JP4388236B2 - Process for producing enyne derivative and styrene derivative - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a process for producing an enyne derivative and a styrene derivative, and more particularly to a process for producing an enyne derivative and a styrene derivative capable of controlling stereoselectivity.
[0002]
[Prior art and problems to be solved by the invention]
Since an enyne derivative has a triple bond and a double bond in one molecule, it has various uses as a raw material for organic synthesis. For example, a styrene derivative can be synthesized by coupling one molecule of an enyne derivative and two molecules of an acetylene derivative. Such a synthesis method is described, for example, in Takahashi et al. Chem. Commun. 1998 1133. And a styrene derivative becomes a raw material of polystyrene. The enyne derivative is a raw material for the synthesis of cholesterols.
[0003]
However, since enyne derivatives have stereoisomers due to carbon-carbon double bonds, it is difficult to produce such enyne derivatives in which the stereochemistry and the position of substituents are completely controlled. there were.
[0004]
Therefore, it is desired to provide a method for producing an enyne derivative in which the stereochemistry and the position of the substituent are completely controlled, and a method for producing a styrene derivative in which the stereochemistry and the position of the substituent are completely controlled. It was.
[0005]
[Means for Solving the Problems]
In one aspect of the present invention, there is provided a process for producing an enyne derivative represented by the following formula (Ia) or the following formula (Ib) or a mixture thereof:
[0006]
[Chemical 9]
[0007]
(Wherein R ¹ , R ² , R ^Three And R ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having hydroxyl group or substituent, provided that R ¹ And R ² Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent. ), A metallacyclopentene represented by the following formula (II),
[0008]
[Chemical Formula 10]
[0009]
(Wherein R ¹ And R ² Has the above meaning.
[0010]
M represents Group 3 to Group 5 of the periodic table or a lanthanide series metal; L ¹ And L ² Are independent of each other and are the same or different and represent an anionic ligand, provided that L represents ¹ And L ² May be cross-linked. ), Reacting an alkyne derivative represented by the following formula (III) to obtain a reaction mixture;
[0011]
Embedded image
[0012]
(Wherein R ^Three Has the above meaning. X is a leaving group. Next, the reaction mixture is reacted with an electrophile represented by the following formula (IV):
R ^Four ―Y (IV)
(Wherein R ^Four Has the above meaning. Y is a leaving group. The process for producing an enyne derivative is provided.
[0013]
In another aspect of the present invention, there is provided a method for producing a styrene derivative represented by the following formula (Va), the following formula (Vb), the following formula (Vc), the following formula (Vd), or a mixture thereof.
[0014]
Embedded image
[0015]
(Wherein R ¹ , R ² , R ^Three , R ^Four , A ¹ And A ² Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having hydroxyl group or substituent, provided that R ¹ And R ² Or A ¹ And A ² Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent, and A ^Three And A ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ Aryloxy group; optionally substituted amino group; hydroxyl group; optionally substituted silyl group; ester group; nitro group; nitrile group; acyl group; carboxyl group; carbamoyl group; formyl group Isocyanato group; thiocyanato group or isothiocyanato group, provided that A ^Three And A ^Four Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent. ), A metallacyclopentene represented by the following formula (II),
[0016]
Embedded image
[0017]
(Wherein R ¹ And R ² Has the above meaning.
[0018]
M represents Group 3 to Group 5 of the periodic table or a lanthanide series metal; L ¹ And L ² Are independent of each other and are the same or different and represent an anionic ligand, provided that L represents ¹ And L ² May be cross-linked. ) Reacting an alkyne derivative represented by the following formula (III) to obtain a first reaction mixture;
[0019]
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[0020]
(Wherein R ^Three Has the above meaning. X is a leaving group. ), And then reacting the first reaction mixture with an electrophile represented by the following formula (IV) to obtain a second reaction mixture;
R ^Four ―Y (IV)
(Wherein R ^Four Has the above meaning. Y is a leaving group. Then, in the presence of a metal compound containing a metal of Groups 4 to 15 of the periodic table, the second reaction mixture is mixed with an alkyne derivative represented by the following formula (VI):
[0021]
Embedded image
[0022]
(Where A ^Three And A ^Four Has the above meaning. ), A metallacycloipentene represented by the following formula (VII)
[0023]
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[0024]
(Where L ¹ , L ² , M, A ¹ And A ² Has the above meaning. And a step of reacting the styrene derivative.
[0025]
In the present invention, M is a group 4 or 5 of the periodic table or a lanthanide series metal, and the anionic ligand is a delocalized cyclic η ^Five -It is preferably a coordination ligand. Also, the delocalized cyclic η ^Five The coordination ligand is more preferably a cyclopentadienyl group, an indenyl group, a fluorenyl group or an azulenyl group which may be substituted.
In the present invention, R ^Four May have a substituent ₂ ~ C ₄₀ It may be an alkynyl group.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
In one aspect of the present invention, a step of reacting a metallacyclopentene represented by the following formula (II) with an alkyne derivative represented by the following formula (III) to obtain a reaction mixture; A process for producing an enyne derivative represented by the following formula (Ia) or the following formula (Ib) or a mixture thereof, characterized by comprising a step of reacting an electrophile represented by (IV).
[0027]
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[0028]
(Wherein R ¹ , R ² , R ^Three , R ^Four , X, Y, M, L ¹ And L ² Has the above meaning. )
One aspect of the present invention is characterized in that the metallacyclopentene ring in the metallacyclopentene represented by the formula (II) specifically undergoes a coupling reaction with the alkyne derivative represented by the formula (III).
[0029]
R ¹ , R ² , R ^Three And R ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ An aryloxy group; an amino group which may have a substituent; a hydroxyl group or a silyl group which may have a substituent.
[0030]
R ¹ , R ² , R ^Three And R ^Four Are independently of each other, the same or different and each may have a hydrogen atom or a substituent. ₁ ~ C ₄₀ It is preferably a hydrocarbon group, and may optionally have a hydrogen atom or a substituent. ₁ ~ C ₂₀ More preferably, it is a hydrocarbon group.
In this specification, C ₁ ~ C ₄₀ The hydrocarbon group may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. C ₁ ~ C ₄₀ When the hydrocarbon group is acyclic, it may be linear or branched. C ₁ ~ C ₄₀ Hydrocarbon groups include C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C _Three ~ C ₄₀ Allyl group, C _Four ~ C ₄₀ Alkyldienyl group, C _Four ~ C ₄₀ Polyenyl group, C ₆ ~ C ₄₀ Aryl group, C ₆ ~ C ₄₀ Alkylaryl group, C ₆ ~ C ₄₀ Arylalkyl group, C _Four ~ C ₄₀ A cycloalkyl group, C _Four ~ C ₄₀ A cycloalkenyl group, (C _Three ~ C ₂₀ Cycloalkyl) C ₁ ~ C ₂₀ Alkyl groups and the like are included.
[0031]
C ₁ ~ C ₄₀ Alkyl group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ Alkynyl group, C _Three ~ C ₄₀ Allyl group, C _Four ~ C ₄₀ An alkyldienyl group and C _Four ~ C ₄₀ Each of the polyenyl groups is C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ Alkenyl group, C ₂ ~ C ₂₀ Alkynyl group, C _Three ~ C ₂₀ Allyl group, C _Four ~ C ₂₀ An alkyldienyl group and C _Four ~ C ₂₀ Polyenyl groups are preferred, each of which is C ₁ ~ C _Ten Alkyl group, C ₂ ~ C _Ten Alkenyl group, C ₂ ~ C _Ten Alkynyl group, C _Three ~ C _Ten Allyl group, C _Four ~ C _Ten An alkyldienyl group and C _Four ~ C _Ten More preferably, it is a polyenyl group.
