2,4-二氟-1-甲苯

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: DE-A 2,333,849 discloses that 2,4-difluorobenzaldehyde can be converted into 2,4-difluorobenzyl alcohol in a yield of 68.6% by hydrogenation over Raney nickel. Disadvantages of this process are not only the large amount of catalyst (31 g per mol) and the large amount of a solvent (1100 ml per mole) but also the unsatisfactory yield of 68.6%. These factors result in an unsatisfactory space-time yield. The aldehyde used was obtained here from the difficult-to-obtain 2,4-difluorotoluene by side-chain chlorination and subsequent hydrolysis. These factors result in an unsatisfactory space-time yield

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: DE-A 2,333,849 discloses that 2,4-difluorobenzaldehyde can be converted into 2,4-difluorobenzyl alcohol in a yield of 68.6% by hydrogenation over Raney nickel. Disadvantages of this process are not only the large amount of catalyst (31 g per mol) and the large amount of a solvent (1100 ml per mole) but also the unsatisfactory yield of 68.6%. These factors result in an unsatisfactory space-time yield. The aldehyde used was obtained here from the difficult-to-obtain 2,4-difluorotoluene by side-chain chlorination and subsequent hydrolysis. These factors result in an unsatisfactory space-time yield

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

实验步骤: DE-A 2,333,849 discloses that 2,4-difluorobenzaldehyde can be converted into 2,4-difluorobenzyl alcohol in a yield of 68.6% by hydrogenation over Raney nickel. Disadvantages of this process are not only the large amount of catalyst (31 g per mol) and the large amount of a solvent (1100 ml per mole) but also the unsatisfactory yield of 68.6%. These factors result in an unsatisfactory space-time yield. The aldehyde used was obtained here from the difficult-to-obtain 2,4-difluorotoluene by side-chain chlorination and subsequent hydrolysis. These factors result in an unsatisfactory space-time yield

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

实验步骤: Chlorosulfonic acid (5.2 mL, 0.078 mol) was added dropwise to a solution of 2,4-difluorotoluene (4.00 g, 0.0312 mol) in chloroform (75 mL, 0.94 mol). The reaction was stirred 2 hours. Additional chlorosulfonic acid (3.1 mL, 0.047 mol) was added and stirring was continued for 18 hours. The reaction was evaporated to an oil and poured onto ice. The mixture was extracted two times with ethyl ether. The combined organic phase was dried over magnesium sulfate and treated with activated carbon. The mixture was filtered through diatomaceous earth and the filtrate was evaporated to give 5.31 g of light brown oil. stirring was continued for 18 hours The reaction was evaporated to an oil poured onto ice The mixture was extracted two times with ethyl ether The combined organic phase was dried over magnesium sulfate treated with activated carbon The mixture was filtered through diatomaceous earth the filtrate was evaporated

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

实验步骤: Chlorosulfonic acid (5.2 mL, 0.078 mol) was added dropwise to a solution of 2,4-difluorotoluene (4.00 g, 0.0312 mol) in chloroform (75 mL, 0.94 mol). The reaction was stirred 2 hours. Additional chlorosulfonic acid (3.1 mL, 0.047 mol) was added and stirring was continued for 18 hours. The reaction was evaporated to an oil and poured onto ice. The mixture was extracted two times with ethyl ether. The combined organic phase was dried over magnesium sulfate and treated with activated carbon. The mixture was filtered through diatomaceous earth and the filtrate was evaporated to give 5.31 g of light brown oil. stirring was continued for 18 hours The reaction was evaporated to an oil poured onto ice The mixture was extracted two times with ethyl ether The combined organic phase was dried over magnesium sulfate treated with activated carbon The mixture was filtered through diatomaceous earth the filtrate was evaporated

实验步骤: CIM100205-52-83: 往三口瓶加入SM1（10g，39.0 mmol），氮气置换3次 15：50 加入四氢呋喃（20V），氮气置换 15：53 降温至-65~-60℃ 16：10 滴加正丁基锂（1.3eq） 16：49 滴毕，保温搅拌30分钟 17：20 滴加液溴（1.3eq） 17：45 滴毕，保温搅拌，内温-65~-47℃ 18：00 反应液自然回温至室温 18：15 送GC中控CIM100205-52-75-ipc-1 19：00 反应液0℃时，加入1 盐酸（5V）淬灭反应 19：03 加入亚硫酸氢钠（1g），室温搅拌 19：20 静置、分相，有机相浓缩得液体粗品 \nCIM100205-52-83-purification: 粗品经柱层析纯化，得11g无色液体产品

实验步骤: CIM100205-52-75: 11：06 往三口瓶加入SM1（1g，7.81mmol），氮气置换3次 11：10 加入四氢呋喃（20V），氮气置换 11：13 降温至-65~-60℃ 11：17 滴加正丁基锂（1.3eq） 11：30 滴毕，保温搅拌20分钟 11：50 滴加液溴（1.3eq） 11：53 滴毕，保温搅拌25min 12：15 送GC中控CIM100205-52-75-ipc-1 12：20 反应液自然回温至室温 13：45 反应液降至0℃，加入0.2M盐酸（5V）淬灭反应 14：00 加入亚硫酸氢钠（0.1g），室温搅拌 14：20 静置、分相，有机相浓缩得液体粗品 14：55 粗品经柱层析纯化，得无色液体500 mg

实验步骤: 04-07 18:02: 往三口瓶加入SM1和超干四氢呋喃，氮气置换3次； 反应液降温至-65~-60℃，滴加正丁基锂； 滴毕，保温30分钟； 滴加液溴，控内温-65~-55℃； 滴毕，保温30分钟； 反应液自然回至室温，搅拌1小时； GC中控反应完全； 往反应液加入水，混合液用乙酸乙酯萃取； 有机相浓缩得无色液体产品

反应条件: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred solution of 2,4-difluorotoluene (25.0 g, 195.3 mmol) in conc. H2SO4 (60 mL) was added fuming HNO3 (30 mL) drop wise at the rate that temperature was maintained between 40-50° C. over a period of 1.5 h. The reaction mixture was stirred at 40° C. for an additional 1 h. The reaction mixture was poured into ice-cold water (500 mL) and the solid precipitated was filtered and washed with water (2×50 mL). The solid residue was dissolved in EtOAc (200 mL), washed with aq. NaHCO3 (2×200 mL). The organic layer was dried over Na2SO4, filtered and evaporated in vacuo to afford 1,5-difluoro-2-methyl-3-nitrobenzene (21.0 g, 62%) as a light brown liquid. the solid precipitated was filtered washed with water (2×50 mL) The solid residue was dissolved in EtOAc (200 mL) washed with aq. NaHCO3 (2×200 mL) The organic layer was dried over Na2SO4 filtered evaporated in vacuo