JP2002012564A - Method for producing polycyclic compound - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To easily produce a polycyclic compound into which an arbitrary substituent is introduced.
To get to. SOLUTION: A diene derivative represented by the following formula (II):
And an organometallic compound represented by the following formula (III):
To obtain a reaction mixture, and then, in the presence of additives,
The reaction mixture and an alkyne derivative represented by the following formula (IV):
Reacting a conductor with a polycyclic compound represented by the following formula (I)
Method of manufacturing a product. Embedded image (Where R¹Is a hydrocarbon group, A is a divalent hydrocarbon group,
M is a transition metal, L¹And L ^TwoIs a ligand, Z¹And Z^TwoIs carbonized
X is a leaving group. )

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polycyclic compound, and more particularly to a simple method for producing a polycyclic compound, which can produce a polycyclic compound in one pot.

[0002]

2. Description of the Related Art Polycyclic compounds into which arbitrary substituents have been introduced are widely useful as intermediates for pharmaceuticals and agricultural chemicals.

However, it has been difficult to introduce an arbitrary substituent into such a polycyclic compound. Therefore, a production method capable of obtaining a polycyclic compound into which an arbitrary substituent is introduced in one pot has been desired.

[0004]

According to the present invention, there is provided a method for producing a polycyclic compound represented by the following formula (I):

[0005]

Embedded image

[0006] (wherein, R ¹ represents, C ₁ may have a substituent -C ₄₀ hydrocarbon group; which may have a substituent group C ₁
-C ₄₀ alkoxy group; which may have a substituent group C ₆ ~
C ₄₀ aryloxy group; C ₆ optionally having substituent (s)
-C ₄₀ alkoxyaryl group; amino group; hydroxyl group or silyl group, and A is a divalent C _{4 which} may have a substituent.
-C ₁₀ hydrocarbon group, an oxygen atom, a sulfur atom, or the formula -N (R ⁴⁾ - group represented by (wherein, R ⁴ is a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon group.) And may have a substituent. A diene derivative represented by the following formula (II):

[0007]

Embedded image

(Wherein A has the above meaning. X
Is a leaving group. Reacting an organometallic compound represented by the following formula (III) to obtain a reaction mixture;

[0009]

Embedded image

(Wherein M represents a metal of Groups 3 to 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 each represents an anionic ligand. Where L ¹ and L ² may be cross-linked,
¹ and Z ² are leaving groups. A) reacting the reaction mixture with an alkyne derivative represented by the following formula (IV) in the presence of an additive:

[0011]

Embedded image

(In the formula, R ¹ has the above-mentioned meaning.)
A method for producing a polycyclic compound is provided.

In the present invention, A is preferably a compound represented by the following formula (Va) or a compound represented by the following formula (Vb).

[0014]

Embedded image

(Wherein, R ² and R ³ are independently of each other and are the same or different and each is a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group or a silyl group; A ¹ and A ² are each independently The same or different, optionally substituted divalent C ₁
-C ₅ hydrocarbon group. In the present invention, M is a metal belonging to Group 4 or 5 of the periodic table or a lanthanide series, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. Preferably, there is. Further, it is more preferable that the delocalized cyclic η ⁵ -coordination system ligand is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a step of reacting a diene derivative represented by the following formula (II) with an organometallic compound represented by the following formula (III) to obtain a reaction mixture:
Producing a polycyclic compound represented by the following formula (I), which comprises a step of reacting the reaction mixture with an alkyne derivative represented by the following formula (IV) in the presence of an additive: A method is provided.

[0017]

Embedded image

In the present invention, when a diene derivative represented by the above formula (II) is reacted with an organometallic compound represented by the above formula (III), a cyclization reaction takes place, and the cyclization reaction takes place. It is believed that an intermediate is produced. Subsequently, when the alkyne derivative represented by the above formula (IV) is reacted with this intermediate in the presence of an additive, a cyclization reaction occurs again, and the alkyne derivative represented by the above formula (I) having a 5-membered ring is obtained. It is believed that a ring compound is formed. That is, according to the present invention, the polycyclic compound of the above formula (I), which is the final product, can be produced in one pot.

R ¹ is a C ₁ -C which may have a substituent.
₄₀ hydrocarbon groups; C ₁ -C ₄₀ alkoxy groups which may have a substituent; C ₆ -C ₄₀ aryloxy groups which may have a substituent; C which may have a substituent ₆ -C ₄₀ alkoxyaryl group; a hydroxyl group or a silyl group; an amino group.

In this specification, C₁-C₄₀Hydrocarbon groups are saturated
It may be a sum or unsaturated acyclic or saturated or
Or an unsaturated cyclic group. C₁-C₄₀Hydrocarbon group
When is acyclic, it may be linear or branched.
No. C₁-C₄₀Hydrocarbon groups include C₁-C₄₀Alkyl group, C
_Two-C₄₀Alkenyl group, C_Two-C₄₀Alkynyl group, C_Three-C ₄₀
Allyl group, C_Four-C₄₀Alkyldienyl group, C_Four-C₄₀Poly
Enyl group, C₆-C₄₀Aryl group, C₆-C₄₀Alkyl ants
Group, C₆-C₄₀Arylalkyl group, C_Four-C ₄₀Cyclo
Alkyl group, C_Four-C₄₀A cycloalkenyl group, (C_Three-C₂₀
Cycloalkyl) C₁-C₂₀And an alkyl group.

