2,5-二氯对苯二醌

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:0.00; pressure:0.00; stir:

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

实验步骤: Under nitrogen atmosphere, 6 mL of THF was added to 1.22 g (2 mmol, 0.6 equivalent) of (BrZnCH2COOEt.THF)2. Under argon atmosphere, a solution of 0.59 g (3.33 mmol) of 2,5-dichloro-p-benzoquinone in 6.5 mL of THF was added dropwise while stirring at 0˜5° C. The mixture was stirred at 20˜25° C. 5 mL of 1N hydrochloric acid was added dropwise at 20° C. or lower, followed by dilution with 25 mL of ethyl acetate, and the layers were separated. The organic layer was washed successively with 5 mL (×2) of 1N hydrochloric acid, 5 mL of water, 5 mL (×2) of an aqueous saturated sodium bicarbonate solution, and 5 mL (2) of an aqueous saturated sodium chloride solution. After washing, the organic layer was dried with anhydrous magnesium sulfate. After concentration under reduced pressure, purification with silica gel column (developing solvent; ethyl acetate/n-hexane=1/3, 1/2) afforded 0.81 g of the desired product (yield 92%). The mixture was stirred at 20˜25° C the layers were separated The organic layer was washed successively with 5 mL (×2) of 1N hydrochloric acid, 5 mL of water, 5 mL (×2) of an aqueous saturated sodium bicarbonate solution, and 5 mL (2) of an aqueous saturated sodium chloride solution After washing the organic layer was dried with anhydrous magnesium sulfate After concentration under reduced pressure, purification with silica gel column (developing solvent; ethyl acetate/n-hexane=1/3, 1/2)

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:; See reaction.notes.procedure_details.

实验步骤: Under nitrogen atmosphere, 6 mL of THF was added to 1.22 g (2 mmol, 0.6 equivalent) of (BrZnCH2COOEt.THF)2. Under argon atmosphere, a solution of 0.59 g (3.33 mmol) of 2,5-dichloro-p-benzoquinone in 6.5 mL of THF was added dropwise while stirring at 0˜5° C. The mixture was stirred at 20˜25° C. 5 mL of 1N hydrochloric acid was added dropwise at 20° C. or lower, followed by dilution with 25 mL of ethyl acetate, and the layers were separated. The organic layer was washed successively with 5 mL (×2) of 1N hydrochloric acid, 5 mL of water, 5 mL (×2) of an aqueous saturated sodium bicarbonate solution, and 5 mL (2) of an aqueous saturated sodium chloride solution. After washing, the organic layer was dried with anhydrous magnesium sulfate. After concentration under reduced pressure, purification with silica gel column (developing solvent; ethyl acetate/n-hexane=1/3, 1/2) afforded 0.81 g of the desired product (yield 92%). The mixture was stirred at 20˜25° C the layers were separated The organic layer was washed successively with 5 mL (×2) of 1N hydrochloric acid, 5 mL of water, 5 mL (×2) of an aqueous saturated sodium bicarbonate solution, and 5 mL (2) of an aqueous saturated sodium chloride solution After washing the organic layer was dried with anhydrous magnesium sulfate After concentration under reduced pressure, purification with silica gel column (developing solvent; ethyl acetate/n-hexane=1/3, 1/2)

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

实验步骤: 05-06 15:03: 4月24日，将25g SM1(1eq)和50.2g SM2(2eq)溶于280ml异丙醇中，加入40.0gTEA，80℃搅拌3h, TLC监测显示溶液反应完全，送LCMS 后处理，旋干溶剂，加入1.5L水和少量MeOH助溶，其中有部分固体难溶，取另外的单口瓶将其溶于MeOH中，用稀HCl将水溶液调pH至3,析出大量固体，过滤， 滤饼用EA和MeOH溶解，用无水硫酸镁干燥过滤，滤液用EA萃取，有机相干燥，合并有机相旋干，得到粗品红色固体40.7g。 5月6日，溶于MeOH的固体完全溶清，将溶液旋蒸浓缩，再加1L水溶解，调pH值，EA萃取，干燥有机相并旋干 用MTBE:PE=5:1打浆，过滤得滤饼20.8g 5月7日，先取5g粗品过柱，100-200目硅胶，用DCM：EA=2：1（0.5%甲酸）过柱，待杂质点全部冲出，用DCM:EA=1:1,纯EA,DCM:MeOH=10:1依次过柱将产物冲出，旋干只含产物的溶液，冻干过夜。获得2.4g产品，与后续产品合并 剩余粗品14g，同样100-200目硅胶过柱，先用DCM:EA=4:1（0.5%甲酸）过柱,慢慢放大极性，后续获得含有单一产物点的溶液，旋干得固体M-C4X-131272-1，6.2g和M-C4X-131272-2，5g。合并得11.2g，收率17.2% 送三谱达标，M-C4X-131272-1 HPLC：97.981%，定量：91.7%；M-C4X-131272-2 HPLC：96.511%，定量：90.7%。 .

实验步骤: 投料: 将1.0g SM1(1eq)和1.8g SM2(2eq)溶于10ml异丙醇中，加入1.47gTEA，80℃搅拌1h, TLC监测显示溶液反应完全，送LCMS 后处理，旋干溶剂，加入70mL水和少量MeOH助溶，用稀HCl调pH至3,析出大量固体，过滤， 滤饼用EA和MeOH溶解，用无水硫酸镁干燥过滤，滤液用EA萃取，有机相干燥，合并有机相旋干，得到粗品红色固体2.1g。 用MTBE:PE=5:1打浆，过滤得滤饼1.0g，用EA:PE=3:1展开剂加两滴乙酸点板，显示两个点，判断产物点位于下方。 分别用MTBE:PE=5:1，MTBE:PE=1:1，MTBE:PE=3:2多次打浆，除杂程度不是很好，固体分别送HPLC结果显示并无太大变化。