Method for producing 4-silyl-2-butenyl carboxylic acid ester compounds

Abstract

To provide a method for efficiently producing various carboxylic acid 4-silyl-2-butenyl ester compounds.SOLUTION: A method for producing a carboxylic acid 4-silyl-2-butenyl ester compound comprises a reaction step to make a 1,3-diene compound, a carboxylic acid compound, and a disilane compound react with one another in an oxygen-containing atmosphere and in the presence of a palladium catalyst and a copper catalyst. In the method for producing the carboxylic acid 4-silyl-2-butenyl ester compound, the palladium catalyst is one or more kinds of compounds selected from a 0 valent palladium compound and a divalent palladium compound, and the carboxylic acid 4-silyl-2-butenyl ester compound has a structure represented by formula (d).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a 4-silyl-2-butenyl carboxylic acid ester compound. [Background technology]

[0002] Compounds with an allyl ester structure (i.e., 2-butenyl carboxylic acid structure) are found in natural products and physiologically active substances, and can be converted into various compounds via the Tsuji-Trost reaction, Claisen rearrangement, etc. In addition, compounds with an allylsilane skeleton can be used as substrates for the Hosomi-Sakurai allylation reaction, Hiyama cross-coupling reaction, and other reactions, and the total synthesis of physiologically active substances using these reactions has also been reported. As described above, compounds having an allyl ester skeleton and compounds having an allylsilane skeleton exhibit high reactivity, and therefore, by using compounds having both of these skeletons as synthetic intermediates, it may be possible to synthesize natural products that have been difficult to synthesize until now.

[0003] As a method for synthesizing a carboxylic acid 4-silyl-2-butenyl ester compound having an allyl ester skeleton and an allylsilane skeleton, for example, a method utilizing a metathesis reaction using a Grubbs catalyst has been reported (Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Org. Lett. 2003, 5, 25, 4891-4893 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the metathesis reaction requires the use of allyl alcohol, a designated toxic substance, in the synthesis of the allyl ester compound used as a raw material, posing safety concerns and calls for improvement. Furthermore, it is difficult to use the metathesis reaction to produce carboxylic acid 4-silyl-2-butenyl ester compounds in which two substituents are introduced to each of the two carbon atoms of a carbon-carbon double bond.

[0006] Therefore, an object of the present invention is to provide a method for efficiently producing various 4-silyl-2-butenyl carboxylic acid ester compounds. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above-mentioned problems. As a result, they have found that various 4-silyl-2-butenyl carboxylic acid ester compounds can be obtained by reacting a 1,3-diene compound, a carboxylic acid compound, and a disilane compound in an oxygen-containing atmosphere in the presence of a palladium catalyst and a copper catalyst, thereby completing the present invention. That is, the gist of the present invention is as follows.

[0008] [1] A method for producing a 4-silyl-2-butenyl carboxylic acid ester compound, comprising the steps of: The method includes a reaction step of reacting a 1,3-diene compound, a carboxylic acid compound, and a disilane compound in an oxygen-containing atmosphere in the presence of a palladium catalyst and a copper catalyst, the palladium catalyst is one or more compounds selected from a zero-valent palladium compound and a divalent palladium compound, The carboxylic acid 4-silyl-2-butenyl ester compound has a structure represented by formula (d). A method for producing a 4-silyl-2-butenyl carboxylic acid ester compound having the formula: [ka] [2] the 1,3-diene compound is a compound represented by general formula (A), the carboxylic acid compound is a compound represented by general formula (B), the disilane compound is a compound represented by general formula (C), The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to [1], wherein the 4-silyl-2-butenyl carboxylic acid ester compound is a compound represented by general formula (D). [ka] (In general formula (A), R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. R 3 (CO2H) n (B) (In general formula (B), R 3 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group; and n represents an integer of 1 or more and 10 or less. (R 4 )3SiSi(R 4 )3(C) (In general formula (C), R 4 each independently represents a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbonoxy group. [ka] (In general formula (D), R 1 , R 2 , R 3 , R 4 and n have the same meanings as defined above.) [3] R in the general formulas (A) and (D) 1 is a hydrocarbon group. [4] The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of [1] to [3], wherein the palladium catalyst is one or more selected from palladium(II) acetate, palladium(II) chloride, and bis(dibenzylideneacetone)palladium(0). [5] The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of [1] to [4], wherein the copper catalyst is a divalent copper salt. [6] The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of [1] to [5], wherein the reaction step is further carried out in the presence of a quinone compound represented by general formula (E1), (E2), or (E3). [ka] (In general formulas (E1) to (E3), R 5 and R 6 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a nitrile group. [7] The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of [1] to [6], wherein the oxygen-containing atmosphere has an oxygen concentration of 60% by volume or more. [Effects of the Invention]

[0009] The present invention provides a method for efficiently producing various 4-silyl-2-butenyl carboxylic acid ester compounds, including 4-silyl-2-butenyl carboxylic acid ester compounds having two substituents introduced into each of the two carbon atoms of a carbon-carbon double bond. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a 1H-NMR spectrum of the product obtained in Example 1-1. [Figure 2] 1 is a 13C-NMR spectrum of the product obtained in Example 1-1. [Figure 3] 1 is a 1D-DPFGSE NOE spectrum of the product obtained in Example 1-1. DETAILED DESCRIPTION OF THE INVENTION

[0011] In explaining the details of the present invention, specific examples will be given, but the present invention is not limited to the following content and can be implemented with appropriate modifications as long as it does not deviate from the spirit of the present invention. In this specification, when a numerical range is described with a lower limit and an upper limit separately, the numerical range can be a combination of any of the lower limit and upper limit values.

