JP5283984B2 - Process for producing transition metal compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for effectively producing a specific transition metal compound useful as a catalyst component for olefin polymerization. <P>SOLUTION: This method for producing the transition metal compound is provided by performing the following "process 1" and "process 2" in this order. [The process 1]: For example, a process of converting a ligand (2,4-di-tert-butyl-6-(9H-fluoren-9-yl)phenol) to a dianionic ligand (L) (potassium(2,4-di-tert-butyl-6-(9H-fluoren-9-yl)phenoxide) by reacting with potassium hydride. [The process 2]: A process of preparing a transition metal compound (2,4-di-tert-butyl-6-(9H-fluoren-9-yl)phenoxy)titanium dichloride) by reacting the di-anionic ligand (L) obtained in the previous [process 1] with a transition metal compound (titanium tetrachloride). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an improved method for producing a transition metal compound useful as a catalyst for olefin polymerization in a high yield with a simple method.

  As an olefin polymerization catalyst, a Kaminsky catalyst having a cyclopentadienyl group as a ligand is known. This catalyst has a feature that a polymer having a high polymerization activity and a narrow molecular weight distribution can be obtained (see Patent Documents 1 and 2). Recently, many improvements have been made to the method of polymerizing olefins using a catalyst system containing a monocyclopentadienyl compound to which groups containing non-carbon atoms such as nitrogen atom, oxygen atom and phosphorus atom are bonded ( Patent Documents 4 and 5, Non-Patent Documents 1 to 6) On the other hand, the inventors of the present invention disclosed in Patent Document 3 a catalyst system containing a transition metal compound exhibiting ethylene polymerization activity. Discloses an olefin polymerization process.

However, in the polymerization using the transition metal compound used in these conventional techniques, there is a problem that the molecular weight of the polymer to be produced is not sufficient, so that a complex which is bulky than the cyclopentadienyl group and can be expected to improve the molecular weight. There is a need for synthesis. A transition metal compound (A) having a fluorenyl ligand is a candidate for a novel polymerization catalyst component capable of satisfying various recent demands on the physical properties of polyolefins. However, since the yield was extremely low and purification was difficult, the quality as an olefin polymerization catalyst was not satisfied.
JP 58-19309 A JP-A 61-130314 JP-A-8-325283 US5856258 gazette JP 2004-13191 A WO2006022355 CN143132 publication Chem. Rev., 1998 (98), 2587 Chem. Rev., 2003 (103), 2633 Organometallics, 1997 (16), 5958 Organometallics, 2003 (22), 3877 Organometallics, 2004 (23), 540 Organometallics, 2006 (25), 631

  An object of the present invention is to provide an improved method for producing a transition metal compound (A) having a fluorenyl ligand in a simple and high yield.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in developing a method for simply synthesizing a transition metal compound (A) represented by the following general formula (4).

The process for producing a transition metal compound (A) of the present invention is characterized by sequentially performing the following [Step 1] and [Step 2].
[Step 1]: By reacting the ligand (l) represented by the following general formula (1) with one or more potassium compounds selected from the group consisting of potassium alkoxide and potassium hydride, the following general formula A step of converting to a dianionic ligand (L) represented by (2),
[Step 2]: By reacting the dianionic ligand (L) obtained in the above [Step 1] with the transition metal compound (a) represented by the following general formula (3), the following general formula The process of preparing the transition metal compound (A) represented by (4).

(In the above formula (1), R ^{1 to} R ¹² may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group or nitrogen. 2 groups adjacent to each other among the atoms or groups represented by R ^{1 to} R ¹² are bonded to each other to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. Q may represent an oxygen atom, a sulfur atom, an NR ^a group or a PR ^b group, and R ^a and R ^b are a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

(In the above formula (2), R ^{1 to} R ¹² and Q each represent the same atom or group as in formula (1).)

(In the above formula (3), M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, and X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing group or nitrogen. And m represents a number satisfying the valence of M. When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of atoms represented by X The groups may be bonded to each other, or may form a conjugated linear diene, a conjugated branched diene, a nonconjugated linear diene or a nonconjugated branched diene, and a plurality of groups represented by X A ring may be bonded to form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a non-conjugated cyclic diene.)

