CN117402172A - Synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride - Google Patents

Synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride Download PDF

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CN117402172A
CN117402172A CN202311327986.9A CN202311327986A CN117402172A CN 117402172 A CN117402172 A CN 117402172A CN 202311327986 A CN202311327986 A CN 202311327986A CN 117402172 A CN117402172 A CN 117402172A
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trifluoromethyl
reaction
bis
durene
tetramethylbenzene
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何正标
程瑾
陈佳孝
胡金波
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
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Abstract

The invention discloses a method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride. The invention discloses a method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride, which comprises the following steps: (1) 1,2,4, 5-tetramethylbenzene is subjected to iodination reaction in the presence of iodine, persulfate, concentrated sulfuric acid and acetic acid to obtain 3, 6-diiodotetramethylbenzene; (2) in polar solvent, 3, 6-diiodotetratoluene and TMSCF are combined in the presence of CuX and MF 3 Carrying out trifluoromethyl reaction on (trifluoromethyl trimethylsilane) to obtain 3, 6-di (trifluoromethyl) -durene, (3-3, 6-diiodo-durene and oxidant are subjected to oxidation reaction to obtain 3, 6-di (trifluoromethyl) -pyromellitic acid, (4-3, 6-di (trifluoromethyl) -pyromellitic acid and acetic anhydride are subjected to dehydration cyclization to obtain 3, 6-di (trifluoromethyl)) Pyromellitic dianhydride. The method has the advantages of mild reaction conditions, simple treatment, high efficiency and low cost.

Description

Synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride.
Background
The fluorine-containing polyimide has low dielectric constant, good solubility, excellent optical performance and low moisture absorption rate; meanwhile, the material has the advantages of corrosion resistance, radiation resistance, high and low temperature resistance, excellent mechanical property, good adhesion and the like, is widely applied to the fields of electronic power, OLED, aerospace, precision machinery and the like, becomes an irreplaceable high-performance polymer material, and has higher development value. There is a need to develop new techniques for preparing fluorine-containing dianhydride monomers to meet the development needs of the fluorine-containing polyimide industry.
3, 6-bis (trifluoromethyl) -pyromellitic dianhydride, white solid powder, melting point 239-240 ℃ and molecular formula C 12 F 6 O 6 Relative molecular weight 354.1164.
The synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride disclosed in the prior art comprises only one of the following steps:
document 1 discloses a method in which 3, 6-diiodo-tetramethylene is prepared from tetramethylene by iodination with periodic acid, and then mixed with trifluoroiodomethane (CF) in the presence of metallic copper 3 I) The 3, 6-bis (trifluoromethyl) -durene is obtained by reaction, and finally the 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride is obtained by oxidation and dehydration cyclization.
The method has the following defects: periodic acid is used in the first step of iodination, but periodic acid is expensive, unstable in property and easy to decompose, and is not suitable for large-scale use. In the second step, trifluoromethyl (CF) is used 3 I) The reaction is sensitive to light, difficult to store, gas at normal temperature, inconvenient to quantitatively use, and the reaction needs high temperature and high pressure (150 ℃ and 50 atm), so that the reaction is not suitable for large-scale industrialization.
Tohru Matsuura et al, "Polyimides Derived from 2, -Bis (trifluoromethyl) -4,4-diaminobiphen yl.2.Synthesis and Characterization of Polyimides Prepared from Fluorinated Benzenetetracarboxylic Dianhydrides," Macromolecules 1992, vol.25, 13, pages 3540-3545.
Disclosure of Invention
The invention aims to overcome the defects of high cost, unstable reactants, harsh reaction conditions and the like in the preparation of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride in the prior art. The invention provides a preparation method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride, which has the advantages of efficient and convenient reaction, suitability for large-scale industrial production and good application prospect and value.
