CN117736172A - Synthesis method of fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile - Google Patents

Synthesis method of fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile Download PDF

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CN117736172A
CN117736172A CN202311760947.8A CN202311760947A CN117736172A CN 117736172 A CN117736172 A CN 117736172A CN 202311760947 A CN202311760947 A CN 202311760947A CN 117736172 A CN117736172 A CN 117736172A
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trifluoromethyl
bis
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dioxole
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任怡文
马小燕
黄林
余文杰
陈文慧
王俊杰
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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Abstract

The invention discloses a method for synthesizing a fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile, which comprises the following steps of:

Description

Synthesis method of fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile.
Background
The amorphous fluoropolymer is a completely amorphous fluoropolymer, has excellent mechanical properties, thermal stability, optical properties, electrical properties and chemical properties, is easily dissolved in specific perfluorinated solvents, has excellent film forming properties and low swelling tendency, and can be applied to high-end fields such as computers, medical treatment, aviation, military industry and the like.
Amorphous fluoropolymers as high value added polyfluoro polymers, on the one hand, due to the relatively small market demand for products, the types and amounts of known amorphous fluoropolymers are quite limited; on the other hand, the research and development of fluorine-containing special monomers for preparing amorphous fluoropolymers are still in the beginning, so that the development of fluorine-containing special monomers containing independent intellectual property rights is becoming particularly important.
However, the existing fluorine-containing special monomer has the disadvantages of more synthesis steps, low yield and large engineering difficulty, and the preparation technology is relatively backward, so that the fluorine-containing special monomer is high in price.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for synthesizing a fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile, which aims to solve the problems of few types of fluorine-containing special monomers, more steps of the synthesis of the existing fluorine-containing special monomers, low yield, large industrial application difficulty and high product price in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing a fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile, wherein the synthetic route of the fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile is as follows:
preferably, the specific steps are as follows:
step 1: the glycidol (compound 1) and hexafluoroacetone trihydrate are subjected to an addition reaction to obtain 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2).
Step 2:2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2) can undergo an oxidation reaction with an oxidant in the presence of water and sodium carbonate to give 2, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3); or, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2) and potassium bromide and an oxidant undergo an oxidation reaction to obtain 2, 2-bis (trifluoromethyl) -4-carboxyl-1, 3-dioxolane (compound 3).
Step 3:2, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (Compound 3) methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (Compound 4) is obtained by reaction.
Step 4: methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4) was reacted with NBS (N-bromosuccinimide), BPO (dibenzoyl peroxide) and azobisisobutyronitrile to give methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5).
Step 5: debrominating 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylic acid methyl ester (compound 5) to give 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylic acid methyl ester (compound 6); namely: the compound 5 was debrominated with DBU ((1, 8-diazabicyclo (5, 4, 0) -7-undecene) or triethylamine to give methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6).
Step 6: methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6) is reacted with ammonia to give 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7).
Step 7:2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxamide (Compound 7) is reacted with TsCl or trifluoroacetic anhydride to give the fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile (Compound 8).
Preferably, in the step 1, tetrabutylammonium bromide or tetrabutylammonium iodide is used as a catalyst, the temperature of the addition reaction is 120-125 ℃, and the reaction time is 24-38 hours; the molar ratio of glycidol (compound 1), catalyst and hexafluoroacetone trihydrate is 1: (0.02-0.3): (1.02-5); the solvent is ethylene glycol dimethyl ether.
Preferably, in step 2, the solvent is water or ethyl acetate; the reaction temperature of the oxidation reaction is 0-35 ℃; the reaction time is 7.5 to 16 hours; the oxidant is potassium permanganate or TEMPO oxidant. When 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), sodium carbonate and an oxidizing agent are reacted, the molar ratio of the 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), sodium carbonate and the oxidizing agent is 1 (1.7-20): 2. When 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), potassium bromide and the oxidizing agent are reacted, the molar ratio of 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), potassium bromide and the oxidizing agent is 1:0.3:0.05. The reaction system is purified after the pH value is regulated to 2-3 by HCl solution with the mass fraction of 35 percent.
