WO2012121340A1

WO2012121340A1 - Preparation method for fluorine-containing olefins having organic-group substituents

Info

Publication number: WO2012121340A1
Application number: PCT/JP2012/055992
Authority: WO
Inventors: 永井　隆文; 足達　健二; 柴沼　俊; 専介生越; 大橋　理人
Original assignee: 国立大学法人大阪大学; ダイキン工業株式会社
Priority date: 2011-03-10
Filing date: 2012-03-08
Publication date: 2012-09-13
Also published as: JP5744175B2; JPWO2012121340A1

Abstract

The purpose of the present invention is to provide a preparation method which enables the easy and efficient (high yield, high selectivity, low cost) preparation of fluorine-containing olefins having organic-group substituents, from fluorine-containing olefins. [Solution] A preparation method for fluorine-containing olefins having organic-group substituents, said method being characterised by including a process in which fluorine-containing olefins and an organic zinc compound are reacted in the absence of a transition metal catalyst.

Description

Method for producing fluorine-containing olefin substituted with organic group

The present invention relates to a method for producing a fluorine-containing olefin substituted with an organic group.

1-Substituted fluorine-containing olefins such as 1,1,2-trifluorostyrene are compounds useful as raw materials for polymer electrolytes, for example, and 1,1-difluoro-2,2-diphenylethylene and the like. 1,1-disubstituted fluorine-containing olefins are useful compounds as raw materials for, for example, pharmaceuticals such as enzyme inhibitors and ferroelectric materials. However, a method for easily and efficiently producing these compounds has not been established.

For example, it has been reported that 1,1-disubstituted fluorine-containing olefins can be produced by a difluoromethylene reaction by a Wittig reaction of a carbonyl compound (Non-patent Document 1).
However, when the carbonyl compound is a ketone, the yield is low even when an excess amount (4-5 equivalents or more) of Wittig reagent is used, and further, carcinogenic hexamethyl phosphite triamide is used as the phosphorus compound. This method is problematic because it is essential.

Therefore, fluorine-containing olefins substituted with organic groups (eg, 1-substituted fluorine-containing olefins, 1,1-disubstituted fluorine-containing olefins, etc.) can be easily obtained from readily available fluorine-containing olefins such as tetrafluoroethylene (TFE). Can be a very useful synthesis technique.

So far, for example, the following method has been reported as a method for producing a fluorine-containing olefin substituted with an organic group.

Non-Patent Document 2 discloses that a carbon-halogen (C—X) bond of CF ₂ ═CFX (X: a halogen atom other than a fluorine atom) is converted into a carbon-lithium (C—Li) bond by butyl lithium. , A method for performing a C—C bond formation reaction is described. In Non-Patent Documents 3, 4 and 5, the C—Li bond Li generated as described above is further reconverted into a metal such as Sn and Si, and then a CC bond generation reaction is performed. A method is described.

However, these methods are relatively difficult or expensive to obtain the raw material CF ₂ ═CFX, and the fluorine-containing lithium reagent having a C—Li bond generated in the first stage is very unstable. However, there is a disadvantage that the reaction needs to be carried out under cooling of about −100 ° C. For this reason, these are not practical methods.

Non-Patent Documents 6 to 8 describe a method of selectively replacing one fluorine atom by reacting TFE with an organolithium reagent or an organomagnesium reagent. In the following reaction formula, Ph represents a substituted or unsubstituted phenyl group.

PhLi + CF ₂ = CF ₂ → PhCF = CF ₂ (Non-patent Document 6)
PhMgBr + CF ₂ = CF ₂ → PhCF = CF ₂ (Non-patent Documents 7 and 8)
These methods have the disadvantages that in order to obtain the desired product with high selectivity, it is necessary to carry out the reaction at a low temperature and to use the raw material TFE in a large excess. When the reaction temperature rises, the progress of the reaction cannot be controlled, and 1,2-adducts and further polysubstituted products are produced together with the target product. For this reason, the yield of a target object falls significantly. On the other hand, even when an organic lanthanide reagent with low nucleophilicity is used, the yield of the target product is not improved (Non-patent Document 9).