The invention provides a method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride, which comprises the following steps,
step (1), in the presence of iodine, persulfate, concentrated sulfuric acid and acetic acid, 1,2,4, 5-tetramethylbenzene is subjected to iodination reaction to obtain 3, 6-diiodotetramethylbenzene,
step (2), in a polar solvent, in the presence of CuX and MF, the compound 3, 6-diiodotetratoluene and TMSCF 3 Carrying out trifluoromethyl reaction on (trifluoromethyl trimethylsilane) to obtain 3, 6-bis (trifluoromethyl) -durene,
step (3), 3, 6-diiodo-tetramethylene and oxidant are subjected to oxidation reaction to obtain 3, 6-di (trifluoromethyl) -pyromellitic acid,
step (4), the 3, 6-bis (trifluoromethyl) -pyromellitic acid and acetic anhydride undergo dehydration cyclization to obtain 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride,
in one embodiment, in the step (1), the persulfate is one or more selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate; potassium persulfate is preferred.
In one embodiment, in the step (1), the molar ratio of the 1,2,4, 5-tetramethylene to the iodine is 1:1 to 1:10, preferably 1:2 to 1:3.
In one embodiment, in the step (1), the molar ratio of the 1,2,4, 5-tetramethylbenzene to the persulfate is 1:1 to 1:10, preferably 1:2 to 1:3.
In one embodiment, in the step (1), the mass ratio of the 1,2,4, 5-tetramethylbenzene to the concentrated sulfuric acid is 1:1 to 1:3, preferably 1:1.46.
In one embodiment, in the step (1), the mass ratio of the 1,2,4, 5-tetramethylene to the acetic acid is 1:20 to 1:60, preferably 1:39.12.
In one embodiment, in the step (1), the reaction temperature of the reaction is 0 to 100 ℃, preferably 0 to 60 ℃.
In one embodiment, in step (1), the progress of the reaction may be monitored by methods conventional in the art (e.g., TLC tracking) of such reactions, typically with the compound 1,2,4, 5-tetramethylbenzene reacting completely and yielding a single product point as the end point of the reaction.
In one embodiment, in step (1), the reaction further comprises a post-treatment step, recrystallization (e.g., using 5% Na in excess 2 SO 3 The aqueous solution of (2) is filtered, the filter cake is dissolved in an organic solvent (such as ethyl acetate), dried (such as anhydrous sodium sulfate), filtered, concentrated and dried to obtain 3, 6-diiodotetratoluene.
In a certain embodiment, in the step (2), the MF is selected from one or more of NaF, KF and CsF, preferably KF.
In one embodiment, in step (2), the TMSCF 3 The molar ratio of the CuX to the CuX is 1:0.5-1:3; preferably 1:0.83 or 1:0.91.
In one aspect of the present invention,in the step (2), the TMSCF 3 The molar ratio of the water to the MF is 1:0.5-1:3; preferably 1:0.92 or 1:1.
In one embodiment, in step (2), the TMSCF 3 The molar ratio of the 3, 6-diiodo-tetramethylene to the 3, 6-diiodo-tetramethylene is 1:0.1-1:4; preferably 1:0.28, 1:0.39 or 1:0.30.
In one embodiment, in the step (2), the polar solvent is selected from one or more of DMF, DMSO, or NMP; DMF is preferred.
In one embodiment, in the step (2), the CuX is one or more selected from CuCl, cuBr, cuI, cuSCN and CuOTf; preferably CuCl.
In a certain scheme, in the step (2), the reaction temperature of the reaction is 0-120 ℃; preferably 60℃or 90 ℃.
In one embodiment, in the step (2), the reaction time of the reaction is 30h to 54h; preferably 30h or 54h.
In one embodiment, in step (2), the progress of the reaction may be monitored by methods conventional in the art (e.g., nuclear magnetic resonance tracking) and the 3, 6-diiodotetratoluene compound is generally used as the reaction endpoint.
In one embodiment, in step (2), the reaction further comprises a post-treatment step of quenching (e.g., quenching in 800mL of ammonia), dilution (e.g., dilution with 500mL of water), extraction (e.g., 3 times n-pentane extraction), drying (anhydrous sodium sulfate), filtration, concentration, and drying to yield the product.