Preferably, in step 3, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3) is reacted under basic conditions to give sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate, sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate is reacted with calcium chloride under room temperature conditions to give calcium 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate, and calcium 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate is reacted with methyl iodide, potassium fluoride under argon protection and room temperature conditions to give methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4). Wherein the alkaline environment is provided by sodium hydroxide aqueous solution, the reaction temperature is room temperature, and the reaction time is 6d; the molar ratio of the compound 3 to the sodium hydroxide is 1:1. The molar ratio of the sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate to the calcium chloride is 1: (0.3-0.7). When 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium reacts with methyl iodide and potassium fluoride, the solvent is N, N-dimethylformamide, and the reaction time is 96 hours; the molar ratio of the 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium salt to the methyl iodide to the potassium fluoride is 1: (8-11): (0.2-0.5).
Preferably, in step 3, 2-bis (trifluoromethyl) -4-carboxyl-1, 3-dioxolane (compound 3) is subjected to esterification reaction with trifluoroacetic anhydride and methanol at room temperature to obtain 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid methyl ester (compound 4). Wherein the solvent is trifluoroacetic anhydride, and the reaction time is 1.5h. The molar ratio of 2, 2-bis (trifluoromethyl) -4-carboxyl-1, 3-dioxolane (compound 3), trifluoroacetic anhydride and methanol is 1:4.1:70.
preferably, in the step 4, the reaction solvent is carbon tetrachloride, the reaction temperature is 60-100 ℃, the reaction condition is reflux, and the ultraviolet lamp is used for irradiation in the reaction process; methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4), NBS, BPO, azobisisobutyronitrile in a molar ratio of 1: (2-5): (0.2-0.7): (0.3-0.8).
Preferably, in step 5, the solvent is one of dichloromethane, diethyl ether or anhydrous tetrahydrofuran; the reaction temperature is 0-70 ℃ and the reaction time is 5-24 hours. When methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5) is reacted with DBU, the molar ratio of compound 5 to DBU is 1: (2.5-5.2). When compound 5 was reacted with triethanolamine, the molar ratio of compound 5 to triethanolamine was 1: (3.1-8.5).
Preferably, in step 6, the solvent is methanol, the reaction temperature is room temperature, and the reaction time is 16-48h. The molar ratio of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6) to ammonia was (0.4-1.6): 4-15.
Preferably, in the step 7, the solvent is pyridine, and the reaction temperature is-10-100 ℃; the reaction time is 2 to 5.5 hours. When 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7) is reacted with TsCl, the molar ratio of compound 7 to TsCl is 1: (1.3-5.5). When compound 7 was reacted with trifluoroacetic anhydride, the molar ratio of compound 7 to trifluoroacetic anhydride was 1: (0.7-2.5).
Compared with the prior art, the invention has the following beneficial effects:
the invention carries out intensive research on the monomer of the amorphous fluoropolymer, designs a novel fluorine-containing monomer synthesis process route, has reasonable design, easily obtained raw materials, relatively fewer reaction steps, simple process operation, easily controlled reaction process, and no harsh reaction condition of the whole process route, and has good industrial application scene.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the present invention fall within the scope of the present invention.
Unless otherwise indicated in the context of the specification, the numerical ranges set forth herein include upper and lower limits, as well as all integers and fractions within the range, and are not limited to the specific values set forth in the limits of the ranges.
1. Synthesis method of fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile
The synthetic route of the fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile is as follows:
in some embodiments, the specific steps are as follows:
step 1: the glycidol (compound 1) and hexafluoroacetone trihydrate are subjected to an addition reaction to obtain 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2).
Step 2:2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2) can undergo an oxidation reaction with an oxidant in the presence of water and sodium carbonate to give 2, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3); or, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2) and potassium bromide and an oxidant undergo an oxidation reaction to obtain 2, 2-bis (trifluoromethyl) -4-carboxyl-1, 3-dioxolane (compound 3).
Step 3:2, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (Compound 3) methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (Compound 4) is obtained by reaction.
Step 4: methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4) was reacted with NBS (N-bromosuccinimide), BPO (dibenzoyl peroxide) and azobisisobutyronitrile to give methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5).
Step 5: debrominating 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylic acid methyl ester (compound 5) to give 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylic acid methyl ester (compound 6); namely: the compound 5 was debrominated with DBU ((1, 8-diazabicyclo (5, 4, 0) -7-undecene) or triethylamine to give methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6).
Step 6: methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6) is reacted with ammonia to give 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7).
Step 7:2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxamide (Compound 7) is reacted with TsCl or trifluoroacetic anhydride to give the fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile (Compound 8).
