CN111333498B - Method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin - Google Patents
Method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin Download PDFInfo
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Abstract
The invention discloses a method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin, which comprises the following steps: a: using fluorinated cyclic olefin as a raw material, and oxidizing the fluorinated cyclic olefin by an oxidant under the action of a solvent and a catalyst to generate corresponding fluorinated dicarboxylic acid; b: and C, under the action of a solvent and a catalyst, carrying out a fluorination reaction on the fluorine-containing dicarboxylic acid prepared in the step A and a fluorination reaction reagent to obtain the fluorine-containing binary acyl fluoride. The method is a process of directly fluorinating fluorine-containing cycloolefin into corresponding fluorine-containing dicarboxylic acid after the fluorine-containing cycloolefin is oxidized to generate the corresponding fluorine-containing dicarboxylic acid under the action of an organic solvent and a Lewis acid catalyst, and the method can effectively promote the fluorine-containing cycloolefin to generate the corresponding acid fluoride with high efficiency and high yield by adopting the organic solvent and the specific catalyst and matching with other conditions.
Description
Technical Field
The invention discloses a method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin, belonging to the technical field of organic fluorine chemistry.
Background
The fluorine-containing binary acyl fluoride is a bifunctional fluorine-containing intermediate with wide application, can be used for synthesizing a perfluoro alkene ether monomer with a special structure, is used for preparing fluorine-containing carboxylic acid type ion exchange resin, and is used for preparing bifunctional perfluoropolyether derivatives, and the substances can be used in the fields of fluorine-containing polyurethane, fluorine-containing polyester and the like.
In the prior art, fluorine-containing binary acyl fluoride can be prepared from corresponding hydrogen-containing dibasic acid, anhydride, ester, acyl chloride, acyl fluoride and lactone by an electrochemical fluorination method, but the method has the advantages of extremely low yield, complex product and difficult separation. The fluorine-containing binary acyl fluoride can also be prepared from corresponding fluorine-containing binary acyl chloride by a fluorine-chlorine exchange method, and the subsequent fluorine-chlorine exchange reaction is difficult or the yield is low due to the accompanied different contents of acid anhydride and acyl chlorination reagents in the fluorine-containing binary acyl chloride prepared from the fluorine-containing binary carboxylic acid.
The literature (J Chem Soc Perkin Trans 1, 1996, 915-920) reports that tetrafluorosuccinic acid disodium salt reacts with sulfur tetrafluoride in a closed container at 150 ℃ for 5 hours to obtain tetrafluorosuccinyl fluoride with the yield of 81 percent, and the sulfur tetrafluoride is known to be an irritant gas with strong toxicity at normal temperature and also has strong corrosivity. The literature (J Fluorine Chem, 2005, 126, 521-527) discloses a method for obtaining tetrafluorosuccinyl fluoride by esterifying 1, 4-butanediol with hexafluoropropylene oxide oligomer acyl fluoride, directly fluorinating with Fluorine gas, and catalytically cracking, which requires a large excess of Fluorine gas and a long fluorination reaction time, usually 48 hours or more, and has a low space-time yield.
Japanese patent JPS568813 discloses an alpha, omega-diiodoperfluoroalkane I (CF) 2 ) n I (n is more than or equal to 6) oxidizing preparation of perfluorinated binary acyl fluoride FOC (CF) 2 ) n-2 The COF (n.gtoreq.6) method produces perfluorolactone during the reaction, resulting in a low yield of the final diacyl fluoride. US4181678 discloses an ICF oxidation of alpha, omega-diiodooxaperfluoroalkanes in the presence of oleum, zinc sulfate and chlorine 2 CF 2 O(CF 2 ) x OCF 2 CF 2 I (x is more than or equal to 2) preparation of perfluorinated binary acyl fluoride FOCCF 2 O(CF 2 ) x OCF 2 COF (x is more than or equal to 2), but the raw materials are not easy to prepare and obtain. US4316986 discloses a FOC-CF 2 -COOCH 3 Preparation of FOC-CF under action of fluorine-containing sulfonic acid and antimony pentafluoride 2 The method of-COF, which is suitable for synthesizing difluoromalonyl fluoride, is difficult to be popularized to the preparation of other fluorine-containing binary acyl fluorides.
Besides, perfluorodiacyl fluoride can also be prepared by decomposing perfluoroalkyl difluorosulfonate through potassium fluoride catalysis, but the perfluoroalkyl difluorosulfonate is prepared by the addition polymerization of perfluorosulfonyl difluoroperoxide and tetrafluoroethylene free radicals, and the preparation process is rigorous and has large popularization difficulty.