In the method described in Non-Patent Document 10, alkyl lithium is reacted with HFC134a (CF ₃ CFH ₂ ), and fluorine-containing vinyl lithium is generated by elimination reaction. Furthermore, a fluorine-containing vinyl group is subjected to a coupling reaction via a vinyl zinc reagent generated by performing metal exchange with zinc.

However, this method has disadvantages in that it is necessary to use an excessive amount of expensive alkyl lithium and that the reaction temperature must be precisely controlled because the fluorine-containing vinyl lithium to be produced has instability.

On the other hand, recently, a method has been reported in which a transition metal catalyst is used to activate a carbon-fluorine bond of TFE, and an organic zinc reagent replaces fluorine with an organic group (Patent Document 1, Non-Patent Document 1). Reference 11).
The advantages of this approach are that the reaction conditions are relaxed compared to the above and the product selectivity is high. However, this method has a disadvantage in that an expensive transition metal such as palladium needs to be used.

On the other hand, in hexafluoropropene (HFP), which is generally used as a raw material for fluororesins as in TFE, the substitution reaction of the carbon-fluorine bond is performed with organolithium (Non-patent documents 12 and 13) and organomagnesium reagent (non-patent). Reference 14). Especially in the reaction with organolithium, the reaction conditions are limited in the same manner as TFE.

From the above, there is a demand for a reaction reagent that enables a reaction with a high yield and that does not require precise control of the reaction temperature.

By the way, since the organozinc reagent has a lower nucleophilicity than the lithium reagent and the magnesium reagent, it can be used under mild conditions. For this reason, organozinc reagents are used in carbon-carbon forming reactions by addition reactions to carbonyl groups and couplings using metal catalysts. However, it has not been reported so far that an organozinc reagent is used for a substitution reaction of a fluorine atom on a sp2-hybridized carbon atom of a fluorine-containing olefin in the absence of a transition metal catalyst.

JP 2010-229129 A

An object of the present invention is to provide a production method capable of producing a fluorinated olefin substituted with an organic group in a simple and efficient manner (high yield, high selectivity, low cost) from a fluorinated olefin.

The inventors initially reacted a fluorine-containing olefin such as TFE with an organic zinc reagent in a suitable solvent in the absence of a transition metal catalyst and in the presence of a metal salt having Lewis acidity. It has been found that olefins can be produced in which the fluorine atom bonded to the sp2 hybrid carbon atom of the olefin is substituted with an organic group of an organozinc reagent.

Specifically, the present inventors reacted a diphenylzinc reagent with TFE in an aprotic solvent having an appropriate polarity such as THF in the absence of a transition metal catalyst and in the presence of a salt such as lithium iodide. It has been found that α, β, β-trifluorostyrene can be obtained. The reaction of the present invention including this reaction is considered to proceed as shown in the following reaction formula. However, the present invention is not limited to this.

As a result of further research based on such knowledge, the present inventors have reacted fluorine-containing olefins substituted with organic groups by reacting fluorine-containing olefins with organic zinc compounds in the absence of a transition metal catalyst. It has been found that it can be produced simply and efficiently (high yield, high selectivity, low cost), and the present invention has been completed.

That is, the present invention relates to the following method for producing a substituted fluorine olefin.

Item 1. A method for producing a fluorine-containing olefin substituted with an organic group, comprising a step of reacting a fluorine-containing olefin and an organic zinc compound in the absence of a transition metal catalyst.
Item 2. Item 2. The production method according to Item 1, wherein at least one fluorine atom bonded to the sp2 hybrid carbon atom of the fluorine-containing olefin is substituted with an organic group in the organozinc compound.
Item 3. Item 3. The method according to Item 1 or 2, wherein the step is performed in a solvent.
Item 4. Item 4. The production method according to any one of Items 1 to 3, wherein the step is performed in the presence of a fluorine affinity compound and / or under heating.
Item 5. The organozinc compound is
1) Formula (6a) or (6b):
R ₂ Zn (6a)
(In the formula, two Rs may be the same or different and each may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted group. Represents an aryl group.)
RZnX (6b)
(Wherein R is as defined in formula (6a); X represents Cl, Br or I), or
2) Formula (7):
ZnX ₂ (7)
(Wherein X has the same meaning as in formula (6a).)
A compound represented by formula (8):
RMgX (8)
(In the formula, R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group. X is as defined in formula (6a).)
Item 5. The production method according to any one of Items 1 to 4, which is a compound produced in a reaction system from a compound represented by the formula:
Item 6. R is
(1) an alkyl group which may be substituted with one or more substituents selected from the group consisting of a lower alkoxy group and an aryl group;
(2) a monocyclic, bicyclic, or optionally substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group, and an aryl group A tricyclic aryl group,
(3) an alkenyl group optionally substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkynyl group, a lower alkoxy group, and an aryl group, or
(4) The production method according to the above item 5, which is an alkynyl group which may be substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkenyl group, a lower alkoxy group, and an aryl group.
Item 7. Item 7. The production method according to any one of Items 4 to 6, wherein the step is carried out in the presence of the fluorine affinity compound, and the fluorine affinity compound is lithium halide, magnesium halide, or zinc halide.
Item 8. Item 8. The method according to Item 7, wherein the fluorine affinity compound is lithium halide.
Item 9. The fluorine-containing olefin substituted with the organic group has the formula (4) or (5):

