4-溴苄基亚磷酸二乙酯

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: 4-bromobenzylbromide (10.0 g, 40.0 mmol) was dissolved in triethylphosphite (8.4 mL, 48.0 mmol) under a nitrogen atmosphere, and the reaction solution was refluxed and stirred for 24 hours. The reaction solution was passed through a silica gel column by using hexane-ethylacetate 7:3 as an eluant. After the solvent was removed, the residue material was dried in vacuum to thereby obtain pale yellow oil (10.0 g, yield: 81%). the reaction solution was refluxed After the solvent was removed the residue material was dried in vacuum

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 22.9 g (74.7 mmol) of diethyl 4-bromobenzylphosphonate were dissolved in 200 ml of DMF and admixed with 14.4 g (149 mmol) of NaOtBu at about 5° C. under protective gas. After stirring at 5° C. for 30 minutes, 13.9 g (34 mmol) of 9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene-2,7-dicarbaldehyde were added at a maximum temperature of 5° C. over a period of 15 minutes and the mixture was subsequently stirred at 5° C. for 1 hour. To work up the mixture, 50 ml of 4M HCl were added dropwise, the precipitate formed was filtered off with suction, washed with water and MeOH and dried. The solid was subsequently recrystallized three times from EtOH/toluene to give 21.1 g (87%) of the monomer having a purity determined by RP-HPLC of 99.8%. the mixture was subsequently stirred at 5° C. for 1 hour were added dropwise the precipitate formed was filtered off with suction washed with water and MeOH dried The solid was subsequently recrystallized three times from EtOH/toluene

反应条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 22.9 g (74.7 mmol) of diethyl 4-bromobenzylphosphonate were dissolved in 200 ml of DMF and admixed with 14.4 g (149 mmol) of NaOtBu at about 5° C. under protective gas. After stirring at 5° C. for 30 minutes, 13.9 g (34 mmol) of 9,10-dibutyl-9,10-dimethoxy-9,10-dihydrophenanthrene-2,7-dicarbaldehyde were added at a maximum temperature of 5° C. over a period of 15 minutes and the mixture was subsequently stirred at 5° C. for 1 hour. To work up the mixture, 50 ml of 4M HCl were added dropwise, the precipitate formed was filtered off with suction, washed with water and MeOH and dried. The solid was subsequently recrystallized three times from EtOH/toluene to give 21.1 g (87%) of the monomer having a purity determined by RP-HPLC of 99.8%. the mixture was subsequently stirred at 5° C. for 1 hour were added dropwise the precipitate formed was filtered off with suction washed with water and MeOH dried The solid was subsequently recrystallized three times from EtOH/toluene

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

实验步骤: 40.69 g (1 molar equivalent, 163 mmol) of 4-bromobenzyl bromide 1 are heated at 160° C. in 28.3 ml (1 molar equivalent, 163 mmol) of triethyl phosphite until the evolution of gas is complete. The batch is distilled in vacuo, and the residue remaining in the form of an oil 2 (48.87 g, 98%) is employed in the subsequent reaction without further purification. The batch is distilled in vacuo is employed in the subsequent reaction without further purification

反应条件: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 203.6 g (815 mmol) of 4-bromobenzyl bromide and 215 ml (1.2 mol) of triethyl phosphite are mixed and heated at 130° C. for 1 h with gas discharge. The product is then subjected to fractional distillation (2×10−2 mbar, 120° C.), giving 224 g (89%) of the product as a colourless liquid. The product is then subjected to fractional distillation (2×10−2 mbar, 120° C.)

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

实验步骤: DMF (anhydrous) (10.5 mL) was added to sodium methoxide (176 mg, 3.26 mmol) and the color was changed to pink. To the above solution diethyl 4-bromobenzylphosphonate (1.0 g, 3.26 mmol) in DMF (6.5 ml) was added dropwise over 2 minutes, followed by 4 (dimethylamino)benzaldehyde (486 mg, 3.26 mmol). The reaction mixture was stirred at room temperature for 24 hours. Deionized water (17 mL) was added. The product was filtered out through vacuum filtration and recrystallized with DCM/hexane to give compound 17. 17: 74%. Yield; tan solid; 1H NMR (400 MHz, CDCl3) δ 7.47-7.32 (m, 6H), 7.04 (d, 1H, J=12.5 Hz), 6.83 (d, 1H, J=16.3 Hz), 6.71 (d, 2H, J=8.9 Hz), 2.99 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 150.5, 137.4, 136.1, 132.1, 131.8, 129.7, 128.3, 128.2, 127.9, 127.7, 125.5, 123.2, 120.3, 112.6, 40.7; HRMS Calc for C16H16BrN 302.0541 found 302.0539. The product was filtered out through vacuum filtration recrystallized with DCM/hexane

反应条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1-bromo-4-(bromomethyl)benzene (5.0 g, 20 mmol) and triethyl phosphite (51 mL, 300 mmol) were mixed in a round bottom flask and refluxed at 90° C. for 19 hours. Excess triethyl phosphite was removed under reduced pressure and the product purified by flash chromatography (1:1 Hexane/EtOAc) to give compound 16. 16: 98% yield; colorless liquid; 1H NMR (400 MHz, CDCl3) δ 7.30 (d, 2H, J=7.5 Hz), 7.05 (d, 2H, J=7.6 Hz), 3.99-3.88 (m, 4H), 2.99 (s, 1H), 2.94 (s, 1H), 1.12 (t, 6H, J=106.9 Hz); 13C NMR (100 MHz, CDCl3) δ 131.7, 131.6, 131.5, 121.0, 62.3, 34.0, 32.0, 16.5; HRMS Calc for C11H16BrO3P (M+H)+ 307.0097 found 307.0093. Excess triethyl phosphite was removed under reduced pressure the product purified by flash chromatography (1:1 Hexane/EtOAc)

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

实验步骤: 4-bromobenzylbromide (10.0 g, 40.0 mmol) was dissolved in triethylphosphite (8.4 mL, 48.0 mmol) under a nitrogen atmosphere, and the reaction solution was refluxed and stirred for 24 hours. The reaction solution was passed through a silica gel column by using hexane-ethylacetate 7:3 as an eluant. After the solvent was removed, the residue material was dried in vacuum to thereby obtain pale yellow oil (10.0 g, yield: 81%). the reaction solution was refluxed After the solvent was removed the residue material was dried in vacuum