The fluorating reagent containing fluoroalkyl amine is a dehydroxylation fluorating reagent with wider application, and is commonly used for preparing fluorine-containing alkane and monoacyl fluoride by fluorinating monohydric alcohol and monocarboxylic acid. However, the fluorination of diols or polyols has not been successful and a large number of cyclic compounds have been formed (see Synthesis, 1984, 1, 31-33). The fluorination reaction of Fluorine-containing carboxylic acid is reported less, and only the documents J Fluorine Chem, 1983, 23, 383-388 and Russ Chem Bull, 1984, 33, 372-375 are disclosed, wherein the yield of Fluorine-containing monoacyl fluoride prepared by fluorinating Fluorine-containing monocarboxylic acid can reach more than 80%, and the yield of hexafluoroglutaryl fluoride prepared by fluorinating Fluorine-containing dicarboxylic acid is only 72% reported as hexafluoroglutaryl fluoride prepared by hexafluoroglutaric acid, which is not satisfactory.
In conclusion, the existing preparation method of the fluorine-containing binary acyl fluoride has the problems of low yield, difficult obtainment of raw materials and the like, so that the large-scale production is difficult to realize. Therefore, a synthetic route which is simple to operate and is economically feasible still needs to be found.
Disclosure of Invention
The invention aims to provide a method for preparing fluorine-containing diacyl fluoride from fluorine-containing cycloolefin, which aims to overcome the defects in the prior art, and provides a process for preparing the corresponding fluorine-containing diacyl fluoride from the fluorine-containing cycloolefin by oxidizing reaction, then directly fluorinating the fluorine-containing dicarboxylic acid into the corresponding fluorine-containing diacyl fluoride under the action of an organic solvent and a Lewis acid catalyst.
The invention is realized by the following technical scheme: a method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin comprises the following steps:
a: using fluorinated cyclic olefin as a raw material, and oxidizing the fluorinated cyclic olefin by an oxidant under the action of a solvent and a catalyst to generate corresponding fluorinated dicarboxylic acid;
b: under the action of solvent and catalyst, the fluorine-containing dicarboxylic acid prepared in the step A and a fluorination reaction reagent are subjected to fluorination reaction to obtain fluorine-containing binary acyl fluoride,
the structural formula of the fluorinated cyclic olefin is as follows:
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl groups, which may be the same or different; r is 5 、R 6 Is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or C 1-3 Alkyl groups, which may be the same or different; a and b are integers of 0-3, n is an integer of 0-5, and a + b + n is more than or equal to 2 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one is a fluorine atom;
the structural formula of the fluorine-containing dicarboxylic acid is as follows:
HOOC-(CR 1 R 2 ) a -(CF 2 ) n -(CR 3 R 4 ) b -COOH
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl groups, which may be the same or different; a and b are integers from 0 to 3, n is an integer from 0 to 5, and a + b + n is more than or equal to 2 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one is a fluorine atom;
the structural formula of the fluorine-containing binary acyl fluoride is as follows:
FOC-(CR 1 R 2 ) a -(CF 2 ) n -(CR 3 R 4 ) b -COF
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl groups, which may be the same or different; a and b are integers from 0 to 3, n is an integer from 0 to 5, and a + b + n is more than or equal to 2 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one is a fluorine atom.
In the step A, the solvent is a mixed solvent composed of an organic solvent and water, wherein the mass ratio of the organic solvent to the water is 1:100 to 10:1; the catalyst is selected from one or the combination of more than two of crown ether, quaternary phosphonium salt and quaternary ammonium salt; the oxidant is selected from one or the combination of more than two of potassium permanganate, sodium permanganate, potassium dichromate and sodium dichromate.
The organic solvent is at least one selected from acetone, dichloromethane, chloroform and benzene.
In the step A, the dosage of the catalyst is 0.1-5% of the mass of the fluorinated cycloolefin, the molar dosage of the oxidant is 1.0-3.5 times of the molar dosage of the fluorinated cycloolefin, and the mass ratio of the solvent to the oxidant is 10:1 to 1:1.
and in the step A, adding the solvent, the catalyst and the oxidant into a reaction vessel, controlling the reaction temperature to be-20-100 ℃ under the stirring condition, adding the fluorinated cyclic olefin for oxidation reaction, and reacting for 0.5-2 h to obtain the corresponding fluorinated dicarboxylic acid.
In the step B, the solvent is one or more of ethers, nitriles and chlorofluorocarbons; the catalyst is Lewis acid catalyst; the fluorinating reagent is a fluoric alkylamine fluorinating reagent.
The solvent is one or more of diethyl ether, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, trichlorotrifluoroethane, acetonitrile, propionitrile and adiponitrile.
The Lewis acid catalyst is one or more of aluminum trichloride, ferric trichloride, titanium tetrachloride, stannic chloride, boron trifluoride and aluminum trifluoride.
The structural formula of the fluorinating reagent containing fluoroalkyl amines is as follows: X-CHF-CF 2 -NR 1 R 2 Wherein, X is fluorine atom, chlorine atom, trifluoromethyl or trifluoromethoxy; r 1 、R 2 Is C 1-3 The alkyl groups, which may be the same or different.
