CN116514642A - Preparation method and application of perfluoro-hexanone - Google Patents

Preparation method and application of perfluoro-hexanone Download PDF

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CN116514642A
CN116514642A CN202310501900.3A CN202310501900A CN116514642A CN 116514642 A CN116514642 A CN 116514642A CN 202310501900 A CN202310501900 A CN 202310501900A CN 116514642 A CN116514642 A CN 116514642A
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perfluoro
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methyl
hexanone
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薛旭金
李凌云
邵龙
胡胜伟
徐刚
赵璐
刘海庆
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Duofudo New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method of perfluoro-hexanone, which comprises the following steps: 1) The perfluoro-4-methyl-2-pentene is subjected to in-situ rearrangement and epoxidation reaction to obtain perfluoro-2-methyl-2, 3-epoxypentane; 2) And carrying out isomerization reaction on the perfluoro-2-methyl-2, 3-epoxypentane to generate the perfluoro-hexanone. According to the technical scheme provided by the invention, the perfluoro-4-methyl-2-pentene is subjected to in-situ rearrangement-epoxidation and catalytic isomerization to prepare the perfluoro-hexanone by reasonably selecting the solvent, the catalyst, the cocatalyst, the oxide, the organic base and the content thereof, so that the separation and purification of a highly flammable intermediate perfluoro-2-methyl-2-pentene are avoided, and the operation is simplified; the invention avoids the defects of large amount of waste brine and the like generated in post-treatment caused by using the highly corrosive and irritant oxidizing reagent hypochlorite solution, and reduces the problems of serious environmental pollution and the like. The method has the advantages of simple process, high efficiency, good catalytic effect and high economy by adopting the cheap and easily available nitrogen-containing compound as the catalyst.

Description

Preparation method and application of perfluoro-hexanone
Technical Field
The invention relates to the technical field of organofluorine chemistry, in particular to a preparation method and application of perfluoro-hexanone.
Background
The Perfluoro-hexanone is named Perfluoro (2-methyl-3-pentanone) (perfluor-2-methyl-3-pentanone) with CAS number: 756-13-8, chemical number FK-5-1-12, molecular formula C 6 F 12 O belongs to perfluoroketone compounds, has a boiling point of 49 ℃ and is colorless liquid at normal temperature and normal pressure. The ozone depletion value (ODP) is 0, the Global Warming Potential (GWP) is 1, and the halogen-free flame retardant can be used as a cleaning agent, a solvent and an ideal substitute for Halon-1301, halon-1211, HFC-227ea and the like in the aspect of fire extinguishing agents.
When used as a fire extinguishing agent, the fire extinguishing agent has the advantages that: (1) The storage is easy, the storage is not a dangerous article, and the harm to the environment and human body is almost zero; (2) The evaporation heat is only 1/25 of that of water, and the vapor pressure is 12 times of that of water, so that the water is easy to gasify, and when sprayed, the water can be rapidly evaporated and cover the whole fire extinguishing area under the drive of carrier gas, and the water can be effectively vaporized even at low temperature, so that the fire extinguishing concentration required by design is achieved; (3) The gas-liquid type electric insulation material has electric insulation property, does not leave residues after release, does not cause loss to valuable properties such as sensitive electronic equipment, control parts, navigation equipment and the like, and can be used for protecting precise instruments, valuable equipment and the like.
The synthesis methods of the perfluorinated hexanone are more, and three types of more common methods are: ring-opening reaction of hexafluoropropylene and hexafluoropropylene oxide; hexafluoropropylene reacts with perfluoropropene fluoride; epoxidation and isomerization of hexafluoropropylene dimer.
1. Ring opening reaction of hexafluoropropylene and hexafluoropropylene oxide
CN110092713 takes ammonia gas as catalyst, hexafluoropropylene oxide, triiodofluoromethane and trifluoroiodomethane are added into a tubular reactor, and the perfluorohexanone is obtained by reaction under 2.5-2.7 atmospheres at the temperature of 75-95 ℃, the yield is up to 95.3%, and the purity is up to 99.7%. The defects are that the operation condition is harsh, the trifluoroiodomethane is difficult to prepare, and the cost is high.
