CN114133403A - Synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride - Google Patents
Synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride Download PDFInfo
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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 esterifies with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxyl tetraester, then condenses with hexafluoroacetone to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxyl tetraester, then hydrolyzes to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid, and finally dehydrates to anhydride 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 synthesis method of 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, photoresists and the like, so that the FPI becomes an irreplaceable high-performance high polymer material.
9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride, 6FCDA for short, CAS number 139162-14-4, molecular formula C19H4F6O7The molecular weight is 458.22, the white solid has a 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:
US patent document US5051520A discloses a 3, 4-dimethylphenol/hydrofluoric acid process: 9, 9-bis (trifluoromethyl) -2,3,6, 7-tetramethylxanthene is obtained by reacting 3, 4-dimethylphenol with hexafluoroacetone under the catalysis of hydrofluoric acid (see example 3, the yield is up to 41%), then the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid is obtained by oxidizing with potassium permanganate (see example 4, the yield is 61%), and finally the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic 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 process (see example 2): the 9, 9-bis (trifluoromethyl) -2,3,6, 7-tetramethyl xanthene is obtained by the reaction of 3, 4-dimethylphenol and hexafluoroacetone under the catalysis of trifluoromethanesulfonic acid (the yield is 36%), then the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid is obtained by oxidizing with potassium permanganate (the yield is 76%), and finally the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride is obtained by dehydration to 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 provide a synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride, which has higher safety, is more friendly to human bodies and environment, particularly has higher yield and is suitable for industrial mass production.
The technical scheme for realizing the purpose of the invention is as follows: a synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride comprises the following steps:
firstly, 4,4' -diphenyl ether dianhydride (ODPA) is taken as a starting material, and is firstly subjected to esterification reaction with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester;
condensation reaction of the 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester obtained in the step one and hexafluoroacetone to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetraester;
③ hydrolyzing the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid tetraester obtained in the step (II) to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid;
fourthly, the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid obtained in the third step is dehydrated into anhydride, and 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride is obtained.
The synthetic route is as follows:
wherein: r represents ethyl [ CH ]2CH3N-propyl [ CH ]2CH2CH3Or n-butyl [ CH ]2CH2CH2CH3】。
In the step I, 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 esterification reaction of the first step 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, and preferably 1: 2-1: 2.5.
The esterification reaction temperature in the first step is 50-80 ℃.
The hexafluoroacetone in the second step is hexafluoroacetone gas prepared from hexafluoroacetone trihydrate and concentrated sulfuric acid; the molar ratio of the hexafluoroacetone trihydrate to the 4,4' -diphenyl ether dianhydride in the step (i) 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 step (II) is carried out in the presence of trifluoromethanesulfonic acid; the molar ratio of the trifluoromethanesulfonic acid to the 4,4' -diphenyl ether dianhydride in the step (i) is 2: 1-5: 1, and preferably 2: 1-2.5: 1.
The condensation reaction of the above-mentioned step (c) is carried out in a toluene solvent.
The condensation reaction temperature of the second step is 50-100 ℃.
The hydrolysis in the third step 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 the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic 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 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 the 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 acidic hydrolysis is 90-110 ℃.
The dehydration to anhydride in the step (iv) is carried out by a conventional method 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 4,4' -diphenyl ether dianhydride used as the raw material in the synthetic method of the invention has the advantages of obviously lower toxicity, higher safety, low price and easy obtainment.
(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 tetraethyl 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid prepared in example 1 step (II).
FIG. 2 is a DSC spectrum of the target product 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride obtained in step (iv) of example 1.
FIG. 3 is a LC-MS spectrum of the target product, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic dianhydride, prepared in EXAMPLE 1 step (iv) after being formulated with methanol.
Detailed Description
(example 1)
The synthetic route of the 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:
firstly, 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, 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 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) removing 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 tetracetyl ester.
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 I in a bottom inserting and bubbling mode by using a conduit (trace nitrogen can be introduced into the 500mL three-necked bottle, the generated hexafluoroacetone gas is introduced into the 2L three-necked bottle in a speeded up manner), 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), stirring for 30min after the dropwise adding, firstly heating to 55 +/-2 ℃, stirring for 1h, 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 of 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-xanthenetetracarboxylate.
③ adding 200g of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetra ethyl ester (0.33 mol) prepared in the step (c) into a 3L three-necked bottle, then adding 600g of ethanol, 400g of water and 263g (1.97 mol) of 30wt% sodium hydroxide aqueous solution, heating to 75 +/-2 ℃, and stirring for reacting for 12-13 h.
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 with 200g of water, and carrying out vacuum drying at 80 ℃ for 15h to obtain 154g of white solid 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid, wherein the yield is 94.5%.
And fourthly, 154g of the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid (0.31 mol) prepared in the third step is added into a 1L three-necked bottle, 539g of acetic anhydride (5.28 mol) is added, and the temperature is raised to 105 +/-2 ℃ to be stirred and reacted for 5-6 h.