In the step B, the dosage of the solvent is 0-200% of the mass of the fluorine-containing dicarboxylic acid, the dosage of the catalyst is 0.1-3% of the mass of the fluorination reagent, and the molar dosage of the fluorination reagent is 2-4 times of the molar dosage of the fluorine-containing dicarboxylic acid.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention provides a new preparation method for industrially producing fluorine-containing diacid fluoride, which is characterized in that under the action of an organic solvent and a Lewis acid catalyst, fluorine-containing dicarboxylic acid prepared by taking fluorine-containing cycloolefin as a raw material and a self-made fluorine-containing alkylamine fluorination reagent are directly fluorinated to obtain the corresponding fluorine-containing diacid fluoride, the method can effectively promote the fluorine-containing dicarboxylic acid to generate the corresponding fluorine-containing diacid fluoride with high conversion rate, the actual yield can reach more than 80 percent, and the method is suitable for industrial large-scale production.
(2) The method comprises the step A of disclosing a novel preparation method of the fluorine-containing dicarboxylic acid, adding a specific catalyst into a mixed solvent system consisting of an organic solvent and water, and matching with other conditions, so that the method can effectively promote the reaction to be carried out stably and rapidly, has the characteristics of short reaction time, high yield of the fluorine-containing dicarboxylic acid, good quality and the like, and is an important link for industrial production of the fluorine-containing dicarboxylic acid fluoride.
(3) The method step A of the invention provides a preparation method of fluorine-containing dicarboxylic acid suitable for industrial large-scale production, the method can complete oxidation reaction within 2h after the raw materials are added through reasonable control of reaction conditions, and the corresponding fluorine-containing dicarboxylic acid is obtained, and the reaction yield can still reach more than 70% in the process of industrial production.
(4) In the process of preparing the fluorine-containing dicarboxylic acid, the method uses a mixed solvent consisting of an organic solvent and water to replace a solvent system which uses water or a pure organic solvent (such as acetone) as an oxidation reaction in the prior art, and particularly limits the mass ratio of the organic solvent to the water in the mixed solvent to be 1:100 to 10:1, and the mass ratio of the mixed solvent to the oxidant is 10:1 to 1: on one hand, the influence of water or pure organic solvents (such as acetone) on the oxidation process is avoided, for example, the solubility of water to fluorinated cyclic olefin is extremely low, and the like; on the other hand, the conditions of the existing oxidation reaction are simplified, the oxidation reaction process can be smoothly carried out by reasonably controlling the proportion of the organic solvent and the water in the mixed solvent and the mass ratio of the mixed solvent to the oxidant, and the reaction conditions have simple operation and are easy to realize industrialized large-scale production.
(5) In the process of preparing the fluorine-containing dicarboxylic acid, the catalyst is added into the mixed solvent during feeding, the amount of the catalyst is 0.1-5% of the mass of the fluorine-containing cycloolefin, the reaction can be further accelerated, the reaction time can be shortened, and the increase of the industrial production cost of the fluorine-containing dicarboxylic acid cannot be caused due to the small amount of the catalyst.
(6) In the process of preparing the fluorine-containing dicarboxylic acid, the method avoids the reaction in an alkaline environment, does not need strong bases such as KOH or NaOH, reduces the cost and labor intensity of raw material use, and is beneficial to continuous implementation of industrial large-scale production.
(7) The mixed solvent used in the reaction process of preparing the fluorine-containing dicarboxylic acid can be recycled by simple filtration and distillation, and the method is favorable for controlling the industrial production cost.
(8) In the fluorination reaction process, the solvent adopted by the method can effectively control the material viscosity of the reaction system after the fluorination reaction, and the fluorination reaction process can be effectively improved by reasonably controlling the ratio of the solvent dosage to the mass of the fluorine-containing dicarboxylic acid, so that the fluorine-containing dicarboxylic acid has higher conversion rate.
(9) In the fluorination reaction process, organic solvents such as diethyl ether, tetrahydrofuran, dichloromethane and the like are used as solvent systems, the difference between the boiling point of the organic solvents and the target product is large, so that the subsequent separation and purification are facilitated, and the solvents are easy to obtain and cheap.
(10) In the fluorination reaction process, the Lewis acid is used as the catalyst, so that the reaction can be effectively promoted, the time is shortened, and the yield is improved.
(11) In the fluorination reaction process, the fluorine-containing alkylamine fluorination reagent with a specific structure is adopted, the fluorine-containing alkylamine fluorination reagent can be prepared on site during actual use, and can be used for reaction after being subjected to simple low-temperature decompression purification and then being premixed and activated with the Lewis acid catalyst, the dosage of the Lewis acid catalyst is limited to 0.1-3% of the mass of the fluorination reagent during actual use, and the fluorine-containing alkylamine fluorination reagent and the Lewis acid catalyst which are used in a matched mode can effectively guarantee that the fluorination reaction is carried out at high efficiency.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
this example provides a method for preparing fluorine-containing binary acyl fluoride.