In some embodiments, in step 1, one of tetrabutylammonium bromide or tetrabutylammonium iodide is employed as a catalyst. The temperature of the addition reaction is 120℃to 125℃and preferably 120℃121℃123℃124℃125℃etc., and all ranges and subranges therebetween. The reaction time is 24h to 38h, preferably 24h, 26h, 28h, 30h, 34h, 36h, 38h, etc., and all ranges and subranges therebetween. The molar ratio of glycidol (compound 1), catalyst and hexafluoroacetone trihydrate is 1: (0.02-0.3): (1.02-5), preferably 1:0.02:1.02, 1:0.05:1.5, 1:0.1:2.0, 1:0.1:3.0, 1:0.25:3.5, 1:0.3:4.0, 1:0.25:4.5, 1:0.3:5.0, etc., as well as all ranges and subranges therebetween. The solvent is ethylene glycol dimethyl ether. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments, in step 2, the solvent is water or ethyl acetate. The reaction temperature of the oxidation reaction is 0℃to 35℃and preferably 0℃to 5℃to 10℃to 15℃to 20℃to 25℃to 30℃to 35℃and the like, and all ranges and subranges therebetween. The reaction time is 7.5h to 16h, preferably 7.5h, 8.0h, 8.5h, 9.0h, 9.5h, 10h, 12h, 15h, 16h, etc., and all ranges and subranges therebetween. The oxidant is one of potassium permanganate and TEMPO oxidant. When 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), sodium carbonate and an oxidizing agent are reacted, the molar ratio of 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), sodium carbonate and oxidizing agent is 1 (1.7 to 20): 2, preferably 1:1.7:2, 1:5:2, 1:10:2, 1:15:2, 1:20:2, etc., as well as all ranges and subranges between the above values. When 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), potassium bromide and the oxidizing agent are reacted, the molar ratio of 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2), potassium bromide and the oxidizing agent is 1:0.3:0.05. The two reaction systems are purified after the pH value is adjusted to 2-3 by HCl solution with the mass fraction of 35%, preferably pH values of 2, 3 and the like, and all ranges and sub-ranges between the values. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In the synthetic route employed in the present invention, there are various methods for synthesizing methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane (compound 3) into methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4), which can be obtained by converting the carboxyl group on compound 3 into the corresponding salt and then esterifying. Compound 3 may also be esterified directly with an alcohol to give compound 4.
In some embodiments, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3) is first reacted at room temperature under an alkaline environment provided by sodium hydroxide to give the sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate in a molar ratio of 6d, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3) to sodium hydroxide of 1:1. Then, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylic acid sodium salt reacts with calcium chloride aqueous solution at room temperature to generate colorless solid, and the colorless solid is dried to obtain 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium. Wherein, the molar ratio of the 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylic acid sodium salt to the calcium chloride is 1: (0.3-0.7), preferably 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, etc., as well as all ranges and subranges therebetween. Finally, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium, methyl iodide and potassium fluoride react under the protection of argon and under the room temperature condition to obtain 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid methyl ester (compound 4). Wherein, N-dimethylformamide is adopted as a solvent, and the reaction time is 96h. The molar ratio of the 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium salt to the methyl iodide to the potassium fluoride is 1: (8-11): (0.2-0.5), preferably 1:8:0.2, 1:10:0.35, 1:11:0.5, etc., as well as all ranges and subranges therebetween. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments, in step 3, 2-bis (trifluoromethyl) -4-carboxy-1, 3-dioxolane (compound 3) is esterified with trifluoroacetic anhydride, methanol at room temperature to provide compound 4. Wherein the solvent is trifluoroacetic anhydride, and the reaction time is 1.5h. The molar ratio of 2, 2-bis (trifluoromethyl) -4-carboxyl-1, 3-dioxolane (compound 3), trifluoroacetic anhydride and methanol is 1:4.1:70. it is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments, in step 4, the reaction solvent is carbon tetrachloride, the reaction temperature is 60 ℃ to 100 ℃, the reaction conditions are reflux, and the irradiation is performed with an ultraviolet lamp during the reaction. The reaction temperature may preferably be 60 ℃, 70 ℃, 80 ℃,90 ℃, 100 ℃, etc., as well as all ranges and subranges between the above values. Methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4), NBS, BPO, azobisisobutyronitrile in a molar ratio of 1: (2-5): (0.2-0.7): (0.3-0.8), preferably 1:2:0.2:0.3, 1:3.5:0.5:0.5, 1:4:0.6:0.7, 1:5:0.7:0.8, etc., as well as all ranges and subranges therebetween. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments, in step 5, the solvent is one of dichloromethane, diethyl ether, or anhydrous tetrahydrofuran. The reaction temperature is 0℃to 70℃and preferably 0℃to 5℃to 10℃to 15℃to 20℃to 25℃to 30℃to 35℃to 40℃to 45℃to 50℃to 55℃to 60℃to 65℃to 70℃and the like, and all ranges and subranges between the above values. The reaction time is 5h to 24h, preferably 5h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, etc., and all ranges and subranges therebetween. When methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5) is reacted with DBU, the molar ratio of compound 5 to DBU is 1: (2.5-5.2), preferably 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.0, 1:5.2, etc., as well as all ranges and subranges therebetween. When compound 5 was reacted with triethanolamine, the molar ratio of compound 5 to triethanolamine was 1: (3.1-8.5), preferably 1:3.1, 1:4.6, 1:6.5, 1:7.3, 1:8.0, 1:8.5, etc., as well as all ranges and subranges therebetween. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
In some embodiments, in step 6, the solvent is methanol, the reaction temperature is room temperature, the reaction time is 16-48h, the reaction time may preferably be 16h, 18h, 20h, 24h, 32h, 40h, 48h, etc., and all ranges and subranges therebetween. The molar ratio of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6) to ammonia is (0.4-1.6): 4-15, and may preferably be 0.4:4, 0.8:4, 1.0:4, 0.5:6, 1.0:10, 1.6:15, 0.4:15, etc., as well as all ranges and subranges therebetween.
In some embodiments, in step 7, the solvent is pyridine, the reaction temperature is-10 ℃ to 100 ℃, preferably-10 ℃,0 ℃, 10 ℃, 20 ℃, 30 ℃,40 ℃, 50 ℃, 80 ℃,90 ℃, 100 ℃, and the like, as well as all ranges and subranges therebetween. The reaction time is 2h to 5.5h, preferably 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, etc., and all ranges and subranges therebetween. When 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7) is reacted with TsCl, the molar ratio of compound 7 to TsCl is 1: (1.3-5.6), preferably 1:1.3, 1:2.0, 1:2.5, 1:3.0, 1:4.0, 1:4.5, 1:5.0, 1:5.6, etc., as well as all ranges and subranges therebetween. When compound 7 was reacted with trifluoroacetic anhydride, the molar ratio of compound 7 to trifluoroacetic anhydride was 1: (0.7-2.5), preferably 1:0.7, 1:0.9, 1:1.0, 1:1.2, 1:1.5, 1:2.0, 1:2.5, etc., as well as all ranges and subranges therebetween. It is to be understood that any of the above ranges may be combined with any of the other ranges in embodiments.
2. Examples
(1) Synthesis of 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (Compound 2)
In both examples 1 and 2, glycidol (compound 1) was used as a starting material to prepare 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2) by synthesis, but the reaction process was different due to the different catalysts.
Example 1:
glycidol (compound 1) (10 g,137.7 mmol) and tetrabutylammonium bromide (86.9 mg,0.27 mmol) were weighed into a 500mL polytetrafluoroethylene-lined hydrothermal kettle, hexafluoroacetone trihydrate (30.3 g,137.7 mmol) was measured and reacted in the system at 125℃for 24h. After the apparatus was cooled, the system was transferred to a separatory funnel, 200mL of water was added to the separatory funnel, the aqueous phase was extracted with ethyl acetate (3X 80 mL), the organic phases were combined, washed with saturated brine (3X 80 mL), and dried over Na 2 SO 4 The ethyl acetate was distilled off under reduced pressure from the water in the solid-dried organic phase, and was purified by SiO 2 Column chromatography separation and purification (PE: ea=3:1, volume ratio) gave 26.4g of colorless oil in 80% yield and 98% purity.
Example 2:
in a single-necked flask containing 100ml of ethylene glycol dimethyl ether, glycidol 1 (10 g,137.7 mmol) and tetrabutylammonium iodide (14.8 g,40.1 mmol) were charged, then the temperature was lowered to-60℃and hexafluoroacetone (111.0 g,668.5 mmol) was added thereto, and the temperature was further raised to 120℃for sealing reaction for 38 hours. Cooling to 23deg.C after the reaction, filtering the reaction system with diatomite, distilling under reduced pressure to remove volatile substances in the filtrate, diluting with ethyl acetate, washing with saturated sodium bicarbonate solution and saturated sodium chloride solution, and collecting water phase with ethyl acetate(3X 80 mL) extraction, collection of organic phase, anhydrous Na 2 SO 4 The water in the organic phase was dried, ethyl acetate was removed by distillation under reduced pressure, and the mixture was purified by SiO 2 Column chromatography separation and purification (PE: ea=5:1, volume ratio) gave 22.5g, yield 70%, purity 98%.
The products obtained in example 1 and example 2 were tested, and the test results were: 1 H NMR(600MHz,CDCl 3 ,ppm)δ＝4.63(m,J＝14.6,11.5,4.1Hz,1H),4.42(dt,J＝14.4,7.2Hz,1H),4.17～4.09(m,1H),3.94(dd,J＝12.7,3.4Hz,1H),3.74(dd,J＝12.7,4.5Hz,1H),2.00(d,J＝53.0Hz,1H).MS(ESI):m/z 241.02(M+H + ).
(2) Synthesis of 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid (Compound 3)
Example 3 and example 4 were each run with different oxidants starting from 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (compound 2).
Example 3:
into a 500mL single-necked flask, 2-bis (trifluoromethyl) -4-hydroxymethyl-1, 3-dioxolane (Compound 2) (30.8 g,128.3 mmol) and H were successively introduced 2 O 300mL、Na 2 CO 3 (23.1 g,218.1 mmol) of solid, KMnO 4 (40.55 g,256.6 mmol) of solid and controlling the system temperature to be less than 30 ℃. After stirring at room temperature for 16h, a saturated sodium bisulfite solution was added and the red liquid was dropped to brown solid, reducing excess potassium permanganate. The system was filtered, the filtrate was collected, and saturated Na was added dropwise 2 CO 3 The solution was adjusted to pH 8-9 and allowed to stand for demixing and the aqueous phase was collected. 2mol/L hydrochloric acid was added dropwise to adjust pH=2 of the aqueous phase, the aqueous phase was extracted with ethyl acetate (3X 100 mL), the organic phases were combined, and the aqueous phase was extracted with anhydrous Na 2 SO 4 The water in the organic phase was dried over solid, filtered, concentrated under reduced pressure to remove ethyl acetate, and finally 23.5g of colorless liquid was obtained in a yield of 72% and a purity of 99%.
Example 4:
potassium bromide (1.5 g,12.5 mmol), TEMPO (0.3 g,2.1 mmol) and 2, 2-bis (trifluoromethyl) -4-hydroxymethyl-1 were placed in a one-necked flask containing 100ml of ethyl acetate3-Dioxolane (Compound 2) (10 g,41.6 mmol) then 12% sodium hypochlorite solution (33.3 ml,54.21 mmol) was added dropwise at 0deg.C over 30 min, then pH of the system was adjusted to 2-3 with 35% hydrochloric acid solution, then 25% sodium chlorite solution (19.6 ml,54.21 mmol) was added at room temperature over 30 min, stirred for 7h, pH of the reaction system was adjusted to 2-3, the organic phase was extracted with ethyl acetate, the organic phase was washed with saturated sodium chloride solution, anhydrous Na 2 SO 4 The solid was dried over water in the organic phase, filtered, and the filtrate was concentrated under reduced pressure and purified by column chromatography to give 9.7 as a colorless liquid in 92% yield and 98% purity.
The products obtained in example 3 and example 4 were tested, and the test results were: 1 H NMR(600MHz,DMSO,ppm)δ＝13.76(s,1H),5.22(t,J＝7.0Hz,1H),4.70(t,J＝7.9Hz,1H),4.42(t,J＝7.5Hz,1H).MS(ESI):m/z 255.00(M+H + )。
(3) Synthesis of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (Compound 4)
Example 5 and example 6 are syntheses of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4) by two different methods.
Example 5:
to a 100mL one-neck flask was added 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid (compound 3) (23.5 g,92.5 mmol), and an aqueous solution of sodium hydroxide (3.7 g,92.5 mmol) was added dropwise, wherein sodium hydroxide in the sodium hydroxide solution: water (w: v=1:1). Stirred at room temperature and monitored by TLC (PE: ea=1:1, volume ratio), and after completion of the reaction, anhydrous Na was used 2 SO 4 The water in the organic phase was dried and filtered to give 25.5g of the product in 100% crude yield. MS (ESI) M/z 276.98 (M+H) + ).