In a certain scheme, in the step (3), the oxidant is potassium permanganate, sodium dichromate, potassium dichromate or nitric acid; potassium permanganate or nitric acid (e.g., 25% nitric acid) is preferred.
In a certain scheme, in the step (3), when the oxidant is potassium permanganate, sodium dichromate or potassium dichromate, the step (3) further comprises a base and a solvent, wherein the base is preferably one or two of sodium hydroxide and pyridine, and more preferably sodium hydroxide and pyridine; the solvent is preferably deionized water.
In one embodiment, in the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the pyridine is 1:20-1:60, preferably 1:43.65.
In one embodiment, in the step (3), the molar ratio of the 3, 6-bis (trifluoromethyl) -durene to the sodium hydroxide is 1:5-1:15, preferably 1:10.
In one embodiment, in the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the deionized water is 1:20-1:60, preferably 1:43.65.
In one embodiment, in the step (3), the reaction temperature of the reaction is 80 to 180 ℃, preferably 90 ℃ or 170 ℃.
In one embodiment, in step (3), the progress of the reaction may be monitored by methods conventional in the art for such reactions (e.g., nuclear magnetic resonance spectroscopy), typically using the 3, 6-bis (trifluoromethyl) -durene oxidation of the compound as the endpoint.
In one embodiment, in step (3), the reaction further comprises a post-treatment step, quenching (e.g., KMnO consuming excess ethanol 4 ) Filtering (for example, filtering while hot), washing the filter cake (for example, washing with hot water), concentrating the filtrate, acidifying to pH2.0 (for example, acidifying with concentrated hydrochloric acid), recrystallizing (cooling the upper layer of the refrigerator overnight to precipitate the product), filtering, and drying to obtain 3, 6-bis (trifluoromethyl) -pyromellitic acid.
In one embodiment, in the step (4), the mass ratio of the 3, 6-bis (trifluoromethyl) -pyromellitic acid to the acetic acid is 1:1.0-1:4.0, preferably 1:2.69.
In one embodiment, in the step (4), the reaction time of the reaction is 3 to 9 hours, preferably 6 hours.
In one embodiment, in step (4), the reaction further comprises a post-treatment step of filtration (e.g., rapid filtration), washing the filter cake (e.g., with a small amount of cooled diethyl ether), collecting the solid, and drying (e.g., 10 hours in a vacuum oven at 50 ℃) to give the product 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride.
In one embodiment, in step (1), the reaction mass of the reaction consists of: the said 1,2,4, 5-tetramethylbenzene, the said iodine, the said persulfate, the said concentrated sulfuric acid and the said acetic acid.
In one embodiment, in step (2), the reaction mass of the reaction consists of: the compound 3, 6-diiodotetratoluene and TMSCF 3 The polar solvent, the CuX and the MF.
In one embodiment, in the step (3), the reaction material of the reaction is one or two of the following materials: the 3, 6-diiodo-tetramethylene, the oxidant, the base, and the solvent; scheme II consists of the following substances: the 3, 6-diiodo-tetramethylene and the oxidant.
In one embodiment, in the step (4), the reaction mass of the reaction consists of: said 3, 6-bis (trifluoromethyl) -pyromellitic acid and said acetic anhydride.
A process for preparing 3, 6-di (trifluoromethyl) -durene includes such steps as mixing 3, 6-diiodo-durene with TMSCF in polar solvent in the presence of CuX and MF 3 Carrying out trifluoromethyl reaction on (trifluoromethyl trimethylsilane) to obtain 3, 6-bis (trifluoromethyl) -durene;
preferably, the operation and conditions of the trifluoromethylation reaction may be as described in any of the present inventions.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the advantages of mild reaction conditions, simple treatment, high efficiency and low cost.