The method comprises the following steps:
A. preparing fluorine-containing dicarboxylic acid:
the preparation method comprises the following steps of taking fluorine-containing cycloolefin as a raw material, taking potassium permanganate and sodium permanganate as oxidants, taking benzo 12-crown-4 as a catalyst, and taking a mixed solvent composed of acetone and water as a solvent system, and reacting to generate corresponding fluorine-containing dicarboxylic acid. During the preparation, solvent, catalyst and oxidant are added into a reaction vessel, the reaction temperature is controlled at-20 ℃ under the stirring condition, fluorinated cyclic olefin is added for oxidation reaction, and after 0.5 hour of reaction, fluorinated dicarboxylic acid shown in the following formula (I) is obtained,
HOOC -CF 2 -CF 2 -COOH （Ⅰ）。
wherein the mass ratio of the organic solvent to the water in the solvent is 10:1, the mass ratio of the solvent to the oxidant is 10:1. in addition, the molar amount of the oxidant is 3.5 times of that of the fluorinated cyclic olefin, and the amount of the catalyst is 0.1 percent of the mass of the fluorinated cyclic olefin.
B. Preparing fluorine-containing binary acyl fluoride:
takes fluorine-containing dicarboxylic acid shown in formula (I) as a raw material, takes a fluorine-containing alkylamine compound shown in formula (II) as a fluorination reagent,
F-CHF-CF 2 -N（CH 3 ） 2（Ⅱ）；
under the action of Lewis acid catalyst (such as aluminum trichloride), carrying out fluorination reaction to obtain fluorine-containing binary acyl fluoride shown in the following formula (III):
FOC -CF 2 -CF 2 -COF （Ⅲ）。
in the preparation process, a solid Lewis acid catalyst with the granularity of 50 meshes is adopted, and the dosage of the solid Lewis acid catalyst is 0.2 percent of the mass of the fluorinating agent. The molar amount of the fluorinating reagent is 4 times of that of the raw material fluorine-containing dicarboxylic acid, and the prepared fluorine-containing dicarboxylic acid fluoride with the content of 88.7 percent has the yield of 80.3 percent.
Example 2:
the embodiment provides a preparation method of fluorine-containing binary acyl fluoride.
The method comprises the following steps:
A. preparing fluorine-containing dicarboxylic acid:
the method comprises the steps of taking fluorine-containing cycloolefin as a raw material, potassium permanganate as an oxidant, benzyltriethylammonium chloride as a catalyst, and a mixed solvent composed of chloroform and water as a solvent system, and reacting to generate corresponding fluorine-containing dicarboxylic acid. During the preparation, the solvent, the catalyst and the oxidant are added into a reaction vessel, the reaction temperature is controlled at 100 ℃ under the stirring condition, the fluorinated cyclic olefin is added for oxidation reaction, the fluorinated dicarboxylic acid shown in the following formula (I) is obtained after the reaction for 1 hour,
HOOC-(CHF) 2 -(CF 2 ) 5 -CHF -COOH （Ⅰ）。
wherein the mass ratio of the organic solvent to the water in the solvent is 1:100, the mass ratio of the solvent to the oxidant is 1:1. in addition, the molar amount of the oxidant is 1.0 time of that of the fluorinated cyclic olefin, and the amount of the catalyst is 5% of the mass of the fluorinated cyclic olefin.
B. Preparing fluorine-containing binary acyl fluoride:
takes fluorine-containing dicarboxylic acid shown in formula (I) as a raw material, takes a fluorine-containing alkylamine compound shown in formula (II) as a fluorination reagent,
Cl-CHF-CF 2 -N(C 2 H 5 ) 2（Ⅱ）；
under the action of solvent (such as dichloroethane) and Lewis acid catalyst (such as ferric trichloride and titanium tetrachloride), carrying out fluorination reaction to obtain fluorine-containing binary acid fluoride shown in the following formula (III):
FOC-(CHF) 2 -(CF 2 ) 5 -CHF –COF （Ⅲ）。
in the preparation process, the solid Lewis acid catalyst with the particle size of 500 meshes is adopted, and the dosage of the solid Lewis acid catalyst is 3 percent of the mass of the fluorinating agent. The dosage of the solvent is 200 percent of the mass of the fluorine-containing dicarboxylic acid. The molar amount of the fluorinating reagent is 4 times of that of the raw material fluorine-containing dicarboxylic acid, the fluorine-containing dicarboxylic acid fluoride with the content of 78.5 percent is prepared, and the yield is 85.2 percent.
Example 3:
this example provides a method for preparing fluorine-containing binary acyl fluoride.
The method comprises the following steps:
A. preparing fluorine-containing dicarboxylic acid:
the preparation method comprises the steps of taking fluorinated cyclic olefin as a raw material, potassium dichromate as an oxidant, dibenzo-18-crown-6 as a catalyst, and a mixed solvent composed of acetone, benzene and water as a solvent system, and reacting to generate the corresponding fluorinated dicarboxylic acid. During the preparation, solvent, catalyst and oxidant are added into a reaction vessel, the reaction temperature is controlled at-10 ℃ under the stirring condition, then fluorinated cyclic olefin is added for oxidation reaction, and the fluorinated dicarboxylic acid shown in the following formula (I) is obtained after the reaction for 2 hours,
HOOC-(CHCl) 2 - (CF 2 ) 2 -COOH （Ⅰ）。
wherein the mass ratio of the organic solvent to the water in the solvent is 2:1, the mass ratio of the solvent to the oxidant is 5:1. in addition, the molar amount of the oxidant is 2.0 times of that of the fluorinated cyclic olefin, and the amount of the catalyst is 0.4 percent of the mass of the fluorinated cyclic olefin.
