JP2001031687A - Synthesis of phosphorus-containing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phosphorus-containing organic compound in high yield by reaction of a specific organometallic compound with a phosphorus compound in the presence of a specific metal compound. SOLUTION: In the presence of a compound of a metal from group 4 to group 15 in the periodic table (for example, CuCl), an organometallic compound represented by formula I [R1 is a (substituted) 1-20C hydrocarbon, a (substituted) 1-20C alkoxy or the like; R2 and R3 are each H, a (substituted) 1-20C hydrocarbon or the like; M is a metal from group 3 to group 5 and lanthanide series; L1 and L2 are each an anionic ligand; A is an eliminating group] is allowed to react with a phosphorus compound of the formula: P(R4)(R5)(X) [R4 and R5 are each H, a (substituted) 1-20C hydrocarbon or the like] (for example, chlorodiphenylphosphine or the like) preferably at -80 to 300 deg.C under a pressure of 0.1-2,500 bar to give a compound of formula II [for example, (4-ethylhexa-3- en-3-yl)diphenylphosphine].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for synthesizing a phosphorus-containing organic compound, and more particularly to a method for synthesizing an alkenyl phosphine or an alkenyl phosphite.

[0002]

2. Description of the Related Art Phosphines and phosphites, particularly phosphines, are widely used as ligands of organometallic compounds, and include metals belonging to groups 3 to 15 of the periodic table. (Eg, FA Cotton and G. Wilkin).
Son, "Advanced Inorganic C
hemistry, 5th edition). An organometallic compound containing a phosphine or the like as a ligand is often used as a catalyst in organic synthesis. When such an organometallic compound is used as a catalyst, phosphines and the like often have a significant effect on the selectivity of the product,
It is desired that various phosphines can be easily obtained.

[0003] However, techniques for easily obtaining phosphorus-containing organic compounds such as phosphines have been limited. Further, alkenyl phosphines and alkenyl phosphites are expected to be capable of being subjected to various modifications since the carbon-carbon double bond is rich in reactivity.

Therefore, an object of the present invention is to provide a method for synthesizing a phosphorus-containing organic compound by a novel reaction using an organometallic compound.

[0005]

According to the present invention, there is provided a method for synthesizing a phosphorus-containing organic compound represented by the following formula (I):

[0006]

Embedded image

(Where R¹May have a substituent
Yes, C₁~ C₂₀May have a hydrocarbon group or a substituent
Yes, C₁~ C₂₀May have an alkoxy group or a substituent
Yes, C₆~ C ₂₀Aryloxy group, amine group, hydroxyl group or
Is of the formula -Si (R⁶) (R⁷) (R⁸) Group (formula
Medium, R⁶, R⁷And R⁸Are independent of each other,
One or different, C₁~ C₂₀Alkyl group, C₆~ C₂₀Ants
Alkyl group, C₁~ C₂₀Alkoxy group, C₆~ C₂₀A
It is a reel alkyloxy group. ) R^TwoAnd R^ThreeAre independent of each other and are the same or different
And a hydrogen atom, which may have a substituent, C₁~
C₂₀A hydrocarbon group, which may have a substituent,₁~ C
₂₀An alkoxy group, optionally having substituent (s), C₆~ C
₂₀Aryloxy group, amine group, hydroxyl group or formula -Si
(R⁶) (R⁷) (R⁸A group represented by the formula:⁶, R⁷
And R⁸Are independent of each other and are the same or different
And C₁~ C₂₀Alkyl group, C₆~ C₂₀Arylalkyl
Group, C₁~ C₂₀Alkoxy group, C₆~ C_{Two 0}Arylalkyl
It is a ruoxy group. ) Where R¹And R^TwoIs
Each may be interrupted by an oxygen atom,
May be, C_Four~ C₂₀Form a saturated or unsaturated ring
May be; R^FourAnd R^FiveAre independent of each other,
One or different may have a hydrogen atom or a substituent
Yes, C₁~ C₂₀May have a hydrocarbon group or a substituent
Yes, C₁~ C₂₀Having an alkoxy group or a substituent
May be, C₆~ C₂₀An aryloxy group,
Then R^FourAnd R^FiveMay be cross-linked to each other. ) In the presence of a metal compound of Groups 4 to 15 of the periodic table, the following formula (I)
An organometallic compound represented by I),

[0008]

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Wherein R ¹ , R ² and R ³ have the above-mentioned meanings, M represents a metal belonging to Group 3 to Group 5 of the periodic table or a lanthanide series metal, and L ¹ and L ² Are independent of each other and are the same or different and represent anionic ligands, provided that L ¹
And L ² may be cross-linked.

A is a leaving group. ) The following formula (III)
Reacting with the phosphorus compound shown in

[0011]

Embedded image P (R ⁴ ) (R ⁵ ) (X) (III) wherein R ⁴ and R ⁵ have the above-mentioned meanings, and X is a leaving group. A method for synthesizing a phosphorus-containing organic compound.

In the present invention, the metal compound is preferably a metal salt. Further, the metal compound is
More preferably, V, Cr, Mn, Fe, Co, Ni, Cu or Zn is included.

Preferably, M is a metal belonging to Group 4 of the periodic table or a lanthanide series, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. The delocalized cyclic eta ⁵ - coordination type ligand may be substituted, cyclopentadienyl group, indenyl group, more preferably a fluorenyl group or an azulenyl group.

In the present invention, R ¹ , R ² and R ³ are each independently of one another and are the same or different and each may be a C ₁ -C ₂₀ hydrocarbon group or a substituent. It is preferably a C ₁ -C ₂₀ alkoxy group which may have, or a C ₆ -C ₂₀ aryloxy group which may have a substituent.

Further, R ¹ and R ² are each independently of each other, the same or different, and may have a C ₁ -C ₁₀ alkyl group which may have a substituent or a substituent. Good C ₅ -C ₁₄ aryl groups or
It is further preferred that the compound forms a C ₄ -C ₂₀ saturated or unsaturated ring which may be interrupted by an oxygen atom or may have a substituent.

Further, R ³ has a C ₁ -C ₁₀ alkyl group which may have a substituent, a C ₃ -C ₂₀ allyl group which may have a substituent, and a substituent. May be
C ₆ -C ₂₀ arylmethyl group, or may have a substituent group, preferably a (C ₃ -C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl group.

R ⁴ and R ⁵ are each independently of the other
The same or different, optionally substituted, C ₁
To C ₂₀ hydrocarbon group, which may have a substituent, a C _{1 to} C ₂₀ alkyl group, which may have a substituent, a C _{4 to} C ₂₀ cycloalkyl group, or And a C ₆ -C ₁₈ aryl group which may have a substituent.

[0018]

DETAILED DESCRIPTION OF THE INVENTION In one aspect of the present invention, there is provided a method for synthesizing a phosphorus-containing organic compound as shown in the following scheme.

[0019]

Embedded image

Where R¹, R^Two, R^Three, R^Four, R^Five, M,
L¹And L^TwoHas the above-mentioned meaning. A represents a leaving group
You. In one aspect of the present invention, the organic gold represented by the above formula (II)
R of the genus compound¹Note that is not a hydrogen atom.
R of the organometallic compound represented by the above formula (II) ¹Is hydrogen
In the case where it is not an atom, the specified metal compound
If not, the organometallic compound represented by the above formula (II)
The compound has the formula P (R^Four) (R^Five) (X) (wherein R^Four, R^FivePassing
And X have the above meaning. ) Phosphorus compound
Alkenylphosphine
No phosphorus-containing organic compounds such as quinone are formed.

On the other hand, in the present invention, by coexisting a predetermined metal compound, even when R ^{1 of the} organometallic compound represented by the above formula (II) is not a hydrogen atom, the formula P (R ^{4) (R 5) (X} ) ( wherein, R ^4, R ⁵ and X
Has the above meaning. ) To produce a phosphorus-containing organic compound such as alkenylphosphine.

Hereinafter, one embodiment of the present invention will be described in more detail. In the present invention, the phosphorus-containing organic compound represented by the above formula (I) is synthesized. R ¹ may have a substituent, may have a C _{1 to} C ₂₀ hydrocarbon group, may have a substituent, may have a C _{1 to} C ₂₀ alkoxy group, may have a substituent. , A C ₆ -C ₂₀ aryloxy group, an amine group, a hydroxyl group or a group represented by the formula —Si (R ⁶ ) (R ⁷ ) (R ⁸ ), wherein R ⁶ , R ⁷ and R ⁸ are Independently, identically or differently, they are a C ₁ -C ₂₀ alkyl group, a C ₆ -C ₂₀ arylalkyl group, a C ₁ -C ₂₀ alkoxy group, and a C ₆ -C ₂₀ arylalkyloxy group.

