JP2003261469A - Method for producing benzene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a benzene derivative, capable of simply producing the multi-substituted benzene derivative at a high yield, while keeping consumption of a transition metal compound such as a nickel complex at the lowest limit. <P>SOLUTION: This method for producing the benzene derivative comprises reacting a metallacyclopentadiene of formula (2) (R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are identical to or different from each other, and are each H, a hydrocarbon residue, or the like; M is a transition metal; and L<SP>1</SP>and L<SP>2</SP>are each a ligand) with an alkyne of formula (3) (R<SP>5</SP>and R<SP>6</SP>are identical to or different from each other, and are each H, a hydrocarbon residue, or the like) in the presence of an oxidizing agent and the transition metal compound in a catalytic amount to form the benzene derivative of formula (1). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a benzene derivative, and more particularly to a method for producing a polysubstituted benzene derivative that requires a catalytic amount of a transition metal compound.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As a method for synthesizing benzenes, a method is known in which two molecules of acetylenes are reacted on zirconium to obtain zirconacyclopentadiene, and then benzene is further reacted with one molecule of acetylenes in the presence of a nickel complex. (Japanese Patent Laid-Open No. 11-263737). However, according to this method, the nickel complex takes part in the reaction stoichiometrically, and therefore an expensive nickel complex was required in an amount of 1 equivalent or more with respect to the zirconacyclopentadiene.

Therefore, it has been desired to easily obtain a polysubstituted benzene derivative in a high yield while minimizing the consumption of nickel complex.

[0004]

The inventor of the present invention has noticed that, according to a conventional method for synthesizing benzenes, a transition metal in a transition metal compound such as a nickel complex is reduced and consumed, By adding an oxidizing agent to the reaction system,
They have found that transition metal compounds can be used catalytically and have completed the present invention.

That is, the present invention provides a method for producing a benzene derivative represented by the following formula (1):

[Chemical 4] [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently, the same or different, a hydrogen atom; C ₁ -C which may have a substituent. ₂₀ hydrocarbon group; C ₁ -C ₂₀ alkoxy group optionally having substituents; C ₆ -C ₂₀ aryloxy group optionally having substituents; amino optionally having substituents Group; a silyl group which may have a substituent, or a hydroxyl group, provided that R ¹ and R ² ,
R ³ and R ⁴ , and R ⁵ and R ⁶ may be bridged with each other to form a C _{4 to} C ₂₀ saturated ring or an unsaturated ring, wherein the ring is an oxygen atom, a sulfur atom, or a silicon atom. An atom, a tin atom, a germanium atom or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or a C _{1 to} C ₂₀ hydrocarbon group), and, It may have a substituent. ] In the presence of an oxidizing agent and a transition metal compound in a catalytic amount, a metallacyclopentadiene represented by the following formula (2):

[Chemical 5] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the above meanings. M represents a transition metal, L ¹ and L ² are respectively
Independently of each other, the same or different, anionic ligands are shown. However, L ¹ and L ² may be crosslinked. ] With an alkyne represented by the following formula (3)

[Chemical 6] [In the formula, R ⁵ and R ⁶ have the above-mentioned meanings. ] Is provided, a method for producing a benzene derivative is provided.

According to the present invention, the oxidizing agent is preferably an organic halide. Further, it is more preferable that the oxidizing agent is a dihalogenoalkane or an allyl halide.

Further, according to the present invention, it is preferable that the transition metal compound is a nickel complex.

According to the present invention, the amount of the catalyst is 0.000 with respect to 1 mol of the metallacyclopentadiene.
It is preferably 1 mol to 0.5 mol.

According to the present invention, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ are each independently, the same or different, and are a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent or a silyl group which may have a substituent. Is preferred.

Further, according to the present invention, it is preferable that M is a transition metal of Groups 4 to 6 of the periodic table. Also, M
Is more preferably zirconium.

Further, according to the present invention, the anionic ligand is a delocalized cyclic η ⁵ -coordination system ligand, which may be substituted cyclopentadienyl group or indenyl group. It is preferably a group, a fluorenyl group or an azulenyl group.