B. Preparing fluorine-containing binary acyl fluoride:
takes fluorine-containing dicarboxylic acid shown in formula (I) as a raw material, takes fluorine-containing alkylamine compound shown in formula (II) as a fluorinating agent,
CF 3 O-CHF-CF 2 -N(CH 3 ) 2（Ⅱ）；
under the action of solvent (such as mixed solution formed from trifluorotrichloroethane, acetonitrile and adiponitrile) and Lewis acid catalyst (such as titanium tetrachloride), making them produce fluorination reaction so as to obtain fluorine-containing binary acyl fluoride represented by following formula (III):
FOC-(CHCl) 2 - (CF 2 ) 2 -COF （Ⅲ）。
in the preparation process, a solid Lewis acid catalyst with the granularity of 200 meshes is adopted, and the dosage of the solid Lewis acid catalyst is 0.1 percent of the mass of the fluorinating agent. The dosage of the solvent is 50 percent of the mass of the fluorine-containing dicarboxylic acid. The molar amount of the fluorinating agent is 2 times of that of the raw material fluorine-containing dicarboxylic acid, the prepared fluorine-containing dicarboxylic acid fluoride with the content of 84.3 percent is obtained, and the yield is 81.1 percent.
Example 4:
this example provides a method for preparing fluorine-containing binary acyl fluoride.
The method comprises the following steps:
A. preparing fluorine-containing dicarboxylic acid:
the method comprises the following steps of taking fluorinated cyclic olefin as a raw material, sodium dichromate as an oxidant, 15-crown-5 and tetra-n-butylphosphonium bromide as catalysts, and a mixed solvent composed of acetone, dichloromethane and water as a solvent system, and reacting to generate the corresponding fluorinated dicarboxylic acid. During the preparation, the solvent, the catalyst and the oxidant are added into a reaction vessel, the reaction temperature is controlled at 30 ℃ under the stirring condition, the fluorinated cyclic olefin is added for oxidation reaction, the fluorinated dicarboxylic acid shown in the following formula (I) is obtained after the reaction for 1.5 hours,
HOOC-C(CH 3 ) 2 -(CF 2 ) 5 -C(CH 3 ) 2 -COOH （Ⅰ）。
wherein the mass ratio of the organic solvent to the water in the solvent is 1:60, the mass ratio of the solvent to the oxidant is 3:1. in addition, the molar amount of the oxidant is 1.5 times of that of the fluorinated cyclic olefin, and the amount of the catalyst is 0.2 percent of the mass of the fluorinated cyclic olefin.
B. Preparing fluorine-containing binary acyl fluoride:
takes fluorine-containing dicarboxylic acid shown in formula (I) as a raw material, takes a fluorine-containing alkylamine compound shown in formula (II) as a fluorination reagent,
F-CHF-CF 2 -N(C 2 H 5 ) 2（Ⅱ）；
under the action of solvent (such as acetonitrile) and Lewis acid catalyst (such as stannic chloride), carrying out fluorination reaction to obtain fluorine-containing binary acyl fluoride shown in the following formula (III):
FOC-C(CH 3 ) 2 -(CF 2 ) 5 -C(CH 3 ) 2 -COF （Ⅲ）。
in the preparation process, a solid Lewis acid catalyst with the granularity of 100 meshes is adopted, and the dosage of the solid Lewis acid catalyst is 1 percent of the mass of the fluorinating agent. The dosage of the solvent is 100 percent of the mass of the fluorine-containing dicarboxylic acid. The molar amount of the fluorinating agent is 3 times of that of the raw material fluorine-containing dicarboxylic acid, so that the prepared fluorine-containing dicarboxylic acid fluoride with the content of 82.6 percent is obtained, and the yield is 86.8 percent.
The following examples 5 to 14 specifically relate to a method for producing a fluorine-containing dicarboxylic acid.
Example 5:
800g of potassium permanganate, 10g of tetrabutylammonium bromide, 400g of acetone and 1200g of water are placed in a 5L four-necked flask with mechanical stirring, a dropping funnel at constant pressure, an ice-water condensation reflux unit and a thermometer tube. 805g (3.81 mol) of 1, 2-dichlorotetrafluorocyclobutene with the content of 92.3 percent is dripped into the solution under stirring, and the internal temperature is controlled between 10 and 20 ℃. After the addition was completed, the reaction was stirred for 0.5 hour while maintaining 20 ℃, and 1g of sodium thiosulfate was added to remove purple color and complete the reaction. The product was filtered and distilled to obtain 1482g of recovered solvent. The residue was washed twice with water (200 ml. Times.2), and the distillation residue was dissolved in 600ml of water, and then 1000ml of the solution was combined and purified by post-treatment to give 621g of tetrafluorosuccinic acid having a purity of 98.5% with a yield of 84.1%.