[0012] A method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to one embodiment of the present invention comprises a reaction step of reacting a 1,3-diene compound, a carboxylic acid compound, and a disilane compound in an oxygen-containing atmosphere in the presence of a palladium catalyst and a copper catalyst. This production method does not require the use of a halogen-containing compound such as acyl chloride as a substrate, and therefore can avoid the by-production of a large amount of halide salt.

[0013] 1.Reaction process 1-1,1,3-Diene Compounds The specific type of 1,3-diene compound is not particularly limited and can be appropriately selected depending on the carboxylic acid 4-silyl-2-butenyl ester compound to be produced. Examples of the 1,3-diene compound include a compound represented by the following general formula (A) (hereinafter, sometimes referred to as "diene compound (A)"). The 1,3-diene compound is either publicly known or can be easily produced by a method similar to a publicly known production method.

[0014] [ka]

[0015] (R 1 and R 2 ) In general formula (A), R 1 and R 2 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

[0016] In this specification, the term "hydrocarbon group" includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group is not limited to a linear hydrocarbon group, but may have a branched structure or a cyclic structure. The aromatic hydrocarbon group may be a monocyclic, polycyclic, or fused ring type, or may be a heterocyclic aromatic hydrocarbon group.

[0017] R 1 and R 2 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is not particularly limited, but when the hydrocarbon group is an aliphatic hydrocarbon group, it is usually 1 or more, and preferably 40 or less, more preferably 32 or less, even more preferably 24 or less, and particularly preferably 16 or less. When the hydrocarbon group is an aromatic hydrocarbon group, it is usually 3 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 10 or less. In this specification, when the hydrocarbon group has a substituent, the number of carbon atoms in the hydrocarbon group is deemed to include the number of carbon atoms in the substituent.

[0018] R 1 and R 2 Examples of the unsubstituted aliphatic hydrocarbon group represented by the formula (I) include linear or branched saturated aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; and saturated aliphatic hydrocarbon groups having a cyclic structure such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.

[0019] R 1 and R 2Examples of the unsubstituted aromatic hydrocarbon group represented by the formula (I) include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a fluorenyl group, an indenyl group, a fluoranthenyl group, a triphenylenyl group, a perylenyl group, a pyrrolyl group, a pyridyl group, a pyrimidyl group, a triazinyl group, a carbazolyl group, a furyl group, a dibenzofuranyl group, a thiophenyl group, a dibenzothiophenyl group, etc. The position of the bond in these groups is not particularly limited.

[0020] R 1 and R 2 When the hydrocarbon group represented by the formula (I) has a substituent, the substituent may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; an alkyl group having from 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, or an n-hexyl group; a cycloalkyl group having from 3 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group; an aryl group such as a phenyl group or a tolyl group; an arylalkyl group such as a benzyl group or a phenethyl group; a methoxy group, or an ethoxy group. alkoxy groups having from 1 to 6 carbon atoms, such as n-propyloxy, isopropyloxy, glycidyloxy, n-butoxy, sec-butoxy, isoisobutoxy, tert-butoxy, and n-hexyloxy; cycloalkyloxy groups having from 3 to 6 carbon atoms, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy; aryloxy groups, such as phenyloxy and tolyloxy; benzyl Examples thereof include arylalkyloxy groups such as an oxy group or a phenethyloxy group; primary to tertiary amino groups such as an amino group, a dimethylamino group, a diethylamino group or a dibutylamino group; and heterocyclic groups having from 3 to 12 carbon atoms such as a pyridyl group, a pyrimidinyl group, a triazinyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, an indolyl group, a carbazolyl group, a morpholino group, an oxiranyl group, an oxetanyl group, an oxiranyl group, a tetrahydrofuryl group, a furyl group or a thienyl group.

[0021] R 1 and R 2 and are each preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, more preferably a hydrogen atom.

[0022] Specific examples of the 1,3-diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1,3-butadiene.

[0023] 1-2. Carboxylic acid compounds The specific type of carboxylic acid compound is not particularly limited and can be appropriately selected depending on the 4-silyl-2-butenyl carboxylic acid ester compound to be produced. In this embodiment, both aliphatic carboxylic acids and aromatic carboxylic acids can be used as substrates for the reaction. Therefore, the production method according to this embodiment can produce a wide variety of 4-silyl-2-butenyl carboxylic acid ester compounds, including those with structures that have been difficult to synthesize in the past.

[0024] Examples of the carboxylic acid compound include a compound represented by the following general formula (B) (hereinafter, sometimes referred to as "carboxylic acid compound (B)"). The carboxylic acid compound is either publicly known or can be easily produced by a method similar to a publicly known production method. R 3 (CO2H) n (B)

[0025] (R 3 ) In general formula (B), R 3 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.