Further, according to the present invention, the benzene derivative represented by the formula (1) is 1,2,3,4-tetraethyl-5,6-dipropylbenzene, 1,2,3,4-tetraethyl. -5-propylbenzene, 1,2,3,4-
Tetraethyl-5-phenylbenzene, 1,2,3
4,5-Pentaethyl-6- (1-butyn-1-yl)
Benzene, 1,2,3,4-tetraethyl-5-dimethylsilyl-6-butylbenzene, 1,2,3,4-tetraethyl-5-methoxymethylbenzene, 1,2-dipropyl-3,4-dimethyl- 5,6-diethylbenzene, 1,2-diphenyl-3,4-dimethyl-5,6-
Dipropylbenzene or 1,2-dibutyl-3,4-
It is preferably dimethyl-5,6-diethylbenzene.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a metallacyclopentadiene represented by the following formula (2) and an alkyne represented by the following formula (3) are reacted in the presence of an oxidizing agent and a catalytic amount of a transition metal compound. A method for producing a benzene derivative represented by the following formula (1) is provided.

[0014]

[Chemical 7] [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , M, L ¹ and L ² have the above meanings. ]

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently of the same or different and are a hydrogen atom; C ₁ which may have a substituent -C ₂₀ hydrocarbon group; which may have a substituent group C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; which may have a substituent A good amino group; a silyl group which may have a substituent; or a hydroxyl group.

In the present specification, the hydrocarbon group of "C ₁ -C ₂₀ hydrocarbon group" may be saturated or unsaturated acyclic, or saturated or unsaturated cyclic. Good. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The "C ₁ -C ₂₀ hydrocarbon group", C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₄ -C ₂₀ alkadienyl group, C ₆ ~ C ₁₈ aryl group, C ₆ -C ₂₀ alkylaryl group, C ₆ -C ₂₀ arylalkyl group, C ₄ ~C _{2 0} cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ -C
₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, the "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₀ alkyl group,
And more preferably a C ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl,
Ethyl, propyl, isopropyl, n-butyl, sec
-Butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like can be mentioned.

In the present specification, the "C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, and more preferably C ₂ -C ₆ alkenyl group.
Examples of alkenyl groups include, but are not limited to,
Examples thereof include vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

In the present specification, "C ₂ -C ₂₀ alkynyl group" is preferably C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₆ alkynyl group.
Examples of alkynyl groups include, but are not limited to,
Examples include ethynyl, 2-propynyl, 2-butynyl and the like.

In the present specification, the "C ₄ -C ₂₀ alkyldienyl group" is preferably C ₄ -C ₁₀ alkyldienyl group, and more preferably C ₄ -C ₆ alkyldienyl group. preferable. Examples of alkyldienyl groups include:
Examples include, but are not limited to, 1,3-butadienyl and the like.

In the present specification, the "C ₆ -C ₁₈ aryl group" is preferably C ₆ -C ₁₀ aryl group.
Examples of aryl groups include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, the "C ₆ -C ₂₀ alkylaryl group" is preferably C ₆ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-
Trilyl, 2,3-xylyl, 2,4-xylyl, 2,5
-Xylyl, o-cumenyl, m-cumenyl, p-cumenyl, mesityl and the like can be mentioned.

In the present specification, the "C ₆ -C ₂₀ arylalkyl group" is preferably C ₆ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl,
Examples thereof include 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and the like.

In the present specification, the "C ₄ -C ₂₀ cycloalkyl group" is preferably C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In the present specification, the "C ₄ -C ₂₀ cycloalkenyl group" is preferably C ₄ -C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, and the like.

In the present specification, the "C ₁ -C ₂₀ alkoxy group" is preferably C ₁ -C ₁₀ alkoxy group, and more preferably C ₁ -C ₆ alkoxy group.
Examples of alkoxy groups include, but are not limited to,
Examples include methoxy, ethoxy, propoxy, butoxy and pentyloxy.

In the present specification, the "C ₆ -C ₂₀ aryloxy group" is preferably C ₆ -C ₁₀ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy and the like.

