JP6410072B2 - Method for producing fluorine-containing olefin substituted with organic group - Google Patents

Description

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

  1-Substituted fluorine-containing olefin such as 1,1,2-trifluorostyrene is a compound useful as a raw material for polymer electrolyte, for example, and also includes 1,1-difluoro-2,2-diphenylethylene and the like. The 1,1-disubstituted fluorine-containing olefin is a compound useful as a raw material for pharmaceuticals such as enzyme inhibitors and ferroelectric materials, for example. However, a method for easily and efficiently producing these compounds has not been established.

For example, it has been reported that a 1,1-disubstituted fluorine-containing olefin 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.) are easily obtained from readily available fluorine-containing olefins such as tetrafluoroethylene (TFE). Can be a very useful synthesis technique.

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

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 C—C 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. 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 a 1,2-adduct and a further multi-substituted product 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 methods described in Non-Patent Documents 10 and 11, alkyl lithium is reacted with HFC134a (CF ₃ CFH ₂ ), and fluorine-containing vinyl lithium is generated by elimination reaction. Further, a fluorine-containing vinyl derivative is synthesized using vinyl zinc produced by exchanging metal with zinc or boron, or a boron reagent.

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

  If TFE, hexafluoropropene (HFP), etc., which are easily available industrially, are used as raw materials, and F (fluorine) on the sp2 hybrid carbon atom in the molecule can be substituted with an organic group in the presence of a transition metal catalyst As a method for synthesizing a fluorine-containing olefin having a substituent, it is more useful than the existing methods as described above.

  In general, there are many reports on the method of introducing a substituent into a non-fluorine olefin using a transition metal as a catalyst. However, the C—C bond in a fluorine-containing olefin is activated and subsequently the C—C bond is formed. There are very few reports on the reaction to be generated. This is because the bond energy of the C—F bond of the fluorinated olefin is compared to the bond of other halogen-containing olefin with C—Y (Y is Cl (chlorine), Br (bromine), I (iodine), etc.). This is considered to be due to the fact that the C—F bond is broken and the oxidative addition reaction of metal to this bond hardly occurs because the fluorine atom is very small and hard.

  However, recently, a method has been reported in which a carbon-fluorine bond of tetrafluoroethylene (TFE) is activated using a transition metal catalyst and fluorine is substituted with an organic group with an organozinc reagent (Patent Document 1, Non-patent document 12).

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 problem in handling the organozinc reagent itself. That is, since the organozinc reagent has low stability to temperature and humidity, it is necessary to carry out the reaction in an inert atmosphere. In addition, since it is difficult to store the reagent for a long time, it is often necessary to prepare it at the time of use.
On the other hand, organoboron reagents are frequently used in the reaction of advancing carbon-carbon bonds in the presence of a transition metal catalyst. These organoboron reagents are less toxic than other organometallic reagents, and the reagents themselves are stable. Among them, boronic acid derivatives have particularly advantageous features such that they can be handled in water. Because of these properties, boronic acid derivatives selectively form a carbon-carbon bond at the desired position even in the presence of a hydroxyl group that cannot be coexistent with other highly nucleophilic reagents such as the above organozinc reagents. I can do it.
Taking advantage of such advantages of organoboron reagents, a method for synthesizing trifluorovinyl derivatives by coupling reaction with chlorotrifluoroethylene (CTFE) and trifluoroethylene (TFE) has recently been reported (Patent Document 2, 3, Non-Patent Document 13). However, CTFE still has problems in terms of cost and TFE in terms of yield.

JP 2010-229129 International Publication No. 2012/121345

L.S.Jeong et al., Organic Letters, 2002, 4, 529 P. Tarrant et al., J. Org. Chem. 1968, 33, 286 F.G.A.Stone1 et al., J.Am.Chem.Soc., 1960, 82, 6232 J-F. Normant et al., J. Organomet. Chem. 1989, 367, 1 W.R.Dolbier, Jr. et al. J.Chem, Soc., Perkin Trans. 1998, 219 S. Dixon, J. Org. Chem. 1956, 21, 41 J.Xikui et al., Huaxue Xuebao, 1983, 41, 637 Aoki et al., J. Fluorine Chem., 1992, 59, 285 A. B. Sigalov et al., Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1988, p. 445 J. Burdon et al., J. Fluorine Chem., 1999, 99, 127 C.C.Tzschucke et al., Chem. Eur. J., 2012, 18, 437 S.Ogoshi et al., J.Am.Chem.Soc., 2011, 133, 3256 T. Yamamoto et al., Organic Letters, 2012, 14, 3454

  An object of this invention is to provide the manufacturing method which can manufacture the fluorine-containing olefin substituted by the organic group efficiently (high yield, high selectivity, low cost) from a fluorine-containing olefin.

