CN113045380B - Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin - Google Patents
Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin Download PDFInfo
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Abstract
The invention discloses a method for preparing fluorine-containing dihydric alcohol by fluorine-containing cycloolefin, which comprises the steps of taking the fluorine-containing cycloolefin as a raw material, oxidizing by an oxidant and treating by strong alkali to generate solid mixed salt containing corresponding fluorine-containing dicarboxylic acid salt, generating corresponding fluorine-containing binary acyl chloride under the action of an acyl chlorination reagent, and finally carrying out reduction reaction on the fluorine-containing binary acyl chloride and a reducing agent under the action of a solvent and a catalyst to obtain the corresponding fluorine-containing dihydric alcohol. The method adopts specific organic solvent and catalyst, and can effectively promote the fluorinated cyclic olefin to generate the corresponding fluorinated dihydric alcohol with high efficiency and high yield by matching with other conditions. The method has the advantages of easily available raw materials, simple process, convenient operation, low cost consumption and the like, and is suitable for large-scale production of the fluorine-containing dihydric alcohol.
Description
Technical Field
The invention belongs to the technical field of organic fluorine chemistry, and particularly relates to a method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin.
Background
The fluorine-containing dihydric alcohol is a widely used bifunctional fluorine-containing intermediate, can derive various fluorine-containing fine chemicals, and is applied to the fields of medicines, materials and the like.
In the prior art, simple Fluorine-containing monohydric alcohols, such as trifluoroethanol and tetrafluoropropanol, can be synthesized by methods such as an oxidation method, a hydrolysis method and a telomerization method, and also can be prepared by using Fluorine-containing carbonyl compounds, such as Fluorine-containing carboxylic acid, fluorine-containing carboxylic ester and the like, as raw materials and adopting a reduction method, and related documents and patents (J. Am. Chem. Soc. 1948, 70, 1968; J. Am Chem. Soc.1952, 74, 5422-5426 synthetic Communications, 2001, 31, 1875-547, J fluorinene Chem 114 (2002) 51-53, US 43967894112.
Compared with simple Fluorine-containing monohydric alcohol, the preparation method of the Fluorine-containing dihydric alcohol is single, and the Fluorine-containing dicarboxylic ester is mostly used as a raw material, and related documents and patents (J, am, chem, soc.1952, 74, 444-446J, am, chem, soc, 1952, 74, 5420J, org, chem, 1965, 30, 3009-3011, polym Sci Pol Chem, 1995, 33, 1615-1625J fluorinine Chem 118 (2002) 107-121, US2911444987. The fluorochemical dicarboxylic acid esters can be prepared by fischer esterification, i.e., the synthesis of esters from carboxylic acids and alcohols by heating under acid catalysis, which is a reversible reaction requiring either continuous removal of product (e.g., water) or addition of excess starting material to increase yield. According to the existing data, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid or acetyl chloride, thionyl chloride and the like are often added in the reaction as catalysts; pyridine, benzotriazole and corresponding derivatives are added as water scavengers, and the main disadvantage of the esterification reaction is that after the reaction is finished, complex post-treatment steps are needed to remove various additives and water as a byproduct of alcohol acid esterification, and the ester is purified.
In conclusion, a preparation method of fluorine-containing diol, which has the advantages of readily available raw materials, simple operation and economic feasibility, still needs to be found.
Disclosure of Invention
The invention aims at the defects in the prior art, and provides a novel method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefins. The method has the advantages of easily available raw materials, simple process, convenient operation and low cost.
The invention is realized by the following technical scheme: a method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin comprises the following steps:
(A) The oxidation is carried out, and the oxidation,
the method comprises the following steps of taking fluorine-containing cycloolefin as a raw material, oxidizing by an oxidizing agent and treating by strong base under the action of a solvent and a catalyst to generate a solid mixed salt containing corresponding fluorine-containing dicarboxylic acid salt, wherein the structural formula of the fluorine-containing cycloolefin is shown as the following formula (1), and the structural formula of the fluorine-containing dicarboxylic acid salt is shown as the following formula (2):
in the formula (1), R 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 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 of which is a fluorine atom,
MOOC-(CR 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -COOM （2）
in the formula (2), R 1 、R 2 、R 3 、R 4 Is a hydrogen atom, a fluorine atom, a chlorine atom or C 1-3 Alkyl radicalMay 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; m is an alkali metal ion;
(B) The acyl chloride is carried out on the mixture of the acyl chloride and the aromatic carboxylic acid,
under the action of an acyl chlorination reagent, preparing the solid mixed salt containing the corresponding fluorine-containing dicarboxylic acid salt prepared in the step A into corresponding fluorine-containing dicarboxylic acid chloride, wherein the structural formula of the fluorine-containing dicarboxylic acid chloride is as follows (3):
ClOC-(CR 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -COCl （3）
in the formula (3), R 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;
(C) The reduction is carried out, and the reaction solution is subjected to reduction,
and (B) under the action of a solvent and a catalyst, carrying out a reduction reaction on the fluorine-containing binary acyl chloride prepared in the step B and a reducing agent to obtain corresponding fluorine-containing binary alcohol, wherein the structural formula of the fluorine-containing binary alcohol is as shown in the following formula (4):
HO-CH 2 -(CR 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -CH 2 -OH （4）
in the formula (4), R 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.