Example 6:
983g of potassium permanganate, 7g of methyltrioctylammonium chloride and 1450g of the solvent recovered in example 1 were placed in a 5L four-neck flask with mechanical stirring, gas line, cryocondensation reflux (approx. -15 ℃ C.) and thermocatheter. Introducing 94 percent of perfluor cyclobutene gas (boiling point is 5-6 ℃) into a reaction flask in a bubbling mode, stirring, controlling the internal temperature to be 3-8 ℃, and continuously introducing 728g (4.22 mol) of perfluor cyclobutene. After the addition was complete, the reaction was continued for 1h with stirring at 10 ℃ and 2g of sodium thiosulfate were added to remove the purple color and the reaction was complete. The product is purified by post-treatment to obtain 651g of tetrafluorosuccinic acid with the purity of 98.4 percent, and the yield is 78.8 percent.
Examples 7 to 14:
different starting materials and catalysts were replaced on the basis of example 5 and example 6, and the results are shown in the following table.
As can be seen from the above examples 5 to 14, the yield of the fluorine-containing dicarboxylic acid can reach 72.2 to 90.5% when the production is carried out by the above method, which proves the feasibility of the industrial mass production of the fluorine-containing dicarboxylic acid.
Comparative example 1:
100g of potassium hydroxide is dissolved in 750ml of water, and after cooling, the potassium hydroxide is added into a 3L four-neck flask with mechanical stirring, a constant pressure dropping funnel, an ice water condensation reflux device and a thermometer catheter, and simultaneously 180g of potassium permanganate is added. 93g of 1, 2-dichlorotetrafluorocyclobutene (0.44 mol) having a content of 92.3% were added dropwise to the flask over 2h with stirring. The reaction temperature is controlled between 60 and 70 ℃. And after the dropwise addition is finished, stirring is continuously carried out for 8 hours until no obvious reflux exists, stirring is continuously carried out for 2 hours to finish the reaction, and 35g of unreacted 1, 2-dichlorotetrafluorocyclobutene is recovered. 49.8g of tetrafluorosuccinic acid with a purity of 94.5% was obtained with a yield of 56.3%.
Comparative example 2:
1000g of acetone and 150g of potassium permanganate are added into a 5L four-neck flask with a mechanical stirring device, a constant pressure dropping funnel, an ice water condensation reflux device and a thermometer catheter, and 80g of 1, 2-dichlorotetrafluorocyclobutene with the content of 92.3 percent is dripped in under the stirring condition. The internal temperature is controlled between 20 and 30 ℃. When cyclobutene is dripped to 1/3, the viscosity of the reaction system is obviously increased, when cyclobutene is dripped to 3/4, the system is almost solid and cannot be stirred, the mass and heat transfer is completely stopped, and the reaction is finished. The tetrafluorosuccinic acid with a purity of 89.5% was obtained in an amount of 50.6g with a yield of 62.9%.
From the comparison of the yields of example 5 and comparative examples 1 and 2 above, it can be seen that: under the same process conditions, the solvent system of the oxidation reaction is changed in the comparative example 1 and the comparative example 2, and the yield of the tetrafluorosuccinic acid prepared by the method is obviously reduced; in addition, the reaction process shows that the reaction system in the comparative example 2 has increased viscosity, difficult heat and mass transfer, easy temperature flushing and material running in the reaction, and hidden danger brought to industrial safety production, and in addition, in the reaction process, the amount of needed acetone is large, and the stable and controllable reaction is not facilitated; the tetrafluorosuccinic acid prepared in example 5 has a purity of > 98%, while the tetrafluorosuccinic acid prepared by the methods described in comparative examples 1 and 2 has a purity of < 95%.
Example 15:
193g (1 mol) of tetrafluorosuccinic acid obtained in the above example 6 was weighed, charged into a 1L three-necked flask equipped with a mechanical stirring, constant pressure addition funnel and a thermometer tube, heated under vacuum (1-3 mmHg) in a 70 ℃ water bath and dried for 3 hours, and 200ml of dry diethyl ether was added under nitrogen protection after the completion of drying. The water bath was started and the fluorinating agent CHFClCF, purified from 500g (2.5 mol) and having a GC content of 95%, was added dropwise with stirring 2 NEt 2 (prepared by equimolar reaction of chlorotrifluoroethylene and diethylamine), 5g of a 46% boron trifluoride ether solution and 200ml of ether. Maintaining the internal temperature at 20-25 ℃ during the dripping, continuing the reaction for 1h after the dripping is finished, heating in water bath to 40 ℃ and keeping the temperature at 60 ℃ for 0.5h respectively to evaporate the materials, and collecting the materials by using an ice water cold trap to obtain 215.7g of tetrafluorosuccinyl fluoride with the content of 78.8 percent, wherein the yield is 87.6 percent.