Among organometallic reagents used in the reaction of advancing carbon-carbon bonds in the presence of a transition metal catalyst, organosilicon reagents are known in addition to organoboron reagents, as they are very easy to handle. Organosilicon reagents have the advantages of being more stable and easier to handle than boron reagents, and having low toxicity and environmental impact. In addition, in vinyl derivative synthesis using a transition metal catalyzed reaction, there are known advantages such that regioselectivity different from that of organoboron reagents can be achieved.
However, there are few application examples of the reaction using the organosilicon reagent, and it has not been reported to use this for the substitution reaction of the fluorine atom on the sp2-hybridized carbon atom of the fluorinated olefin.
If the substitution reaction of the fluorine atom on the sp2 hybrid carbon atom of the fluorine-containing olefin can proceed while taking advantage of the organosilicon reagent, it becomes possible to produce a fluorine-containing olefin having many kinds of substituents. Become.
When the present inventors reacted a fluorine-containing olefin such as TFE with an organosilicon compound in the presence of a specific transition metal catalyst, the fluorine atom bonded to the sp2 hybrid carbon atom of the fluorine-containing olefin is an organic silicon compound. It has been found that olefins substituted with groups can be produced.

  Specifically, α, β, β-trifluorostyrene, 1,1-difluoro-2,2-diphenylethylene is obtained by reacting TFE with a silicon reagent described later in the presence of an organic nickel complex or an organic palladium complex. Etc. This reaction is considered to proceed through the catalyst cycle shown in the following reaction formula. However, the present invention is not limited to this.

In the scheme, R, R ′, and R ″ each represents an organic group.

The transition metal complex [1] coordinates to CF ₂ = CF ₂ [2] at a ratio of 1: 1 to selectively form the complex [3]. Complex [3] is isomerized to complex [4] by addition of an additive or heating. Reaction of the complex [4] with an organosilicon reagent [5] activated by coordination of a base such as a fluorine anion produces a new fluorinated olefin [7] via the complex [6] The metal complex [1] is regenerated to form a catalytic cycle.

As a result of further research based on such findings, the present inventors have
Fluorine-containing substituted with an organic group by reacting a fluorine-containing olefin with a silicon compound in the presence of an organic transition metal catalyst containing a transition metal selected from nickel, palladium, platinum, rhodium, ruthenium, and cobalt It has been found that olefins can be produced simply and efficiently (high yield, high selectivity, low cost), and the present invention has been completed.

  That is, this invention relates to the manufacturing method of the following substituted fluorine olefins.

Item 1
A method for producing a fluorine-containing olefin substituted with an organic group,
A process comprising reacting a fluorine-containing olefin with an organosilicon compound in the presence of an organic transition metal catalyst containing a transition metal selected from nickel, palladium, platinum, rhodium, ruthenium, and cobalt .
Item 2
Item 2. The method according to Item 1, wherein the transition metal is selected from nickel and palladium.
Item 3
The organosilicon compound has the formula (1):
R-SiY ₃ (1)
(Where
R is an optionally substituted aryl group, an optionally substituted heteroaryl group bonded via carbon, an optionally substituted cycloalkyl group, an optionally substituted alkyl group, a substituted Represents an alkenyl group which may be substituted or an alkynyl group which may be substituted; Y is the same or different at each occurrence and represents a hydroxy group, a hydroxide group, an alkoxy group, an alkyl group or a fluoro group.
Two or three alkoxy groups or alkyl groups each represented by Y may be linked to each other to form a ring with the adjacent silicon atom. )
Item 3. The method according to Item 1 or 2, which is an organosilicon compound represented by the formula:
Item 4
Item 4. The production method according to Item 3, wherein R is an optionally substituted monocyclic, bicyclic or tricyclic aryl group.
Item 5
Item 5. The production method according to Item 3 or 4, wherein at least one fluorine atom bonded to the sp2-hybridized carbon atom of the fluorinated olefin is substituted with the group represented by R.
Item 6
Item 6. The production method according to any one of Items 1 to 5, wherein the step is carried out in the presence of a base.
Item 7
Item 7. The production method according to any one of Items 1 to 6, wherein the organic transition metal catalyst is an organic palladium complex.
Item 8
The fluorine-containing olefin substituted with the organic group has the formula (2):
(In the formula, R is as defined above.)
The manufacturing method in any one of claim | item 3 -7 which is a compound represented by these.

  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).

  Hereinafter, terms used in the present invention will be described.

In the present specification, “substitution” means replacement of a hydrogen atom or a fluorine atom in a molecule with another atom or group.
As used herein, “substituent” means another atom or group that replaces one or more hydrogen atoms or fluorine atoms in a molecule.
In the present specification, examples of the “lower alkyl group” (including lower alkyl in the substituent) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n Examples include C1-6 alkyl groups such as -pentyl, isopentyl, neopentyl, 1-methylpentyl, n-hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, and 3,3-dimethylbutyl.

  In the present specification, examples of the “lower alkoxy group” (including lower alkoxy in the substituent) include C1-6 alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and the like.

  In the present specification, examples of the “lower alkenyl group” include vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1- C2-6 such as butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl Alkenyl is mentioned.

  In the present specification, examples of the “lower alkynyl group” include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4 -C2-6 alkynyl groups such as -pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl and the like can be mentioned.

  In the present specification, examples of the “5- or 6-membered monocyclic aromatic heterocycle” include a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, Pyrazole ring, 1,2,3-oxadiazole ring, 1,2,4-oxadiazole ring, 1,3,4-oxadiazole ring, furazane ring, 1,2,3-thiadiazole ring, 1, 2,4-thiadiazole ring, 1,3,4-thiadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine 5- or 6-membered monocyclic aromatic containing 1 to 3 heteroatoms selected from oxygen, sulfur and nitrogen atoms in addition to carbon atoms as ring-constituting atoms such as rings Ring, and the like.

  Below, the manufacturing method of this invention is demonstrated.

The production method of the present invention comprises a step of reacting a fluorine-containing olefin with an organosilicon compound in the presence of an organic transition metal catalyst containing a transition metal selected from nickel, palladium, platinum, rhodium, ruthenium, and cobalt (this book). In the specification, it may be simply referred to as a reaction step).

  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. Specific examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), trifluoroethylene, 1,1-difluoroethylene (vinylidene fluoride), 1,2-difluoroethylene, and the like. From the viewpoint of versatility in fluorine chemistry, TFE, trifluoroethylene, HFP and the like are preferable.

The organosilicon 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 hybridized carbon atom of the fluorinated olefin, and functions as a nucleophile.

  Examples of the organic group of the organosilicon compound include an optionally substituted aryl group, an optionally substituted heteroaryl group bonded via carbon, an optionally substituted cycloalkyl group, and an unsubstituted group. An alkyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, and the like.

The organosilicon compound used in the production method of the present invention is preferably an organosilicon compound represented by the formula (1). Below, the symbol in Formula (1) is demonstrated.

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:
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms, (g) a lower (particularly C2-6) alkenyl group,
(h) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(i) an aryl group (eg, phenyl, naphthyl),
(j) a lower alkyl-sulfanyl group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(k) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(l) formyl group,
(m) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(n) a lower alkyl-carbonylamino group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(o) a lower alkoxy-carbonyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms.
The aryl group may be substituted with one or more (for example, 1 to 4 (especially 1 to 2)) of the above substituents.

Examples of the heteroaryl group bonded through carbon of the “optionally substituted heteroaryl group bonded through carbon” represented by R include, for example, pyrrolyl (eg, 2-pyrrolyl, 3-pyrrolyl), furyl (Eg, 2-furyl, 3-furyl), thienyl (eg, 2-thienyl, 3-thienyl), pyrazolyl (eg, 3-pyrazolyl, 4-pyrazolyl), imidazolyl (eg, 2-imidazolyl, 4-imidazolyl) , Isoxazolyl (eg, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl), oxazolyl (eg, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl), isothiazolyl (eg, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl) ), Thiazolyl (eg, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl) ), Triazolyl (eg, 1,2,3-triazol-4-yl, 1,2,4-triazol-3-yl), oxadiazolyl (eg, 1,2,4-oxadiazol-3-yl, 1 , 2,4-oxadiazol-5-yl), thiadiazolyl (eg, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl), tetrazolyl, pyridyl (eg, 2) -Pyridyl, 3-pyridyl, 4-pyridyl), pyridazinyl (eg, 3-pyridazinyl, 4-pyridazinyl), pyrimidinyl (eg, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl), pyrazinyl and the like as ring-constituting atoms, A 5- or 6-membered monocyclic heteroaryl group containing 1 to 3 hetero atoms selected from an oxygen atom, a sulfur atom and a nitrogen atom in addition to the carbon atom; A bicyclic or tricyclic heteroaryl group formed by condensing a monocyclic heteroaryl group with 1 or 2 benzene rings; and a phenyl group having 1 or 2 5 or 6 membered And bicyclic or tricyclic heteroaryl groups formed by condensation with monocyclic aromatic heterocycles.
Examples of the substituent on the heteroaryl group include:
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms, (g) a lower (particularly C2-6) alkenyl group,
(h) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(i) an aryl group (eg, phenyl, naphthyl),
(j) a lower alkyl-sulfanyl group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(k) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(l) formyl group,
(m) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(n) a lower alkyl-carbonylamino group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(o) a lower alkoxy-carbonyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms.
The heteroaryl group may be substituted with one or more (for example, 1 to 4 (especially 1 to 2)) substituents.

Examples of the cycloalkyl group of the “optionally substituted cycloalkyl group” represented by R include C3-6 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
Examples of the substituent on the cycloalkyl group include:
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms, (g) a lower (particularly C2-6) alkenyl group,
(h) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(i) an aryl group (eg, phenyl, naphthyl),
(j) a lower alkyl-sulfanyl group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(k) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(l) formyl group,
(m) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(n) a lower alkyl-carbonylamino group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(o) a lower alkoxy-carbonyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms.
The cycloalkyl group may be substituted with one or more (for example, 1 to 4 (particularly 1 to 2)) of the above substituents.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R include a lower alkyl group.
Examples of the substituent on the alkyl group include:
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(g) an aryl group (eg, phenyl, naphthyl),
(h) a lower alkyl-sulfanyl group optionally substituted with one or more (especially 1 to 3) halogen atoms,
(i) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms;
(j) formyl group,
(k) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(l) a lower alkyl-carbonylamino group optionally substituted by one or more (particularly 1 to 3) halogen atoms,
(m) a lower alkoxy-carbonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms.
The alkyl group may be substituted with one or more (for example, 1 to 3 (especially 1 to 2)) of the substituents.

Examples of the alkenyl group of the “optionally substituted alkenyl group” represented by R include a lower alkenyl group.
Examples of the substituent on the alkenyl group include:
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms, (g) a lower (particularly C2-6) alkenyl group,
(h) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(i) an aryl group (eg, phenyl, naphthyl),
(j) a lower alkyl-sulfanyl group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(k) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(l) formyl group,
(m) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(n) a lower alkyl-carbonylamino group optionally substituted by one or more (especially 1 to 3) halogen atoms,
(o) a lower alkoxy-carbonyl group which may be substituted with one or more (particularly 1 to 3) halogen atoms.
The alkenyl group may be substituted with 1 or more (for example, 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 a lower alkynyl group.
As a substituent on the alkynyl group,
For example,
(a) a halogen atom,
(b) a nitro group,
(c) a cyano group,
(d) an amino group,
(e) a carboxy group,
(f) a lower alkoxy group which may be substituted with one or more (especially 1 to 3) halogen atoms,
(g) an aryl group (eg, phenyl, naphthyl),
(h) a lower alkyl-sulfanyl group optionally substituted with one or more (especially 1 to 3) halogen atoms,
(i) a lower alkyl-sulfonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms;
(j) formyl group,
(k) a lower alkyl-carbonyl group (lower alkanoyl group) optionally substituted with one or more (especially 1 to 3) halogen atoms,
(l) a lower alkyl-carbonylamino group optionally substituted by one or more (particularly 1 to 3) halogen atoms,
(m) a lower alkoxy-carbonyl group which may be substituted with one or more (especially 1 to 3) halogen atoms.
The alkynyl group may be substituted with one or more (for example, 1 to 3 (especially 1 to 2)) of the above substituents.

  R is preferably an optionally substituted monocyclic, bicyclic or tricyclic aryl group, more preferably a phenyl group or a naphthyl group.

Examples of the “alkoxy group” represented by Y include a lower alkoxy group.
Examples of the “alkyl group” represented by Y include a lower alkyl group.
Y is preferably an alkoxy group (preferably a methoxy group or an ethoxy group), a hydroxy group, or a fluoro group.
Examples of the ring formed by connecting two or three alkoxy groups each represented by Y or an alkyl group together with adjacent silicon atoms include silacyclobutane having a silicon-containing 4-membered ring structure shown below. A ring is formed. The ring is preferable because it is highly reactive due to strain.

  As the organosilicon compound used in the present invention, for example, a known organosilicon reagent can be used. Examples of such organosilicon reagents include organosilicon reagents listed in the catalogs of Azmax Corporation or Sigma-Aldrich Corporation. Specifically, the organosilicon compound used in the present invention is preferably, for example, trimethoxyphenylsilane, triethoxyphenylsilane, trimethoxy (4-methoxyphenyl) silane or 2-naphthylsilane.

The usage-amount of a fluorine-containing olefin and an organosilicon compound can be suitably set according to the number of the fluorine atoms which carry out a substitution reaction in a 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 organosilicon compound.