2. Hexafluoropropylene and perfluoropropylene fluorine addition reaction
U.S. 3M innovation in patent US6630075 reports the use of perfluoropropionyl fluoride and hexafluoropropylene in an autoclave reactor with an ethereal condensate as the reaction medium to give a perfluorohexanone product under the action of KF. The method needs to be operated under pressure, and the raw material perfluoropropionyl fluoride has strong corrosiveness and has high requirements on container materials. And the preparation difficulty of the raw material perfluoropropionyl fluoride is high, the reaction yield is low, the cost is high, and the industrialization of the product is not realized at home.
3. Epoxidation and isomerization of hexafluoropropylene dimer
The most common oxidation methods for perfluoropropylene dimers are the hydrogen peroxide oxidation method and the hypochlorite oxidation method. The hydrogen peroxide oxidation method is low in reaction temperature, high in energy consumption, and generally has a conversion rate of about 30%, so that the method is not suitable for large-scale industrial production. Although the hypochlorite oxidation method has certain candling property for reaction equipment, the hypochlorite oxidation method has the advantages of high product selectivity and high purity.
Patent CN103787854 uses perfluoro-2-methyl-2-pentene as raw material, sodium hypochlorite solution as oxidant, aprotic polar solvent as solvent, and makes epoxidation reaction by continuous liquid phase method. After the epoxy compound is obtained, the perfluorinated hexanone is obtained through continuous gas phase catalytic reaction under the catalytic action of a fluoride salt catalyst loaded by active carbon, and the purity of the obtained product reaches 99.7%. The method avoids the use of a large amount of solvents, can continuously carry out isomerization, reduces cost and environmental pollution, has the advantages of high process automation degree, high reaction equipment efficiency and the like, but has the defects of severe reaction temperature control and no contribution to industrial production.
CN107235834 is prepared by taking perfluoro-4-methyl-2-pentene as a raw material, alkali metal fluoride and the like as main catalysts, organic alkali as a cocatalyst, crown ether, polyethylene glycol and quaternary ammonium salt as catalyst promoters, carrying out isomerization reaction in a solvent-free or polar aprotic solvent to prepare perfluoro-2-methyl-2-pentene, then adopting tertiary amine nitrogen oxide or N, N-dialkylhydroxylamine as an epoxidation reagent, quantitatively converting perfluoro-2-methyl-2-pentene into perfluoro-2-methyl-2, 3-pentane, and carrying out catalytic rearrangement reaction by using only a catalytic amount of organic amine or Lewis acid to ensure that the conversion rate of perfluoro-ethyl isopropyl ketone is more than 95%.
CN105198719 uses perfluoro-2-methyl-2-pentene as raw material, and makes gas phase reaction with a certain amount of oxygen or air and other oxidizing gas in the presence of catalyst in a fixed bed reactor, and makes one-step or two-step gas phase reaction directly produce perfluoro-hexanone, in which the two-step gas phase reaction mainly includes perfluoro-2-methyl-2-pentene epoxidation reaction and epoxy compound gas phase isomerization reaction. But the conversion and selectivity are low. The method has the advantages of no need of solvent in the production process, greatly reduced cost and environmental pollution, improved process safety, and avoidance of problems of separation of solvent from products, recovery treatment of solvent from catalyst, etc., thus the method has the characteristics of low cost, convenient preparation, easy control of technological parameters in the catalytic reaction process, simple separation and purification of products, etc., and is extremely suitable for industrial production.
In addition to the above three methods, there are other methods such as: CN107778150 is prepared from perfluoropropylene and oxygen, fluoride salt as catalyst, and pressure of 1Mpa, and reacting under ultraviolet irradiation to obtain perfluorohexanone. The method can obtain the product by one-step reaction, is simple and easy to operate, has easily available raw materials, low price and less side reaction. However, the content of the obtained perfluorinated hexanone is only 61% at maximum, which is inconvenient for industrial production.
Besides the above, there are also perfluorocarboxylic acid ester decomposition reaction, perfluorocarboxylic acid salt and perfluoropropionyl fluoride reaction, perfluorocarboxylic acid salt and perfluorocarboxylic acid anhydride reaction, perfluoroisopropyl iodide and perfluoropropionyl chloride reaction, etc. these methods have more side reactions, or the raw materials are difficult to prepare, or the temperature requirement is severe, which is not beneficial to industrialization.
Disclosure of Invention
Aiming at the limitations of the prior art, the invention provides a preparation method and application of perfluoro-hexanone. The invention discovers that the intermediate product of the perfluoro-2-methyl-2-pentene of the perfluoro-hexanone is very sensitive to heat and highly flammable. The experimental steps of generating perfluoro-2-methyl-2-pentene through rearrangement reaction and rectifying and purifying perfluoro-2-methyl-2-pentene are at great risk, and the perfluoro-2-methyl-2-pentene needs to be provided with a perfluoro-hexanone production process for directly carrying out the next epoxidation reaction without separation. The perfluoro-2-methyl-2-pentene in the method of the invention is directly used for producing the perfluoro-hexanone by the next epoxidation reaction without separation, and has the characteristics of simple operation, high yield, less impurities and simple synthesis method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention aims at providing a preparation method of perfluoro-hexanone, which comprises the following steps:
1) The perfluoro-4-methyl-2-pentene is subjected to in-situ rearrangement and epoxidation reaction to obtain perfluoro-2-methyl-2, 3-epoxypentane;
2) And carrying out isomerization reaction on the perfluoro-2-methyl-2, 3-epoxypentane to generate the perfluoro-hexanone.
In the method for producing perfluoro hexanone of the present invention, preferably, step 1) includes:
1.1 Perfluoro-4-methyl-2-pentene as a raw material, fluoride salt as a catalyst and a phase transfer catalyst as a cocatalyst in a polar aprotic solvent to obtain a mixed solution A;
1.2 Taking peroxide as an oxidant and taking a polar aprotic solvent as a solvent, dropwise adding organic alkali under the stirring condition, uniformly mixing, and cooling to obtain a mixed solution B;
1.3 Dropwise adding the mixed solution A into the mixed solution B, and obtaining perfluoro-2-methyl-2, 3-epoxypentane after the reaction is finished.
In the process for the preparation of perfluoro-hexanone according to the invention, preferably, in step 1.1),
the fluoride salt is at least one selected from sodium fluoride, potassium fluoride, lithium fluoride, cesium fluoride and aluminum fluoride; and/or the number of the groups of groups,
the phase transfer catalyst is at least one selected from 18-crown ether-6, 15-crown ether-5, dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, hole ether, acetone furan crown ether and polyethylene glycol; preferably, the molecular weight of the polyethylene glycol is 400-4000; it is further preferred that the polyethylene glycol is at least one selected from the group consisting of PEG-400, PEG-600, PEG-800, PEG-1000, and PEG-4000; and/or the number of the groups of groups,
the polar aprotic solvent in the step 1.1) is at least one selected from acetonitrile, benzyl cyanide, dimethyl sulfoxide, DMF and diethylene glycol dimethyl ether;
in the method for preparing the perfluorinated hexanone, preferably, the molar ratio of the fluoride salt to the perfluoro-4-methyl-2-pentene is 0.02-0.3:1; and/or the number of the groups of groups,
the molar ratio of the phase transfer catalyst to the fluoride salt is 0.2-5.0:1; and/or the number of the groups of groups,
the molar volume ratio of the perfluoro-4-methyl-2-pentene to the polar aprotic solvent is 1:0.1-10; and/or the number of the groups of groups,
the reaction temperature is 30-50 ℃; and/or the number of the groups of groups,
the reaction time is 6-20 h.
In the process for the preparation of perfluoro-hexanone according to the invention, preferably, in step 1.2),
the organic base is at least one of triethylamine, trimethylamine, tributylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylmorpholine, pyridine, quinoline and 1, 8-diazabicyclo [5.4.0] undec-7-ene;
the oxidant is at least one selected from m-chloroperoxybenzoic acid, peracetic acid, peroxybenzoic acid, trifluoroacetic acid peracid and phthaloyl peroxide; and/or the number of the groups of groups,
the polar aprotic solvents in step 1.2) are each independently selected from at least one of acetonitrile, phenylacetonitrile, dimethyl sulfoxide, DMF, diethylene glycol dimethyl ether.
In the method for preparing the perfluorinated hexanone, preferably, the molar ratio of the oxidant to the perfluoro-4-methyl-2-pentene is 1.05-5.0:1; and/or the number of the groups of groups,
the molar ratio of the organic base to the perfluoro-4-methyl-2-pentene is 1.05-5.0:1; and/or the number of the groups of groups,
the molar volume ratio of the perfluoro-4-methyl-2-pentene to the polar aprotic solvent is 1:0.1-10; and/or the number of the groups of groups,
cooling to 0-10 ℃.