To a 100mL single-neck flask containing sodium 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (25.5 g,92.4 mmol) was added dropwise a solution of calcium chloride (5.1 g,46.2 mmol), wherein the calcium chloride in the calcium chloride solution: water (w: v=1:1). At the moment of completion of the dropping, the colorless solution became a colorless solid. The colorless solid was placed in an oven at 60 ℃ until oven dried to give 42.9g of white solid, 97% purity, 85% yield. Detection of the product：MS(ESI):m/z 293.96(M+H + ).
500mL of super-dry N, N-dimethylformamide, calcium 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (50.5 g,92.5 mmol) was sequentially added to a 1000mL two-necked flask under an argon atmosphere, the dried potassium fluoride (1.9 g,32.4 mmol) was in the form of a white suspension, methyl iodide (131.1 g,925 mmol) was added dropwise to the system, and the mixture was stirred at room temperature for 96 hours, the color of the solution was changed from white to yellow. 200mL of diethyl ether was added to the system for dilution, followed by washing with water (3X 100 mL), followed by washing with saturated NaCl solution (3X 100 mL) and drying the combined organic phases over anhydrous sodium sulfate. Filtering, distilling under reduced pressure to remove diethyl ether, and passing through SiO 2 Column chromatography was used to isolate and purify (PE: ea=15:1, volume ratio) to give 16.1g of colorless, odoriferous oil in 65% yield and 97% purity.
Example 6:
to a 250mL one-necked flask containing 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid (compound 3) (5.6 g,22.0 mmol) was added trifluoroacetic anhydride (12.7 mL,90.2 mmol), and after stirring at room temperature for 40min, the trifluoroacetic anhydride was distilled off under reduced pressure, methanol (62.6 mL,1540 mmol) was then added, stirring was carried out for 1.5 hours, and methanol was distilled off under reduced pressure, and crystallization was carried out with diethyl ether and n-hexane to give 2.9g of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate in a yield of 50% and a purity of 96%.
The final products of example 5 and example 6 were tested and the test results were: 1 H NMR(600MHz,CDCl 3 ,ppm)δ＝4.94(t,J＝7.1Hz,1H),4.58(t,J＝7.8Hz,1H),4.40(t,J＝7.6Hz,1H),3.82(s,3H).MS(ESI):m/z 269.02(M+H + ).
(4) Synthesis of methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (Compound 5)
Example 7:
to a 100mL quartz tube reactor under nitrogen was successively charged methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 4) (5 g,18.6 mmol), dried carbon tetrachloride solution (50 mL), NBS (11 g,61.5 mmol), BPO (1.4 g,5.6 mmol), azobisisobutyronitrile (0.92 g,5.6 mmol) to 85℃under reflux and irradiated with a UV lamp. Reaction 7After h, the carbon tetrachloride is removed by reduced pressure distillation, and SiO is used for removing the carbon tetrachloride 2 Column chromatography was used to isolate and purify (PE: ea=30:1, volume ratio) to give 645.4mg of a colorless, yellow oil with a specific odor in a yield of 10% and a purity of 98%.
The product obtained in example 7 was tested and the test results were: 1 H NMR(600MHz,CDCl 3 ,ppm)δ＝5.02(d,J＝10.1Hz,1H),4.89(dd,J＝10.1,0.9Hz,1H),3.93(d,J＝10.6Hz,3H).MS(ESI):m/z 346.93(M+H + ).
(5) Synthesis of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (Compound 6)
Examples 8-10 are synthetic preparation of methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (compound 6) using different solvent systems.
Example 8:
to a 50mL single-necked flask was successively added methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5) (645.4 mg,1.9 mmol) and methylene chloride (10 mL) under ice-water bath conditions, DUB (723.2 mg,4.8 mmol) was added dropwise, and the mixture was stirred at 0℃for 5 hours. After the completion of the reaction, the system was washed with 1M hydrochloric acid (3X 30 mL), the aqueous phase was extracted with methylene chloride (3X 30 mL), the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure at room temperature to remove methylene chloride, and SiO was used as a catalyst 2 Column chromatography was used to isolate and purify (PE: ea=20:1, volume ratio) to give 495.5mg of yellow oil in 98% yield and 96% purity.