  The organic transition metal catalyst used in the present invention is an organic transition metal catalyst containing a transition metal selected from nickel, palladium, platinum, rhodium, ruthenium, and cobalt. The transition metal is preferably selected from nickel and palladium. The organic transition metal catalyst containing a transition metal selected from nickel and palladium is specifically an organic nickel complex or an organic palladium complex.

  A nickel complex and a palladium complex mean both what is added as a reagent and what is produced in the reaction system.

  As the palladium complex, a zero-valent palladium complex; a zero-valent palladium complex generated during the reaction from a divalent palladium complex; or at least one compound selected from the group consisting of diketone, phosphine, diamine and bipyridyl (ligand) ) And a complex obtained by mixing.

The zero-valent palladium complex is not particularly limited. For example, Pd ₂ (dba) ₃ (dba is dibenzylideneacetone), Pd (COD) ₂ (COD is cycloocta-1,5-diene), Pd (DPPE) (DPPE is 1,2-bisdiphenylphosphinoethane), Pd (PCy ₃ ) ₂ (Cy is a cyclohexyl group), Pd (Pt-Bu ₃ ) ₂ (t-Bu is a t-butyl group) and Pd (PPh ₃ ) ₄ (Ph is a phenyl group) and the like.

Examples of the divalent palladium complex include palladium chloride, palladium bromide, palladium acetate, bis (acetylacetonato) palladium (II), dichloro (η ⁴ -1,5-cyclooctadiene) palladium (II), or these And a complex in which a phosphine ligand such as triphenylphosphine is coordinated. These II-valent palladium complexes are reduced by, for example, reducing species (phosphine, zinc, organometallic reagents, etc.) coexisting during the reaction to form zero-valent palladium complexes.

  The zero-valent palladium complex produced by reduction from the above-mentioned zero-valent palladium complex or II-valent palladium complex acts in the reaction with a compound (ligand) such as diketone, phosphine, diamine, or bipyridyl added as necessary. Thus, it can be converted into a zero-valent palladium complex involved in the reaction. In the reaction, it is not always clear how many of these ligands are coordinated to the zero-valent palladium complex.

These palladium complexes are often used in the reaction by forming a uniform solution with the reaction substrate by using the ligand as described above, but in addition to this, they are dispersed or supported in polymers such as polystyrene and polyethylene. It can also be used as a heterogeneous catalyst. Such heterogeneous catalysts have process advantages such as catalyst recovery. Specific examples of the catalyst structure include those in which metal atoms are fixed with a polymer phosphine in which phosphine is introduced into a crosslinked polystyrene (PS) chain as shown in the following chemical formula. In addition, the following:
1) Kanbara et al., Macromolecules, 2000, 33, 657 2) Yamamoto et al., J. Polym. Sci., 2002, 40, 2637 3) JP-A-06-32763 4) JP-A 2005 No. 281454 5) The polymer phosphine described in the literature shown in JP2009-527352A can also be used.

(In the formula, PS represents polystyrene and Ph represents a phenyl group.)

  Examples of the diketone include β diketones such as acetylacetone, 1-phenyl-1,3-butanedione, and 1,3-diphenylpropanedione.

The palladium complex is preferably Pd ₂ (dba) ₃ .

As the phosphine, trialkylphosphine or triarylphosphine is preferable.
Specific examples of the trialkylphosphine include tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, triisobutylphosphine, tritexylphosphine, tridamantylphosphine, tricyclopentylphosphine, and dit-butylmethyl. Examples include tri (C3-20 alkyl) phosphine such as phosphine, tribicyclo [2,2,2] octylphosphine, and trinorbornylphosphine.
Specific examples of the triarylphosphine include tri (monocyclic aryl) phosphine such as triphenylphosphine, trimesitylphosphine, and tri (o-tolyl) phosphine.
Among these, tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, triisobutylphosphine, and di-t-butylmethylphosphine are preferable. In addition, bidentate ligands such as 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) propane, and 1,1′-bis (diphenylphosphino) ferrocene Is also effective.

  As described above, arylphosphine for heterogeneous catalysts in which a phosphine unit is introduced into a polymer chain can also be preferably used. Specific examples include triarylphosphine having one phenyl group of triphenylphosphine bonded to a polymer chain represented by the following chemical formula.

(In the formula, PS represents polystyrene and Ph represents a phenyl group.)

  Examples of the diamine include tetramethylethylenediamine and 1,2-diphenylethylenediamine.

  Of these ligands, phosphine, diamine, bipyridyl and the like are preferable, trialkylphosphine and triarylphosphine are more preferable, tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, triisobutyl. More preferred are phosphine and di-t-butylmethylphosphine. Usually, the use of a palladium complex having a bulky ligand such as phosphine can provide the desired substituted fluorine-containing olefin with higher yield. In particular, a bulky and highly basic phosphine is effective. Specifically, bulky alkylphosphines such as tricyclopentylphosphine, tricyclohexylphosphine, and isopropylphosphine are effective phosphines that can give a high yield.