Drawings
FIG. 1 shows the hydrogen spectrum (CDCl) of 3, 6-diiodotetratoluene 3 )。
FIG. 2 is a hydrogen spectrum (CDCl) of 3, 6-bis (trifluoromethyl) -durene 3 )。
FIG. 3 is a fluorine spectrum (CDCl) of 3, 6-bis (trifluoromethyl) -durene 3 )。
FIG. 4 is a hydrogen spectrum (DMSO-d) of 3, 6-bis (trifluoromethyl) -pyromellitic acid 6 )。
FIG. 5 is a fluorine spectrum (DMSO-d) of 3, 6-bis (trifluoromethyl) -pyromellitic acid 6 )。
FIG. 6 is a fluorine spectrum (DMSO-d) of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride 6 )。
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1
(1) Under the protection of nitrogen, adding I into a 1000mL three-port reaction bottle 2 (200 mmol,50.8 g), 500mL glacial acetic acid and 19.6g concentrated sulfuric acid (98%) were stirred. Potassium persulfate (202.5 mmol,54.83 g) was slowly added, then heating to 60℃was started and held at that temperature for 30min, then 1,2,4, 5-tetramethylbenzene (100 mmol,13.42 g) was slowly added, followed by TLC tracking at 60℃until 1,2,4, 5-tetramethylbenzene was completely reacted and a single product spot was produced, then the reaction was stopped and cooled to room temperature. The reaction solution was poured into an excessive amount of 5% Na 2 SO 3 In the aqueous solution of (2), colorless solid is precipitated, the solid is collected by filtration, and then the solid is dissolved in BEthyl acetate, followed by drying over anhydrous sodium sulfate, filtration, concentration and drying gave 37.83g of 3, 6-diiodo-tetramethylene in 98% yield. 1 H NMR(CDCl 3 400 MHz): delta 2.63 (s, 12H); the specific nuclear magnetic spectrum is shown in figure 1.
②
2.1 first step, under the protection of nitrogen, dry KF, activated CuCl, dry DMF, stirring at room temperature, and then TMSCF were added dropwise slowly 3 After the completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
And secondly, adding the 3, 6-diiodo-tetramethylene (substrate A) prepared in the step (1) under the protection of nitrogen, and heating to a preset temperature for reacting for a corresponding time. After stopping the reaction and cooling to room temperature, adding an internal standard PhOCF 3 And (5) sampling nuclear magnetism detection. (fluorine spectral yield in PhOCF) 3 Is an internal standard
The specific reaction conditions are shown in Table 1
TABLE 1
2.2A 1000mL three port flask was charged with dry KF (427.4 mmol,24.83g,3.3 equiv.) under nitrogen, activated treated CuCl (388.6 mmol,38.47g,3.0 equiv.), dry DMF (500 mL), stirred at room temperature (20-35 ℃ C.) and then TMSCF was slowly added dropwise 3 (427.4 mmol,60.78 g) and allowed to react at room temperature for 24 hours after completion of the dropwise addition. Then 3, 6-diiodo-tetramethylene (129.5 mmol,50.0g,1.0 equiv.) prepared in step (1) was added and the reaction was continued for 6 hours at 90 ℃. Nuclear magnetic tracking, has reacted completely. The reaction was stopped, the reaction solution was poured into 800mL of aqueous ammonia, then 500mL of water was added, followed by extraction three times with n-pentane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and dried to give 34.78g of pale yellow product in 99% yield. 1 HNMR(CDCl 3 ,400MHz):δ2.15(s,12H)； 19 F NMR(CDCl 3 376 MHz): delta-52.44(s); the specific nuclear magnetic spectrum is shown in figure 2 and figure 3.
(3) Under the protection of nitrogen, adding 3, 6-bis (trifluoromethyl) -durene (40 mmol,10.81 g) prepared in the step (2) into a 1000mL three-port reaction bottle, heating 480mL pyridine and 80mL deionized water to 90 ℃, and then adding 56.88g (360 mmol) KMnO in portions 4 The reaction was continued at 90℃overnight. Filtering while the mixture is hot, washing the filtered insoluble solid with hot water for several times, combining the filtrates, and spin-drying to obtain a solid. 400mL of deionized water and 16g of NaOH were added to the solid to form a solution. The solution was transferred to a 1000mL three-port reaction flask, heated to 90℃and 27.20g KMnO was added in portions 4 (172 mmol) the reaction was continued and followed by nuclear magnetic resonance spectroscopy until oxidation was complete [ remark, KMnO 4 The actual amount of (2) needed to be determined by the case of nuclear magnetic resonance fluorine spectrum tracking if 27.20g KMnO 4 (172 mmol) the starting material cannot be oxidized completely, and may require additional KMnO 4 The process is carried out. Then adding ethanol to quench the reaction [ consume excess KMnO ] 4 The solution is filtered while the solution is hot, filter cakes are washed by hot water for a plurality of times, the filtrates are combined and concentrated to about 200mL, the solution is acidified to pH2.0 by concentrated hydrochloric acid, and then the solution is placed on a refrigerator to be cooled to the upper layer for precipitation of a product overnight. Filtration and drying gave 14.36g of product in 92% yield. 19 F NMR(CDCl 3 376 MHz): delta-55.21(s); the specific nuclear magnetic spectrum is shown in fig. 4 and 5.
(4) 3, 6-bis (trifluoromethyl) -pyromellitic acid (11.70 g,30 mmol) prepared in step (3) was added to 30mL of acetic anhydride under reflux with heating under nitrogen for 6h, rapidly filtered and washed with a small amount of cooled diethyl ether. The solid was collected and dried in a vacuum oven at 50℃for 10 hours to give 9.56g of the product 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride in 90% yield; mp 239-240 ℃. 19 F NMR(CDCl 3 376 MHz): delta-54.645(s); the specific nuclear magnetic spectrum is shown in figure 6.
Example 2
(1) Under the protection of nitrogen, adding I into a 1000mL three-port reaction bottle 2 (200 mmol,50.8 g), 500mL glacial acetic acid and 19.6g concentrated sulfuric acid (98%) were stirred. Slowly adding potassium persulfate (2)02.5mmol,54.83 g) then starts to heat to 60℃and is held at that temperature for 30min, then 1,2,4, 5-tetramethylbenzene (100 mmol,13.42 g) is slowly added, the reaction is continued at 60℃and TLC is followed until 1,2,4, 5-tetramethylbenzene is reacted completely and a single product spot is produced, then the reaction is stopped and cooled to room temperature. The reaction solution was poured into an excessive amount of 5% Na 2 SO 3 The colorless solid was precipitated, and the solid was collected by filtration, and then dissolved in ethyl acetate, followed by drying over anhydrous sodium sulfate, filtration, concentration and drying to give 37.83g of 3, 6-diiodo-tetramethylene in 98% yield.
(2) To a 1000mL three port reaction flask, under nitrogen, was added dry KF (427.4 mmol,24.83g,3.3 equiv.), activated treated CuI (388.6 mmol,74.01g,3.0 equiv.), dry DMF (500 mL), stirred at room temperature, and then TMSCF was slowly added dropwise 3 (427.4 mmol,60.78 g) and allowed to react at room temperature for 24 hours after completion of the dropwise addition. Then 3, 6-diiodo-tetramethylene (129.5 mmol,50.0g,1.0 equiv.) prepared in step (1) was added and the reaction was continued for 6 hours at 90 ℃. Nuclear magnetic tracking, has reacted completely. The reaction was stopped, the reaction solution was poured into 800mL of aqueous ammonia, then 500mL of water was added, followed by extraction three times with n-pentane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and dried to give 34.29g of pale yellow product in 98% yield.
(3) 3, 6-bis (trifluoromethyl) -durene (40 mmol,10.81 g) prepared in the step (2) is added into a 500mL high-pressure reaction kettle, 160mL of 25% nitric acid is heated to 170 ℃ for reaction for 17h, solid is separated out after cooling to room temperature, the solid is dissolved in a small amount of hot water, the aqueous solution is placed in the upper layer of a refrigerator for overnight separation, the solid is quickly filtered, and the product is obtained by drying, wherein 13.26g of the product is obtained in 85% yield.
