white solid. The resulting mixture was refluxed for 4 h the solution was refluxed for 10 h After cooling extracted with diethyl ether (3×100 mL) The ether layers were dried over magnesium sulfate the solvent was removed in vacuo The residue was dissolved in 60 mL of diethyl ether Concentrated HCl (60 mL) was added the solution refluxed for 16 h After cooling the layers separated The aqueous layer was extracted with diethyl ether (2×75 mL) The combined organic fractions were then dried over sodium sulfate filtered concentrated in vacuo The solid residue was recrystallized from MeOH

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

実験手順: To a solution of propylamine (5.5 mL, 0.067 mol) in EtOH (100 mL) is added 3-bromo-N,N,N-trimethylpropan-1-aminium bromide (5.0 g, 0.0191 mol) portionwise at 0° C. over 20 minutes. The solution is warmed to room temperature and then refluxed for 4 hours. The solution is cooled to room temperature, and the solvent is removed via rotary evaporator to provide the crude di-bromo salt (5.69 g, 0.0179 mol). The salt is dissolved in MeOH (200 mL) and NaOH is added portionwise (0.717 g, 0.0179 mol) in MeOH (50 mL) over 30 minutes at room temperature. The solution is stirred an additional 2 hours at room temperature after addition is complete and then the solvent is removed via rotary evaporator. The residue is stirred with CH3CN (150 mL) for 30 minutes and the solids filtered off. The filtrate is concentrated via rotary evaporation and the residue is pumped on 24 h under vacuum to provide the 3-(propylamino)-N,N,N-trimethylpropan-1-aminium bromide (4.07 g, 0.017 mol), which is used without further purification. The 3-(propylamino)-N,N,N-trimethylpropan-1-aminium bromide (4.07 g, 0.017 mol) is dissolved in EtOH (100 mL) and 1-bromododecane (4.55 mL, 0.019 mol) is added dropwise over 15 minutes. The reaction is refluxed 24 hours, cooled to room temperature, and solid NaOH (0.68 g, 0.017 mol) is added. The reaction is stirred 2 hours at room temperature, and then the solids are filtered off. The filtrate is concentrated to give a white solid. The solid is dissolved in water (200 mL) and extracted with EtOAc (3×150 mL). The organic layers are combined and discarded, and the aqueous layer is frozen and lyophilized under vacuum for 48 hours to provide 3-(dodecyl(propyl)amino)-N,N,N-trimethylpropan-1-aminium bromide as a white solid (5.29 g, 0.013 mol). is used without further purification The reaction is refluxed 24 hours the solids are filtered off The filtrate is concentrated to give a white solid extracted with EtOAc (3×150 mL) the aqueous layer is frozen lyophilized under vacuum for 48 hours

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

実験手順: A mixture of 1-bromododecane (261 mg, 0.11 mmol) and magnesium turnings (27 mg, 0.11 mmol) in tetrahydrofuran (7 ml) was refluxed under argon for 1 hour. After cooling to room temperature, a solution of 5-methyl-2-trimethylsilyl-4-furaldehyde (158.6 mg, 0.87 mmol) in tetrahydrofuran (1 ml) was added, followed by acetic anhydride (0.25 ml, 2.6 mmol) after 1 hour. Stirring was continued at room temperature overnight and the mixture was quenched with water. Extraction (ethyl ether) and evaporation of the dried (magnesium sulphate) extracts gave an oil, which was purified by preparative TLC (20×20 cm, 1000 micron silica plate; developed with 5% ethyl ether/hexane). The title ester was obtained as a light yellow oil. was refluxed under argon for 1 hour the mixture was quenched with water Extraction (ethyl ether) and evaporation of the dried (magnesium sulphate) extracts gave an oil, which was purified by preparative TLC (20×20 cm, 1000 micron silica plate; developed with 5% ethyl ether/hexane)

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

実験手順: Following example 10, 15.3 g of 50% sodium hydride-mineral oil dispersion (7.65 g NaH, 0.319 M), 30 g (0.266 M) of azacycloheptan-2-one and 66.1 g (0.265 M) of 1-bromododecane on 20 hr. reflux gave 60 g (80%) of colorless product; b.p. 175°-180°/0.3 mm. on 20 hr reflux

反応条件: temp:0.00; pressure:0.00; stir: