Preparation method of fluorinated cyclic ether

Abstract

The present invention relates to a method for preparing a fluorinated cyclic ether, comprising the following steps: subjecting a compound (1) and a compound (2) to a first substitution reaction to prepare a compound (3); subjecting the compound (3) and a fluoride to a second substitution reaction to prepare a fluorinated cyclic ether represented by formula (4). The structures of the compound (1), the compound (2), the compound (3) and the fluorinated cyclic ether represented by formula (4) are as follows: The method for preparing a fluorinated cyclic ether has a high yield and the raw materials are easily available.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing a fluorinated cyclic ether. Background Art

[0002] Fluorinated cyclic ethers are a type of commonly used industrial products with a wide range of applications. They can be used as reaction solvents, in the preparation of electrolytes, as cleaning agents in the electronics industry, and can also be used in the preparation of resins, etc.

[0003] Traditional methods for preparing fluorinated cyclic ethers mainly include thermal decomposition, which involves thermally decomposing a fluorinated substrate to obtain a fluorinated unsaturated cyclic ether, which is then reduced to obtain a fluorinated saturated cyclic ether. However, the fluorinated substrate used in this method is not easy to obtain, the cost is high, and the yield is low.

[0004] Therefore, the traditional technology still needs to be improved. Summary of the invention

[0005] Based on this, it is necessary to provide a method for preparing fluorinated cyclic ethers, which has a high yield and readily available raw materials.

[0006] The present application is implemented through the following technical solutions.

[0007] In a first aspect of the present application, a method for preparing a fluorinated cyclic ether is provided, comprising the following steps:

[0008] subjecting compound (1) to a first substitution reaction with compound (2) to prepare compound (3);

[0009] The compound (3) is subjected to a second substitution reaction with a fluoride to prepare a fluorinated cyclic ether represented by formula (4);

[0010] The structures of the compound (1), the compound (2), the compound (3) and the fluorinated cyclic ether represented by the formula (4) are as follows:

[0011]

[0012] in, represents a cycloalkyl ether group or a cycloalkenyl ether group having T ring atoms, wherein the ring atoms contain H1 oxygen atoms and H2 carbon atoms, wherein the H2 carbon atoms form H3 olefinic bonds; each occurrence of R1 is independently selected from any one of H, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 15 carbon atoms, and a nitro group;

[0013] T, H1, H2, H3, n1 and n2 are all integers and satisfy: 5≤T≤8, T=H1+H2,

[0014] H1≥1, H2≥3, H3≥0, n1+n2=2(H2-H3), and n2≥1;

[0015] Each occurrence of R2 is independently selected from any one of an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 15 carbon atoms.

[0016] In the preparation method of the fluorinated cyclic ether of the present application, the compound (1) and the compound (2) are first subjected to a first substitution reaction, and then the obtained compound (3) and a fluoride are subjected to a second substitution reaction to prepare the fluorinated cyclic ether represented by formula (4). The raw materials are easily available and the yield is high.

[0017] In some embodiments, the compound (1) In the formula (a), the number n3 of hydroxyl groups connected to any carbon atom in the ring atoms satisfies: n3≤1, and n3 is an integer.

[0018] The applicant's research found that: control In the step, the number of hydroxyl groups connected to the same carbon atom in the ring atom n3≤1, that is, the same carbon atom has only one reaction site when undergoing the first substitution reaction, which can avoid competition caused by multiple reaction sites on the same carbon atom and further improve the yield.

[0019] In some of these embodiments, 1≤H1≤(T-2);

[0020] Optionally, H1 is 1 or 2;

[0021] Optionally, H1 is 1.

[0022] In some embodiments, H1≥2, and at least one carbon atom is arranged between any two oxygen atoms in the ring atoms.

[0023] In some of these embodiments, 3≤H2≤(T-1);

[0024] Optionally, H2 = (T-1);

[0025] Optionally, H2 is 4.

[0026] In some embodiments, H3 satisfies: 0≤H3≤(T-H1) / 2;

[0027] Optionally, H3 is 0 or 1;

[0028] Optionally, H3 is 0.

[0029] In some embodiments, T is 5 or 6;

[0030] Optionally, T is 5.

[0031] In some embodiments, said n2 is 1 or 2;

[0032] Optionally, n2 is 1.

[0033] In some embodiments, each occurrence of R1 is independently selected from H or an alkyl group having 1 to 8 carbon atoms;

[0034] Optionally, each occurrence of R1 is independently selected from H or a chain alkyl group having 1 to 5 carbon atoms;

[0035] Optionally, each occurrence of R1 is independently selected from any one of H, methyl, ethyl, propyl and butyl.

[0036] The applicant has found that in compound (1), the smaller the volume of the substituent is, the smaller the reaction steric hindrance is, which can further improve the efficiency of the first substitution reaction.

[0037] In some embodiments, each occurrence of R2 is independently selected from any one of a chain alkyl group having 1 to 4 carbon atoms, and a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms;

[0038] Optionally, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms, and an aromatic group having 6 to 8 carbon atoms which is unsubstituted or substituted by an alkyl group;

[0039] Optionally, each occurrence of R2 is independently selected from any one of methyl, ethyl and tolyl;

[0040] Optionally, compound (2) comprises at least one of methanesulfonyl chloride and p-toluenesulfonyl chloride.

[0041] In some embodiments, the compound (1) is any one of formulas (1-1) to (1-3):

[0042]

[0043] In some embodiments, the second substitution reaction is carried out under the action of a catalyst, wherein the catalyst comprises Cu 2+ 、Na + , K + 、Zn 2+ At least one ion in

[0044] Optionally, the catalyst includes at least one of copper iodide, sodium iodide, potassium iodide, zinc iodide, copper bromide, sodium bromide, potassium bromide and zinc bromide;

[0045] Optionally, the molar ratio of the catalyst to the compound (3) is (0.001-0.1):1.

[0046] The applicant further discovered through research that under the catalytic action of a specific type of catalyst, the activation energy of the second substitution reaction can be greatly reduced, the reaction efficiency can be improved, and thus the yield can be improved.

[0047] In some embodiments, the second substitution reaction satisfies at least one of the following conditions (1) to (4):

[0048] (1) The temperature of the second substitution reaction is 0°C to 220°C, and the time is 0.5h to 10h;

[0049] Optionally, the temperature of the second substitution reaction is 30°C to 160°C, and the time is 1h to 6h;

[0050] The temperature of the second substitution reaction is further regulated to avoid the occurrence of side reactions while maintaining a high reaction activity.

[0051] (2) The molar ratio of the compound (3) to the fluoride is 1:(1-20);

[0052] (3) The fluoride includes a fluorine-containing salt compound;

[0053] Optionally, the fluoride includes at least one of lithium fluoride, sodium fluoride, potassium fluoride, antimony trifluoride, pyridine hydrofluoride and triethylamine trihydrofluoride;

[0054] The feed ratio of the substrate is further regulated to further improve the yield.

[0055] (4) the second substitution reaction is carried out in an organic solvent A;

[0056] Optionally, the organic solvent A includes at least one of N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol, diethylene glycol and sulfolane;

[0057] Optionally, the mass ratio of the organic solvent A to the compound (3) is (1-20):1.

[0058] In some embodiments, the process for preparing the fluorinated cyclic ether represented by formula (4) further comprises the following steps:

[0059] The product of the second substitution reaction is subjected to distillation treatment to prepare the fluorinated cyclic ether represented by the formula (4).

[0060] The purity of the obtained product can be improved by post-treatment.

[0061] In some embodiments, the first substitution reaction satisfies at least one of the following conditions (5) to (8):

[0062] (5) The temperature of the first substitution reaction is -20°C to 120°C, and the time is 0.5h to 10h;

[0063] Optionally, the temperature of the first substitution reaction is 0°C to 80°C, and the time is 2h to 7h;

[0064] The temperature of the first substitution reaction is further regulated to avoid side reactions while maintaining a high reaction activity, thereby improving the yield and purity and further ensuring the yield of subsequent steps.

[0065] (6) The molar ratio of the compound (1) to the compound (2) is 1:(1-10);

[0066] The feed ratio of the substrate is further regulated to further improve the yield.

[0067] (7) The first substitution reaction is carried out under the action of a basic compound:

[0068] Optionally, the basic compound includes at least one of an organic basic compound and an inorganic basic compound;

[0069] Optionally, the alkaline compound includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, piperidine and quinoline;

[0070] Optionally, the molar ratio of the compound (1) to the basic compound is 1:(1-10);

[0071] (8) The first substitution reaction is carried out in an organic solvent B;

[0072] Optionally, the organic solvent B includes at least one of acetonitrile, tetrahydrofuran, dichloromethane, dioxane, N,N-dimethylformamide and dimethyl sulfoxide;

[0073] Optionally, the mass ratio of the organic solvent B to the compound (1) is (1-20):1.

[0074] In some embodiments, the first substitution reaction is carried out in the organic solvent B, and the process for preparing the compound (3) further comprises the following steps:

[0075] The product of the first substitution reaction is washed with water and then an organic phase is taken;

[0076] The solvent B in the organic phase is removed to prepare the compound (3).

[0077] The purity of the obtained compound (3) is improved by post-treatment, thereby preventing impurities from having a negative impact on subsequent reactions. DETAILED DESCRIPTION

[0078] In order to make the above-mentioned purpose, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0079] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0080] In addition, the terms "first", "second", "A", "B" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number or type of the indicated technical features. Therefore, the features defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0081] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0082] In the present application, the term "alkyl" refers to a group formed when an alkane loses a hydrogen, such as methane losing a hydrogen to form a methyl group.

[0083] The term "chain alkyl" refers to a group formed by losing one hydrogen in an alkane in which the carbon atoms are connected by single carbon-carbon bonds and do not form a ring, and the remaining valence bonds are bonded to hydrogen, including straight-chain alkyl and branched-chain alkyl.

[0084] In the present application, the number of carbon atoms of "alkyl" can be 1 to 8, i.e., including 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms, and refers to a group formed after an alkane containing 1 to 8 carbon atoms (i.e., C1 to C8 alkane) loses one hydrogen. Non-limiting examples of "C1 to C8 alkane" include methane, ethane, n-propane, isopropane, n-butane, isobutane, 2-ethylbutane, 3,3-dimethylbutane, and n-pentane. In other words, non-limiting examples of "C1 to C8 alkane group" include groups formed after the above alkanes lose one hydrogen.

[0085] In the present invention, the "number of ring atoms" means the number of atoms bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of cyclohexane is 6, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of thiophene is 5.

[0086] In the present application, the single bond to which the substituent is attached runs through the corresponding ring, indicating that the substituent can be attached to any position of the ring, for example R is connected to any substitutable position of the cycloalkyl group.

[0087] In the present invention, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When substituted, if the attachment site of the substituent is not specified in the group, it means that the attachment site may be any attachable site on the substituted group.

[0088] An embodiment of the present application provides a method for preparing a fluorinated cyclic ether, comprising the following steps S10 to S20:

[0089] Step S10: Compound (1) and compound (2) undergo a first substitution reaction to prepare compound (3).