Example 9:
to a 50mL single-necked flask were successively added diethyl ether (10 mL), methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5) (645.4 mg,1.9 mmol) and DUB (723.2 mg,4.8 mmol), and the mixture was reacted at room temperature for 24 hours. After the completion of the reaction, the system was diluted with diethyl ether (10 mL), then washed with 1M (3X 30 mL) hydrochloric acid solution, the aqueous phase was extracted with methylene chloride (3X 30 mL), the organic phases were combined, the water in the organic phase was dried over anhydrous sodium sulfate solid, filtered, and the volatile solvent was distilled off under reduced pressure, followed by SiO 2 Column chromatography was used to isolate and purify (PE: ea=20:1, volume ratio) to give 490.4 as a yellow oil in 97% yield and 98% purity.
Example 10:
in a 50mL single-necked flask, methyl 5-bromo-2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate (compound 5) (645.4 mg,1.9 mmol) was dissolved in dry tetrahydrofuran (10 mL), and anhydrous triethylamine (1001.9 mg,9.9 mmol) was added thereto for reflux reaction for 24 hours. After the reaction was completed, the system was filtered through celite, washed with tetrahydrofuran, distilled under reduced pressure to remove volatile matters, and subjected to SiO 2 (PE: ea=45:1, volume ratio) column chromatography to isolate and purify gave 389.3mg of yellow oil in 77% yield and 97% purity. MS (ESI) M/z 267.00 (M+H) + ).
(6) Synthesis of 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (Compound 7)
Example 11:
in a 25mL single-necked flask, methyl 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carboxylate (Compound 6) (495.5 mg,1.9 mmol) was dissolved in methanol (10 mL), then 30% aqueous ammonia solution was added to methanol to form a 50% aqueous methanol-aqueous ammonia solution, this solution was added to a methanol solution of Compound 6 at room temperature, stirred for 24 hours, the solvent was distilled off under reduced pressure, and SiO was used as a solvent 2 (PE: ea=1:1, volume ratio) column chromatography to isolate and purify gave 429.3mg of oil in 90% yield and 98% purity. MS (ESI) M/z 252.00 (M+H) + ).
(7) Synthesis of 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile (Compound 8)
Example 12 and example 13 each used a different starting material, namely TsCl and trifluoroacetic anhydride, and 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7) to synthesize the fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile (compound 8).
Example 12:
2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (Compound 7) (1000 mg,4.0 mmol) was dissolved in 4mL1, 4-dioxane, and 10mL pyridine and trifluoroacetic anhydride (1092.2 mg,5.2 mmol) were added. The reaction system is stirred for 2h to 3h at the temperature of minus 10 ℃ to 0 ℃, after the reaction is completed, dichloromethane is used for dilution, the organic phase is washed by saturated sodium chloride solution, and the organic phase is combined with anhydrous sulfuric acidDrying sodium, filtering, vacuum distilling to remove volatile substances, and passing through SiO 2 Column chromatography separation and purification (PE: ea=10:1) gave 525.3mg of the oily compound in 70% yield and 98% purity.
Example 13:
TsCl (5181 mg,27.2 mmol) was added to 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-amide (compound 7) (1240.2. Mg,4.9 mmol), pyridine (155 mL) was added, the reaction was warmed to 100deg.C for 5.5h, the reaction mixture was cooled overnight, water (3X 30 mL) was added, the aqueous phase was extracted with diethyl ether (3X 30 mL), the organic phases were combined, and the organic phase was washed with 10% KOH (3X 30 mL) and saturated NaCl (3X 30 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure, followed by SiO 2 Column chromatography separation and purification (PE: ea=15:1) gave 525.3mg of the oily compound in 46% yield and 99% purity. 1 H NMR(CDCl 3 ,600MHz)δ6.13ppm(s,1H)； 19 F NMR(CDCl 3 ,564MHz)δ-80.5(q,J＝8Hz,3F),-82.2ppm(q,J＝8Hz,3F)；MS(ESI)：m/z 233.99(M+H + ).
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.

Claims (10)

1. The synthesis method of the fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile is characterized in that the synthesis route of the fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile is as follows:
2. the method for synthesizing the fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 1, which is characterized by comprising the following specific steps:
step 1: performing addition reaction on the compound 1 and hexafluoroacetone trihydrate to obtain a compound 2;
step 2: the compound 2 can be subjected to oxidation reaction with an oxidant in the presence of water and sodium carbonate to obtain a compound 3; or, reacting the compound 2 with potassium bromide and an oxidant to obtain a compound 3;
step 3: compound 3 is reacted to obtain compound 4;
step 4: reacting the compound 4 with NBS, BPO and azodiisobutyronitrile to obtain a compound 5;
step 5: debrominating the compound 5 to obtain a compound 6;
step 6: reacting the compound 6 with ammonia to obtain a compound 7;
step 7: the compound 7 is reacted with TsCl or trifluoroacetic anhydride to obtain the fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile.
