阅读说明：本技术 一种新型芳基化试剂合成的芳基三氟乙烯及其制备方法 (Novel aryl trifluoroethylene synthesized by arylation reagent and preparation method thereof ) 是由 刘波 钟志刚 张鸣 龚蓉 陈立义 于 2019-11-18 设计创作，主要内容包括：本发明涉及化学合成领域,尤其涉及一种新型芳基化试剂合成的芳基三氟乙烯及其制备方法；本发明所述的制备方法以三氟乙烯与芳基磺酰肼为原料,在配体的作用下进行反应；优选所述配体选自三苯基膦、二氮类配体、氮氧类配体、二甲基亚砜、N,N-二甲基甲酰胺中的一种或几种。本发明利用芳基化试剂为主要原料制备芳基三氟乙烯,避免使用芳基碘鎓盐时所存在的技术问题,有效提高了原子经济性,同时使分离纯化更加容易。本发明所述的制备方法反应条件简单温和、成本低廉、操作简便、成本低廉、普适性广、环境污染小、原子经济性高,有望实现工业化大规模生产。(The invention relates to the field of chemical synthesis, in particular to aryl trifluoroethylene synthesized by a novel arylation reagent and a preparation method thereof; the preparation method takes trifluoroethylene and aryl sulfonyl hydrazide as raw materials to react under the action of a ligand; preferably, the ligand is selected from one or more of triphenylphosphine, a dinitrogen ligand, a nitrogen-oxygen ligand, dimethyl sulfoxide and N, N-dimethylformamide. The method utilizes arylation reagent as main raw material to prepare aryl trifluoroethylene, avoids the technical problem existing when aryl iodonium salt is used, effectively improves atom economy, and simultaneously makes separation and purification easier. The preparation method disclosed by the invention is simple and mild in reaction conditions, low in cost, simple and convenient to operate, low in cost, wide in universality, small in environmental pollution and high in atom economy, and is expected to realize industrial large-scale production.)

1. A preparation method of aryl trifluoroethylene synthesized by a novel arylation reagent is characterized in that trifluoroethylene and aryl sulfonyl hydrazide are used as raw materials and react under the action of a ligand; preferably, the ligand is selected from one or more of triphenylphosphine, a dinitrogen ligand, a nitrogen-oxygen ligand, dimethyl sulfoxide and N, N-dimethylformamide.

2. The preparation method according to claim 1, wherein the molar charge ratio of the trifluoroethylene to the aryl sulfonyl hydrazide is 1: 0.1-1: 5; preferably 1: 1.2.

3. The production method according to claim 1 or 2, characterized in that the reaction is carried out under the action of a metal catalyst; preferably, the metal catalyst is a transition metal catalyst; more preferably, the metal catalyst is a group IB metal salt.

4. The method according to claim 3, wherein the metal catalyst is used in an amount of 1 to 100 mol% equivalent relative to trifluoroethylene; preferably 5 mol%.

5. The method according to claim 4, wherein the ligand is used in an amount of 0.1 to 10 equivalents relative to the metal catalyst; preferably 1.0 equivalent.

6. The method according to any one of claims 1 to 5, wherein the reaction is carried out in a solvent which is a nonpolar solvent or a polar solvent; preferably, the solvent is selected from one or more of 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide and toluene.

7. The method according to any one of claims 1 to 6, wherein the reaction temperature is 20 to 140 ℃; preferably 100 ℃;

and/or the reaction time is 1-48 h; preferably 10 hours.

8. The method according to any one of claims 1 to 7, further comprising a step of separating and purifying: and after the reaction is finished, removing the solvent, adding the low-boiling-point solvent again, performing suction filtration, concentrating and separating.

9. The production method according to claim 8, wherein the low-boiling point solvent is a nonpolar solvent; preferably dichloromethane;

and/or, the separation after concentration adopts column chromatography or recrystallization.

10. An aryltrifluoroethylene produced by the production process according to any one of claims 1 to 9.

Technical Field

The invention relates to the field of chemical synthesis, in particular to aryl trifluoroethylene synthesized by a novel arylation reagent and a preparation method thereof.

Background

Trifluoroethylene (TrFE or HFC-1123 for short) is used as a byproduct in the production of tetrafluoroethylene in the organic fluorine industry, and is usually directly burned, so that the environment is polluted and the raw materials are wasted. The invention adopts the waste gas generated in the industrial production of tetrafluoroethylene as the raw material to prepare the aryl trifluoroethylene compound. Wherein, the trifluoroethylene benzene (alpha, beta-trifluorostyrene, TFS for short) is used as a fluorine-containing monomer and can be used for preparing fluorine-containing polymers. The polymer has the characteristics of radiation resistance, heat resistance, good solubility, high transparency, low power-saving loss and the like.