[0090] Step S20: subjecting the compound (3) to a second substitution reaction with a fluoride to prepare a fluorinated cyclic ether represented by formula (4).

[0091] The structures of the above compound (1), the compound (2), the compound (3) and the fluorinated cyclic ether represented by formula (4) are as follows:

[0092]

[0093] in, represents a cycloalkyl ether group or a cycloalkenyl ether group having T ring atoms, the ring atoms containing H1 oxygen atoms, H2 carbon atoms, and the H2 carbon atoms forming H3 olefinic bonds; each occurrence of R1 is independently selected from any one of H, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 15 carbon atoms, and a nitro group;

[0094] T, H1, H2, H3, n1 and n2 are all integers and satisfy: 5≤T≤8, T=H1+H2,

[0095] H1≥1, H2≥3, H3≥0, n1+n2=2(H2-H3), and n2≥1;

[0096] Each occurrence of R2 is independently selected from any one of an alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, and a substituted or unsubstituted heteroaromatic group having 5 to 15 carbon atoms.

[0097] It should be noted that when H3 is 0, it means The H2 carbon atoms in the ring atoms are connected by single bonds, that is represents a cycloalkyl ether group having T as the number of ring atoms.

[0098] In the preparation method of the fluorinated cyclic ether of the present application, the compound (1) and the compound (2) are first subjected to a first substitution reaction, and then the obtained compound (3) and a fluoride are subjected to a second substitution reaction to prepare the fluorinated cyclic ether represented by formula (4). The raw materials are easily available and the yield is high.

[0099] In some embodiments, compound (1) In the formula (a), the number n3 of hydroxyl groups connected to any carbon atom in the ring atoms satisfies: n3≤1, and n3 is an integer.

[0100] The applicant's research found that: control In the embodiment, the number of hydroxyl groups connected to the same carbon atom in the ring atom n3≤1, that is, when the first substitution reaction is carried out, there is only one reaction site on the same carbon atom, which can avoid competition caused by multiple reaction sites on the same carbon atom and further improve the yield.

[0101] It can be understood that, since n2≥1, the number of hydroxyl groups connected to at least one carbon atom in the ring atoms is 1.

[0102] Optionally, the number of hydroxyl groups connected to at least two carbon atoms in the ring atoms is 1; further optionally, the number of hydroxyl groups connected to at least three carbon atoms in the ring atoms is 1.

[0103] In some of these embodiments, 1≤H1≤(T-2).

[0104] In some of these embodiments, 1≤H1≤(T-3).

[0105] In some of these embodiments, 1≤H1≤(T-4).

[0106] In some of these embodiments, H1 is 1 or 2.

[0107] In some of these embodiments, H1 is 1.

[0108] In some embodiments, H1≥2, and any two oxygen atoms in the ring atoms are separated by at least one carbon atom.

[0109] In other words, when there are multiple oxygen atoms in the ring atoms, there is at least one carbon between any two oxygen atoms, that is, any two oxygen atoms are not directly connected.

[0110] In some of these embodiments, 3≤H2≤(T-1).

[0111] In some of these embodiments, (T-2)≤H2≤(T-1).

[0112] In some of these embodiments, H2=(T-1).

[0113] In some of these embodiments, H2 is 4.

[0114] In some of these embodiments, H3 satisfies: 0≤H3≤(T-H1) / 2.

[0115] It can be understood that an olefinic bond requires two carbon atoms to form, so H3≤(T-H1) / 2.

[0116] In some embodiments, when H3≥2, at least one single bond is arranged between any two olefinic bonds.

[0117] Optionally, H3 is 0 or 1;

[0118] Optionally, H3 is 0.

[0119] In some of these embodiments, T is 5 or 6.

[0120] In some of these embodiments, T is 5.

[0121] In some embodiments, n2 is any integer from 1 to 5, such as 1, 2, 3, 4 or 5.

[0122] In some embodiments, n2 is any integer from 1 to 4.

[0123] In some embodiments, n2 is any integer from 1 to 3.

[0124] In some embodiments, n2 is 1 or 2.

[0125] In some of these embodiments, n2 is 1.

[0126] In some embodiments, each occurrence of R1 is independently selected from H or an alkyl group having 1 to 8 carbon atoms.

[0127] In some embodiments, each occurrence of R1 is independently selected from H or an alkyl radical having 1 to 5 carbon atoms.

[0128] In some embodiments, each occurrence of R1 is independently selected from H or a linear alkyl group having 1 to 5 carbon atoms.

[0129] In some embodiments, each occurrence of R1 is independently selected from H or a linear alkyl group having 1 to 4 carbon atoms.

[0130] In some embodiments, each occurrence of R1 is independently selected from any one of H, methyl, ethyl, propyl and butyl.

[0131] The applicant has found that in compound (1), the smaller the volume of the substituent is, the smaller the reaction steric hindrance is, which can further improve the efficiency of the first substitution reaction.

[0132] Furthermore, the other substituent on the carbon atom connected to the hydroxyl group is H, that is, the R1 connected to the carbon atom connected to the hydroxyl group is H. The reaction steric hindrance can be further reduced.

[0133] In some embodiments, each occurrence of R2 is independently selected from any one of a chain alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.

[0134] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms, and an aromatic group having 6 to 8 carbon atoms which is unsubstituted or substituted with an alkyl group.

[0135] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms, and an aromatic group having 6 to 8 carbon atoms which is unsubstituted or substituted with a linear alkyl group having 1 to 3 carbon atoms.

[0136] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms, and an aromatic group having 6 to 8 carbon atoms which is unsubstituted or substituted with a linear alkyl group having 1 to 2 carbon atoms.

[0137] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms, and a phenyl group which is unsubstituted or substituted with a linear alkyl group having 1 to 2 carbon atoms.

[0138] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 3 carbon atoms, and a phenyl group which is unsubstituted or substituted with a linear alkyl group having 1 to 2 carbon atoms.

[0139] In some embodiments, each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 2 carbon atoms, and a phenyl group which is unsubstituted or substituted with a linear alkyl group having 1 to 2 carbon atoms.

[0140] In some embodiments, each occurrence of R2 is independently selected from any one of methyl, ethyl and tolyl;

[0141] In some embodiments, compound (2) comprises at least one of methanesulfonyl chloride and p-toluenesulfonyl chloride.

[0142] In some embodiments, compound (1) is any one of formulas (1-1) to (1-3):

[0143]

[0144] In some embodiments, compound (1) is any one of the following:

[0145]

[0146] In some embodiments, the temperature of the first substitution reaction in step S10 is -20°C to 120°C, and the time is 0.5h to 10h.

[0147] In some embodiments, the temperature of the first substitution reaction in step S10 is 0° C. to 80° C., and the time is 2 h to 7 h.

[0148] By further regulating the temperature of the first substitution reaction, the side reactions can be avoided while maintaining a high reaction activity, thereby improving the yield and purity, thereby further ensuring the yield of subsequent steps.

[0149] In the above-mentioned "-20℃~120℃", the temperature value includes the minimum and maximum values ​​of the range, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: -20℃, -15℃, -10℃, -5℃, 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 115℃, 120℃; or a range consisting of any two values, for example, it can be: -20℃~115℃, -20℃~110℃, -20℃~100℃ ℃、-20℃~95℃、-20℃~90℃、-20℃~85℃、-20℃~80℃、-20℃~75℃、-20℃~70℃、-15℃~115℃、-15℃~110℃、-15℃~100℃、-15℃~95℃、-15℃~90℃、-15℃~85℃、-15℃~80℃、-15℃~75℃、-15℃~70℃、-5℃~120℃、-5℃~115℃、-5℃~110℃、-5℃~100℃、-5℃~95℃、-5℃~90℃、-5℃~85℃、-5℃~80℃、-5℃~75℃、-5℃~70℃、0℃~120℃、0℃~1 15℃、0℃~110℃、0℃~100℃、0℃~95℃、0℃~90℃、0℃~85℃、0℃~80℃、0℃~75℃、0℃~70℃、5℃~120℃、5℃~115℃、5℃~110℃、5℃~100℃、5℃~95℃、5℃~90℃、5℃~85℃、5℃~80℃、5℃~75℃、5℃~70℃、10℃~120℃、10℃~115℃、10℃~110℃、10℃~100℃、10℃~95℃、10℃~90℃、10℃~85℃、10℃~80℃、10℃~75℃、10℃~70℃、20℃~120℃、20℃~115 ℃, 20℃~110℃, 20℃~100℃, 20℃~95℃, 20℃~90℃, 20℃~85℃, 20℃~80℃, 20℃~75℃, 20℃~70℃, 25℃~120℃, 25℃~115℃, 25℃~110℃, 25℃~100℃, 25℃~95℃, 25℃~90℃, 25℃~85℃, 25℃~80℃, 25℃~75℃, 25℃~70℃, 35℃~120℃, 35℃~115℃, 35℃~110℃, 35℃~100℃, 35℃~95℃, 35℃~90℃, 35℃~85℃, 35℃~80℃, 35℃~75℃, 35℃~70℃.

[0150] In some embodiments, the molar ratio of compound (1) to compound (2) is 1:(1-10).

[0151] By further regulating the feed ratio of the first substitution reaction, the side reactions can be avoided while maintaining a high reaction efficiency, thereby improving the yield and purity.

[0152] In the above "1: (1-10)", the molar ratio includes the minimum and maximum values ​​of the range, and each value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.10, 1:3.11, 1:3.12, 1:3.13, 1:3.14, 1:3.15, 1:3.16, 1:3.17, 1:3.18, 1:3.19, 1:3.2 2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9 , 1:5, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7 or a range consisting of any two values.

[0153] In some embodiments, the first substitution reaction is performed under the action of a basic compound.

[0154] The reaction sites in the first substitution reaction are the acyl chloride group and the hydroxyl group, which first form the corresponding ester and then are removed to release hydrogen chloride. During the reaction, an alkaline compound is added to neutralize the hydrogen chloride, that is, as an acid-binding agent, which can accelerate the reaction and improve the reaction efficiency.

[0155] In some embodiments, the basic compound includes at least one of an organic basic compound and an inorganic basic compound.

[0156] In some embodiments, the basic compound includes at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, piperidine and quinoline.

[0157] In some embodiments, the molar ratio of compound (1) to the basic compound is 1:(1-10).

[0158] In the above "1: (1-10)", the molar ratio includes the minimum and maximum values ​​of the range, and each value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.10, 1:3.11, 1:3.12, 1:3.13, 1:3.14, 1:3.15, 1:3.16, 1:3.17, 1:3.18, 1:3.19, 1:3.2 2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9 , 1:5, 1:5.1, 1:5.2, 1:5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7 or a range consisting of any two values.

[0159] Further adjusting the ratio of compound (1) to the basic compound can further avoid the occurrence of side reactions.

[0160] In some embodiments, the first substitution reaction is carried out in an organic solvent B.

[0161] In some embodiments, the organic solvent B includes at least one of acetonitrile, tetrahydrofuran, dichloromethane, dioxane, N,N-dimethylformamide and dimethyl sulfoxide.

[0162] In some of the embodiments, the mass ratio of the organic solvent B to the compound (1) is (1-20):1.