In the process for the preparation of perfluoro-hexanone according to the invention, preferably, in step 1.3),
the reaction temperature is-5-50 ℃; and/or the number of the groups of groups,
the reaction time is 0.5-10 h;
after the reaction is finished, standing for layering, distilling, and collecting fractions to obtain the purified perfluoro-2-methyl-2, 3-epoxypentane.
In the method for preparing perfluoro hexanone of the present invention, preferably, the step 2) includes:
the perfluoro-2-methyl-2, 3-epoxypentane is used as a raw material, a polar aprotic solvent is used as a solvent, an organic base is used as a catalyst, and liquid phase isomerization reaction is carried out to obtain the perfluoro-hexanone after the reaction is finished.
In the process for the preparation of perfluoro-hexanone according to the invention, preferably, in step 2),
the polar aprotic solvent is at least one selected from acetonitrile, dimethyl sulfoxide, DMF and diethylene glycol dimethyl ether; and/or the number of the groups of groups,
the organic base is at least one selected from triethylamine, trimethylamine, tributylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylmorpholine, pyridine, quinoline and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
In the preparation method of the perfluoro-hexanone, preferably, the molar ratio of the organic base to perfluoro-2-methyl-2, 3-pentane oxide is 0.02-0.3:1; and/or the number of the groups of groups,
the volume ratio of the polar aprotic solvent to the perfluoro-2-methyl-2, 3-epoxypentane is 0.1-10:1; and/or the number of the groups of groups,
the reaction temperature is 0-52 ℃; and/or the number of the groups of groups,
the reaction time is 2-18 hours;
and after the reaction is finished, layering and distilling to obtain the purified perfluorinated hexanone.
Compared with the prior art, the invention has at least the following advantages:
1. according to the technical scheme provided by the invention, the perfluoro-4-methyl-2-pentene is subjected to in-situ rearrangement-epoxidation and catalytic isomerization to prepare the perfluoro-hexanone by reasonably selecting the solvent, the catalyst, the cocatalyst, the oxide, the organic base and the content thereof, so that the separation and purification of a highly flammable intermediate perfluoro-2-methyl-2-pentene are avoided, and the operation is simplified;
2. the defects of a large amount of waste brine and the like generated in post-treatment caused by using a highly corrosive and irritant oxidizing reagent hypochlorite solution are avoided, and the problems of serious environmental pollution and the like are reduced.
3. The process is simple, the efficiency is high, the cheap and easily available nitrogen-containing compound is adopted as the catalyst, the catalytic effect is good, and the economy is high.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw material sources are as follows:
the raw materials used in the present invention can be obtained directly by purchase.
The in-situ rearrangement-epoxy synthesis of perfluoro-2-methyl-2, 3-epoxypentane is carried out according to the following steps:
preparation example 1:
100g of perfluoro-4-methyl-2-pentene, 30mL of acetonitrile, 1.76g of 18-crown-6 and 0.9g of powdery potassium fluoride were added to the reaction vessel A, and the mixture was stirred at 40℃for 6 hours and cooled to room temperature. Simultaneously, 69.02g of m-chloroperoxybenzoic acid and 50mL of acetonitrile are added into a reaction bottle B, 40.48g of triethylamine is added dropwise under stirring, the stirring is carried out for a while, and the temperature is reduced to 5 ℃. And (3) dropwise adding the solution in the reaction bottle A into the reaction bottle B, reacting for 3 hours at 20 ℃, standing for layering, distilling, and collecting the fraction at 48-53 ℃ to obtain the perfluoro-2-methyl-2, 3-pentane with the yield of 91% and the purity of 96%.
Preparation example 2:
100g of perfluoro-4-methyl-2-pentene, 30mL of acetonitrile, 1.76g of 18-crown-6 and 0.9g of powdery potassium fluoride were added to the reaction vessel A, and the mixture was stirred at 40℃for 4 hours and cooled to room temperature. Simultaneously, 69.02g of m-chloroperoxybenzoic acid and 50mL of DMF are added into a reaction bottle B, 40.48g of triethylamine is added dropwise under stirring, the mixture is stirred for a while, and the temperature is reduced to 5 ℃. And (3) dropwise adding the solution in the reaction bottle A into the reaction bottle B, reacting for 2 hours at the temperature of 0 ℃, standing for layering, distilling, and collecting the fraction at the temperature of 48-53 ℃ to obtain the perfluoro-2-methyl-2, 3-pentane with the yield of 83% and the purity of 91%.
Preparation example 3:
100g of perfluoro-4-methyl-2-pentene, 30mL of acetonitrile, 1.76g of 18-crown-6 and 0.9g of powdery potassium fluoride were added to the reaction vessel A, and the mixture was stirred at 40℃for 6 hours and cooled to room temperature. Simultaneously, 69.02g of m-chloroperoxybenzoic acid and 50mL of acetonitrile are added into a reaction bottle B, 65.3g of N, N-dimethylbenzylamine is dropwise added under stirring, the mixture is stirred for a while, and the temperature is reduced to 5 ℃. And (3) dropwise adding the solution in the reaction bottle A into the reaction bottle B, reacting for 3 hours at 20 ℃, standing for layering, distilling, and collecting the fraction at 48-53 ℃ to obtain the perfluoro-2-methyl-2, 3-pentane with the yield of 87% and the purity of 92%.
Preparation example 4:
100g of perfluoro-4-methyl-2-pentene, 30mL of acetonitrile, 1.47g of 15-crown-5 and 0.7g of sodium fluoride were added to the reaction vessel A, and the mixture was stirred at 40℃for 6 hours and cooled to room temperature. Simultaneously, 69.02g of m-chloroperoxybenzoic acid and 50mL of acetonitrile are added into a reaction bottle B, 40.48g of triethylamine is added dropwise under stirring, the stirring is carried out for a while, and the temperature is reduced to 5 ℃. And (3) dropwise adding the solution in the reaction bottle A into the reaction bottle B, reacting for 3 hours at 20 ℃, standing for layering, distilling, and collecting the fraction at 48-53 ℃ to obtain the perfluoro-2-methyl-2, 3-pentane with the yield of 88% and the purity of 91%.
Preparation example 5:
100g of perfluoro-4-methyl-2-pentene, 30mL of acetonitrile, 1.76g of 18-crown-6 and 0.9g of powdery potassium fluoride were added to the reaction vessel A, and the mixture was stirred at 40℃for 6 hours and cooled to room temperature. Simultaneously, 69.02g of m-chloroperoxybenzoic acid and 50mL of acetonitrile are added into a reaction bottle B, 60.9g of DBU (1, 8-diazabicyclo undec-7-ene) is dropwise added under stirring, the stirring is carried out for a while, and the temperature is reduced to 5 ℃. And (3) dropwise adding the solution in the reaction bottle A into the reaction bottle B, reacting for 3 hours at 20 ℃, standing for layering, distilling, and collecting the fraction at 48-53 ℃ to obtain the perfluoro-2-methyl-2, 3-pentane with the yield of 83% and the purity of 92%.
Preparation examples 6 to 11:
it uses substantially the same preparation conditions as in preparation example 1, except that the phase transfer catalyst is different (i.e., the phase transfer catalyst in example 1 is replaced with an equimolar amount of other phase transfer catalyst), and specific reaction conditions and results are shown in table 1 below.
TABLE 1
Comparative example 1
The same preparation conditions as in preparation example 1 were used, except that the peroxide oxidizing agent was replaced with an equimolar amount of NaClO to obtain perfluoro-2-methyl-2, 3-pentalene oxide in a yield of 78% and a purity of 90%.
Comparative example 2
The same preparation conditions as in preparation example 1 were adopted except that the peroxide oxidizing agent was replaced with an equimolar amount of NaClO and no organic base was added to obtain perfluoro-2-methyl-2, 3-epoxypentane in a yield of 83% and a purity of 89%.
The isomerization and synthesis of the perfluoro-hexanone are carried out according to the following steps:
example 1:
to 30mL of acetonitrile was added, in order, 100g of perfluoro-2-methyl-2, 3-epoxypentane obtained in preparation example 1 and 1.6g of triethylamine. Reacting for 12h at 20 ℃, stopping stirring, layering, rectifying, and collecting the fraction at 47-51 ℃ to obtain the perfluorinated hexanone with the yield of 96% and the purity of 99%.
Example 2:
to 30mL of DMF was added, in order, 100g of perfluoro-2-methyl-2, 3-epoxypentane obtained in preparation 1 and 1.6g of triethylamine. Reacting at 20 ℃ for 8 hours, stopping stirring, layering, rectifying, and collecting fractions at 47-51 ℃ to obtain the perfluorinated hexanone with the yield of 90% and the purity of 99%.
Example 3:
to 30mL of acetonitrile was added, in order, 100g of perfluoro-2-methyl-2, 3-epoxypentane obtained in preparation example 1 and 1.6g of triethylamine. Reacting at 40 ℃ for 5 hours, stopping stirring, layering, rectifying, and collecting fractions at 47-51 ℃ to obtain the perfluorinated hexanone with the yield of 87% and the purity of 98%.
Example 4:
to 30mL of DMF was added, in order, 100g of perfluoro-2-methyl-2, 3-epoxypentane obtained in preparation 1 and 2.1g of N, N-dimethylbenzylamine. Reacting at 20 ℃ for 14 hours, stopping stirring, layering, rectifying, and collecting fractions at 47-51 ℃ to obtain the perfluorinated hexanone with the yield of 91% and the purity of 96%.
Example 5:
to 30mL of acetonitrile was added, in order, 100g of perfluoro-2-methyl-2, 3-epoxypentane obtained in preparation example 1 and 2.9g of tributylamine. Reacting at 40 ℃ for 5 hours, stopping stirring, layering, rectifying, and collecting fractions at 47-51 ℃ to obtain the perfluorinated hexanone with the yield of 88% and the purity of 96%.
Examples 6 to 13:
substantially the same preparation conditions as in example 3 were employed, except that the organic base was different (i.e., the organic base in example 3 was replaced with an equimolar amount of other organic base), and specific reaction conditions and results are shown in Table 2 below.
TABLE 2
Examples 14 to 16:
substantially the same preparation conditions as in example 3 were employed, except that the polar aprotic solvent was different, and the specific reaction conditions and results are shown in table 3 below.
TABLE 3 Table 3
Implementation of the embodimentsExample(s) Polar aprotic solvents Yield of perfluoro hexanone% Perfluor hexanone purity%
Example 14 Dimethyl sulfoxide 85％ 97％
Example 15 DMF 90％ 95％
Example 16 Diethylene glycol dimethyl ether 86％ 99％
Comparative example 3
The same preparation conditions as in example 1 were employed, except that the reaction time was 15min and the reaction temperature was 50℃to obtain perfluorohexanone in 85% yield and 72% purity.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.

Claims (10)

1. The preparation method of the perfluorinated hexanone is characterized by comprising the following steps of:
1) The perfluoro-4-methyl-2-pentene is subjected to in-situ rearrangement and epoxidation reaction to obtain perfluoro-2-methyl-2, 3-epoxypentane;
2) And carrying out isomerization reaction on the perfluoro-2-methyl-2, 3-epoxypentane to generate the perfluoro-hexanone.
2. The method for preparing perfluorinated hexanone according to claim 1, wherein:
step 1) comprises:
1.1 Perfluoro-4-methyl-2-pentene as a raw material, fluoride salt as a catalyst and a phase transfer catalyst as a cocatalyst in a polar aprotic solvent to obtain a mixed solution A;
1.2 Taking peroxide as an oxidant and taking a polar aprotic solvent as a solvent, dropwise adding organic alkali under the stirring condition, uniformly mixing, and cooling to obtain a mixed solution B;
1.3 Dropwise adding the mixed solution A into the mixed solution B, and obtaining perfluoro-2-methyl-2, 3-epoxypentane after the reaction is finished.
3. A process for the preparation of perfluoro hexanone according to claim 2, characterized in that:
in the step 1.1) of the process,
the fluoride salt is at least one selected from sodium fluoride, potassium fluoride, lithium fluoride, cesium fluoride and aluminum fluoride; and/or the number of the groups of groups,
the phase transfer catalyst is at least one selected from 18-crown ether-6, 15-crown ether-5, dibenzo-18-crown ether-6, dicyclohexyl-18-crown ether-6, hole ether, acetone furan crown ether and polyethylene glycol; preferably, the molecular weight of the polyethylene glycol is 400-4000; it is further preferred that the polyethylene glycol is at least one selected from the group consisting of PEG-400, PEG-600, PEG-800, PEG-1000, and PEG-4000; and/or the number of the groups of groups,
the polar aprotic solvent in step 1.1) is at least one selected from acetonitrile, benzyl cyanide, dimethyl sulfoxide, DMF and diethylene glycol dimethyl ether.