[0032]
C ₆ ~ C ₄₀ Aryl group, C ₆ ~ C ₄₀ Alkylaryl group, C ₆ ~ C ₄₀ Arylalkyl group, C _Four ~ C ₄₀ A cycloalkyl group, C _Four ~ C ₄₀ A cycloalkenyl group and (C _Three ~ C ₂₀ Cycloalkyl) C ₁ ~ C ₂₀ Each alkyl group is C ₆ ~ C ₂₀ Aryl group, C ₆ ~ C ₂₀ Alkylaryl group, C ₆ ~ C ₂₀ Arylalkyl group, C _Four ~ C ₂₀ A cycloalkyl group, C _Four ~ C ₂₀ A cycloalkenyl group and (C _Three ~ C _Ten Cycloalkyl) C ₁ ~ C _Ten Preferred are alkyl groups, each of C ₆ ~ C _Ten Aryl group, C ₆ ~ C ₁₂ Alkylaryl group, C ₆ ~ C ₁₂ Arylalkyl group, C _Four ~ C _Ten A cycloalkyl group and C _Four ~ C _Ten A cycloalkenyl group is more preferred.
Examples of optionally substituted alkyl groups useful in the practice of the present invention include, but are not limited to, methyl, ethyl, propyl, n-butyl, t-butyl, dodecanyl, trifluoromethyl. Perfluoro-n-butyl, 2,2,2-trifluoroethyl, benzyl, 2-phenoxyethyl and the like.
[0033]
Examples of optionally substituted aryl groups useful in the practice of the present invention include, but are not limited to, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, naphthyl, biphenyl, 4 -Phenoxyphenyl, 4-fluorophenyl, 3-carbomethoxyphenyl, 4-carbomethoxyphenyl and the like.
[0034]
Examples of optionally substituted alkoxy groups useful in the practice of the present invention include, but are not limited to, methoxy, ethoxy, 2-methoxyethoxy, t-butoxy and the like.
[0035]
Examples of optionally substituted aryloxy groups useful in the practice of the present invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, 2-tolyloxy, 3- There are tolyloxy, 4-tolyloxy, naphthyloxy, biphenyloxy, 4-phenoxyphenyloxy, 4-fluorophenyloxy, 3-carbomethoxyphenyloxy, 4-carbomethoxyphenyloxy and the like.
[0036]
Examples of optionally substituted amino groups useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.
[0037]
Examples of optionally substituted silyl groups useful in the practice of the present invention include, but are not limited to, trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, dimethylethylsilyl, methyl Examples include methoxyphenylsilyl, methylethylphenoxysilyl and the like.
[0038]
C ₁ ~ C ₄₀ Hydrocarbon group, C ₁ ~ C ₄₀ Alkoxy group, C ₆ ~ C ₄₀ A substituent may be introduced into the aryloxy group, amino group, and silyl group, and examples of the substituent include a halogen atom, amino group, hydroxyl group, silyl group, alkoxy group, and aryloxy group. It is done.
[0039]
However, R ¹ And R ² Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed.
[0040]
The ring formed by these substituents is preferably a 4- to 10-membered ring, more preferably a 4- to 6-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring.
[0041]
The saturated or unsaturated ring may be an oxygen atom, a sulfur atom or a formula —N (R ^Five ) — (Wherein R ^Five Is a hydrogen atom, C ₁ ~ C ₄₀ It is a hydrocarbon group or a halogen atom. ) May be interrupted. That is, the saturated or unsaturated ring may be a heterocyclic ring.
[0042]
R ^Five Is a hydrogen atom or C ₁ ~ C ₂₀ It is preferably a hydrocarbon group, a hydrogen atom or C ₁ ~ C ₁₄ More preferably, it is a hydrocarbon group, R ^Five Is a hydrogen atom, C ₁ ~ C ₆ More preferably, they are an alkyl group, a phenyl group, a naphthyl group, a benzyl group, and a naphthylmethyl group.
[0043]
This saturated or unsaturated ring may have a substituent, and C ₁ ~ C ₄₀ Hydrocarbon group, C ₁ ~ C ₄₀ Alkoxy group, C ₆ ~ C ₄₀ Substituents such as an aryloxy group, amino group, hydroxyl group or silyl group may be introduced.
[0044]
R ^Four Is C ₂ ~ C ₄₀ Preferably it is an alkynyl group, C ₂ ~ C ₂₀ More preferably an alkynyl group, C ₂ ~ C _Ten Even more preferred is an alkynyl group.
[0045]
R ¹ And R ² May be the same group. This is because the enyne derivative represented by the above formula (Ia) and the enyne derivative represented by the above formula (Ib) are the same.
[0046]
R ^Four Is a hydrogen atom, deuterium atom, halogen atom, C ₁ ~ C ₂₀ Hydrocarbon group, C ₁ ~ C ₂₀ Alkylcarbonyl group, C ₁ ~ C ₂₀ Alkoxycarbonyl group, C ₆ ~ C ₂₀ Arylcarbonyl group or C ₆ ~ C ₂₀ An aryloxycarbonyl group is preferred. R ^Four Is due to the electrophile, and considering the reactivity of the electrophile and the like, it is easy to introduce such substituents.
[0047]
In one aspect of the present invention, metallacyclopentene represented by the following formula (II) is used.
[0048]
Embedded image
[0049]
(Wherein R ¹ And R ² Has the above meaning. )
M represents a group 3 to group 5 or lanthanide series metal of the periodic table. M is preferably a Group 4 or Lanthanide series metal, and more preferably a Group 4 metal, ie, titanium, zirconium and hafnium.
[0050]
L ¹ And L ² Are independent of each other and are the same or different and each represents an anionic ligand. However, L ¹ And L ² May be cross-linked. The anionic ligand is a delocalized cyclic η ^Five -Coordination ligand, C ₁ ~ C ₂₀ Alkoxy group, C ₆ ~ C ₂₀ An aryloxy group or a dialkylamide group is preferred.
[0051]
L ¹ And L ² Is the delocalized cyclic η ^Five -It is preferably a coordination ligand. Delocalized cyclic η ^Five Examples of the coordination ligand are an unsubstituted cyclopentadienyl group and a substituted cyclopentadienyl group. This substituted cyclopentadienyl group includes, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, Diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl group, 2-methyl-4-phenylindenyl group, A tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group.
[0052]
Delocalized cyclic η ^Five In the coordination ligand, one or more atoms of the delocalized cyclic π system may be substituted with a hetero atom. In addition to hydrogen, it may contain one or more heteroatoms such as elements of group 14 of the periodic table and / or elements of groups 15, 16 and 17 of the periodic table.
[0053]
Delocalized cyclic η ^Five -Coordination ligands, for example cyclopentadienyl groups, may be bridged with the central metal by one or more bridging ligands which may be cyclic. Examples of the bridging ligand include CH. ₂ , CH ₂ CH ₂ , CH (CH _Three ) CH ₂ , CH (C _Four H ₉ ) C (CH _Three ) ₂ , C (CH _Three ) ₂ , (CH _Three ) ₂ Si, (CH _Three ) ₂ Ge, (CH _Three ) ₂ Sn, (C ₆ H _Five ) ₂ Si, (C ₆ H _Five ) (CH _Three ) Si, (C ₆ H _Five ) ₂ Ge, (C ₆ H _Five ) ₂ Sn, (CH ₂ ) _Four Si, CH ₂ Si (CH _Three ) ₂ , O-C ₆ H _Four Or 2, 2 ′-(C ₆ H _Four ) ₂ Is mentioned.
[0054]
2 or more delocalized cyclic η ^Five -Coordination ligands, for example cyclopentadienyl groups, may be cross-linked by one or more cross-linking groups which may be cyclic to one another. Examples of the crosslinking group include CH. ₂ , CH ₂ CH ₂ , CH (CH _Three ) CH ₂ , CH (C _Four H ₉ ) C (CH _Three ) ₂ , C (CH _Three ) ₂ , (CH _Three ) ₂ Si, (CH _Three ) ₂ Ge, (CH _Three ) ₂ Sn, (C ₆ H _Five ) ₂ Si, (C ₆ H _Five ) (CH _Three ) Si, (C ₆ H _Five ) ₂ Ge, (C ₆ H _Five ) ₂ Sn, (CH ₂ ) _Four Si, CH ₂ Si (CH _Three ) ₂ , O-C ₆ H _Four Or 2, 2 ′-(C ₆ H _Four ) ₂ Is mentioned.