C₁-C₄₀Alkyl group, C_Two-C₄₀Alkenyl
Group, C_Two-C₄₀Alkynyl group, C_Three-C ₄₀Allyl group, C_Four-C
₄₀An alkyldienyl group and C_Four-C₄₀Polyenyl group
Is C₁-C₂₀Alkyl group, C_Two-C₂₀Alkene
Group, C_Two-C₂₀Alkynyl group, C_Three-C₂₀Allyl group, C_Four-
C₂₀An alkyldienyl group and C_Four-C₂₀Polyenyl group
And each is preferably C₁-C_TenAlkyl
Group, C_Two-C_TenAlkenyl group, C_Two-C_TenAlkynyl group, C
_Three-C_TenAllyl group, C_Four-C_TenAn alkyldienyl group, and
C_Four-C_TenMore preferably, it is a polyenyl group.

C₆-C₄₀Aryl group, C₆-C₄₀Alkyria
Reel base, C₆-C₄₀Arylalkyl group, C_Four-C₄₀Shiku
Loalkyl group, C_Four-C₄₀A cycloalkenyl group, and
(C_Three-C₂₀Cycloalkyl) C₁-C₂₀Alkyl groups are
Each C₆-C₂₀Aryl group, C₆-C₂₀Alkyl ally
Group, C₆-C₂₀Arylalkyl group, C_Four-C₂₀Cycloa
Alkyl group, C_Four-C₂₀A cycloalkenyl group and (C_Three-
C_TenCycloalkyl) C ₁-C_TenAlkyl groups are preferred,
Each C₆-C_TenAryl group, C₆-C₁₂Alkyl ants
Group, C₆-C₁₂Arylalkyl group, C_Four-C_TenCyclo
An alkyl group and C_Four-C_TenFurther cycloalkenyl groups
preferable.

Examples of 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.

Examples of aryl groups useful in the practice of this 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.

Examples of 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.

Examples of aryloxy groups useful in the practice of this invention include, but are not limited to, phenoxy,
Naphthoxy, phenylphenoxy, 4-methylphenoxy, 2-tolyloxy, 3-tolyloxy, 4-tolyloxy, naphthyloxy, biphenyloxy, 4-phenoxyphenyloxy, 4-fluorophenyloxy,
3-carbomethoxyphenyloxy, 4-carbomethoxyphenyloxy and the like.

Examples of amino groups useful in the practice of the present invention include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

Examples of silyl groups useful in the practice of the present invention include, but are not limited to, trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, dimethylethylsilyl, methylmethoxyphenylsilyl, methylethylphenoxy. Silyl and the like.

C₁-C₄₀Hydrocarbon group, C₁-C₄₀Alkoxy
Group, C₆-C₄₀Aryloxy group, C ₆-C₄₀Alkoxya
A substituent may be introduced into the reel group.
Examples of the substituent include a halogen atom, an amino group, and a hydroxyl group.
Group, silyl group, alkoxy group, aryloxy group, etc.
No.

A represents a divalent C _4- which may have a substituent.
It is a C ₁₀ hydrocarbon group. As the divalent hydrocarbon group, a C _{4 to} C ₁₀ such as an ethylene group which may have a branch.
Examples thereof include C ₄ -C ₁₀ alkenylene groups such as an alkylene group and a propenylene group, C ₄ -C ₁₀ alkynylene groups such as a propynylene group, and C ₆ -C ₁₀ arylene groups such as a phenylene group. The ring constituted by the substituent A may be a saturated or unsaturated ring.

A is an oxygen atom, a sulfur atom, or a compound of the formula -N
A group represented by (R ⁴ ) — (wherein R ⁴ is a hydrogen atom or C ₁
~C ₄₀ hydrocarbon group. ) May be interrupted.
That is, the saturated or unsaturated ring may be a hetero ring.

R ⁴ is preferably a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group, more preferably a hydrogen atom or a C ₁ -C ₁₄ hydrocarbon group, and R ⁴ is a hydrogen atom,
Even more preferred are C ₁ -C ₆ alkyl, phenyl, naphthyl, benzyl and naphthylmethyl.

The saturated or unsaturated ring may have a substituent, and may be a C ₁ -C ₄₀ hydrocarbon group, a C ₁ -C ₄₀ alkoxy group, a C ₆ -C ₄₀ aryloxy group, an amine group, A substituent such as a hydroxyl group or a silyl group may be introduced.

A may be a compound represented by the following formula (Va) or a compound represented by the following formula (Vb).

[0035]

Embedded image

R ² and R ³ are independent of each other and are the same or different and each represent a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group or a silyl group. It is preferably a C ₁ -C ₁₀ hydrocarbon group, more preferably a C ₁ -C ₄ hydrocarbon group.

A ¹ and A ² are independently of each other, the same or different, and may be a divalent C ₁ -C ₅ hydrocarbon group which may have a substituent. It is preferably a divalent C ₁ -C ₃ hydrocarbon group, and more preferably an ethylene group.

In the present invention, a diene derivative represented by the following formula (II) is used.