(In the formula, R represents an optionally substituted aryl group, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted alkynyl group.)
Item 9. The production method according to any one of Items 1 to 8, which is a compound represented by the formula:

According to the production method of the present invention, a fluorine-containing olefin substituted with an organic group can be produced from a fluorine-containing olefin simply and efficiently (high yield, high selectivity, low cost).
Furthermore, the process of the present invention has significant advantages in alkylating fluorinated olefins for the reasons described below.
When a reaction between an alkylzinc compound having β hydrogen and a fluorine-containing olefin is carried out using a transition metal catalyst, a product in which the C—F bond is reduced is produced in addition to the alkylated product. This not only reduces the yield of alkylated product, but also becomes a barrier in purification. In contrast, the method of the present invention does not produce a reduced compound regardless of the structure of the alkyl group. As described above, the present invention has not only a cost advantage by not using a catalyst but also a process advantage such as an improvement in yield and ease of product isolation and purification.

In the present specification, “substitution” means replacement of a hydrogen atom or a fluorine atom in a molecule with another atom or group.
In the present specification, the “substituent” means another atom or group replacing one or more hydrogen atoms or fluorine atoms in a molecule.

The production method of the present invention includes a step of reacting a fluorine-containing olefin and an organic zinc compound in the absence of a transition metal catalyst (sometimes referred to simply as a reaction step in the present specification).

In the present invention, examples of the fluorinated olefin used as a substrate include compounds in which at least one fluorine atom is bonded to two sp2 hybrid carbon atoms forming the olefin. Specifically, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoroethylene, 1,1-difluoroethylene (vinylidene fluoride), 1,2-difluoroethylene, 1,1,2-chlorotri Fluoroethylene and the like can be mentioned, and TFE, trifluoroethylene, HFP and the like are preferable from the viewpoints of easy availability and versatility in fluorine chemistry.

The organozinc compound used in the production method of the present invention is a compound having an organic group capable of substituting a fluorine atom on the sp2 hybrid carbon atom of the fluorinated olefin, and functions as a nucleophile.

Examples of the organic group of the organozinc compound include an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted aryl group. Is mentioned.

As an organic zinc compound,
1) Formula (6a) or (6b):
R ₂ Zn (6a)
Wherein two Rs are the same or different (preferably the same), an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or a substituted group Represents an aryl group which may be substituted.)
RZnX (6b)
(Wherein R has the same meaning as in formula (6a); X represents Cl, Br, or I)).
Alternatively, as an organozinc compound,
2) Formula (7):
ZnX ₂ (7)
(Wherein X has the same meaning as in formula (6a).)
A compound represented by formula (8):
RMgX (8)
(Wherein R is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group; X Is the same meaning as in formula (6a).)
A compound that is generated in the reaction system by introducing the compound represented by formula (1) into the reaction system may be used.
The amount of the compound of formula (8) to be used is usually about 0.1 to 2 mol with respect to 1 mol of the compound of formula (7).

In addition, these compounds may form a solvate with a solvent used in the reaction system.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Examples include lower (particularly C1-6) alkyl groups such as isopentyl, neopentyl, 1-methylpentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, and 3,3-dimethylbutyl.
Examples of the substituent on the alkyl group include:
Lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy;
And aryl groups such as phenyl and naphthyl.
The alkyl group may be substituted with one or more (for example, 1 to 3 (particularly 1 to 2)) of the above substituents.
The production method of the present invention is simple and efficient even when R is a C2-6 alkyl group (high yield, high selectivity, low cost), and fluorine-containing substituted with an organic group (C2-6 alkyl group). It is particularly excellent in that olefin can be produced.

Examples of the alkenyl group of the “optionally substituted alkenyl group” represented by R include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl. 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5 -Lower (particularly C2-6) alkenyl groups such as hexenyl.
Examples of the substituent on the alkenyl group include:
Lower (especially C1-6) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl;
Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, Lower (particularly C2-6) alkynyl groups such as 4-hexynyl, 5-hexynyl;
Lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy;
And aryl groups such as phenyl and naphthyl.
The alkenyl group may be substituted with one or more (eg, 1 to 3 (especially 1 to 2)) of the above substituents.

Examples of the alkynyl group of the “optionally substituted alkynyl group” represented by R include, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2- Examples include lower (particularly C2-6) alkynyl groups such as pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like.
Examples of the substituent on the alkynyl group include:
Lower (especially C1-6) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl;
Vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4 A lower (especially C2-6) alkenyl group such as pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl;
Lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy;
And aryl groups such as phenyl and naphthyl.
The alkynyl group may be substituted with one or more (eg, 1 to 3 (particularly 1 to 2)) of the above substituents.

Examples of the aryl group of the “optionally substituted aryl group” represented by R include monocyclic, bicyclic or tricyclic aryl groups such as phenyl, naphthyl, anthracenyl and phenanthryl groups. .
Examples of the substituent on the aryl group include:
Lower (especially C1-6) alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl;
Lower (particularly C2-6) alkenyl groups such as vinyl, allyl and crotyl;
Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, Lower (particularly C2-6) alkynyl groups such as 4-hexynyl, 5-hexynyl;
Lower (particularly C1-6) alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy;
And aryl groups such as phenyl and naphthyl.
The aryl group may be substituted with one or more (for example, 1 to 4 (particularly 1 to 2)) of the above-described substituents.

R is preferably an alkyl group optionally substituted with one or more substituents selected from the group consisting of a lower alkoxy group and an aryl group, or a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group And a monocyclic, bicyclic or tricyclic aryl group optionally substituted with one or more substituents selected from the group consisting of aryl groups, more preferably a phenyl group or a lower group ( In particular, it is a C1-6 alkyl group.

X is preferably Br or Cl.

Specific examples of the organic zinc compound include diphenyl zinc and diethyl zinc.

The above-mentioned organozinc compound can be obtained as a commercial product or synthesized by a known method.

The amount of the fluorine-containing olefin and the organic zinc compound can be appropriately set according to the number of fluorine atoms that undergo substitution reaction in the fluorine-containing olefin. Usually, the amount of the fluorine-containing olefin used is usually about 0.1 to 100 mol, preferably about 0.5 to 10 mol, per 1 mol of the organic zinc compound.

The reaction process of the present invention is carried out in the absence of a transition metal catalyst.
In the present specification, the term “transition metal catalyst” should be understood in the usual sense in the field of chemical synthesis.
The absence of a transition metal catalyst means that the amount of the transition metal catalyst is less than or equal to the amount that can substantially act as a catalyst.

In the production method of the present invention, the reaction step is carried out in the presence of a fluorine-affinity compound and / or under heating, whereby the reaction intermediate (2) or (2 ′) of the product (4) or (5) ) To facilitate the conversion to the product (4) or (5).

Fluorine-affinity compounds include a salt of a metal (hard metal) having an affinity with a fluorine atom and a weak acid (eg, lithium acetate), and a metal having an affinity for a fluorine atom (hard metal) and a halogen. Mention may be made of metal halides having Lewis acidity consisting of atoms. Examples of the metal halide include lithium halide, magnesium halide, and zinc halide. Specifically, lithium halides such as lithium chloride, lithium bromide and lithium iodide; magnesium halides such as magnesium bromide and magnesium iodide; zinc halides such as zinc chloride, zinc bromide and zinc iodide, etc. Is mentioned. Lithium halide such as lithium iodide is preferable.