R^TwoAnd R^ThreeAre independent of each other,
Same or different, even if it has a hydrogen atom or a substituent
Good, C₁~ C₂₀May have a hydrocarbon group or a substituent
Yes, C₁~ C₂₀May have an alkoxy group or a substituent
Yes, C₆~ C₂₀Aryloxy group, amine group, hydroxyl group or
Is of the formula -Si (R⁶) (R⁷) (R⁸) Group (formula
Medium, R⁶, R⁷And R⁸Are independent of each other,
One or different, C₁~ C₂₀Alkyl group, C₆~ C₂₀Ants
Alkyl group, C₁~ C₂₀Alkoxy group, C₆~ C_{Two 0}A
It is a reel alkyloxy group. ).

R ¹ , R ² and R ³ are each independently of one another and are the same or different and each may have a C ₁ -C ₂₀ hydrocarbon group or a substituent; And a C ₁ -C ₂₀ alkoxy group or a C ₆ -C ₂₀ aryloxy group which may have a substituent.

R ¹ and R ² are each independently of the other
Same or different, C _1- which may have a substituent
A C ₁₀ alkyl group or a C ₅ -C ₁₄ aryl group which may have a substituent, or may be mutually interrupted by an oxygen atom, and may have a substituent , C ₄ -C ₂₀ may form a saturated or unsaturated ring.

In this specification, C₁~ C₂₀The hydrocarbon group is
It may be saturated or unsaturated, acyclic,
Or an unsaturated cyclic group. C₁~ C₂₀Hydrocarbon
When the radical is acyclic, it may be linear or branched.
Is also good. C₁~ C₂₀Hydrocarbon groups include C₁~ C₂₀Alkyl
Group, C_Two~ C₂₀Alkenyl group, C_Two~ C₂₀Alkynyl group,
C_Three~ C₂₀Allyl group, C_Four~ C₂₀Alkyldienyl group, C
_Four~ C₂₀Polyenyl group, C₆~ C₁₈Aryl group, C₆~ C
₂₀Alkylaryl group, C₆~ C₂₀Arylalkyl
Group, C_Four~ C₂₀Cycloalkyl group, C_Four~ C₂₀Cycloal
Kenyl group, (C _Three~ C_TenCycloalkyl) C₁~ C_TenAl
And a kill group.

C₁~ C₂₀Alkyl group, C_Two~ C₂₀Alkene
Group, C_Two~ C₂₀Alkynyl group, C_Three~ C₂₀Allyl group, C
_Four~ C₂₀An alkyldienyl group and C_Four~ C₂₀Polyeni
The radicals are each C₁~ C_TenAlkyl group, C_Two~ C_TenA
Lucenyl group, C_Two~ C_TenAlkynyl group, C_Three~ C_TenAllyl
Group, C_Four~ C_TenAn alkyldienyl group and C_Four~ C_{1 0}Po
It is preferably a phenyl group.

C ₆ -C ₁₈ aryl groups, C ₆ -C ₂₀ alkylaryl groups, C ₆ -C ₂₀ arylalkyl groups, C ₄ -C ₂₀
Cycloalkyl group, and, C ₄ -C ₂₀ cycloalkenyl group, each, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₂ alkylaryl group, C ₆ -C ₁₂ arylalkyl group, C ₄ ~
C ₁₀ cycloalkyl group, and, C ₄ -C ₁₀ cycloalkenyl group.

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 the present invention include, but are not limited to, phenoxy, naphthoxy, phenylphenoxy, 4-methylphenoxy, and the like.

Examples of aryloxy groups useful in the practice of this invention include, but are not limited to, phenyloxy, 2-tolyloxy, 3-tolyloxy, 4-tolyloxy, naphthyloxy, biphenyloxy, 4-phenoxyphenyl Oxy, 4-fluorophenyloxy,
3-carbomethoxyphenyloxy, 4-carbomethoxyphenyloxy and the like.

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

The group represented by the formula -Si (R ⁶ ) (R ⁷ ) (R ⁸ ) includes, but is not limited to, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, Examples include triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, methylmethoxyphenyl and the like.

The C ₁ -C ₂₀ hydrocarbon group, C ₁ -C ₂₀ alkoxy group and C ₆ -C ₂₀ aryloxy group may have a substituent introduced therein. Examples of the substituent include halogen. Examples include an atom, a hydroxyl group, and an amino group.

However, R ¹ and R ² are the same or different and may be mutually interrupted by an oxygen atom and may have a substituent, and may be a C ₄ -C ₂₀ saturated or unsaturated. A ring may be formed. The unsaturated ring may be an aromatic ring such as a benzene ring.

The ring formed by these substituents is a four-membered ring
It is preferably a 16-membered ring, and more preferably a 4- to 12-membered ring. This ring may be an aromatic ring or an aliphatic ring. This ring contains C ₁ -C
₂₀ hydrocarbon groups, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₂₀ aryloxy groups, amine groups, hydroxyl groups or formula —Si (R ⁶ )
(R ⁷ ) a group represented by (R ⁸ ) wherein R ⁶ , R ⁷ and R ⁸
Are each independently of one another, identical or different, C ₁
-C ₂₀ alkyl group, C ₆ -C ₂₀ arylalkyl group, C ₁
-C ₂₀ alkoxy group, a C ₆ -C ₂₀ arylalkyl group. ) May be introduced.

R ³ represents an optionally substituted C _1-
C ₁₀ alkyl group, which may have a substituent, C ₃ -C
₂₀ allyl group, which may have a substituent, C ₆ -C ₂₀ arylmethyl group, or may have a substituent,
(C ₃ -C ₁₀ cycloalkyl) It is preferably a C ₁ -C ₁₀ alkyl group.

Examples of the C ₆ -C ₂₀ arylmethyl group include a benzyl group and a naphthalenylmethyl group. (C ₃ -C ₁₀ cycloalkyl) Examples of the C ₁ -C ₁₀ alkyl group include a cyclopropenylmethyl group and a cyclopropenylethyl group. The (C ₃ -C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl group is preferably a (C ₃ -C ₁₀ cycloalkyl) C ₁ -C ₆ alkyl group, or a (C ₃ -C ₆ cycloalkyl) ) C ₁ -C ₁₀
It is preferably an alkyl group, more preferably a (C ₃ -C ₆ cycloalkyl) C ₁ -C ₆ alkyl group.

R ⁴ and R ⁵ are each independently of the other
The same or different, a hydrogen atom, a C ₁ -C ₂₀ hydrocarbon group which may have a substituent, a C ₁ -C ₂₀ alkoxy group which may have a substituent, or a substituent A C ₆ -C ₂₀ aryloxy group which may be present. A description of each of these substituents, which may be R ⁴ and R ⁵ , is
The same as the substituent which may be R ¹ , R ² and R ³ .

R ⁴ and R ⁵ are each independently of the other
The same or different, optionally substituted, C ₁
-C ₂₀ is preferably a hydrocarbon group, C ₁ -C ₂₀ alkyl group, C ₄ -C ₂₀ cycloalkyl group, or C ₆ -C ₁₈
It is more preferably an aryl group, and even more preferably a C ₁ -C ₆ alkyl group, a C ₄ -C ₁₀ cycloalkyl group or a C ₆ -C ₁₀ aryl group.

R ⁴ and R ⁵ may be cross-linked to each other. For example, when R ⁴ and R ⁵ are both naphthalene rings, the two naphthalene rings may be directly bonded or may be cross-linked with a lower alkylene group such as a methylene group.

In the present invention, an organometallic compound represented by the above formula (II) is used. 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, and more preferably a metal belonging to Group 4 of the periodic table, that is, titanium, zirconium and hafnium.

L ¹ and L ² are independent of each other and are the same or different and represent an anionic ligand. The anionic ligand is non-localized cyclic eta ⁵ - it is preferred coordination type ligand, 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. This substituted cyclopentadienyl group is, for example, methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclo. Pentadienyl, di-t
-Butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, benzoindenyl, fluorenyl, benzofur An oleenyl 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 element 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.

The 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 formula (II) is
Also included are compounds having more than one metallocene moiety. Such compounds are known as polynuclear metallocenes. The polynuclear metallocene may have any substitution mode and any bridged form. The independent metallocene moieties of the polynuclear metallocene may each be the same or different. Examples of the polynuclear metallocene include, for example, EP-
A-632063, JP-A-4-80214, JP-A-4-20214
-85310, EP-A-654476.

A is a leaving group. Examples of the leaving group include a halogen atom such as F, Cl, Br, and I;
Toluenesulfonyl group, trifluoromethane sulfonate (triflate), C ₁ -C ₂₀ alkoxy group (preferably a C ₁ -C ₁₀ alkoxy groups, more preferably, C ₁ -C ₆ alkoxy group), C ₆ ~ And a C ₂₀ aryloxy group and a tri-lower alkylsilyloxy group. As the leaving group, Cl, Br, a C ₁ -C ₂₀ alkoxy group, and a tri-lower alkylsilyloxy group are preferable. Alternatively, it is a group in which a proton has been dissociated from the above weak acid. For example, when the weak acid is water, it is a hydroxyl group.

