阅读说明：本技术 具有含有氢且含有氟和/或氯的丁二烯骨架的化合物的制造方法 (method for producing compound having butadiene skeleton containing hydrogen and fluorine and/or chlorine ) 是由 网井秀树 下田光春 池谷庆彦 木村凉 于 2018-04-26 设计创作，主要内容包括：本发明的目的在于,提供一种简便地以低成本工业制造具有含有氢且含有氟和/或氯的多烯骨架的化合物的方法。一种卤代二烯的制造方法,所述卤代二烯用式(1)：A<Sup>1</Sup>A<Sup>2</Sup>C＝CA<Sup>3</Sup>-CA<Sup>4</Sup>＝CA<Sup>5</Sup>A<Sup>6</Sup>[式中,A<Sup>1</Sup>、A<Sup>2</Sup>、A<Sup>5</Sup>和A<Sup>6</Sup>独立地表示氢、氟或氯、碳数1～3的(全氟)烷基、或者(全氟)烯基；A<Sup>3</Sup>和A<Sup>4</Sup>独立地表示氢、氟或氯；A<Sup>1</Sup>～A<Sup>6</Sup>中的至少1者表示氢；A<Sup>1</Sup>～A<Sup>6</Sup>中的至少1者表示氟或氯。]表示,所述制造方法包括如下工序：在0价金属的存在下,使式(2)：A<Sup>7</Sup>A<Sup>8</Sup>C＝CA<Sup>9</Sup>X[式中,A<Sup>7</Sup>和A<Sup>8</Sup>独立地表示氢、氟或氯、碳数1～3的(全氟)烷基、或者(全氟)烯基；A<Sup>9</Sup>独立地表示氢、氟或氯；X表示溴或碘。]所示的相同或不同的卤代烯烃发生偶联反应的工序。(An object of the present invention is to provide a method for industrially producing a compound having a polyene skeleton containing fluorine and/or chlorine, which contains hydrogen, easily and at low cost. A process for producing a halogenated diene represented by the formula (1): a1A2C ═ CA3-CA4 ═ CA5a6[ in the formula, A1, A2, a5, and a6 independently represent hydrogen, fluorine, or chlorine, (perfluoro) alkyl group having 1 to 3 carbon atoms, or (perfluoro) alkenyl group; a3 and a4 independently represent hydrogen, fluorine or chlorine; at least 1 of A1-A6 represents hydrogen; at least 1 of A1-A6 represents fluorine or chlorine. And the manufacturing method comprises the following steps: reacting a compound of formula (2) in the presence of a 0-valent metal: a7A8C ═ CA9X [ in the formula, A7 and A8 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl group having 1 to 3 carbon atoms, or (perfluoro) alkenyl group; a9 independently represents hydrogen, fluorine or chlorine; x represents bromine or iodine. And the same or different halogenated olefins are subjected to coupling reaction.)

1. A process for producing a halogenated diene represented by the formula (1):

In the formula (1), the reaction mixture is,

A1, A2, A5 and A6 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl having 1 to 3 carbon atoms, or (perfluoro) alkenyl;

A3 and a4 independently represent hydrogen, fluorine or chlorine;

at least 1 of A1-A6 represents hydrogen; at least 1 of A1-A6 represents fluorine or chlorine,

The manufacturing method comprises the following steps: a step of subjecting the same or different halogenated olefins represented by the formula (2) to a coupling reaction in the presence of a 0-valent metal,

In the formula (2), A7 and A8 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl having 1 to 3 carbon atoms, or (perfluoro) alkenyl; a9 independently represents hydrogen, fluorine or chlorine; x represents bromine or iodine.

2. The method of claim 1, comprising: and a step of subjecting the same halogenated olefin to a coupling reaction.

3. The method of claim 1, comprising: and (3) a step of causing different halogenated olefins to undergo coupling reactions.

4. the process according to any one of claims 1 to 3, wherein at least one of the halogenated olefins represented by formula (2) is 1, 1-difluoro-2-iodoethylene.