  The nickel complex may be a zero-valent nickel complex; a zero-valent nickel complex generated during the reaction from a II-valent nickel complex; or at least one compound selected from the group consisting of diketone, phosphine, diamine and bipyridyl And a complex obtained by mixing a ligand.

The zero-valent nickel complex is not particularly limited. For example, Ni (COD) ₂ , Ni (CDD) ₂ (CDD is cyclodeca-1,5-diene), Ni (CDT) ₂ (CDT is cyclodeca-1, 5,9-triene), Ni (VCH) ₂ (VCH is 4-vinylcyclohexene), Ni (CO) ₄ , (PCy ₃ ) ₂ Ni—N≡N—Ni (PCy ₃ ) ₂ , Ni (PPh ₃ ) ₄ etc. are mentioned.

  Examples of the II-valent nickel complex include nickel chloride, nickel bromide, nickel acetate, bis (acetylacetonato) nickel (II), and a complex in which a phosphine ligand such as triphenylphosphine is coordinated. It is done. These II-valent nickel complexes are reduced by, for example, reducing species (phosphine, zinc, organometallic reagents, etc.) coexisting during the reaction to form zero-valent nickel complexes.

  The zero-valent nickel complex produced by reduction from the above-mentioned zero-valent nickel complex or II-valent nickel complex acts in the reaction with a ligand that is added as necessary to form a zero-valent nickel complex involved in the reaction. It can also be converted. It is not always clear how many of these ligands are coordinated to the zerovalent nickel complex during the reaction. As the nickel complex, one having a high function of stabilizing the zero-valent nickel complex generated in the system is desirable. Specifically, those having a ligand such as phosphine, diamine and bipyridyl are preferred, and those having phosphine are particularly preferred.

  Here, as a phosphine, a trialkyl phosphine or a triaryl phosphine is preferable. Specific examples of the trialkylphosphine include tricyclohexylphosphine, triisopropylphosphine, tri-t-butylphosphine, tritexylphosphine, triadamantylphosphine, tricyclopentylphosphine, di-t-butylmethylphosphine, tribicyclo [2,2, 2] Tri (C3-20 alkyl) phosphine such as octylphosphine and trinorbornylphosphine. Specific examples of the triarylphosphine include tri (monocyclic aryl) phosphine such as triphenylphosphine, trimesitylphosphine, and tri (o-tolyl) phosphine. Among these, triphenylphosphine, tricyclohexylphosphine, tri-t-butylphosphine and triisopropylphosphine are preferable.

  As described above, arylphosphine for heterogeneous catalysts in which a phosphine unit is introduced into a polymer chain can also be preferably used. Specific examples include triarylphosphine having one phenyl group of triphenylphosphine bonded to a polymer chain represented by the following chemical formula.

(In the formula, PS represents polystyrene and Ph represents a phenyl group.)

  Examples of the diamine include tetramethylethylenediamine and 1,2-diphenylethylenediamine.

  Among these ligands, bulky ligands such as triarylphosphine such as triphenylphosphine and tri (o-tolyl) phosphine, tricyclohexylphosphine and trit-butylphosphine are preferable. Usually, the target substituted fluorine-containing olefin can be obtained in a higher yield by using a nickel complex having a bulky ligand such as triarylphosphine. In particular, a bulky and highly basic phosphine is effective. Specifically, bulky alkylphosphines such as tricyclopentylphosphine, tricyclohexylphosphine, and isopropylphosphine are effective phosphines that can give a high yield.

  The organic transition metal catalyst is preferably an organic palladium complex from the viewpoint of the yield and selectivity of the fluorine-containing olefin substituted with an organic group.

The amount of the organic transition metal catalyst used is not particularly limited, but is usually about 0.0001 to 1 mol, more preferably about 0.001 to 0.2 mol, and still more preferably 0 to 1 mol of the organosilicon compound. About 0.01 to 0.2 mol.

When the ligand is added, the amount of the ligand used is usually about 0.0002 to 2 mol, preferably about 0.02 to 0.4 mol, based on 1 mol of the organosilicon compound. Preferably it is about 0.05-0.2 mol.
The molar ratio of the ligand to be added and the organic transition metal catalyst is usually 2/1 to 10/1, preferably 2/1 to 4/1.

The reaction step is preferably carried out in the presence of a base as an additive. Examples of the base include hydroxide compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide;
Carbonate compounds such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, magnesium carbonate, calcium carbonate, barium carbonate, cesium carbonate; phosphates such as lithium phosphate, sodium phosphate, potassium phosphate Compound; Acetate compound such as lithium acetate, sodium acetate, magnesium acetate, calcium acetate;
Examples thereof include alkoxides such as lithium methoxide, lithium-t-butoxide, sodium methoxide, sodium-t-butoxide, and potassium-t-butoxide.

The usage-amount of a base is 0.1-10 mol normally with respect to 1 mol of organosilicon compounds, Preferably, it is 0.1-5 mol.
In the reaction step, since the fluorine anion generated in the substitution reaction acts as a base, the reaction preferably proceeds even under the condition where no other base is added. The reaction under these conditions is advantageous in terms of reaction operation and cost.

  Although reaction temperature in particular is not restrict | limited, Usually, -100 degreeC-200 degreeC, Preferably it is 0 degreeC-150 degreeC, More preferably, room temperature (about 20 degreeC)-120 degreeC are mentioned. 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 60 ° C. to 120 ° 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.

  The reaction time is not particularly limited, and the lower limit thereof is, for example, 10 minutes, 1 hour, 2 hours, 5 hours, while the upper limit thereof is, for example, about 15 days, about 7 days, 72 About time, about 50 hours, and about 24 hours are mentioned.

  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 transition metal catalyst. Further, the reaction pressure may be increased, normal pressure, or reduced pressure. Usually, it is preferably performed under pressure, and the pressure in that case 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, etc .; nitrile solvents such as acetonitrile, propionitrile, dimethylcyanamide, t-butylnitrile; amide solvents such as dimethylformamide (DMF) can do. Of these, cyclohexane, THF, DMF and the like are preferable.

  The fluorine-containing olefin substituted with an organic group thus obtained is preferably, for example, the formula (2):

(In the formula, R is as defined above.)
It is a compound represented by these.

  The fluorine-containing olefin having a substituent obtained in the reaction step can be purified by a known purification method such as distillation, if necessary.

  The fluorine-containing olefin having a substituent thus obtained includes, for example, fluororubber, antireflection membrane material, ion exchange membrane, fuel cell electrolyte membrane, liquid crystal material, piezoelectric element material, enzyme inhibitor, insecticide, etc. It is useful as a raw material. In particular, according to the present invention, the synthesis of a fluorinated olefin having a plurality of vinyl groups in the aryl group is also easy. These are useful as a crosslinkable group of a fluororesin. Further, by using these monomers, it is possible to produce a composite material having both fluorine-non-fluorine polymer chain components. Furthermore, if it is possible to make use of the fact that the organosilicon compound can coexist with many substituents, polar groups that enhance water solubility in the molecule of the fluorinated olefin, such as hydroxyl group, carboxyl group, amino group, formyl group, etc. Can be introduced. Thus, by using the novel fluorine-containing olefin obtained by the present invention as a monomer component, it is possible to develop functions that cannot be obtained with existing fluororesins.

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

  The abbreviations used in the examples are as follows.

Cy: cyclohexyl
Cyp: cyclopentyl
TFE: tetrafluoroethylene
THF: Tetrahydrofuran
dba: dibenzylideneacetone

Example 1
Pd ₂ (dba) ₃ (10 mg, 0.01 mmol), PCy ₃ (5.6 mg, 0.02 mmol), trimethoxy in an inert atmosphere (in a nitrogen atmosphere: the same in the following examples) in a glove box A solution of phenylsilane (19.8 mg, 0.1 mmol) in C6D6 (0.5 mL) was prepared in a pressure tube (volume 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: ¹⁹ F- Internal standard at the time of NMR measurement) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 22 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 44%.

Example 2
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (10 mg, 0.01 mmol), PCy ₃ (5.6 mg, 0.02 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol). A THF-d8 (0.5 mL) solution was prepared in a pressure tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 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 capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 2 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 85%.

Example 3
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (10 mg, 0.01 mmol), PCy ₃ (5.6 mg, 0.02 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol). A DMF-d7 (0.5 mL) solution was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal standard for ¹⁹ F-NMR measurement) was added thereto. . Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 18 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that α, β, β-trifluorostyrene was obtained in a yield of 22% from the internal standard.

Example 4
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (10 mg, 0.01 mmol), PCy ₃ (5.6 mg, 0.02 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol). A THF-d8 (0.5 mL) solution was prepared in a pressure tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 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 capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 80 ° C. for 49 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 80%.

Example 5
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (10 mg, 0.01 mmol), PCy ₃ (5.6 mg, 0.02 mmol), triethoxyphenylsilane (24.0 mg, 0.1 mmol). A THF-d8 (0.5 mL) solution was prepared in a pressure tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 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 capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 19 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 50%.