[0039]

Embedded image

(Wherein, A has the above meaning.) X is a leaving group. As the leaving group, for example, F, C
a halogen atom such as l, Br, I, a tosylate group (-
_{O-S (= O) 2} -C 6 H 4 -CH 3), trifluoromethanesulfonic acid ester (triflate), C ₁ -C ₂₀ alkoxy group (preferably a C ₁ -C ₁₀ alkoxy groups, more preferably Is a C ₁ -C ₆ alkoxy group), C _6-
And a C ₂₀ aryloxy group and a tri-lower alkylsilyloxy group. The leaving group, Cl, Br, tosylate group, C ₁ -C ₂₀ alkoxy group, and a tri-lower alkyl silyl group are preferred.

In the present invention, an organometallic compound represented by the following formula (III) is used.

[0042]

Embedded image

Z ¹ and Z ² are leaving groups. The leaving group is preferably a C ₁ -C ₄₀ hydrocarbon group, C ₁
-C ₁₀ alkyl group, C ₂ -C ₁₀ alkenyl group, C ₂ -C ₁₀
Alkynyl group, C ₃ -C ₁₀ allyl group, C ₄ -C ₁₀ alkadienyl group, C ₄ -C ₁₀ polyenyl group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₂ alkylaryl group, C ₆ -C ₁₂ arylalkyl group, C ₄ -C ₁₀ cycloalkyl group, or C ₄
-C ₁₀ cycloalkenyl group. The leaving group is more preferably a C ₁ -C ₆ alkyl group.

M represents a metal belonging to Groups 3 to 5 of the periodic table or a lanthanide series. M is preferably a metal belonging to Group 4 of the periodic table or a lanthanide series, more preferably a metal belonging to Group 4 of the periodic table, namely, titanium, zirconium and hafnium, and still more preferably zirconium.

L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand. However, L ¹ and L ² may be cross-linked. The anionic ligand is preferably a delocalized cyclic η ⁵ -coordination ligand, a C ₁ -C ₂₀ alkoxy group, a C ₆ -C ₂₀ aryloxy group or a dialkylamide group.

L ¹ and L ² are preferably delocalized cyclic η ⁵ -coordination ligands. Delocalized cyclic eta ⁵ - Example of the coordination type ligand is an unsubstituted cyclopentadienyl group and substituted cyclopentadienyl groups. The substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, t
-Butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl group, 2-methylindenyl Group, 2-methyl-4-
A phenylindenyl group, a tetrahydroindenyl group, a benzoindenyl group, a fluorenyl group, a benzofluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl 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. In addition to hydrogen, one such as an element of group 14 of the periodic table and / or an element of groups 15, 16 and 17 of the periodic table
It can contain more than one heteroatom.

Delocalized ring η^Five-Coordination ligands, for example
For example, a cyclopentadienyl group is
May be cross-linked by one or more cross-linking ligands.
It may be. Examples of the bridging ligand include C
H_Two, CH_TwoCH_Two, CH (CH_Three) CH_Two, CH (C
_FourH₉) C (CH_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi,
(CH_Three) _TwoGe, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi,
(C₆H_Five) (CH_Three) Si, (C₆H _Five)_TwoGe, (C
₆H_Five)_TwoSn, (CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two,
o-C₆H_FourOr 2, 2 '-(C₆H_Four)_TwoIs mentioned.

Two or more delocalized cyclic η^Five-Coordination coordination
, For example, cyclopentadienyl groups,
May be cross-linked by one or more cross-linking groups.
It may be. Examples of the crosslinking group include, for example, CH_Two, C
H_TwoCH_Two, CH (CH_Three) CH_Two, CH (C_FourH₉) C (C
H_Three)_Two, C (CH_Three)_Two, (CH_Three)_TwoSi, (CH_Three)_TwoG
e, (CH_Three)_TwoSn, (C₆H_Five)_TwoSi, (C₆H_Five)
(CH_Three) Si, (C₆H_Five) _TwoGe, (C₆H_Five)_TwoSn,
(CH_Two)_FourSi, CH_TwoSi (CH_Three)_Two, O-C₆H_Fouror
Is 2,2 '-(C₆H_Four)_TwoIs mentioned.

The organometallic compound represented by the above formula (III) has two or more metallacyclopentadiene moieties (moie
ty). Such compounds are known as polynuclear metallocenes. The polynuclear metallocene is
It may have any substitution mode and any cross-linking form. The independent metallocene moieties of the polynuclear metallocene may each be the same or different. Examples of the polynuclear metallocene are described in, for example, EP-A-632063,
-80214, JP-A-4-85310, EP-A-6
54476.

In the present invention. An alkyne derivative represented by the following formula (IV) is used.

[0052]

Embedded image

(In the formula, R ¹ has the above-mentioned meaning.) In the present invention, the diene derivative represented by the above formula (II) is reacted with the organometallic compound represented by the above formula (III), Next, an alkyne derivative represented by the above formula (IV) is added in the presence of the additive. Typically, the above formula (II) is added to the solution of the above formula (III) and reacted. Next, an additive and an alkyne derivative represented by the above formula (IV) are added.

By adding an additive, a polymerization reaction between the intermediate and the alkyne derivative represented by the above formula (IV) becomes possible.