[0026] R 3The number of carbon atoms in the hydrocarbon group represented by the formula (I) is not particularly limited, but when the hydrocarbon group is an aliphatic hydrocarbon group, it is usually 1 or more, and preferably 40 or less, more preferably 32 or less, even more preferably 24 or less, and particularly preferably 16 or less. When the hydrocarbon group is an aromatic hydrocarbon group, it is usually 3 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 10 or less.

[0027] R 3 The hydrocarbon group represented by the formula (I) is an n-valent hydrocarbon group obtained by removing n hydrogen atoms from any position of a hydrocarbon compound. Examples of the hydrocarbon compound include straight-chain or branched aliphatic hydrocarbons such as methane, ethane, propane, n-butane, 2-methylpropane, n-pentane, 2-methylbutane, neopentane, n-hexane, 2-methylpentane, 2,3-dimethylbutane, n-heptane, n-octane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, and n-eicosane; alicyclic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane; benzene, naphthalene, acenaphthylene, anthracene, phenanthrene, pyrene, fluorene, fluoranthene, triphenylene, perylene, pyrrole, pyridine, pyrimidine, carbazole, furan, and dibenzofuran. aromatic hydrocarbons such as benzophenone, thiophene, and dibenzothiophene;

[0028] R 3 When the hydrocarbon group represented by the formula (I) has a substituent, the substituent may be R 1 and R 2 Examples of the substituents for the hydrocarbon groups represented by the following formulae are given below.

[0029] R 3 are preferably each independently a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group.

[0030] (n) In the general formula (B), n represents an integer of 1 or more and 10 or less. n is preferably an integer of 6 or less, more preferably an integer of 4 or less, even more preferably an integer of 2 or less, and particularly preferably 1.

[0031] Specific examples of carboxylic compounds include formic acid; linear or branched aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, isovaleric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, succinic acid, and adipic acid; and alicyclic carboxylic acids such as cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, and 1-adamantanecarboxylic acid. aromatic carboxylic acids such as benzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, p-methoxybenzoic acid, terephthalic acid, isophthalic acid, trimesic acid, 1,2,4,5-benzenetetracarboxylic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 9-phenanthrenecarboxylic acid, 4,5-phenanthrenedicarboxylic acid, 4-pyridinecarboxylic acid, and 2,6-pyridinedicarboxylic acid; and the like.

[0032] 1-3. Disilane compounds The specific type of disilane compound is not particularly limited and can be appropriately selected depending on the carboxylic acid 4-silyl-2-butenyl ester compound to be produced. Examples of disilane compounds include compounds represented by the following general formula (C) (hereinafter, sometimes referred to as "disilane compound (C)"). Disilane compounds are either publicly known or can be easily produced by a method similar to a publicly known production method. (R 4 )3SiSi(R 4 )3(C)

[0033] (R 4 ) In general formula (C), R 4each independently represents a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbonoxy group.

[0034] R 4 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is not particularly limited, but when the hydrocarbon group is an aliphatic hydrocarbon group, it is usually 1 or more, and preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. When the hydrocarbon group is an aromatic hydrocarbon group, it is usually 3 or more, and preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less.

[0035] R 4 The hydrocarbon group represented by R 1 and R 2 Examples of the hydrocarbon group include those shown in the description of the hydrocarbon group represented by the formula: and are preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group or an ethyl group. Also, R 4 The hydrocarbon group in the hydrocarbonoxy group represented by R 4 The definition and preferred embodiments are the same as for the hydrocarbon group represented by the following formula:

[0036] R 4 is preferably a substituted or unsubstituted hydrocarbon group, more preferably a substituted or unsubstituted aliphatic hydrocarbon group. 4 and three R bonded to the other silicon atom 4 and the six R in the disilane compound (C) are preferably the same combination. 4 It is more preferable that all of are the same group.

[0037] Specific examples of the disilane compound include hexamethyldisilane, hexaethyldisilane, hexaphenyldisilane, hexamethoxydisilane, and hexaethoxydisilane.

[0038] 1-4. Carboxylic acid 4-silyl-2-butenyl ester compounds The 4-silyl-2-butenyl carboxylic acid ester compound produced by the production method according to this embodiment is a compound having a structure represented by the following formula (d). The * in formula (d) is bonded to a group derived from a 1,3-diene compound, a carboxylic acid compound, or a disilane compound, or a group converted from such a group. The structure represented by formula (d) is a structure represented by formula (d1) or formula (d2), and preferably a structure represented by formula (d1).

[0039] [ka] [ka]

[0040] The specific structure of the 4-silyl-2-butenyl carboxylic acid ester compound is not particularly limited, and may be a wide variety of compounds derived from various 1,3-diene compounds, carboxylic acid compounds, and disilane compounds. Examples of the 4-silyl-2-butenyl carboxylic acid ester compound include a compound represented by general formula (D) obtained by the reaction of a diene compound (A), a carboxylic acid compound (B), and a disilane compound (C). It is preferred that at least a portion of the 4-silyl-2-butenyl carboxylic acid ester structure in the compound represented by general formula (D) is a structure represented by formula (d1), and it is more preferred that all of the 4-silyl-2-butenyl carboxylic acid ester structure is a structure represented by formula (d1). That is, it is more preferred that the compound represented by general formula (D) is a compound represented by general formula (D1).