3. The method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 1, tetrabutylammonium bromide or tetrabutylammonium iodide is used as a catalyst, the temperature of the addition reaction is 120-125 ℃, and the reaction time is 24-38 hours; the molar ratio of the compound 1, the catalyst and the hexafluoroacetone trihydrate is 1: (0.02-0.3): (1.02-5); the solvent is ethylene glycol dimethyl ether.
4. The method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 2, the solvent is water or ethyl acetate; the reaction temperature of the oxidation reaction is 0-35 ℃; the reaction time is 7.5 to 16 hours; the oxidant is potassium permanganate or TEMPO oxidant; when the compound 2, sodium carbonate and oxidant react, the mol ratio of the compound 2, sodium carbonate and oxidant is 1 (1.7-20): 2; when compound 2, potassium bromide and the oxidizing agent are reacted, the molar ratio of compound 2, potassium bromide and the oxidizing agent is 1:0.3:0.05; the pH value of the reaction system is regulated to 2-3 through HCl solution with the mass fraction of 35%.
5. The method for synthesizing fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 3, compound 3 is reacted with sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate and calcium chloride under alkaline environment to obtain 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate, and the calcium 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylate is reacted with methyl iodide and potassium fluoride under argon protection and room temperature to obtain compound 4;
wherein the alkaline environment is provided by sodium hydroxide aqueous solution, the reaction temperature is room temperature, and the reaction time is 6d; the molar ratio of the compound 3 to the sodium hydroxide is 1:1; the molar ratio of the sodium salt of 2, 2-bis (trifluoromethyl) 1, 3-dioxolane-4-carboxylate to the calcium chloride is 1: (0.3-0.7); when 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium reacts, the solvent is N, N-dimethylformamide, and the reaction time is 96 hours; the molar ratio of the 2, 2-bis (trifluoromethyl) -1, 3-dioxolane-4-carboxylic acid calcium salt to the methyl iodide to the potassium fluoride is 1: (8-11): (0.2-0.5).
6. The method for synthesizing fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 3, the compound 3 is esterified with trifluoroacetic anhydride and methanol at room temperature to obtain compound 4; wherein the solvent is trifluoroacetic anhydride, and the reaction time is 1.5h; the molar ratio of the compound 3, the trifluoroacetic anhydride and the methanol is 1:4.1:70.
7. the method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 4, the reaction solvent is carbon tetrachloride, the reaction temperature is 60 ℃ to 100 ℃, the reaction condition is reflux, and the irradiation is performed by an ultraviolet lamp during the reaction; the molar ratio of compound 4, NBS, BPO, azobisisobutyronitrile is 1: (2-5): (0.2-0.7): (0.3-0.8).
8. The method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 5, the solvent is one of dichloromethane, diethyl ether or anhydrous tetrahydrofuran; the reaction temperature is 0-70 ℃ and the reaction time is 5-24 hours; when compound 5 is reacted with DBU, the molar ratio of compound 5 to DBU is 1: (2.5-5.2); when compound 5 was reacted with triethanolamine, the molar ratio of compound 5 to triethanolamine was 1: (3.1-8.5).
9. The method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 6, the solvent is methanol, the reaction temperature is room temperature, and the reaction time is 16-48 hours; the molar ratio of the compound 6 to the ammonia is (0.4-1.6): 4-15.
10. The method for synthesizing a fluoromonomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile according to claim 2, wherein in step 7, the solvent is pyridine and the reaction temperature is-10 ℃ to 100 ℃; the reaction time is 2 to 5.5 hours; when compound 7 was reacted with TsCl, the molar ratio of compound 7 to TsCl was 1: (1.3-5.6); when compound 7 was reacted with trifluoroacetic anhydride, the molar ratio of compound 7 to trifluoroacetic anhydride was 1: (0.7-2.5).
CN202311760947.8A 2023-12-20 2023-12-20 Synthesis method of fluorine-containing monomer 2, 2-bis (trifluoromethyl) -1, 3-dioxole-4-carbonitrile Pending CN117736172A (en)

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