* 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.
Stage #1: With N-benzyl-N,N,N-triethylammonium chloride; sodium hydroxide In water at 85 - 172℃; for 15 h; Stage #2: at 130 - 145℃; for 5 h;
79 g (0.63 mol) of a 32percent by weight aqueous sodium hydroxide solution and 62.4 g (0.3 mol) of bisphenol A were charged into the reactor.Stir and dissolve,The temperature rises to 85 ° C and the solution is transparent.Next, 510 g of a trimethylbenzene solvent and 4.2 g of a benzyltriethylammonium chloride catalyst were added.Warming and refluxing,The temperature rose to 172 ° C,Stirring reaction for 15 hours,Then cool down to 130 ° C,108 g (0.6 mol) of 4-chlorophthalic anhydride and 4.86 g of benzyltriethylammonium chloride catalyst were added.Heating from 140 ° C to 145 ° C,Reflow reaction for 5 hours,Then filter hot,Pumping the filtrate into the crystallization kettle,The filtrate is cooled to room temperature.Crystallized for 12 hours,filter,The precipitate is washed with ion-free water,Filtration, precipitation was obtained and washed with 250 g of ethanol.Stirring for 2 hours,filter,Get wet material 125g,After drying, 120 g of bisphenol A diether dianhydride product (yield 85percent),The product is white powder,
Reference：
[1] Patent: CN108148029, 2018, A, . Location in patent: Paragraph 0011; 0012; 0014
2
[ 319-03-9 ]
[ 2444-90-8 ]
[ 38103-06-9 ]
Yield
Reaction Conditions
Operation in experiment
90%
at 180℃; for 0.25 h;
A dry 100 mL flask was charged with 1.69 g (7.3 mmol) of the disodium salt of biphenol, 2.44 g, (146 mmol) of 4-fluorophthalic anhydride, 2 mL (14 mmol) of hexaethylguanidinium chloride as a 15 weight percent solution in o-dichlorobenzene, and 44 g of dry o-dichlorobenzene. The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. After 15 minutes, the reaction mixture was filtered hot to remove the sodium fluoride by-product. The filtrate was allowed to cool to room temperature and the product dianhydride crystallized from the solvent as a cream colored solid which was isolated by filtration (3.1 g, 90percent yield).
82%
at 175℃; for 1 h;
A dry 25 mL flask was charged with 403 mg (1.482 mmol) of the disodium salt of bisphenol A, 500 mg (3.012 mmol) of 4-fluorophthalic anhydride, 46 mg (0.148 mmol) of 4-(N,N-dibutylamino)-N-neopentylpyridinium chloride, 8.5 g (10percent solids) of dry o-dichlorobenzene and 55 mg of o-terphenyl (internal standard). The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. The temperature within the reaction flask was about 175° C. Samples (0.1 mL) were withdrawn periodically dissolved in 6 mL of acetic acid and approximately. 0.5 mL of methylamine (40percent aqueous soln.) and heated at 125-130° C. for 1.5 hours. These samples were analyzed for the bis N-methyl imide of bisphenol A dianhydride by liquid chromatography. By following the diether dianhydride formation in this manner it was determined that the yield of product bisphenol A dianhydride (BPADA) had reached 82percent after one hour.
A dry 100 mL flask was charged with 2.0 g (7.3 mmol) of the disodium salt of bisphenol A, 2.67 g (14.6 mmol) of 4-chlorophthalic anhydride, 4 mL (14 mmol) of hexaethylguanidinium chloride as a 15 weight percent solution in o-dichlorobenzene, 48 g of dry o-dichlorobenzene, and 100 mg of o-terphenyl (internal standard). The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. The reaction was followed as in Example 1. The yield of biphenol dianhydride had reached 25percent after 5 hours.