[0055]
The metallacyclopentene represented by the above formula (II) includes a compound having two or more metallacyclopentene moieties (moiety). Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution pattern and any bridge form. The independent metallocene portions of the polynuclear metallocene may be the same or different. Examples of the polynuclear metallocene are described in, for example, EP-A-632063, JP-A-4-80214, JP-A-4-85310, and EP-A-654476.
[0056]
The metallacyclopentene represented by the above formula (II) can be obtained by allowing 1 equivalent of alkyne and 1 equivalent of alkene to act on a metallocene such as biscyclopentadienylzirconium dialkyl, particularly biscyclopentadienylzirconium diethyl. it can. The production of metallacyclopentadiene by the action of 2 equivalents of alkyne is described, for example, in T. Takahashi et al. J. Org. Chem. 1995, 60, 4444, and the same or similar conditions. The reaction proceeds.
[0057]
In one aspect of the present invention, an alkyne derivative represented by the following formula (III) is used.
[0058]
Embedded image
[0059]
(Wherein R ^Three Has the above meaning. )
X is a leaving group. Examples of the leaving group include halogen atoms such as F, Cl, Br, and I, p-toluenesulfonyl group, tosylate group (—O—S (═O) ₂ -C ₆ H _Four -CH _Three ), Trifluoromethanesulfonic acid ester (triflate), and more preferably a halogen atom. As the leaving group, Cl and Br are particularly preferable.
[0060]
One aspect of the present invention is characterized in that the alkyne derivative represented by the above formula (III) contains a halogen atom. When the metallacyclopentene ring in the metallacyclopentene represented by the formula (II) reacts with the alkyne derivative represented by the formula (III), together with the eneyne derivative represented by the formula (I), biscyclopentadienyl Dihalide is expected to form. In addition, as a by-product, ethylene or ethane resulting from the metallacyclopentene ring in the metallacyclopentene represented by the above formula (II) may also be generated. The halogen atom in the by-product biscyclopentadienyl dihalide is derived from the halogen atom in the alkyne derivative represented by the above formula (III), and the production of biscyclopentadienyl dihalide is It seems that it is the driving force to advance this reaction in enthalpy or entropy. And since the alkyne derivative shown by the said Formula (III) is a supply source of a halogen atom, it is thought that reaction advances even if catalysts, such as a transition metal complex, do not exist.
[0061]
In one aspect of the present invention, an electrophilic reagent represented by the following formula (IV) is used.
[0062]
R ^Four ―Y (IV)
(Wherein R ^Four Has the above meaning. )
Y is a leaving group. Examples of the leaving group include a hydroxyl group, a halogen atom such as F, Cl, Br, and I, a p-toluenesulfonyl group, a tosylate group (—O—S (═O). ₂ -C ₆ H _Four -CH _Three ), Trifluoromethanesulfonic acid ester (triflate), C ₁ ~ C ₂₀ An alkoxy group (preferably C ₁ ~ C _Ten An alkoxy group, more preferably C ₁ ~ C ₆ Alkoxy group), C ₆ ~ C ₂₀ An aryloxy group, a tri-lower alkylsilyloxy group, etc. are mentioned. As the leaving group, Cl, Br, tosylate group, C ₁ ~ C ₂₀ An alkoxy group and a tri-lower alkylsilyloxy group are preferred.
[0063]
Leaving group Y and substituent R ^Four In particular, the leaving group Y and the substituent R ^Four The polarity of the bond with the carbon atom in the medium is one factor that determines whether or not the compound represented by formula (IV) is an electrophile. For example, when water is used as the electrophilic reagent (IV), R ^Four A hydrogen atom is introduced into.
[0064]
Examples of the electrophile (IV) include water; alkyl halides such as alkyl iodide, alkenyl iodide and alkynyl iodide; aryl halides such as benzene iodide; acetyl chloride and benzoyl bromide. An acid halide may be used. Furthermore, a group represented by the formula —COOR (wherein R is a lower alkyl group such as an ethyl group) may be introduced using chloroformate. In the reaction with the electrophile (IV), a metal compound may coexist if desired.
[0065]
In one aspect of the present invention, the metallacyclopentene represented by the above formula (II) and the alkyne derivative represented by the above formula (III) are reacted to obtain a reaction mixture, and then the above reaction mixture is mixed with the above formula ( The electrophile shown in IV) is reacted.
[0066]
Typically, the alkyne derivative represented by the above formula (III) is added to the solution of the metallacyclopentene represented by the above formula (II), and then the electrophile represented by the above formula (IV) is added. Alternatively, the alkyne derivative (III) and the electrophilic reagent (IV) are added simultaneously. It is not necessary to use an isolated metallacyclopentene, and a metallacyclopentene prepared in a solution may be used as it is.
[0067]
In the present invention, the above reaction may be performed in the presence of a metal compound containing a metal of Groups 4 to 15 of the periodic table. R of the electrophile represented by the above formula (IV) ^Four Is a group other than a hydrogen atom, the reaction is preferably performed in the presence of the metal compound.
[0068]
The metal compound is preferably a salt and may be a complex. The metal compound may be a salt containing copper ions, nickel ions, bismuth ions, zinc ions, chromium ions, cobalt ions, or palladium ions. The metal compound is CuX, NiX ₂ , PdX ₂ , BiX _Three , ZnX ₂ , CrX ₂ , CrX _Three , CoX ₂ Or BiX _Three (Wherein X represents a halogen atom such as a chlorine atom or a bromine atom).
[0069]
Alternatively, the metal compound is a nickel complex or a palladium complex, and the nickel complex and the palladium complex may have a substituent containing a halogen atom. ₁ ~ C ₄₀ Alkylcarbonyloxy group, C optionally having a substituent containing a halogen atom ₁ ~ C ₄₀ At least one of an arylcarbonyloxy group, a phosphine or a halogen atom may be bonded as a ligand to nickel metal and palladium metal, respectively.
[0070]
The nickel complex is NiX ₂ P ¹ P ² (In the formula, X represents a halogen atom such as a chlorine atom or a bromine atom; ¹ And P ² Each independently of one another and the same or different and represents a phosphine ligand, provided ¹ And P ² May be cross-linked with each other. ). The phosphine may be triphenylphosphine, triethylphosphine, bis (diphenylphosphine) alkylene, or the like. A nickel salt such as nickel chloride may be used, but it is preferable in the presence of phosphine because a nickel complex is formed and the solubility in an organic solvent is increased.
[0071]
The palladium complex is Pd (Q ¹ (Q ² (Q ^Three (Q ^Four (Where Q ¹ , Q ² , Q ^Three And Q ^Four Are each independently the same or different and may have a phosphine and a substituent containing a halogen atom. ₁ ~ C ₄₀ Alkylcarbonyloxy group, C optionally having a substituent containing a halogen atom ₁ ~ C ₄₀ An arylcarbonyloxy group or a halogen atom, provided that Q ¹ , Q ² , Q ^Three And Q ^Four Any two, three and four of may be cross-linked to each other. ). For example, Pd (O—C (═O) R) _Four (In the formula, R is an alkyl group or an aryl group, and may be cross-linked to each other), [PdX _Four ] ^2- It is.
[0072]
The amount of the metal compound is 0.0001 mol to 20 mol, preferably 0.1 mol to 10 mol, more preferably 0.9 mol to 3 mol, relative to 1 mol of metallacyclopentene (II). is there.
[0073]
The amount of the alkyne derivative (III) and the amount of the electrophile (IV) are each preferably 0.1 mol to 10 mol, preferably 0.8 mol to 5 mol, relative to 1 mol of the metallacyclopentene (II). More preferably, it is 0.9 mol-3 mol, and still more preferably 0.9 mol-2 mol.
[0074]
The reaction is preferably performed in a temperature range of −100 ° C. to 300 ° C., particularly preferably in a temperature range of −80 ° C. to 100 ° C., and more preferably in a temperature range of −50 ° C. to 50 ° C. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably in the range from 0.5 bar to 10 bar.
[0075]
As the solvent, a solvent capable of dissolving the reaction product represented by the above formula (II) is preferable. As the solvent, an aliphatic or aromatic organic solvent is used. Ether 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 dimethyl sulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.
[0076]
In another aspect of the present invention, a step of reacting a metallacyclopentene represented by the following formula (II) with an alkyne derivative represented by the following formula (III) to obtain a first reaction mixture; In the presence of a metal compound containing a metal of Groups 4 to 15 in the periodic table, and a step of reacting an electrophile represented by the following formula (IV) with the reaction mixture of The second reaction mixture includes a step of reacting an alkyne derivative represented by the following formula (VI) with a metallacyclopentene represented by the following formula (VII), the following formula (Va), A method for producing a styrene derivative represented by the formula (Vb), the following formula (Vc), the following formula (Vd), or a mixture thereof is provided.
[0077]
Embedded image
[0078]
(Wherein R ¹ , R ² , R ^Three , R ^Four , X, Y, M, L ¹ And L ² Has the above meaning. )
In the method for producing a styrene derivative of the present invention, an alkyne derivative represented by the above formula (VI) is used.
[0079]
A ^Three And A ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ Aryloxy group; optionally substituted amino group; hydroxyl group; optionally substituted silyl group; ester group; nitro group; nitrile group; acyl group; carboxyl group; carbamoyl group; formyl group Isocyano group; isocyanato group; thiocyanato group or isothiocyanato group.
[0080]
However, A ^Three And A ^Four Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent.
[0081]
Moreover, in the manufacturing method of the styrene derivative of this invention, the metallacyclopentene shown by said formula (VII) is used.
[0082]
A ¹ And A ² Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ An aryloxy group; an amino group which may have a substituent; a hydroxyl group or a silyl group which may have a substituent.
[0083]
However, A ¹ And A ² Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent.
[0084]
Typically, the alkyne derivative represented by the above formula (III) is added to the solution of the metallacyclopentene represented by the above formula (II), and then the electrophile represented by the above formula (IV) is added. Next, the metallacyclopentene represented by the above formula (VII) and the alkyne derivative represented by the above formula (VI) are added in the presence of a metal compound containing a metal of Groups 4 to 15 of the periodic table. The alkyne derivative represented by the above formula (III) and the electrophile represented by the above formula (IV) may be added simultaneously. The metal compound may be added before adding the alkyne derivative represented by the above formula (III), and after adding the alkyne derivative (III) and before adding the electrophilic reagent (IV). The above metal compound may be added.
[0085]
In addition, the description about the metal compound containing the metal of the 4th-15th group of the periodic table is the same as that described in one aspect of the present invention.
[0086]
The amount of the metal compound is 0.0001 mol to 20 mol, preferably 0.1 mol to 10 mol, more preferably 0.9 mol to 3 mol, relative to 1 mol of metallacyclopentene (II). is there.
[0087]
The amount of the alkyne derivative (III) and the amount of the electrophile (IV) are each preferably 0.1 mol to 10 mol, preferably 0.8 mol to 5 mol, relative to 1 mol of the metallacyclopentene (II). More preferably, it is 0.9 mol-3 mol, and still more preferably 0.9 mol-2 mol.
[0088]
The amount of the alkyne derivative represented by the above formula (VI) and the amount of the metallacyclopentene represented by the above formula (VII) were each 0.01 mol to 20 mol relative to 1 mol of the metallacyclopentene (II). Preferably, it is 0.1 mol-10 mol, More preferably, it is 0.9 mol-2 mol.
[0089]
The reaction is preferably performed in a temperature range of −100 ° C. to 300 ° C., particularly preferably in a temperature range of −80 ° C. to 100 ° C., and more preferably in a temperature range of −50 ° C. to 50 ° C. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably in the range from 0.5 bar to 10 bar.
[0090]
As the solvent, a solvent capable of dissolving the metallacyclopentene represented by the above formula (II) is preferable. As the solvent, an aliphatic or aromatic organic solvent is used. Ether 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 dimethyl sulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.
[0091]
The metallacyclopentene used in the present invention can be synthesized using, for example, the following metallocene.
[0092]
Bis (cyclopentadienyl) dichlorozirconium; bis (methylcyclopentadienyl) dichlorozirconium; bis (butylcyclopentadienyl) dichlorozirconium; bis (indenyl) dichlorozirconium; bis (fluorenyl) dichlorozirconium; (indenyl) ) (Fluorenyl) dichlorozirconium; bis (cyclopentadienyl) dichlorotitanium; (dimethylsilanediyl) bis (indenyl) dichlorozirconium; (dimethylsilanediyl) bis (tetrahydroindenyl) dichlorozirconium; (dimethylsilanediyl) (indenyl) ) Dichlorozirconium; (dimethylsilanediyl) bis (2-methylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethylindene) (Dimethylsilanediyl) bis (2-methyl-4,5-benzoindenyl) dichlorozirconium; (Dimethylsilanediyl) bis (2-ethyl-4,5-benzoindenyl) dichlorozirconium; (Dimethylsilanediyl) bis (2-methyl-4-phenylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-) The dichloro form such as 4,6-diisopropylindenyl) dichlorozirconium is reduced with a strong base such as an alkali metal such as sodium or an alkaline earth metal such as magnesium, or a diethyl form such as a Grignard reagent. Used after conversion to dialkyl form It is possible.
[0093]
Bis (methylcyclopentadienyl) diethylzirconium;
Bis (butylcyclopentadienyl) diethylzirconium;
Bis (cyclopentadienyl) diethylzirconium;
Bis (indenyl) diethylzirconium;
Bis (fluorenyl) diethylzirconium;
(Indenyl) (fluorenyl) diethylzirconium;
(3-methyl-5-naphthylindenyl) (2,7-di-tert-butylfluorenyl) diethylzirconium;
(3-methyl-5-naphthylindenyl) (3,4,7-trimethoxyfluorenyl) diethylzirconium;
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) diethylzirconium;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) diethylzirconium;
(Indenyl) (1-buten-4-ylcyclopentadienyl) diethylzirconium;
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) diethylzirconium;
Bis (cyclopentadienyl) diethyltitanium;
Dimethylsilanediylbis (indenyl) diethylzirconium;
Dimethylsilanediylbis (tetrahydroindenyl) diethylzirconium;
Dimethylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium;
Dimethylsilanediylbis (2-methylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-ethylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-methyl-4,5-benzoindenyl) diethylzirconium;
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethylzirconium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethylzirconium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethylzirconium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) diethylzirconium;
Dimethylsilanediyl (2-ethylindenyl) (2-ethyl-4-phenylnaphthyl) diethylzirconium;
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-ethyl-4-phenylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-methyl-4-naphthylindenyl) diethylzirconium;
Dimethylsilanediylbis (2-ethyl-4-naphthylindenyl) diethylzirconium;
Methylphenylsilanediylbis (indenyl) diethylzirconium;
Methylphenylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium;
Methylphenylsilanediylbis (tetrahydroindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-methylindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-ethylindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
Methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethylzirconium;
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethylzirconium;
Methylphenylsilanediyl (2-ethylindenyl) (2-methyl-4-phenylindenyl) diethylzirconium;
Methylphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) diethylzirconium;
Methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-indenyl) diethylzirconium;
Methylphenylsilanediyl (2-methylindenyl) (4-phenylindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-methyl-4phenylindenyl) diethylzirconium;
Methylphenylsilanediylbisdiethylzirconium;
Methylphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium;
Methylphenylsilanediylbis (4-naphthylindenyl) diethylzirconium;
Methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) diethylzirconium;
Diphenylsilanediylbis (indenyl) diethylzirconium;
Diphenylsilanediylbis (2-methylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-ethylindenyl) diethylzirconium;
Diphenylsilanediyl (cyclopentadienyl) (indenyl) diethylzirconium;
Diphenylsilanediylbis (2-methyl-4,5-benzoindenyl) diethylzirconium;
Diphenylsilanediylbis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) diethylzirconium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) diethylzirconium;
Diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4phenylindenyl) diethylzirconium;
Diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4naphthylindenyl) diethylzirconium;
Diphenylsilanediyl (2-methylindenyl) (4phenylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-methyl-4phenylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-ethyl-4phenylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium.
[0094]
Diphenylsilanediylbis (2-methyl-4-naphthylindenyl) diethylzirconium;
Diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (indenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-methylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-ethylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4,5-benzoindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) diethylzirconium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) diethylzirconium;
1-silacyclopentane-1- (2-methyl-4,5-benzoindenyl) -1- (2-ethyl-4-phenylindenyl) diethylzirconium;
1-silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) diethylzirconium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4-phenylindenyl) diethylzirconium;
[0095]
1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-4-naphthylindenyl) diethylzirconium;
1-silacyclopentane-1,1-bis (2-ethyl-4-naphthylindenyl) diethylzirconium;
[0096]
Bis (cyclopentadienyl) diethyltitanium;
Ethylene-1,2-bis (indenyl) diethylzirconium;
Ethylene-1,2-bis (tetrahydroindenyl) diethylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (1-indenyl) diethylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (2-indenyl) diethylzirconium;
Ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) diethylzirconium;
Ethylene-1,2-bis (2-methylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-ethylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) diethylzirconium;
Ethylene-1,2-bis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethylzirconium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethylzirconium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethylzirconium;
Ethylene-1- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) diethylzirconium;
Ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) diethylzirconium;
Ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-methyl-4-phenylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-methyl-4-naphthylindenyl) diethylzirconium;
Ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) diethylzirconium;
[0097]
Propylene-2,2-bis (indenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (1-indenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethoxy-9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dibromo-9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- (2,7-dimethyl-9-fluorenyl) diethylzirconium;
Propylene-2- (3-methylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) diethylzirconium;
Propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) diethylzirconium;
Propylene-2- (3-trimethylsilylcyclopentadienyl) -2- (3,6-di-tert-butyl-9-fluorenyl) diethylzirconium;
Propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] diethylzirconium;
Propylene-2-cyclopentadienyl-2- (3-tert-butyl-9-fluorenyl) diethylzirconium;
[0098]
Propylene-2,2-bis (tetrahydroindenyl) diethylzirconium;
Propylene-2,2-bis (2-methylindenyl) diethylzirconium;
Propylene-2,2-bis (2-ethylindenyl) diethylzirconium;
Propylene-2,2-bis (2-methyl-4,5-benzoindenyl) diethylzirconium;
Propylene-2,2-bis (2-ethyl-4,5-benzoindenyl) diethylzirconium;
Propylene-2,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethylzirconium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethylzirconium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) diethylzirconium;
Propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) diethylzirconium;
Propylene-2- (2-ethyl-4,5-benzoindenyl) -2- (2-ethyl-4-naphthylindenyl) diethylzirconium;
Propylene-2- (2-methylindenyl) -2- (4-phenylindenyl) diethylzirconium;
Propylene-2,2-bis (2-methyl-4-phenylindenyl) diethylzirconium;
Propylene-2,2-bis (2-ethyl-4-phenylindenyl) diethylzirconium;
[0099]
Propylene-2,2-bis (2-methyl-4,6-diisopropylindenyl) diethylzirconium;
Propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) diethylzirconium;
Propylene-2,2-bis (2-methyl-4-naphthylindenyl) diethylzirconium;
Propylene-2,2-bis (2-ethyl-4-naphthylindenyl) diethylzirconium;
1,6-bis [methylsilylbis (2-methyl-4-phenylindenyl) diethylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,5-benzoindenyl) diethylzirconium] hexane;
1,6-bis [methylsilylbis (2-ethyl-4-phenylindenyl) diethylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4-naphthylindenyl) diethylzirconium] hexane;
1,6-bis [methylsilylbis (2-methyl-4,6-diisopropylindenyl) diethylzirconium] hexane;
1,6-bis [methylsilyl (2-methyl-4phenylindenyl) (4,5-benzoindenyl) diethylzirconium] hexane;
1- [methylsilylbis (tetrahydroindenyl) diethylzirconium] -6- [ethylstannyl (cyclopentadienyl) (fluorenyl) diethylzirconium] hexane;
1,6-disila-1,1,6,6-tetramethyl-1,6-bis [methylsilylbis (2-methyl-4phenylindenyl) diethylzirconium] hexane;
1,4-disila 1,4-bis [methylsilylbis (2-methyl-4phenylindenyl) diethylzirconium] cyclohexane;
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (pentamethylcyclopentadienyldiethylzirconium);
[1,4-bis (9-fluorenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldiethylzirconium);
[1,4-bis (1-indenyl) -1,1,4,4-tetramethyl-1,4-disilabutane] bis (cyclopentadienyldiethylzirconium);
[1- (1-Indenyl) -6- (2-phenyl-1-indenyl) -1,1,6,6-tetraethyl-1,6-disila-4-oxahexane] bis (tert-butylcyclopentadi Enildiethylzirconium);
[1,10-bis (2,3-dimethyl-1-indenyl) -1,1,10,10-tetramethyl-1,10-digermadecane] bis (2-methyl-4-phenylindenyldiethylzirconium);
(1-methyl-3-tert-butylcyclopentadienyl) (1-phenyl-4-methoxy-7-chlorofluorenyl) diethylzirconium;
(4,7-dichloroindenyl) (3,6-dimesitylfluorenyl) diethylzirconium;
Bis (2,7-di-tert-butyl-9-cyclohexylfluorenyl) diethylzirconium;
(2,7-Dimesitylfluorenyl) [2,7-bis (1-naphthyl) fluorenyl] diethylzirconium;
[0100]
Dimethylsilylbis (fluorenyl) diethylzirconium;
Dibutylstannylbis (2-methylfluorenyl) diethylzirconium;
1,1,2,2-tetraethyldisilanediyl (2-methylindenyl) (4-phenylfluorenyl) diethylzirconium;
Propylene-1- (2-indenyl) -2- (9-fluorenyl) diethylzirconium;
1,1-dimethyl-1-silaethylenebis (fluorenyl) diethylzirconium;
[4- (cyclopentadienyl) 4,7,7-trimethyl (tetrahydroindenyl) diethylzirconium;
[4- (Cyclopentadienyl) 4,7-dimethyl-7-phenyl (5,6-dimethyltetrahydroindenyl) diethylzirconium;
[4- (cyclopentadienyl) -4,7-dimethyl-7- (1-naphthyl) (7-phenyltetrahydroindenyl)] diethylzirconium;
[4- (cyclopentadienyl) -4,7-dimethyl-7-butyl (6,6-diethyltetrahydroindenyl)] diethylzirconium;
[4- (3-tert-butylcyclopentadienyl) -4,7,7-trimethyl (tetrahydroindenyl)] diethylzirconium;
[4- (1-indenyl) -4,7,7-trimethyl (tetrahydroindenyl)] diethylzirconium;
Bis (cyclopentadienyl) diethylhafnium;
Bis (indenyl) diethylvanadium;
Bis (fluorenyl) diethyl scandium;
[0101]
(Indenyl) (fluorenyl) diethylniobium;
(2-methyl-7-naphthylindenyl) (2,6-di-tert-butylfluorenyl) diethyltitanium;
(Pentamethylcyclopentadienyl) (tetrahydroindenyl) butyl hafnium bromide;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) diethylhafnium;
(Indenyl) (2-buten-4-ylcyclopentadienyl) diethyltitanium;
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) diethyl niobium;
Bis (cyclopentadienyl) diethyltitanium;
Dimethylsilanediylbis (indenyl) diethyltitanium;
Dimethylsilanediylbis (tetrahydroindenyl) diethylhafnium;
Dimethylsilanediyl (cyclopentadienyl) (indenyl) diethyltitanium;
[0102]
Dimethylsilanediylbis (2-methylindenyl) diethylhafnium;
Dimethylsilanediylbis (2-ethylindenyl) methylscandium;
Dimethylsilanediylbis (2-butyl-4,5-benzoindenyl) diethyl niobium;
Dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) diethyltitanium;
Dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) diethyltitanium;
Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethyltitanium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) diethylhafnium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) methylscandium;
Dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4-naphthylindenyl) diethyltitanium;
Dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl) diethylhafnium;
Dimethylsilanediylbis (2-methyl-4-phenylindenyl) diethyl niobium.