When a fluorine-affinity compound is added to the reaction system, the input amount is usually about 0.5 to 10 mol, preferably about 1 to 5 mol, relative to 1 mol of the organozinc reagent used. it can.

The reaction temperature is not particularly limited, but is usually −100 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably room temperature (about 20 ° C.) to 100 ° C. As described above, the reaction step of the present invention is preferably carried out under heating. “Under heating” means that a temperature condition higher than room temperature is used. Specifically, for example, the reaction temperature is 30 ° C. to 70 ° C. In addition, since dimerization of the product trifluorovinyl derivative may proceed at high temperatures, the upper limit reaction temperature can be set within a range in which dimerization does not proceed.

Also, the reaction time is not particularly limited, and the lower limit thereof is, for example, 10 minutes, 2 hours, 5 hours, 3 hours, while the upper limit thereof is, for example, about 15 days, about 7 days, 72 The time is about 50 hours.

The reaction atmosphere is not particularly limited, but is usually performed in an inert gas atmosphere such as argon or nitrogen in consideration of the activity of the organic zinc compound. Further, the reaction pressure may be increased, normal pressure, or reduced pressure. Usually, it is preferably carried out under pressure. In this case, the pressure is about 0.1 to 10 MPa, preferably about 0.1 to 1 MPa.

The reaction step of the present invention is preferably carried out in a solvent. The solvent to be used is not particularly limited as long as it does not adversely affect the reaction. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane and cyclohexane; tetrahydrofuran (THF), ether solvents such as dioxane, diethyl ether, glyme, diglyme and the like; nitrile solvents such as acetonitrile, propionitrile, dimethylcyanamide, t-butyl nitrile and the like can be used. Of these, ether solvents such as THF; nitrile solvents such as acetonitrile, propionitrile, and t-butylnitrile are preferable.

The fluorine-containing olefin substituted with an organic group thus obtained is preferably, for example, the formula (4) or (5):

(In the formula, R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group.)
It is.

The compound of formula (4) and the compound of formula (5) may be produced as a mixture. The production ratio of the compound of the formula (4) and the compound of the formula (5) can be controlled, for example, by the amount ratio of the fluorine-containing olefin and the organic zinc compound used as the substrate, the reaction time, and the like. By increasing the amount of fluorine-containing olefin and / or shortening the reaction time, the compound of formula (4) is preferentially produced, increasing the amount of the organic zinc compound, and / or the reaction time. By lengthening, the compound of formula (5) is preferentially produced. Moreover, the compound of Formula (4) and the compound of Formula (5) can be refine | purified by well-known purification methods, such as distillation, as needed.
In the formula (5), two Rs may be the same or different. For example, the compound of formula (5) in which two Rs are different from each other is obtained by reacting the compound of formula (4) with an organozinc compound having an organic group different from the organozinc compound used for the production of formula (4). Can be synthesized.

When isobutyronitrile is used as the solvent, the compound:

Is generated. The compound is a novel compound.

Also as an impurity, the formula:

(The symbols in the formula are as defined above.)
Can also be produced. The compound can be easily removed by known purification methods.

Examples of the fluorine-containing olefin having an organic group thus obtained include fluororubber, antireflection membrane material, ion exchange membrane, electrolyte membrane for fuel cell, liquid crystal material, piezoelectric element material, enzyme inhibitor, insecticide, etc. It is useful as a raw material.

Hereinafter, the present invention will be described more specifically with reference to examples. Needless to say, the present invention is not limited to the following examples.

Example 1
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in acetonitrile (0.4 mL) in a pressure-resistant tube (2 ml capacity) in a glove box under an inert atmosphere. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume of 2 ml and the introduction pressure of 0.35 MPa, the same applies hereinafter) was added thereto. The reaction solution was left at 60 ° C. for 8 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that 1,1,2-trifluoro-1-butene was obtained at a yield of 22% from the internal standard.
1,1,2-trifluoro-1-butene:
¹⁹ F-NMR (C ₆ D ₆ ): δ -109.6--110.0 (m, 1F), -128.0--129.0 (m, 1F), -177.8--78.3 (m, 1F).