bis(3-aminopropyl)-terminated poly(permethylsiloxane)[ No CAS ]
[ 108-45-2 ]
[ 38103-06-9 ]
reaction product of bis(3-aminopropyl)-terminated poly(permethylsiloxane) with 2,2-di[4-[(1,3-dioxo-1,3-dihydro-2-benzofuran-5-yl)oxy]phenyl]propane and 1,3-diaminobenzene, Mw = 39350, Mn = 18880, Mw/Mn = 2, Mpeak = 38750[ No CAS ]
polymer, polyamic acid, polycondensation equimolar amount of monomers; monomer(s): 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 2,2-[bis[4-(4-aminophenyl)phenyl]]propane[ No CAS ]
polymer, polyamic acid, polycondensation equimolar amount of monomers; monomer(s): 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; 4,4-diaminodiphenylmethane[ No CAS ]
polymer, polyamic acid, polycondensation equimolar amount of monomers; monomer(s): 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride; benzidine[ No CAS ]
With acetic acid; at 125℃; for 10h;Product distribution / selectivity;
A 1000 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 80.298 g (0.154 mol) of BPA dianhydride, 33.66 g (0.308 mol) of 4-aminophenol, and 400 ml of acetic acid. The mixture was then purged with nitrogen and allowed to react for a period of 10 hours at 125C under continuous stirring. The reaction product was the poured into an excess of warm water (2L) and stirred for 30 minutes with a magnetic stirrer. The resulting macromer crystals were filtered, and subsequently washed with water until the pH was 6.6. The crystals were then washed with cold methanol to facilitate drying, and dried in-vacuoat for approximately 8 hours at 75C. The product was soluble in DMSO, hot ODCB, and THF. The product was insoluble in toluene, water, methanol, and methylene chloride In an alternative reaction, a flask equipped with a mechanical stirrer and condenser was charged 40.148 g (0.771 mol) BPA dianhydride, 16.83 g (0.154 mol) 4-aminophenol, 200 ml of ODCB, 25 ml of toluene (to remove reaction product), and 0.5 ml of triehtyl amine. The mixture was allowed to stir at 130C for a period of 4.5 hours, under nitrogen atmosphere, after which the temperature was reduced to room temperature. 500 ml of cold methanol was then added to the reaction mixture to crystallize the product. This mixture was allowed to stir for 30 minutes. The crystals were then recovered by filtration, added to 400 ml of cold methanol, and allowed to stir an additional 30 minutes. The product was then filtered again, and dried in-vacuoat 75C for approximately 20 hours. This reaction is represented below. Bisphenol Diimide
With triethylamine; In 1,2-dichloro-benzene; toluene; at 130℃; for 4.5h;Product distribution / selectivity;
A 1000 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 80.298 g (0.154 mol) of BPA dianhydride, 33.66 g (0.308 mol) of 4-aminophenol, and 400 ml of acetic acid. The mixture was then purged with nitrogen and allowed to react for a period of 10 hours at 125C under continuous stirring. The reaction product was the poured into an excess of warm water (2L) and stirred for 30 minutes with a magnetic stirrer. The resulting macromer crystals were filtered, and subsequently washed with water until the pH was 6.6. The crystals were then washed with cold methanol to facilitate drying, and dried in-vacuoat for approximately 8 hours at 75C. The product was soluble in DMSO, hot ODCB, and THF. The product was insoluble in toluene, water, methanol, and methylene chloride In an alternative reaction, a flask equipped with a mechanical stirrer and condenser was charged 40.148 g (0.771 mol) BPA dianhydride, 16.83 g (0.154 mol) 4-aminophenol, 200 ml of ODCB, 25 ml of toluene (to remove reaction product), and 0.5 ml of triehtyl amine. The mixture was allowed to stir at 130C for a period of 4.5 hours, under nitrogen atmosphere, after which the temperature was reduced to room temperature. 500 ml of cold methanol was then added to the reaction mixture to crystallize the product. This mixture was allowed to stir for 30 minutes. The crystals were then recovered by filtration, added to 400 ml of cold methanol, and allowed to stir an additional 30 minutes. The product was then filtered again, and dried in-vacuoat 75C for approximately 20 hours. This reaction is represented below. Bisphenol Diimide
With acetic acid; for 16h;Heating / reflux;Product distribution / selectivity;
A three liter, four neck flask equipped with an overhead stirrer, a thermometer, a condenser, an argon inlet and outlet, was charged with: 104.10 grams of BPA-dianhydride (200mmol.) from the Ultem plant93 grams of 2-(4-Aminophenyl)-2-4'-Hydroxyphenyl)-propane (96%), and1000 ml of glacial acetic acid. The resulting mixture was refluxed for 16 hours under a flow of argon. By the time reflux started, all the reactants had passed into solution and no precipitation was observed throughout the reflux period. After 16 hours, the reaction was cooled to room temperature and quenched by pouring the reaction mixture into two 4L beakers each filled with water. A white precipitate formed. After stirring, the precipitate was isolated by filtration. The precipitate was then oven dried at 50C. The dried crystals were further purified by refluxing in 500 mL of ODCB for about 5 hours, subsequently re-precipitating by the crystals adding 100 mL of Xylene. The crystal composition was confirmed by 1H, 13C NMR.
With triethylamine; In 1,2-dichloro-benzene; toluene; at 130℃; for 4.5h;Product distribution / selectivity;
A 500 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 20 g (0.088 mol) of amino-BPA, 22.9 g (0.044 mol) of BPA dianhydride, 160 g of OBCB, 10.7 g of toluene, and 330 ppm triethyl amine. The flask was then purged with nitrogen and the reaction mixture heated to 130C and allowed to stir for 2 hours. An additional 10 ml of toluene was then added and the reaction allowed to continue for an additional 2.5 hours. The macromer was precipitated by adding 30 g of O-xylene while allowing the reaction mixture to cool. The macromonomer was filtered and dried at 50C for 10 hours. This product was soluble in tetrahydrofuran (THF), anisole, ODCB, dimethyl sulfoxide (DMSO), acetonitrile, and warm chlorobenzene. It was insoluble in diethyl ether, chloroform, and methylenechloride. An alternative "melt" route polymerization was as follows. A 100 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 11.45 g (0.050 mol) BPA dianhydride and 10.0 g (0.044 mol) amino-BPA. This mixture was then heated to 200C, and allowed to react for 1 hour under a nitrogen blanket. The product was then cooled and ground into a fine powder.
at 200℃; for 1h;Neat (no solvent);Product distribution / selectivity;
A 500 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 20 g (0.088 mol) of amino-BPA, 22.9 g (0.044 mol) of BPA dianhydride, 160 g of OBCB, 10.7 g of toluene, and 330 ppm triethyl amine. The flask was then purged with nitrogen and the reaction mixture heated to 130C and allowed to stir for 2 hours. An additional 10 ml of toluene was then added and the reaction allowed to continue for an additional 2.5 hours. The macromer was precipitated by adding 30 g of O-xylene while allowing the reaction mixture to cool. The macromonomer was filtered and dried at 50C for 10 hours. This product was soluble in tetrahydrofuran (THF), anisole, ODCB, dimethyl sulfoxide (DMSO), acetonitrile, and warm chlorobenzene. It was insoluble in diethyl ether, chloroform, and methylenechloride. An alternative "melt" route polymerization was as follows. A 100 ml three-neck flask equipped with a mechanical stirrer and condenser was charged with 11.45 g (0.050 mol) BPA dianhydride and 10.0 g (0.044 mol) amino-BPA. This mixture was then heated to 200C, and allowed to react for 1 hour under a nitrogen blanket. The product was then cooled and ground into a fine powder.