(In the above formula (4), M and X represent the same atom or group as in formula (3), L represents a dianionic ligand represented by the above general formula (2), and n represents M When n is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other, A conjugated linear diene, conjugated branched diene, non-conjugated linear diene or non-conjugated branched diene may be formed, and a plurality of groups represented by X are bonded to each other to form a ring. In addition, an aromatic ring, an aliphatic ring, a conjugated cyclic diene, and a non-conjugated cyclic diene may be formed with each other.
In the method for producing a transition metal compound (A) of the present invention, the potassium compound in [Step 1] is preferably potassium hydride.

  In addition, the method for producing the transition metal compound (A) of the present invention is such that Q is an oxygen atom, transition metal group M has a divalent, trivalent or tetravalent valence state in the periodic table group 4 transition. A metal atom, particularly a transition metal atom M is a titanium atom, or a conjugated, non-conjugated acyclic or cyclic diene in which m is 2 or more and a plurality of groups represented by X are bonded to each other It is preferably used for manufacturing products.

  According to the present invention, the transition metal compound (A) represented by the general formula (4) can be easily produced in a high yield and with a good purity. Is extremely valuable.

Hereafter, the manufacturing method of the transition metal compound (A) based on this invention is demonstrated concretely.
<Step of converting ligand (l) to dianionic ligand (L) [Step 1]>
In [Step 1] of the present invention, the ligand (l) is reacted with a potassium compound to convert to a dianionic ligand (L).
The ligand (l) used in the method of the present invention is a compound of the following general formula (1).

In the above formula (1), R ^{1 to} R ¹² may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a halogenated hydrocarbon group having 1 to 30 carbon atoms, A C1-C30 silylated hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group are shown. Moreover, two adjacent groups among the atoms or groups represented by R ^{1 to} R ¹² may be bonded to form an aromatic ring, an aliphatic ring, or a heterocyclic ring together with the carbon atoms to which they are bonded. .

Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and preferable halogen atom includes chlorine.
Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; the number of carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl 3-30 cycloalkyl groups; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, Examples thereof include aryl groups such as naphthyl, methylnaphthyl, anthryl, phenanthryl and the like. Of these, those having 1 to 20 carbon atoms are preferred.

Examples of the halogenated hydrocarbon group having 1 to 30 carbon atoms include groups in which at least one hydrogen of the hydrocarbon group having 1 to 30 carbon atoms is substituted with the halogen atom. Of these, those having 1 to 20 carbon atoms are preferred.
Examples of the silylated hydrocarbon group having 1 to 30 carbon atoms include groups in which at least one hydrogen of the above hydrocarbon group having 1 to 30 carbon atoms is substituted with a silyl group. Specific examples of the silyl group include trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl groups.

  Specific examples of the oxygen-containing group include an oxy group, a peroxy group, a hydroxy group, a hydroperoxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as phenylethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like. Preferred oxygen-containing groups include hydroxy groups.

  Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino Arylamino groups or alkylarylamino groups such as; silylamino groups such as bistrimethylsilylamino group and bistriethylsilylamino group; alkylimino groups such as methylimino, ethylimino group, i-propylimino group, t-butylimino group; 2-methylphenylimino group, 2,6-dimethylphenylimino group, 2,4,6-trimethylphenylimino group, 2-i-propylphenylimino group, 2,6-di-i-propylphenyl Mino group, 2,4,6-tri-i-propylphenylimino group, 2-t-butylphenylimino group, 2,6-di-t-butylphenylimino group, 2,4,6-tri-t- Examples include arylimino groups such as butylphenylimino group.

In the formula (1), Q is an oxygen atom, a sulfur atom, NR ^a group, or PR ^b group, ^{R a} and ^{R b} is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include those having 1 to 20 carbon atoms among the groups exemplified as the hydrocarbon groups of R ^{1 to} R ¹² .

  Synthesis of the ligand (1) represented by the general formula (1) is described in Bull. Chem. Soc. Jpn, 1980 (53), 3248, Organometallics, 2003 (22), 3877, Organometallics, 2004 (23). 540, etc., or similar methods. That is, approximately 2.1 times the molar amount of alkyllithium is allowed to act on brominated substituted phenol, then fluorenone or substituted fluorenone is reacted to synthesize fluorenol, and subsequently hydroiodic acid is reacted in acetic acid. Thus, the target product can be synthesized.

