* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
With methanol; Methyl formate; copper(l) chloride; at 115℃; for 2.0h;Autoclave; Green chemistry;
General procedure: A Teflon-lined autoclave (25 mL) was charged with MeONa (1.08 g, 20.0 mmol), MeOH (10 mL), CuCl (40 mg, 0.40 mmol), HCOOMe (0.25 mL, 0.97 g/mL, 4.0 mmol), and monohaloarene (10.0 mmol) then heated to 115 °C, with stirring, for 2 h. After completion of the reaction, the reactor was cooled to room temperature. The mixture was stirred for 0.5 h in the open, then concentrated to recover pure MeOH. Diethyl ether (15 mL) and dilute hydrochloric acid (1.6 M, 15 mL) were added to the residue. The mixture separated into two layers, and the aqueous phase was extracted with diethyl ether (15 mL x 3). The combined organic layers were dried over anhydrous Na2SO4 and concentrated to give a residue which was purified by column chromatography on silica gel (mobile phase: petroleum ether?ethyl acetate 15:1) to furnish 1 (conversion and selectivity were determined by GC?MS analysis). The purity of the recovered MeOH was measured as more than 99 percent by GC, and the water content of the recovered MeOH was measured as less than 0.12 percent by use of the Karl Fischer method.
3-(2,6-dibromo-4-methylphenoxy)-4,5-bis(2,5-dichlorophenoxy)-6-fluorophthalonitrile[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80.5 mol%
With potassium fluoride; In acetone;
SYNTHESIS EXAMPLE 2 Synthesis of 3-(2,6-dibromo-4-methylphenoxy)-4,5-bis(2,5-dichlorophenoxy)-6-fluorophthalonitrile In a four-neck separable flask having an inner volume of 500 ml, 60 g (0.30 mol) of <strong>[1835-65-0]tetrafluorophthalonitrile</strong>, 41.8 g (0.72 mol) of potassium fluoride, and 160 ml of acetone were placed. Further, in a dropping funnel attached thereto, 97.8 g (0.60 mol) of 2,5-dichlorophenol and 110 ml of acetone were placed. The 2,5-dichlorophenol/acetone mixed solution was added dropwise from the dropping funnel to the flask over a period of about two hours while kept stirred at -1° C. The stirring was subsequently continued for about two hours. Thereafter, the contents of the flask were stirred overnight, with the reaction temperature thereof slowly raised to room temperature. Then, to this flask, 79.8 g (0.30 mol) of 2,6-dibromo-4-methylphenol, 20.9 g (0.36 mol) of potassium fluoride, and 15.0 ml of acetone were charged and the mixture was kept stirred at 40° C. for 10 hours. The reaction solution was cooled and filtered. The filtrate was distilled by a rotary evaporator to expel the acetone and was recrystallized from methanol. The produced crystals were separated by filtration and vacuum dried to afford 176.8 g of 3-(2,6-dibromo-4-methylphenoxy)-4,5-bis(2,5-dichlorophenoxy)-6-fluorophthalonitrile (yield: 80.5 mol percent).
With pyridine; sodium methylate; sodium;copper(I) chloride; In methanol; toluene;
EXAMPLE 14 Preparation of 3,5-dimethoxy-4-hydroxytoluene To a solution of freshly prepared sodium methoxide (from 12.4 g. of sodium and 75 ml. of methanol) was added 100 ml. of toluene and 4 ml. of pyridine. 1.114 G. of cuprous chloride and 23.94 g. of 3,5-dibromo-4-hydroxytoluene were then added. The mixture was boiled under reflux for 2 hours, cooled to room temperature, and acidified with 35 ml. concentrated hydrochloric acid. The mixture was filtered, the filtrate was extracted with methylene chloride (3*50 ml.), and the extract was washed with saturated brine, dried over magnesium sulfate and evaporated to give an oil. Distillation gave 13.61 g. (90percent) of 3,5-dimethoxy-4-hydroxytoluene, bp 91°/0.2 mm.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