"C ₁ -C ₂₀ hydrocarbon group", "C ₁ -C ₂₀ alkoxy group" and "C ₆ -C ₂₀ " represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ A substituent may be introduced into the “aryloxy group”, the “amino group” and the “silyl group”. Examples of this substituent include a C _{1 to} C ₁₀ hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), a C _{1 to} C ₁₀ alkoxy group (eg, , Methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ -C ₁₀
Examples thereof include an aryloxy group (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine, iodine) and a silyl group. In this case, one or more substituents may be introduced at the substitutable position, and preferably one to four substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

In the present specification, examples of the "amino group which may have a substituent (s)" include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like. .

In the present specification, examples of the "silyl group which may have a substituent (s)" include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl and triethoxy. Examples include silyl, diphenylmethylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

In the present invention, R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bridged with each other to form a C ₄ -C ₂₀ saturated ring or unsaturated ring. Good. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, more preferably a 4-membered ring to a 12-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. Further, the ring formed by these substituents may further have a single ring or a plurality of rings.

The saturated ring or unsaturated ring is an oxygen atom,
Even if it is interrupted by a sulfur atom, a silicon atom, a tin atom, a germanium atom or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or a C _{1 to} C ₂₀ hydrocarbon group). Good. That is, the saturated ring or unsaturated ring may be a heterocycle. Moreover, it may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring.

B is preferably a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group, more preferably a hydrogen atom or a C _{1 to} C ₇ hydrocarbon group, and B is a hydrogen atom or C ₁
More preferably, it is a C ₃ alkyl group, a phenyl group or a benzyl group.

This saturated ring or unsaturated ring may have a substituent, for example, a C ₁ -C ₁₀ hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ -C.
₁₀ alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ -C _{1 0} aryl group (e.g., phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (e.g.,
Fluorine, chlorine, bromine, iodine) or a substituent such as a silyl group may be introduced.

In the present invention, R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are each independently, the same or different, and are a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent or a silyl group which may have a substituent. Preferably, a C _{1 to} C ₁₀ alkyl group; a C _{6 to} C ₁₀ aryl group;
Alternatively, a silyl group which may have a substituent is more preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,
More preferably, it is phenyl, dimethylsilyl, diethylsilyl, trimethylsilyl or triethylsilyl.

Further, R ¹ and R ² , R ³ and R ⁴ , and
It is further preferred that R ⁵ and R ⁶ are the same group.

In the present invention, the benzene derivative represented by the above formula (1) is 1,2,3,4-tetraethyl-
5,6-dipropylbenzene, 1,2,3,4-tetraethyl-5-propylbenzene, 1,2,3,4-tetraethyl-5-phenylbenzene, 1,2,3,4,5
-Pentaethyl-6- (1-butyn-1-yl) benzene, 1,2,3,4-tetraethyl-5-dimethylsilyl-6-butylbenzene, 1,2,3,4-tetraethyl-5-methoxymethyl Benzene, 1,2-dipropyl-3,4-dimethyl-5,6-diethylbenzene, 1,
It is preferably 2-diphenyl-3,4-dimethyl-5,6-dipropylbenzene or 1,2-dibutyl-3,4-dimethyl-5,6-diethylbenzene.

In the method for producing a benzene derivative of the present invention,
A metallacyclopentadiene represented by the following formula (2) is used.

[0039]

[Chemical 8] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the above meanings. ]

M represents a transition metal. M is preferably a transition metal of Group 4 to Group 6 of the periodic table, more preferably a metal of Group 4 of the periodic table, that is, titanium, zirconium and hafnium, and particularly preferably zirconium. preferable.

L ¹ and L ² are independent of each other,
The same or different, the anionic ligand is shown. However, L ¹ and L ² may be crosslinked. The anionic ligand is a delocalized cyclic η ⁵ -coordination system ligand, C _1-
It is preferably a C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or a dialkylamido group, and more preferably a delocalized cyclic η ⁵ -coordination system ligand. Examples of the delocalized cyclic η ⁵ -coordination ligand include an optionally substituted cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group, and an unsubstituted cyclopentadienyl group. A group and a substituted cyclopentadienyl group are preferred.

This substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl. Pentadienyl, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl group, 2-methyl-4-phenyl An indenyl group,
And tetrahydroindenyl group, benzoindenyl group, fluorenyl group, benzofluorenyl group, tetrahydrofluorenyl group, octahydrofluorenyl group and azulenyl group.

In the delocalized cyclic η ⁵ -coordination system ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. 1 in addition to hydrogen, such as elements of group 14 of the periodic table and / or elements of groups 15, 16 and 17 of the periodic table
It can contain one or more heteroatoms.

Delocalized ring η^Five-Coordinating ligands, eg
For example, a cyclopentadienyl group has a central metal and a cyclic
May be bridged by one or more bridging ligands.
It may be. Examples of the bridging ligand include C
H₂, CH₂CH₂, CH (CH₃) CH₂, CH (C
_FourH₉) C (CH₃)₂, C (CH₃)₂, (CH₃)₂Si,
(CH₃) ₂Ge, (CH₃)₂Sn, (C₆H_Five)₂Si,
(C₆H_Five) (CH₃) Si, (C₆H _Five)₂Ge, (C
₆H_Five)₂Sn, (CH₂)_FourSi, CH₂Si (CH₃)₂,
o-C₆H_FourOr 2, 2 '-(C₆H_Four)₂Is mentioned.

The metallacyclopentadiene represented by the above formula (2) also includes a compound having two or more metallocene moieties. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution pattern and any bridged morphology. The independent metallocene moieties of the polynuclear metallocene may be the same or different. Examples of the polynuclear metallocene include EP-A-632063 and JP-A-4-802.
14, JP-A-4-85310, EP-A-65447.
6 are described.

In the method for producing a benzene derivative of the present invention,
An alkyne represented by the following formula (3) is used.

[0047]

[Chemical 9] [In the formula, R ⁵ and R ⁶ have the above-mentioned meanings. ]

The amount of alkyne represented by the above formula (3) is
Each of them is 0.1 to 100 mol, preferably 0.5 to 1 mol of metallacyclopentadiene (2).
Mol to 3 mol, more preferably 0.8 mol to 1.
It is 5 mol.

In the method for producing a benzene derivative of the present invention, the reaction is carried out in the presence of a catalytic amount of a transition metal compound.

In the present specification, the transition metal compound may be a metal salt or a metal complex. In the case of a metal salt, for example, a salt of nickel, palladium, copper, ruthenium or rhodium with an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as a carboxylic acid may be used. For example, nickel (II) halide, palladium (II) halide, copper (I) halide, ruthenium (III) halide,
It may be a metal salt such as rhodium (III) halide, and nickel (II) halide and the like are particularly preferable and used.

When the transition metal compound is a metal complex, 4
It is preferably coordinated or hexacoordinated. As the ligand, phosphine, phosphite, amine, nitrile, halogen atom or the like is preferable. The ligand is monodentate (un
It may be an identate or a two-seater (bide)
ntate), three-dentate (terdentate), or
It may be tetradentate.

Phosphines include diarylphosphines such as diphenylphosphine, triarylphosphines such as triphenylphosphine, trialkylphosphines such as triethylphosphine, alkyldiarylphosphines, dialkylarylphosphines, 1,2-
Α, ω-like bis (diphenylphosphino) ethane
Bis (diarylphosphino) alkane, P, P,
P ', P', P ", P" -P, P, P ', P', P ", P" such as hexaphenyl-trisethylenetetraphosphine
It may be a hexasubstituted-trisalkylenetetraphosphine or the like. Phosphite is similar to phosphine.

The amine may be an aromatic amine such as pyridine, bipyridine or quinoline as a ligand, or an alkylenediamine such as ethylenediamine,
N, N, N ', N'-tetrasubstituted alkylenediamines, such as N, N, N', N'-tetraalkylethylenediamine,
It may be an aliphatic amine such as trisalkylenediamine such as trisethylenediamine.

In the present invention, the transition metal compound is preferably a nickel complex.

The nickel complex is preferably tetracoordinated. The nickel complex is, for example, NiX ₂ P ¹ P ² (wherein, X represents a halogen atom such as a chlorine atom or a bromine atom, P ¹ and P ² are independently of each other, the same or different, and are phosphine). , Phosphite or amine, preferably phosphine or amine, more preferably phosphine, provided that P ¹ and P ² may be cross-linked with each other. The phosphine, phosphite, or amine is as described above.

Examples of the nickel complex include bis.
(Triphenylphosphine) dichloronickel, dichloro
(2,2'-bipyridine) nickel. N
iX₂P ¹P²The nickel complex represented by is NiX₂Indicated by
Better solubility in organic solvents than nickel salts
Therefore, it is preferable depending on the application. For example, Ni
X₂Solvent containing the reaction system of nickel salt
And, if desired, additional phosphine in the solvent.
In situ to form nickel phosphine complex
Yes.

In the present invention, the transition metal compound is involved in the reaction as a catalyst. In the present invention, it is considered that the transition metal compound reacts with the metallacyclopentadiene represented by the above formula (2) to form an intermediate. As the intermediate, for example, one metal in the metallacyclopentadiene (2) is substituted with one or two transition metals in the transition metal compound by a transmetallation reaction, and 1,4-dimetalla-1,3 -A metallacyclopentadiene containing a butadiene derivative or a transition metal is produced. Then, the 1,4-dimetalla-1,3-butadiene derivative or the metallacyclopentadiene containing a transition metal is represented by the above formula (3).
It is considered that the benzene derivative represented by the above formula (1) is produced by reacting with the alkyne represented by At this time, the reduced transition metal is oxidized by the oxidizing agent described later,
It is thought that they will be involved again in the reaction system.

However, such a reaction route is merely an inference, and the present invention is not limited to such a reaction route.

In the present invention, the amount of transition metal compound is
With respect to 1 mol of metallacyclopentadiene (2), 0.
The amount is preferably 0001 mol to 0.5 mol and is preferably 0.
More preferably 001 mol to 0.3 mol,
It is more preferably 0.01 mol to 0.2 mol.

In the method for producing a benzene derivative of the present invention, the reaction is carried out in the presence of an oxidizing agent.

In the present specification, the oxidizing agent may include, without particular limitation, a compound capable of oxidizing the reduced transition metal. In the present invention, the oxidizing agent is preferably an organic halide, more preferably a dihalogenoalkane or an allyl halide.

[0062] In this specification, the "dihalogeno alkane" may include dihalogeno -C ₁ -C _{2 0} alkane is preferably dihalogeno -C ₁ -C ₁₀ alkane, dihalogeno -C ₁ ~ More preferably it is a C ₆ alkane. Examples of dihalogenoalkanes include, but are not limited to, dichloromethane, dibromomethane, diiodomethane, dichloroethane, dibromoethane, diiodoethane, dichloropropane, dibromopropane, diiodopropane, and the like.

In the present specification, examples of "allyl halide" include allyl chloride, allyl bromide and the like.

In the present invention, it is preferable to use dibromomethane or allyl chloride as the oxidizing agent.

In the present invention, the amount of the oxidizing agent is 0.1 mol to 1 mol per 1 mol of the metallacyclopentadiene (2).
The amount is 00 mol, preferably 0.5 mol to 10 mol, and more preferably 1.0 mol to 3.0 mol.

In the present invention, the benzene derivative is typically prepared by adding the alkyne (3), the oxidizing agent and the transition metal compound to a solution of the metallacyclopentadiene represented by the above formula (2) and stirring the mixture. To do. The metallacyclopentadiene (2) does not need to be isolated, and the metallacyclopentadiene prepared in the solution may be used as it is.

The reaction is preferably -100 ° C to 300 ° C.
Temperature range of 80 to 200 ° C.
It is carried out in the temperature range of ℃, more preferably in the temperature range of -80 ℃ ~ 60 ℃. The pressure is, for example, 0.1 bar to 25 bar.
Within the range of 00 bar, preferably 0.5 bar to 10
Within the bar range.

As the solvent, a solvent capable of dissolving the metallacyclopentadiene represented by the above formula (2) is preferable. As the solvent, an aliphatic or aromatic organic solvent is used. Ethereal solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide, sulfoxides such as dimethylsulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.

The metallacyclopentadiene represented by the above formula (2) can be obtained by reacting 1 mol of metallocene such as biscyclopentadienyl metal dialkyl with about 2 mol of alkyne or about 1 mol of diyne. it can. In the present invention, when zirconacyclopentadiene is used as the metallacyclopentadiene represented by the above formula (2), it can be synthesized using, for example, the following zirconocene.

Bis (cyclopentadienyl) dibutylzirconium; Bis (methylcyclopentadienyl) dibutylzirconium; Bis (butylcyclopentadienyl) dibutylzirconium; Bis (isopropylcyclopentadienyl) dibutylzirconium; Bis (n- Butyl (cyclopentadienyl) dibutylzirconium; bis (t-butylcyclopentadienyl) dibutylzirconium; bis (dimethylcyclopentadienyl) dibutylzirconium; bis (diethylcyclopentadienyl) dibutylzirconium; bis (diisopropylcyclopentadiene) (Enyl) dibutyl zirconium; bis (di-
t-butylcyclopentadienyl) dibutylzirconium; bis (tetramethylcyclopentadienyl) dibutylzirconium.

Bis (cyclopentadienyl) dichlorozirconium; bis (methylcyclopentadienyl) dichlorozirconium; bis (butylcyclopentadienyl) dichlorozirconium; bis (isopropylcyclopentadienyl) dichlorozirconium; bis ( n-butylcyclopentadienyl) dichlorozirconium; bis (t-butylcyclopentadienyl) dichlorozirconium; bis (dimethylcyclopentadienyl) dichlorozirconium; bis (diethylcyclopentadienyl) dichlorozirconium; bis (diisopropylcyclo) Pentadienyl) dichlorozirconium; bis (di-t-butylcyclopentadienyl) dichlorozirconium; bis (tetramethylcyclopentadienyl) dichlorozirconium For what dichloro body, an alkali metal such as sodium, or reduction with a strong base such as an alkaline earth metal such as magnesium, or, convert the dialkyl body, to produce a zirconacyclopenta cyclopentadiene.

[0072]

EXAMPLES The present invention will be described below based on examples.
However, the present invention is not limited to the following examples.

All reactions were carried out under a dry nitrogen atmosphere unless otherwise stated. Tetrahydrofuran (THF) used as a solvent was distilled under a nitrogen stream with sodium metal and benzophenone to be anhydrous. The zirconocene dichloride used was purchased from Aldrich Chemical. The n-butyl lithium (1.59 M hexane solution) purchased from Kanto Kagaku was used. The alkyne used was purchased from Tokyo Chemical Industry. The nickel (II) complex was prepared by a known method. As for the other reagents, commercially available products were purchased and used as they were.

¹ H and ¹³ C NMR spectra show room temperature CDCl ₃
Alternatively, C ₆ D ₆ (containing 1% TMS) solution was used for measurement on a JEOL NMR spectrometer. Gas chromatographic analysis
Silica glass capillary column SHIMADZU CBP1-M25-O25
And SHIMADZU GC-14A gas chromatograph equipped with SHIMADZU C-R6A-Chromatopac integrator.

Reference Example 1 Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-
Tetraethyl-1-zircona-2,4-cyclopentadiene bis (η ⁵ -cyclopentadienyl) dichlorozirconium (1.2 mmol) and THF (10 ml) were charged into a Schlenk tube. The solution was cooled to −78 ° C. then n-butyllithium (2.4 mmol) was added. This solution was stirred at −78 ° C. for 1 hour to give bis (η
⁵ -Cyclopentadienyl) dibutylzirconium was obtained. 3-Hexine (2.0 mmol) was added to the reaction mixture at −78 ° C., then warmed to room temperature and left for 1 hour to give the title compound. The title compound was used as such without isolation.

Reference Example 2 Bis (η ⁵ -cyclopentadienyl) 2,3-dipropyl-4,5-dimethyl-1-zircona-2,4-cyclopentadiene The procedure was as in Reference Example 1. However, ethyl magnesium bromide was used instead of n-butyl lithium. Moreover, 4-octyne (1.0 mmol) and 2-butyne (1.0 mmol) were used instead of 3-hexyne (2.0 mmol).

Reference Example 3 Bis (η ⁵ -cyclopentadienyl) 2,3-diphenyl-4,5-dimethyl-1-zircona-2,4-cyclopentadiene The procedure was the same as in Reference Example 1. However, ethyl magnesium bromide was used instead of n-butyl lithium. Also, instead of 3-hexyne (2.0 mmol), 1,2-diphenylacetylene (1.0 mmol)
And 2-butyne (1.0 mmol) were used.

Reference Example 4 Bis (η ⁵ -cyclopentadienyl) 2,3-dibutyl-4,5-dimethyl-1-zircona-2,4-cyclopentadiene The procedure was as in Reference Example 1. However, ethyl magnesium bromide was used instead of n-butyl lithium. Moreover, 5-decyne (1.0 mmol) and 2-butyne (1.0 mmol) were used instead of 3-hexyne (2.0 mmol).

Example 1 1,2,3,4-tetraethyl-5,6-dipropylbenzene Bis (η ⁵ -cyclopentadienyl) 2,3,4,5-tetraethyl-obtained in Reference Example 1 1-Zircona
To a solution of 2,4-cyclopentadiene (1.0 mmol) in 5 ml of THF, 4-octyne (1.5 mmol), dibromomethane and NiBr ₂ (PPh ₃ ) ₂ (5 mol%) were added at room temperature. The mixture was stirred for 6 hours, quenched with 3 N HCl and extracted with hexane. The extract was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography to give the title compound. GC yield 85%, isolation yield 70%.

Example 2 1,2,3,4-tetraethyl-5-propylbenzene The same procedure as in Example 1 was carried out. However, 1-pentyne was used instead of 4-octyne. GC yield 71%, isolation yield 60%.

Example 3 1,2,3,4-tetraethyl-5-phenylbenzene The procedure was as in Example 1. However, phenylacetylene was used instead of 4-octyne. GC yield 66
%, Isolated yield 57%.

Example 4 1,2,3,4,5-Pentaethyl-6- (1-butyn-1-yl) benzene The procedure was as in Example 1. However, octa-3,5-diyne was used instead of 4-octyne. GC yield 93%, isolation yield 80%.

Example 5 1,2,3,4-tetraethyl-5-dimethylsilyl-
6-Butylbenzene The procedure was the same as in Example 1. However, 1-dimethylsilyl-1-hexyne was used instead of 4-octyne. GC yield 90%, isolated yield 76%.

Example 6 1,2,3,4-tetraethyl-5-methoxymethylbenzene The procedure was as in Example 1. However, 2-methoxy-1-propyne was used instead of 4-octyne. GC
Yield 60%, isolated yield 52%.

Example 7 1,2-Dipropyl-3,4-dimethyl-5,6-diethylbenzene The procedure of Example 1 was repeated. However, instead of the compound obtained in Reference Example 1, the bis (η obtained in Reference Example 2 was used.
⁵ -cyclopentadienyl) 2,3-dipropyl-4,
5-Dimethyl-1-zircona-2,4-cyclopentadiene was used. Also, 3-hexyne was used instead of 4-octyne. GC yield 61%, isolation yield 51%.

Example 8 1,2-Diphenyl-3,4-dimethyl-5,6-dipropylbenzene A procedure similar to that in Example 1 was carried out. However, instead of the compound obtained in Reference Example 1, the bis (η obtained in Reference Example 3 was used.
⁵ -cyclopentadienyl) 2,3-diphenyl-4,
5-Dimethyl-1-zircona-2,4-cyclopentadiene was used. GC yield 91%, isolated yield 78%.

Example 9 1,2-Dibutyl-3,4-dimethyl-5,6-diethylbenzene A procedure similar to that in Example 1 was carried out. However, instead of the compound obtained in Reference Example 1, the bis (η obtained in Reference Example 4 was used.
⁵ -Cyclopentadienyl) 2,3-dibutyl-4,5
-Dimethyl-1-zircona-2,4-cyclopentadiene was used. Also, 3-hexyne was used instead of 4-octyne. GC yield 87%, isolation yield 77%.

The starting materials, products and yields of Examples 1 to 9 are shown in Table 1. In the table, the yield shows the GC yield, and the parentheses show the isolated yield.

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[Table 1]

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According to the method of the present invention, a polysubstituted benzene derivative can be easily obtained in a high yield while using a catalytic amount of nickel complex.

Claims (10)

[Claims] 1. A method for producing a benzene derivative represented by the following formula (1), wherein: [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently, the same or different, a hydrogen atom; C ₁ -C which may have a substituent. ₂₀ hydrocarbon group; C ₁ -C ₂₀ alkoxy group optionally having substituents; C ₆ -C ₂₀ aryloxy group optionally having substituents; amino optionally having substituents Group: a silyl group which may have a substituent, or a hydroxyl group, provided that R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶
May each be crosslinked with each other to form a C ₄ -C ₂₀ saturated ring or unsaturated ring, wherein the ring has an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom or a formula —N.
A group represented by (B)-(in the formula, B is a hydrogen atom or C ₁ to
It is a C ₂₀ hydrocarbon group. ) And may have a substituent. ] In the presence of an oxidizing agent and a catalytic amount of a transition metal compound, a metallacyclopentadiene represented by the following formula (2): [In the formula, R ¹ , R ² , R ³ and R ⁴ have the above meanings. M represents a transition metal, and L ¹ and L ² each independently represent the same or different anionic ligand. However, L ¹ and L
² may be crosslinked. ] An alkyne represented by the following formula (3) and [In the formula, R ⁵ and R ⁶ have the above-mentioned meanings. ] The method of manufacturing the benzene derivative characterized by making it react. 2. The oxidant is an organic halide,
The method for producing the benzene derivative according to claim 1. 3. The method for producing a benzene derivative according to claim 1, wherein the oxidizing agent is a dihalogenoalkane or an allyl halide. 4. The method for producing a benzene derivative according to claim 1, wherein the transition metal compound is a nickel complex. 5. The method for producing a benzene derivative according to claim 1, wherein the amount of the catalyst is 0.0001 mol to 0.5 mol with respect to 1 mol of the metallacyclopentadiene. 6. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently of each other, the same or different, and are C _{1 to} C ₂₀ carbon atoms which may have a substituent. The method for producing a benzene derivative according to any one of claims 1 to 5, which is a hydrogen group or a silyl group which may have a substituent. 7. The method for producing a benzene derivative according to claim 1, wherein M is a transition metal of Groups 4 to 6 of the periodic table. 8. The method according to claim 1, wherein M is zirconium.
A method for producing the benzene derivative according to any one of 1. 9. The anionic ligand is a delocalized cyclic η ⁵ -coordination system ligand, which may be substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl. It is a group, The manufacturing method of the benzene derivative in any one of Claims 1-8. 10. The benzene derivative represented by the formula (1) is 1,2,3,4-tetraethyl-5,6-dipropylbenzene, 1,2,3,4-tetraethyl-5-propylbenzene, 1,2,3,4-tetraethyl-5
Phenylbenzene, 1,2,3,4,5-pentaethyl-6- (1-butyn-1-yl) benzene, 1,2,
3,4-tetraethyl-5-dimethylsilyl-6-butylbenzene, 1,2,3,4-tetraethyl-5-methoxymethylbenzene, 1,2-dipropyl-3,4-dimethyl-5,6-diethylbenzene, 1,2-diphenyl-3,4-dimethyl-5,6-dipropylbenzene,
Alternatively, it is 1,2-dibutyl-3,4-dimethyl-5,6-diethylbenzene, and the method for producing a benzene derivative according to any one of claims 1 to 9.