Example 2
In a glove box under an inert atmosphere, a solution of diphenylzinc (22.0 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in THF-d8 (0.3 mL) / THF (0.2 mL) 2 ml), and α, α, α-trifluorotoluene (12.3 μL, 0.100 mmol: internal standard for ¹⁹ F-NMR measurement) was added thereto. Furthermore, hexafluoropropene (HFP: 0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 40 ° C. for 18 hours and further at 60 ° C. for 24 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that 1-phenylperfluoroprop-1-ene was obtained at a yield of 23% (E / Z = 5.5: 1) from the internal standard.
(E) -1-phenylperfluoroprop-1-ene ((E) -1-phenylperfluoroprop-1-ene):
¹⁹ F NMR (THF-d ₈ ): -174.1 (dq, J _FF = 11, 133 Hz, 1F), -148.0 (dq, J _FF = 22, 133 Hz, 1F), -69.6 (dd, J _FF = 11, 22 Hz, 3F).
(Z) -1-phenylperfluoroprop-1-ene ((Z) -1-phenylperfluoroprop-1-ene):
¹⁹ F NMR (THF-d ₈ ): -159.3 (dq, J _FF = 12, 13 Hz, 1F), -109.9 (dq, J _FF = 12, 8 Hz, 1F), -68.5 (dd, J _FF = 8, 13 Hz, 3F).

Example 3
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in dimethylcyanamide (0.4 mL) in a pressure-resistant tube (capacity 2 ml) under an inert atmosphere in a glove box. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 8 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, it was confirmed that 1,1,2-trifluoro-1-butene was obtained in a yield of 20%.

Example 4
Prepare an isopropionitrile (0.4 mL) solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in a pressure-resistant tube (2 ml capacity) in a glove box under an inert atmosphere. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 48 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that 1,1,2-trifluoro-1-butene was obtained in a yield of 30%.

Example 5
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in t-butylnitrile (0.4 mL) in a pressure tube (2 ml capacity) in a glove box under an inert atmosphere. Then, α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 8 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, 1,1,2-trifluoro-1-butene was obtained in a yield of 54% and 3,4-difluoro-3-hexene in a yield of 6%. It was confirmed.

Example 6
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in deuterated acetonitrile (0.4 mL) in a pressure-resistant tube (2 ml capacity) in a glove box under an inert atmosphere. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was allowed to stand at 20 ° C. for 330 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, 1,1,2-trifluoro-1-butene was obtained in a yield of 67% and 3,4-difluoro-3-hexene in a yield of 5%. It was confirmed.

Example 7
Prepare a heavy THF (0.4 mL) solution of diphenylzinc (22.0 mg, 0.100 mmol) and lithium iodide (32.2 mg, 0.240 mmol) in a pressure tube (volume 2 ml) under an inert atmosphere in a glove box, Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 45 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, α, α, β-trifluorostyrene was obtained in a yield of 33% and 1,2-difluoro-1,2-diphenylethylene in a yield of 5%. It was confirmed.
α, α, β-Trifluorostyrene:
¹ H-NMR (C ₆ D ₆ ): δ 7.16 (tt, J = 7.5, 1.5Hz, 1H), 7.47 (dd, J = 8.5, 7.5 Hz, 2H), 7.59 (dd, J = 8.5, 1.5 Hz , 2H).
¹⁹ F-NMR (C ₆ D ₆ ): δ -103.5 (dd, J = 72, 32 Hz, 1F), -118.0 (dd, J = 72, 107 Hz, 1F), -179.2 (dd, J = 107, 32 Hz, 1F).
1,2-difluoro-1,2-diphenylethylene:
¹⁹ F-NMR (C ₆ D ₆ ): δ trans -154.8 (s), cis -130.5 (s).

Example 8
Prepare a solution of diphenylzinc (22.0 mg, 0.100 mmol) in deuterated THF (0.4 mL) in a pressure tube (2 ml capacity) under an inert atmosphere in a glove box, and add α, α, α-trifluorotoluene to it. (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 44 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, α, α, β-trifluorostyrene was obtained in a yield of 22% and 1,2-difluoro-1,2-diphenylethylene in a yield of 3%. It was confirmed.