Aryl fluoroethylenes are structurally complex in both the stereoelectronic nature and reactivity of the reaction sites due to the introduction of fluorine atoms. The synthesis of aryl trifluoroethylene compounds dates back to the 40 th century, Cohen et al prepared trifluorostyrene [ Cohen S.G. ] from aryl compounds as raw materials through Friedel-crafts acylation, carbonyl chlorination, fluorohalide exchange, zinc powder reduction dehalogenation and other steps; wolosinski h.t.; scheuer P.J.J.Am.chem.Soc.2002,71, 3439-.

US2874166 reports that phenyl lithium and tetrafluoroethylene are used to synthesize trifluorovinyl benzene, and this process, although the line is simple, uses phenyl lithium with extremely strong activity, so the reaction system needs to be controlled in strict anhydrous and oxygen-free environment, and phenyl lithium also limits the compatibility of substituents on aromatic ring due to too high activity, and is easy to generate a large amount of polysubstituted by-products, making the post-treatment separation difficult. 2011, Masato o et al, utilized phenylmagnesium chloride to react directly with tetrafluoroethylene and obtained moderate yields of trifluorovinylbenzene [ Masato o.; tadashi K; tsusa H; hiroki S; ryohei D; sensuke O.J.Am.chem.Soc.2011,133,3256-3259. In 2012, shanghai sainfu company reported in CN103708988A a method for preparing trifluorostyrene by using phenyl magnesium halide and excess tetrafluoroethylene at a controlled low temperature, which can effectively inhibit the generation of byproducts. The method using the grignard reagent can produce a product relatively easily, but still easily causes the formation of secondary attack by-products.

In 2012, in Shanghai province of Chinese academy of sciences, CN102241554A and CN102532202A, trifluorochloro (bromo) ethylene and a mild nucleophilic reagent phenylboronic acid are subjected to cross-coupling reaction under the catalysis of palladium to prepare trifluorostyrene and derivatives in one step. The method adopts phenylboronic acid as a nucleophilic reagent, has good stability and few byproducts, but adopts expensive palladium as a catalytic reagent, and the synthesis of the phenylboronic acid needs to be carried out through multiple steps, so that the method is not beneficial to industrialization.

CN201610932354.9 discloses a method for synthesizing a trifluoroaryl ethylene compound, which uses copper salt as a catalyst and trifluoroethylene and iodonium salt as starting materials to prepare the aryl trifluoroethylene compound under mild conditions. The method has the advantages that copper salt is used as a catalyst, but the synthesis of aryl iodonium salt is relatively complex, the synthesis cost is high, equivalent aryl iodonium substance is lost when each aryl is used, the atom economy is extremely poor, and different types of aryl trifluoroethylene compounds can be obtained by asymmetric aryl iodonium salt, so that the separation and the purification are difficult.

The synthesis of the aryl trifluoroethylene compound in the prior art has the technical problems of harsh reaction conditions or complex raw material synthesis, high cost and difficulty in realizing large-scale production.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of aryl trifluoroethylene synthesized by a novel arylation reagent.

Specifically, the preparation method takes trifluoroethylene and aryl sulfonyl hydrazide as raw materials to react under the action of a ligand.

Preferably, the ligand is selected from one or more of triphenylphosphine, a dinitrogen ligand, a nitrogen-oxygen ligand, dimethyl sulfoxide (DMSO) and N, N-Dimethylformamide (DMF).

Preferably, the aryl sulfonyl hydrazide is phenyl sulfonyl hydrazide or 4-fluorophenyl sulfonyl hydrazide.

Preferably, the molar charge ratio of the trifluoroethylene to the aryl sulfonyl hydrazide is 1: 0.1-1: 5.

As a better technical scheme of the invention, the molar charge ratio of the trifluoroethylene to the aryl sulfonyl hydrazide is 1: 1.2.

Preferably, the reaction is carried out under the action of a metal catalyst; preferably, the metal catalyst is a transition metal catalyst; more preferably, the metal catalyst is a group IB metal salt.

Preferably, the metal catalyst is used in an amount of 1 to 100 mol% equivalent to trifluoroethylene.

In a preferred embodiment of the present invention, the metal catalyst is used in an amount of 5 mol% relative to trifluoroethylene.

Preferably, the ligand is used in an amount of 0.1 to 10 equivalents with respect to the metal catalyst.

In a preferred embodiment of the present invention, the ligand is used in an amount of 1.0 equivalent to the metal catalyst.

Preferably, the reaction is carried out in a solvent, which is a non-polar solvent or a polar solvent; preferably, the solvent is selected from one or more of 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide and toluene.

When dimethyl sulfoxide or N, N-dimethylformamide is used as a solvent, the solvent is used as a ligand in the reaction.

Preferably, the reaction temperature is 20-140 ℃; preferably 100 deg.c.

Preferably, the reaction time is 1-48 h; preferably 10 hours.

The synthetic route of the preparation method is as follows:

wherein, the substrate 1 is reactant trifluoroethylene, the substrate 2 is aryl sulfonyl hydrazide, and the product 3 is aryl trifluoroethylene.

Preferably, the preparation method of the present invention further comprises the steps of separating and purifying: and after the reaction is finished, removing the solvent, adding the low-boiling-point solvent again, performing suction filtration, concentrating and separating.

Preferably, the low boiling point solvent is a non-polar solvent; preferably dichloromethane.

Preferably, the separation after concentration is performed by column chromatography or recrystallization.

The invention also provides the aryl trifluoroethylene prepared by the preparation method.

The invention has the beneficial effects that:

(1) the method utilizes arylation reagent as main raw material to prepare aryl trifluoroethylene, avoids the technical problem existing when aryl iodonium salt is used, effectively improves atom economy, and simultaneously makes separation and purification easier.

(2) The preparation method disclosed by the invention is simple and mild in reaction conditions, low in cost, simple and convenient to operate, low in cost, wide in universality, small in environmental pollution and high in atom economy, and is expected to realize industrial large-scale production.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Example 1 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a), and the preparation method of the trifluorovinyl benzene (3a) comprises the following steps:

(1) adding 82g of trifluoroethylene, 206.4g of phenylsulfonyl hydrazide, 9.1g of anhydrous copper acetate, 13.1g of triphenyl phosphorus and 200mL of 1, 4-dioxane serving as a weak polar solvent into a reactor, and reacting at 100 ℃ for 10 hours;

(2) after the reaction is finished, the 1, 4-dioxane is removed and CH is used₂Cl₂The catalyst was removed by dissolution and suction filtration, and purified by column chromatography to give trifluorovinylbenzene (3a) (145g) as a colorless liquid in 91.8% yield.

Nuclear magnetic spectrum data of the trifluorovinylbenzene (3 a):¹H-NMR(CDCl₃)δ：7.16-7.46(m，5H)；¹⁹F-NMR(CDCl₃)δ：-100.1(1F)，-114.9(1F)，-177.2(1F)。

example 24-fluoro-trifluorovinylbenzene (3b)

This example provides a 4-fluoro-trifluorovinylbenzene (3b) which is prepared by a process different from that of example 1 only in that: substituting phenylsulfonyl hydrazide with 4-fluorophenyl sulfonyl hydrazide (228 g);

the product obtained in this example was 4-fluoro-trifluorovinylbenzene (3b) (160g) with a yield of 90.9%.

Nuclear magnetic spectrum data of the 4-fluoro-trifluorovinylbenzene (3 b):¹H-NMR(CDCl₃)δ：7.09-7.15(m，2H)，7.04-7.14(m，2H)；¹⁹F-NMR(CDCl₃)δ：-100.6(1F)，-112.1(1F)，-115.6(1F)，-176.2(1F)。

example 3 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: reducing the amount of the phenylsulfonyl hydrazide to 172 g;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 76%.

Example 4 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: increasing the amount of phenylsulfonyl hydrazide to 344 g;

the product obtained in this example was trifluorovinylbenzene (3a) in 92.1% yield.

Example 5 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: anhydrous copper acetate was replaced with anhydrous nickel acetate (12.4 g);

the product obtained in this example was trifluorovinylbenzene (3a) in 59% yield.

Example 6 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: increasing the amount of anhydrous copper acetate to 18.2 g;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 91.9%.

Example 7 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: 1, 4-dioxane was replaced with DMF (200 mL);

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 74%.

Example 8 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: no triphenylphosphine was added, the ligand triphenylphosphine was replaced with DMSO (10 mL);

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 61%.

Example 9 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: increasing the amount of triphenylphosphine to 26.2 g;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 87.3%.

Example 10 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: replacing 200mL of a non-solvent polar solvent toluene with the weak polar solvent 1, 4-dioxane;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 27%.

Example 11 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: the temperature is reduced to 80 ℃;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 57%.

Example 12 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: the temperature was raised to 140 ℃;

the product obtained in this example was trifluorovinylbenzene (3a) with a yield of 91.3%.

Example 13 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: reducing the reaction time to 1 hour;

the product obtained in this example was trifluorovinylbenzene (3a) in 42% yield.

Example 14 Trifluorovinylbenzene (3a)

This example provides a trifluorovinyl benzene (3a) prepared by a process that differs from that of example 1 only in that: increasing the reaction time to 48 hours;

the product obtained in this example was trifluorovinylbenzene (3a) in 92.1% yield.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.