WO2019165636A1 - 含氟1，3-二氧环烷类烯烃的制备方法 - Google Patents

含氟1，3-二氧环烷类烯烃的制备方法 Download PDF

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WO2019165636A1
WO2019165636A1 PCT/CN2018/077856 CN2018077856W WO2019165636A1 WO 2019165636 A1 WO2019165636 A1 WO 2019165636A1 CN 2018077856 W CN2018077856 W CN 2018077856W WO 2019165636 A1 WO2019165636 A1 WO 2019165636A1
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formula
compound
fluorine
preparation
olefin
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PCT/CN2018/077856
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French (fr)
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张�浩
温乐乐
李丹
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博容新材料（深圳）有限公司
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Priority to PCT/CN2018/077856 priority Critical patent/WO2019165636A1/zh
Priority to CN201880002719.5A priority patent/CN109689638B/zh
Publication of WO2019165636A1 publication Critical patent/WO2019165636A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/42—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/16—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F116/12—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F116/14—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/24—Monomers containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F16/14—Monomers containing only one unsaturated aliphatic radical
    • C08F16/26—Monomers containing oxygen atoms in addition to the ether oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/38—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical

Definitions

  • the present invention relates to the field of organic synthesis, and in particular to a method for preparing a fluorine-containing 1,3-dioxane-based olefin.
  • Fluorinated polymer means a polymer compound in which all or part of carbon-hydrogen bonds are substituted by carbon-fluorine bonds, and generally has chemical corrosion resistance, weather resistance, excellent dielectric properties, unique low surface energy, and broadness.
  • the use temperature characteristics and other characteristics, are widely used in atomic energy, aerospace, electronics, machinery manufacturing, chemical and other industries.
  • the basic unit of the fluorine-containing polymer is a fluorine-containing monomer, usually a fluorine-containing olefin, but the synthesis process of the currently disclosed fluorine-containing olefin monomer for polymerization is extremely complicated and expensive, especially a fluorine-containing heterocyclic compound.
  • Olefin is an extremely popular target compound in the field of high-end perfluoropolymer synthesis technology.
  • the perfluoropolymer obtained by its polymerization is the most technically expensive and most expensive material category in fluorine-containing materials; currently 1,3-dioxane There is only one method for the synthesis of pentocyclic fluorinated olefins.
  • the present invention provides a method for preparing a fluorine-containing 1,3-dioxane olefin, and the method provided by the invention is suitable for preparation of a plurality of heterocyclic fluoroolefins, and the preparation process is relatively simple, and the yield is relatively simple. Better, suitable for industrial production.
  • the invention provides a preparation method of a fluorine-containing 1,3-dioxocycloalkane olefin, comprising:
  • X, R 1 and R 2 are independently selected from a hydrogen atom or a fluorine atom
  • Z is a hydroxyl group, a chlorine atom or a bromine atom
  • M 1 , M 2 , M 3 , M 4 , M 5 and M 6 are independently selected from a hydrogen atom, a fluorine atom, a C1-C8 alkyl group or a C1-C8 fluorine-containing alkyl group;
  • n 0, 1 or 2;
  • M 11 , M 12 , M 13 , M 14 , M 15 and M 16 are independently selected from a fluorine atom or a C1-C8 perfluoroalkyl group;
  • the compound of the formula (I) is prepared according to the following method:
  • X, R 1 and R 2 are independently selected from a hydrogen atom or a fluorine atom
  • Y is a hydroxyl group, a chlorine atom or a bromine atom.
  • the compound of the formula (I-a) and the compound of the formula (I-b) are first mixed at -30 to -60 ° C and then reacted at room temperature to give a compound of the formula (I).
  • the solvent for the reaction in the step 1) is one or two of toluene and benzene.
  • the catalyst reacted in the step 1) is one or more of Amberlyst 15 acidic resin, Amberlyst 36 acidic resin and Amberlyst 16 acidic resin.
  • the solvent reacted in the step 2) is FC-75.
  • the fluorine source in the step 2) is a 20% fluorine/nitrogen gas mixture.