Example 9
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) in deuterated acetonitrile (0.4 mL) in a pressure tube (2 ml capacity) in an inert atmosphere in a glove box, and add α, α, α-trifluorotoluene to it. (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 24 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that 1,1,2-trifluoro-1-butene was obtained in a yield of 6%.

Example 10
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium acetate (15.8 mg, 0.240 mmol) in deuterated acetonitrile (0.4 mL) in a pressure tube (2 ml capacity) under an inert atmosphere in a glove box. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 140 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, it was confirmed that 1,1,2-trifluoro-1-butene was obtained in a yield of 36%.

Example 11
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium acetate (36.0 mg, 0.240 mmol) in deuterated acetonitrile (0.4 mL) in a pressure tube (2 ml capacity) under an inert atmosphere in a glove box. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 16 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, it was confirmed that 1,1,2-trifluoro-1-butene was obtained in a yield of 26%.

Example 12
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium bromide (20.8 mg, 0.240 mmol) in deuterated acetonitrile (0.4 mL) in a pressure tube (2 ml capacity) under an inert atmosphere in a glove box, Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard at the time of ¹⁹ F-NMR measurement) was added thereto. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 24 hours. The reaction was monitored by ¹⁹ F-NMR. Based on the internal standard, 1,1,2-trifluoro-1-butene was obtained in a yield of 28% and 3,4-difluoro-3-hexene in a yield of 3%. It was confirmed.

Example 13
Prepare a solution of diethylzinc (12.5 mg, 0.100 mmol) and lithium chloride (10.2 mg, 0.240 mmol) in deuterated acetonitrile (0.4 mL) in a pressure tube (2 ml capacity) under an inert atmosphere in a glove box. Α, α, α-trifluorotoluene (14 μL, 0.114 mmol: internal standard for ¹⁹ F-NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container volume and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 60 ° C. for 4 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that 1,1,2-trifluoro-1-butene was obtained in a yield of 16%.

According to the present invention, a fluorine-containing olefin substituted with an organic group can be easily and efficiently produced (high yield, high selectivity, and low cost).

Claims

A method for producing a fluorine-containing olefin substituted with an organic group, comprising a step of reacting a fluorine-containing olefin and an organic zinc compound in the absence of a transition metal catalyst.
The production method according to claim 1, wherein at least one fluorine atom bonded to the sp2 hybrid carbon atom of the fluorine-containing olefin is substituted with an organic group in the organozinc compound.
The method according to claim 1 or 2, wherein the step is carried out in a solvent.
The production method according to any one of claims 1 to 3, wherein the step is carried out in the presence of a fluorine affinity compound and / or under heating.
The organozinc compound is
1) Formula (6a) or (6b):
R 2 Zn (6a)
(In the formula, two Rs may be the same or different and each may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted group. Represents an aryl group.)
RZnX (6b)
(Wherein R is as defined in formula (6a); X represents Cl, Br or I), or
2) Formula (7):
ZnX 2 (7)
(Wherein X has the same meaning as in formula (6a).)
A compound represented by formula (8):
RMgX (8)
(In the formula, R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group. X is as defined in formula (6a).)
The production method according to any one of claims 1 to 4, which is a compound produced in a reaction system from a compound represented by the formula:
R is
(1) an alkyl group which may be substituted with one or more substituents selected from the group consisting of a lower alkoxy group and an aryl group;
(2) a monocyclic, bicyclic, or optionally substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group, and an aryl group A tricyclic aryl group,
(3) an alkenyl group optionally substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkynyl group, a lower alkoxy group, and an aryl group, or
(4) The production method according to claim 5, which is an alkynyl group which may be substituted with one or more substituents selected from the group consisting of a lower alkyl group, a lower alkenyl group, a lower alkoxy group and an aryl group.
The production method according to any one of claims 4 to 6, wherein the step is carried out in the presence of the fluorine affinity compound, and the fluorine affinity compound is lithium halide, magnesium halide, or zinc halide.
The production method according to claim 7, wherein the fluorine affinity compound is lithium halide.
The fluorine-containing olefin substituted with the organic group has the formula (4) or (5):

(In the formula, R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group.)
The production method according to any one of claims 1 to 8, which is a compound represented by the formula: