Method for producing cyclopentadienyl group-containing hydrocarbon compounds or cyclopentadienyl group-containing silicon-substituted hydrocarbon compounds using magnesium halide

Abstract

To provide a method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound, which can reduce persistence of unreacted raw materials and generation of an overreacted product, and which can improve the yield.SOLUTION: Provided is a method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound, comprising reacting a metal salt of a specific cyclopentadiene derivative or indene derivative with a specific halogenated hydrocarbon compound or halogenated silicon compound in the presence of a magnesium halide.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound. [Background technology]

[0002] Cyclopentadiene and indene become aromatic 6π-system anions by dehydrogenation from the five-membered ring, and are widely used as ligands that form stable complexes with various transition metals. Various transition metal complexes are useful as catalysts for a variety of chemical reactions, and the introduction of various substituents to the cyclopentadienyl group, indenyl group, etc. is effective for controlling the reaction. The introduction of substituents to the five-membered ring of cyclopentadiene and indene is achieved by nucleophilic substitution reaction of alkyl halides or halogenated silanes with alkali metal salts, such as lithium salts.

[0003] To date, techniques using CuCN or CuSCN have been developed to improve the yield in nucleophilic substitution reactions with halogenated silanes, but the use of highly toxic compounds has been problematic (Patent Document 1). In response to this, a technique has been developed to improve the reactivity of halogenated silane compounds by adding 1-methylimidazole (Patent Document 2). On the other hand, Patent Document 3 describes a nucleophilic addition reaction between cyclopentadienyl Li and a ketone having a highly acidic α-hydrogen in the presence of magnesium chloride. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-120688 [Patent Document 2] Japanese Patent Application Publication No. 10-265490 [Patent Document 3] JP 2014-218445 A Summary of the Invention [Problem to be solved by the invention]

[0005] The above-mentioned conventional techniques using CuCN or CuSCN and 1-methylimidazole are limited to the introduction of silicon substituents using halogenated silanes and are ineffective for the introduction of hydrocarbon substituents such as alkyl substituents.

[0006] The present inventors have noticed that in the nucleophilic substitution reaction of halogenated silanes or halogenated hydrocarbons with alkali metal salts such as cyclopentadiene or indene, alkali metal-hydrogen exchange occurs between the hydrogen of the cyclopentadiene ring regenerated in the reaction and the unreacted alkali metal salt, and the yield is likely to decrease due to the remaining unreacted raw materials and the by-production of over-reactants. Therefore, the present invention aims to provide a method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound, which can reduce the remaining unreacted raw materials and the production of over-reactants, and thus improve the yield. [Means for solving the problem]

[0007] As a result of intensive research conducted by the inventors in order to solve the above-mentioned problems, they have found that by adding a magnesium halide to a reaction system of a nucleophilic substitution reaction between an alkali metal salt of a cyclopentadiene derivative and a halogenated silane or a halogenated hydrocarbon to form an Mg ate complex between magnesium, a cyclopentadiene derivative, and an alkali metal, the basicity of the alkali metal ion can be reduced and the above-mentioned alkali metal-hydrogen exchange, which is a side reaction, can be suppressed, thereby completing the present invention.

[0008] That is, the present invention relates to the following. [1] In an ether solvent, The following formula (1) [ka] During the ceremony, L is lithium, sodium or potassium; R a is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R a may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R a When there are multiple, they may be the same or different, m is an integer from 1 to 4; and a metal salt of a cyclopentadiene derivative represented by the formula: The following formula (2) or (3) [ka] During the ceremony, R d , R e and R f are each independently a hydrogen atom, an aromatic hydrocarbon group, or a linear or branched alkyl group having 1 to 20 carbon atoms, and in formula (2), R d , R e and R f At least one of R d and R e At least one of the is not hydrogen, M is carbon or silicon; X is a halogen atom, and in formula (3), two X's may be the same or different. and a halogenated hydrocarbon compound or a halogenated silicon compound represented by the following formula: By reacting in the presence of magnesium halide, The following formula (4) or (5) [ka] During the ceremony, R a , R d , R e , R f , M and m are as defined above. A method for producing a compound represented by the formula:

[0009] [2] The compound represented by formula (1), The following formula (1-A) [ka] During the ceremony, L is lithium, sodium or potassium; R b is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R b may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R b When there are a plurality of, they may be the same or different, R c is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R c may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R c When there are a plurality of, they may be the same or different, q is an integer from 1 to 4, n is an integer from 1 to 2; A compound represented by the formula: The compound represented by formula (4) or (5) The following formula (6) or (7) [ka] During the ceremony R b , R c , q and n are as defined above, and R d , R e , R f and M is as defined in claim 1; The method according to the above [1], wherein the compound is represented by the formula:

[0010] [3] The method according to [1] or [2] above, wherein the magnesium halide is magnesium chloride. [4] The method according to any one of the above [1] to [3], wherein L is lithium. [5] The method according to any one of [1] to [4] above, wherein the ether solvent is tetrahydrofuran or tert-butyl methyl ether. [6] The method according to any one of [1] to [5] above, wherein X is chlorine or bromine. [7] The method according to any one of the above [1] to [6], comprising the steps of: mixing a compound represented by formula (1) with a magnesium halide to obtain a mixture; and mixing the mixture with a halogenated hydrocarbon compound or a halogenated silicon compound represented by formula (2) or (3). Effect of the Invention

[0011] According to the present invention, in the reaction of an alkali metal salt of a cyclopentadiene derivative with a halogenated silane or a halogenated hydrocarbon, a side reaction due to alkali metal-hydrogen exchange can be suppressed, and the remaining unreacted raw material and the by-production of an over-reactant can be suppressed, so that a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound can be synthesized at a high reaction rate. In addition, since the product can be obtained with high purity, there is an advantage that purification of the product when used as a catalyst ligand can be facilitated or purification itself can be omitted. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below based on preferred embodiments of the present invention.

[0013] The metal salt of a cyclopentadiene derivative used in the method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound of the present invention is represented by the following formula (1): The following formula (1) [ka] During the ceremony, L is lithium, sodium or potassium; R a is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R a may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R a When there are multiple, they may be the same or different, m is an integer from 1 to 4; It is expressed as:

[0014] In the formula (1), L is lithium, sodium or potassium, and from the viewpoint of practicality, lithium and sodium are particularly preferred.

[0015] R in formula (1) a The aromatic ring group refers to a group containing a ring structure having aromaticity, and examples of the aromatic ring group include an aromatic hydrocarbon group and an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group include monocyclic or polycyclic hydrocarbon groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. The polycyclic ring may be a condensed ring. Alternatively, the polycyclic ring may be formed by bonding the same or different monocyclic rings and / or the same or different condensed rings with a single bond. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a benzyl group, and a phenanthryl group. From the viewpoint of practicality, a phenyl group and a benzyl group are preferred.

[0016] R in formula (1) a Examples of the aromatic heterocyclic group include monocyclic or polycyclic heterocyclic groups having 5 to 30 carbon atoms, preferably 5 to 20 carbon atoms, containing one or more atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom, such as a pyridyl group, a furyl group, a pyryl group, a thienyl group, an indolyl group, a carbazolyl group, and a benzoxazolyl group. From the viewpoint of practicality, a furyl group and a pyryl group are particularly preferred.

[0017] The aromatic ring group may be unsubstituted or may have a substituent. When a plurality of substituents are present, the substituents may be the same or different. The substituents include, but are not limited to, the following substituent A.

[0018] The substituent A includes a saturated or unsaturated hydrocarbon group, particularly a C1 to C20 saturated or unsaturated hydrocarbon group, an aryl group in which a carbon atom may be replaced with a heteroatom, particularly an aryl group having 6 to 20 ring members in which a carbon atom may be replaced with a heteroatom, a heterocyclyl group, particularly a heterocyclyl group having 3 to 20 ring members, a fluoroalkyl group, a silyl group, or a halogen group.

[0019] The saturated or unsaturated hydrocarbon group of the substituent A, preferably a C1-20 saturated or unsaturated hydrocarbon group, includes a saturated or unsaturated linear or cyclic hydrocarbon group. For example, the saturated or unsaturated linear hydrocarbon group includes a saturated or unsaturated linear or branched alkyl group, and the saturated or unsaturated cyclic hydrocarbon includes a saturated or unsaturated cycloalkyl group and an aryl group. The "saturated or unsaturated alkyl group" includes a saturated linear or branched alkyl group and an unsaturated linear or branched alkyl group such as an alkynyl group and an alkenyl group. The alkyl group is preferably a C1-20 alkyl group, more preferably a C1-10 alkyl group, and even more preferably a C1-5 alkyl group. In the present specification, the term "saturated or unsaturated cycloalkyl group" includes saturated cycloalkyl groups and unsaturated cycloalkenyl groups. As the cycloalkyl group, a C3 to C20 cycloalkyl group is preferable, and a C5 to C10 cycloalkyl group is more preferable.

[0020] "Heterocyclyl groups" include groups in which one or more carbon atoms of a saturated or unsaturated cycloalkyl group are replaced by a heteroatom, such as nitrogen, oxygen, and sulfur atoms. In this specification, for example, an "aryl group having 6 to 20 ring members in which carbon atoms may be replaced with heteroatoms" includes an aromatic heterocyclic group having 6 to 20 ring members in which one or more carbon atoms of an aromatic hydrocarbon group are replaced with one or more heteroatoms selected from a nitrogen atom, an oxygen atom, a sulfur atom, and the like.

