4,4′-Oxydibenzoyl chloride

4, 4'-diphenyl ether dicarboxylic acid 25.3 g (0.096 mol), 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. For the first mixed solution in the stirring state, 58.4 g (0.46 mol) of thionyl chloride, And 20 ml of toluene Was gradually added dropwise at room temperature. After completion of the dropwise addition, the liquid obtained was heated to 95 ° C., It was refluxed for 3 h. Then, by allowing the yellow transparent liquid obtained after heating / refluxing to cool, It has the following molecular structure 4, 4'-diphenyl ether dicarboxylic acid chloride (Hereinafter referred to as 'acid chloride (A) In some cases) as a toluene solution. further, The toluene solution was applied to a rotary evaporator, and toluene, Thionyl chloride and hydrogen chloride were removed, 4, 4'- Diphenyl ether dicarboxylic acid chloride solid 26.9 g (0.091 mol, 95percent yield) Was obtained.4, 4'-diphenyl ether dicarboxylic acid 25.3 g (0.096 mol), 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene To prepare a first mixed solution. A second mixed solution consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was gradually added dropwise to the first mixed solution under stirring at room temperature. After completion of the dropwise addition, the liquid obtained was heated to 95 ° C. and refluxed for 3 hours. Then, by allowing the yellow transparent liquid obtained after warming / refluxing to cool, 4, 4'-diphenyl ether dicarboxylic acid chloride having the following molecular structure (hereinafter, referred to as 'acid chloride (A) A certain amount of toluene solution was obtained. Further, the toluene solution was subjected to rotary evaporation, and toluene, thionyl chloride and hydrogen chloride were removed at 40 ° C., and 26.9 g (0.091 mol) of 4, 4'-diphenyl ether dicarboxylic acid chloride solid, Yield: 95percent).4, 4' - 25.3 g (0.096mol) [jihuenirueterujikarubon[jihuenirueterujikarubon] acid, 80 ml of toluene was made 0.85 g of dimethylformamide (0.012mol) and first mixture. To a stirring mixture of first, second and 20 ml toluene liquid mixture composed of 58.4 g of thionyl chloride (0.46mol) at room temperature was added dropwise slowly. After the completion of the dripping liquid heated to 95 °C obtained, 3h to reflux. The yellow transparent liquid reflux obtained after heating at · cold, shown below having a molecular structure 4, 4' - (hereinafter, referred to as 'the acid chloride (A) if) [jihuenirueterujikarubon[jihuenirueterujikarubon] acid chloride in toluene solution was obtained. Further, the toluene solution were subjected to a rotary evaporator, in toluene at 40 °C, thionyl chloride was removed and hydrogen chloride, 4, 4' - 26.9 g of solid (0.091mol, 95percent yield) was obtained [jihuenirueterujikarubon[jihuenirueterujikarubon] acid chloride.4, 4'-diphenyl ether dicarboxylic acid25.3 g (0.096 mol), 0.85 g (0.012 mol) of dimethylformamide, And 80 ml of toluene was prepared.For the first mixed solution in the stirring state, A second mixed solution consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was gradually added dropwise at room temperature.After completion of the dropwise addition, the liquid obtained was heated to 95 ° C. and refluxed for 3 hours.And warming ·By cooling the yellow transparent liquid obtained after refluxing, 4, 4'-diphenyl ether dicarboxylic acid chloride (hereinafter referred to as 'Toluene solution of 'acid chloride (A)) was obtained. Further, this toluene solution was subjected to rotary evaporation, and toluene, Thionyl chloride and hydrogen chloride were removed, A solid of 4, 4'-diphenyl ether dicarboxylic acid chloride26.9 g (0.091 mol, yield 95percent) was obtained.A first mixed solution of 25.3 g (0.096 mol) of 4, 4'-diphenyl ether dicarboxylic acid, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene was prepared. A second mixed solution consisting of 58.4 g (0.46 mol) of thionyl chloride and 20 ml of toluene was gradually added dropwise to the first mixed solution under stirring at room temperature. After completion of the dropwise addition, the liquid obtained was heated to 95 ° C. and refluxed for 3 hours. Then, by allowing the yellow transparent liquid obtained after warming / refluxing to cool, 4, 4'-diphenyl ether dicarboxylic acid chloride having the following molecular structure (hereinafter, referred to as 'acid chloride (A) A certain amount of toluene solution was obtained. Further, this toluene solution was rotary evaporated, toluene, thionyl chloride and hydrogen chloride were removed at 40 ° C., 26.9 g (0.091 mol, yield 95percent) of 4, 4'-diphenyl ether dicarboxylic acid chloride solid was obtained.General procedure: A mixture of naphthalene-2, 6-dicarboxylic acid 0.93 g (4.3 mmol) and VR22.0 g (0.085 mol) of 4, 4'-diphenyl ether dicarboxylic acid, 99.0 g of toluene and 0.20 g (0.003 mol) of N, N-dimethylformamide were charged into a 300 mL four-necked flask and heated to 75 ° C. The temperature was raised and 30.4 g (0.256 mol) of thionyl chloride was