Example 16:
124g (0.5 mol) of hexafluoroglutaric acid obtained in example 11 was weighed out and charged into a three-necked flask, dried in a 70 ℃ water bath under vacuum (1-3 mmHg) for 3 hours, and after the drying, 100ml of calcium hydride-dried acetonitrile was added under nitrogen protection to dissolve the hexafluoroglutaric acid, and the solution was accelerated by slight heating.
Prepared by reacting equimolar hexafluoropropylene and diethylamineOf a fluorinating agent CF 3 CHFCF 2 NEt 2 (GC content 78%) 295g (1.03 mol) was charged into a 1L three-necked flask equipped with a mechanical stirring, constant pressure addition funnel and a thermometer tube, 3.0g of pulverized aluminum trichloride (about 150 mesh) and 100ml of acetonitrile dried with calcium hydride were further added, the mixture was stirred at 20 ℃ for 0.5 hour, then the dropwise addition of the acetonitrile solution of hexafluoroglutaric acid was started through the constant pressure addition funnel while maintaining the internal temperature at 25 to 30 ℃ and after the dropwise addition, the reaction was continued with stirring for 0.5 hour, then the temperature of the water bath was raised to 50 ℃ and 70 ℃ for 0.5 hour respectively to distill off the material, and the material was collected using an ice water cooling trap to obtain 123.8g of hexafluoroglutaryl fluoride having a content of 85.4% and a yield of 85.9%.
Example 17:
97g (0.5 mol) of tetrafluorosuccinic acid obtained in the above example 5 was weighed, charged into a 1L three-necked flask equipped with a mechanical stirring, constant pressure feeding funnel and a thermometer tube, and dried under vacuum (1-3 mmHg) in a 70 ℃ water bath for 3 hours for standby.
170g (1.14 mol) of a fluorination reagent CHF having a content of 97% after purification was placed in another 250ml three-necked flask 2 CF 2 NMe 2 (prepared by equimolar reaction of tetrafluoroethylene and dimethylamine) and 2g of titanium tetrachloride were stirred at room temperature for 1 hour under a nitrogen blanket.
The fluorination reagent is dropwise added into a three-neck flask of tetrafluorosuccinic acid through a constant-pressure feeding funnel for reaction, the internal temperature is kept at 25 ℃ after the dropwise addition, the stirring reaction is carried out for 1h, the materials are evaporated at 40 ℃ and 60 ℃ for 0.5h respectively, and the materials are collected by an ice water cold trap to obtain 89.5g of tetrafluorosuccinyl fluoride with the content of 90.2 percent, and the yield is 83.4 percent.
Example 18:
150g (0.5 mol) of octafluoroadipic acid obtained in example 12 above was weighed into a 500ml three-necked flask equipped with a mechanical stirrer, a constant pressure addition funnel and a thermometer tube, dried under vacuum (1-3 mmHg) in a 70 ℃ water bath for 3 hours under nitrogen blanket.
Into another 250ml three-necked flask was charged 210g of a fluorinating agent CHFClCF having a GC content of 98% after purification 2 NEt 2 (1.08 mol), 1.5g of pulverized aluminum trichloride (about 250 mesh) was added thereto, and the mixture was purged with nitrogenThe reaction was stirred at room temperature for 1h.
Dropwise adding the fluorination reagent into octafluoro adipic acid through a constant-pressure feeding funnel for reaction, maintaining the internal temperature at 40-45 ℃ after dropwise adding, stirring for reaction for 1h, heating in a water bath to 90 ℃ for 1h, evaporating the material, and collecting the material by using an ice water cold trap to obtain 130.2g of octafluoro adipoyl fluoride with the content of 91.5%, wherein the yield is 82.1%.
Comparative example 1:
reference (J Fluorine Chem, 1983, 23, 383-388) method, 95g (0.38 mol) of hexafluoroglutaric acid with a purity of 97%, 16g (0.38 mol) of dried sodium fluoride are charged under nitrogen into a 1L three-necked flask with mechanical stirring, a constant pressure addition funnel and a thermometer tube, and the fluorinating agent CF is added dropwise via the addition funnel 3 CHFCF 2 NEt 2 (GC content 78%) 220g (0.77 mol), stirring and reacting at 25 ℃ internal temperature after dropwise addition, heating the water bath to 50 ℃ and keeping the temperature at 70 ℃ for 0.5h respectively to evaporate the materials, and collecting the materials by using an ice water cold trap to obtain 79.4g of hexafluoroglutaryl fluoride with the content of 82.3%, wherein the yield is 70.5%.