1,1,2,2,3,3-Hexaethylguanidiniumchlorid; In 1,2-dichloro-benzene; at 180℃; for 0.25h;Product distribution / selectivity;
A dry 100 mL flask was charged with 1.69 g (7.3 mmol) of the disodium salt of biphenol, 2.44 g, (146 mmol) of 4-fluorophthalic anhydride, 2 mL (14 mmol) of hexaethylguanidinium chloride as a 15 weight percent solution in o-dichlorobenzene, and 44 g of dry o-dichlorobenzene. The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. After 15 minutes, the reaction mixture was filtered hot to remove the sodium fluoride by-product. The filtrate was allowed to cool to room temperature and the product dianhydride crystallized from the solvent as a cream colored solid which was isolated by filtration (3.1 g, 90percent yield).
82%
N-neopentyl chloride of 4-dibutylaminopyridine; In 1,2-dichloro-benzene; at 175℃; for 1.0h;Product distribution / selectivity;
A dry 25 mL flask was charged with 403 mg (1.482 mmol) of the disodium salt of bisphenol A, 500 mg (3.012 mmol) of 4-fluorophthalic anhydride, 46 mg (0.148 mmol) of 4-(N,N-dibutylamino)-N-neopentylpyridinium chloride, 8.5 g (10percent solids) of dry o-dichlorobenzene and 55 mg of o-terphenyl (internal standard). The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. The temperature within the reaction flask was about 175° C. Samples (0.1 mL) were withdrawn periodically dissolved in 6 mL of acetic acid and approximately. 0.5 mL of methylamine (40percent aqueous soln.) and heated at 125-130° C. for 1.5 hours. These samples were analyzed for the bis N-methyl imide of bisphenol A dianhydride by liquid chromatography. By following the diether dianhydride formation in this manner it was determined that the yield of product bisphenol A dianhydride (BPADA) had reached 82percent after one hour.
1,1,2,2,3,3-Hexaethylguanidiniumchlorid; In 1,2-dichloro-benzene; at 180℃; for 5.0h;Product distribution / selectivity;
A dry 100 mL flask was charged with 2.0 g (7.3 mmol) of the disodium salt of bisphenol A, 2.67 g (14.6 mmol) of <strong>[118-45-6]4-chlorophthalic anhydride</strong>, 4 mL (14 mmol) of hexaethylguanidinium chloride as a 15 weight percent solution in o-dichlorobenzene, 48 g of dry o-dichlorobenzene, and 100 mg of o-terphenyl (internal standard). The flask was immersed in an oil bath maintained at 180° C. and the mixture was stirred magnetically. The reaction was followed as in Example 1. The yield of biphenol dianhydride had reached 25percent after 5 hours.
With methanesulfonic acid; triethylamine; In toluene; at 20℃; for 13h;Heating / reflux;
[0073] EXAMPLE 2 PREPARATION OF IMIDE-ALCOHOL FROM 4,4:-BISPHENOL-A DLANHYDRIDE AND 4-AMINOPHENETHYL ALCOHOL; [0074] T?ethylamine (58 6 grams, 0 5796 mol) and toluene ( mL) were combined in a 1L 4-neck round- bottom reaction flask equipped with a thermometer and mechanical mixer Methanesulfonic acid (57 3 grams, 0 5962 mol) was slowly added with moderate mixing. An exotherm was generated but a temperature of <45 C was maintained by controlling the rate of addition The addition was completed within one hour After the addition, the reaction appeared as a colorless hazy solution and was mixed for ten minutes. 4-Amiotanophenethyl alcohol (25 0 grams, 0 1822 mol) was added (generation of an exotherm was not observed on this scale) Within 20 minutes, all solids dissolved forming a dark brown solution 4,4'-Bisphenol A dianhyd?de (43 1 grams, 0 0828 mol) was added over five minutes The dark gold-brown reaction mixture was stirred for one hour at room temperature (no exotherm was noted) The reaction flask was fitted with a Dean-Stark trap and condenser, placed in a hot oil bath (preheated to 145C) and mixed/heated at reflux for 12 hours Note that within the first 30 minutes of heating, all solids dissolved During the reaction nearly all theoretical water generated by the reaction was collected in the trap After heating, the reaction was cooled to room temperature, placed in a separatory funnel and allowed to phase-out The top colorless phase was separated from the dark-brown bottom phase and discarded The dark brown phase was dissolved in 250 mL of dichforomethane and washed twice in the separatory funnel