Such additives include methylalumoxane (MAO), tris (pentafluorophenyl)
Examples thereof include borane, triphenylborane, silver perchlorate, sodium tetraphenylborate, and silver nitrate, and preferably include methylalumoxane.

In the present invention, the amount of the diene derivative represented by the above formula (II) and the amount of the alkyne derivative represented by the above formula (IV) are respectively different from those of the organometallic compound 1 represented by the above formula (III). 1.8 mol to 10 mol
Mol, preferably 1.8 mol to 8 mol, more preferably 1.9 mol to 5 mol, even more preferably 1.9 mol to 2 mol.

In the present invention, the amount of the additive is determined by the above formula (II)
0.0 mol per 1 mol of the organometallic compound represented by I)
001 mol to 0.2 mol, preferably 0.001 mol to 0.1 mol, more preferably,
0.005 mol to 0.1 mol.

The reaction is preferably carried out at -80 ° C to 300 ° C.
The temperature is preferably in the range of 0 ° C. to 150 ° C.
The temperature range is as follows. 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.

As the solvent, an aliphatic or aromatic solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride and dichloroethane; halogenated aromatic hydrocarbons such as o-dichlorobenzene; and aromatic hydrocarbons such as benzene and toluene are used.

The organometallic compound (III) used in the present invention
Can be synthesized, for example, using the following metallocene.

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-ethyl) Ndeniru) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4,
(5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-ethyl-4,5-benzoindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4-phenylindenyl)
Dichloro zirconium; (dimethylsilanediyl) bis (2-ethyl-4-phenylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methyl-4,6-diisopropylindenyl) dichlorozirconium , Or a strong base such as an alkali metal such as sodium or an alkaline earth metal such as magnesium, or converted into a dialkyl compound.

The organometallic compound (III) used in the present invention
Examples thereof include the following metallocenes. Bis (cyclopentadienyl) dibutylzirconium; bis (methylcyclopentadienyl) dibutylzirconium; bis (butylcyclopentadienyl) dibutylzirconium; bis (indenyl) dibutylzirconium; bis (fluorenyl) dibutylzirconium;
(Indenyl) (fluorenyl) dibutylzirconium; (3-methyl-5-naphthylindenyl) (2,7
-Di-tert-butylfluorenyl) dibutylzirconium; (3-methyl-5-naphthylindenyl)
(3,4,7-trimethoxyfluorenyl) dibutylzirconium; (pentamethylcyclopentadienyl)
(Tetrahydroindenyl) dibutylzirconium;
(Cyclopentadienyl) (1-octen-8-ylcyclopentadienyl) dibutylzirconium; (indenyl) (1-buten-4-ylcyclopentadienyl)
[1,3-bis (trimethylsilyl) cyclopentadienyl] (3,4-benzofluorenyl) dibutylzirconium;

Bis (cyclopentadienyl) dibutyltitanium; dimethylsilanediylbis (indenyl) dibutylzirconium; dimethylsilanediylbis (tetrahydroindenyl) dibutylzirconium; dimethylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; Dimethylsilanediylbis (2-methylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4,
5-benzoindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-4,5-benzoindenyl) dibutylzirconium; dimethylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] Acenaphthylene-7-ylidene) dibutylzirconium; dimethylsilanediyl (2-methyl-4,
5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-methyl-4-phenylindenyl) dibutylzirconium; Dimethylsilanediyl (2-methyl-4,5-benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediyl (2
-Ethylindenyl) (2-ethyl-4-phenylnaphthyl) dibutylzirconium; dimethylsilanediyl (2-methylindenyl) (4-phenylindenyl)
Dibutyl zirconium; dimethylsilanediylbis (2
-Methyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-4-phenylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium; Dimethylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; dimethylsilanediylbis (2-methyl-4-naphthylindenyl) dibutylzirconium; dimethylsilanediylbis (2-ethyl-
4-naphthylindenyl) dibutylzirconium;

Methylphenylsilanediylbis (indenyl) dibutylzirconium; methylphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; methylphenylsilanediylbis (tetrahydroindenyl) dibutylzirconium; methylphenylsilanediylbis (2 -Methylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium; methylphenylsilanediylbis ( 2-ethyl-4,5-benzoindenyl) dibutylzirconium; methylphenylsilanediylbis (4,5-dihydro-8-methyl-7H-cyclopent [e] a Naphthylene-7-ylidene) dibutyl zirconium; methylphenyl silane diyl (2-
Methyl-4,5-benzoindenyl) (2-methyl-4
-Phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-ethylindenyl) (2-
Methyl-4-phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-methyl-4,5
-Benzoindenyl) (2-ethyl-4-phenylindenyl) dibutylzirconium; methylphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2
-Ethyl-indenyl) dibutylzirconium; methylphenylsilanediyl (2-methylindenyl) (4phenylindenyl) dibutylzirconium;

Methylphenylsilanediylbis (2-methyl-4phenylindenyl) dibutylzirconium;
Methylphenylsilanediylbisdibutylzirconium; methylphenylsilanediylbis (2-methyl-
4,6-diisopropylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethyl-
4,6-diisopropylindenyl) dibutylzirconium; methylphenylsilanediylbis (4-naphthylindenyl) dibutylzirconium; methylphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium; diphenylsilanediylbis ( Indenyl) dibutylzirconium; diphenylsilanediylbis (2-methylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethylindenyl) dibutylzirconium; diphenylsilanediyl (cyclopentadienyl) (indenyl) dibutylzirconium; diphenylsilane Diylbis (2-methyl-4,5-benzoindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4,5
-Benzoindenyl) dibutylzirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4phenylindenyl) dibutylzirconium; diphenylsilanediyl (2-ethyl-4,5-benzoindenyl) (2-ethyl-4naphthylindenyl) dibutylzirconium; diphenylsilanediyl (2-methylindenyl) (4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2
-Methyl-4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4phenylindenyl) dibutylzirconium; diphenylsilanediylbis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium;

Diphenylsilanediylbis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconiumdiphenylsilanediylbis (2-methyl-4
-Naphthylindenyl) dibutylzirconium; diphenylsilanediylbis (2-ethyl-4-naphthylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (indenyl) dibutylzirconium; 1-silacyclopentane-1 1-bis (2-methylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-
Bis (2-methyl-4,5-benzoindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,5-benzoindenyl) dibutylzirconium; 1-silacyclopentane- 1- (2-methyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium; 1
-Silacyclopentane-1- (2-ethyl-4,5-benzoindenyl) -1- (2-methyl-4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1- (2-methyl- 4,5-benzoindenyl)
-1- (2-ethyl-4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1- (2-
Ethyl-4,5-benzoindenyl) -1- (2-ethyl-4-naphthylindenyl) dibutylzirconium;
1-silacyclopentane-1- (2-methylindenyl) -1- (4-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-
Methyl-1-phenylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4-phenylindenyl) dibutylzirconium;
1-silacyclopentane-1,1-bis (2-methyl-
4,6-diisopropylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis ( 2-methyl-4-naphthylindenyl) dibutylzirconium; 1-silacyclopentane-1,1-bis (2
-Ethyl-4-naphthylindenyl) dibutylzirconium; bis (cyclopentadienyl) dibutyltitanium;
Ethylene-1,2-bis (indenyl) dibutylzirconium; ethylene-1,2-bis (tetrahydroindenyl) dibutylzirconium; ethylene-1- (cyclopentadienyl) -2- (1-indenyl) dibutylzirconium; ethylene -1- (cyclopentadienyl)
-2- (2-indenyl) dibutyl zirconium; ethylene-1- (cyclopentadienyl) -2- (2-methyl-1-indenyl) dibutyl zirconium; ethylene-1,2-bis (2-methylindenyl) Dibutyl zirconium; ethylene-1,2-bis (2-ethylindenyl) dibutyl zirconium; ethylene-1,2-bis (2-methyl-4,5-benzoindenyl) dibutyl zirconium; ethylene-1,2-bis (2-ethyl-
4,5-benzoindenyl) dibutylzirconium;

Ethylene-1,2-bis (4,5-dihydro-8-methyl-7H-cyclopent [e] acenaphthylene-7-ylidene) dibutylzirconium; ethylene-1- (2-methyl-4,5-benzoin Denenyl) -2
-(2-methyl-4-phenylindenyl) dibutylzirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2-methyl-4-phenylindenyl) dibutylzirconium; ethylene -1- (2
-Methyl-4,5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium; ethylene-1- (2-ethyl-4,5-benzoindenyl) -2- (2 -Ethyl-4-naphthylindenyl) dibutylzirconium; ethylene-1- (2-methylindenyl) -2- (4-phenylindenyl) dibutylzirconium; ethylene-1,2-bis (2-methyl-4- Phenylindenyl) dibutylzirconium;
Ethylene-1,2-bis (2-ethyl-4-phenylindenyl) dibutylzirconium; ethylene-1,2-
Bis (2-methyl-4,6-diisopropylindenyl) dibutylzirconium; ethylene-1,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; ethylene-1,2-bis (2- Methyl-4-naphthylindenyl) dibutylzirconium; ethylene-1,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium; propylene-
2,2-bis (indenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (1-indenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (4-phenyl-1-indenyl) Dibutyl zirconium; propylene-2-cyclopentadienyl-2- (9-fluorenyl) dibutyl zirconium; propylene-2-cyclopentadienyl-2
-(2,7-dimethoxy-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (2,7-di-tert-butyl-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentane Dienyl-2- (2,7-dibromo-9-fluorenyl) dibutylzirconium; propylene-2-cyclopentadienyl-2- (2,7-diphenyl-9-fluorenyl) dibutylzirconium; propylene-2-
Cyclopentadienyl-2- (2,7-dimethyl-9-
Fluorenyl) dibutylzirconium; propylene-2
-(3-methylcyclopentadienyl) -2- (2,7
-Dibutyl-9-fluorenyl) dibutylzirconium; propylene-2- (3-tert-butylcyclopentadienyl) -2- (2,7-dibutyl-9-fluorenyl) dibutylzirconium; propylene-2- (3
-Trimethylsilylcyclopentadienyl) -2-
(3,6-di-tert-butyl-9-fluorenyl)
Dibutyl zirconium; propylene-2-cyclopentadienyl-2- [2,7-bis (3-buten-1-yl) -9-fluorenyl] dibutyl zirconium; propylene-2-cyclopentadienyl-2- (3 −ter
t-butyl-9-fluorenyl) dibutylzirconium; propylene-2,2-bis (tetrahydroindenyl) dibutylzirconium; propylene-2,2-bis (2-methylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4,5-benzoindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4,5-
Benzoindenyl) dibutylzirconium; propylene-2,2-bis (4,5-dihydro-8-methyl-7H
-Cyclopent [e] acenaphthylene-7-ylidene)
Dibutyl zirconium; propylene-2- (2-methyl-4,5-benzoindenyl) -2- (2-methyl-4
-Phenylindenyl) dibutylzirconium; propylene-2- (2-ethyl-4,5-benzoindenyl)
-2- (2-methyl-4-phenylindenyl) dibutylzirconium; propylene-2- (2-methyl-4,
5-benzoindenyl) -2- (2-ethyl-4-phenylindenyl) dibutylzirconium; propylene-
2- (2-ethyl-4,5-benzoindenyl) -2-
(2-ethyl-4-naphthylindenyl) dibutylzirconium; propylene-2- (2-methylindenyl)
-2- (4-phenylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4-phenylindenyl) dibutylzirconium; propylene-
2,2-bis (2-ethyl-4-phenylindenyl)
Dibutyl zirconium; propylene-2,2-bis (2
-Methyl-4,6-diisopropylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4,6-diisopropylindenyl) dibutylzirconium; propylene-2,2-bis (2-methyl-4
-Naphthylindenyl) dibutylzirconium; propylene-2,2-bis (2-ethyl-4-naphthylindenyl) dibutylzirconium.