[0041] [ka] [ka]

[0042] In general formulas (D) and (D1), R 1 represents R in general formula (A).1 is synonymous with ;R 3 and n are R in general formula (B), respectively. 3 and n; R 4 is R in general formula (C) 4 is synonymous with.

[0043] 1-5. Catalyst In the production method according to this embodiment, the reaction of the 1,3-diene compound, the carboxylic acid compound, and the disilane compound is carried out in the presence of a palladium catalyst and a copper catalyst.

[0044] (Palladium catalyst) The palladium catalyst used in the reaction step is a compound selected from zero-valent palladium compounds and divalent palladium compounds. The palladium catalyst may be used alone or in any combination and ratio of two or more types.

[0045] Specific examples of divalent palladium compounds include palladium(II) chloride, palladium(II) bromide, palladium(II) nitrate, palladium(II) sulfate, palladium(II) oxalate, palladium(II) acetate, palladium(II) acetate trimer, palladium(II) trifluoroacetate, bis(acetonitrile)palladium(II) dichloride, bis(benzonitrile)palladium(II) dichloride, and bis(benzonitrile)palladium(II) dibromide. Examples of suitable palladium catalysts include palladium(II) 2,2-dimethylpropanoate, bis(2,4-pentanedionato)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), 2,5-norbornadienepalladium(II) dichloride, bis(acetylacetonato)palladium(II), bis(1,1,1-5,5,5-hexafluoroacetylacetonato)palladium(II), and dichlorobis(triphenylphosphine)palladium(II). Among these, the palladium catalyst is preferably palladium(II) chloride or palladium(II) acetate, and more preferably palladium(II) acetate.

[0046] Examples of zero-valent palladium compounds include bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), bis(hexafluoroacetylacetone)palladium(0), etc. Among these, the palladium catalyst is preferably bis(dibenzylideneacetone)palladium(0).

[0047] (copper catalyst) As the copper catalyst used in the reaction step, various copper compounds can be used. The copper catalyst may be used alone or in any combination and ratio of two or more kinds.

[0048] Specific examples of copper catalysts include copper halides such as copper chloride(I), copper bromide(I), copper iodide(I), copper chloride(II), copper bromide(II), and copper iodide(II); organic copper salts such as copper acetate(I), copper acetate(II), copper trifluoromethanesulfonate, and copper trifluoromethanesulfonate(II); inorganic copper salts such as copper nitrate(II) and copper sulfate(II); and copper oxides such as copper oxide(I) and copper oxide(II). Of these, the copper catalyst is preferably a divalent copper salt, more preferably a divalent copper halide, and even more preferably copper bromide(II), from the viewpoints of improving the conversion rate of the carboxylic acid compound and improving the yield of the product.

[0049] 1-6.Additives In the reaction step, additives may be added to the reaction system as long as they do not impair the effects of the present invention. Suitable additives include quinone compounds represented by general formula (E1), (E2), or (E3). The quinone compound is thought to function as a reoxidizing agent for the catalyst or as a ligand that contributes to stabilizing the reaction intermediate in the reaction system. By carrying out the reaction in the presence of a quinone compound, the yield of the 4-silyl-2-butenyl carboxylic acid ester compound can be improved.

[0050] [ka]

[0051] In general formulas (E1) to (E3), R 5 and R 6 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a nitrile group.

[0052] R 5 and R 6 The number of carbon atoms in the alkyl group represented by the formula (I) is usually 1 or more, and preferably 8 or less, more preferably 4 or less, and even more preferably 2 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group.

[0053] R 5 and R 6 The number of carbon atoms in the alkoxy group represented by the formula (I) is usually 1 or more, and preferably 8 or less, more preferably 4 or less, and even more preferably 2 or less. Specific examples of the alkyl group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentyloxy group, an iso-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, and a 2-ethylhexyloxy group.

[0054] R 5 and R 6 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0055] R 5 is preferably a hydrogen atom, an alkyl group, a halogen atom, or a nitrile group. , a hydrogen atom, a methyl group, a chlorine atom, or a nitrile group is more preferred, and a hydrogen atom is even more preferred. Also, R 6is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0056] Specific examples of the quinone compound include 1,4-benzoquinone, 2-chloro-1,4-benzoquinone, tetrachloro-1,4-benzoquinone, 1,4-naphthoquinone, and anthraquinone, with 1,4-benzoquinone being preferred.