with 500 mL of 5 % hydrogen chloride solution These washes serve to protonate and remove residual/excess 4-amiotanophenethyl alcohol. The efficiency of these washes can be monitored by TLC eluting in a 5/1 (volume) acetone/methanol solvent system The acid washes were followed by a distilled water wash of 500 mL Following the washes, the bottom organic phase was collected as a hazy gold-brown solution, which was dried over 40 grams of magnesium sulfate Filtration resulted in a clear amber reaction solution Solvent was stripped from the solution on a roto- evaporator at 401C leaving 45 grams of a tan crystalline solid, a yield of 71% The identity of the product was confirmed using 1 H-NMR, see Figure 2
71%
Example 2Preparation of Imide-Alcohol from 4,4'-Bisphenol-A Dianhydride and 4-Aminophenethyl Alcohol Triethylamine (58.6 grams, 0.5796 mol) and toluene (300 mL) were combined in a 1 L 4-neck round-bottom reaction flask equipped with a thermometer and mechanical mixer. Methanesulfonic acid (57.3 grams, 0.5962 mol) was slowly added with moderate mixing. An exotherm was generated but a temperature of <45 C. was maintained by controlling the rate of addition. The addition was completed within one hour. After the addition, the reaction appeared as a colorless hazy solution and was mixed for ten minutes. 4-Aminophenethyl alcohol (25.0 grams, 0.1822 mol) was added (generation of an exotherm was not observed on this scale). Within 20 minutes, all solids dissolved forming a dark brown solution. 4,4'-Bisphenol A dianhydride (43.1 grams, 0.0828 mol) was added over five minutes. The dark gold-brown reaction mixture was stirred for one hour at room temperature (no exotherm was noted). The reaction flask was fitted with a Dean-Stark trap and condenser, placed in a hot oil bath (preheated to 145 C.) and mixed/heated at reflux for 12 hours. Note that within the first 30 minutes of heating, all solids dissolved. During the reaction nearly all theoretical water generated by the reaction was collected in the trap. After heating, the reaction was cooled to room temperature, placed in a separatory funnel and allowed to phase-out. The top colorless phase was separated from the dark-brown bottom phase and discarded. The dark brown phase was dissolved in 250 mL of dichloromethane and washed twice in the separatory funnel with 500 mL of 5% hydrogen chloride solution. These washes serve to protonate and remove residual/excess 4-aminophenethyl alcohol. The efficiency of these washes can be monitored by TLC eluting in a 5/1 (volume) acetone/methanol solvent system. The acid washes were followed by a distilled water wash of 500 mL. Following the washes, the bottom organic phase was collected as a hazy gold-brown solution, which was dried over 40 grams of magnesium sulfate. Filtration resulted in a clear amber reaction solution. Solvent was stripped from the solution on a roto-evaporator at 40 C. leaving 45 grams of a tan crystalline solid, a yield of 71%.The identity of the product was confirmed using 1H-NMR, see FIG. 2.
3.33 g (6.39 mmol) of BSAA, 1.68 g (12.77 mmol) of isoleucine and 10 ml of EDM were added to a reaction vessel and stirred at 170 ° C for 3 hours. After completion of the reaction, EDM and water generated by the reaction were removed. Subsequently, 20 ml of toluene and 3.11 g (26.13 mmol) of thionyl chloride were added to the above reaction vessel, and the mixture was stirred at 70 ° C for 3 hours. Removal of toluene and thionyl chloride gave acid chloride. In a separate reaction vessel, 1.57 g (13.52 mmol) of 3-ethyl-3-oxetane methanol, 1.60 g (15.83 mmol) of triethylamine and 20 ml of toluene were mixed, and to which the previously prepared acid chloride was dropped. After completion of the dropwise addition, the mixture was further stirred for 1 hour. The reaction solution was poured into a separating funnel and washed with 1 M hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated saline in this order. After washing, anhydrous magnesium sulfate was added and the solution was dried. After drying, anhydrous magnesium sulfate was filtered off and the solvent was removed to obtain 6.76 g of oxetane imide 5.
With 4,4'-diphenoxy diphenylmethanetetracarboxylic dianhydride and4- (3-aminophenoxy) phthalonitrile as starting material,4,4'-diphenoxy diphenylmethanetetracarboxylic dianhydride andThe molar ratio of 4- (3-aminophenoxy) phthalonitrile was 1.0: 4.0;The polar solvent DMF is used in such a manner that the solid content in the reaction solution is 15%The solid content =(Mass of 4,4'-diphenoxy diphenylmethane tetracarboxylic dianhydride + mass of phthalonitrile): polar solvent volume,The mass units of 4,4'-diphenoxydiphenylmethane tetracarboxylic dianhydride and phthalonitrile are in grams,The volume of the polar solvent is in milliliter, the volume of the polar solvent is VDMF = (solid mass (g) * 4) mL); the volume ratio of toluene to the polar solvent is 1.0: 1.0.Will be 9.41g4- (3-aminophenoxy) phthalonitrile was charged into 97 ml of DMF,After 4- (3-aminophenoxy) phthalonitrile was completely dissolved, at room temperatureTo a solution of 4- (3-aminophenoxy) phthalonitrile was added 5.20 g4,4'-diphenoxy diphenylmethanetetracarboxylic dianhydride,After reaction at room temperature for 12 h, toluene was added to the reaction solution,The temperature was refluxed for 12 hours, toluene was removed, and the resulting reaction was precipitated with about 380 ml of anhydrous methanol and removed.Filtering and collecting the filter cake, washing the filter cake with deionized water, filtering the filter cake, filtering the filter cake in a vacuum oven at 70 DEG C to constant weight to obtain phthalonitrileTerminating monome
With urea; In N,N-dimethyl-formamide; at 150℃; for 9h;
With 4,4'-diphenoxydiphenylmethanetetracarboxylic dianhydride and urea as raw materials,4,4'-diphenoxy diphenylmethane The molar ratio of tetraacid dianhydride to urea is 1.0: 10.0; the polar solvent DMF is used in such a way that the solid content in the reaction solution is 30% The solid content = mass of 4,4'-diphenoxydiphenylmethane tetracarboxylic dianhydride + mass of urea): the volume of the polar solvent,4,4'-diphenoxy diphenylmethane tetracarboxylic dianhydride and urea in grams of mass, the polar solvent volume unit in milliliters;Will be 10g4,4'-diphenoxy diphenylmethanetetracarboxylic dianhydrideAnd 11.53g urea into the three-necked flask,72 ml of DMF was added and incubated at 150 C for 9 h,After the reaction is finally cooled to room temperature,The resulting reaction was precipitated with about 280 ml of anhydrous methanol and removed,Filter the filter cake, wash the filter cake with deionized water,The resulting filter cake was dried to a constant weight of the phthalimide-terminated monomer
With N-ethyl-N,N-diisopropylamine; In 1,4-dioxane;Inert atmosphere; Reflux;
In a 250mL round bottomed flask with stirring bar was placed 4,4'-(4,4'-Isopropylidinediphenoxy)bis(phthalic anhydride) (1.5g, 2.9mmol) and dioxane (50mL). Ethanolamine (435 L, 7.2mmol) and diisopropylethylamine (2.5mL) were added, the flask was equipped with a reflux condenser and the mixture heated to reflux overnight. The reaction was cooled and concentrated on a rotovap to a paste which was partitioned between dichloromethane and water. The organic layer was retained and the aqueous layer was extracted two additional times with dichloromethane. The organic layers were combined, dried over sodium sulfate and concentrated to the final solid product (400mg). Overall purity is ~89%. Predicted MW is 606.6. MW found is 606.4.
With N-ethyl-N,N-diisopropylamine; In 1,4-dioxane;Reflux;
In a 250mL round bottomed flask with stirring bar was placed 4,4'-(4,4'- Isopropylidinediphenoxy)bis(phthalic anhydride) (1.5g, 2.9mmol) and dioxane (50mL). Ethanolamine (435 L, 7.2mmol) and diisopropylethylamine (2.5mL) were added, the flask was equipped with a reflux condenser and the mixture heated to reflux overnight. The reaction was cooled and concentrated on a rotovap to a paste which was partitioned between dichloromethane and water. The organic layer was retained and the aqueous layer was extracted two additional times with dichloromethane. The organic layers were combined, dried over sodium sulfate and concentrated to the final solid product (400mg). (0644) Overall urity is -89%. Predicted MW is 606.6. MW found is 606.4.
To the reaction vessel, 3.33 g (6.39 mmol) of BSAA, 1.68 g (12.77 mmol) of isoleucine and 40 ml of xylene were added, a Dean-Stark apparatus was attached and refluxed for 3 hours while removing water generated by the reaction. After completion of the reaction, xylene was removed. Subsequently, 20 ml of tetrahydrofuran and 2.86 g (34.62 mmol) of thionyl chloride were added to the reaction vessel, followed by stirring at 70 C. for 3 hours. Removal of toluene and thionyl chloride gave the acid chloride.
3.32 g (6.39mmol) BSAA, 1.67 g (12.77mmol) of isoleucine, and 10-ml EDM were added to the reaction container, and it flowed back for 3 hours. The water which arose at EDM and a reaction was removed after ending reaction. Continuously, 20 ml of toluene and a 4.71 g (39.59mmol) thionyl chloride were added to the aforementioned reaction container, and it stirred at 70 degrees C for 3 hours. The acid chloride was obtained by removing toluene and a thionyl chloride.
3.73 g (7.16 mmol) of BSAA, 1.28 g (14.31 mmol) of 2-amino-1-butanol and 10 ml of EDM were added to the reaction vessel and refluxed for 3 hours. After completion of the reaction, water generated by EDM and reaction was removed. Subsequently, 20 ml of methyl ethyl ketone, 0.01 g (0.01 mmol) of dibutyltin dilaurate and 0.01 g (0.10 mmol) of 4-methoxyphenol were mixed in the reaction vessel. To this was added dropwise 2.42 g (17.17 mmol) of 2-isocyanatoethyl acrylate. After completion of the dropwise addition, the mixture was stirred at 45 C for 2 hours. After the reaction, in order to react excess 2-isocyanatoethyl acrylate, 2 ml of methanol was poured into the reaction solution and the mixture was stirred on an ice bath for 30 minutes. After stirring, the solvent was removed to obtain 7.36 g of acrylic imide 5 .
To a reaction vessel, 1.35 g (5.0 mmol) of the compound (Z-1-1): 1,4,5,8-naphthalene tetracarboxylic acid dianhydride and 2.94 g (12 mmol) of compound (I-1): and 15 millilitre of toluene (hereinafter milliliter is referred to as mL) were added and reacted under reflux for 3 hours. During the reaction, water produced as a by-product was removed using a Dean-Stark trap. After completion of the reaction, the reaction mixture was cooled, & 50 mL of methanol was added, and the precipitated crystals were filtered. The resulting crystals were suspended in methanol and then purified with tetrahydrofuran and activated carbon to obtain 0.80 g (yield 22%) of the compound (ZI-11) of Chemical Formula 8.
Based on 5.20 g of 4,4'-diphenoxydiphenylmethanetetracarboxylic dianhydride, 4-(3-aminophenoxy)phthalonitrile, acetic anhydride and pyridine, 4,4'- The molar ratio of diphenoxydiphenylmethanetetracarboxylic dianhydride to 4-(3-aminophenoxy)phthalonitrile was 1.0:1.0, and the molar ratio of tetracarboxylic dianhydride, acetic anhydride, and pyridine was: Tetracarboxylic dianhydride: acetic anhydride: pyridine = 1.0:7.0:9.0;Dissolve 4,4'-diphenoxydiphenylmethanetetracarboxylic dianhydride in 13.0 mL of DMAC, heat to completely dissolve the solution, and cool to room temperature. The 4-(3-aminophenoxy)phthalonitrile is removed. Dissolve 4-(3-aminophenoxy)-phthalonitrile solution at a rate of 0.45 mL/min with stirring in a 2.5-fold volume (mL) limit solvent (DMF). A solution of 4,4'-diphenoxydiphenylmethanetetracarboxylic acid dianhydride was added dropwise. After completion of the dropwise addition, the reaction mixture was allowed to react at room temperature for 10 hours while stirring. Then, acetic anhydride and pyridine were added to the above reaction mixture with stirring, and the temperature was increased. The reaction was incubated at 120 C. for 4 hours. After the reaction, the mixture was naturally cooled to room temperature. The reaction solution was then poured into anhydrous methanol, stirred, filtered, and the filtrate was collected. The filtrate was distilled under reduced pressure to remove anhydrous methanol, and the concentrated solution was stirred with water. Wash 2 times, suction filtration, collect the filter cake, and place the filter cake in a vacuum oven at 70C to obtain the intermediate 1 whose structural formula is as follows:
79 g (0.63 mol) of a 32% by weight aqueous sodium hydroxide solution and 62.4 g (0.3 mol) of bisphenol A were charged into the reactor.Stir and dissolve,The temperature rises to 85 C and the solution is transparent.Next, 510 g of a trimethylbenzene solvent and 4.2 g of a benzyltriethylammonium chloride catalyst were added.Warming and refluxing,The temperature rose to 172 C,Stirring reaction for 15 hours,Then cool down to 130 C,108 g (0.6 mol) of <strong>[118-45-6]4-chlorophthalic anhydride</strong> and 4.86 g of benzyltriethylammonium chloride catalyst were added.Heating from 140 C to 145 C,Reflow reaction for 5 hours,Then filter hot,Pumping the filtrate into the crystallization kettle,The filtrate is cooled to room temperature.Crystallized for 12 hours,filter,The precipitate is washed with ion-free water,Filtration, precipitation was obtained and washed with 250 g of ethanol.Stirring for 2 hours,filter,Get wet material 125g,After drying, 120 g of bisphenol A diether dianhydride product (yield 85%),The product is white powder,
In a typical procedure, a reactor was charged with 4,4?-bisphenol A-bis-N- methylphthalimide (which can also include small amounts of 3,4?-bisphenol A-bis-N- methylphthalimide and 3,3?-bisphenol A-bis-N-methylphthalimide) (32.93 grams, 0.0602 mole) and phthalic anhydride (29.98 grams, 0.2024 mole). The reaction was conducted in the presence of a triethylamine (TEA) exchange catalyst, which was provided in the form of an aqueous solution having the following composition: 15.1 wt. % triethylamine, and 13.0 wt.% phthalic anhydride, with the balance being water. 23.53 grams of this aqueous solution were added to the exchange reaction. Water was used as the solvent to provide an aqueous reaction mixture having a solids content (%solids) in the range of 13 to 15%. The bisimide/dianhydride exchange reaction was carried out at l70C for 2 hours. For simplicity of the discussion that follows,?N- methylphthalimide? will be referred to as?PI?, the?4,4?-bisphenol A-bis-N-methylphthalimide? mixture will be referred to as?BI?, and the?4,4?-bisphenol A dianhydride? product will be referred to as?DA?.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
Life Science
For Research Only
100K+ Compounds
Competitive Price
1-2 Day Shipping