4. A process for the preparation of perfluoro hexanone according to claim 2, characterized in that:
the molar ratio of the fluoride salt to the perfluoro-4-methyl-2-pentene is 0.02-0.3:1; and/or the number of the groups of groups,
the molar ratio of the phase transfer catalyst to the fluoride salt is 0.2-5.0:1; and/or the number of the groups of groups,
the molar volume ratio of the perfluoro-4-methyl-2-pentene to the polar aprotic solvent is 1:0.1 mol-10 mL; and/or the number of the groups of groups,
the reaction temperature is 30-50 ℃; and/or the number of the groups of groups,
the reaction time is 6-20 h.
5. A process for the preparation of perfluoro hexanone according to claim 2, characterized in that:
in the step 1.2) of the process,
the organic base is at least one of triethylamine, trimethylamine, tributylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylmorpholine, pyridine, quinoline and 1, 8-diazabicyclo [5.4.0] undec-7-ene;
the oxidant is at least one selected from m-chloroperoxybenzoic acid, peracetic acid, peroxybenzoic acid, trifluoroacetic acid peracid and phthaloyl peroxide; and/or the number of the groups of groups,
the polar aprotic solvents in step 1.2) are each independently selected from at least one of acetonitrile, phenylacetonitrile, dimethyl sulfoxide, DMF, diethylene glycol dimethyl ether.
6. A process for the preparation of perfluoro hexanone according to claim 2, characterized in that:
in the step 1.2) of the process,
the molar ratio of the oxidant to the perfluoro-4-methyl-2-pentene is 1.05-5.0:1; and/or the number of the groups of groups,
the molar ratio of the organic base to the perfluoro-4-methyl-2-pentene is 1.05-5.0:1; and/or the number of the groups of groups,
the molar volume ratio of the perfluoro-4-methyl-2-pentene to the polar aprotic solvent is 1:0.1-10; and/or the number of the groups of groups,
cooling to 0-10 ℃.
7. A process for the preparation of perfluoro hexanone according to claim 2, characterized in that:
in the step 1.3) of the process,
the reaction temperature is-5-50 ℃; preferably 20-40 ℃; and/or the number of the groups of groups,
the reaction time is 0.5-10 h; preferably 2 to 5 hours; and/or the number of the groups of groups,
after the reaction is finished, standing for layering, distilling, and collecting fractions to obtain the purified perfluoro-2-methyl-2, 3-epoxypentane.
8. A process for preparing perfluorinated hexanone according to claim 1, wherein,
the step 2) comprises the following steps:
the perfluoro-2-methyl-2, 3-epoxypentane is used as a raw material, a polar aprotic solvent is used as a solvent, an organic base is used as a catalyst, and liquid phase isomerization reaction is carried out to obtain the perfluoro-hexanone after the reaction is finished.
9. A process for preparing perfluorohexanone according to claim 8,
in the step 2) of the process, the process is carried out,
the polar aprotic solvent is at least one selected from acetonitrile, dimethyl sulfoxide, DMF and diethylene glycol dimethyl ether; and/or the number of the groups of groups,
the organic base is at least one selected from triethylamine, trimethylamine, tributylamine, N-dimethylbenzylamine, N-diethylbenzylamine, N-methylmorpholine, pyridine, quinoline and 1, 8-diazabicyclo [5.4.0] undec-7-ene.
10. A process for preparing perfluorohexanone according to claim 9,
the molar ratio of the organic base to the perfluoro-2-methyl-2, 3-epoxypentane is 0.02-0.3:1; and/or the number of the groups of groups,
the volume ratio of the polar aprotic solvent to the perfluoro-2-methyl-2, 3-epoxypentane is 0.1-10:1; and/or the number of the groups of groups,
the reaction temperature is 0-52 ℃; preferably 20 to 40 ℃; and/or the number of the groups of groups,
the reaction time is 2-18 hours; preferably 5 to 14 hours;
and after the reaction is finished, layering and distilling to obtain the purified perfluorinated hexanone.
CN202310501900.3A 2023-05-06 2023-05-06 Preparation method and application of perfluoro-hexanone Pending CN116514642A (en)

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