[0163] In the above “(1-20): 1”, the mass ratio includes the minimum and maximum values ​​of the range, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1; or a range consisting of any two values.

[0164] In some embodiments, in step S10, the first substitution reaction is carried out in an organic solvent B, and the process for preparing the compound (3) further comprises the following steps:

[0165] The product of the first substitution reaction is washed with water and then an organic phase is taken;

[0166] The solvent B in the organic phase is removed to prepare the compound (3).

[0167] The purity of the obtained compound (3) is improved by post-treatment, thereby preventing impurities from having a negative impact on subsequent reactions.

[0168] In some embodiments, before the step of removing the solvent B in the organic phase, the step of using a dehydrating agent to dehydrate the organic phase is also included to remove the water mixed in the organic phase. Further, after the dehydrating treatment, filtration is performed to obtain the filtered organic phase.

[0169] The dehydrating agent may be any dehydrating agent commonly used in the art, including but not limited to: at least one of anhydrous magnesium chloride, anhydrous calcium chloride, anhydrous magnesium sulfate and anhydrous sodium sulfate.

[0170] In the step of removing the solvent B in the organic phase, the commonly used methods for removing the solvent in the art may be adopted, including but not limited to direct evaporation, distillation, rotary evaporation, etc.

[0171] In some embodiments, the second substitution reaction is carried out under the action of a catalyst, the catalyst comprising Cu 2+ 、Na + , K + 、Zn 2+ At least one ion in the

[0172] The applicant further discovered through research that under the catalytic action of a specific type of catalyst, the activation energy of the second substitution reaction can be greatly reduced, the reaction efficiency can be improved, and thus the yield can be improved.

[0173] In some of the embodiments, the catalyst further contains halogen ions; optionally, at least one of iodide ions and bromide ions.

[0174] In some embodiments, the catalyst includes at least one of copper iodide, sodium iodide, potassium iodide, zinc iodide, copper bromide, sodium bromide, potassium bromide and zinc bromide.

[0175] In some of the embodiments, the molar ratio of the catalyst to the compound (3) is (0.001-0.1):1.

[0176] Further adjusting the ratio of the catalyst to the compound (3) can further avoid the occurrence of side reactions.

[0177] In the above “(0.001~0.1):1”, the molar ratio includes the minimum and maximum values ​​of the range, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 0.001:1, 0.002:1, 0.003:1, 0.004:1, 0.005:1, 0.006:1, 0.007:1, 0.008:1, 0.009:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1; or a range consisting of any two values.

[0178] In some embodiments, the temperature of the second substitution reaction in step S20 is 0° C. to 220° C., and the time is 0.5 h to 10 h;.

[0179] In some embodiments, the second substitution reaction is carried out at a temperature of 30° C. to 160° C. and for a time of 1 h to 6 h.

[0180] The temperature of the second substitution reaction is further regulated to avoid the occurrence of side reactions while maintaining a high reaction activity.

[0181] In the above “0°C~220°C”, the temperature value includes the minimum and maximum values ​​of the range, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C, 220°C;Or a range consisting of any two numerical values, for example, it can be: 0℃~215℃, 0℃~210℃, 0℃~190℃, 0℃~180℃, 0℃~170℃, 0℃~160℃, 0℃~150℃, 0℃~140℃, 0℃~130℃, 0℃~120℃, 0℃~115℃, 0℃~110℃, 0℃~100℃, 0℃~95℃, 0℃~90℃, 0℃~85℃, 0℃~80℃, 0℃~75℃, 0℃~70℃, 5℃~215℃, 5℃~210℃, 5℃~190℃, 5℃~180℃, 5℃~150℃, 0℃~140℃, 0℃~130℃, 0℃~120℃, ~170℃、5℃~160℃、5℃~150℃、5℃~140℃、5℃~130℃、5℃~120℃、5℃~115℃、5℃~110℃、5℃~100℃、5℃~95℃、5℃~90℃、5℃~85℃、5℃~80℃、5℃~75℃、5℃~70℃、10℃~215℃、10℃~210℃、10℃~190℃、10℃~180℃、10℃~170℃、10℃~160℃、10℃~150℃、10℃~140℃、10℃~130℃、10℃~120 ℃、10℃~115℃、10℃~110℃、10℃~100℃、10℃~95℃、10℃~90℃、10℃~85℃、10℃~80℃、10℃~75℃、10℃~70℃、20℃~160℃、20℃~150℃、20℃~140℃、20℃~130℃、20℃~120℃、20℃~115℃、20℃~110℃、20℃~100℃、20℃~95℃、20℃~90℃、20℃~85℃、20℃~80℃、20℃~75℃、20℃~70℃、25℃ ~120℃、25℃~115℃、25℃~110℃、25℃~100℃、25℃~95℃、25℃~90℃、25℃~85℃、25℃~80℃、25℃~75℃、25℃~70℃、35℃~160℃、35℃~150℃、35℃~140℃、35℃~130℃、35℃~120℃、35℃~115℃、35℃~110℃、35℃~100℃、35℃~95℃、35℃~90℃、35℃~85℃、35℃~80℃、35℃~75℃、35℃~70℃. ;

[0182] In some embodiments, the molar ratio of compound (3) to fluoride is 1:(1-20).

[0183] Further adjusting the ratio of compound (3) to fluoride can further avoid the occurrence of side reactions.

[0184] In the above "1: (1-20)", the molar ratio includes the minimum and maximum values ​​of the range, and each value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2 .5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5, 1:5.1, 1:5.2, 1:5.3, 1: 5.4, ​​1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, 1:6, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9, 1:7, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7.6, 1:7.7, 1:7.8, 1:7.9, 1:8, 1:8.1, 1:8.2, 1 or a range consisting of any two values.

[0185] In some embodiments, the fluoride includes a fluorine-containing salt compound.

[0186] In some embodiments, the fluoride includes at least one of lithium fluoride, sodium fluoride, potassium fluoride, antimony trifluoride, pyridine hydrofluoride and triethylamine trihydrofluoride.

[0187] In some embodiments, the second substitution reaction is carried out in organic solvent A.

[0188] Optionally, the organic solvent A comprises at least one of N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol, diethylene glycol and sulfolane,

[0189] Optionally, the mass ratio of organic solvent A to compound (3) is (1-20):1.

[0190] In the above “(1-20): 1”, the mass ratio includes the minimum and maximum values ​​of the range, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiments and the following point values: 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1; or a range consisting of any two values.

[0191] In some embodiments, the process for preparing the fluorinated cyclic ether represented by formula (4) further comprises the following steps:

[0192] The product of the second substitution reaction is subjected to distillation to prepare the fluorinated cyclic ether represented by formula (4).

[0193] The purity of the obtained product can be improved by post-treatment.

[0194] In some of the embodiments, during the preparation of the fluorinated cyclic ether represented by formula (4), during the second reaction, a distillation treatment can be simultaneously performed to separate the product, thereby further improving the yield.

[0195] In some embodiments, when the second reaction is carried out, a water separator can be connected to the reactor, and the product can be distilled out during the heating and reaction, and condensed in the water separator to separate the product, which can further improve the reaction efficiency.

[0196] The present invention will be described below in conjunction with specific embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should realize that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0197] The following are specific embodiments. Specific embodiments

[0199] Example 1

[0200] (1) Into a 1L four-necked flask, 150g of dichloromethane, 44.1g (0.5mol) of 2-hydroxytetrahydrofuran, and 33.6g (0.6mol) of potassium hydroxide were added, 114.4g (0.6mol) of p-toluenesulfonyl chloride was dissolved in 260g of dichloromethane, and then added dropwise to the flask at 20°C. After the addition was complete, the mixture was reacted at 20°C for 4h. The product was washed with water, the organic phase was dried with a dehydrating agent (anhydrous sodium sulfate) to remove water, and then the solvent was removed by rotary evaporation to obtain an intermediate product.

[0201] (2) 109.0 g (0.45 mol) of the intermediate product, 300 g of cyclopentane sulfone, 63 g (1.5 mol) of sodium fluoride, and 0.35 g (0.0018 mol) of catalyst copper iodide were placed in a 1 L four-necked flask and reacted at 150° C. for 5 h. The crude product was collected by a water separator and then subjected to vacuum distillation to obtain 31.3 g of 2-fluorotetrahydrofuran.

[0202] (3) The obtained 2-fluorotetrahydrofuran was subjected to gas chromatography analysis to test its purity, and the GC purity was measured to be: 99.3%;

[0203] The yield Y of the product (2-fluorotetrahydrofuran) in step (2) is calculated according to the following formula:

[0204] Y = the number of moles of the product (2-fluorotetrahydrofuran) in step (2) / the number of moles of the starting material (2-hydroxytetrahydrofuran) in step (1) × 100

[0205] Please see Table 1 for specific results.

[0206] Embodiments 2 to 4

[0207] Examples 2 to 4 are basically the same as Example 1, except that the type of catalyst in step (2) is different from that in Example 1. For details, please see Table 1.

[0208] The remaining steps are the same as those in Example 1.

[0209] Embodiments 5 to 7

[0210] Examples 5 to 7 are basically the same as Example 4, except that the catalyst feed ratio in step (2) is different from that in Example 4. Please see Table 1 for details.

[0211] The remaining steps are the same as those in Example 1.

[0212] Example 8

[0213] (1) Into a 1L four-necked flask, 150g of tetrahydrofuran, 51.0g (0.5mol) of 2-hydroxy-4-methyltetrahydrofuran, and 47.5g (0.6mol) of pyridine were added, 86.7g (0.75mol) of methylsulfonyl chloride was dissolved in 200g of tetrahydrofuran, and then added dropwise to the flask at 0°C. After the addition was complete, the mixture was reacted at 0°C for 4h, the product was washed with water, the organic phase was dried with a dehydrating agent (anhydrous sodium sulfate), and the solvent was removed by rotary evaporation to obtain an intermediate product.

[0214] (2) 107.5 g (0.42 mol) of the intermediate product, 300 g of diethylene glycol, 247.8 g (1.39 mol) of antimony trifluoride, and 2.9 g (0.013 mol) of zinc bromide catalyst were placed in a 1 L four-necked flask and reacted at 130° C. for 5 h. The crude product evaporated was collected using a water separator and then subjected to vacuum distillation to obtain 2-fluoro-4-methyltetrahydrofuran.

[0215] The remaining steps are the same as those in Example 1. Please see Table 1 for specific results.

[0216] Example 9

[0217] (1) Into a 1L four-necked flask, 150g of dichloromethane, 58.1g (0.5mol) of 3-hydroxy-4-ethyltetrahydrofuran, and 51.1g (0.6mol) of piperidine were added, 114.4g (0.6mol) of p-toluenesulfonyl chloride was dissolved in 260g of tetrahydrofuran, and then added dropwise to the flask at 20°C. After the addition was complete, the mixture was reacted at 20°C for 4h. The product was washed with water, the organic phase was dried with a dehydrating agent (anhydrous sodium sulfate) to remove water, and then the solvent was removed by rotary evaporation to obtain an intermediate product.