  • the step 3) is specifically: mixing a compound of the formula (IV), potassium fluoride and a solvent to obtain a compound of the formula (V);
  • the solvent is a dimethyl ether compound containing an active hydroxyl group.
  • the step 4) is specifically: reacting a compound of the formula (V) with a hydroxide to obtain a corresponding salt; and thermally decomposing the salt to obtain a fluorine-containing 1,3 having a structure of the formula (VI) - Dioxacycloalkane olefins.
  • the temperature of the thermal decomposition is 280 to 350 °C.
  • the present invention provides a method for preparing a fluorine-containing 1,3-dioxocycloalkane olefin, which is obtained by first reacting a compound of the formula (I) with a compound of the formula (II).
  • a compound of the formula (III) then reacting a compound of the formula (III) with a source of F to obtain a compound of the formula (IV), and finally converting the compound of the formula (IV) to a structure of the formula (V) a compound, which is then converted into a fluorine-containing 1,3-dioxane olefin having a structure of the formula (V);
  • the method not only has a wide range of raw materials, but also has wide applicability and can be used for many
  • the preparation of a heterocyclic fluorine-containing olefin, and the preparation process is relatively simple, the yield is good, and is suitable for industrial production.
  • the invention provides a preparation method of a fluorine-containing 1,3-dioxocycloalkane olefin, comprising:
  • X, R 1 and R 2 are independently selected from a hydrogen atom or a fluorine atom
  • Z is a hydroxyl group, a chlorine atom or a bromine atom
  • M 1 , M 2 , M 3 , M 4 , M 5 and M 6 are independently selected from a hydrogen atom, a fluorine atom, a C1-C8 alkyl group or a C1-C8 fluorine-containing alkyl group;
  • n 0, 1 or 2;
  • M 11 , M 12 , M 13 , M 14 , M 15 and M 16 are independently selected from a fluorine atom or a C1-C8 perfluoroalkyl group;
  • the present invention reacts a compound of the formula (I) with a compound of the formula (II) to give a compound of the formula (III); wherein the present invention has no particular requirement for the ratio of the starting materials of the reaction,
  • the solvent of the reaction is preferably one or two of toluene and benzene
  • the catalyst for the reaction is preferably Amberlyst 15 acidic resin and Amberlyst 36 acid.
  • One or more of the resin and the Amberlyst 16 acidic resin are more preferably an Amberlyst 15 acidic resin;
  • the temperature of the reaction is preferably from 100 to 130 ° C, more preferably from 110 to 120 ° C.
  • the compound of the formula (I) is preferably prepared according to the following method:
  • X, R 1 and R 2 are independently selected from a hydrogen atom or a fluorine atom
  • Y is a hydroxyl group, a chlorine atom or a bromine atom.
  • the present invention firstly mixes the compound of the formula (I-a) and the compound of the formula (I-b) at -30 to -60 ° C, and then reacts at room temperature to obtain a compound of the formula (I).
  • the present invention also reacts a compound of the formula (III) with a fluorine source to obtain a compound of the formula (IV).
  • M 11 , M 12 , M 13 , M 14 , M 15 and M 16 are independently selected from a fluorine atom or a C1-C8 perfluoroalkyl group; wherein the fluorine source is preferably a 20% fluorine/nitrogen mixture
  • the solvent of the reaction is preferably a solvent of FC-75; the temperature of the reaction is preferably -5 to 0 ° C; the ratio of the amount of the reaction raw materials of the present invention is not particularly required, and those skilled in the art can select according to actual needs. The right amount ratio.
  • the present invention also converts a compound of the formula (IV) into a compound of the formula (V); preferably, the present invention reacts a compound of the formula (IV), potassium fluoride and a solvent to obtain a formula ( V) a compound of a structure; more preferably, the present invention slowly mixes a mixed solution of a compound of the formula (IV) and a solvent and a mixed solution of potassium fluoride and a solvent to obtain a compound of the formula (V); wherein
  • the solvent is preferably a dimethyl ether compound containing a reactive hydroxyl group, more preferably one or two of triethylene glycol dimethyl ether and diethylene glycol dimethyl ether; further, the ratio of the amount of the reaction raw materials in the present invention is not Special requirements, those skilled in the art can select an appropriate dosage ratio according to actual needs.
  • the present invention converts a compound of the formula (V) into a fluorine-containing 1,3-dioxane olefin having a structure of the formula (VI); in particular, the present invention preferably has a structure of the formula (V)
  • the compound is reacted with a hydroxide to obtain a corresponding salt; and then the salt is thermally decomposed to obtain a fluorine-containing 1,3-dioxane olefin having a structure of the formula (VI); wherein the hydroxide is preferably hydrogen Potassium oxide; the temperature of the thermal decomposition is preferably 280 to 350 ° C, more preferably 300 to 320 ° C.
  • reaction scheme of the fluorine-containing 1,3-dioxane olefin having the structure of the formula (VI) of the present invention is the first step, the second step or the third step;
  • n 0, 1 or 2
  • the method for preparing a fluorine-containing 1,3-dioxocycloalkane olefin comprises first reacting a compound of the formula (I) with a compound of the formula (II) to obtain a compound of the formula (III); Further reacting a compound of the formula (III) with a fluorine source to obtain a compound of the formula (IV), and finally converting the compound of the formula (IV) into a compound of the formula (V), followed by the structure of the formula (V)
  • the compound is converted into a fluorine-containing 1,3-dioxane olefin having the structure of the formula (VI); the method not only has a wide range of raw materials, but also has wide applicability, and can be used for preparation of various heterocyclic fluoroolefins.
  • the preparation process is simple, the yield is good, and it is suitable for industrial production.
  • the temperature of the reaction system was maintained at zero. After the injection of the raw material liquid is completed, the flow rate of the fluorine gas is maintained, and the fluorine gas is continuously supplied for half an hour. After completion of the reaction, the crude product was distilled under reduced pressure, and the residue was purified to give chlorobenzene (2-methyl-1,3-dioxolan-2-yl)methyl ester (352 g) (yield: 111-113 ° C). The purity is 98% and the yield is 80%.
  • Example 2 Method for synthesizing 1,3-dioxane-based fluorinated olefin
  • the temperature of the reaction system was maintained at zero. After the injection of the raw material liquid is completed, the flow rate of the fluorine gas is maintained, and the fluorine gas is continuously supplied for half an hour. After the completion of the reaction, the crude product was distilled under reduced pressure, and the residue was purified to give 388 g of (2-methyl-1,3-dioxolan-2-yl)methyl perfluorotrifluoroacetate, and the boiling point was 116 to 118 ° C. The purity was 97% and the yield was 83%.
  • the six-membered cyclic perfluoroolefin is synthesized analogously to the patent US7635780 mentioned in the background.
  • FC-75 100 g of (2-methyl-1,3-dioxan-2-yl)methyl acetate was dissolved in 300 ml of FC-75 and thoroughly stirred to form a raw material liquid.
  • 1.5 L of FC-75 was added to a 5 liter nickel reactor and cooled to zero, and the condenser temperature was minus 10 degrees.
  • the air in the reaction system was purged by nitrogen for half an hour, and then 20% fluorine gas (diluted with nitrogen) was introduced at a rate of 0.5 liter/min for half an hour, and then the flow rate of the fluorine gas was slowly increased to 0.8 liter/min, and within 26 hours. Inject the raw material liquid.
  • the temperature of the reaction system was maintained at zero.