Comparative example 2:
97g (0.5 mol) of tetrafluorosuccinic acid with the purity of 98.1 percent is weighed, added into a three-neck flask, heated and dried for 3 hours in a water bath kettle at the temperature of 70 ℃ under vacuum (1-3 mmHg), and 100ml of acetonitrile dried by calcium hydride is added under the protection of nitrogen after the drying is finished for dissolving for standby. 210g (1.05 mol) of a fluorinating agent CHFClCF with a GC content of 95% after purification are added dropwise with stirring 2 NEt 2 The internal temperature was kept at 20 to 25 ℃ during the dropwise addition, and 84.6g of tetrafluorosuccinyl fluoride having a content of 78% was collected in the same manner as in example 15 with a yield of 68%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (1)
1. A method for preparing fluorine-containing binary acyl fluoride from fluorine-containing cycloolefin is characterized in that: the method comprises the following steps:
a: adding solvent, catalyst and oxidant into a reaction vessel, controlling the reaction temperature at-20-100 ℃ under the condition of stirring, adding fluorinated cycloolefin to carry out oxidation reaction, reacting for 0.5-2 h to obtain corresponding fluorinated dicarboxylic acid,
in the step A, the solvent is a mixed solvent composed of an organic solvent and water, wherein the mass ratio of the organic solvent to the water is 1:100 to 10:1,
in the step A, the catalyst is selected from one or the combination of more than two of crown ether, quaternary phosphonium salt and quaternary ammonium salt, and the amount of the catalyst is 0.1-5% of the mass of the fluorinated cycloolefin,
the oxidant is selected from one or the combination of more than two of potassium permanganate, sodium permanganate, potassium dichromate and sodium dichromate, the molar usage of the oxidant is 1.0 to 3.5 times of that of the fluorinated cycloolefin, and the mass ratio of the solvent to the oxidant is 10:1 to 1:1,
the structural formula of the fluorinated cyclic olefin is as follows:
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl groups, which may be the same or different; r 5 、R 6 Is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or C 1-3 Alkyl groups, which may be the same or different; a and b are integers of 0-3, n is an integer of 0-5, and a + b + n is more than or equal to 2 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one of which is a fluorine atom,
the fluorine-containing dicarboxylic acid has the following structural formula:
HOOC-(CR 1 R 2 ) a -(CF 2 ) n -(CR 3 R 4 ) b -COOH
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl radical, can phaseThe same or different; a and b are integers from 0 to 3, n is an integer from 0 to 5, and a + b + n is more than or equal to 1 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one is a fluorine atom;
b: under the action of solvent and catalyst, the fluorine-containing dicarboxylic acid prepared in step A and fluorination reagent are subjected to fluorination reaction to obtain fluorine-containing dicarboxylic acid fluoride,
in the step B, the solvent is one or more of diethyl ether, tetrahydrofuran, dichloromethane, chloroform, dichloroethane, trichlorotrifluoroethane, acetonitrile, propionitrile and adiponitrile, the dosage of the solvent is 50-200 percent of the mass of the fluorine-containing dicarboxylic acid,
in the step B, the catalyst is Lewis acid catalyst which is one or more of aluminum trichloride, ferric trichloride, titanium tetrachloride, stannic chloride, boron trifluoride and aluminum trifluoride, the dosage of the Lewis acid catalyst is 0.1-3% of the mass of the fluorinating agent,
the fluorinating reagent is a fluoric alkylamine fluorinating reagent, and the structural formula is as follows:
X-CHF-CF 2 -NR 1 R 2
wherein X is fluorine atom, chlorine atom, trifluoromethyl or trifluoromethoxy; r 1 、R 2 Is C 1-3 The alkyl groups, which may be the same or different,
the molar amount of the fluorine-containing alkylamine fluorination reagent is 2 to 4 times of that of the fluorine-containing dicarboxylic acid,
the fluorine-containing binary acyl fluoride satisfies the following formula:
FOC-(CR 1 R 2 ) a -(CF 2 ) n -(CR 3 R 4 ) b -COF
wherein R is 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl groups, which may be the same or different; a and b are integers from 0 to 3, n is an integer from 0 to 5, and a + b + n is more than or equal to 1 and less than or equal to 8; when n is 0, R 1 、R 2 、R 3 、R 4 At least one is a fluorine atom.
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| US5329042A (en) * | 1991-04-26 | 1994-07-12 | Japan Tobacco Inc. | Cyclohexene derivative and method of producing the same |
| CN1461293A (en) * | 2000-07-11 | 2003-12-10 | 旭硝子株式会社 | Method for producing fluorine-containing compound |
| CN107867997A (en) * | 2016-09-28 | 2018-04-03 | 中化近代环保化工(西安)有限公司 | A kind of method for preparing two fluoracyl fluorides |
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2018
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| US5329042A (en) * | 1991-04-26 | 1994-07-12 | Japan Tobacco Inc. | Cyclohexene derivative and method of producing the same |
| CN1461293A (en) * | 2000-07-11 | 2003-12-10 | 旭硝子株式会社 | Method for producing fluorine-containing compound |
| CN107867997A (en) * | 2016-09-28 | 2018-04-03 | 中化近代环保化工(西安)有限公司 | A kind of method for preparing two fluoracyl fluorides |
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| Title |
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| Positive Bromine from Perfluorinated N-Bromoimides;Albert L. Henne等;《Journal of the American Chemical Society》;19510331;第73卷(第3期);第1103-1104页 * |
| THE FACILE PREPARATION OF HF FREE POLYFLUORINATED ACYL FLUORIDES;DARYL G.COX等;《Journal of Fluorine Chemistry》;19831231;第23卷;第383-388页 * |
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