Example 6
Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), PCy ₃ (2.8 mg, 0.01 mmol), trimethoxy (4-methoxyphenyl) silane (22.8 mg, 0) in a glove box under an inert atmosphere. .1 mmol) in THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal standard at the time of ¹⁹ F-NMR measurement). ) Was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 58 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that 1-methoxy-4- (1,2,2-trifluorovinyl) benzene was obtained at a yield of 40% from the internal standard.

Example 7
In a glove box under an inert atmosphere, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), PCy ₃ (2.8 mg, 0.01 mmol), trimethoxynaphthylsilane (24.8 mg, 0.1 mmol). A THF-d8 (0.5 mL) solution was prepared in a pressure tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 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 capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 17 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that 2- (1,2,2-trifluorovinyl) naphthalene was obtained with a yield of 65% from the internal standard.

Example 8
In a glove box under an inert atmosphere, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), PCy ₃ (2.8 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol). A THF-d8 (0.5 mL) solution was prepared in a pressure tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 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 capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 78%.

Example 9
Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), Pt-Bu ₂ Me (1.6 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.005%) in an inert atmosphere in a glove box. 1 mmol) in THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal standard for ¹⁹ F-NMR measurement). Was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 5%.

Example 10
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), P (n-Bu) ₃ (2.0 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol) of THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal during ¹⁹ F-NMR measurement) Standard) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 3%.

Example 11
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), P (t-Bu) ₃ (2.0 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol) of THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal during ¹⁹ F-NMR measurement) Standard) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that a small amount of α, β, β-trifluorostyrene was obtained from the internal standard.

Example 12
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), P (i-Pr) ₃ (1.6 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol) of THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal during ¹⁹ F-NMR measurement) Standard) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that α, β, β-trifluorostyrene was obtained in a yield of 73% from the internal standard.

Example 13
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), P (i-Bu) ₃ (2.0 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.1 mmol) of THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal during ¹⁹ F-NMR measurement) Standard) was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 20 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 6%.

Example 14
Under an inert atmosphere in a glove box, Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), P (Cyp) ₃ (2.4 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0. 1 mmol) in THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal standard for ¹⁹ F-NMR measurement). Was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 7 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed that α, β, β-trifluorostyrene was obtained in 84% yield from the internal standard.

Example 15
Pd ₂ (dba) ₃ (5 mg, 0.005 mmol), Pt-Bu ₂ Me (1.6 mg, 0.01 mmol), trimethoxyphenylsilane (19.8 mg, 0.005%) in an inert atmosphere in a glove box. 1 mmol) in THF-d8 (0.5 mL) was prepared in a pressure-resistant tube (capacity 2 ml), and α, α, α-trifluorotoluene (0.01 mmol: internal standard for ¹⁹ F-NMR measurement). Was added. Further, TFE (0.313 mmol: calculated from the above-mentioned container capacity and introduction pressure 0.35 MPa) was added thereto. The reaction solution was left at 100 ° C. for 7 hours. The reaction was monitored by ¹⁹ F-NMR, and it was confirmed from the internal standard that α, β, β-trifluorostyrene was obtained in a yield of 5%.

  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 (5)

Formula (2):
(In the formula, R is an optionally substituted aryl group, an optionally substituted heteroaryl group bonded via carbon, an optionally substituted cycloalkyl group, an optionally substituted alkyl group, An alkenyl group which may be substituted or an alkynyl group which may be substituted;
A process for producing a compound represented by
Reacting tetrafluoroethylene, hexafluoropropylene, or trifluoroethylene with an organosilicon compound in the presence of an organic transition metal catalyst containing a transition metal selected from nickel, palladium, rhodium, ruthenium, and cobalt. [1] The organosilicon compound is represented by the formula (1):
R-SiY ₃ (1)
Wherein R is as defined above;
Y is the same or different at each occurrence and represents a hydroxy group, a hydroxide group, an alkoxy group, an alkyl group or a fluoro group.
Two or three alkoxy groups or alkyl groups each represented by Y may be linked to each other to form a ring with the adjacent silicon atom. )
And an organosilicon compound represented by:
[2] A production method in which at least one fluorine atom bonded to the sp2 hybrid carbon atom of the fluorine-containing olefin is substituted with the group represented by R. The manufacturing method according to claim 1, wherein the transition metal is selected from nickel and palladium. The production method according to claim 1 or 2, wherein R is a monocyclic, bicyclic or tricyclic aryl group which may be substituted. The production method according to claim 1, wherein the step is performed in the presence of a base. The method according to claim 1, wherein the organic transition metal catalyst is an organic palladium complex.