Specific fluorine-containing dihydric alcohol includes chlorotrifluorobutylene, 2-difluorobutanediol, tetrafluorobutanediol, 2-difluoropentanediol, 2, 4-tetrafluoropentanediol, hexafluoropentanediol, and 3, 4-dichlorohexafluorohexanediol, 3, 4-tetrafluorohexanediol, 2, 3-tetrafluorohexanediol, 3-trifluoromethyl heptafluorohexanediol, octafluorohexanediol, decafluoroheptanediol, etc.
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.
in the step (A), adding a solvent, a catalyst and an oxidant into a reaction vessel, controlling the reaction temperature to be-20-100 ℃ under the stirring condition, adding fluorinated cycloolefin to perform an oxidation reaction, performing suction filtration on an oxidation product after the reaction is completed for 0.5-2 h, adding a strong base into a filtrate to adjust the pH value to be alkaline, and fully drying to obtain a solid mixed salt containing the corresponding fluorinated dicarboxylic acid salt.
In the step (A), the solvent is a mixed solvent composed of an organic solvent and water, and the mass ratio of the organic solvent to the water is 1:100 to 10:1, selecting at least one organic solvent from acetone, dichloromethane, chloroform and benzene; the catalyst is selected from at least one of crown ether, quaternary phosphonium salt and quaternary ammonium salt; the oxidant is at least one selected from potassium permanganate, sodium permanganate, potassium dichromate and sodium dichromate; the strong base is sodium hydroxide or potassium hydroxide.
In the step (B), the equivalent ratio of the acyl chlorination reagent to the fluorine-containing dicarboxylic acid salt is 1.8-3.5, the temperature of the acyl chlorination reaction is 10-150 ℃, preferably 30-100 ℃, and the acyl chlorination reagent is selected from at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, triphosgene, diphosgene, phosgene and oxalyl chloride.
In the step (B), an organic base is also added as a catalyst during the acyl chlorination reaction, the addition amount of the organic base is 0-3% of the mass of the fluorine-containing dicarboxylic acid salt, the organic base is selected from at least one of imidazole, N-methylimidazole, N-dimethylformamide, N-methylpyrrolidone, pyridine, picoline and triethylamine, and the functions of the organic base are to promote the reaction and reduce the dosage of the acyl chlorination reagent.
In the step (B), a phase transfer catalyst is also added during the acyl chlorination reaction, the addition amount of the phase transfer catalyst is 0-5% of the mass of the fluorine-containing dicarboxylic acid salt, and the phase transfer catalyst is selected from at least one of crown ether, quaternary phosphonium salt and quaternary ammonium salt.
Among the useful crown ethers are 18-crown-6, 15-crown-5, 12-crown-4 or derivatives thereof such as dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and dibenzo-24-crown-8, and benzo-12-crown-4, among others. Useful quaternary ammonium salts include benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium bisulfate, and the like. Useful quaternary phosphonium salts include tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, benzyltriphenylphosphonium chloride, and the like.
In the step (B), an organic solvent is also added during the acyl chlorination reaction, the addition amount of the organic solvent is 0-300% of the mass of the fluorine-containing dicarboxylic acid salt, the organic solvent is selected from at least one of dichloromethane, chloroform, benzene, toluene, xylene, ethylbenzene and chlorobenzene, and the function of the organic solvent is to better disperse the fluorine-containing dicarboxylic acid salt, so that the heat transfer and mass transfer are facilitated.
In the step (C), the solvent is an alcohol solvent, the catalyst is an alkali metal hydroxide, and the reducing agent is metal borohydride or metal alkyl borohydride.
The alcohol solvent is both a reactant and a solvent, alcohol can be quickly converted into corresponding ester by reacting with the fluorine-containing diacid chloride, and the rest alcohol can be used as a solvent for the next reduction reaction without separating and purifying the ester. Therefore, in the step (C), the solvent is selected from at least one of methanol, ethanol, propanol and isopropanol, and ethanol or isopropanol is more preferable as the solvent in consideration of toxicity, cost and the like. Compared with the fluorine-containing binary acyl chloride raw material, the alcohol solvent needs to be excessive, and in the invention, the molar mass ratio of the fluorine-containing binary acyl chloride to the solvent is 1:4 to 1:100. the esterification reaction of acyl chloride and alcohol has no special requirement on temperature, theoretically, the temperature does not exceed the boiling point of reactants, and the reaction temperature is maintained at room temperature by adjusting according to the exothermic condition.
The catalyst is alkali metal hydroxide and is mainly used for neutralizing byproduct HCl generated by esterification of acyl chloride and alcohol, and adjusting a reduction reaction system to be an alkaline environment, so that the stable operation of the reduction reaction can be effectively promoted, the time is shortened, and the yield is improved. In the step (C), the catalyst is sodium hydroxide or potassium hydroxide which are cheap and easily available bulk chemical products, and can be added in solid in batches or in the form of aqueous solutions with various concentrations, and the addition of water has no influence on the subsequent reaction according to specific process operation. The dosage of the catalyst is proper to ensure that the reaction system is alkaline, namely the pH value of the system is adjusted to be 7.5-10, and in the invention, the molar mass ratio of the fluorine-containing binary acyl chloride to the catalyst is 1: 2.1-1: 3, excessive catalyst usage does not further increase reaction yield, and also increases cost and difficulty of post-treatment.
The reducing agent is metal borohydride or metal alkyl borohydride, the reducing agent can use alcohols as a solvent, and has low requirement on the water content of a system, while the common Bouveault-Blanc reaction uses metal sodium and ethanol to reduce esters, and Lithium Aluminum Hydride (LAH) as the reducing agent has high requirement on the solvent type and the water content of the system, and has complex operation and great potential safety hazard. Because the metal alkyl borohydride is expensive and cannot be prepared on site, the preferable reducing agent is the metal borohydride, and more preferably, in the step (C), the reducing agent is sodium borohydride or potassium borohydride, both of which are commercially available products, so that the cost is low and the use is convenient. The mol ratio of the reducing agent to the fluorine-containing binary acyl chloride is 1:1 to 2:1.
in the step (C), fluorine-containing binary acyl chloride and a solvent are added into a reaction vessel, a catalyst (alkali metal hydroxide) is added after the reaction under the conditions of stirring and room temperature, the reaction system is adjusted to be alkalescent, a reducing agent is added for reduction reaction to obtain the corresponding fluorine-containing binary alcohol, and in order to prevent the reducing agent from being rapidly decomposed, the reduction reaction temperature is generally 0-40 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention provides a new preparation method for producing fluorine-containing dihydric alcohol in large scale, which takes fluorine-containing cycloolefin as a raw material, generates solid mixed salt containing corresponding fluorine-containing dicarboxylic acid salt by oxidizing with an oxidant and treating with strong alkali, generates corresponding fluorine-containing binary acyl chloride by the action of an acyl chlorination reagent, and performs a reduction reaction between the fluorine-containing binary acyl chloride and a reducing agent under the action of a solvent and a catalyst to obtain the corresponding fluorine-containing dihydric alcohol. The method adopts an organic solvent and a specific catalyst, and can effectively promote the fluorinated cyclic olefin to generate the corresponding fluorinated diol with high efficiency and high yield by matching with other conditions. The method has the advantages of easily available raw materials, simple process, convenient operation, low risk and low cost.
(2) The method disclosed in step (A) of the invention is a novel preparation method of fluorine-containing dicarboxylic acid salt, and the method is characterized in that a specific catalyst is added into a mixed solvent system consisting of an organic solvent and water, and other conditions are matched, so that the reaction can be effectively promoted to be safely, stably and rapidly carried out, the method has the characteristics of short reaction time, convenience in operation, simple post-treatment and the like, and is an important link for large-scale production of fluorine-containing dihydric alcohol.
(3) In the process of preparing fluorine-containing dicarboxylic acid salt, the mixed solvent composed of the organic solvent and water is used to replace the solvent system using water or pure organic solvent (such as acetone) as oxidation reaction in the prior art, and the mass ratio of the organic solvent to the water in the mixed solvent is particularly limited to 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 are simple to operate and easy to realize large-scale mass production.
(4) In the process of preparing the fluorine-containing dicarboxylic acid salt, the step (A) of the method adds the catalyst into the mixed solvent during feeding, the dosage 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 production cost of the fluorine-containing dicarboxylic acid salt can not be caused due to the small dosage of the catalyst.
(5) In the process of preparing the fluorine-containing dicarboxylic acid salt, the oxidation product is required to be filtered after the oxidation is completed, the filtrate is added with strong base to adjust the pH value to be alkaline, and the solid mixed salt containing the corresponding fluorine-containing dicarboxylic acid salt is obtained after the filtrate is fully dried.
(6) In the reaction process of preparing the fluorine-containing dicarboxylic acid chloride, the raw material is solid mixed salt containing corresponding fluorine-containing dicarboxylic acid salt, and the fluorine-containing dicarboxylic acid chloride can be efficiently prepared by matching optimized process conditions, so that the method is an important link for producing fluorine-containing dicarboxylic acid chloride on a large scale.
(7) In the reaction process for preparing the fluorine-containing binary acyl chloride, after the acyl chlorination reaction is finished, the solvent, the product and the residual inorganic salt can be separated by conventional normal pressure distillation or reduced pressure distillation, so that the method is simple and practical.
(8) In the step (C) of the method, in the reaction process of preparing the fluorine-containing dihydric alcohol by a reduction method, the adopted alcohol solvent is simultaneously used as a reactant and a solvent, and directly reacts with the fluorine-containing binary acyl chloride, so that the reaction product can be quickly converted into corresponding ester, and meanwhile, the rest alcohol can be used as a solvent for the next reduction reaction without separating and purifying the ester, and the step is simple and convenient. The boiling point of the alcohol solvent is greatly different from that of the target product, so that the later separation and purification are facilitated, and the solvent is easy to obtain, cheap and recyclable.
(9) In the step (C) of the method, in the reaction process of preparing the fluorine-containing dihydric alcohol by a reduction method, the alkali metal hydroxide is used as a catalyst and is mainly used for neutralizing byproduct HCl generated by esterification of acyl chloride and alcohol, and a reduction reaction system is adjusted to be an alkaline environment, so that the stable operation of the reduction reaction can be effectively promoted, the time is shortened, and the yield is improved. Alkali metal hydroxides such as potassium hydroxide and sodium hydroxide are inexpensive and readily available bulk chemical products and can be added in the form of a solid or aqueous solution, depending on the particular process operation, the addition of water has no effect on the reaction.
(10) In the step (C) of the method, in the reaction process of preparing the fluorine-containing dihydric alcohol by the reduction method, the metal borohydride is used as a reducing agent, and the reduction reaction can be promoted to be efficiently, quickly and stably carried out by matching with the optimized solvent and the optimized catalyst, and meanwhile, the quick decomposition of the metal borohydride in the reduction process can be avoided.
(11) In the reaction process of preparing the fluorine-containing dihydric alcohol from the fluorine-containing cycloolefin, each step of reaction can be carried out at normal temperature and normal pressure, complex equipment and operation are not needed, and the method is simple and practical.
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 relates to the overall procedure for the preparation of fluorodiols from fluorinated cycloalkenes.
800g of potassium permanganate, 10g of tetrabutylammonium bromide, 400g of acetone and 1200g of water are placed in a 5L four-neck 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 92.3 percent 1, 2-dichlorocyclobutene tetrafluoride is added dropwise 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. Filtering the reaction solution, washing the filter residue twice (200 ml × 2), combining the filtrate and the washing solution, adding 78g of potassium hydroxide to adjust the pH value to 9, and fully drying the solution to obtain 1488g of mixed salt which mainly contains potassium tetrafluorosuccinate, excessive potassium hydroxide and potassium chloride.
The mixed salt was charged with 1600g of chloroform into a 3L three-necked flask equipped with a mechanical stirring, constant pressure dropping funnel and a thermometer tube. Under the condition of stirring, 950g of thionyl chloride mixed with 5g of N, N-dimethylformamide (the molar ratio of the thionyl chloride to potassium tetrafluorosuccinate is about 2.1). Under the condition of normal pressure, firstly heating to 60-65 ℃ to recover the solvent, then heating to 90 ℃ and collecting 732g of product by using an ice water cold trap, wherein the content of tetrafluorosuccinyl chloride is 98.5% by GC analysis, and the total yield of oxidation and acyl chlorination is 83.4%.
500g of absolute ethyl alcohol is added into a 3L three-neck flask with a mechanical stirring device, a constant pressure dropping funnel, a gas guide tube (a communicated calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 732g of tetrafluorosuccinyl chloride (3.18 mol) prepared in the previous step is dripped at room temperature, the internal temperature is maintained to be not higher than 30 ℃ in the dripping process, the room temperature stirring reaction is carried out for 1h after the dripping is finished, sampling GC detection shows that the acyl chloride is completely converted, 720g of a prepared 50wt% potassium hydroxide aqueous solution is dripped, and the pH value is about 9.
And after the internal temperature is reduced to room temperature, dropwise adding a suspension prepared from 122g (3.21 mol) of sodium borohydride and 250g of ethanol, controlling the internal temperature to be 10 to 20 ℃, and intermittently bubbling with middle tail gas. After the reaction is carried out until no heat release, stirring is continued for 30min, a small amount of concentrated hydrochloric acid is added for quenching, 452g of white solid is obtained after treatment, the melting point is determined to be 80.4 ℃ (the literature value is 79-82 ℃), the content of the tetrafluorobutanediol is identified as GC-MS, and the reduction yield is 86.8%.
The total yield of the three steps of oxidation, acyl chlorination and reduction is 72.4 percent.
The following examples 2 to 10 relate to the preparation of fluorine-containing dicarboxylic acid salts by oxidation of fluorine-containing cycloalkenes.
Example 2:
983g of potassium permanganate, 7g of methyltrioctylammonium chloride, 360g of acetone and 1140g of deionized water were charged into a 3L four-neck flask with mechanical stirring, gas-line, cryocondensation reflux (ca. -15 c) and thermometer tube. Introducing perfluorocyclobutene gas (boiling point is 5-6 ℃) with the content of 94% 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 perfluorocyclobutene. 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. Filtering the reaction solution, washing the filter residue twice (200 ml × 2), combining the filtrate and the washing solution, adding 95g of potassium hydroxide to adjust the pH value to 10, and drying the solution to obtain 1617g of mixed salt, wherein the mixed salt mainly contains potassium tetrafluoro succinate, excessive potassium hydroxide and potassium fluoride.
Examples 3 to 10:
different starting materials and catalysts were replaced on the basis of examples 1 and 2, and the results are shown in the following table.
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 to be 60 to 70 ℃. And after the dropwise addition is finished, stirring is continuously carried out for 8 hours until no obvious reflux exists, then stirring is continuously carried out for 2 hours to finish the reaction, and 35g of unreacted 1, 2-dichlorotetrafluorocyclobutene is recovered. Even the overall conversion yield of the starting materials for the reaction was only 62.4%.
Comparative example 2:
1000g of acetone and 150g of potassium permanganate are added into a 3L 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 to be 20-30 ℃. 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 following examples 11 to 13 relate to the preparation of fluorine-containing diacid chlorides from fluorine-containing dicarboxylic acid salts.
Example 11:
1453g of the dried mixed salt obtained in example 6 (mainly containing sodium hexafluoroglutarate, sodium sulfate, excess sodium hydroxide and sodium chloride), 6g of imidazole, 10g of crown ether (18-crown-6) and 500g of dichloromethane were charged together into a 3L three-necked flask equipped with a mechanical stirring, constant pressure dropping funnel and a thermometer tube. 450g of oxalyl chloride was dropped into the flask through a constant pressure dropping funnel with stirring, and the internal temperature was controlled to about 55 ℃. And absorbing tail gas by using alkali liquor. After the addition was completed for 2h, stirring was continued for 0.5h to complete the reaction. Under the condition of normal pressure, firstly heating to 40-45 ℃ to recover the solvent, then heating to 65-70 ℃ to recover excessive oxalyl chloride, finally collecting the product of reduced pressure (80 ℃ and less than or equal to 20 mmHg) distillation by using a dry ice alcohol cold trap to obtain 804.5g of colorless transparent liquid, and analyzing the content of the hexafluoroglutaryl chloride by GC to be 97.5%. The total yield of oxidation and acyl chlorination is 90.1%.
Example 12
1328g of the dried mixed salt obtained in example 9 (mainly containing sodium 3,3,4,4-tetrafluoroadipate, sodium sulfate, excess sodium hydroxide and sodium chloride) was charged into a 3L three-necked flask equipped with a mechanical stirring, constant pressure dropping funnel and a thermometer tube, together with 400g of methylene chloride. 1000g of thionyl chloride mixed with 5g of triethylamine was dropped into the flask through a constant pressure dropping funnel with stirring, the internal temperature was controlled at about 30 ℃ and the tail gas was absorbed with an alkali solution. After the addition was completed for 3 hours, stirring was continued for 1 hour to complete the reaction. The work-up gave 786.3g of a colorless, transparent liquid product having a content of 3, 4-tetrafluoroadipoyl chloride of 97.2% by GC analysis. The total yield of oxidation and acylchlorination was 72.3%.
Example 13
541g of the mixed salt containing potassium octafluoro adipate, potassium chloride and a small amount of potassium hydroxide obtained in example 10, 2g of N-methylpyrrolidone, 3g of benzyltriphenylphosphonium chloride and 400g of chloroform were charged together into a 2L three-necked flask equipped with a mechanical stirring, constant pressure dropping funnel and a thermometer tube. 240g of phosphorus trichloride is dripped into a flask through a constant-pressure dropping funnel under the condition of stirring, the internal temperature is controlled to be about 45 ℃, and tail gas is absorbed by alkali liquor. After the addition was completed for 2h, stirring was continued for 0.5h to complete the reaction. After the solvent and the excessive phosphorus trichloride are recovered, a dry ice alcohol cold trap is used for collecting a product distilled under reduced pressure (80 ℃ and less than or equal to 20 mmHg) to obtain 335.4g of colorless transparent liquid, and the content of the octafluoro glutaryl chloride is 96.5 percent by GC analysis. The total yield of oxidation and acylchlorination was 74.3%.
The following examples 14-18 relate to the reduction of fluorine-containing diacid chlorides to make fluorine-containing diols.
Example 14: 200g of absolute ethyl alcohol is added into a 0.5L three-neck flask with a mechanical stirring and constant pressure dropping funnel, a gas-guide tube (communicated with a calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 200g of hexafluoroglutaryl chloride (0.7 mol) with the content of 97.5 percent is dripped at room temperature, the internal temperature is maintained to be not higher than 35 ℃ in the dripping process, the room temperature stirring reaction is carried out for 1.5h after the dripping is finished, GC sampling detection shows that the acyl chloride is completely converted, 120g of a prepared 50 weight percent sodium hydroxide aqueous solution is dripped, and the pH value is about 10.
After the internal temperature is reduced to room temperature, a suspension prepared from 32g (0.85 mol) of sodium borohydride and 50g of ethanol is added dropwise, the internal temperature is controlled to be 10-20 ℃, and the tail gas in the dropwise adding process is intermittently bubbled. After the reaction is carried out until no heat release, stirring is continuously carried out for 30min, a small amount of concentrated hydrochloric acid is added for quenching, 124.6g of white solid is obtained after treatment, the melting point is determined to be 79.5 ℃ (the literature value is 78-81 ℃), and GC-MS is identified to be hexafluoropentanediol, the content is 98.6 percent, and the yield is 82.8 percent.
Example 15:
100g of absolute ethyl alcohol is added into a 0.5L three-neck flask with a mechanical stirring and constant pressure dropping funnel, a gas-guide tube (communicated with a calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 100g of octafluoro adipoyl chloride (0.3 mol) with the content of 96.5 percent is dripped at room temperature, the internal temperature is maintained to be not higher than 20 ℃ in the dripping process, the stirring reaction at room temperature is carried out for 2 hours after the dripping is finished, sampling GC detection shows that the conversion of acyl chloride is complete, 50g of a prepared 50 weight percent sodium hydroxide aqueous solution is dripped, and the pH value is about 8.5.
After the internal temperature is reduced to room temperature, a suspension prepared from 19g (0.5 mol) of sodium borohydride and 50g of ethanol is added dropwise, the internal temperature is controlled to be 15-30 ℃, and the intermittent bubbling of the tail gas in the dropwise adding process is carried out. After the reaction is carried out until no heat is released, stirring is continued for 30min, a small amount of concentrated hydrochloric acid is added for quenching, 68.2g of white solid is obtained after treatment, the melting point is determined to be 68.7 ℃ (the literature value is 67-70 ℃), and GC-MS is identified to be octafluorohexanediol, the content is 97.5%, and the yield is 84.6%.
Example 16:
300g of absolute ethyl alcohol is added into a 1L three-neck flask with a mechanical stirring device, a constant pressure dropping funnel, a gas-guide tube (communicated with a calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 150g of 97.2 percent 3, 4-tetrafluoro adipyl chloride (0.57 mol) is dripped at room temperature, the internal temperature is maintained to be not higher than 20 ℃ in the dripping process, the room temperature stirring reaction is carried out for 2h after the dripping is finished, sampling GC detection shows that the acyl chloride is completely converted, then, a prepared 30 weight percent potassium hydroxide aqueous solution 220g is dripped, and the pH value is about 10.
After the internal temperature is reduced to room temperature, a suspension prepared from 30g (0.79 mol) of sodium borohydride and 70g of ethanol is added dropwise, the internal temperature is controlled to be 15-25 ℃, and the tail gas in the dropwise adding process is intermittently bubbled. After the reaction is finished and heat release does not exist, stirring is continued for 1h, a small amount of concentrated hydrochloric acid is added for quenching, 97g of white solid is obtained after treatment, and the white solid is identified as 3, 4-tetrafluorohexanediol by GC-MS, the content is 98.2 percent, and the yield is 88 percent.
Example 17:
1000g of absolute ethyl alcohol is added into a 2L three-neck flask with a mechanical stirring device, a constant pressure dropping funnel, a gas guide tube (communicated with a calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 210g of 98.2 percent 2, 2-difluorosuccinyl chloride (1.08 mol) is dripped at room temperature, the internal temperature is maintained to be not higher than 30 ℃ in the dripping process, room temperature stirring reaction is carried out for 1 hour after dripping is finished, sampling detection shows that acyl chloride is completely converted by GC, then 90g of flaky sodium hydroxide is added in batches, and the pH value is about 9.5.
After the internal temperature is reduced to room temperature, suspension prepared from 50g (1.32 mol) of sodium borohydride and 150g of ethanol is dripped, the internal temperature is controlled to be 10 to 20 ℃, and middle tail gas is dripped for intermittent bubbling. After the reaction was carried out until no heat was released, stirring was continued for 1 hour, and a small amount of concentrated hydrochloric acid was added to quench, 117.6g of a white solid was obtained after the treatment, and GC-MS was identified as 2, 2-difluorobutanediol, the content of which was 97.9%, and the yield was 84.6%.
Example 18:
200g of absolute ethyl alcohol is added into a 0.5L three-neck flask with a mechanical stirring and constant pressure dropping funnel, a gas guide tube (a communicated calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, stirring is started, 55g of 96.4 percent 2, 4-tetrafluoroglutaryl chloride (0.22 mol) is dripped at room temperature, the internal temperature is maintained to be not higher than 25 ℃ in the dripping process, the room temperature stirring reaction is carried out for 30min after the dripping is finished, sampling GC (gas chromatography) detection shows that the acyl chloride is completely converted, 42g of a prepared 60 weight percent potassium hydroxide aqueous solution is dripped, and the pH value is about 9.
And after the internal temperature is reduced to room temperature, dropwise adding a suspension prepared from 22g (0.41 mol) of potassium borohydride and 50g of ethanol, controlling the internal temperature to be 15-25 ℃, and intermittently bubbling the dropwise added tail gas. After the reaction was carried out until no heat was released, stirring was continued for 1 hour, and a small amount of concentrated hydrochloric acid was added to quench it, whereby 36.7g of a white solid was obtained after the treatment, which was identified as 2, 4-tetrafluoropentanediol by GC-MS, and the content was 97.6% and the yield was 92.5%.
Comparative example 3:
(esterification) adding 120g (0.49 mol) of commercial 98.5 percent hexafluoroglutaric acid and 200g of absolute ethyl alcohol (molecular sieve drying) into a four-mouth flask with a mechanical stirring, constant-pressure dropping funnel, an ice water condensation reflux device and a thermometer catheter, dripping 100g of concentrated sulfuric acid at room temperature, raising the temperature to the reflux temperature after dripping, stirring for reaction for 10 hours, evaporating most of ethyl alcohol while hot, adding 20 weight percent sodium hydroxide solution to adjust the pH value to be about 6.5, separating liquid, collecting organic phase, washing with deionized water and 5 weight percent sodium bicarbonate solution to obtain 134g of diethyl hexafluoroglutarate, detecting the purity by GC to be 92.5 percent, obtaining the esterification yield of 85.4 percent, and adding anhydrous magnesium sulfate for drying for later use.
(catalyst-free sodium borohydride reduction) 11.4g (0.3 mol) of sodium borohydride and 200g of absolute ethyl alcohol are added into a four-neck flask with a mechanical stirring device, a constant pressure dropping funnel, a gas-guide tube (communicated with a calcium chloride drier and an alkali liquor tail gas indicating bottle) and a thermometer guide tube, after the mixture is fully stirred to disperse solids, 60g (0.19 mol) of diethyl hexafluoroglutarate prepared by the esterification reaction is slowly dropped through the constant pressure dropping funnel, the temperature in the reaction is controlled below 20 ℃, and a large amount of tail gas is generated in the dropping process. After the reaction is carried out until no heat release, stirring is carried out continuously for 30min, and after post-treatment such as quenching, 26.7g of white solid product with the content of 94.3 percent and the yield of 62.5 percent is obtained, 11.4g of unreacted diethyl hexafluoroglutarate is recovered, and the GC purity is 87.6 percent. The total yield of the two reactions of esterification and reduction is 53.4%.
(lithium aluminum hydride reduction) 11.4g (0.3 mol) of lithium aluminum hydride and 200g of anhydrous ether were added to a four-neck flask equipped with a mechanical stirrer, a constant pressure dropping funnel, an ice water condensation reflux unit, a gas-guide tube (communicating with a calcium chloride drier and an alkali solution tail gas indicator bottle) and a thermometer catheter, and the mixture was stirred to disperse the solid. 60g (0.19 mol) of diethyl hexafluoroglutarate prepared by the above esterification reaction was slowly dropped through a constant pressure dropping funnel, and the internal temperature was maintained at about 10 ℃. After no obvious heat release and tail gas disappearance, a small amount of deionized water is added for quenching, and after post-treatment and recrystallization, 27.5g of off-white product with the content of 81.6 percent and the yield of only 55.7 percent is obtained.
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 (4)
1. A method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin is characterized by comprising the following steps: the method comprises the following steps:
(A) The oxidation is carried out, and the oxidation,
adding a solvent, a catalyst and an oxidant into a reaction vessel, controlling the reaction temperature to be-20-100 ℃ under the stirring condition, adding fluorinated cycloolefin for oxidation reaction, filtering an oxidation product after the reaction is completely oxidized for 0.5-2 h, adding potassium hydroxide into filtrate to adjust the pH value to be alkaline, fully drying to obtain solid mixed salt containing corresponding fluorinated dicarboxylic acid salt,
the solvent is a mixed solvent composed of an organic solvent and water, and the mass ratio of the organic solvent to the water is 1:100 to 10:1, the organic solvent is selected from at least one of acetone, dichloromethane, chloroform and benzene; the catalyst is at least one of crown ether, quaternary phosphonium salt and quaternary ammonium salt; the oxidant is at least one selected from potassium permanganate, sodium permanganate, potassium dichromate and sodium dichromate; the strong base is sodium hydroxide or potassium hydroxide,
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,
the structural formula of the fluorinated cyclic olefin is shown as the following formula (1), and the structural formula of the fluorinated dicarboxylic acid salt is shown as the following formula (2):
in the formula (1), R 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 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 of which is a fluorine atom,
MOOC-(CR 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -COOM （2）
in the formula (2), R 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; m is an alkali metal ion;
(B) The acyl chlorination is carried out on the mixture of the acyl chloride,
adding an acyl chlorination reagent and a phase transfer catalyst into the solid mixed salt containing the corresponding fluorine-containing dicarboxylic acid salt prepared in the step A to perform acyl chlorination reaction to prepare the corresponding fluorine-containing dicarboxylic acid chloride,
the acyl chlorination reagent is selected from at least one of thionyl chloride, phosphorus trichloride, phosphorus pentachloride, triphosgene, diphosgene, phosgene and oxalyl chloride,
the equivalent ratio of the acyl chlorination reagent to the fluorine-containing dicarboxylic acid salt is 1.8-3.5, the temperature of acyl chlorination reaction is 10-150 ℃,
the structural formula of the fluorine-containing binary acyl chloride is shown as the following formula (3):
ClOC-(CR 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -COCl （3）
in the formula (3), R 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;
(C) The reduction is carried out, and the reaction solution is subjected to reduction,
adding the fluorine-containing binary acyl chloride prepared in the step B and a solvent into a reaction vessel, adding a catalyst after the reaction under the stirring condition, adding a reducing agent for reduction reaction to obtain the corresponding fluorine-containing binary alcohol, wherein the reduction reaction temperature is 0-40 ℃,
the solvent is selected from at least one of methanol, ethanol, propanol and isopropanol; the catalyst is sodium hydroxide or potassium hydroxide,
the molar mass ratio of the fluorine-containing binary acyl chloride to the solvent is 1:4 to 1:100, wherein the molar ratio of the reducing agent to the fluorine-containing binary acyl chloride is 1:1 to 2:1,
the structural formula of the fluorine-containing dihydric alcohol is shown as the following formula (4):
HO-CH 2 -(C 1 R 2 ) b -(CF 2 ) n -(CR 3 R 4 ) a -CH 2 -OH （4）
in the formula (4), R 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.
2. The method of claim 1, wherein: in the step (B), an organic base is also added during the acyl chlorination reaction, the addition amount of the organic base is 0-3% of the mass of the fluorine-containing dicarboxylic acid salt, and the organic base is selected from at least one of imidazole, N-methylimidazole, N-dimethylformamide, N-methylpyrrolidone, pyridine, picoline and triethylamine.
3. The method of claim 1, wherein: in the step (B), a phase transfer catalyst is also added during the acyl chlorination reaction, the addition amount of the phase transfer catalyst is 0-5% of the mass of the fluorine-containing dicarboxylic acid salt, and the phase transfer catalyst is selected from at least one of crown ether, quaternary phosphonium salt and quaternary ammonium salt.
4. The method of claim 1, wherein: in the step (B), an organic solvent is also added during the acyl chlorination reaction, the addition amount of the organic solvent is 0-300% of the mass of the fluorine-containing dicarboxylic acid salt, and the organic solvent is selected from at least one of dichloromethane, chloroform, benzene, toluene, xylene, ethylbenzene and chlorobenzene.
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