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
However, the present invention is not limited to the following examples.

All reactions were performed under a nitrogen atmosphere. Toluene used as a solvent was sodium metal,
Distilled to anhydrous with benzophenone ketyl. Zirconocene dichloride, butyl lithium (1.6 M hexane solution), zinc chloride, zinc bromide, methylalumoxane (MAO),
The acetylene derivative was purchased from Kanto Chemical, and 2-chloro-4,5-diethyl-1,4 (Z), 7-triene was purchased from Tokyo Chemical Industry.

¹ H-NMR (400 MHz) and ¹³ C-NMR (100 MHz)
The spectrum was measured at 25 ° C. using a Bruker ARX-400. At this time, TMS was used as an internal standard using deuterated chloroform (containing 1% of TMS as an internal standard). Gas chromatography is SHIMADZU CBP1-M25-025
SHIMADZU GC-1 equipped with fused silica capillary column
4 Measured by Agas chromatograph, recording is SHIMADZU CR6A-C
hromatopac integrator was used. When the yield was determined by GC, n-dodecane was used as an internal standard. It was charged - (cyclopentadienyl eta ⁵⁾ dichlorozirconium (1.2 mmol) and THF (10 ml) in a Schlenk tube - Reference Example 1 bis (eta ⁵ cyclopentadienyl) dibutyl zirconium bis. The solution was cooled to -78 C and then n-butyllithium (2.4 mmol) was added. This solution was stirred at -78 ° C for 1 hour, and bis (η
⁵ -cyclopentadienyl) dibutylzirconium was obtained.

Embodiment 1

[0072]

Embedded image

(3aR *, 7aR *)-3a, 4,7,7a-tetrahydro-
2-phenyl-3a-methyl-5,6-diethylindene The bis (cyclopentadienyl) dibutylzirconium (Cp ₂ ZrBu ₂ ) obtained in Reference Example 1 and 2-chloro-4,5-diethyl-1, Biscyclopentadienylchloro ((3,3) obtained by reacting 4 (Z), 7-triene (199 mg, 1 mmol)
A toluene solution of methylalumoxane (MAO) (1 ml) and phenylacetylene (1 mmol) were added to a toluene solution of 4-diethyl-6-methylene-3-cyclohexene) methyl) zirconium (1 mmol). Added at ° C.
The reaction mixture was warmed to room temperature and stirred for 3 hours, then 3N
The reaction was terminated by the addition of HCl. The usual treatment was carried out, followed by column chromatography packed with silica gel to give the title compound. Colorless liquid. Isolation yield 56%. GC yield 71%.

A general reaction scheme is shown below.

[0075]

Embedded image

3: 1 mixture of isomers Trans isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.90 (t, J = 7.5 Hz,
6H), 1.12 (s, 3H), 1.19-1.27 (m, 10H), 2.92-2.99
(m, 1H), 5.87 (s, 1H), 7.17-7.44 (m, 5H); ¹³ CNMR
(CDCl ₃ , Me ₄ Si) 13.42, 13.47, 25.89, 25.98, 28.61,
34.12, 40.42, 40.44, 43.76, 49.73, 125.48, 126.73,
127.49, 127.94, 128.17, 131.98, 132.96, 135.76, 1
36.78, 139.17. Cis isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.90 (t, J = 7.5 Hz, 6
H), 1.12 (s, 3H), 5.73 (s, 1H), and other peaks overlap with the peak of the trans isomer and are not separated. ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 13.27, 16.16, 25.
76, 26.17, 26.75,32.65, 37.38, 39.27, 46.34, 49.0
5, 125.34, 126.51, 126.82, 127.03, 128.25, 130.92,
131.94, 136.50, 138.20, 141.45. HRMS Calculated C ₂₀ H
₂₆ 266.2034, experimental value 266.2034.