[0021] Preferred examples of the substituent that the aromatic ring group in formula (1) may have include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, and particularly preferred are a methyl group, an ethyl group, a propyl group, and a butyl group.

[0022] R in formula (1) a Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. From the viewpoint of practicality, a linear alkyl group having 1 to 6 carbon atoms is preferable.

[0023] R in formula (1) a Examples of the branched alkyl group having 1 to 20 carbon atoms include 1-methylethyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-n-propylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 1-propylbutyl group, 1-n-butylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-n-propylpentyl group, 1-n-pentylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-n-propylhexyl group, 1-n-butylhexyl group, 1-n-pentylhexyl group, 1-n-hexylhexyl group, 1-methylheptyl group, 1-ethylheptyl group, 1-n-propylheptyl group, 1-n-butylheptyl group, 1-n-pentylheptyl group, etc. From the viewpoint of practicality, a branched alkyl group having 1 to 6 carbon atoms is preferable.

[0024] R in the above formula (1) aThe linear or branched alkyl group having 1 to 20 carbon atoms may be unsubstituted or may have a substituent. When a plurality of substituents are present, the substituents may be the same or different. Examples of the substituent include, but are not limited to, the above-mentioned substituent A.

[0025] Preferred examples of the substituent that the linear or branched alkyl group having 1 to 20 carbon atoms may have include a phenyl group and a furyl group. In one embodiment of the present invention, the substituent that the linear or branched alkyl group having 1 to 20 carbon atoms may have is not an alkyl group.

[0026] Adjacent R a may form a hydrocarbon ring. In particular, adjacent R a It is preferred that the benzene ring is formed so that, together with the cyclopentadienyl group, an indene ring structure is formed. Also, adjacent R a can be expressed by, but is not limited to, the following formula together with the cyclopentadienyl group: Ring structure A: [ka] As the ring structure, for example, a ring structure represented by the following formula: [ka] The structure is as follows. Furthermore, the adjacent R a can be expressed by, but is not limited to, the following formula together with the cyclopentadienyl group: Ring structure B: [ka] It is also possible to form a ring structure represented by the following formula:

[0027] Adjacent R in the above formula (1) aThe hydrocarbon ring formed by may be unsubstituted or may have a substituent. When there are a plurality of substituents, the substituents may be the same or different. The substituents include, but are not limited to, the following substituent B. The substituent B is hydrogen, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and adjacent substituents B may form a hydrocarbon ring, and the hydrocarbon ring may have a substituent. When there are a plurality of substituents B, they may be the same or different. For the aromatic ring group and the linear or branched alkyl group having 1 to 20 carbon atoms, the above R a The substituents that the aromatic ring group and the linear or branched alkyl group having 1 to 20 carbon atoms may have include, but are not limited to, the above-mentioned substituent A.

[0028] Preferred examples of the substituent that the hydrocarbon ring may have include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.

[0029] Adjacent substituents B may form a hydrocarbon ring. Examples of the ring formed by the substituents B include, but are not limited to, a cyclopentadienyl group and R a Together with the hydrocarbon ring formed, Ring structure C: [ka] or ring structure D: [ka] It is possible to form a ring structure represented by the following formula: In addition, adjacent substituents B and adjacent R a may simultaneously form a separate ring. Examples of such a ring structure include, but are not limited to, a ring included in the ring structure C or D formed by the substituent B and a ring not involved in the ring formation, such as R aand a ring contained in the ring structure B formed by the above formula (I) can be mentioned.

[0030] R in the above formula (1) a is R a When there are multiple R, they may be the same or different. a can also be appropriately selected depending on the desired substituent when the cyclopentadienyl group-containing hydrocarbon compound or silicon-substituted hydrocarbon compound produced by the present invention is finally used as a ligand. From a practical standpoint, R a is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like. Also, adjacent R a It is preferred that the benzene ring is formed so that, together with the cyclopentadienyl group, an indene ring structure is formed.

[0031] The metal salt of the cyclopentadiene derivative represented by the above formula (1) is, for example, a lithium salt, a potassium salt, or a sodium salt of cyclopentadiene or indene, but is not limited thereto.

[0032] In a preferred embodiment of the present invention, the metal salt of a cyclopentadiene derivative represented by the above formula (1) is a compound represented by the following formula (1-A) (hereinafter also referred to as a metal salt of an indene derivative). Formula (1-A) [ka] During the ceremony, L is lithium, sodium or potassium; R b is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R b may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R b When there are a plurality of, they may be the same or different, R cis a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R c may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R c When there are a plurality of, they may be the same or different, q is an integer from 1 to 4, n is an integer of 1 to 2.

[0033] In formula (1-A), L is lithium, sodium or potassium, and from the viewpoint of practicality, lithium and sodium are particularly preferred. R in formula (1-A) b and R c are each independently selected. R in formula (1-A) b and R c As the aromatic ring group, R a The same can be mentioned.

[0034] The aromatic ring group may be unsubstituted or may have a substituent. When a plurality of substituents are present, the substituents may be the same or different. The substituents include, but are not limited to, the above-mentioned substituent A.

[0035] Preferred substituents which the aromatic ring group in the above formula (1-A) may have are a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group, in particular a methyl group, an ethyl group, a propyl group or a butyl group.

[0036] R in the above formula (1-A) b and R c As the linear or branched alkyl group having 1 to 20 carbon atoms, R a The same can be mentioned.

[0037] R in the above formula (1-A) b and R cThe linear or branched alkyl group having 1 to 20 carbon atoms may be unsubstituted or may have a substituent. When a plurality of substituents are present, the substituents may be the same or different. Examples of the substituent include, but are not limited to, the above-mentioned substituent A.

[0038] Preferred examples of the substituent that the linear or branched alkyl group having 1 to 20 carbon atoms may have include a phenyl group and a furyl group. In one embodiment of the present invention, the substituent that the linear or branched alkyl group having 1 to 20 carbon atoms may have is not an alkyl group.

[0039] Adjacent R b may form a hydrocarbon ring, and may form a ring structure represented by the ring structure C or ring structure D, which is the same as the ring formed by the above-mentioned substituent B, but is not limited thereto. From the viewpoint of practicality, R b The hydrocarbon ring formed by is preferably a hydrocarbon ring having 6 to 7 carbon atoms.

[0040] Adjacent R c may form a hydrocarbon ring, and may form a ring structure represented by the ring structure B, but is not limited thereto. From the viewpoint of practicality, R c The hydrocarbon ring formed by is preferably a hydrocarbon ring having 6 to 7 carbon atoms. Also, adjacent R b R c may simultaneously form separate rings, and examples thereof include, but are not limited to, R b and a ring contained in the ring structure C or D formed by R c and a ring contained in the ring structure B formed by the above formula (I) can be mentioned.

[0041] Adjacent R in the above formula (1-A) b The hydrocarbon ring formed by and the adjacent R cThe hydrocarbon ring formed by may be unsubstituted or may have a substituent. When a plurality of substituents are present, the substituents may be the same or different. The substituents include, but are not limited to, the above-mentioned substituent A.

[0042] Adjacent R b Preferred examples of the substituent that the hydrocarbon ring formed by the formula (I) may have include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. Adjacent R c Preferred examples of the substituent that the hydrocarbon ring formed by the formula (I) may have include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.

[0043] R in the above formula (1-A) b is R b When there are a plurality of them, they may be the same or different. R in the above formula (1-A) c is R c When there are a plurality of them, they may be the same or different. R in the above formula (1-A) b and R c can also be appropriately selected depending on the desired substituent when the cyclopentadienyl group-containing hydrocarbon compound or cyclopentadienyl group-containing silicon-substituted hydrocarbon compound produced in the present invention is finally used as a ligand.

[0044] R b is preferably a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group. R c is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a phenyl group.

[0045] Examples of metal salts of the indene derivative represented by the above formula (1) include, but are not limited to, lithium salts, potassium salts, and sodium salts of indene.

[0046] The halogenated hydrocarbon compound or halogenated silicon compound used in the process for producing the cyclopentadienyl group-containing hydrocarbon compound or the cyclopentadienyl group-containing silicon-substituted hydrocarbon compound of the present invention is The following formula (2) or (3) [ka] R d , R e and R f are each independently a hydrogen atom, an aromatic hydrocarbon group, or a linear or branched alkyl group having 1 to 20 carbon atoms, and in formula (2), R d , R e and R f At least one of R d and R e At least one of the is not hydrogen, M is carbon or silicon; X is a halogen atom, and in formula (3), two X's may be the same or different. It is expressed as either

[0047] R in the above formulas (2) and (3) d , R e and R f The aromatic hydrocarbon group may be a monocyclic or polycyclic hydrocarbon group having 5 to 25 carbon atoms, preferably 5 to 9 carbon atoms. The polycyclic ring may be a condensed ring. Alternatively, the polycyclic ring may be formed by bonding the same or different monocyclic rings and / or the same or different condensed rings with a single bond. Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a benzyl group, a phenanthryl group, a cyclopentadienyl group, and an indenyl group. From the viewpoint of practicality, a phenyl group, a cyclopentadienyl group, or an indenyl group is preferred.

[0048] R in the above formulas (2) and (3) d , R e and R fExamples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. From the viewpoint of practicality, a linear alkyl group having 1 to 6 carbon atoms is preferable.

[0049] R in the above formulas (2) and (3) d , R e and R f Examples of the branched alkyl group having 1 to 20 carbon atoms include 1-methylethyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-n-propylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 1-propylbutyl group, 1-n-butylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-n-propylpentyl group, 1-n-pentylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-n-propylhexyl group, 1-n-butylhexyl group, 1-n-pentylhexyl group, 1-n-hexylhexyl group, 1-methylheptyl group, 1-ethylheptyl group, 1-n-propylheptyl group, 1-n-butylheptyl group, 1-n-pentylheptyl group, etc. From the viewpoint of practicality, a branched alkyl group having 1 to 6 carbon atoms is preferable.

[0050] X in the above formulas (2) and (3) is a halogen atom, preferably fluorine, chlorine, bromine or iodine, and particularly preferably chlorine or bromine.

[0051] Examples of the halogenated hydrocarbon compound represented by the above formula (2) include, but are not limited to, the following: methyl iodide, ethyl bromide, propyl bromide, isopropyl bromide, butyl bromide, pentyl bromide, hexyl bromide, phenyl bromide, and benzyl bromide. Examples of the halogenated silicon compound represented by the above formula (2) include, but are not limited to, trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, t-butyldimethylsilyl chloride, t-butyldiphenylsilyl chloride, and triphenylsilyl chloride.

[0052] Examples of the halogenated hydrocarbon compound represented by the above formula (3) include, but are not limited to, diiodomethane, dibromomethane, dichloromethane, 1,1-diiodoethane, and 1,1-dibromoethane. Examples of the halogenated silicon compound represented by the above formula (3) include, but are not limited to, dichlorodimethylsilane, dichlorodiphenylsilane, and 1,1-dichlorosilacyclobutane.

[0053] The magnesium halide used in the method for producing the cyclopentadienyl group-containing hydrocarbon compound or the cyclopentadienyl group-containing silicon-substituted hydrocarbon compound of the present invention includes magnesium chloride, magnesium bromide, magnesium iodide, etc. Magnesium chloride is particularly preferred.

[0054] The cyclopentadienyl group-containing hydrocarbon compound or silicon-substituted hydrocarbon compound produced by the production method of the present invention is represented by the following formula (4) or (5): [ka] During the ceremony, R a , R d , R e , R f , M and m are as defined above. It is expressed as either

[0055] Examples of the cyclopentadienyl group-containing hydrocarbon compound or silicon-substituted hydrocarbon compound represented by the above formula (4) or (5) include, but are not limited to, methylcyclopentadiene, t-butylcyclopentadiene, trimethylsilylcyclopentadiene, bis(methylcyclopentyl)methane, 1-trimethylsilylindene, bisindenyldimethylsilane, and bis(2-methylindenyl)dimethylsilane.

[0056] In one embodiment of the present invention, when the compound represented by formula (1) is a metal salt of an indene derivative represented by formula (1-A), the indenyl group-containing hydrocarbon compound or silicon-substituted hydrocarbon compound produced by the production method of the present invention is represented by the following formula (6) or (7): [ka] During the ceremony R b , R c , q and n are as defined in formula (1-A), and R d , R e , R f and M is as defined in formulas (4) and (5) above. It is expressed as either

[0057] The ether solvent used in the method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound of the present invention is not particularly limited, but examples include diethyl ether, tetrahydrofuran, tert-butyl methyl ether, dioxane, cyclopentyl methyl ether, and the like, with tetrahydrofuran, cyclopentyl methyl ether and tert-butyl methyl ether being particularly preferred from the viewpoint of practicality.

[0058] The method for producing a cyclopentadienyl group-containing hydrocarbon compound or a cyclopentadienyl group-containing silicon-substituted hydrocarbon compound of the present invention comprises the step of reacting, in an ether solvent, a metal salt of a cyclopentadiene derivative represented by the above formula (1) or a metal salt of an indene derivative represented by the above formula (1-A) with a halogenated hydrocarbon compound or halogenated silicon compound represented by the above formula (2) or (3) in the presence of magnesium halide.

[0059] In one embodiment of the present invention, a metal salt of a cyclopentadiene derivative represented by the above formula (1) can be mixed with a magnesium halide in advance, and then a halogenated hydrocarbon compound or a halogenated silicon compound represented by the above formula (2) or (3) can be added. This method is believed to allow a Mg ate complex to be formed in advance in a reaction vessel, reducing the basicity of the alkali metal, before reaction with a halogenated hydrocarbon compound or a halogenated silicon compound can be carried out.

[0060] Therefore, in one aspect, the present invention comprises a step of mixing a metal salt of a cyclopentadiene derivative represented by the above formula (1) with a magnesium halide to obtain a mixture, and a step of mixing the mixture with a halogenated hydrocarbon compound or a halogenated silicon compound represented by the above formula (2) or (3).

[0061] The temperature at which the metal salt of the cyclopentadiene derivative represented by the above formula (1) and the magnesium halide are mixed in advance can be appropriately selected depending on the solvent used, and is, for example, 20°C to 60°C. The mixing time can be selected depending on the solvent and alkali metal species used, and is, for example, 0.5 to 2 hours. Heating means such as heating under reflux or an oil bath, or cooling means such as an ice bath or a low-temperature reaction apparatus can be used.

[0062] The temperature at which the halogenated hydrocarbon compound or halogenated silicon compound represented by the above formula (2) or (3) is added can also be appropriately selected depending on the solvent used, and is, for example, from -10°C to 20°C. The mixing time can be selected depending on the reaction rate, and is, for example but not limited to, 1 hour to 24 hours. Heating means such as heating under reflux or an oil bath, or cooling means such as an ice bath or a low-temperature reaction apparatus can be used.

[0063] In the method of the present invention, the molar ratio of the metal salt of the cyclopentadiene derivative represented by the above formula (1) to the magnesium halide is preferably 1: 1. Also, the molar ratio of the metal salt of the cyclopentadiene derivative represented by the above formula (1) to the halogenated hydrocarbon compound represented by the above formula (2) or (3) is preferably 1: 1 to 1: 5.

[0064] After the reaction is completed, the target compound can be obtained by purification means such as extraction, washing with an acid or alkali, washing with water or saturated saline, concentration, concentration under reduced pressure, filtration, chromatography, distillation, sublimation, recrystallization, etc. Alternatively, the compound can be subjected to another reaction, for example, the production of various transition metal complexes, without employing these purification means.

[0065] The target compound produced by the method according to the present invention, the over-reactants, and the unreacted raw materials were identified by nuclear magnetic resonance (NMR) with tetramethylsilane (TMS) as an internal standard, and its signal was set to δ=0 (δ is a chemical shift). The reaction rate was calculated and evaluated from the peaks of the target compound, the over-reactants, and the unreacted raw materials by gas chromatography (GC) or liquid chromatography (LC). EXAMPLES

[0066] The present invention will be described in more detail below with reference to examples, which are intended to illustrate specific embodiments of the present invention and are not intended to limit the present invention. In the following Comparative Examples and Examples, JEOL's JNM-ECX400P was used for NMR, Shimadzu's GC-2010 for GC, and Shimadzu's LC-20AT, SPD-20A, and CBM-20A for LC.

[0067] (1) n-Propylation [Comparative Example 1] In a 1000ml Schlenk flask, 20.0g (1.0eq) of cyclopentadiene and 240ml of tetrahydrofuran were added under argon, and 194.0ml (1.0eq) of 1.56M n-BuLi hexane solution was added dropwise while cooling in an ice-water bath, and the mixture was stirred at room temperature for 1 hour. Next, 66.2ml (2.0eq.) of DMI was added and dissolved, and then 27.4ml (1.0eq.) of nPrBr was added while cooling in an ice-water bath, and the mixture was stirred overnight at room temperature. The reaction was confirmed by GC (nPrCp / 88.4%, over-reactant / 8.2%), and 300ml of water was added to quench the mixture while cooling in an ice-water bath. 300ml of hexane was further added for extraction, and the organic layer was separated and washed with 300ml of water x 3 times and 300ml of saline, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure and purified by distillation to obtain nPrCp: 25.2 g, yield: 77%, GC: 95.2%.

[0068] [Comparative Example 2] In a 1000ml Schlenk flask, 20.0g (1.0eq) of cyclopentadiene, 240ml of tetrahydrofuran, and 1.21ml (0.05eq.) of N-methylimidazole were added under argon, and 194.0ml (1.0eq.) of 1.56M n-BuLi hexane solution was added dropwise while cooling in an ice-water bath, and the mixture was stirred at room temperature for 1 hour. Next, 27.4ml (1.0eq.) of nPrBr was added while cooling in an ice-water bath, and the mixture was stirred overnight at room temperature. The reaction was confirmed by GC (nPrCp / 77.7%, over-reactant / 14.1%), and quenched by adding 300ml of water while cooling in an ice-water bath. 300ml of hexane was further added for extraction, and the organic layer was separated and washed with 300ml of water x 3 times and 300ml of saline, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure and purified by distillation to obtain nPrCp: 24.6 g, yield: 75%, GC: 94.8%.

[0069] [Example 1] In a 1000ml Schlenk flask, 20.0g (1.0eq) of cyclopentadiene and 240ml of tetrahydrofuran were added under argon, and 194.0ml (1.0eq) of 1.56M n-BuLi hexane solution was added dropwise while cooling in an ice water bath, and stirred at room temperature for 1 hour. While cooling in an ice water bath, 28.8g (1.0eq.) of anhydrous magnesium chloride was added and stirred at 45°C for 1 hour. Next, while cooling in an ice water bath, 27.4ml (1.0eq.) of nPrBr was added and stirred overnight at room temperature. The reaction was confirmed by gas chromatography (GC) (nPrCp / 97.6%, over reactant / 1.2%), and quenched by adding 300ml of water while cooling in an ice water bath. Further, 300ml of hexane was added for extraction, and the organic layer was separated and washed with 300ml of water x 3 times and 300ml of saline, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure and purified by distillation to obtain nPrCp: 27.8 g, yield: 85%, GC: 99.0%.

[0070] In the method not using magnesium chloride (Comparative Example 1) and the method of Patent Document 2 (Comparative Example 2), Li-hydrogen exchange occurs between hydrogen of n-PrCp produced in the reaction and unreacted Li salt, and the amount of over-reactants is about 8 to 14%, but in the present invention, the amount of over-reactants could be suppressed to 1.2% as in Example 3. Moreover, the method of the present invention had a higher yield than the method of Patent Document 2 (Comparative Example 2).

[0071] Table 1 Experimental results of n-propylation reaction [Table 1]

[0072] (2) Trimethylsilylation (TMS) [Comparative Example 3] In a 200 ml Schlenk flask, 11.8 g (1.0 eq) of TMSCp and 70 ml of tetrahydrofuran were added under argon, and 52.0 ml (1.0 eq) of 1.64 M n-BuLi hexane solution was added dropwise while cooling in an ice water bath, and the mixture was stirred at room temperature for 1 hour. Next, 10.8 ml (1.0 eq.) of chlorotrimethylsilane was added while cooling in an ice water bath, and the mixture was stirred at room temperature for 1 hour. The reaction was confirmed by GC (TMSCp / 12.5%, (TMS)2Cp / 82.9%), and quenched by adding 50 ml of water while cooling in an ice water bath. The organic layer was washed with 50 ml of water x 3 and 100 ml of saline, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure to obtain (TMS)2Cp: 16.7 g, crude yield: 93%, GC: 83.0% (TMSCp / 12.6%). Further purification by distillation gave (TMS)2Cp: 12.6 g, yield: 70%, GC: 93.2% (TMSCp / 2.6%).

[0073] [Example 2] In a 200 ml Schlenk flask, 11.8 g (1.0 eq) of TMSCp and 70 ml of tetrahydrofuran were added under argon, and 52.0 ml (1.0 eq) of 1.64 M n-BuLi hexane solution was added dropwise while cooling in an ice water bath, and the mixture was stirred at room temperature for 1 hour. While cooling in an ice water bath, 8.13 g (1.0 eq.) of anhydrous magnesium chloride was added and stirred at 45 ° C. for 1 hour. Next, while cooling in an ice water bath, 10.8 ml (1.0 eq.) of chlorotrimethylsilane was added and stirred at room temperature for 1 hour. The reaction was confirmed by GC (TMSCp / 1.6%, (TMS) 2Cp / 93.8%), and quenched by adding 50 ml of water while cooling in an ice water bath. The organic layer was separated and washed with 50 ml of water x 3 times and 100 ml of saline, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure to obtain (TMS)2Cp: 16.9 g, yield: 94%, GC: 94.4% (TMSCp / 1.5%).

[0074] The results of Comparative Example 3 and Example 2 are shown in Table 2 below. As shown in Table 2, in Comparative Example 3, which did not use magnesium chloride, 12.5% ​​of the raw material TMSCp remained unreacted, whereas in Example 2 of the present invention, the remaining unreacted TMSCp was reduced to 1.6%, making it possible to omit distillation purification.

[0075] Table 2. Trimethylsilylation (TMS) experiment results [Table 2]

[0076] (3) Reaction of indene with dichlorodimethylsilane [Comparative Example 4] In a 1000ml Schlenk flask, 41.4ml (1eq.) of indene, 414ml of t-butyl methyl ether, and 1.42ml (0.05eq.) of N-methylimidazole were added under argon and cooled to below 10℃ in an ice-water bath, 218.0ml (1.0eq.) of 1.64M n-BuLi hexane solution was added dropwise, and the mixture was stirred at room temperature for 2 hours. The mixture was cooled to 0℃ in an ice-methanol bath, 21.3ml (0.5eq.) of dichlorodimethylsilane was added dropwise, and the mixture was stirred overnight at room temperature. The reaction was confirmed by LC (2 / 66.1%, indene / 10.0%, over reactant / 22.1%), and the mixture was cooled in an ice-water bath, followed by quenching with 300ml of water. The organic layer was separated and washed with 300ml of ammonium chloride aqueous solution and 300ml of water twice, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure to obtain 51.0 g of the target product 2, crude yield: 97%, LC: 66.0%.

[0077] [Example 3] In a 500 ml Schlenk flask, 18.1 ml (1 eq.) of indene and 145 ml of t-butyl methyl ether were added under argon, and the mixture was cooled to below 10°C in an ice-water bath, 100.2 ml (1.0 eq.) of 1.56 M n-BuLi hexane solution was added dropwise, and the mixture was stirred at room temperature for 2 hours. The mixture was cooled again in an ice-water bath, and 14.8 g (1.0 eq.) of anhydrous magnesium chloride was added, and the mixture was heated to 45°C and reacted for 1 hour. The mixture was cooled to 0°C in an ice-methanol bath, and 9.28 ml (0.5 eq.) of dichlorodimethylsilane was added dropwise, and the mixture was stirred overnight at room temperature. The reaction was confirmed by LC (2 / 89.1%, indene / 2.3%, over-reactant / 3.3%), and the mixture was cooled in an ice-water bath, and then quenched by adding 120 ml of water. The organic layer was separated and washed with 100 ml of ammonium chloride aqueous solution and 100 ml of water twice, and dried over sodium sulfate. The sodium sulfate was filtered off, and the organic layer was concentrated under reduced pressure to obtain 22.4 g of the target product 2, crude yield: 99%, LC: 89.0%. 150 ml of methanol was added to the crude product, and the mixture was cooled to -20°C. The precipitate was collected by filtration to obtain 13.6 g of the target product 2, yield: 60%, LC: 99.0%.

[0078] The results of Comparative Example 4 and Example 3 are shown in Table 3 below. In Comparative Example 4, the conditions of Patent Document 2 were used, but the target product 2 was 66.1%, the unreacted raw materials were 10.0%, and the over-reactants were 22.1%. In contrast, in Example 3 of the present invention, the target product 2 was 89.1%, the raw materials were 2.3%, and the over-reactants were 3.3%, which was a significant improvement in purity. This high-purity product could be easily recrystallized and purified when used as a catalyst ligand, and was used in the catalyst synthesis in the next step. On the other hand, the low-purity product of Comparative Example 4 could not be recrystallized and purified, and the catalyst synthesis in the next step was also difficult.

[0079] Table 3. Experimental results of the reaction of indene with dichlorodimethylsilane [Table 3]

Claims

1. In an ether solvent, The following formula (1) 【Chemistry 1】 During the ceremony, L is lithium, sodium or potassium; R ａ is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R ａ may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R ａ When there are multiple, they may be the same or different, m is an integer from 1 to 4; and a metal salt of a cyclopentadiene derivative represented by the formula: The following formula (2) or (3) 【Chemistry 2】 During the ceremony, R ｄ , R ｅ and R ｆ are each independently a hydrogen atom, an aromatic hydrocarbon group, or a linear or branched alkyl group having 1 to 20 carbon atoms; ｄ , R ｅ and R ｆ At least one of R ｄ and R ｅ At least one of the is not hydrogen, M is carbon or silicon; X is a halogen atom, and in formula (3), two X's may be the same or different. and a halogenated hydrocarbon compound or a halogenated silicon compound represented by the following formula: By reacting in the presence of magnesium halide, The following formula (4) or (5) 【Chemistry 3】 During the ceremony, R ａ , R ｄ , R ｅ , R ｆ , M and m are as defined above. A method for producing a compound represented by the formula:

2. A metal salt of a cyclopentadiene derivative represented by formula (1) The following formula (1-A) 【Chemistry 4】 During the ceremony, L is lithium, sodium or potassium; R ｂ is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R ｂ may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R ｂ When there are a plurality of, they may be the same or different, R ｃ is a hydrogen atom, a trimethylsilyl group, an aromatic ring group which may have a substituent, or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and the adjacent R ｃ may form a hydrocarbon ring, the hydrocarbon ring may have a substituent, R ｃ When there are a plurality of, they may be the same or different, q is an integer from 1 to 4, n is an integer from 1 to 2; A compound represented by the formula: The compound represented by formula (4) or (5) The following formula (6) or (7) 【Chemistry 5】 During the ceremony R ｂ , R ｃ , q and n are as defined above, R ｄ , R ｅ , R ｆ and M is as defined in claim 1; The compound represented by the formula: The method of claim 1.

3. 3. The method according to claim 1 or 2, wherein the magnesium halide is magnesium chloride.

4. The method of any one of claims 1 to 3, wherein L is lithium.

5. The process according to any one of claims 1 to 4, wherein the ether solvent is tetrahydrofuran or tert-butyl methyl ether.

6. The process according to any one of claims 1 to 5, wherein X is chlorine or bromine.

7. The method according to any one of claims 1 to 6, comprising the steps of: mixing a compound represented by formula (1) with a magnesium halide to obtain a mixture; and mixing the mixture with a halogenated hydrocarbon compound or a halogenated silicon compound represented by formula (2) or (3).

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