[0218] (2) 108.1 g (0.4 mol) of the intermediate product, 300 g of dimethyl sulfoxide, 161.2 g (1 mol) of triethylamine trihydrofluoride, and 2.7 g (0.012 mol) of zinc bromide catalyst were placed in a 1 L four-necked flask and reacted at 80° C. for 5 h. The crude product was collected by a water separator and then subjected to vacuum distillation to obtain 53.3 g of 3-fluoro-4-ethyltetrahydrofuran.

[0219] The remaining steps are the same as those in Example 1. Please see Table 1 for specific results.

[0220] Example 10

[0221] (1) Into a 1L four-necked flask, 150g of tetrahydrofuran, 51.0g (0.5mol) of 3-hydroxy-5-methyltetrahydrofuran, and 82.9g (0.6mol) of potassium carbonate were added, 85.9g (0.75mol) of methylsulfonyl chloride was dissolved in 200g of tetrahydrofuran, and then added dropwise to the flask at 0°C. After the addition was complete, the mixture was reacted at 0°C for 4h, the product was washed with water, the organic phase was dried with a dehydrating agent (anhydrous sodium sulfate), and the solvent was removed by rotary evaporation to obtain an intermediate product.

[0222] (2) 110.2 g (0.43 mol) of the intermediate product, 300 g of cyclopentane sulfone, 99.1 g (1 mol) of pyridine hydrofluoride, and 2.9 g (0.013 mol) of zinc bromide catalyst were placed in a 1 L four-necked flask and reacted at 90° C. for 5 h. The crude product was collected using a water separator and then subjected to vacuum distillation to obtain 45.9 g of 3-fluoro-5-methyltetrahydrofuran.

[0223] The remaining steps are the same as those in Example 1. Please see Table 1 for specific results.

[0224] Embodiment 11

[0225] (1) Into a 1L four-necked flask, 150g of dichloromethane, 58.1g (0.5mol) of 2-hydroxy-5-ethyltetrahydrofuran, and 60.7g (0.6mol) of triethylamine were added, 114.4g (0.6mol) of p-toluenesulfonyl chloride was dissolved in 260g of tetrahydrofuran, and then added dropwise to the flask at 20°C. After the addition was complete, the mixture was reacted at 20°C for 4h. The product was washed with water, the organic phase was dried with a dehydrating agent (anhydrous sodium sulfate) to remove water, and then the solvent was removed by rotary evaporation to obtain an intermediate product.

[0226] (2) 108.1 g (0.4 mol) of the intermediate product, 300 g of dimethyl sulfoxide, 38.9 g (1.5 mol) of lithium fluoride, and 2.7 g (0.012 mol) of zinc bromide catalyst were placed in a 1 L four-necked flask and reacted at 150° C. for 5 h. The crude product was collected using a water separator and then subjected to vacuum distillation to obtain 50.8 g of 2-fluoro-5-ethyltetrahydrofuran.

[0227] The remaining steps are the same as those in Example 1. Please see Table 1 for specific results.

[0228] Examples 12 to 17

[0229] Examples 12 to 17 are basically the same as Example 1, except that the solvent in step (1) or step (2) is replaced, the reaction temperature is controlled differently from that in Example 1, and the feed ratio in step (2) is adjusted. For specific variable parameters, see Table 1

[0230] The remaining steps are the same as those in Example 1.

[0231] Examples 18 to 27

[0232] Examples 18 to 27 are basically the same as Example 1, except that the feed ratio control in step (1) or step (2) is different from that in Example 1, and the remaining steps are the same as Example 1. For specific parameter results, see Table 1

[0233] Embodiment 28

[0234] Example 28 is basically the same as Example 1, except that in step (2) of Example 28, no catalyst copper iodide is added, and the remaining steps are the same as Example 1. Please see Table 1 for specific results.

[0235] The relevant physical parameters and test results in each embodiment and comparative example are shown in Table 1:

[0236] Wherein, A1 represents the molar ratio of compound (1), compound (2) and the basic compound in the first substitution reaction of step (1); A2 represents the molar ratio of the intermediate product, the fluoride and the catalyst in the second substitution reaction of step (2); Y and GC represent the yield and purity of the product obtained in step (2), respectively.

[0237] Table 1

[0238]

[0239]

[0240] It can be seen from the experimental results in the above table that in the preparation method of the fluorinated cyclic ether of the present application, the compound (1) and the compound (2) are first subjected to a first substitution reaction, and then the obtained compound (3) and a fluoride are subjected to a second substitution reaction to prepare the fluorinated cyclic ether represented by formula (4). The raw materials are easily available and the yield is high, which can reach more than 90%.

[0241] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0242] The above-mentioned embodiments only express several implementation methods of the present invention, and the description is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several modifications and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description can be used to interpret the content of the claims.

Claims

1. A method for preparing a fluorinated cyclic ether, characterized in that: The steps include: subjecting compound (1) to a first substitution reaction with compound (2) to prepare compound (3); The compound (3) is subjected to a second substitution reaction with a fluoride to prepare a fluorinated cyclic ether represented by formula (4); The compound (1), the compound (2), the compound (3) and the fluorinated cyclic compound represented by formula (4) The structure of an ether is as follows: 、 、 、 in, represents a cycloalkyl ether group having T ring atoms, wherein the ring atoms contain H1 oxygen atoms and H2 carbon atoms; each occurrence of R1 is independently selected from any one of H, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms; T, H1, H2, n1 and n2 are all integers and satisfy: 5≤T≤8, T = H1+H2, H1≥1, H2≥3, n1+n2= 2H2, and n2≥1; Each occurrence of R2 is independently selected from any one of an alkyl group having 1 to 8 carbon atoms and a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms; The second substitution reaction is carried out under the action of a catalyst, and the catalyst includes at least one of copper iodide, sodium iodide, potassium iodide, zinc iodide, copper bromide, sodium bromide, potassium bromide and zinc bromide.

2. The method for preparing a fluorinated cyclic ether according to claim 1, wherein The compound (1) In the formula (a), the number n3 of hydroxyl groups connected to any carbon atom in the ring atoms satisfies: n3≤1, and n3 is an integer.

3. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, wherein: 1≤H1≤(T-2).

4. The method for preparing a fluorinated cyclic ether according to claim 3, wherein: The H1 is 1 or 2.

5. The method for preparing a fluorinated cyclic ether according to claim 4, characterized in that: H1 is 1.

6. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, wherein: The H1≥2, and there is at least one carbon atom between any two oxygen atoms in the ring atoms.

7. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: 3≤H2≤(T-1).

8. The method for preparing a fluorinated cyclic ether according to claim 7, characterized in that: H2=(T-1).

9. The method for preparing a fluorinated cyclic ether according to claim 8, characterized in that: H2 is 4.

10. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The T is 5 or 6.

11. The method for preparing a fluorinated cyclic ether according to claim 10, characterized in that: The T is 5.

12. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The n2 is 1 or 2.

13. The method for preparing a fluorinated cyclic ether according to claim 12, characterized in that: The n2 is 1.

14. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: Each occurrence of R1 is independently selected from H or an alkyl group having 1 to 8 carbon atoms.

15. The method for preparing a fluorinated cyclic ether according to claim 14, characterized in that: Each occurrence of R1 is independently selected from H or an alkyl radical having 1 to 5 carbon atoms.

16. The method for preparing a fluorinated cyclic ether according to claim 15, characterized in that: Each occurrence of R1 is independently selected from any one of H, methyl, ethyl, propyl and butyl.

17. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: Each occurrence of R2 is independently selected from any one of a chain alkyl group having 1 to 4 carbon atoms and a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.

18. The method for preparing a fluorinated cyclic ether according to claim 17, characterized in that: Each occurrence of R2 is independently selected from any one of a linear alkyl group having 1 to 4 carbon atoms and an unsubstituted or alkyl-substituted aromatic group having 6 to 8 carbon atoms.

19. The method for preparing a fluorinated cyclic ether according to claim 18, characterized in that: Each occurrence of R2 is independently selected from any one of methyl, ethyl and tolyl.

20. The method for preparing a fluorinated cyclic ether according to claim 19, characterized in that: The compound (2) includes at least one of methanesulfonyl chloride and p-toluenesulfonyl chloride.

21. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The compound (1) is any one of formulas (1-1) to (1-3): 、 、 。 22. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The molar ratio of the catalyst to the compound (3) is (0.001-0.1):

1.

23. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The second substitution reaction satisfies at least one of the following conditions (1) to (4): (1) The temperature of the second substitution reaction is 0°C to 220°C, and the time is 0.5h to 10h; (2) The molar ratio of the compound (3) to the fluoride is 1:(1-20); (3) The fluoride includes a fluorine-containing salt compound; (4) The second substitution reaction is carried out in an organic solvent A.

24. The method for preparing a fluorinated cyclic ether according to claim 23, characterized in that: The second substitution reaction satisfies at least one of the following conditions (1) to (4): (1) The temperature of the second substitution reaction is 30°C to 160°C, and the time is 1h to 6h; (2) The fluoride comprises at least one of lithium fluoride, sodium fluoride, potassium fluoride, antimony trifluoride, pyridine hydrofluoride and triethylamine trihydrofluoride; (3) the organic solvent A comprises at least one of N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol, diethylene glycol and sulfolane; (4) The mass ratio of the organic solvent A to the compound (3) is (1-20):

1.

25. The method for preparing a fluorinated cyclic ether according to claim 23, characterized in that: The process of preparing the fluorinated cyclic ether represented by formula (4) further includes the following steps: The product of the second substitution reaction is subjected to distillation treatment to prepare the fluorinated cyclic ether represented by the formula (4).

26. The method for preparing a fluorinated cyclic ether according to any one of claims 1 to 2, characterized in that: The first substitution reaction satisfies at least one of the following conditions (1) to (4): (1) The temperature of the first substitution reaction is -20°C to 120°C, and the time is 0.5h to 10h; (2) The molar ratio of the compound (1) to the compound (2) is 1:(1-10); (3) the first substitution reaction is carried out under the action of a basic compound; (4) The first substitution reaction is carried out in an organic solvent B.

27. The method for preparing a fluorinated cyclic ether according to claim 26, characterized in that: The first substitution reaction satisfies at least one of the following conditions (1) to (6): (1) The temperature of the first substitution reaction is 0°C to 80°C, and the time is 2h to 7h; (2) the basic compound comprises at least one of an organic basic compound and an inorganic basic compound; (3) the alkaline compound comprises at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, piperidine and quinoline; (4) The molar ratio of the compound (1) to the basic compound is 1:(1-10); (5) the organic solvent B comprises at least one of acetonitrile, tetrahydrofuran, dichloromethane, dioxane, N,N-dimethylformamide and dimethyl sulfoxide; (6) The mass ratio of the organic solvent B to the compound (1) is (1-20):

1.

28. The method for preparing a fluorinated cyclic ether according to claim 26, characterized in that: The first substitution reaction is carried out in the organic solvent B. The process for preparing the compound (3) further comprises the following steps: The product of the first substitution reaction is washed with water and then an organic phase is taken; The organic solvent B in the organic phase is removed to prepare the compound (3).

Images