Embodiment 2

[0078]

Embedded image

(3aR *, 7aR *)-3a, 4, 7,7a-tetrahydro
2- (4-methoxy) phenyl-3a-methyl-5,6-diethylindene The same procedure as in Example 1 was performed. However, (4-methoxy) phenylacetylene was used instead of phenylacetylene. Colorless liquid. Isolation yield 49%. GC yield 65%.

1.6: 1 mixture trans isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.89 (t, J = 7.5 Hz,
6H), 1.11 (s, 3H), 1.18-1.27 (m, 10H), 2.41-2.50
(m, 1H), 3.79 (s, 3H), 5.74 (s, 1H), 6.82-6.86 (m,
2H), 7.25 -7.32 (m, 2H); ¹³ C NMR (CDCl ₃ , Me ₄ Si)
δ 13.42, 13.47, 25.89, 25.96, 28.73, 34.17, 3
9.27, 40.58, 43.81, 49.70, 55.26, 113.35 (2C), 125.
78, 126.61 (2C), 128.53, 131.00, 131.95, 138.53, 1
58.53. Cis isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.94 (t, J = 7.5 Hz, 6
H), 1.15 (s, 3H), 1.88-2.17 (m, 10H), 2.85-2.95
(m, 1H), 3.81 (s, 3H), 5.74 (s, 1H), 6.82-6.86 (m,
2H), 7.25-7.32 (m, 2H) ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 13.
42,13.50, 25.76, 25.99, 26.84, 32.74, 37.27, 40.5
8, 46.35, 49.01, 55.19, 113.56 (2C), 126.61 (2C), 12
7.14,131.68, 133.03, 137.76, 151.84, 158.34, HRMS
Calculated value C ₂₁ H ₂₈ 0296.2140, experimental value 296.2136.

Embodiment 3

[0082]

Embedded image

(3aR *, 7aR *)-3a, 4, 7,7a-tetrahydro-
2- (Phenylmethyl) -3a-methyl-5,6-diethylindene The procedure was the same as in Example 1. However, 3-phenyl-1-propyne was used instead of phenylacetylene. Colorless liquid. Isolation yield 52%. GC yield 72%.

A 1: 1 mixture of isomers. Trans isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.87 (t, J = 7.5 Hz,
6H), 1.02 (s, 3H), 1.75-2.10 (m, 10H), 2.35-2.40
(m, 1H), 3.24-3.30 (m, 2H), 5.03 (s, 1H), 7.13-7.2
7 (m, 5H); ¹³ C NMR (CDCl ₃ , Me ₄ Si) 13.33, 13.46, 2
5.90, 25.93, 28.90, 34.15, 37.72, 40.70, 42.19, 4
4.10, 49.29, 125.70, 128.09 (2C), 128.76 (2C), 131.
18, 135.71, 138.18, 140.11, 140.71. Cis isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.90 (t, J = 7.5 Hz, 6
H), 1.01 (s, 3H), 4.85 (s, 1H), and other peaks overlap the peak of the trans isomer and are not separated. ¹³ C NMR (CDCl ₃ , Me ₄ Si) δ 13.42, 13.56, 25.
82, 25.94, 26.91, 33.76, 33.96, 37.50, 38.62, 45.4
5, 49.79, 123.96, 125.67, 129.34 (2C), 131.94, 13
2.31, 133.18, 135.73, 140.57, 150.97.HRMS Calculated
C ₂₁ H ₂₈ 280.2191, experimental 280.2187.

Embodiment 4

[0086]

Embedded image

(3aR *, 7aR *)-3a, 4,7,7a-tetrahydro-
2- (2-phenylethyl) -3a-methyl-5,6-diethylindene The same procedure as in Example 1 was performed. However, 4-phenyl-1-butyne was used instead of phenylacetylene. Colorless liquid. Isolation yield 40%. GC yield 56%.

3: 1 mixture of isomers. Trans isomer¹ H NMR (CDCl_Three, Me_FourSi) δ 0.90 (t, J = 7.5 Hz,
6H), 0.98 (s, 3H), 1.75-2.23 (m, 12H), 2.40-2.52
(m, 1H), 2.80 (t, J = 7.4 Hz, 2H), 5.28 (s, 1H),
7.16-7.30 (m, 5H);¹³C NMR (CDCl_Three, Me_FourSi) 13.44, 1
3.48, 25.82, 25.88, 26.74, 28.99, 33.76, 34.34, 3
7.71, 38.60, 45.156, 49.91, 121.01, 125.70, 128.28
(4C), 131.88, 132.27, 142.86, 150.83. Cis isomer¹ H NMR (CDCl_Three, Me_FourSi) δ 0.94 (t, J = 7.5 Hz, 6
H), 1.00 (s, 3H), 2.70 (t, J = 7.4, 2H), 5.15 (s, 1
H), other peaks overlap with the trans isomer peak
And not separated.¹³C NMR (CDCl_Three, Me_FourSi)
 δ 13.44, 13.48, 25.91, 25.94, 26.74, 28.92, 3
2.97, 34.24, 40.71, 42.62, 44.06, 49.10, 125.61, 12
8.18 (4C), 133.20, 133.99, 141.16, 142.52.HRMS total
Arithmetic C_{twenty two}H₃₀ 294.2348, experimental value 294.2352.

Embodiment 5

[0090]

Embedded image

(3aR *, 7aR *)-3a, 4, 7,7a-tetrahydro-
2-n-hexyl-3a-methyl-5,6-diethylindene The same procedure as in Example 1 was performed. However, 1-octyne was used instead of phenylacetylene. Colorless liquid.
Isolation yield 41%. GC yield 57%.

A 2: 1 mixture of isomers. (1: 1 according to GC
Trans isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.80-0.94 (m, 9H), 1.
00 (s, 3H), 1.20-1.40 (m, 8H) 1.76-2.10 (m, 12H), 2.4
1-2.50 (m, 1H), 4.95 (s, 1H) ¹³ C NMR (CDCl ₃ , Me ₄ Si) 1
3.42 (2C), 14.13, 22.65, 25.88, 25.93, 27.68, 29.0
3 (2C), 30.99, 31.78, 34.28, 40.80, 42.44, 45.21, 4
9.05, 131.88, 133.24, 133.38, 141.99. Cis isomer ¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.80-0.90 (m, 9H), 0.9
6 (s, 1H), 1.20-1.40 (m, 8H), 1.76-2.10 (m, 12H), 2.
41-2.50 (m, 1H0, 5.17 (s, 1H). ¹³ C NMR (CDCl ₃ , Me ₄ S
i) d 13.42 (2C), 14.13, 25.80, 26.34, 26.80, 27.94,
29.03, 29.60, 31.87, 32.00, 33.72, 37.60, 38.64,
45.21, 49.69, 120.31, 131.77, 132.28, 151.80.HRMS
Calculated value C ₂₀ H ₃₄ 274.2661, experimental value 274.2687.

Reference Example 2

[0094]

Embedded image

5- (2,3-butadien-1-yl) -4-methylene-
1,2-Diethylcyclohex-1-ene colorless liquid. Isolation yield
37%. GC yield 50%.

¹ H NMR (CDCl ₃ , Me ₄ Si) δ 0.94 (t,
J = 7.5 Hz, 3H), 0.97 (t, J = 7.5 Hz, 3H), 1.86-2.
11 (m, 6H), 2.20-2.38 (m, 3H), 2.71 (bs, 2H), 4.62-
4.75 (m, 4H), 5.75 (tdd, J = 6.9, 6.9, 6.9 Hz, 1H),
¹³ C NMR (CDCl ₃ , Me ₄ Si) 13.19 (2C), 25.36, 25.54,
31.42, 36.46, 36.76, 41.13, 74.32, 88.57, 105.93,
129.93, 129.95, 149.21, 205.90; HRMS Calculated C ₁₅ H
₂₂ 202.1721, experimental value 202.1712.

[0097]

According to the present invention, a polycyclic compound having an arbitrary substituent can be easily obtained by a one-pot reaction.

Claims (4)

[Claims] 1. A method for producing a polycyclic compound represented by the following formula (I): (Wherein, R ¹ is a C ₁ -C ₄₀ hydrocarbon group which may have a substituent; a C ₁ -C ₄₀ alkoxy group which may have a substituent; A C ₆ -C ₄₀ aryloxy group; a C ₆ -C ₄₀ alkoxyaryl group which may have a substituent; an amino group; a hydroxyl group or a silyl group; and A may have a substituent. A divalent C ₄ -C ₁₀ hydrocarbon group, an oxygen atom, a sulfur atom, or a compound of the formula —N (R ⁴ ) —
(Wherein R ⁴ is a hydrogen atom or a C ₁ -C ₄₀ hydrocarbon group), and may have a substituent. A diene derivative represented by the following formula (II): (Where A has the above meaning; X is a leaving group). A step of reacting with an organometallic compound represented by the following formula (III) to obtain a reaction mixture: (Wherein M represents a metal of Groups 3 to 5 of the periodic table or a lanthanide series; L ¹ and L ² independently of each other, the same or different, represent an anionic ligand, ,
L ¹ and L ² may be crosslinked, and Z ¹ and Z ² are leaving groups. A) reacting the reaction mixture with an alkyne derivative represented by the following formula (IV) in the presence of an additive: (Wherein, R ¹ has the meaning described above). 2. The method for producing a polycyclic compound according to claim 1, wherein A is a compound represented by the following formula (Va) or a compound represented by the following formula (Vb). Embedded image (Wherein, R ² and R ³ are independently of each other and are the same or different and are a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group or a silyl group; A ¹ and A ² are each independently of each other and are the same or Differently, it is a divalent C ₁ -C ₅ hydrocarbon group which may have a substituent.) 3. M is a metal of Group 4 or 5 of the periodic table or a lanthanide series metal, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. A method for producing the polycyclic compound according to claim 1. 4. The method according to claim 3, wherein the delocalized cyclic η ⁵ -coordination system ligand is an optionally substituted cyclopentadienyl group, indenyl group, fluorenyl group or azulenyl group. A method for producing a polycyclic compound.