After the reaction, 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 analyzed by 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 the melting point of the target product is matched with that of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic 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 is 523.0, which is consistent with the use of methanol as a sample for 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride.
(example 2)
The synthetic route of the 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:
firstly, 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 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) removing 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 the toluene solution of the 3,3',4,4' -diphenyl ether tetracarboxylic acid tetra-n-propyl ester.
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 I in a bottom inserting and bubbling mode by using a conduit (trace nitrogen can be introduced into the 500mL three-necked bottle, the generated hexafluoroacetone gas is introduced into the 2L three-necked bottle in a speeded up manner), 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), stirring for 30min after the dropwise adding, firstly heating to 55 +/-2 ℃, stirring for 1h, 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 347g of white solid 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetra-n-propyl ester, wherein the yield of the two steps is 81.2%.
③ adding 200g of the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetra-n-propyl ester (0.30 mol) prepared in the step (c) into a 3L three-necked bottle, adding 600g of methanol, 400g of water and 336g (1.8 mol) of 30wt% potassium hydroxide aqueous solution, heating to 75 +/-2 ℃, and stirring for reacting for 12-13 h.
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 with 200g of water, and carrying out vacuum drying at 80 ℃ for 15h to obtain 137g of white solid 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid, wherein the yield is 91.8%.
And fourthly, adding 130g of the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid (0.26 mol) prepared in the third step 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 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 then 110g of white powdery solid 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxyl dianhydride is obtained, and the yield is 91.3%.
The total molar yield of the four steps is about 68.1%.
(example 3)
The synthetic route of the 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:
firstly, 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 ℃, stirring and reacting are carried out for 4-5 h, and 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) removing 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 the 3,3',4,4' -diphenyl ether tetracarboxylic acid tetra-n-butyl ester.
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 I in a bottom inserting and bubbling mode by using a conduit (trace nitrogen can be introduced into the 500mL three-necked bottle, the generated hexafluoroacetone gas is introduced into the 2L three-necked bottle in a speeded up manner), 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), stirring for 30min after the dropwise adding, firstly heating to 55 +/-2 ℃, stirring for 1h, 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 363g of white solid 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetra-n-butyl ester, wherein the yield of the two steps is 78.4%.
③ adding 200g of the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetra-n-butyl ester (0.28 mol) prepared in the step (b) into a 2L three-necked bottle, adding 400g of concentrated hydrochloric acid (4 mol) with the concentration of 36wt% and 300g of glacial acetic acid (5 mol), heating to 100 +/-2 ℃, stirring and reacting for 18-20 h (the solid is dissolved and then separated out).
After the reaction, the temperature was reduced to 5. + -. 2 ℃ and the mixture was filtered, and the filter cake was rinsed with 300g of water and dried under vacuum at 80 ℃ for 15 hours to obtain 117g of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid as a white solid with a yield of 85.0%.
And fourthly, adding 100g of the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid (0.20 mol) prepared in the third step into a 1L three-necked 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, and the yield is 92.8%.
The total molar yield of the four steps is about 61.8%.
Claims (9)
1. A synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride comprises the following steps:
firstly, 4,4' -diphenyl ether dianhydride is taken as a starting material, and is firstly subjected to esterification reaction with lower alcohol to obtain 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester;
condensation reaction of the 3,3',4,4' -diphenyl ether tetracarboxylic acid tetraester obtained in the step one and hexafluoroacetone to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid tetraester;
③ hydrolyzing the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid tetraester obtained in the step (II) to obtain 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthenetetracarboxylic acid;
fourthly, the 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic acid obtained in the third step is dehydrated into anhydride, and 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride is obtained.
2. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 1, wherein: in the step I, 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 second step is hexafluoroacetone gas prepared from hexafluoroacetone trihydrate and concentrated sulfuric acid; the molar ratio of the hexafluoroacetone trihydrate to the 4,4' -diphenyl ether dianhydride in the step (i) is 1: 1-2: 1.
3. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 1, wherein: the esterification reaction of the first step 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; the condensation reaction of the step (II) is carried out in the presence of trifluoromethanesulfonic acid; the molar ratio of the trifluoromethanesulfonic acid to the 4,4' -diphenyl ether dianhydride in the step (i) is 2: 1-5: 1; the condensation reaction of the above-mentioned step (c) is carried out in a toluene solvent.
4. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 1, wherein: the esterification reaction temperature in the first step is 50-80 ℃, and the condensation reaction temperature in the second step is 50-100 ℃.
5. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 1, wherein: the hydrolysis in the third step is alkaline hydrolysis; the reaction temperature of the alkaline hydrolysis is 50-80 ℃.
6. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 5, 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-xanthenetetracarboxylic acid tetraester to the inorganic base is 1: 2-1: 10.
7. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 5, 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 according to claim 1, wherein: the hydrolysis in the third step is acidic hydrolysis; the reaction temperature of the acidic hydrolysis is 90-110 ℃.
9. The method of synthesizing 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride according to claim 8, 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 the 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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