According to one aspect of the present invention, an organometallic compound represented by the above formula (II) and a compound of the formula P (R ⁴ ) (R ⁵ ) (X) in the presence of a metal compound belonging to Groups 4 to 15 of the periodic table. (Where R
⁴ , R ⁵ and X have the same meaning as described above).

X is a leaving group. Examples of the leaving group include a halogen atom such as F, Cl, Br, and I;
Examples thereof include a toluenesulfonyl group and trifluoromethanesulfonic acid ester (triflate). As the leaving group, Cl and Br are preferable.

As the phosphorus compound (III), for example,
Halogenodiphenylphosphine such as chlorodiphenylphosphine, halogeno lower alkylphenylphosphine such as halogenomethylphenylphosphine, and halogenodi lower alkylphosphine such as chloromethylisopropylphosphine are used.

Typically, a phosphorus compound (III) and a metal compound are added to a solution of the organometallic compound represented by the above formula (II). The order of adding the phosphorus compound (III) and the metal compound is not limited. Phosphorus compound (II
I) and the metal compound may be added at the same time, the metal compound may be added after the phosphorus compound (III) is added, or the phosphorus compound (II) may be added after the metal compound is added.
I) may be added.

The metal compound is preferably a metal salt, and when the metal compound is V, Cr, Mn, Fe, Co, N
More preferably, i, Cu or Zn, for example,
Even more preferably, it contains V, Cr, Mn, Cu or Zn, particularly preferably it contains Cu. For example, V,
Salts of inorganic acids such as hydrochloric acid and sulfuric acid for Cr, Mn, Fe, Co, Ni, Cu or Zn can be used. In particular, CuCl is preferred and used.

The reaction may be carried out in the presence of a stabilizer for stabilizing the metal compound in a solvent. In particular, when the metal compound is a metal salt and the solvent is an organic solvent, the stabilizer stabilizes the metal salt in the organic solvent.
Examples of the stabilizer include dimethylpropylene urea, hexamethylphosphamide and the like.

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, a solvent capable of dissolving the organometallic compound represented by the above formula (II) is preferable. As the solvent, an aliphatic or aromatic organic solvent is used,
Preferably, a polar solvent is used. Ether solvents,
For example, tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide; and sulfoxides such as dimethylsulfoxide are used.

The organometallic compound represented by the above formula (II) need not be isolated. The organometallic compound of the above formula (II) present in the solution is further added to the formula (III)
And a predetermined metal compound may be added.

The organometallic compound represented by the above formula (II) can be obtained by a known method. For example, T.Takaha
shi et al. Chem. Soc. Chem. Comm
un. 1993, 1042; Takahas
hi et al. Tetrahedron 199
5, 51, 4519.

The organometallic compound represented by the above formula (II) can be obtained, for example, by reacting a metallacyclopentene represented by the following formula (V) with a weak proton-donating acid. The proton-donating weak acid is composed of metal (M) of metallacyclopentene (V) represented by the following formula (V) and s
p ³ can be selectively cleaved the bond between the carbon atoms,
Does not break the bond between the metal (M) and the sp ² carbon.

[0062]

Embedded image

Alternatively, the metallacyclopentene represented by the above formula (V) is reacted with an allyltrialkylsilane such as allyltrimethylsilane and an arylmethyltrialkylsilane such as benzyltrimethylsilane to form a compound represented by the formula (II) An organometallic compound can be obtained.

The weak acid is preferably water, a lower alcohol, a phenol or an acid addition salt of an amine. Preferably, the weak acid has a pKa that is equal to or close to that of water, methanol, aniline hydrochloride, tributylammonium chloride.

As used herein, unless otherwise specified.
"Lower" refers to containing 1 to 6 carbons. The lower alcohol refers to a linear or branched alcohol having 1 to 6 carbon atoms, and includes, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol and the like.

As used herein, the term “phenols” refers to a compound in which a hydroxy group is directly bonded to an aromatic ring.
Substituents other than the hydroxy group are further directly on the aromatic ring,
They may be combined. Further, it is preferable that a hydroxy group is directly bonded to an aromatic ring which is a carbon ring. Examples of the phenols include phenol (C ₆ H ₅ OH); lower alkoxycarbonyl phenols such as methyl salicylate; lower alkyl phenols such as methyl phenol;
Halogeno lower alkylphenols such as -bromo-4-methylphenol; nitrophenol; benzenetriol, quinolinol and the like.

The acid addition salt of an amine may be an acid addition salt of an aliphatic amine such as triethylamine or ethylenediamine, or an acid addition salt of an arylamine such as aniline. The acid may be an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as trifluoroacetic acid.

Preferably, a weak protic acid is added to the solution of metallacyclopentene represented by the above formula (V). The reaction is preferably carried out in a temperature range of -120 ° C to 50 ° C, particularly preferably in a temperature range of -120 ° C to 0 ° C. The pressure is, for example, from 0.1 bar to 25
In the range of 00 bar, preferably 0.5 bar to 1 bar
It is in the range of 0 bar.

The method for synthesizing the metallacyclopentene represented by the above formula (V) is described in, for example, T.W. Takahashi
et al. J. Org. Chem. 1995,6
0,4444. In this document, bis (η ⁵ -cyclopentadienyl) dichlorozirconium is used as a starting material, but the following metallocene may be used.

Bis (indenyl) dichlorozirconium; bis (fluorenyl) dichlorozirconium; (indenyl) (fluorenyl) dichlorozirconium; bis (cyclopentadienyl) dichlorotitanium; (dimethylsilanediyl) bis (indenyl) dichlorozirconium; (Silanediyl) bis (tetrahydroindenyl) dichlorozirconium; (dimethylsilanediyl) (indenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-methylindenyl) dichlorozirconium; (dimethylsilanediyl) bis (2-
(Ethylindenyl) dichlorozirconium; (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-4,6-
Diisopropylindenyl) dichlorozirconium.

Alternatively, the following metallocene may be used.
No. Bis (cyclopentadienyl) dibutyl zirconium
Bis (indenyl) dibutylzirconium; bis
(Fluorenyl) dibutyl zirconium; (indeni
Le) (fluorenyl) dibutyl zirconium;
Tyl-5-naphthylindenyl) (2,7-di-ter
(t-butylfluorenyl) dibutylzirconium; (3
-Methyl-5-naphthylindenyl) (3,4,7-to
(Limethoxyfluorenyl) dibutylzirconium;
N-methylcyclopentadienyl) (tetrahydroin
(Denyl) dibutylzirconium; (cyclopentadienyl)
) (1-octen-8-ylcyclopentadienyl)
Dibutyl zirconium; (indenyl) (1-butene-
4-ylcyclopentadienyl) dibutylzirconium
[1,3-bis (trimethylsilyl) cyclopenta
Dienyl] (3,4-benzofluorenyl) dibutyldi
Ruconium; bis (cyclopentadienyl) dibutylthio
Tan; dimethylsilanediylbis (indenyl) dibutyl
Ruzirconium; dimethylsilanediylbis (tetrahi
Droindenyl) dibutylzirconium; dimethylsila
Ndiyl (cyclopentadienyl) (indenyl) dib
Tyl zirconium; dimethylsilanediylbis (2-meth
Tylindenyl) dibutylzirconium; dimethylsila
Diylbis (2-ethylindenyl) dibutylzirco
And dimethylsilanediylbis (2-methyl-4,
5-benzoindenyl) dibutylzirconium; dimethyl
Lusilanediylbis (2-ethyl-4,5-benzoin
Denenyl) dibutylzirconium; dimethylsilanediyl
Bis (4,5-dihydro-8-methyl-7H-cyclope
[E] acenaphthylene-7-ylidene) dibutyldi
Ruconium; dimethylsilanediyl (2-methyl-4,
5-benzoindenyl) (2-methyl-4-phenyli
Ndenyl) dibutylzirconium; dimethylsilanediyl
(2-ethyl-4,5-benzoindenyl) (2-meth
Tyl-4-phenylindenyl) dibutylzirconium
Dimethylsilanediyl (2-methyl-4,5-ben
Zoindenyl) (2-ethyl-4-phenylindenyl
B) dibutyl zirconium; dimethylsilanediyl (2
-Ethylindenyl) (2-ethyl-4-phenylnaph
Chill) dibutyl zirconium; dimethylsilanediyl
(2-methylindenyl) (4-phenylindenyl)
Dibutyl zirconium; dimethylsilanediylbis (2
-Methyl-4-phenylindenyl) dibutylzirconi
Dimethylsilanediylbis (2-ethyl-4-f
Enylindenyl) dibutylzirconium;
Landiylbis (2-methyl-4,6-diisopropyl
Indenyl) dibutylzirconium; dimethylsilanedi
Irbis (2-ethyl-4,6-diisopropylindene
Nyl) dibutylzirconium; dimethylsilanediylbi
(2-methyl-4-naphthylindenyl) dibutyldi
Ruconium; dimethylsilanediylbis (2-ethyl-
4-naphthylindenyl) dibutylzirconium; methyl
Luphenylsilanediylbis (indenyl) dibutyldi
Ruconium; methylphenylsilanediyl (cyclopen
Tadienyl) (indenyl) dibutylzirconium;
Tylphenylsilanediylbis (tetrahydroindeni
B) dibutyl zirconium; methylphenylsilanediyl
Rubis (2-methylindenyl) dibutylzirconium
Methyl; methylphenylsilanediylbis (2-ethylin
Denenyl) dibutylzirconium; methylphenylsilane
Diylbis (2-methyl-4,5-benzoindenyl)
Dibutyl zirconium; methylphenylsilanediylbi
(2-ethyl-4,5-benzoindenyl) dibutyl
Zirconium; methylphenylsilanediylbis (4,
5-dihydro-8-methyl-7H-cyclopent [e]
Acenaphthylene-7-ylidene) dibutylzirconium
Methyl; methylphenylsilanediyl (2-methyl-4,5
-Benzoindenyl) (2-methyl-4-phenylin
Denenyl) dibutylzirconium; methylphenylsilane
Diyl (2-ethylindenyl) (2-methyl-4-f
Enylindenyl) dibutylzirconium; methylphen
Nylsilanediyl (2-methyl-4,5-benzoinde
Nyl) (2-ethyl-4-phenylindenyl) dibutyi
Ruzirconium; methylphenylsilanediyl (2-E
Tyl-4,5-benzoindenyl) (2-ethyl-yne
Denenyl) dibutylzirconium; methylphenylsilane
Diyl (2-methylindenyl) (4-phenylindenyl
B) dibutyl zirconium; methylphenylsilanediyl
Rubis (2-methyl-4phenylindenyl) dibutyl
Zirconium; methylphenylsilanediylbisdibutyl
Ruzirconium; methylphenylsilanediylbis (2
-Methyl-4,6-diisopropylindenyl) dibuty
Ruzirconium; methylphenylsilanediylbis (2
-Ethyl-4,6-diisopropylindenyl) dibutyl
Ruzirconium; methylphenylsilanediylbis (4
-Naphthylindenyl) dibutylzirconium; methyl
Phenylsilanediylbis (2-ethyl-4-naphthyl
Indenyl) dibutylzirconium; diphenylsilane
Diylbis (indenyl) dibutylzirconium; diph
Phenylsilanediylbis (2-methylindenyl) dib
Tyl zirconium; diphenylsilanediylbis (2-
Ethylindenyl) dibutylzirconium; diphenyl
Silanediyl (cyclopentadienyl) (indenyl)
Dibutyl zirconium; diphenylsilanediylbis
(2-methyl-4,5-benzoindenyl) dibutyldi
Ruconium; diphenylsilanediylbis (2-ethyl
-4,5-benzoindenyl) dibutylzirconium;
Diphenylsilanediyl (2-methyl-4,5-benzo
Indenyl) (2-methyl-4phenylindenyl) di
Butyl zirconium; diphenylsilanediyl (2-E
Tyl-4,5-benzoindenyl) (2-methyl-4f
Phenylindenyl) dibutylzirconium; diphenyl
Silanediyl (2-methyl-4,5-benzoindenyl)
L) (2-ethyl-4phenylindenyl) dibutyldi
Ruconium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-ethyl-4naphthyl
Indenyl) dibutylzirconium; diphenylsilane
Diyl (2-methylindenyl) (4-phenylindenyl
B) dibutyl zirconium; diphenylsilanediylbi
(2-methyl-4phenylindenyl) dibutylzyl
Conium; diphenylsilanediylbis (2-ethyl-
4phenylindenyl) dibutylzirconium; dife
Nylsilanediylbis (2-methyl-4,6-diisoprop
Ropylindenyl) dibutylzirconium; diphenyl
Silanediylbi; s (2-ethyl-4,6-diisopro
Pyrindenyl) dibutylzirconium diphenylsila
Ndiylbis (2-methyl-4-naphthylindenyl)
Dibutyl zirconium; diphenylsilanediylbis
(2-ethyl-4-naphthylindenyl) dibutylzyl
Conium; 1-silacyclopentane-1,1-bis (I
Ndenyl) dibutylzirconium; 1-silacyclopen
Tan-1,1-bis (2-methylindenyl) dibutyl
Zirconium; 1-silacyclopentane-1,1-bis
(2-ethylindenyl) dibutylzirconium; 1-
Silacyclopentane-1,1-bis (2-methyl-4,
5-benzoindenyl) dibutylzirconium;
Lacyclopentane-1,1-bis (2-ethyl-4,5
-Benzoindenyl) dibutylzirconium; 1-sila
Cyclopentane-1- (2-methyl-4,5-benzoi
Ndenyl) -1- (2-methyl-4-phenylindenyl)
1) dibutyl zirconium; 1-silacyclopentane
1- (2-ethyl-4,5-benzoindenyl) -1-
(2-methyl-4-phenylindenyl) dibutylzyl
Conium; 1-silacyclopentane-1- (2-methyl
-4,5-benzoindenyl) -1- (2-ethyl-4
-Phenylindenyl) dibutylzirconium;
Lacyclopentane-1- (2-ethyl-4,5-benzo
Indenyl) -1- (2-ethyl-4-naphthylinde
Nyl) dibutylzirconium; 1-silacyclopentane
-1- (2-methylindenyl) -1- (4-phenyl
Indenyl) dibutylzirconium; 1-silacyclope
1,1-bis (2-methyl-4-phenylin
Denenyl) dibutylzirconium; 1-silacyclopenta
1,1-bis (2-ethyl-4-phenylindenyl)
1) dibutyl zirconium; 1-silacyclopentane
1,1-bis (2-methyl-4,6-diisopropyli
Ndenyl) dibutylzirconium; 1-silacyclopen
Tan-1,1-bis (2-ethyl-4,6-diisopro
Pyrindenyl) dibutylzirconium; 1-silashic
Lopentane-1,1-bis (2-methyl-4-naphthyl
Indenyl) dibutylzirconium; 1-silacyclope
1,1-bis (2-ethyl-4-naphthylin
Denenyl) dibutyl zirconium; bis (cyclopentadi
Enyl) dibutyltitanium; ethylene-1,2-bis (a
Ndenyl) dibutylzirconium; ethylene-1,2-
Bis (tetrahydroindenyl) dibutyl zirconium
Ethylene; 1- (cyclopentadienyl) -2-
(1-indenyl) dibutylzirconium; ethylene-
1- (cyclopentadienyl) -2- (2-indenyl
B) dibutyl zirconium; ethylene-1- (cyclope
Antadienyl) -2- (2-methyl-1-indenyl)
Dibutyl zirconium; ethylene-1,2-bis (2-
Methylindenyl) dibutylzirconium; ethylene-
1,2-bis (2-ethylindenyl) dibutyl zircon
Ium; ethylene-1,2-bis (2-methyl-4,5
-Benzoindenyl) dibutylzirconium; ethylene
-1,2-bis (2-ethyl-4,5-benzoindenyl)
B) dibutyl zirconium; ethylene-1,2-bis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutylzirco
Ium; ethylene-1- (2-methyl-4,5-benzo)
Indenyl) -2- (2-methyl-4-phenylindene
Nyl) dibutylzirconium; ethylene-1- (2-e
Tyl-4,5-benzoindenyl) -2- (2-methyl
-4-phenylindenyl) dibutylzirconium; d.
Tylene-1- (2-methyl-4,5-benzoindeni)
) -2- (2-ethyl-4-phenylindenyl) di
Butyl zirconium; ethylene-1- (2-ethyl-
4,5-benzoindenyl) -2- (2-ethyl-4-
Naphthylindenyl) dibutylzirconium; ethylene
-1- (2-methylindenyl) -2- (4-phenyl
Indenyl) dibutylzirconium; ethylene-1,2
-Bis (2-methyl-4-phenylindenyl) dibutyl
Ruzirconium; ethylene-1,2-bis (2-ethyl
-4-phenylindenyl) dibutylzirconium; d.
Tylene-1,2-bis (2-methyl-4,6-diisoprop
Ropylindenyl) dibutylzirconium; ethylene-
1,2-bis (2-ethyl-4,6-diisopropyli
Ndenyl) dibutylzirconium; ethylene-1,2-
Bis (2-methyl-4-naphthylindenyl) dibutyl
Zirconium; ethylene-1,2-bis (2-ethyl-
4-naphthylindenyl) dibutylzirconium; pro
Pyrene-2,2-bis (indenyl) dibutylzirconi
Propylene-2-cyclopentadienyl-2-
(1-indenyl) dibutyl zirconium; propylene
-2-cyclopentadienyl-2- (4-phenyl-1
-Indenyl) dibutylzirconium; propylene-2
-Cyclopentadienyl-2- (9-fluorenyl) di
Butyl zirconium; propylene-2-cyclopentadi
Enyl-2- (2,7-dimethoxy-9-fluorenyl
L) dibutyl zirconium; propylene-2-cyclope
Antadenyl-2- (2,7-di-tert-butyl-
9-fluorenyl) dibutylzirconium; propylene
-2-cyclopentadienyl-2- (2,7-dibromo
-9-fluorenyl) dibutylzirconium; propyle
2-cyclopentadienyl-2- (2,7-dife
Nil-9-fluorenyl) dibutylzirconium;
Pyrene-2-cyclopentadienyl-2- (2,7-di
Methyl-9-fluorenyl) dibutylzirconium;
Ropylene-2- (3-methylcyclopentadienyl)-
2- (2,7-dibutyl-9-fluorenyl) dibutyl
Zirconium; propylene-2- (3-tert-butyl)
Rucyclopentadienyl) -2- (2,7-dibutyl-
9-fluorenyl) dibutylzirconium; propylene
-2- (3-trimethylsilylcyclopentadienyl)
-2- (3,6-di-tert-butyl-9-fluoro)
Nyl) dibutylzirconium; propylene-2-cyclo
Pentadienyl-2- [2,7-bis (3-butene-1
-Yl) -9-fluorenyl] dibutylzirconium;
Propylene-2-cyclopentadienyl-2- (3-t
tert-butyl-9-fluorenyl) dibutylzirconi
Propylene-2,2-bis (tetrahydroindene
Nyl) dibutylzirconium; propylene-2,2-bi
(2-methylindenyl) dibutyl zirconium;
Ropylene-2,2-bis (2-ethylindenyl) dib
Tyl zirconium; propylene-2,2-bis (2-meth
Tyl-4,5-benzoindenyl) dibutylzirconium
Propylene-2,2-bis (2-ethyl-4,5-
Benzoindenyl) dibutyl zirconium; 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; propyl
Len-2- (2-ethyl-4,5-benzoindenyl)
-2- (2-methyl-4-phenylindenyl) dibuty
Ruzirconium; propylene-2- (2-methyl-4,
5-benzoindenyl) -2- (2-ethyl-4-fe
Nylindenyl) dibutylzirconium; propylene-
2- (2-ethyl-4,5-benzoindenyl) -2-
(2-ethyl-4-naphthylindenyl) dibutylzyl
Conium; propylene-2- (2-methylindenyl)
-2- (4-phenylindenyl) dibutylzirconium
Propylene-2,2-bis (2-methyl-4-fe
Nylindenyl) dibutylzirconium; propylene-
2,2-bis (2-ethyl-4-phenylindenyl)
Dibutyl zirconium; propylene-2,2-bis (2
-Methyl-4,6-diisopropylindenyl) dibuty
Ruzirconium; propylene-2,2-bis (2-ethyl
-4,6-diisopropylindenyl) dibutylzyl
Conium; propylene-2,2-bis (2-methyl-4
-Naphthylindenyl) dibutylzirconium;
Len-2,2-bis (2-ethyl-4-naphthylindene
Nyl) dibutylzirconium; 1,6-bis [methylsi
Rilbis (2-methyl-4-phenylindenyl) dib
Tyl zirconium] hexane; 1,6-bis [methylsi
Lilbis (2-methyl-4,5-benzoindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-ethyl-4-phenylindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-methyl-4-naphthylindenyl) di
Butylzirconium] hexane; 1,6-bis [methyl
Silylbis (2-methyl-4,6-diisopropylin
Denenyl) dibutylzirconium] hexane; 1,6-bi
[Methylsilyl (2-methyl-4phenylindenyl)
Le) (4,5-benzoindenyl) dibutyl zirconium
Hexane]; 1- [methylsilylbis (tetrahydro
Indenyl) dibutylzirconium] -6- [ethyls
Tanyl (cyclopentadienyl) (fluorenyl) dib
Tyl zirconium] hexane; 1,6-disila-1,
1,6,6-tetramethyl-1,6-bis [methylsilyl
Rubis (2-methyl-4phenylindenyl) dibutyl
Zirconium] hexane; 1,4-disila 1,4-bis
[Methylsilylbis (2-methyl-4phenylindenyl)
L) dibutylzirconium] cyclohexane; [1,4
-Bis (1-indenyl) -1,1,4,4-tetrame
Tyl-1,4-disilabutane] bis (pentamethylcyclyl
Lopentadienyl dibutyl zirconium); [1,4-
Bis (9-fluorenyl) -1,1,4,4-tetrame
Tyl-1,4-disilabutane] bis (cyclopentadie
Nyldibutylzirconium); [1,4-bis (1-a
Ndenyl) -1,1,4,4-tetramethyl-1,4-
Disilabutane] bis (cyclopentadienyldibutyldi
Ruconium); [1- (1-indenyl) -6- (2-
Phenyl-1-indenyl) -1,1,6,6-tetra
Ethyl-1,6-disila-4-oxahexane] bis
(Tert-butylcyclopentadienyldibutylzyl
Conium); [1,10-bis (2,3-dimethyl-1)
-Indenyl) -1,1,10,10-tetramethyl-
1,10-Digelmadecan] bis (2-methyl-4-f
(Enylindenyldibutylzirconium); (1-methyl
3-tert-butylcyclopentadienyl) (1
-Phenyl-4-methoxy-7-chlorofluorenyl)
Dibutyl zirconium; (4,7-dichloroindeni
Le) (3,6-dimesitylfluorenyl) dibutylzyl
Conium; bis (2,7-di-tert-butyl-9-
Cyclohexylfluorenyl) dibutylzirconium;
(2,7-dimesitylfluorenyl) [2,7-bis
(1-Naphthyl) fluorenyl] dibutylzirconium
Dimethylsilylbis (fluorenyl) dibutylzyl
Conium; dibutylstannylbis (2-methylfluore
Nyl) dibutylzirconium; 1,1,2,2-tetra
Ethyldisilanediyl (2-methylindenyl) (4-
Phenylfluorenyl) dibutylzirconium; propyl
Len-1- (2-indenyl) -2- (9-fluorenyl)
L) dibutyl zirconium; 1,1-dimethyl-1-si
Laethylenebis (fluorenyl) dibutylzirconium
[4- (cyclopentadienyl) 4,7,7-tri
Methyl (tetrahydroindenyl) dibutyl zirconium
[4- (cyclopentadienyl) 4,7-dimethyl
-7-phenyl (5,6-dimethyltetrahydroindene
Nyl] dibutylzirconium; [4- (cyclopentadi
Enyl) -4,7-dimethyl-7- (1-naphthyl)
(7-phenyltetrahydroindenyl)] dibutyldi
Ruconium; [4- (cyclopentadienyl) -4,7
-Dimethyl-7-butyl (6,6-diethyltetrahydride
Loindenyl)] dibutylzirconium; [4- (3-
tert-butylcyclopentadienyl) -4,7,7
-Trimethyl (tetrahydroindenyl)] dibutyldi
Ruconium; [4- (1-indenyl) -4,7,7-
Trimethyl (tetrahydroindenyl)] dibutylzyl
Conium; bis (cyclopentadienyl) dibutylhaf
Bis (indenyl) dibutyl vanadium; bis
(Fluorenyl) dibutyl scandium; (indeni
L) (fluorenyl) dibutyl niobium; (2-methyl-
7-naphthylindenyl) (2,6-di-tert-butyl
Tylfluorenyl) dibutyltitanium; bromide (pentamethyi)
Rucyclopentadienyl) (tetrahydroindenyl)
Butylhafnium; (cyclopentadienyl) (1-O
Octen-8-ylcyclopentadienyl) dibutylhaf
Ium; (indenyl) (2-buten-4-ylcyclo)
[Pentadienyl) dibutyltitanium; [1,3-bis (g
[Limethylsilyl) cyclopentadienyl] (3,4-
Bis (fluorenyl) dibutylniobium; bis (cyclopentene)
Tadienyl) dibutyltitanium; dimethylsilanediylbi
(Indenyl) dibutyltitanium; dimethylsilanediyl
Rubis (tetrahydroindenyl) dibutylhafnium
Dimethylsilanediyl (cyclopentadienyl)
(Indenyl) dibutyltitanium; dimethylsilanediyl
Bis (2-methylindenyl) dibutylhafnium; di
Methylsilanediylbis (2-ethylindenyl) methyl
Luscandium; dimethylsilanediylbis (2-buty
-4,5-benzoindenyl) dibutylniobium;
Tylsilanediylbis (2-ethyl-4,5-benzoy
Ndenyl) dibutyltitanium; dimethylsilanediylbis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutyl tita
Dimethylsilanediyl (2-methyl-4,5-ben
Zoindenyl) (2-methyl-4-phenylindenyl
B) dibutyltitanium; dimethylsilanediyl (2-ethyl
-4,5-benzoindenyl) (2-methyl-4-f
Enylindenyl) dibutylhafnium; dimethylsila
Ndiyl (2-ethyl-4,5-benzoindenyl)
(2-ethyl-4-phenylindenyl) methyl scan
Diium; dimethylsilanediyl (2-ethyl-4,5-
Benzoindenyl) (2-ethyl-4-naphthylinde
Nil) dibutyltitanium; dimethylsilanediyl (2-
Tylindenyl) (4-phenylindenyl) dibutyl
Hafnium; dimethylsilanediylbis (2-methyl-
4-phenylindenyl) dibutylniobium;
Landiylbis (2-ethyl-4-phenylindenyl)
B) Dibutyl vanadium; dimethylsilanediylbis
(2-methyl-4,6-diisopropylindenyl) di
Butylhafnium; dimethylsilanediylbis (2-E
Cyl-4,6-diisopropylindenyl) dibutylba
Nadium; dimethylsilanediyl bis (2-methyl bromide)
-4-naphthylindenyl) butylhafnium; dimethyl
Lusilanediylbis (2-ethyl-4-naphthylindene
Nyl) dibutyltitanium; methylphenylsilanediylbi
(Indenyl) dibutyltitanium; methylphenylsila
Ndiyl (cyclopentadienyl) (indenyl) Hough
Ium; methylphenylsilanediylbis (tetrahydrid
Loindenyl) dibutyl hafnium; methyl phenyl
Landiyl bis (2-methylindenyl) dibutyl tita
Methylphenylsilanediylbis (2-ethylin
Denenyl) dibutylhafnium; methylphenylsilanedi
Ilbis (2-methyl-4,5-benzoindenyl) di
Butylhafnium; methylphenylsilanediylbis
(2-ethyl-4,5-benzoindenyl) dibutylba
Nadium; methylphenylsilanediylbis (4,5-
Dihydro-8-methyl-7H-cyclopent [e] ace
Naphthylene-7-ylidene) dibutyltitanium;
Ruphenylsilanediylbis (2-methyl-4,5-
Nzoindenyl) (2-methyl-4-phenylindenyl
Le) Butyl titanium; methylphenylsilanediylbis
(2-ethyl-4,5-benzoindenyl) (2-methyl
Ru-4-phenylindenyl) dibutyltitanium; methyl
Phenylsilanediylbis (2-methyl-4,5-ben
Zoindenyl) (2-ethyl-4-phenylindenyl
Le) dibutyl hafnium; methylphenylsilanediyl
Bis (2-ethyl-4,5-benzoindenyl) (2-
Ethyl-4-phenylindenyl) dibutylhafnium
Methyl; methylphenylsilanediyl (2-methylindeni
M) (4-phenylindenyl) dibutyltitanium;
Ruphenylsilanediylbis (2-methyl-4-phenyl
Ruindenyl) dibutylhafnium;
Landiylbis (2-ethyl-4-phenylindenyl)
B) dibutyl vanadium; methylphenylsilanediyl
Bis (2-methyl-4,6-diisopropylindeni
B) dibutyl titanium; methylphenylsilanediylbis
(2-ethyl-4,6-diisopropylindenyl) di
Butylhafnium; methylphenylsilanediylbis
(2-methyl-4-naphthylindenyl) dibutylhaf
And methylphenylsilanediylbis (2-ethyl
-4-naphthylindenyl) dibutyltitanium; diphenyl
Disilanediylbis (indenyl) dibutyltitanium; di
Phenylsilanediylbis (2-methylindenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Ethylindenyl) dibutyltitanium; diphenylsilane
Diylbis (cyclopentadienyl) (indenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Methyl-4,5-benzoindenyl) dibutyltitanium;
Diphenylsilanediylbis (2-ethyl-4,5-
Nzoindenyl) dibutylhafnium; diphenylsila
Ndiyl (2-methyl-4, -benzoindenyl)
(2-methyl-4,5-phenylindenyl) dibutyl
Hafnium; diphenylsilanediyl (2-ethyl-
4,5-benzoindenyl) (2-methyl-4,5-f
Enylindenyl) dibutyltitanium; diphenylsilane
Diyl (2-methyl-4,5-benzoindenyl) (2
-Ethyl-4,5-phenylindenyl) dibutylhaf
And diphenylsilanediyl (2-ethyl-4,5
-Benzoindenyl) (2-ethyl-4,5-phenyl
Indenyl) dibutyltitanium; diphenylsilanediyl
(2-methylindenyl) (4-phenylindenyl)
Dibutyltitanium; diphenylsilanediylbis (2-meth
Tyl-4-phenylindenyl) dibutyltitanium; diph
Enylsilanediylbis (2-ethyl-4-phenyli
Ndenyl) dibutylhafnium; diphenylsilanedii
Rubis (2-methyl-4,6-diisopropylindeni
B) dibutylhafnium; diphenylsilanediylbis
(2-ethyl-4,6-diisopropylindenyl) di
Butylhafnium; diphenylsilanediylbis (2-
Methyl-4-naphthylindenyl) dibutylhafnium
Diphenylsilanediylbis (2-ethyl-4-na)
Fthylindenyl) dibutyltitanium; 1-silacyclope
1,1-bis (indenyl) dibutylhafnium
1-silacyclopentane-1,1-bis (2-methyl
Ruindenyl) dibutylhafnium; 1-silacyclope
1,1-bis (2-ethylindenyl) dibutyl
Luhafnium; 1-silacyclopentane-1,1-bis
(2-methyl-4,5-benzoindenyl) dibutylthio
Tan; 1-silacyclopentane-1,1-bis (2-e
Tyl-4,5-benzoindenyl) dibutylhafnium
1-silacyclopentane-1- (2-methyl-4,
5-benzoindenyl) -1- (2-methyl-4-fe
Nylindenyl) methyl scandium; 1-silacyclo
Pentane-1- (2-ethyl-4,5-benzoindenyl)
L) -1- (2-Methyl-4-phenylindenyl) di
Butylhafnium; 1-silacyclopentane-1- (2
-Methyl-4,5-benzoindenyl) -1- (2-E
Tyl-4-phenylindenyl) dibutyltitanium; 1-
Silacyclopentane-1- (2-ethyl-4,5-ben
Zoindenyl) -1- (2-ethyl-4-phenylin
Denenyl) dibutylhafnium; 1-silacyclopentane
-1- (2-methylindenyl) -1- (4-phenyl
Indenyl) dibutylhafnium; 1-silacyclopen
Tan-1,1-bis (2-methyl-4-phenylindene
Nyl) dibutylhafnium; 1-silacyclopentabromide
1,1-bis (2-ethyl-4-phenylindenyl)
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-methyl-4,6-diisopropylindenyl
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-ethyl-4,6-diisopropylindeni
1) dibutyl titanium; 1-silacyclopentane-1,1
-Bis (2-methyl-4-naphthylindenyl) methyl
Scandium; 1-silacyclopentane-1,1-bis
(2-ethyl-4-naphthylindenyl) dibutylhaf
Ium; bis (cyclopentadienyl) dibutyl tita
Ethylene-1,2-bis (indenyl) methylska
Nd; ethylene-1,2-bis (tetrahydroin
Denenyl) dibutyltitanium; ethylene-1- (cyclopen
Tadienyl) -2- (1-indenyl) dibutylhafni
Um; ethylene-1- (cyclopentadienyl) -bromide
2- (2-indenyl) butyl titanium; ethylene-1-
(Cyclopentadienyl) -2- (2-methyl-1-i
Ndenyl) dibutylhafnium; ethylene-1,2-bi
2- (2-methylindenyl) dibutylhafnium;
Len-1,2-bis (2-ethylindenyl) dibutyl
Hafnium; ethylene-1,2-bis (2-methyl-
4,5-benzoindenyl) dibutylhafnium;
Len-1,2-bis (2-ethyl-4,5-benzoin
Denenyl) dibutyltitanium; ethylene-1,2-bis
(4,5-dihydro-8-methyl-7H-cyclopent
[E] acenaphthylene-7-ylidene) dibutyl tita
Ethylene-1- (2-methyl-4,5-benzoin)
Denenyl) -2- (2-methyl-4-phenylindenyl)
B) dibutyl titanium; ethylene-1- (2-ethyl-
4,5-benzoindenyl) -2- (2-methyl-4-
Phenylindenyl) dibutyltitanium; ethylene-1-
(2-methyl-4,5-benzoindenyl) -2- (2
-Ethyl-4-phenylindenyl) methylscandiu
Ethylene; 1- (2-ethyl-4,5-benzoin)
Denenyl) -2- (2-ethyl-4-naphthylindenyl
L) dibutyl hafnium; ethylene-1- (2-methyl)
Indenyl) -2- (4-phenylindenyl) dibutyi
Rutitanium; ethylene-1,2-bis (2-methyl-4-
Phenylindenyl) dibutylhafnium; ethylene-
1,2-bis (2-ethyl-4-phenylindenyl)
Dibutylhafnium; ethylene-1,2-bis (2-meth
Butyl-4,6-diisopropylindenyl) dibutyl
Funium; ethylene-1,2-bis (2-ethyl-4,
6-diisopropylindenyl) dibutyltitanium;
Len-1,2-bis (2-methyl-4-naphthylindene
Nyl) dibutyltitanium; ethylene-1,2-bis (2-
Ethyl-4-naphthylindenyl) dibutylhafnium
Propylene-2,2-bis (indenyl) dibutyl
Hafnium; propylene-2-cyclopentadienyl-
2- (1-indenyl) dibutyltitanium.

[0072]

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

The following reactions were performed using standard Schlenk techniques under an argon or nitrogen atmosphere. The solvent was refluxed in the presence of a suitable desiccant and then made anhydrous by distillation under a stream of argon or nitrogen before use. Reference Example 1 bis (η ⁵ -cyclopentadienyl) (methoxy) (4
- ethylhex-3-en-3-yl) zirconium bis (eta ⁵ - was charged cyclopentadienyl) dichloro zirconium (2.5 mmol) and THF (10 ml) in a Schlenk tube. The solution was cooled to -78 ° C., then, 0.9 CH ₃ CH ₂ MgBr (5.0mmol)
A 6M solution was added. This solution was allowed to stand at -78 ° C for 1 hour,
Stirred. Then, at -78 ° C, 3-hexyne (2.01 mmol) was added to the reaction mixture, and the mixture was stirred at 0 ° C for 3 hours, and bis (η ⁵ -cyclopentadienyl) 2,3-
TH of diethyl-1-zirconacyclopenta-2-ene
An F solution was obtained.

The THF solution was cooled from 0 ° C. to −78 ° C., then methanol (0.102 ml, 2.52 mmol) was added,
The mixture was stirred at -40 ° C for 1 hour to obtain a THF solution of the title compound. Example 1 (4-ethylhex-3-en-3-yl) diphenylphosphine To the THF solution obtained in Reference Example 1, chlorodiphenylphosphine (2.00 mmol) and CuCl (2.03
mmol) were added sequentially and the reaction mixture was stirred at room temperature for 6 hours. The reaction was terminated by adding 3N hydrochloric acid. It was then extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Column chromatography was performed using hexane with silica gel as the filler. The solvent was removed and recrystallized from THF / hexane to obtain colorless needles (183.2 mg, 31% yield). ¹ H NMR (CDCl ₃ ) δ 7.46 (4H, m, Ph), 7.31 (2H, m, Ph)
7.23 (4H, t, J = 7Hz, Ph) 2.50, 2.28 (2H, q, J = 7Hz,
Et-methylene) 2.08 (2H, m, Et-methylene) 1.06 (3H,
t, J = 7Hz, Et-methyl) 0.75 (3H, t, J = 7Hz, Et-methy
l) 0.58 (3H, t, J = 7Hz, Et-methyl). ¹³ C NMR (CDCl ₃ ) δ 157.3, J = 17 Hz, alkenyl) 133.8
(d, J = 13Hz, Ph) 132.9 (d, J = 29Hz, Ph) 129.2 (s, Ph) 1
28.1 (d, J = 7Hz, Ph) 124.6 (d, J = 26Hz, Ph) 28.6 (d, J
= 25Hz, Et-methylene) 24.7 (d, J = 5Hz, Et-methylen
e) 24.2 (s, Et-methylene) 14.4, 13.1 12.4 (s, Et-met
hyl). ³¹ P NMR (external standard: PPh ₃ = -6.25 ppm, CDCl ₃ ) δ-8.
91 Example 2 (4-Ethylhex-3-en-3-yl) diisopropylphosphine The reaction was carried out in the same manner as in Example 1 using the THF solution obtained in Reference Example 1. However, different from Example 1, chlorodiisopropylphosphine was used instead of chlorodiphenylphosphine. Purification using silica gel column chromatography gave a white solid (317.
4 mg, 35%). ¹ H NMR (CDCl ₃ ) δ 2.75 (2H, q, J = 7Hz, Et-methylen
e) 2.16 (2H, q, J = 7Hz, Et-methylene) 2.07 (2H, m,
ⁱ Pr-methne) 1.28, 1.24 (3H, d, J = 7Hz, ⁱ Pr-methyl)
1.07, 0.95 (15H, m, ⁱ Pr or Et-methyl). ¹³ C NMR (CDCl ₃ ) δ 160.9 (d, J = 13 Hz, alkenyl) 124.0
(d, J = 29Hz, alkenyl) 27.6 (d, J = 22Hz, Et-methylen
e) 25.3 (d, J = 9Hz, Et-methylene) 24.1 (s, Et-methyl
ene) 20.7 (d, J = 11Hz, ⁱ Pr -methyl) 20.2 (d, J = 5H
z, ⁱ Pr-methyl) 15.4, 14.0, 12.9 (s, Et-methyl). ³¹ P NMR (external standard: PPh ₃ = -6.25 ppm, CDCl ₃ ) δ 18.
0 Example 3 (4-ethylhex-3-en-3-yl) dicyclohexylphosphine Using the THF solution obtained in Reference Example 1, the reaction was carried out in the same manner as in Example 1. However, different from Example 1, chlorodicyclohexylphosphine was used instead of chlorodiphenylphosphine. Purification using silica gel column chromatography gave a white solid (7
0%).

The results of Reference Example 1 and Examples 1 to 3 are summarized below.

[0076]

Embedded image

Reference Example 2 Bis (η ⁵ -cyclopentadienyl) (trimethylsilyloxy) (5-allyl-oct-4-en-4-yl) zirconium Bis (η ⁵ -cyclopentadienyl) dichlorozirconium (731 mg) , 2.50 mmol) was dissolved in 10 ml of THF, and EtMgBr (0.96 M, 5.2 ml, 5.0 mmol) was added at −78 ° C., followed by stirring for 1 hour. Add 4-octyne (0,300ml, 2.02mmol) to this and add 0
Stirred at C for 3 hours. Then, allyloxytrimethylsilane (allyloxytrimethylsilane) (0.688 ml, 4.0 mmol)
And heated to 50 ° C. and stirred for 4 hours.
An HF solution was obtained. Example 4 (5-allyl-oct-4-en-4-yl) diphenylphosphine After the THF solution obtained in Reference Example 2 was returned to room temperature, chlorodiphenylphosphine (Ph ₂ PCl) (0.376 ml, 2.00 mmol) )
And CuCl (206.9 mg, 2.09 mmol) were sequentially added, and the mixture was stirred at room temperature for 6 hours. After adding 3N hydrochloric acid, the mixture was extracted with ethyl acetate.
And dried over SO _4. After filtering the drying agent, the solvent was removed and the residue was purified using silica gel column chromatography to obtain a colorless solid (106.8 mg, 80%). ¹ H NMR (CDCl ₃ ) δ 7.56 (4H, m, Ph) 7.37 (6H, m,
Ph) 5.08 (1H, m, allyl) 4.48 (2H, m, allyl) 3.02 (2H,
d, J = 6Hz, allyl-methylene) 2.25, 2.14, 1.55 (2H,
m, Pr-methylene) 1.01 (3H, t, J = 7Hz, Pr-methyl)
0.67 (2H, m, Pr-methylene) 0.46 (3H, t, J = 7Hz, Pr-m
ethyl). ¹³ C NMR (CDCl ₃ ) δ 155.3 (d, J = 18 Hz, alkenyl) 133.6
(d, J = 14Hz, Ph) 131.0 (d, J = 29Hz, Ph) 130.0 (s, Ph) 1
28.7 (d, J = 10Hz, Ph) 124.9 (d, J = 27Hz, alkenyl) 11
0.8 (s, allyl) 88.5 (s, allyl) 38.9 (d, J = 11Hz, Et-
methylene) 38.5 (d, J = 19Hz, Et-methylene) 33.8 (s,
allyl-methylene) 23.3, 21.6 (s, Et-methylne) 14.4,
14.1 (s, Et-methyl). ³¹ P NMR (external standard: PPh ₃ = -6.25 ppm, CDCl ₃ ) δ-6.
86 Example 5 (5-allyl-oct-4-en-4-yl) diisopropylphosphine The THF solution obtained in Reference Example 2 was returned to room temperature and then 1M
Chlorodiisopropylphosphine (2.0ml) and CuCl (206.9m
g, 2.09 mmol), and the mixture was stirred at room temperature for 9 hours. 3N
After adding hydrochloric acid, the mixture was extracted with ethyl acetate and dried over MgSO ₄ . After filtering the drying agent, the solvent was removed. Then, purification was performed using silica gel column chromatography to obtain a solid (300.0 mg, 76%).

¹ H-NMR (CDCl ₃ ) δ 5.02 (1 H, m, allyl)
4.41 (2H, m, allyl) 2.99 (2H, d, J = 6Hz, allyl-methyl
ene) 2.21 (6H, m,) 1.47 (4H, m, Pr-methylene or ⁱ P
r-methyne) 1.37, 1.33, 1.12, 1.09 (3H, t, J = 7Hz, ⁱ
Pr-methyl) 0.97 (6H, m, Pr-methyl). ¹³ C NMR (CDCl ₃ ) δ 156.3 (d, J = 15Hz, alkenyl) 12
5.2 (d, J = 23Hz, alkenyl) 110.0 (s, allyl) 87.4 (s, a
llyl) 38.6 (d, J = 11Hz, Et-methylene) 37.6 (d, J = 18
Hz, Et-methylene) 23.9 (s, allyl-methylene) 23.7,
(d, J = 18Hz, ⁱ Pr-methyne) 20.8 (s, Et-methylene) 19.
7 (d, J = 5Hz, ⁱ Pr-methyl) 19.4 (d, J = 10Hz, ⁱ Pr-meth
yl) 14.4, 13.8 (s, Et-methyl). ³¹ P NMR (external standard: PPh ₃ = -6.25 ppm, CDCl ₃ ) δ 12.8 Reference Example 3 bis (η ⁵ -cyclopentadienyl) (5- (cyclopropyl) methyl-oct-4-en-4-yl ) bromo zirconium bis (eta ⁵ - cyclopentadienyl) zirconium dichloride (731 mg, 2.50 mmol) was dissolved in 10 ml of THF, at -78 ℃, EtMgBr (0.96M, 5.2ml , 5.0mmol) and stirring for 1 hour added did. Add 4-octyne (0,300ml, 2.02mmol) to this and add 0
Stirred at C for 3 hours. Then, 4-bromo-1-butene
(4.0 mmol), and the mixture was heated to 50 ° C. and stirred for 4 hours to obtain a THF solution of the title compound. Example 6 (5- (cyclopropyl) methyl-oct-4-ene-
4-yl) diphenylphosphine After the THF solution obtained in Reference Example 3 was returned to room temperature, chlorodiphenylphosphine (Ph ₂ PCl) (0.376 ml, 2.00 mmol)
And CuCl (206.9 mg, 2.09 mmol) were sequentially added, and the mixture was stirred at room temperature for 6 hours. After adding 3N hydrochloric acid, the mixture was extracted with ethyl acetate.
And dried over SO _4. After filtering the drying agent, the solvent was removed and the residue was purified using silica gel column chromatography to obtain a colorless solid (67%). Example 7 (5- (cyclopropyl) methyl-oct-4-ene-
4-yl) diisopropylphosphine The THF solution obtained in Reference Example 3 was returned to room temperature, and then 1M
Chlorodiisopropylphosphine (2.0ml) and CuCl (206.9m
g, 2.09 mmol), and the mixture was stirred at room temperature for 9 hours. 3N
After adding hydrochloric acid, the mixture was extracted with ethyl acetate and dried over MgSO ₄ . After filtering the drying agent, the solvent was removed. Then, purification was performed using silica gel column chromatography to obtain a solid (66%).

The results of Reference Examples 2 and 3 and Examples 4 to 7 are summarized below.

[0080]

Embedded image

(Wherein R ¹ and R ² have the same meanings as above. Cp represents a cyclopentadienyl ring;
Represents trimethylsilyl. )

[0082]

Embedded image

(Wherein R ¹ and R ² have the same meanings as above. Cp represents a cyclopentadienyl ring, and TMS
Represents trimethylsilyl. The schemes of Reference Examples 1 to 3 and Examples 1 to 7 are summarized below.

[0084]

Embedded image

(Wherein R ¹ and R ² have the same meanings as above. Cp represents a cyclopentadienyl ring, and TMS
Represents trimethylsilyl. )

[0086]

According to the method of the present invention, a phosphorus-containing organic compound such as alkenylphosphine can be easily obtained.

Claims (11)

[Claims] An organic compound containing phosphorus represented by the following formula (I):
A method for synthesizing a compound, comprising:(Where R¹Is an optionally substituted C.₁~ C₂₀
A hydrocarbon group, which may have a substituent,₁~ C₂₀A
Alkoxy group, optionally having substituent (s), C₆~ C ₂₀A
Reeloxy group, amine group, hydroxyl group or formula -Si
(R⁶) (R⁷) (R⁸A group represented by the formula:⁶, R⁷
And R⁸Are independent of each other and are the same or different
And C₁~ C₂₀Alkyl group, C₆~ C₂₀Arylalkyl
Group, C₁~ C₂₀Alkoxy group, C₆~ C₂₀Arylalkyl
It is a ruoxy group. ) R^TwoAnd R^ThreeAre independent of each other and are the same or different
And a hydrogen atom, which may have a substituent, C₁~
C₂₀A hydrocarbon group, which may have a substituent,₁~ C
₂₀An alkoxy group, optionally having substituent (s), C₆~ C
₂₀Aryloxy group, amine group, hydroxyl group or formula -Si
(R⁶) (R⁷) (R⁸A group represented by the formula:⁶, R⁷
And R⁸Are independent of each other and are the same or different
And C₁~ C₂₀Alkyl group, C₆~ C₂₀Arylalkyl
Group, C₁~ C₂₀Alkoxy group, C₆~ C_{Two 0}Arylalkyl
It is a ruoxy group. ) Where R¹And R^TwoAre mutually interrupted by oxygen atoms
C, which may have a substituent,_Four~ C₂₀Bored
R or R may form a sum or unsaturated ring;^FourAnd R^FiveIs it
Each independently of one another, identical or different, a hydrogen atom,
C which may have a substituent₁~ C₂₀Hydrocarbon group
C which may have a substituent₁~ C₂₀An alkoxy group, or
Is an optionally substituted C.₆~ C₂₀Arlio
A xy group, provided that R^FourAnd R^FiveMay be cross-linked to each other. ) In the presence of a metal compound of Groups 4 to 15 of the periodic table, the following formula (I)
An organometallic compound represented by I), and(Where R¹, R^TwoAnd R^ThreeHas the meaning described above, and M is a group 3-5 group of the periodic table or a lanthanide-series gold
Genus, L¹And L^TwoAre independent of each other and are the same or different
2 shows an on-active ligand. Where L¹And L^TwoIs crosslinked
May be. A is a leaving group. Reacting with a phosphorus compound represented by the following formula (III):
## STR3 ## P (R^Four) (R^Five) (X) (III) wherein R^FourAnd R^FiveHas the meaning described above, and X is a leaving group. ), Characterized by organic phosphorus
How to synthesize the compound. 2. The method for synthesizing a phosphorus-containing organic compound according to claim 1, wherein the metal compound is a metal salt. 3. The method according to claim 2, wherein the metal compound is V, Cr, Mn, F
The method for synthesizing a phosphorus-containing organic compound according to claim 1, wherein the method includes e, Co, Ni, Cu, or Zn. 4. The method according to claim 1, wherein M is a metal belonging to Group 4 of the periodic table or a lanthanide series, and the anionic ligand is a delocalized cyclic η ⁵ -coordination ligand. A method for synthesizing any of the phosphorus-containing organic compounds according to any one of the above. 5. The cyclopentadienyl group, wherein the delocalized cyclic η ⁵ -coordination ligand may be substituted.
The method for synthesizing a phosphorus-containing organic compound according to claim 4, which is an indenyl group, a fluorenyl group, or an azulenyl group. 6. R ¹ , R ² and R ³ are each independently of one another and are the same or different and each have a C ₁ -C ₂₀ hydrocarbon group or a substituent, which may have a substituent. The synthesis of the phosphorus-containing organic compound according to any one of the above claims, which is a C _{1 to} C ₂₀ alkoxy group or a C _{6 to} C ₂₀ aryloxy group which may have a substituent. Method. 7. The method according to claim ¹ , wherein R ¹ , R ² and R ³ are each independently a C _{1 to} C ₂₀ hydrocarbon group which may be the same or different and may have a substituent. A method for synthesizing the phosphorus-containing organic compound according to any one of the above. 8. R ¹ and R ² are each independently of one another and are the same or different and each may have a substituent.
₁ -C ₁₀ alkyl group, or whether it is good C ₅ -C ₁₄ aryl group which may have a substituent group, or, together, may be interrupted by oxygen atoms, substituted the method of synthesis may also, C ₄ -C ₂₀ saturated or phosphorus-containing organic compound according to any one of the preceding claims forming an unsaturated ring. 9. R ¹ is C ₁ which may have a substituent.
-C ₁₀ alkyl group, which may have a substituent, C _3-
C ₂₀ allyl group, optionally having a substituent, C ₆ -C ₂₀
An arylmethyl group, or, which may have a substituent,
(C ₃ -C ₁₀ cycloalkyl) method for synthesizing C ₁ -C ₁₀ phosphorus-containing organic compound according to any preceding claim is an alkyl group. 10. R ⁴ and R ⁵ are each independently of one another, the same or different, and may have a substituent;
The method of synthesis C ₁ -C ₂₀ phosphorus-containing organic compound according to any of the claims is a hydrocarbon group. 11. R ⁴ and R ⁵ are each independently of one another and may be the same or different and may have a substituent;
C ₁ -C ₂₀ alkyl group, which may have a substituent, C ₄
-C ₂₀ cycloalkyl group, or may have a substituent group, a method of synthesizing a phosphorus-containing organic compound according to any preceding claim which is C ₆ -C ₁₈ aryl group.