added dropwise at 75 to 80 ° C. After holding at the same temperature for 7 hours, it was cooled to 30 ° C., and after adding 2.19 g of activated carbon, it was kept for 1 hour. After filtering the activated carbon and washing the activated carbon with toluene, the solvent was distilled off until the total amount of the substance in the flask reached 50 g. 21.6 g of heptane was added dropwise at room temperature, the temperature was raised to 70 ° C. and dissolved. The insoluble matter was filtered while maintaining the temperature at 60 ° C. or higher, the filtrate obtained was cooled to 50 ° C., 1 g of seed crystals was added, and after cooling to 0 ° C., it was kept for 2 hours. The precipitated crystals were filtered, washed with a mixed solvent of 10.0 g of heptane and 6.60 g of toluene, and dried under reduced pressure at 20 ° C. to obtain 21.0 g of 4, 4'-diphenyl ether dicarboxylic acid chloride. The yield was 83.4percent, and the HPLC purity was 99.4percent.N, N-dimethylchloromethyleneiminium chloride was similarly synthesized by substituting the solvent 1, 4-dioxane of Example I-101 with orthochlorotoluene. Namely, 90 g (1.23 mol) of N, N-dimethylformamide and 310 mL (canned) of orthochlorotoluene were placed in a 1 L four-necked flask, and 84.5 g (0.418 mol) of phthalic acid chloride was stirred at room temperature It took a minute to drip. Stirring was continued for 3 hours and a half in a 50 ° C. oil bath, and pressure filtration with nitrogen was carried out with a glass filter, N, N-dimethylchloromethyleneiminium chloride crystals were collected by filtration, washed twice with 150 mL of orthochlorotoluene WashedThe whole amount of the crystals of N, N-dimethylchloromethyleneiminium chloride was transferred to a 1 L four-necked flask without drying, 300 mL of orthochlorotoluene and 45 g (0.174 mol) of 4, 4'-oxybisbenzoic acid were added, When stirring was continued in an oil bath at 70 ° C., it gradually became a homogeneous solution. The reaction was terminated in 4 hours and 25 mL of a brown liquid layer (mainly unreacted N, N-dimethylchloromethylene iminium chloride and N, N-dimethylformamide) was removed by decantation at the bottom.The reaction solution was concentrated to 70 mL with an evaporator. After cooling to 10 ° C., the crystals were collected by filtration and the crystals were washed with 30 mL of hexane. 35.8 g (yield: 70percent) of white crystals of 4, 4'-oxybisbenzoic acid chloride were obtained at room temperature under vacuum drying for 1 hour. HPLC analysis: 99.70percentTo a solution of 25 g of 4, 4-dicarboxybiphenyl ether, 0.85 g (0.012 mol) of dimethylformamide and 80 ml of toluene, 58.4 g (0.46 mol) of thionyl chloride and a solution of toluene were added dropwise at room temperature. After completion of the dropwise addition, the obtained solution was stirred at 95 ° C. for 3 hours. After leaving the reaction solution to cool, toluene and thionyl chloride hydrogen chloride were removed using a rotary evaporator to obtain 27.4 g of a white solid of 4, 4-di (benzoyl chloride) ether2.7 g (9.15 mmol) of 4, 4'-dicarboxylic acid diphenyl ether was dissolved in a certain amount of dichloromethane.Will be 13.02g(20.13 mmol) OP-10, 0.134 g (1.83 mmol) DMF, 2.04 g (20.13 mmol) TEA (triethylamine) and 0.403 g(1.83 mmol) of antioxidant BHT (2, 6-di-tert-butyl-4-methylphenol)Add to a three-necked flask equipped with a stirrer and add a certain amount of dichloromethane to dissolve.A solution of 4, 4'-diformyl chloride diphenyl ether in dichloromethane was slowly added dropwise to the above three-necked flask.The reaction was carried out for 4 h at room temperature (TLC was used to monitor the end of the reaction). After the reaction is finished, it is quenched with water and separated.The organic phase is recovered, concentrated to dryness, and purified by column.(column condition V (petroleum ether): V (ethyl acetate) EA = 10:1), That is, a brown oily product (octylphenol polyoxyethylene ether disubstituted)Diphenyl dicarboxylate 8.3 g (5.49 mmol).General procedure: To a 250 mL flame dried Schlenk flask, 1.0 equiv (2.95 g, 10 mmol)of 4, 4?-oxybis (benzoyl chloride) dissolved in 80 mL of dry CH2Cl2 was added with stirring under nitrogen atmosphere. The solution was cooled to 0 C and then 2.1 equiv of the 10-undecen-1-ol (3.58 g, 21 mmol) and 2.1 equiv of pyridine (1.66 g, 21 mmol) were slowly added to the solution via syringe. The mixture was allowed to warm to room temperature for 24 h and quenched with addition of 1M HCl (100 mL) and deionized water (100 mL). The organic layer was dried over anhydrous Mg2SO4, filtered, concentrated in vacuum, and purified by column chromatography using n-hexane/ethyl acetate (7/1) as an eluent to yield a white solid. (yield=83%).

Molecular Weight:295.1
XLogP3:4.5
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:4
Exact Mass:293.9850495
Monoisotopic Mass:293.9850495
Topological Polar Surface Area:43.4
Heavy Atom Count:19
Complexity:298
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes