CN114133403B - 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride synthesis method - Google Patents
9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride synthesis method Download PDFInfo
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- CN114133403B CN114133403B CN202111295485.8A CN202111295485A CN114133403B CN 114133403 B CN114133403 B CN 114133403B CN 202111295485 A CN202111295485 A CN 202111295485A CN 114133403 B CN114133403 B CN 114133403B
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Abstract
The invention discloses a synthesis method of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride, which takes 4,4' -diphenyl ether dianhydride as a starting material, firstly carries out esterification with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxyl ester, then carries out condensation with hexafluoroacetone to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl ester, then carries out hydrolysis to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl acid, and finally carries out dehydration to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride. The synthesis method of the invention does not need a potassium permanganate oxidation step, greatly improves the reaction safety, reduces three wastes, is more friendly to human body and environment, has a total molar yield of about 70 percent in four steps, is obviously superior to the prior art, and is more suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride.
Background
The fluorine-containing polyimide (FPI) is a rigid polymer with a main chain containing imide rings and a highly regular chemical structure, and is a high molecular material obtained by performing melt polycondensation or solution polycondensation reaction on fluorine-containing dianhydride and fluorine-containing diamine to generate fluorine-containing polyamic acid (FPAA) and then performing imidization on the fluorine-containing polyamic acid. The FPI has good light transmission, thermal-oxidative aging resistance superior to that of most PI, and dielectric constant lower than 3, and is the lowest dielectric constant type in PI series products. FPI is widely applied in the high and new technical fields of aerospace, electronic power, precision machinery and the like, and comprises special plastics, composite materials, films, adhesives, fibers, liquid crystal orientation agents, separation films, photoresist and the like, so that the FPI becomes an irreplaceable high-performance high polymer material.
9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride (6 FCDA for short), CAS number 139162-14-4, molecular formula C 19 H 4 F 6 O 7 The molecular weight is 458.22, the white solid has the melting point of 359-361 ℃, and the structural formula is as follows:
as a novel fluorine-containing dianhydride monomer, 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride has better application prospect. The synthesis method of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride disclosed by the prior art mainly comprises the following steps:
U.S. patent document US5051520a discloses a 3,4-dimethylphenol/hydrofluoric acid process: 9,9-bis (trifluoromethyl) -2,3,6,7-tetramethylxanthene is obtained by 3,4-dimethylphenol and hexafluoroacetone under the catalysis of hydrofluoric acid (see example 3, the yield is up to 41%), then 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid is obtained by potassium permanganate oxidation (see example 4, the yield is 61%), and finally 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride is obtained by dehydration to anhydride.
The method of the document has the following disadvantages: (1) Hydrofluoric acid has strong corrosivity, can strongly corrode metal, glass and silicon-containing objects, such as burns which are difficult to cure caused by steam inhalation or skin contact, belongs to high-toxicity substances and is harmful to human bodies and the environment; (2) the yield is low, and the yield of the first two steps is less than 30 percent; (3) Tetramethyl oxidation belongs to high-risk reaction, amplification production has larger potential safety hazard, tetramethyl oxidation difficulty is larger, reaction is easy to stay in an intermediate state of oxidizing one, two or three methyl, so that the yield and purity of the intermediate are lower, and a large amount of manganese dioxide waste solids and waste water are formed by adopting potassium permanganate oxidation, so that the method is not environment-friendly.
Chinese patent document CN111303183A discloses a 3,4-dimethylphenol/trifluoromethanesulfonic acid method (see example 2): 9,9-bis (trifluoromethyl) -2,3,6,7-tetramethylxanthene (yield: 36%) is obtained by the reaction of 3,4-dimethylphenol and hexafluoroacetone under the catalysis of trifluoromethanesulfonic acid, and then 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid (yield: 76%) is obtained by the oxidation of potassium permanganate, and finally 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride is obtained by dehydration into anhydride.
The process of this document avoids the use of highly corrosive hydrofluoric acid, but still suffers from low yields (also less than 30% in the first two steps) and the above-mentioned problems of tetramethyl oxidation by potassium permanganate.
Disclosure of Invention
The invention aims to solve the problems and provides a method for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride, which has high safety, is more friendly to human bodies and environment, particularly has high yield and is suitable for industrial mass production.
The technical scheme for realizing the purpose of the invention is as follows: a method for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride comprises the following steps:
(1) using 4,4' -diphenyl ether dianhydride (ODPA) as a starting material, and firstly carrying out esterification reaction with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester;
(2) carrying out condensation reaction on 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester obtained in the step (1) and hexafluoroacetone to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester;
(3) hydrolyzing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester obtained in the step (2) to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid;
(4) and (4) dehydrating 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid obtained in the step (3) into anhydride to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride.
The synthetic route is as follows:
wherein: r represents ethyl [ CH ] 2 CH 3 - [ propyl ] and [ CH ] 2 CH 2 CH 3 N-butyl [ CH ] 2 CH 2 CH 2 CH 3 】。
The molar ratio of the 4,4' -diphenyl ether dianhydride to the lower alcohol in the step (1) is 1: 10-1: 15; the lower alcohol is ethanol, n-propanol or n-butanol.
The esterification reaction of the step (1) is carried out in the presence of thionyl chloride; the molar ratio of 4,4' -diphenyl ether dianhydride to thionyl chloride is 1: 2-1: 5, preferably 1: 2-1: 2.5.
The esterification reaction temperature in the step (1) is 50-80 ℃.
The hexafluoroacetone in the step (2) is hexafluoroacetone gas prepared from hexafluoroacetone trihydrate and concentrated sulfuric acid; the molar ratio of the hexafluoroacetone trihydrate to the 4,4' -biphenyl ether dianhydride in the step (1) is 1: 1-2: 1, and preferably 1: 1-1.5: 1.
And the hexafluoroacetone gas is introduced in a mode of bottom inserting bubbling.
The condensation reaction of the above step (2) is carried out in the presence of trifluoromethanesulfonic acid; the molar ratio of the trifluoromethanesulfonic acid to the 4,4' -biphenyl ether dianhydride in step (1) is 2: 1-5: 1, preferably 2: 1-2.5: 1.
The condensation reaction of the above step (2) is carried out in a toluene solvent.
The condensation reaction temperature of the step (2) is 50-100 ℃.
The hydrolysis in the step (3) is alkaline hydrolysis or acidic hydrolysis.
The alkaline hydrolysis is carried out in the presence of an inorganic base; the inorganic alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide; the molar ratio of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the inorganic base is 1: 2-1: 10.
The alkaline hydrolysis is carried out in a mixed solvent; the mixed solvent consists of one of methanol, ethanol or tetrahydrofuran and water.
The reaction temperature of the alkaline hydrolysis is 50-80 ℃.
The acidic hydrolysis is carried out in the presence of a mineral acid; the inorganic acid is hydrochloric acid and acetic acid; the molar ratio of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the hydrochloric acid is 1: 10-1: 20; the molar ratio of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the acetic acid is 1: 10-1: 20.
The reaction temperature of the acid hydrolysis is 90-110 ℃.
The dehydration to anhydride in step (4) above is carried out by methods conventional in the art.
The invention has the following positive effects:
(1) The synthesis method of the invention does not need the step of oxidizing potassium permanganate, greatly improves the reaction safety, reduces three wastes and is more friendly to human body and environment.
(2) The four-step total molar yield of the synthesis method can reach about 70 percent, is obviously superior to the prior art, and is more suitable for industrial mass production.
(3) Compared with 3,4-dimethylphenol, the raw material 4,4' -diphenyl ether dianhydride adopted by the synthetic method provided by the invention is obviously lower in toxicity, higher in safety, low in price and easy to obtain.
(4) The synthesis method of the invention adopts hexafluoroacetone trihydrate to prepare hexafluoroacetone gas, which not only can further reduce the cost, but also is more convenient for transportation and operation compared with hexafluoroacetone gas cylinders.
Drawings
FIG. 1 is an LC-MS spectrum of 9,9-bis (trifluoromethyl) -2,3,6,7-tetraethylxanthenetetracarboxylate prepared in step (2) of example 1.
FIG. 2 is the DSC chart of the target product 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride prepared in step (4) of example 1.
FIG. 3 is the LC-MS spectrum of the target product 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride prepared in step (4) of example 1 after sample preparation with methanol.
Detailed Description
(example 1)
The synthetic route of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride of this example is as follows:
the specific synthesis method comprises the following steps:
(1) under the protection of nitrogen, 200g of 4,4' -diphenyl ether dianhydride (0.65 mol) and 400g of ethanol (8.70 mol) are added into a 2L three-necked bottle, stirred for 1-2 h and completely dissolved, then cooled to 0-5 ℃, 168g of thionyl chloride (1.41 mol) is dripped, the temperature is controlled to 0-15 ℃ in the dripping process, the dripping stirring is finished for 30min, then the temperature is raised to 70-75 ℃, the stirring reaction is carried out for 4-5 h, and the tail gas absorption is well carried out in the reaction process.
After the reaction is finished, cooling to 30-40 ℃, controlling the temperature below 40 ℃, and concentrating the reaction liquid to 200-300 mL under reduced pressure; then adding 800g of toluene and 300g of water, stirring for 30min, and standing for layering; after the water phase is separated, firstly adding 300g of water into the organic phase, then adjusting the pH = 8-9 of the solution by using a 15wt% sodium carbonate aqueous solution, and standing for layering; after the water phase is separated, 300g of water is added into the organic phase, and the mixture is stirred for 30min and then is kept stand for layering; and (3) separating the water phase, heating the organic phase to 100-110 ℃, refluxing the organic phase with water by using a water separator for 3-4 h, and cooling to 20-30 ℃ to obtain a toluene solution of 3,3',4,4' -diphenyl ether tetracetyl ester.
(2) Adding 100g of 98wt% concentrated sulfuric acid into a 500mL three-necked bottle, controlling the temperature to be below 50 ℃, dropwise adding 170g of hexafluoroacetone trihydrate (0.77 mol), introducing generated hexafluoroacetone gas into the 2L three-necked bottle in the step (1) by a guide pipe in a bottom inserting bubbling mode (trace nitrogen can be introduced into the 500mL three-necked bottle to accelerate the generated hexafluoroacetone gas to be introduced into the 2L three-necked bottle), removing the 500mL three-necked bottle after the ventilation is finished, regulating the temperature of the 2L three-necked bottle to be 25 +/-2 ℃, controlling the temperature to be below 30 ℃, dropwise adding 210g of trifluoromethanesulfonic acid (1.40 mol), dropwise stirring for 30min, firstly heating to 55 +/-2 ℃, stirring for 1h, then heating to 75 +/-2 ℃, stirring for 1h, and finally heating to 95 +/-2 ℃, preserving the temperature, stirring and reacting for 5-6 h.
After the reaction is finished, cooling to 20-30 ℃, adding 300g of water, stirring for 30min, standing for layering, separating a water phase, adding 300g of water into an organic phase, stirring for 30min, standing for layering, separating a water phase, controlling the temperature to be below 50 ℃, concentrating an organic layer under reduced pressure to reach the volume of 300-400 mL, then adding 700g of ethanol, controlling the temperature to be 20-30 ℃, stirring for 1-2 h, filtering, rinsing a filter cake with 100g of ethanol, and drying in vacuum for 15h at 50 ℃ to obtain 328g of white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraethyl ester, wherein the yield in the two steps is 83.9%.
The product was subjected to LC-MS detection, and the results are shown in FIG. 1.
As can be seen from fig. 1: the molecular weight of the product is 607.2, which is identical to 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraethyl ester.
(3) 200g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid tetraethyl ester (0.33 mol) prepared in the step (2) are added into a 3L three-neck flask, then 600g of ethanol, 400g of water and 263g (1.97 mol) of 30wt% sodium hydroxide aqueous solution are added, the temperature is raised to 75 +/-2 ℃, and the reaction is stirred for 12 to 13 hours.
After the reaction is finished, cooling to 25 +/-2 ℃, adding 600g of toluene, stirring for 30min, standing, separating a lower-layer water phase, returning the water phase to the 3L three-necked bottle, controlling the temperature to be below 30 ℃, dropwise adding 36wt% of concentrated hydrochloric acid until the pH value of the water phase is = 2-3, continuously stirring for 1-2 h, filtering, rinsing a filter cake with 200g of water, and performing vacuum drying for 15h at 80 ℃ to obtain white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid 154g, wherein the yield is 94.5%.
(4) 154g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid (0.31 mol) prepared in the step (3) is added into a 1L three-necked bottle, then 539g of acetic anhydride (5.28 mol) is added, and the temperature is raised to 105 +/-2 ℃ to stir and react for 5 to 6 hours.
After the reaction is finished, the temperature is reduced to 25 +/-2 ℃, the mixture is filtered, a filter cake is rinsed by 300g of toluene and dried for 15 hours in vacuum at the temperature of 80 ℃, and white powdery solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride 131g with the purity (HPLC) of 99.6 percent and the yield of 91.8 percent is obtained.
The total molar yield of the four steps is about 72.8%.
The target product was subjected to differential scanning calorimetry, and the results are shown in FIG. 2.
As can be seen from fig. 2: the melting point of the target product is 360.4 ℃, and is matched with 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride.
The target product was subjected to LC-MS detection after methanol sample preparation, and the results are shown in FIG. 3.
As can be seen from fig. 3: the molecular weight was 523.0, which is consistent with 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride using a methanol formulation.
(example 2)
The synthetic route of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride of this example is as follows:
the specific synthesis method comprises the following steps:
(1) under the protection of nitrogen, 200g of 4,4' -diphenyl ether dianhydride (0.65 mol) and 500g of n-propanol (8.33 mol) are added into a 2L three-necked bottle, stirred for 1-2 h and completely dissolved, then cooled to 0-5 ℃, 168g of thionyl chloride (1.41 mol) is dripped, the temperature is controlled to 0-15 ℃ in the dripping process, stirring is finished for 30min, then the temperature is raised to 70-75 ℃, stirred and reacted for 4-5 h, and tail gas absorption is well performed in the reaction process.
After the reaction is finished, cooling to 30-40 ℃, controlling the temperature below 40 ℃, and concentrating the reaction liquid to 200-300 mL under reduced pressure; then adding 800g of toluene and 300g of water, stirring for 30min, and standing for layering; after the water phase is separated, 300g of water is firstly added into the organic phase, then 15wt% of sodium carbonate aqueous solution is used for regulating the pH value of the solution to be between 8 and 9, and the solution is kept stand for layering; after the water phase is separated, 300g of water is added into the organic phase, and the mixture is stirred for 30min and then is kept stand for layering; and (3) separating the water phase, heating the organic phase to 100-110 ℃, refluxing the organic phase with water by using a water separator for 3-4 h, and cooling to 20-30 ℃ to obtain a toluene solution of 3,3',4,4' -diphenyl ether tetracarboxylic acid tetra-n-propyl ester.
(2) Adding 100g of 98wt% concentrated sulfuric acid into a 500mL three-necked bottle, controlling the temperature to be below 50 ℃, dropwise adding 170g of hexafluoroacetone trihydrate (0.77 mol), introducing generated hexafluoroacetone gas into the 2L three-necked bottle in the step (1) by a guide pipe in a bottom inserting bubbling mode (trace nitrogen can be introduced into the 500mL three-necked bottle to accelerate the generated hexafluoroacetone gas to be introduced into the 2L three-necked bottle), removing the 500mL three-necked bottle after the ventilation is finished, regulating the temperature of the 2L three-necked bottle to be 25 +/-2 ℃, controlling the temperature to be below 30 ℃, dropwise adding 210g of trifluoromethanesulfonic acid (1.40 mol), dropwise stirring for 30min, firstly heating to 55 +/-2 ℃, stirring for 1h, then heating to 75 +/-2 ℃, stirring for 1h, and finally heating to 95 +/-2 ℃, preserving the temperature, stirring and reacting for 5-6 h.
After the reaction is finished, cooling to 20-30 ℃, adding 300g of water, stirring for 30min, standing for layering, separating a water phase, adding 300g of water into an organic phase, stirring for 30min, standing for layering, separating a water phase, controlling the temperature to be below 50 ℃, concentrating an organic layer under reduced pressure to reach the volume of 300-400 mL, then adding 700g of ethanol, controlling the temperature to be 20-30 ℃, stirring for 1-2 h, filtering, rinsing a filter cake with 100g of ethanol, and drying in vacuum for 15h at 50 ℃ to obtain a white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetra-n-propyl ester 347g, wherein the yield of the two steps is 81.2%.
(3) 200g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid tetra-n-propyl ester (0.30 mol) prepared in the step (2) are added into a 3L three-necked bottle, 600g of methanol, 400g of water and 336g (1.8 mol) of 30wt% potassium hydroxide aqueous solution are added, the temperature is raised to 75 +/-2 ℃, and the mixture is stirred and reacted for 12 to 13 hours.
After the reaction is finished, cooling to 25 +/-2 ℃, adding 600g of toluene, stirring for 30min, standing, separating a lower-layer water phase, returning the water phase to the 3L three-necked bottle, controlling the temperature to be below 30 ℃, dropwise adding 36wt% of concentrated hydrochloric acid until the pH of the water phase is = 2-3, continuously stirring for 1-2 h, filtering, rinsing a filter cake by 200g of water, and carrying out vacuum drying for 15h at 80 ℃ to obtain white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid 137g, wherein the yield is 91.8%.
(4) Adding 130g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid (0.26 mol) prepared in the step (3) into a 1L three-necked bottle, then adding 520g of acetic anhydride (5.10 mol), heating to 105 +/-2 ℃, and stirring for reaction for 5-6 h.
After the reaction is finished, the temperature is reduced to 25 +/-2 ℃, the filtration is carried out, a filter cake is rinsed by 300g of toluene and dried for 15 hours in vacuum at the temperature of 80 ℃, and 110g of white powdery solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride is obtained, wherein the yield is 91.3%.
The total molar yield over the four steps was about 68.1%.
(example 3)
The synthetic route of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride of this example is as follows:
the specific synthesis method comprises the following steps:
(1) under the protection of nitrogen, 200g of 4,4' -diphenyl ether dianhydride (0.65 mol) and 600g of n-butanol (8.11 mol) are added into a 2L three-necked bottle, stirred for 1-2 h and completely dissolved, then cooled to 0-5 ℃, 168g of thionyl chloride (1.41 mol) is dripped, the temperature is controlled to 0-15 ℃ in the dripping process, stirring is finished for 30min, then the temperature is raised to 70-75 ℃, stirred and reacted for 4-5 h, and tail gas absorption is well performed in the reaction process.
After the reaction is finished, cooling to 30-40 ℃, controlling the temperature below 40 ℃, and concentrating the reaction liquid to 200-300 mL under reduced pressure; then adding 800g of toluene and 300g of water, stirring for 30min, and standing for layering; after the water phase is separated, firstly adding 300g of water into the organic phase, then adjusting the pH = 8-9 of the solution by using a 15wt% sodium carbonate aqueous solution, and standing for layering; after the water phase is removed, adding 300g of water into the organic phase, stirring for 30min, and standing for layering; and (3) separating the water phase, heating the organic phase to 100-110 ℃, refluxing the organic phase with water by using a water separator for 3-4 hours, and cooling to 20-30 ℃ to obtain a toluene solution of 3,3',4,4' -diphenyl ether tetracarboxylic acid tetra-n-butyl ester.
(2) Adding 100g of 98wt% concentrated sulfuric acid into a 500mL three-necked bottle, controlling the temperature to be below 50 ℃, dropwise adding 170g of hexafluoroacetone trihydrate (0.77 mol), introducing generated hexafluoroacetone gas into the 2L three-necked bottle in the step (1) by a guide pipe in a bottom inserting bubbling mode (trace nitrogen can be introduced into the 500mL three-necked bottle to accelerate the generated hexafluoroacetone gas to be introduced into the 2L three-necked bottle), removing the 500mL three-necked bottle after the ventilation is finished, regulating the temperature of the 2L three-necked bottle to be 25 +/-2 ℃, controlling the temperature to be below 30 ℃, dropwise adding 210g of trifluoromethanesulfonic acid (1.40 mol), dropwise stirring for 30min, firstly heating to 55 +/-2 ℃, stirring for 1h, then heating to 75 +/-2 ℃, stirring for 1h, and finally heating to 95 +/-2 ℃, preserving the temperature, stirring and reacting for 5-6 h.
After the reaction is finished, cooling to 20-30 ℃, adding 300g of water, stirring for 30min, standing for layering, separating a water phase, adding 300g of water into an organic phase, stirring for 30min, standing for layering, separating a water phase, controlling the temperature to be below 50 ℃, concentrating an organic layer under reduced pressure to reach the volume of 300-400 mL, then adding 800g of ethanol, controlling the temperature to be 20-30 ℃, stirring for 1-2 h, filtering, rinsing a filter cake with 100g of ethanol, and drying in vacuum for 15h at 50 ℃ to obtain a white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetra-n-butyl ester 363g, wherein the yield in the two steps is 78.4%.
(3) 200g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid tetra-n-butyl ester (0.28 mol) prepared in the step (2) is added into a 2L three-mouth bottle, 400g of concentrated hydrochloric acid (4 mol) with the concentration of 36wt% and 300g of glacial acetic acid (5 mol) are added, the temperature is increased to 100 +/-2 ℃, and the mixture is stirred and reacted for 18 to 20 hours (solid is dissolved and precipitated).
After the reaction is finished, the temperature is reduced to 5 +/-2 ℃, the filtration is carried out, a filter cake is rinsed by 300g of water and is dried for 15 hours in vacuum at the temperature of 80 ℃, and 117g of white solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid is obtained, and the yield is 85.0 percent.
(4) Adding 100g of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid (0.20 mol) prepared in the step (3) into a 1L three-neck bottle, then adding 400g of acetic anhydride (3.92 mol), heating to 105 +/-2 ℃, and stirring for reaction for 5-6 h.
After the reaction is finished, the temperature is reduced to 25 +/-2 ℃, the filtration is carried out, a filter cake is rinsed by 250g of toluene and dried for 15 hours in vacuum at the temperature of 80 ℃, and 86g of white powdery solid 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride is obtained, wherein the yield is 92.8 percent.
The total molar yield of the four steps is about 61.8%.
Claims (9)
1. A method for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride comprises the following steps:
(1) 4,4' -diphenyl ether dianhydride is used as a starting material, and is subjected to esterification reaction with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester;
(2) carrying out condensation reaction on 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester obtained in the step (1) and hexafluoroacetone to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester; the condensation reaction is carried out in the presence of trifluoromethanesulfonic acid; the molar ratio of the trifluoromethanesulfonic acid to the 4,4' -diphenyl ether dianhydride in step (1) is 2: 1-5: 1; the condensation reaction is carried out in a toluene solvent;
(3) hydrolyzing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid tetraester obtained in the step (2) to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthenetetracarboxylic acid;
(4) and (4) dehydrating 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid obtained in the step (3) into anhydride to obtain 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxyl dianhydride.
2. The method of synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride as claimed in claim 1, wherein: in the step (1), the molar ratio of the 4,4' -diphenyl ether dianhydride to the lower alcohol is 1: 10-1: 15; the lower alcohol is ethanol, n-propanol or n-butanol; the hexafluoroacetone in the step (2) is hexafluoroacetone gas prepared from hexafluoroacetone trihydrate and concentrated sulfuric acid; the molar ratio of the hexafluoroacetone trihydrate to the 4,4' -biphenyl ether dianhydride in the step (1) is 1: 1-2: 1.
3. The method of synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride as claimed in claim 1, wherein: the esterification reaction of the step (1) is carried out in the presence of thionyl chloride; the molar ratio of the 4,4' -diphenyl ether dianhydride to the thionyl chloride is 1: 2-1: 5.
4. The method of synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride as claimed in claim 1, wherein: the esterification reaction temperature of the step (1) is 50-80 ℃, and the condensation reaction temperature of the step (2) is 50-100 ℃.
5. The method of synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride as claimed in claim 1, wherein: the hydrolysis in the step (3) is alkaline hydrolysis; the reaction temperature of the alkaline hydrolysis is 50-80 ℃.
6. The method of claim 5 for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride, wherein: the alkaline hydrolysis is carried out in the presence of an inorganic base; the inorganic alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide; the molar ratio of the 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the inorganic base is 1: 2-1: 10.
7. The method of claim 5 for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride, wherein: the alkaline hydrolysis is carried out in a mixed solvent; the mixed solvent consists of one of methanol, ethanol or tetrahydrofuran and water.
8. The method of synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride as claimed in claim 1, wherein: the hydrolysis in the step (3) is acidic hydrolysis; the reaction temperature of the acid hydrolysis is 90-110 ℃.
9. The method of claim 8 for synthesizing 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride, wherein: the acidic hydrolysis is carried out in the presence of a mineral acid; the inorganic acid is hydrochloric acid and acetic acid; the molar ratio of the 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the hydrochloric acid is 1: 10-1: 20; the molar ratio of 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic acid tetraester to the acetic acid is 1: 10-1: 20.
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