(4) 3, 6-bis (trifluoromethyl) -pyromellitic acid (11.70 g,30 mmol) prepared in step (3) was added to 30mL of acetic anhydride under reflux with heating under nitrogen for 6h, rapidly filtered and washed with a small amount of cooled diethyl ether. The solid was collected and dried in a vacuum oven at 50℃for 10 hours to give 9.56g of the product 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride in 90% yield.

Claims (10)

1. A method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride, which is characterized by comprising the following steps:
(1) in the presence of iodine, persulfate, concentrated sulfuric acid and acetic acid, 1,2,4, 5-tetramethylbenzene is subjected to iodination reaction to obtain 3, 6-diiodotetramethylbenzene,
(2) in polar solvent, 3, 6-diiodotetratoluene and TMSCF are combined in the presence of CuX and MF 3 (trifluoromethyl trimethylsilane) to obtain 3, 6-bis (trifluoromethyl) -durene,
(3) 3, 6-diiodo-tetramethylbenzene and oxidant are subjected to oxidation reaction to obtain 3, 6-di (trifluoromethyl) -pyromellitic acid,
(4) the 3, 6-di (trifluoromethyl) -pyromellitic acid and acetic anhydride undergo a dehydration cyclization reaction to obtain 3, 6-di (trifluoromethyl) -pyromellitic dianhydride,
2. the method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 1, wherein the step (1) satisfies one or more of the following conditions,
(1) In the step (1), the persulfate is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate;
(2) In the step (1), the molar ratio of the 1,2,4, 5-tetramethylbenzene to the iodine is 1:1-1:10;
(3) In the step (1), the molar ratio of the 1,2,4, 5-tetramethylbenzene to the persulfate is 1:1-1:10;
(4) In the step (1), the mass ratio of the 1,2,4, 5-tetramethylbenzene to the concentrated sulfuric acid is 1:1-1:3;
(5) In the step (1), the mass ratio of the 1,2,4, 5-tetramethylbenzene to the acetic acid is 1:20-1:60;
and (6) in the step (1), the reaction temperature is 0-100 ℃.
3. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 2, wherein the step (1) satisfies one or more of the following conditions,
(1) In the step (1), the persulfate is potassium persulfate;
(2) In the step (1), the molar ratio of the 1,2,4, 5-tetramethylbenzene to the iodine is 1:2-1:3;
(3) In the step (1), the molar ratio of the 1,2,4, 5-tetramethylbenzene to the persulfate is 1:2-1:3;
(4) In the step (1), the mass ratio of the 1,2,4, 5-tetramethylbenzene to the concentrated sulfuric acid is 1:1.46;
(5) In the step (1), the mass ratio of the 1,2,4, 5-tetramethylbenzene to the acetic acid is 1:39.12;
and (6) in the step (1), the reaction temperature of the reaction is 0-60 ℃.
4. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 1, wherein the step (2) satisfies one or more of the following conditions,
(1) The MF in the step (2) is one or more selected from NaF, KF and CsF;
(2) In the step (2), the TMSCF 3 The molar ratio of the CuX to the CuX is 1:0.5-1:3;
(3) In the step (2), the TMSCF 3 The molar ratio of the water to the MF is 1:0.5-1:3;
(4) In the step (2), the TMSCF 3 The molar ratio of the 3, 6-diiodo-tetramethylene to the 3, 6-diiodo-tetramethylene is 1:0.1-1:4;
(5) In the step (2), the polar solvent is selected from one or more of DMF, DMSO or NMP;
(6) In the step (2), the CuX is one or more selected from CuCl, cuBr, cuI, cuSCN or CuOTf;
(7) In the step (2), the reaction temperature of the reaction is 0-120 ℃;
and (8) in the step (2), the reaction time of the reaction is 30-54 h.
5. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 2, wherein the step (2) satisfies one or more of the following conditions,
(1) In the step (2), the MF is KF;
(2) In the step (2), the TMSCF 3 The molar ratio of the CuX to the CuX is 1:0.83 or 1:0.91;
(3) In the step (2), the TMSCF 3 The molar ratio of the water-soluble polymer to the MF is 1:0.92 or 1:1;
(4) In the step (2), the TMSCF 3 The molar ratio of the 3, 6-diiodo-tetramethylene to the 3, 6-diiodo-tetramethylene is 1:0.28, 1:0.39 or 1:0.30;
(5) In the step (2), the polar solvent is DMF;
(6) In the step (2), the CuX is CuCl;
(7) In the step (2), the reaction temperature of the reaction is 60 ℃ or 90 ℃;
and (8) in the step (2), the reaction time of the reaction is 30h or 54h.
6. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 1, wherein the step (3) satisfies one or more of the following conditions,
(1) In the step (3), the oxidant is potassium permanganate, sodium dichromate, potassium dichromate or nitric acid;
(2) In the step (3), when the oxidant is potassium permanganate, sodium dichromate or potassium dichromate, the step (3) further comprises a base and a solvent, wherein the base is preferably one or two of sodium hydroxide and pyridine, and the solvent is preferably deionized water;
(3) In the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the pyridine is 1:20-1:60;
(4) In the step (3), the molar ratio of the 3, 6-bis (trifluoromethyl) -durene to the sodium hydroxide is 1:5-1:15;
(5) In the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the deionized water is 1:20-1:60;
and (6) in the step (3), the reaction temperature of the reaction is 80-180 ℃.
7. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 6, wherein the step (3) satisfies one or more of the following conditions,
(1) In the step (3), the oxidant is potassium permanganate or nitric acid;
(2) In the step (3), the alkali is sodium hydroxide and pyridine;
(3) In the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the pyridine is 1:43.65;
(4) In the step (3), the molar ratio of the 3, 6-bis (trifluoromethyl) -durene to the sodium hydroxide is 1:10;
(5) In the step (3), the mass ratio of the 3, 6-bis (trifluoromethyl) -durene to the deionized water is 1:43.65;
and (6) in the step (3), the reaction temperature of the reaction is 90 ℃ or 170 ℃.
8. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 7, wherein the nitric acid in the step (3) is 25% nitric acid.
9. The method for synthesizing 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride according to claim 1, wherein one or more of the following conditions are satisfied,
(1) In the step (4), the mass ratio of the 3, 6-bis (trifluoromethyl) -pyromellitic acid to the acetic anhydride is 1:1.0-1:4.0; preferably 1:2.69;
(2) In the step (4), the reaction time of the reaction is 3-9h; preferably 6h;
(3) In the step (1), the reaction material of the reaction consists of the following substances: the said 1,2,4, 5-tetramethylbenzene, the said iodine, the said persulfate, the said concentrated sulfuric acid and the said acetic acid;
(4) In the step (2), the reaction material of the reaction consists of the following substances: the compound 3, 6-diiodotetratoluene and TMSCF 3 The polar solvent, the CuX and the MF;
(5) In the step (3), the reaction material of the reaction is a first scheme or a second scheme, wherein the first scheme consists of the following substances: the 3, 6-diiodo-tetramethylene, the oxidant, the base, and the solvent; scheme II consists of the following substances: said 3, 6-diiodotetratoluene and said oxidizing agent;
and (6) in step (4), the reaction mass of the reaction consists of: said 3, 6-bis (trifluoromethyl) -pyromellitic acid and said acetic anhydride.
10. A process for preparing 3, 6-di (trifluoromethyl) -durene includes such steps as mixing 3, 6-diiodo-durene with TMSCF in polar solvent in the presence of CuX and MF 3 Carrying out trifluoromethyl reaction on (trifluoromethyl trimethylsilane) to obtain 3, 6-bis (trifluoromethyl) -durene,
preferably, the operations and conditions of the trifluoromethylation reaction are as described in any one of claims 1,2,4 or 5.
CN202311327986.9A 2023-10-13 2023-10-13 Synthesis method of 3, 6-bis (trifluoromethyl) -pyromellitic dianhydride Pending CN117402172A (en)

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