[0103]
【Example】
Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples.
[0104]
All reactions were performed under a nitrogen atmosphere. THF, ether, hexane and benzene used as solvents were distilled with sodium metal and benzophenone under nitrogen flow to make anhydrous, and 1,2-dichloroethane was distilled with phosphorus pentoxide under nitrogen pressure. Zirconocene dichloride was purchased from Aldrich Chemical Company, Inc., Nichia Corporation, and other reagents were purchased from Kanto Chemical, Tokyo Chemical Industry, and Aldrich. ¹ H-NMR and ¹³ C-NMR spectrum was measured using Bruker ARX-400 or JEOL JNM-LA300.
At this time, ¹ H-NMR: tetramethylsilane; ¹³ C-NMR: Deuterated chloroform was used as an internal standard. The gas chromatographic analysis was performed with a SHIMADZU GC-14A gas chromatograph equipped with silica glass capillary columns SHIMADZU CBP1-M25-O25 and SHIMADZU C-R6A-Chromatopac integrator. When the yield was determined by GC, mesitylene and n-dodecane were used as internal standards. Kanto Chemical Silica Gel 60N (spherical, neutral) 40-100 micrometers was used as a column packing material for column chromatography.
[0105]
Example 1
(E) -1-Phenyl-3-ethyl-3-hexen-1-yne
Ethyl Grignard (EtMgBr) (5.0 mmol) was added to a THF (10 mL) solution of zirconocene dichloride (2.5 mmol) at −78 ° C., and the mixture was stirred at the same temperature for 1 hour to obtain zirconocene diethyl. To this solution was added 3-hexyne (2.0 mmol) at -78 ° C, and the reaction mixture was stirred at 0 ° C for 3 hours. Phenylethynyl chloride (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 12 hours. The title compound was obtained in 58% yield.
[0106]
¹ H NMR (CDCl _Three , TMS) δ1.01 (t, J = 7.5Hz, 3H), 1.15 (t, J = 7.6Hz, 3H), 2.12-2.26 (m, 4H), 5.93 (t, J = 7.5, 1H), 7.25 -7.44 (m, 5H). ¹³ C NMR (CDCl _Three , TMS) δ 13.33, 13.93, 21.57, 23.93, 86.76, 91.47, 123.86, 124.09, 127.65, 128.21, 131.43, 139.36.
[0107]
Example 2
(E) -1-Phenyl-3-butyl-3-octen-1-yne
The same procedure as in Example 1 was performed. However, 5-decin was used instead of 3-hexyne. Instead of adding phenylethynyl chloride (2.5 mmol) and stirring the reaction mixture at 50 ° C. for 12 hours, phenylethynyl chloride (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 9 hours.
[0108]
¹ H NMR (CDCl _Three , TMS) δ0.90-0.96 (m, 6H), 1.35-1.41 (m, 6H), 1.41-1.56 (m, 2H), 2.14-2.24 (m, 4H), 5.96 (t, J = 7.5, 1H ), 7.25-7.43 (m, 5H). ¹³ C NMR (CDCl _Three , TMS) δ 13.97, 14.05, 22.33, 22.40, 28.09, 30.39, 30.71, 31.50, 123.06, 123.91, 127.61, 128.20, 131.42, 138.56.
[0109]
Example 3
(E) -1,2-Diphenyl-1-decene-3-yne
The same procedure as in Example 1 was performed. However, 1,2-diphenylacetylene was used in place of 3-hexyne. Alternatively, phenylethynyl chloride (2.5 mmol) was added, and instead of stirring the reaction mixture at 50 ° C. for 12 hours, 1-chloro-1-octyne (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 9 hours. did.
[0110]
¹ H NMR (CDCl _Three , TMS) δ0.89 (t, J = 7Hz, 3H), 1.29-1.58 (m, 8H), 2.37 (t, J = 7.1Hz, 2H), 6.95 (s, 1H), 7.01-7.34 (m, 10H). ¹³ C NMR (CDCl _Three , TMS) δ14.07, 19.59, 22.58, 28.64, 28.76, 31.36, 83.36, 91.17, 124.81, 127.22, 127.61, 128.02, 128.35, 129.01, 129.22, 135.06, 136.40, 138.34. Elemental analysis: C _{twenty two} H _{twenty four} Experimental value C: 91.38%, H: 8.47%. Calculated value C: 91.61%, H: 8.39%.
[0111]
Example 4
(E) -9-hexanyl-9-hexadecene-7-yne
The same procedure as in Example 1 was performed. However, 7-tetradecine was used instead of 3-hexyne. Further, 1-chloro-1-octyne was used in place of phenylethynyl chloride.
[0112]
¹ H NMR (CDCl _Three , TMS) δ0.89-0.91 (m, 9H), 1.27-1.54 (m, 24H), 2.03-2.11 (m, 4H), 2.28 (t, J = 6.9, 2H), 5.74 (t, J = 6.9 , 1H). ¹³ C NMR (CDCl _Three , TMS) δ 14.03, 14.07, 19.30, 22.58, 22.63, 22.65, 28.17, 28.39, 28.57, 28.92, 28.96, 29.02, 29.21, 29.40, 30.90, 31.38, 31.75, 31.79, 82.64, 87.01, 123.44, 136.41.
[0113]
Example 5
(E) -1,3,4-Triphenyl-3-buten-1-yne
The same procedure as in Example 1 was performed. However, diphenylacetylene was used instead of 3-hexyne. In addition, phenylethynyl chloride (2.5 mmol) was added, and instead of stirring the reaction mixture at 50 ° C. for 12 hours, phenylethynyl chloride (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 6 hours.
[0114]
¹ H NMR (CDCl _Three , TMS) δ7.01 (s, 1H), 7.05-7.40 (m, 15H). ¹³ C NMR (CDCl _Three , TMS) δ90.23, 92.66, 123.76, 124.67, 128.06, 128.30, 128.55, 128.62, 128.72, 128.96, 129.50, 129.80, 132.02, 136.52, 138.17 Elemental analysis: C _{twenty two} H ₁₆ Experimental value C: 94.22%, H: 5.73%. Calculated value C: 94.25%, H: 5.75%.
[0115]
Example 6
(E) -1-Tolyl-3,4-diphenyl-3-buten-1-yne
The same procedure as in Example 1 was performed. However, diphenylacetylene was used instead of 3-hexyne. Also, phenylethynyl chloride (2.5 mmol) was added, and instead of stirring the reaction mixture at 50 ° C. for 12 hours, tolyl ethynyl chloride (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 6 hours.
[0116]
¹ H NMR (CDCl _Three , TMS) δ 2.35 (s, 3H), 7.08 (s, 1H), 7.10-7.42 (m, 15H). ¹³ C NMR (CDCl _Three , TMS) δ21.51, 90.05, 91.62, 120.46, 124.42, 127.53, 127.82, 128.10, 128.50, 129.07, 129.09, 129.45, 131.49, 136.10, 136.20, 137.87, 138.33. _{twenty three} H ₁₈ Experimental value C: 93.79%, H: 6.15%. Calculated value C: 93.83%, H: 6.16%.
[0117]
Example 7
1,3-diphenyl-3-pentene-1-yne (isomer)
The same procedure as in Example 1 was performed. However, 1-phenyl-1-propyne was used instead of 3-hexyne. In addition, phenylethynyl chloride (2.5 mmol) was added, and instead of stirring the reaction mixture at 50 ° C. for 12 hours, phenylethynyl chloride (2.5 mmol) was added and the reaction mixture was stirred at 50 ° C. for 9 hours.
[0118]
¹ H NMR (CDCl _Three , TMS) δ2.17 (s, 3H), 6.79 (s, 1H), 7.24-7.48 (m, 10H). ¹³ C (CDCl _Three , TMS) δ15.69, 126.33, 127.20, 127.25, 128.07, 128.29, 128.31, 129.01, 129.37, 131.53, 136.10, 138.68, 139.00.High-resolution mass spectrometry (HR-MS (EI ⁺ )): Chemical formula: C ₁₇ H ₁₄ Experimental mass: 218.1099; Calculated mass: 218.1096.
[0119]
Example 8A
(Z) -1,4-diphenyl-3- (trimethylsilyl) -3-buten-1-yne
The same procedure as in Example 1 was performed. However, 1-phenyl-2-trimethylsilylacetylene was used instead of 3-hexyne.
[0120]
¹ H NMR (CDCl _Three , TMS) δ0.14-0.15 (m, 9H), 7.24-7.47 (m, 10H), 7.79 (s, 1H). ¹³ C (CDCl _Three , TMS) δ0.07, 92.42, 93.60, 124.17, 126.78, 127.75, 127.87, 127.95, 128.28, 128.43, 131.39, 138.72, 151.28.High-resolution mass spectrometry (HR-MS (EI ⁺ )): Chemical formula: C ₁₉ H ₂₀ Si Experimental mass: 276.1331; Calculated mass: 276.1334.
[0121]
Example 8B
(Z) -1,3-diphenyl-4- (trimethylsilyl) -3-buten-1-yne
The same procedure as in Example 1 was performed. However, 1-phenyl-2-trimethylsilylacetylene was used instead of 3-hexyne.
[0122]
¹ H NMR (CDCl _Three , TMS) δ 0.12-0.23 (m, 9H), 6.63 (s, 1H), 7.43-7.61 (m, 10H). ¹³ C (CDCl _Three , TMS) δ 0.01, 89.53, 92.18, 123.24, 127.97, 127.99, 128.19, 128.22, 128.24, 131.58, 139.08, 140.59, 141.25.High resolution mass spectrometry (HR-MS (EI ⁺ )): Chemical formula: C ₁₉ H ₂₀ Si Experimental mass: 276.1345; Calculated mass: 276.1334.
[0123]
Example 9
1-Tolyl-3-phenyl-4- (trimethylsilyl) -3-buten-1-yne (isomer)
The same procedure as in Example 1 was performed. However, 1-phenyl-2-trimethylsilylacetylene was used instead of 3-hexyne. Moreover, tolylethynyl chloride (2.5 mmol) was used instead of phenylethynyl chloride.
[0124]
¹ H NMR (CDCl _Three , TMS) δ 0.048-0.36 (m, 9H), 2.37-2.41 (m, 3H), 6.48 (s, 0.57H), 7.13-7.48 (m, 10H), 7.81 (s, 0.27H). ¹³ C (CDCl _Three , TMS) δ 0.27, 21.53, 89.85, 91.66, 120.22, 128.01, 128.22, 128.32, 128.48, 128.96, 131.64, 138.38, 139.31, 140.83.High resolution mass spectrometry (HR-MS (EI ⁺ )): Chemical formula: C ₂₀ H _{twenty two} Si Experimental mass: 290.1486 Calculated mass: 290.1491.
[0125]
The results of Examples 1 to 9 and the general formula of the reaction are shown in Table 1. However, the yield indicates the GC yield, and the parenthesis indicates the isolated yield.
[0126]
[Table 1]
[0127]
Example 10
cis-1,3,4,6-Tetraphenylhex-3-ene-1,5-diyne
Ethyl Grignard (EtMgBr) (2.5 mmol, 1.0 M THF solution, 2.5 mL) was added to a THF solution (6 mL) of zirconocene dichloride (1.25 mmol, 0.365 g) at -78 ° C and stirred at the same temperature for 1 hour. did. Diphenylacetylene (1 mmol) was added to the reaction mixture, and the temperature was raised to 0 ° C. After stirring for 3 hours, 1-phenyl-2-chloroacetylene (0.14 g, 1.0 mmol) was added, and the reaction mixture was stirred at 50 ° C. for 3 hours (Condition A). Thereafter, 1-phenyl-2-bromoacetylene (0.23 g, 1.25 mmol) and CuCl (0.01 g, 0.1 mmol) were added to the reaction mixture, and the mixture was further stirred at 50 ° C. for 3 hours (Condition B). 3 N HCl was added to the reaction mixture to terminate the reaction. Extracted with hexane, washed with water, and dried over anhydrous magnesium sulfate. Purification by silica gel column chromatography gave the title compound. Isolated yield 63%. When the cis isomer was placed in a hexane / acetone (5: 1) solution for 15 days, cis-trans isomerization occurred and a pure trans isomer was precipitated. The X-ray crystal structure analysis of the trans isomer of the title compound is shown in FIG.
[0128]
cis-1,3,4,6-Tetraphenylhex-3-ene-1,5-diyne
¹ H NMR (CDCl _Three , Me _Four Si) δ 7.19-7.22 (m, 6H), 7.29-7.34 (m, 10H), 7.53-7.56 (m, 4H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ 91.79, 96.85, 123.39, 127.83, 128.06, 128.37, 128.53, 129.22, 129.74, 131.67, 137.47. Elemental analysis. Calculated value C ₃₀ H ₂₀ : C, 94.70; H, 5.30. Found: C, 94.80; H, 5.32.
[0129]
trans-1,3,4,6-tetraphenylhex-3-ene-1,5-diyne
¹ H NMR (CDCl _Three , Me _Four Si) δ7.24-7.30 (m, 10H), 7.37-7.41 (m, 2H), 7.44-7.48 (m, 4H), 7.97-7.99 (m, 4H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ 90.92, 98.55, 123.23, 127.84, 128.29, 128.30, 128.46, 128.62, 129.25, 131.41, 139.02 Elemental analysis. Calculated value C ₃₀ H ₂₀ : C, 94.70; H, 5.30. Found: C, 94.81; H, 5.42.
[0130]
Example 11
cis-3,4-Diethyl-1,6-diphenylhex-3-ene-1,5-diyne
The same procedure as in Example 10 was performed. However, diethylacetylene was used instead of diphenylacetylene. As condition A, the reaction mixture was stirred at 50 ° C. for 6 hours. As condition B, the reaction mixture was stirred at 50 ° C. for 9 hours.
[0131]
1H NMR (CDCl _Three , Me _Four Si) δ 1.20 (t, J = 7.5 Hz, 6H), 2.36 (q, J = 7.5 Hz, 4H), 7.27-7.30 (m, 6H), 7.48 -7.50 (m, 4H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ13.35, 25.23, 90.76, 94.30, 123.81, 128.02, 128.28, 130.22, 131.49.High resolution mass spectrometer Calculated value C _{twenty two} H ₂₀ 284.1574. Found 284.1565.
[0132]
Example 12
cis-3,4-Dibutyl-1,6-diphenylhex-3-ene-1,5-diyne
The same procedure as in Example 10 was performed. However, dibutylacetylene was used in place of diphenylacetylene. Further, 1-phenyl-2-chloroacetylene was used in place of 1-phenyl-2-bromoacetylene.
[0133]
¹ H NMR (CDCl _Three , Me _Four Si) δ 0.96 (t, J = 7.3 Hz, 6H), 1.37-1.46 (m, 4H), 1.60-1.66 (m, 4H), 2.35 (t, J = 7.5 Hz, 4H), 7.24-7.32 (m , 6H), 7.47-7.50 (m, 4H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ 14.02, 22.43, 30.88, 31.71, 91.04, 94.03, 123.79, 127.96, 128.24, 129.37, 131.46. Elemental analysis. Calculated value C ₂₆ H ₂₈ : C, 91.71; H, 8.29. Found: C, 91.76; H, 8.41.
[0134]
Example 13
cis-3,4-Di (2-thienyl) -1,6-ditolylhex-3-ene-1,5-diyne
The same procedure as in Example 10 was performed. However, 1,2-di (2-thienyl) acetylene was used in place of diphenylacetylene. Further, 1-tolyl-2-chloroacetylene was used instead of 1-phenyl-2-chloroacetylene, and 1-tolyl-2-bromoacetylene was used instead of 1-phenyl-2-bromoacetylene.
[0135]
¹ H NMR (CDCl _Three , Me _Four Si) δ 2.35 (s, 6H), 6.97 (dd, J = 5.0, 4.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 4H), 7.21-7.22 (m, 2H), 7.31-7.32 (m , 2H), 7.44 (d, J = 8.0 Hz, 4H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ 21.55, 90.13, 97.37, 120.04, 121.83, 126.92, 127.87, 129.14, 129.24, 131.49, 138.87, 139.25. Elemental analysis. Calculated value C28H20S2: C, 79.96; H, 4.79; S, 15.25. 79.94; H, 4.84; S, 15.39.
[0136]
Example 14
cis-3,4-Diphenyl-1,6-ditrimethylsilylhex-3-ene-1,5-diyne
The same procedure as in Example 10 was performed. However, 1-trimethylsilyl-2-bromoacetylene was used instead of 1-phenyl-2-chloroacetylene, and 1-trimethylsilyl-2-bromoacetylene was used instead of 1-phenyl-2-bromoacetylene. For condition B, the reaction mixture was stirred at 50 ° C. for 6 hours.
[0137]
¹ H NMR (CDCl _Three , Me _Four Si) δ 0.15 (s, 18H), 7.02-7.14 (m, 10H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ 0.03, 102.43, 106.04, 127.75, 127.92, 129.66, 129.84, 137.15. Elemental analysis. Calculated value C _{twenty four} H ₂₈ Si ₂ : C, 77.55; H, 7.57. Found: C, 77.85; H, 7.40.
[0138]
Example 15
cis-1,3,4, -Triphenyl-6-trimethylsilylhex-3-ene-1,5-diyne
The same procedure as in Example 10 was performed. However, 1-trimethylsilyl-2-bromoacetylene was used in place of 1-phenyl-2-bromoacetylene. For condition B, the reaction mixture was stirred at 50 ° C. for 6 hours.
[0139]
1H NMR (CDCl _Three , Me _Four Si) δ 0.26 (s, 9H), 7.17-7.20 (m, 6H), 7.22 -7.27 (m, 4H), 7.33-7.34 (m, 3H), 7.52-7.54 (m, 2H). ¹³ C NMR (CDCl _Three , Me _Four Si) δ -0.03, 91.55, 96.71, 102.30, 106.24, 123.28, 127.75, 137.83, 127.95, 128.02, 128.26, 128.50, 128.96, 129.63, 129.72, 130.14, 131.73, 137.12, 137.35. ₂₇ H _{twenty four} Si: C, 86.12; H, 6.42. Found: C, 86.11; H, 6.31.
[0140]
The results of Examples 10 to 15 and the general formula of the reaction are shown in Table 2. However, the yield indicates the isolated yield.
[0141]
[Table 2]
[0142]
【The invention's effect】
By the method of the present invention, an enyne derivative and a styrene derivative in which the stereochemistry and the position of the substituent are controlled can be easily produced.
[Brief description of the drawings]
FIG. 1 is a single crystal X-ray structural analysis of trans-1,3,4,6-tetraphenylhex-3-ene-1,5-diyne.

Claims (5)

A method for producing an enyne derivative represented by the following formula (Ia) or the following formula (Ib) or a mixture thereof,
(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently the same or different and are each a hydrogen atom; a C ₁ -C ₄₀ hydrocarbon group optionally having substituent (s); good C ₁ -C ₄₀ alkoxy group which may have a group, which may have a substituent group C ₆ -C ₄₀ aryloxy group; optionally substituted amino group; a hydroxyl group or a substituent A silyl group optionally having
However, R ¹ and R ² may form a C ₄ -C ₁₀ saturated or unsaturated ring bridged to each other, the saturated or unsaturated ring, oxygen atom, sulfur atom, or the formula -N (R ⁵⁾ -. group (wherein represented by, R ⁵ is a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon group) may be interrupted by, and, rather it may also have a substituent, R ⁴ is a group other than a hydrogen atom . )
A metallacyclopentene represented by the following formula (II):
(Wherein R ¹ and R ² have the above meanings; M represents titanium, zirconium or hafnium ; L ¹ and L ² are independent of each other and are the same or different and are delocalized cyclic η ⁵ represents a coordination ligand , provided that L ¹ and L ² may be cross-linked.)
Reacting an alkyne derivative represented by the following formula (III) to obtain a reaction mixture;
(In the formula, R ³ has the above-mentioned meaning. X is a halogen atom .)
Next, the reaction mixture is reacted with an electrophile represented by the following formula (IV): R ⁴ —Y (IV)
(Wherein, R ⁴ has the above-mentioned meaning. Y is a halogen atom ). The delocalized cyclic η ⁵ -coordination ligand is a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, an n-butylcyclopentadienyl group, or t-butyl. Cyclopentadienyl group, dimethylcyclopentadienyl group, diethylcyclopentadienyl group, diisopropylcyclopentadienyl group, di-t-butylcyclopentadienyl group, tetramethylcyclopentadienyl group, indenyl group, 2 -Methylindenyl group, 2-methyl-4-phenylindenyl group, tetrahydroindenyl group, benzoindenyl group, fluorenyl group, benzofluorenyl group, tetrahydrofluorenyl group or octahydrofluorenyl group The manufacturing method of the enyne derivative of Claim 1 . The method for producing an enyne derivative according to claim 1 or 2 , wherein R ⁴ is an optionally substituted C _{2 to} C ₄₀ alkynyl group. A method for producing an enyne derivative represented by the following formula (Ia) or the following formula (Ib) or a mixture thereof,
(Wherein R ¹ , R ² And R ^Three Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₄₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₄₀ Alkoxy group; C which may have a substituent ₆ ~ C ₄₀ An aryloxy group; an amino group which may have a substituent; a hydroxyl group or a silyl group which may have a substituent;
However, R ¹ And R ² Are cross-linked to form C _Four ~ C _Ten A saturated or unsaturated ring may be formed, and the saturated or unsaturated ring may be an oxygen atom, a sulfur atom, or a formula —N (R ^Five )-Group (wherein R ^Five Is a hydrogen atom or C ₁ ~ C ₄₀ It is a hydrocarbon group. ) And may have a substituent, R ^Four Is a hydrogen atom. )
A metallacyclopentene represented by the following formula (II):
(Wherein R ¹ And R ² Has the above meaning. M represents titanium, zirconium or hafnium; L ¹ And L ² Are independent of each other, the same or different, and a delocalized cyclic η ^Five -Represents a coordinating ligand, provided that L ¹ And L ² May be cross-linked. )
The step of reacting with an alkyne derivative represented by the following formula (III)
(Wherein R ^Three Has the above meaning. X is a halogen atom, p-toluenesulfonyl group, tosylate group or trifluoromethanesulfonic acid ester. And a method for producing an enyne derivative. The delocalized cyclic η ⁵ -coordination ligand is a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, an n-butylcyclopentadienyl group, or t-butyl. Cyclopentadienyl group, dimethylcyclopentadienyl group, diethylcyclopentadienyl group, diisopropylcyclopentadienyl group, di-t-butylcyclopentadienyl group, tetramethylcyclopentadienyl group, indenyl group, 2 -Methylindenyl group, 2-methyl-4-phenylindenyl group, tetrahydroindenyl group, benzoindenyl group, fluorenyl group, benzofluorenyl group, tetrahydrofluorenyl group or octahydrofluorenyl group The manufacturing method of the enyne derivative of Claim 4.