[0057] 1-8.Reaction conditions (Atmospheric gas, etc.) The reaction step is carried out in an oxygen-containing atmosphere. An oxygen-containing atmosphere is an atmosphere having an oxygen concentration of typically 20% by volume or more; therefore, the reaction step can also be carried out in an air atmosphere. However, from the viewpoint of improving the reaction rate and the product yield, the upper limit of the oxygen concentration in the oxygen-containing atmosphere is preferably 40% by volume or more, more preferably 60% by volume or more, even more preferably 80% by volume or more, and particularly preferably 90% by volume or more. The upper limit of the oxygen concentration in the oxygen-containing atmosphere is not particularly limited and is typically 100% by volume or less, and may be 98% by volume or less or 95% by volume or less. Note that the above-mentioned oxygen concentration refers to the oxygen concentration of the atmosphere introduced into the reactor at the start of the reaction (before heating, if the reaction is carried out under heating conditions). Therefore, for example, as in the examples described below, when the reaction is carried out by replacing the reactor with oxygen gas of 99.9% purity, the oxygen concentration in the oxygen-containing atmosphere is 99.9% by volume. The gas other than oxygen in the oxygen-containing atmosphere is not particularly limited as long as it does not inhibit the reaction in the reaction step, and examples thereof include inert gases such as nitrogen, argon, and helium. The reaction step may be carried out under normal pressure or under increased pressure.

[0058] (catalyst amount) The amount (charge amount) of the palladium catalyst used in the reaction step is not particularly limited, and is, for example, usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1.0 mol% or more, and particularly preferably 5.0 mol% or more, relative to the carboxy groups of the carboxylic acid compound, and is usually 20.0 mol% or less, preferably 15.0 mol% or less, and more preferably 10.0 mol% or less.

[0059] (Amount of substrate used) The amount of the 1,3-diene compound used (charge amount) relative to the amount of the carboxylic acid compound used (charge amount) is not particularly limited, but is usually 1.0 equivalent or more, preferably 2.0 equivalents or more, more preferably 3.0 equivalents or more, relative to the carboxy group of the carboxylic acid compound, and is usually 50.0 equivalents or less, preferably 20 equivalents or less, more preferably 10.0 equivalents or less, and even more preferably 5.0 equivalents or less. Furthermore, the amount of disilane compound used (charge amount) relative to the amount of carboxylic acid compound used (charge amount) is not particularly limited, but is usually 1.0 equivalent or more, preferably 2.0 equivalents or more, more preferably 3.0 equivalents or more, relative to the carboxy group of the carboxylic acid compound, and is usually 50.0 equivalents or less, preferably 20 equivalents or less, more preferably 10.0 equivalents or less, and even more preferably 5.0 equivalents or less. By setting the amounts of the 1,3-diene compound and disilane compound used relative to the carboxylic acid compound within the above ranges, the yield of the carboxylic acid 4-silyl-2-butenyl ester compound can be improved and purification after the reaction can be facilitated.

[0060] (Amount of additives used) The amount of additive used (charged amount) is not particularly limited as long as it does not inhibit the reaction. When the additive is a quinone compound, the amount of the quinone compound used is the amount of the carboxylic acid compound. The amount of the quinone compound used is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 40 mol % or more, based on the carboxyl groups, and is preferably 200 mol % or less, more preferably 150 mol % or less, and even more preferably 100 mol % or less. As will be shown in the Examples below, when the amount of the quinone compound used is within the above range, a carboxylic acid 4-silyl-2-butenyl ester compound can be obtained in a higher yield than when the reaction is carried out in the absence of the quinone compound.

[0061] (Reaction solvent) The reaction step may be carried out without a solvent or in a reaction solvent. The reaction solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, benzene, toluene, and xylene; ether solvents such as diethyl ether, 1,4-dioxane, diglyme, cyclopentyl methyl ether (CPME), and tetrahydrofuran (THF); ester solvents such as ethyl acetate and butyl acetate; halogenated hydrocarbon solvents such as 1,2-dichloroethane and chloroform; nitrile solvents such as acetonitrile and benzonitrile; protic polar solvents such as acetic acid, ethanol, butanol, ethylene glycol, and glycerin; and aprotic polar solvents such as acetone, N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO). Among these, the solvent is preferably an aprotic polar solvent. The reaction solvent may be used alone or in any combination and ratio of two or more.

[0062] (Reaction temperature) The reaction temperature may be appropriately selected depending on reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction time. Specifically, the lower limit of the reaction temperature is usually 0°C or higher, preferably 24°C (room temperature) or higher, more preferably 40°C or higher, and even more preferably 60°C or higher. The upper limit of the reaction temperature is preferably 180°C or lower, more preferably 150°C or lower, even more preferably 120°C or lower, and particularly preferably 100°C or lower, from the viewpoints of suppressing decomposition or inactivation of the catalyst and suppressing volatilization or decomposition of the substrate. In this embodiment, as shown in the examples described below, the reaction proceeds rapidly even under relatively mild temperature conditions of about 70°C, and a 4-silyl-2-butenyl carboxylic acid ester compound can be obtained in sufficient yield.

[0063] (Reaction time) The reaction time is not particularly limited and may be appropriately selected depending on reaction conditions such as the type of catalyst, the reactivity of the substrate, the type of reaction solvent, and the reaction temperature. Specifically, from the viewpoint of improving the product yield, the reaction time is preferably 5 hours or more, more preferably 10 hours or more, and even more preferably 20 hours or more. Furthermore, from the viewpoint of suppressing side reactions, the reaction time is preferably 60 hours or less, more preferably 50 hours or less, and even more preferably 40 hours or less.

[0064] 1-9.Reaction mechanism The present inventors speculate that in the production method according to this embodiment, a 4-silyl-2-butenyl carboxylic acid ester compound is produced by the following reaction mechanism: Note that the following reaction mechanism is an example in which a compound represented by general formula (A) is used as the 1,3-diene compound, a compound represented by general formula (B) is used as the carboxylic acid compound, a compound represented by general formula (C) is used as the disilane compound, a divalent palladium compound is used as the palladium catalyst, and a divalent copper salt is used as the copper catalyst.

[0065] [ka]

[0066] Regarding the above reaction mechanism, first, divalent copper salt I forms a copper-silicon complex II together with a disilane compound, and this copper-silicon complex II coordinates to the unsaturated site of the 1,3-diene compound, thereby forming a copper complex III. Subsequently, a coupling compound IV of the disilane compound and the 1,3-diene compound is formed. The formed coupling compound IV is isomerized to a more stable intermediate V. Next, transmetalation from copper to palladium proceeds, and a π-allyl-palladium complex VII is formed via a palladium complex VI. Thereafter, a carboxylic acid compound is introduced, and it is considered that a carboxylic acid 4-silyl-2-butenyl ester compound is produced. Also, palladium and copper are reoxidized by oxygen and, if necessary, a quinone compound (VIII→X, IX→I), and it is considered that this constitutes a catalytic cycle.

[0067] 2. Other steps The method for producing a carboxylic acid 4-silyl-2-butenyl ester compound according to this embodiment may include any arbitrary steps in addition to the above reaction steps. Examples of arbitrary steps include a purification step for increasing the purity of the carboxylic acid 4-silyl-2-butenyl ester compound. In the purification step, purification methods commonly used in the field of organic synthesis, such as filtration, adsorption, column chromatography, distillation, etc., can be employed.

[0068] Also, when the oxygen-containing atmosphere is not air, the production method according to this embodiment may include an atmosphere substitution step of substituting the reactor with an oxygen-containing atmosphere as other steps. As the method of atmosphere substitution, known methods commonly used in the field of organic synthesis can be employed.

Examples

[0069] Examples are given below to explain the present invention more specifically, but it can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[0070] <GC measurement> The measurement conditions for the conversion rate of raw materials and the yield of products by gas chromatography (GC) are as follows. Apparatus name: GC-2010 (Shimadzu Corporation) Detector: FID (hydrogen flame ionization detector) Column: BP-5 (Trajan Scientific and Medical) Carrier gas: nitrogen Internal standard substance: n-decane Data processing: Analytical Data System Lab Solutions 10 (Shimadzu Corporation)

[0071] <NMR measurement> The products were identified by a Fourier transform nuclear magnetic resonance apparatus (FT-NMR). The measurement conditions are as follows. Apparatus name: JNM-ECS400 or JNM-ECZ400 (JEOL Ltd.) Frequency: 400 MHz ( 1 H-NMR), 100 MHz ( 13 C-NMR) Solvent: CDCl3 or C6D6 ( 1 H-NMR), CDCl3 ( 13 C-NMR)

[0072] <Mass spectrometry> The products were identified by a high-resolution mass spectrometer (HRMS). The analysis conditions are as follows. Apparatus name: JMS-T100GCV (JEOL Ltd.) Ionization method: electron impact method (EI)

[0073] <Production of carboxylic acid 4-silyl-2-butenyl ester compound> A carboxylic acid 4-silyl-2-butenyl ester compound was produced from a 1,3-diene compound, a carboxylic acid compound, and a disilane compound. In each example, since the main product was the Z-form carboxylic acid 4-silyl-2-butenyl ester compound having the structure represented by the formula (d1), only the Z-form was described in the reaction formula, and the description of the slightly produced E-form was omitted.

[0074] (Example 1-1: Examination of types of palladium catalyst) [ka]

[0075] A recovery flask was charged with bis(dibenzylideneacetone)palladium(0) (0.05 mmol, 28.8 mg), copper(II) bromide (0.10 mmol, 22.3 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL). The flask was purged with oxygen gas (99.9% purity) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction mixture.

[0076] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 1. Also, the product 1 H-NMR spectrum, 13 The C-NMR spectrum and 1D-DPFGSE NOE spectrum are shown in Figures 1, 2, and 3, respectively. Furthermore, the mass spectrometry results of the product are shown below. HRMS(EI) m / z calculation for C 16 H 24 O2Si1[M+H] + : 276,1546 found 276.1555

[0077] (Examples 1-2 to 1-3, Comparative Examples 1-1 to 1-2: Examination of the type of palladium catalyst) The reaction was carried out in the same manner as in Example 1-1, except that the palladium catalyst was changed as shown in Table 1. The conversion of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 1.

[0078] [Table 1]

[0079] From Table 1, it was found that when palladium(II) acetate was used as the palladium catalyst (Example 1-2), the conversion rate of benzoic acid was the highest and a 4-silyl-2-butenyl carboxylic acid ester compound was obtained in high yield. It was also confirmed that the reaction proceeded and a 4-silyl-2-butenyl carboxylic acid ester compound was obtained when bis(dibenzylideneacetone)palladium(0) and palladium(II) chloride were used as the palladium catalyst.

[0080] (Example 2-1: Examination of types of copper catalyst) [ka]

[0081] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(I) chloride (0.10 mmol, 10 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (99.9% purity) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0082] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 2.

[0083] (Examples 2-2 to 2-5, Comparative Example 2-1: Examination of the type of copper catalyst) The reaction was carried out in the same manner as in Example 2-1, except that the copper catalyst was changed as shown in Table 2. The conversion rate of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 2.

[0084] [Table 2]

[0085] Table 2 shows that various copper catalysts can be used to produce 4-silyl-2-butenyl carboxylic acid ester compounds, and that the highest yield of 4-silyl-2-butenyl carboxylic acid ester compounds can be obtained when copper (II) bromide is used as the copper catalyst. Furthermore, when Examples 2-1 and 2-2, and Examples 2-3 and 2-4 were compared, it was found that the catalytic activity of the divalent copper salt was high.

[0086] (Example 3-1: Examination of the amount of copper catalyst used) [ka]

[0087] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.05 mmol, 11.2 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (purity 99.9%) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0088] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 3.

[0089] (Examples 3-2 to 3-5, Comparative Example 3-1: Examination of the amount of copper catalyst used) The reaction was carried out in the same manner as in Example 3-1, except that the amount of copper catalyst used was changed as shown in Table 3. The conversion rate of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 3.

[0090] [Table 3]

[0091] Table 3 shows that in the absence of a copper catalyst, the conversion of the carboxylic acid compound was less than 1%, and the target 4-silyl-2-butenyl carboxylic acid ester compound was hardly obtained (Comparative Example 3-1). Furthermore, it was confirmed that when the amount of copper catalyst was 10 mol% relative to the carboxylic acid compound, an excellent balance between the conversion of each substrate and the yield of the product was achieved (Example 3-2).

[0092] (Example 4-1: Study of reaction atmosphere) [ka]

[0093] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.10 mmol, 22.3 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (purity 99.9%) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0094] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 4.

[0095] (Example 4-2: Study of reaction atmosphere) The reaction was carried out in the same manner as in Example 4-1, except that the reaction was carried out under an air atmosphere (open system) without replacing the atmosphere in the recovery flask with oxygen. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 4.

[0096] (Comparative Example 4-1: Examination of reaction atmosphere) The reaction was carried out in the same manner as in Example 4-1, except that the atmosphere in the recovery flask was purged with argon instead of oxygen. The conversion rate of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 4.

[0097] [Table 4]

[0098] Table 4 shows that the reaction of a carboxylic acid compound, a 1,3-diene compound, and a disilane compound must be carried out in an oxygen-containing atmosphere, and that the higher the oxygen concentration in the atmosphere, the higher the yield of a carboxylic acid 4-silyl-2-butenyl ester compound obtained.

[0099] (Example 5-1: Examination of the amount of quinone compound used) [ka]

[0100] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.10 mmol, 22.3 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (purity 99.9%) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0101] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 5.

[0102] (Examples 5-2 to 5-4: Examination of the amount of quinone compound used) A 4-silyl-2-butenyl carboxylic acid ester compound was produced in the same manner as in Example 5-1, except that in addition to palladium(II) acetate, copper bromide, benzoic acid, and DMF, 1,4-benzoquinone was added to the eggplant-shaped flask in the amount shown in Table 5. The conversion of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 5.

[0103] [Table 5]

[0104] Table 5 shows that by adding a palladium catalyst and a copper catalyst to the reaction of a carboxylic acid compound, a 1,3-diene compound, and a disilane compound in the presence of benzoquinone, the catalytic activity can be improved and the yield of a 4-silyl-2-butenyl carboxylic acid ester compound can be increased.

[0105] (Example 6-1: Examination of the amount of substrate used) [ka]

[0106] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.10 mmol, 22.3 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (99.9% purity) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (1 mmol, 82.2 mg) and hexamethyldisilane (1 mmol, 146 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0107] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 6.

[0108] (Examples 6-2 to 6-6: Examination of the amount of substrate used) The reaction was carried out in the same manner as in Example 6-1, except that the amounts of 2,3-dimethyl-1,3-butadiene and hexamethyldisilane used were changed as shown in Table 6. The conversion of the substrate and the yield of the product calculated from the results of GC measurement are shown in Table 6.

[0109] [Table 6]

[0110] (Example 7-1: Examination of reaction temperature) [ka]

[0111] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.10 mmol, 22.3 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (99.9% purity) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 40 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0112] GC measurements were performed using n-decane as an internal standard. The conversion rates of the substrate and the yields of the products calculated from the GC measurement results are shown in Table 7.

[0113] (Examples 7-2 to 7-5: Examination of reaction temperature) The reaction was carried out in the same manner as in Example 7-1, except that the reaction temperature was changed as shown in Table 7. Table 7 shows the conversion rate of the substrate and the yield of the product calculated from the results of GC measurement.

[0114] [Table 7]

[0115] Table 7 shows that the reaction proceeds quickly even under relatively mild temperature conditions of about 100°C, and 4-silyl-2-butenyl carboxylic acid ester compounds can be obtained in sufficient yields.

[0116] (Example 8-1: Examination of types of carboxylic acid compounds) [ka]

[0117] Palladium(II) acetate (0.05 mmol, 11.2 mg), copper(II) bromide (0.10 mmol, 22.3 mg), 1,4-benzoquinone (0.4 mmol, 43.2 mg), benzoic acid (1 mmol, 122 mg), and DMF (3 mL) were added to a recovery flask. The flask was purged with oxygen gas (purity 99.9%) and stirred at room temperature (24 °C) for 30 minutes. 2,3-dimethyl-1,3-butadiene (3 mmol, 246 mg) and hexamethyldisilane (4 mmol, 582 mg) were added to the resulting solution, and the reaction was carried out at 70 °C for 24 hours. The reaction was then terminated by adding 10 mL of toluene to the reaction solution.

[0118] GC measurements were performed using n-decane as an internal standard. The conversion rate of the substrate and the yield of the product calculated from the GC measurement results are shown in Table 8. Data on various compounds in the product are shown in Table 9.

[0119] (Examples 8-2 to 8-8: Examination of types of carboxylic acid compounds) The reaction was carried out in the same manner as in Example 8-1, except that the type of carboxylic acid compound was changed as shown in Table 8. The yields of the products calculated from the GC measurement results are shown in Table 8. In addition, data on various compounds of the products (6e to 6h) in Examples 8-5 to 8-8 are shown in Table 9.

[0120] [Table 8]

[0121] [Table 9]

[0122] Table 8 shows that by using the production method according to the present invention, 4-silyl-2-butenyl carboxylic acid ester compounds can be produced from various aromatic carboxylic acids and aliphatic carboxylic acids, and that when a linear aliphatic carboxylic acid is used as the carboxylic acid compound, 4-silyl-2-butenyl carboxylic acid ester compounds can be obtained in particularly high yields. [Industrial Applicability]

[0123] According to the present invention, various 4-silyl-2-butenyl carboxylic acid ester compounds can be efficiently produced in one step from a 1,3-diene compound, a carboxylic acid compound, and a disilane compound. In conventional production methods using metathesis reactions, it has been difficult to produce 4-silyl-2-butenyl carboxylic acid ester compounds in which two substituents are introduced to each of the two carbon atoms of a carbon-carbon double bond. However, the production method according to the present invention makes it possible to produce such compounds. Synthesis is also possible. Furthermore, the production method of the present invention does not require the use of a halogen-containing compound such as acyl chloride as a substrate, thereby avoiding the large amount of by-product halide salts. Furthermore, the reaction can proceed under relatively mild conditions of 100°C or less. In other words, the production method of the present invention is environmentally friendly and highly useful.

[0124] The 4-silyl-2-butenyl carboxylic acid ester compound obtained by the production method according to the present invention can be applied to the Tsuji-Trost reaction, Claisen rearrangement, Hosomi-Sakurai allylation reaction, Hiyama cross-coupling reaction, etc., and is therefore expected to be used as a synthetic intermediate for physiologically active substances, etc. Furthermore, functional chemicals such as silane coupling agents can also be produced by hydrolyzing the 4-silyl-2-butenyl carboxylic acid ester compound, etc.

Claims

1. A method for producing a carboxylic acid 4-silyl-2-butenyl ester compound, comprising: The method includes a reaction step of reacting a 1,3-diene compound, a carboxylic acid compound, and a disilane compound in an oxygen-containing atmosphere in the presence of a palladium catalyst and a copper catalyst, the palladium catalyst is one or more compounds selected from a zero-valent palladium compound and a divalent palladium compound, the 1,3-diene compound is a compound represented by general formula (A), the carboxylic acid compound is a compound represented by general formula (B), the disilane compound is a compound represented by general formula (C), The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound, wherein the 4-silyl-2-butenyl carboxylic acid ester compound is a compound represented by general formula (D). 【Chemical 1】 (In general formula (A), R １ and R ２ each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. R ３ (CO ２ H) ｎ (B) (In general formula (B), R ３ represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group; and n represents an integer of 1 or more and 10 or less. (R ４ ) ３ SiSi(R ４ ) ３ (C) (In general formula (C), R ４ each independently represents a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbonoxy group. 【Chemistry 2】 (In general formula (D), R １ , R ２ , R ３ , R ４ , and n have the same meanings as defined above.)

2. R in the general formulas (A) and (D) １ The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to claim 1, wherein is a hydrocarbon group.

3. 2. The method of claim 1, wherein the palladium catalyst is one or more selected from palladium(II) acetate, palladium(II) chloride, and bis(dibenzylideneacetone)palladium(0).

3. A method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to claim 2.

4. The carboxylic acid 4 according to any one of claims 1 to 3, wherein the copper catalyst is a divalent copper salt. A method for producing 2-butenyl-silyl ester compounds.

5. The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of claims 1 to 4, wherein the reaction step is further carried out in the presence of a quinone compound represented by general formula (E1), (E2), or (E3). 【Chemistry 3】 (In general formulas (E1) to (E3), R ５ and R ６ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, or a nitrile group.

6. The method for producing a 4-silyl-2-butenyl carboxylic acid ester compound according to any one of claims 1 to 5, wherein the oxygen-containing atmosphere has an oxygen concentration of 60% by volume or more.

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