5. a process according to any one of claims 1 to 4, wherein the metal is copper.

6. The method according to any one of claims 1 to 5, wherein the step of performing the coupling reaction is performed in a solvent or without a solvent.

7. The method according to claim 6, wherein the solvent is 1 or more selected from amide solvents.

8. The method according to any one of claims 1 to 7, wherein the reaction temperature of the step of causing the coupling reaction is in the range of 20 to 200 ℃.

Technical Field

The present invention relates to a method for producing a compound having a polyene skeleton containing hydrogen and fluorine and/or chlorine, particularly a butadiene skeleton containing hydrogen and fluorine and/or chlorine.

Background

As a method for synthesizing a Hydrofluorocarbon (HFC) compound having a1, 3-butadiene skeleton, a coupling reaction using 2 metals as shown in the following formula is known (non-patent document 1).

In this reaction, an excess amount of zinc metal is mixed with the raw material 1, 1-difluoroiodoethylene, and then a coupling reaction is carried out using a catalytic but expensive palladium catalyst. Further, it is known that 1,1,4, 4-tetrafluoro-1, 3-butadiene can be synthesized by a cyclization reaction of tetrafluoroethylene with acetylene, which is represented by the following formula, accompanied by thermal decomposition, but the cyclization reaction requires a high temperature of 600 ℃.

Further, as a method for producing a fluorocarbon which is not a hydrofluorocarbon but has no hydrogen atom bonded to a double bond, hexafluoro-1, 3-butadiene is obtained by reacting 1,1, 2-trifluoro-2-iodoethylene with copper powder as shown in the following formula (patent document 1).

Disclosure of Invention

Problems to be solved by the invention

However, the above-mentioned conventional techniques cannot be said to be applicable to mass production of hydrofluorobutadiene because the metal catalyst is expensive, the reaction conditions are high, and the reaction substrate is limited to perhalogenated ethylene. Accordingly, an object of the present invention is to provide a method for industrially producing a compound having a polyene skeleton containing hydrogen and fluorine and/or chlorine, particularly a butadiene skeleton containing hydrogen and fluorine and/or chlorine, easily at low cost.

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, they have found a method for industrially producing a compound having a polyene skeleton containing hydrogen and fluorine in a high yield, simply and at low cost, and have completed the present invention. That is, the present invention provides the following aspects.

[1] A process for producing a halogenated diene represented by the formula (1):

[ in the formula,

a1, A2, A5 and A6 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl having 1 to 3 carbon atoms, or (perfluoro) alkenyl;

A3 and a4 independently represent hydrogen, fluorine or chlorine;

At least 1 of A1-A6 represents hydrogen; at least 1 of A1-A6 represents fluorine or chlorine. ]

The manufacturing method comprises the following steps: a step of subjecting the same or different halogenated olefins represented by the formula (2) to a coupling reaction in the presence of a 0-valent metal.

[ wherein A7 and A8 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl having 1 to 3 carbon atoms, or (perfluoro) alkenyl; a9 independently represents hydrogen, fluorine or chlorine; x represents bromine or iodine. ]

[2] The method of [1], comprising: and a step of subjecting the same halogenated olefin to a coupling reaction.

[3] The method of [1], comprising: and (3) a step of causing different halogenated olefins to undergo coupling reactions.

[4] The method according to any one of [1] to [3], wherein at least one of the halogenated olefins represented by the formula (2) is 1, 1-difluoro-2-iodoethylene.

[5] The method according to any one of [1] to [4], wherein the metal is copper.

[6] The method according to any one of [1] to [5], wherein the step of causing the coupling reaction is performed in a solvent or without a solvent.

[7] the process according to [6], wherein the solvent is 1 or more selected from amide solvents.

[8] the method according to any one of [1] to [7], wherein the reaction temperature in the step of causing the coupling reaction is in the range of 20 to 200 ℃.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a halogenated diene represented by the above formula (1) having at least 1 hydrogen atom and at least 1 fluorine atom and/or chlorine atom can be industrially produced with high yield and at low cost.

Detailed Description

(action)

The present invention is a method for producing a halogenated diene represented by the formula (1), comprising the steps of: a step of subjecting the same or different halogenated olefins represented by the above formula (2) to a coupling reaction in the presence of a 0-valent metal.

To the knowledge of the applicant, no reaction has been proposed for coupling halogenated olefins having 1 or more hydrogen atoms bonded to double-bonded carbons to each other using 0-valent metals, particularly 0-valent copper, without using expensive noble metal catalysts. The present invention has been found experimentally in this situation and is completely unexpected to those skilled in the art.

(reaction substrate)

The reaction substrate of the present invention is a halogenated olefin represented by the aforementioned formula (2). In formula (2), A7 and A8 independently represent hydrogen, fluorine or chlorine, (perfluoro) alkyl having 1 to 3 carbon atoms, or (perfluoro) alkenyl; a9 represents hydrogen, fluorine or chlorine; x represents bromine or iodine. The same or different two of the reaction substrates are coupled at the site to which X is bonded to produce the halogenated diene of the aforementioned formula (1). Under the condition that at least 1 of A1-A6 in the formula (1) represents hydrogen and at least 1 of A1-A6 represents fluorine or chlorine, 2 same or different halogenated olefins represented by the formula (2) are selected as reaction substrates. Examples of the (perfluoro) alkyl group having 1 to 3 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and a heptafluoroisopropyl group. The number of carbon atoms of the (perfluoro) alkenyl group is not limited, and it is preferably selected so that the number of double bonds in the product polyene becomes 2 to 6. Specific examples thereof include a trifluorovinyl group, 1,2,3,4, 4-pentafluoro-1, 3-butadienyl group, and 1,2,3,4,5,6, 6-heptafluoro-1, 3, 5-hexanetrienyl group.

Specific examples of the halogenated olefin represented by the formula (2) include 1, 1-difluoroiodoethylene, 1, 2-difluoro-iodoethylene, 2-fluoroiodoethylene, 1-fluoroiodoethylene, iodoethylene, 1-difluorobromoethylene, 1-dichloroiodoethylene, and 1,1, 2-trifluoroiodoethylene.

(0 valent metal)

In the present invention, the 0-valent metal is present in the reaction system as a catalyst. Examples of the metal include copper, zinc, magnesium, iron, silver, aluminum, and nickel, and copper is preferably used. The metal is preferably in the form of particles in order to increase the surface area of the reaction, and the particle diameter in this case is, for example, preferably 10 to 1mm, and more preferably about 20 to 80 μm. On the surface of the metal, oxidation of the metal generally occurs and the catalytic activity decreases. Therefore, it is preferable to perform pretreatment for removing ionized metal such as oxide and nitride from the metal surface before charging into the reaction system. Examples of such pretreatment include mixing with an acid, stirring, filtering, washing with pure water or acetone, and heating and vacuum-drying.

(reaction conditions)

The coupling reaction of the present invention is carried out by heating the halogenated olefin represented by the aforementioned formula (2) in the presence of a 0-valent metal. The reaction temperature is preferably 20 to 200 ℃, and more preferably 100 to 150 ℃. The reaction pressure is usually carried out under atmospheric pressure, and when the reaction substrate is a gas, it can be carried out by introducing a 0-valent metal into a pressure-resistant reaction vessel and introducing the gas. The reaction can be terminated by lowering the temperature to room temperature.

When the reaction substrate is a liquid, the coupling reaction is preferably carried out in a solvent so that the coupling reaction can be carried out uniformly. Examples of the solvent include amide solvents, and specifically, DMF (N, N-dimethylformamide), NMP (N-methyl-2-pyrrolidone), and the like can be used.

The purification process of the halogenated diene of the formula (1) as the product of the present invention can be carried out by a method known in the art, and can be usually carried out by distillation.