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Abstract

本发明提供了一种含氟1，3-二氧环烷类烯烃的制备方法，通过首先将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；然后再将式(III)结构的化合物与F源反应，得到式(IV)结构的化合物，最后将式(IV)结构的化合物先转化为式(V)结构的化合物，接着将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；该方法不仅原料来源广泛，而且制备方法适用性广，可用于多种杂环含氟烯烃的制备，且制备工艺简单，收率较好，适应于工业化生产。

Description

含氟1，3-二氧环烷类烯烃的制备方法 技术领域
本发明涉及有机合成领域，特别涉及含氟1，3-二氧环烷类烯烃的制备方法。
背景技术
含氟高分子是指全部或部分的碳-氢键为碳-氟键取代的高分子化合物，通常具有耐化学腐蚀性、耐大气老化性、优良的介电性能、独特的低表面能、宽广的使用温度范围等特性，广泛应用于原子能、航天、电子、机械制造、化学等工业。
含氟高分子的基本单元是含氟单体，通常为含氟烯烃，但是，目前公开的用于聚合的含氟烯烃单体的合成工艺极为复杂，成本高昂，尤其是含氟的杂环类烯烃是目前高端全氟高分子合成技术领域极其热门的目标化合物，由其聚合得到的全氟高分子是含氟类材料中技术门槛最高，价格最昂贵的材料品类；目前1,3-二氧戊环类含氟烯烃的合成方法只有一种，于2009年获得专利授权，由日本科学振兴机构(JST)持有(US7635780)，但是，该法仅适用于1,3-二氧戊环类含氟烯烃的制备，且成本高昂，工艺复杂，产率低，而1,3-二氧杂环己烷类含氟烯烃则没有任何可产业化的有效合成方法。
发明内容
有鉴于此，本发明提供一种含氟1，3-二氧环烷类烯烃的制备方法，本发明提供的方法适用于多种杂环含氟烯烃的制备，且制备工艺相对简单，收率较好，适应于工业化生产。
本发明提供了一种含氟1，3-二氧环烷类烯烃的制备方法，包括：
1)将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；
Figure PCTCN2018077856-appb-000001
式(I)，
Figure PCTCN2018077856-appb-000002
式(II)，
Figure PCTCN2018077856-appb-000003
式(III)，
其中，X、R 1和R 2独立的选自氢原子或氟原子；
Z为羟基、氯原子或溴原子；
M 1、M 2、M 3、M 4、M 5和M 6独立的选自氢原子、氟原子、C1～C8的烷基或C1～C8的含氟烷基；
n为0、1或2；
2)将式(III)结构的化合物与氟源反应，得到式(IV)结构的化合物，
Figure PCTCN2018077856-appb-000004
式(IV)，
其中，M 11、M 12、M 13、M 14、M 15和M 16独立的选自氟原子或C1～C8的全氟烷基；
3)将式(IV)结构的化合物转化为式(V)结构的化合物；
Figure PCTCN2018077856-appb-000005
式(V)；
4)将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；
Figure PCTCN2018077856-appb-000006
式(VI)。
优选的，所述式(I)结构的化合物按照以下方法制备得到：
将式(I-a)的化合物和式(I-b)的化合物混合反应，得到式(I)结构的化合物，
Figure PCTCN2018077856-appb-000007
式(I-a)，
Figure PCTCN2018077856-appb-000008
式(I-b)，
其中，X、R 1和R 2独立的选自氢原子或氟原子；
Y为羟基、氯原子或溴原子。
优选的，首先将式(I-a)的化合物和式(I-b)的化合物在-30～-60℃条件下混合，然后在室温反应，得到式(I)结构的化合物。
优选的，所述步骤1)反应的溶剂为甲苯和苯中的一种或两种。
优选的，所述步骤1)反应的催化剂为Amberlyst 15酸性树脂、Amberlyst 36酸性树脂和Amberlyst 16酸性树脂中的一种或几种。
优选的，所述步骤2)中反应的溶剂为FC-75。
优选的，所述步骤2)中的氟源为20％氟气/氮气混合气。
优选的，所述步骤3)具体为：将式(IV)结构的化合物、氟化钾和溶剂混合反应，得到式(V)结构的化合物；
所述溶剂为含活性羟基的二甲醚类化合物。
优选的，所述步骤4)具体为：将式(V)结构的化合物与氢氧化物反应，得到相对应的盐；将盐进行热分解，得到具有式(VI)结构的含氟1，3-二氧环烷类烯烃。
优选的，所述热分解的温度为280～350℃。
与现有技术相比，本发明提供了一种含氟1，3-二氧环烷类烯烃的制备方法，通过首先将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；然后再将式(III)结构的化合物与F源反应，得到式(IV)结构的化合物，最后将式(IV)结构的化合物先转化为式(V)结构的化合物，接着将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；该方法不仅原料来源广泛，而且制备方法适用性广，可用于多种杂环含氟烯烃的制备，且制备工艺相对简单，收率较好，适应于工业化生产。
具体实施方式
本发明提供了一种含氟1，3-二氧环烷类烯烃的制备方法，包括：
1)将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；
Figure PCTCN2018077856-appb-000009
式(I)，
Figure PCTCN2018077856-appb-000010
式(II)，
Figure PCTCN2018077856-appb-000011
式(III)，
其中，X、R 1和R 2独立的选自氢原子或氟原子；
Z为羟基、氯原子或溴原子；
M 1、M 2、M 3、M 4、M 5和M 6独立的选自氢原子、氟原子、C1～C8的烷基或C1～C8的含氟烷基；
n为0、1或2；
2)将式(III)结构的化合物与F源反应，得到式(IV)结构的化合物，
Figure PCTCN2018077856-appb-000012
式(IV)，
其中，M 11、M 12、M 13、M 14、M 15和M 16独立的选自氟原子或C1～C8的全氟烷基；
3)将式(IV)结构的化合物转化为式(V)结构的化合物；
Figure PCTCN2018077856-appb-000013
式(V)；
4)将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；
Figure PCTCN2018077856-appb-000014
式(VI)。
按照本发明，本发明将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；其中，本发明对反应原料的用量比并没有特殊要求，本领域技术人员可以根据实际需要，选择合适的用量比；本发明中，所述反应的溶剂优选为甲苯和苯中的一种或两种，所述反应的催化剂优选为Amberlyst 15酸性树脂、Amberlyst 36酸性树脂和Amberlyst 16酸性树脂中的一种或几种，更优选为Amberlyst 15酸性树脂；所述反应的温度优选为100～130℃，更优选为110～120℃。
本发明中，所述式(I)结构的化合物优选按照以下方法制备得到：
将式(I-a)的化合物和式(I-b)的化合物混合反应，得到式(I)结构的化合物，
Figure PCTCN2018077856-appb-000015
式(I-a)，
Figure PCTCN2018077856-appb-000016
式(I-b)，
其中，X、R 1和R 2独立的选自氢原子或氟原子；
Y为羟基、氯原子或溴原子。
具体的，本发明首先将式(I-a)的化合物和式(I-b)的化合物在-30～-60℃条件下混合，然后在室温反应，得到式(I)结构的化合物。
按照本发明，本发明还将式(III)结构的化合物与氟源反应，得到式(IV)结构的化合物，
Figure PCTCN2018077856-appb-000017
式(IV)，
其中，M 11、M 12、M 13、M 14、M 15和M 16独立的选自氟原子或C1～C8的全氟烷基；其中，所述氟源优选为20％氟气/氮气混合气，所述反应的溶剂优选为FC-75溶剂；所述反应的温度优选为-5～0℃；，本发明对反应原料的用量比并没有特殊要求，本领域技术人员可以根据实际需要选择合适的用量比。
按照本发明，本发明还将式(IV)结构的化合物转化为式(V)结构的化合物；优选的，本发明将式(IV)结构的化合物、氟化钾和溶剂混合反应，得到式(V)结构的化合物；更优选的，本发明将式(IV)结构的化合物和溶剂的混合溶液和氟化钾和溶剂的混合溶液缓慢混合，得到式(V)结构的化合物；其中，所述溶剂优选为含活性羟基的二甲醚类化合物，更优选为三甘醇二甲醚和二乙二醇二甲醚中的一种或两种；此外，本发明对反应原料的用量比并没有特殊要求，本领域技术人员可以根据实际需要选择合适的用量比。
按照本发明，本发明将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；具体的，本发明优选将将式(V)结构的化合物与氢氧化物反应，得到相应的盐；而后将盐进行热分解，得到具 有式(VI)结构的含氟1，3-二氧环烷类烯烃；其中，所述氢氧化物优选为氢氧化钾；所述热分解的温度优选为280～350℃，更优选为300～320℃。
具体的，本发明所述的具有式(VI)结构的含氟1，3-二氧环烷类烯烃的反应流程为流程一、流程二或流程三；
Figure PCTCN2018077856-appb-000018
流程一
Figure PCTCN2018077856-appb-000019
流程二
Figure PCTCN2018077856-appb-000020
n为0、1或2
流程三
本发明提供的含氟1，3-二氧环烷类烯烃的制备方法，通过首先将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；然后再将式(III)结构的化合物与氟源反应，得到式(IV)结构的化合物，最后将式(IV)结构的化合物先转化为式(V)结构的化合物，接着将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；该方法不仅原料来源广泛，而且制备方法适用性广，可用于多种杂环含氟烯烃的制备，且制备工艺简单，收率较好，适应于工业化生产。
下面将结合本发明实施例的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1、1,3-二氧戊环类含氟烯烃的合成
将265克三氟乙酰氯以1克每分钟的速度缓慢通入150克羟基丙酮中，反应体系温度保持在零下三十度，待三氟乙酰氯全部通完后，缓慢将反应温度升至室温，精馏粗产物得三氟乙酸基丙酮325克，纯度99％，产率95％。
19FNMR(核磁共振氟谱)分析，-82.1ppm(-CF 3，3F)。HNMR(核磁共振氢谱)分析，5.96ppm(-CH 2-,单峰，2H),2.33ppm(CH 3-,单峰，3H)。
将325克三氟乙酸基丙酮和120克乙二醇溶于一升甲苯中，加入10克Amberlyst 15酸性树脂为催化剂，回流六小时，加压蒸馏除去溶剂后减压精馏(0.02大气压)，在38～40摄氏度收集产品，得三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯320克，纯度99％，产率78％。
19FNMR(核磁共振氟谱)分析，-81.9ppm(-CF 3，3F)。HNMR(核磁共振氢谱)分析，4.08ppm(-CH 2-CH 2-,多重峰，4H),4.93ppm(-CH 2-,单峰，2H),1.86ppm(CH 3-,单峰，3H)。
将250克三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯溶解在300毫升FC-75中，充分搅拌成原料液。在5升镍制反应釜中加入FC-75 2.5升，三氟化钴10克，充分搅拌并保持在零度，冷凝器温度为零下20度。通氮气半小时赶走反应体系内空气，再以0.5升/分钟的速度通入20％氟气(氮气稀释)半小时，而后缓慢将氟气流速提高至0.8升/分钟，并在24小时内注入原料液。反应体系温度保持在零度。原料液注入结束后，维持氟气流速不变，继续通氟气半小时。反应结束后，减压蒸馏得到粗产物，精馏得到全氟三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯352克，沸点111-113摄氏度，纯度98％，产率80％。
将300克全氟三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯与100毫升二乙二醇二甲醚充分混合，缓慢加入含有5克氟化钾的10毫升二乙二醇二甲醚溶液，立刻产生白色雾状气体(三氟乙酰氟)，反应结束后的液相部分精馏，收集沸点在57～59摄氏度范围的馏分，得2-甲基-1,3-二氧戊环-2-酰氟116克，纯度98％，产率56％。
19FNMR(核磁共振氟谱)分析，-88.1ppm(-CF 2-，4F)，-82.9ppm(-CF 3，3F),42ppm(-COF,1F)。
2-甲基-1,3-二氧戊环-2-酰氟100克用氢氧化钾中和后，所得钾盐充分干燥，在300摄氏度、氮气保护环境下进行热分解，粗产物精馏后得无色透明液体产物，全氟2-亚甲基-1,3-二氧戊环45克，纯度98％，产率60％，沸点22摄氏度。
19FNMR(核磁共振氟谱)分析，-88.9ppm(-CF 2-，4F)，-128ppm(＝CF 2，2F)。
将45克全氟2-亚甲基-1,3-二氧戊环、50毫克全氟过氧丙酰溶于100克Freon113中充分混合，将混合液注入500毫升高压反应釜中密封，零下70摄氏度用氩气除氧30分钟后，缓慢升温至零上70摄氏度，聚合12小时。除去溶剂并充分干燥后得半透明高分子产物42克，聚合转化率93％。此高分子结晶度较高，难溶于大部分含氟溶剂，熔点230度。
对比例1：
将325克三氟乙酸基丙酮和120克乙二醇溶于一升环己烷中，加入10克Amberlyst 15酸性树脂为催化剂，回流六小时，加压蒸馏除去溶剂后减压精馏(0.02大气压)，在38～40摄氏度收集产品，得三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯184克，纯度99％，产率45％。
对比例2
将325克三氟乙酸基丙酮和120克乙二醇溶于一升甲苯中，加入15克对甲苯磺酸为催化剂，回流六小时，加压蒸馏除去溶剂后减压精馏(0.02大气压)，在38～40摄氏度收集产品，得三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯240克，纯度99％，产率58％。
实施例2、1,3-二氧杂环己烷类含氟烯烃的合成方法
按实施例1中同样方法制备300克三氟乙酸基丙酮，并与135克1,3-丙二醇一同溶于1.5升甲苯中，加入10克Amberlyst 15酸性树脂为催化剂，回流八小时，加压蒸馏除去溶剂后精馏，得三氟乙酸基(2-甲基-1,3-二氧杂环己烷-2-基)甲酯310克，纯度99％，产率77％。
19FNMR(核磁共振氟谱)分析，-81.7ppm(-CF 3，3F)。
1HNMR(核磁共振氢谱)分析，4.13ppm(-O-CH 2-,多重峰，4H),1.89ppm(-CH 2-，多重峰，2H),4.91ppm(-CH 2-,单峰，2H),1.88ppm(CH 3-,单峰，3H)。
将250克三氟乙酸基(2-甲基-1,3-二氧杂环己烷-2-基)甲酯溶解在300毫升FC-75中，充分搅拌成原料液。在5升镍制反应釜中加入FC-752.5升，三氟化钴10克，充分搅拌并保持在零度，冷凝器温度为零下20度。通氮气半小时赶走反应体系内空气，再以0.5升/分钟的速度通入20％氟气(氮气稀释)半小时，而后缓慢将氟气流速提高至0.8升/分钟，并 在26小时内注入原料液。反应体系温度保持在零度。原料液注入结束后，维持氟气流速不变，继续通氟气半小时。反应结束后，减压蒸馏得到粗产物，精馏得到全氟三氟乙酸基(2-甲基-1,3-二氧戊环-2-基)甲酯388克，沸点116～118摄氏度，纯度97％，产率83％。
将300克全氟三氟乙酸基(2-甲基-1,3-二氧杂环己烷-2-基)甲酯与100毫升三甘醇二甲醚充分混合，缓慢加入含有6克氟化钾的10毫升三甘醇二甲醚溶液，立刻产生白色雾状气体(三氟乙酰氟)，反应结束后的液相部分精馏，收集沸点在60到62摄氏度范围的馏分，得2-甲基-1,3-二氧杂环己烷-2-酰氟132克，纯度98％，产率60％。
19FNMR(核磁共振氟谱)分析，-88.6ppm(-O-CF 2-，4F)，-81.3ppm(-CF 2-,2F),-82.7ppm(-CF 3，3F),41.6ppm(-COF,1F)。
2-甲基-1,3-二氧杂环己烷-2-酰氟100克用氢氧化钾中和后，所得钾盐充分干燥，在300摄氏度、氮气保护环境下进行热分解，粗产物精馏后得无色透明液体产物，全氟2-亚甲基-1,3-二噁烷58克，纯度98％，产率73％，沸点33.5摄氏度。
19FNMR(核磁共振氟谱)分析，-89.0ppm(-O-CF 2-，4F)，-81.2ppm(-CF 2-,2F),-128.3ppm(＝CF 2，2F)。
将50克全氟2-亚甲基-1,3-二噁烷、50毫克全氟过氧丙酰溶于100克Freon113中充分混合，将混合液注入500毫升高压反应釜中密封，零下70摄氏度用氩气除氧30分钟后，缓慢升温至零上70摄氏度，聚合24小时。除去溶剂并充分干燥后得絮状高分子产物23克，聚合转化率45％。此高分子结晶度较高，难溶于大部分含氟溶剂，可溶于热的六氟苯。熔点216度。
对比例3
用背景技术提到的专利US7635780做类比，合成六元环类全氟烯烃。
将300克丙酮酸甲酯和224克1,3-丙二醇溶于1.5升甲苯中，加入10克Amberlyst 15酸性树脂为催化剂，回流六小时充分除水，加压蒸馏除去溶剂后减压精馏(0.02大气压)，在46～48摄氏度收集产品，得乙酸基(2- 甲基-1,3-二氧杂环己烷-2-基)甲酯98克，纯度99％，产率21％。
将100克乙酸基(2-甲基-1,3-二氧杂环己烷-2-基)甲酯溶解在300毫升FC-75中，充分搅拌成原料液。在5升镍制反应釜中加入FC-75 1.5升并冷却至零度，冷凝器温度为零下10度。通氮气半小时赶走反应体系内空气，再以0.5升/分钟的速度通入20％氟气(氮气稀释)半小时，而后缓慢将氟气流速提高至0.8升/分钟，并在26小时内注入原料液。反应体系温度保持在零度。原料液注入结束后，维持氟气流速不变，继续通氟气半小时。反应结束后，减压蒸馏得到粗产物，精馏得到2-甲基-1,3-二氧杂环己烷-2-酰氟17.5克，产率9％。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 含氟1，3-二氧环烷类烯烃的制备方法，包括：
    1)将式(I)结构的化合物与式(II)结构的化合物反应，得到式(III)结构的化合物；
    Figure PCTCN2018077856-appb-100001
    其中，X、R 1和R 2独立的选自氢原子或氟原子；
    Z为羟基、氯原子或溴原子；
    M 1、M 2、M 3、M 4、M 5和M 6独立的选自氢原子、氟原子、C1～C8的烷基或C1～C8的含氟烷基；
    n为0、1或2；
    2)将式(III)结构的化合物与氟源反应，得到式(IV)结构的化合物，
    Figure PCTCN2018077856-appb-100002
    其中，M 11、M 12、M 13、M 14、M 15和M 16独立的选自氟原子或C1～C8的全氟烷基；
    3)将式(IV)结构的化合物转化为式(V)结构的化合物；
    Figure PCTCN2018077856-appb-100003
    4)将式(V)结构的化合物转化为具有式(VI)结构的含氟1，3-二氧环烷类烯烃；
    Figure PCTCN2018077856-appb-100004
  2. 根据权利要求1所述的制备方法，其特征在于，所述式(I)结构 的化合物按照以下方法制备得到：
    将式(I-a)的化合物和式(I-b)的化合物混合反应，得到式(I)结构的化合物，
    Figure PCTCN2018077856-appb-100005
    其中，X、R 1和R 2独立的选自氢原子或氟原子；
    Y为羟基、氯原子或溴原子。
  3. 根据权利要求2所述的制备方法，其特征在于，首先将式(I-a)的化合物和式(I-b)的化合物在-30～-60℃条件下混合，然后在室温反应，得到式(I)结构的化合物。
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)反应的溶剂为甲苯和苯中的一种或两种。
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)反应的催化剂为Amberlyst 15酸性树脂、Amberlyst 36酸性树脂和Amberlyst 16酸性树脂中的一种或几种。
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤2)中反应的溶剂为FC-75。
  7. 根据权利要求1所述的制备方法，其特征在于，所述步骤2)中的氟源为20％氟气/氮气混合气。
  8. 根据权利要求1所述的制备方法，其特征在于，所述步骤3)具体为：将式(IV)结构的化合物、氟化钾和溶剂混合反应，得到式(V)结构的化合物；
    所述溶剂为含活性羟基的二甲醚类化合物。
  9. 根据权利要求1所述的制备方法，其特征在于，所述步骤4)具体为：将式(V)结构的化合物与氢氧化物反应，得到相对应的盐；将盐进行热分解，得到具有式(VI)结构的含氟1，3-二氧环烷类烯烃。
  10. 根据权利要求9所述的制备方法，其特征在于，所述热分解的温度为280～350℃。
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