  In the reaction using alkyllithium, the reaction temperature is usually from −100 ° C. to the boiling point of the solvent, preferably about −80 ° C., and gradually raised to near room temperature. The solvent to be used is not particularly limited, but ether solvents such as tetrahydrofuran and diethyl ether or a mixed solution thereof is preferable. After completion of the reaction, it is used for the next reaction without purification. The reaction using hydroiodic acid is preferably performed at room temperature for about 5 hours. After confirming the progress of the reaction, it is preferable to use a separation operation by column chromatography as a method for purely removing the ligand.

  The potassium compound used in the method of the present invention is at least one potassium compound selected from the group consisting of potassium alkoxide and potassium hydride. Examples of the potassium alkoxide include potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide, potassium tert-butoxide, and the like. Of these potassium compounds, potassium tert-butoxide or potassium hydride is preferred because of its high reactivity and availability, and potassium hydride is particularly preferred because no by-products remain after the reaction.

  The amount of the potassium compound used is usually 1 to 10 times mol, preferably 1 to 5 times mol, more preferably 2 to 2.5 times the ligand (l) represented by the general formula (1). The range is double moles.

  The reaction between the ligand (l) and the potassium compound is carried out by adding the ligand (l) dissolved in the solvent to the potassium compound dissolved or suspended in the solvent and stirring. Can do.

  The solvent to be used is not particularly limited as long as it is inert to the reaction between the ligand (l) and the potassium compound. For example, petroleum ether, hexane, carbon tetrachloride, toluene, benzene , Dichloromethane, chloroform, tetrahydrofuran, diethyl ether, or a mixed solution thereof. The amount of the solvent used is not particularly limited, but is 10 to 5000 times the weight of the potassium compound for dissolving or suspending the potassium compound, and the ligand (l) for dissolving the ligand (l). It is the range of 10 to 5000 times by weight. Further, the solvent for dissolving or suspending the potassium compound and the solvent for dissolving the ligand (l) may be the same or different.

  The temperature at which the ligand (l) is reacted with the potassium compound is usually in the range of −100 ° C. or higher to the boiling point of the solvent, preferably −80 to 120 ° C., particularly preferably 0 to 40 ° C. The reaction time is usually in the range of 5 minutes to 48 hours, preferably 1 hour to 30 hours. If necessary, the reaction temperature can be changed over part or all of the reaction time.

After completion of the reaction, the desired dianionic ligand (L) can be obtained as a solid by carrying out a usual solvent removal method such as a method of removing the solvent under reduced pressure. Alternatively, the solvent can be used as it is in the subsequent [Step 2] while the dianionic ligand (L) is dissolved in a solution state without removing the solvent. In particular, when potassium hydride is used as the potassium compound, the by-product compound in the reaction is hydrogen, and there is substantially no residual by-product in the reaction solution. As it is, it can be suitably used in [Step 2].
Further, the dianionic ligand (L) can be subjected to a purification operation such as extraction / recrystallization, if necessary, in the above-mentioned solution state or as a solid substance.

  The dianionic ligand (L) produced by the reaction between the ligand (1) and the potassium compound is a compound represented by the following general formula (2), and cyclopentadiene and QH group in the fluorene ligand. The top is anionized. This compound is easily protonated when it comes into contact with water, alcohol or the like, and changes to the original ligand (l).

<Step of preparing transition metal compound (A) [Step 2]>
In [Step 2] of the present invention, the transition metal compound (A) is prepared by reacting the dianionic ligand (L) obtained in [Step 1] with the transition metal compound (a). .
The transition metal compound (a) used in the present invention is a compound represented by the following general formula (3).

  In the above formula (3), M represents a transition metal atom selected from Groups 4 to 6 of the periodic table, specifically, Group 4 metal atoms of titanium, zirconium and hafnium, Group 5 of vanadium, niobium and tantalum. Group 6 metal atoms of metal atoms, chromium, molybdenum and tungsten. Of these, transition metals such as titanium, zirconium, hafnium, vanadium, niobium, tantalum, and chromium are preferable. Among them, Group 4 metal atoms and Group 5 metal atoms are preferable, and the valence state of transition metal atom M Is more preferably a divalent, trivalent or tetravalent group 4 or 5 transition metal atom of the periodic table, particularly preferably titanium, zirconium, hafnium or vanadium.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, a halogenated hydrocarbon group having 1 to 30 carbon atoms, a silylated hydrocarbon group having 1 to 30 carbon atoms, an oxygen-containing group, or a nitrogen-containing group. Show.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl, benzyl, phenylethyl, phenylpropyl And aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl and the like.

Specific examples of the halogenated hydrocarbon group having 1 to 30 carbon atoms include those in which the halogen atom is substituted for the hydrocarbon group having 1 to 30 carbon atoms.
Specific examples of the silylated hydrocarbon group having 1 to 30 carbon atoms include those having a silyl group substituted on the hydrocarbon group having 1 to 30 carbon atoms. Specific examples of the silyl group include trimethylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, and triphenylsilyl groups.
Examples of the oxygen-containing group and the nitrogen-containing group include the same as those exemplified as examples of R ^{1 to} R ^{12 in} the general formula (1).

  m is a number satisfying the valence of M. When m is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. Or a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene or a non-conjugated branched diene, and a plurality of groups represented by X are bonded to each other to form a ring. They may be formed, and an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a non-conjugated cyclic diene may be formed.

  The amount of the transition metal compound (a) used is in an equimolar amount or more, preferably in the range of 1.00 to 1.50 times moles relative to the dianionic ligand (L). In particular, it is preferable to carry out the reaction in a small excess amount, for example, 1.01-1.20 moles.

  The reaction between the dianionic ligand (L) and the transition metal compound (a) is performed by dissolving the dianionic ligand dissolved in the solvent with respect to the transition metal compound (a) dissolved or suspended in the solvent under a nitrogen atmosphere. Ligand (L) can be added dropwise and stirred.

  As the solvent used in the reaction, the solvents exemplified in the above [Step 1] can be used. Although there is no restriction | limiting in particular in the usage-amount of a solvent, The range of 10-5000 weight times with respect to the transition metal compound (a) for the melt | dissolution or suspension of a transition metal compound (a), a dianionic ligand (L) The amount is 10 to 5000 times the weight of the dianionic ligand (L). The solvent for dissolving or suspending the transition metal compound (a) and the solvent for dissolving the dianionic ligand (L) may be the same or different.

  In the above reaction, the solid dianionic ligand (L) obtained by removing the solvent in [Step 1] can be dissolved in the above solvent, and used in [Step 1]. Without removing the solvent, the dianionic ligand (L) can be used as it is in a solution state in which the dianionic ligand (L) is dissolved. In this case, the solvent used for dissolving or suspending the transition metal compound (a) and the solvent used in [Step 1] may be the same or different.

  The temperature at the time of reacting the dianionic ligand (L) and the transition metal compound (a) is usually in the range of −100 ° C. or more to the boiling point of the solvent, preferably −80 to 120 ° C., particularly −20. ~ 40 ° C is preferred. The reaction time is usually in the range of 5 minutes to 100 hours, preferably 20 minutes to 30 hours. If necessary, the reaction temperature can be changed over part or all of the reaction time.

  After completion of the reaction, if it is confirmed by NMR or the like that the reaction is proceeding quantitatively, the target transition metal can be obtained by carrying out a normal solvent removal method such as a method of removing the solvent under reduced pressure. Compound (A) can be obtained as a solid. When a by-product is included, a normal operation used when purifying the transition metal compound such as extraction or recrystallization is used as a method for purely extracting the desired transition metal compound (A).

  The solvent used for extraction and recrystallization is not particularly limited, and examples thereof include petroleum ether, hexane, carbon tetrachloride, toluene, benzene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether, or a mixed solution thereof. It is done.

  The transition metal compound (A) thus prepared is a compound represented by the following general formula (4).

  In the above formula (4), M and X represent the same atom or group as in formula (3), L represents the dianionic ligand represented by the general formula (2), and n represents the valence of M. When n is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other or conjugated. A linear diene, a conjugated branched diene, a nonconjugated linear diene or a nonconjugated branched diene may be formed, and a plurality of groups represented by X may be bonded to each other to form a ring. In addition, an aromatic ring, an aliphatic ring, a conjugated cyclic diene, and a non-conjugated cyclic diene may be formed.

Specific examples of the structure of the transition metal compound (A) produced by the method of the present invention are shown below, but the present invention is not limited thereto. In this specification, the methyl group is Me, the ethyl group is Et, the n-propyl group is ⁿ Pu, the tert-butyl group is ^t Bu, the adamantyl group is Ad, the cumyl group is Cu, the trimethylsilyl group is TMS, and triphenyl. The silyl group may be abbreviated as TPS, the trityl group as Tr, and the phenyl group as Ph.

The method of the present invention makes it possible to easily synthesize a complex having a fluorenyl-phenoxy ligand, which has been difficult to synthesize with the prior art, in a high yield and with a high purity. This is an industrially very useful synthesis method for the production of
[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

<< Synthesis of (2,4-di-tert-butyl-6- (9H-fluoren-9-yl) -phenoxy) titanium dichloride >>
[Synthesis of potassium (2,4-di-tert-butyl-6- (9H-fluoren-9-yl) -phenoxide)]
A rotor was placed in a sufficiently dry and nitrogen-substituted reaction vessel, and 2,4-di-tert-butyl-6- (9H-fluoren-9-yl) phenol (0) obtained by the method described in WO2006 / 022355A1. .10 g, 0.27 mmol) and potassium hydride (0.022 g, 0.54 mmol) were added, and toluene (10 mL) was added thereto and reacted at room temperature for 18 hours with stirring. The obtained red suspension was solidified to obtain the target product quantitatively. The result of NMR analysis of the obtained product was as follows.
¹ H NMR (THF-d ₈ ): δ 8.01 (d, J = 7.25 Hz, 2H, Fluorenyl), 7.51 (d, J = 8.25 Hz, 2H, Fluorenyl), 7.22 (d, J = 2.64 Hz, 1H, Phenoxy), 6.90 (d, J = 2.64 Hz, 1H, Phenoxy), 6.88 (t, J = 7.26 Hz, 2H, Fluorenyl), 6.49 (t, J = 7.26 Hz, 2H, Fluorenyl).
[Synthesis of (2,4-di-tert-butyl-6- (9H-fluoren-9-yl) -phenoxy) titanium dichloride]
A rotor was placed in a reaction vessel sufficiently dried and purged with nitrogen, and titanium tetrachloride (0.19 g, 1.00 mmol) and toluene (10 mL) were placed therein, and the potassium ( A toluene solution (10 mL) of 2,4-di-tert-butyl-6- (9H-fluoren-9-yl) -phenoxide) (0.09 g, 0.20 mmol) was slowly added dropwise at room temperature. For 30 minutes with stirring. The obtained brown suspension was dried, dissolved again in toluene, filtered through a glass filter filled with celite, and the filtrate was concentrated and dried to quantitatively obtain the desired product. The results of analyzing the obtained product by NMR and FD-MS were as follows.
Elemental analysis: Calc .: C, 66.55; H, 5.79. Found: C, 67.79; H, 5.46.
¹ H NMR (CDCl ₃ ): δ 8.29 (d, J = 8.24 Hz, 2H, Fluorenyl), 7.67-7.51 (m, 6H, Aromatics), 7.41 (dd, J = 6.77 2.14 Hz, 2H, Aromatics), 1.41 (s, 9H, tBu ), 1.32 (s, 9H, tBu ).
¹³ C { ¹ H} NMR (CDCl ₃ ): d 171.3 (Ti-O- C ), 146.8, 138.3, 134.1, 131.0, 128.5, 128.2, 127.1, 126.0, 125.5, 124.4, 122.1 (unsaturated C ); 35.2, 35.0 ( C Me ₃ ); 31.9, 29.8 (C Me ₃ ).
FD-MS: 486 (M +).

[Synthesis Example 1]
[1,1,4,4,7,7,10,10-octamethyl-3,4,7,8,9,10-hexahydro-1H-dibenzo [b, h] fluoren-12 (2H) -one Composition]
1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro synthesized according to the method described in Organometallics., 2004 (23) 1777 A method similar to the method described in J. Org. Chem., 1997 (62) 8767 using -1H-dibenzo [b, h] fluorene (octamethyloctahydrodibenzofluorene; 5.00 g, 12.93 mmol) After the oxidation reaction, purification was performed using a silica gel-packed flash column chromatograph (eluent: hexane / methylene chloride = 1/1) to obtain 3.44 g of the desired product (66%, yellow solid). The results of analysis of the obtained product by elemental analysis, NMR, and FD-MS were as follows.
Elemental analysis: Calc .: C, 86.95; H, 9.06.
Found: C, 86.90; H, 8.67.
¹ H NMR (CDCl ₃ ): δ 7.61 (s, 2H, Flu), 7.41 (s, 2H, Flu); 1.70 (s, 8H, C H ₂ ); 1.35 (s, 12H, C Me ₃ ), 1.29 (s, 12H, C Me ₃ ).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ194.0 (O = C ); 151.8, 145.4, 141.3, 132.6, 122.7, 117.9 (unsaturated C); 35.3, 34.92, 34.85, 34.7, 31.6 ( C H ₃ and C H ₂ ). FD-MS: 400 (M +).

[Synthesis Example 2]
[12- (3,5-di-tert-butyl-2-hydroxyphenyl) -1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9, Synthesis of 10,12-octahydro-1H-dibenzo [b, h] fluoren-12-ol]
A rotor is placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and 2-bromo-4,6-di-tert-butylphenol (2.36 g, 8.29 mmol) is added thereto, and tetrahydrofuran (30 mL) is added. In addition, the mixture was dissolved with stirring, and normal butyl lithium (1.56 M hexane solution; 11.2 mL, 17.41 mmol) was slowly added at 0 ° C., then the temperature was slowly raised, and the reaction was allowed to proceed with stirring at room temperature for 12 hours. . The obtained mixture was cooled again to -78 ° C, and 1,1,4,4,7,7,10,10-octamethyl-3,4,7,8,9,10-hexahydro obtained in the above reaction was obtained. After slowly adding a solution of -1H-dibenzo [b, h] fluoren-12 (2H) -one (2.36 g, 18.29 mmol) in tetrahydrofuran (50 mL), the temperature was raised slowly, and the mixture was heated at room temperature for 16 hours. The reaction was carried out with stirring. After the reaction, water (100 mL) was added to the reaction solution to stop the reaction, the mixture was transferred to a separatory funnel, shaken with diethyl ether, the organic layer was separated, dried over magnesium sulfate, concentrated and dried. The desired 12- (3,5-di-tert-butyl-2-hydroxyphenyl) -1,1,4,4,7,7,10,10-octamethyl-2,3,4,7, 8,9,10,12-Octahydro-1H-dibenzo [b, h] fluoren-12-ol was obtained in a crude state (brown solid).

[Synthesis Example 3]
[2,4-Di-tert-butyl-6- (1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- Synthesis of 1H-dibenzo [b, h] fluoren-12-yl) phenol]
A rotor is placed in a Schlenk-type reaction vessel sufficiently dried and purged with nitrogen, and the crude 12- (3,5-di-tert-butyl-2-hydroxyphenyl) -1, 1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-ol (8. 29 g), acetic acid (70 mL) and 57% hydroiodic acid (14 mL) were added, and the mixture was stirred and reacted for 7 hours while refluxing. The resulting brown suspension was poured into water (300 mL) and extracted with diethyl ether, and the resulting organic layer was washed with an aqueous sodium bicarbonate solution, followed by an aqueous sodium hydrogen sulfite solution (10 wt%, ca. 150 mL), Magnesium sulfate was added to the washed organic layer, dried and filtered to obtain a yellow solution. This solution was slowly concentrated and the precipitated 1,1,4,4,7,7,10,10-octamethyl-3,4,7,8,9,10-hexahydro-1H-dibenzo [b, h] fluorene The -12 (2H) -one crystals were removed by filtration. The filtrate is once concentrated and dried, and the resulting solid is dissolved by adding a mixed solution of hexane / diethyl ether (= 95/5, 20 mL), and silica gel-packed flash column chromatograph (eluent: hexane / diethyl ether = 95/5) to give 1.04 g of crude product (21%, pale yellow solid). Hexane was added thereto, followed by filtration after stirring, and the resulting white powder was dried to obtain 0.54 g of the desired product (6.6%). The results of analyzing the obtained product by NMR and FD-MS were as follows.
¹ H NMR (CDCl ₃ ): δ 9.67 (s, 1H, Fluorenyl- H -9), 7.78 (s, 2H, Fluorenyl), 7.52 (s, 2H, Fluorenyl), 7.20 (d, J = 2.39 Hz, 1H , Phenoxy), 6.47 (d, J = 2.47 Hz, 1H, Phenoxy), 1.70 (s, 8H, C H ₂ ), 1.51, (s, 9H, tBu ), 1.373 (s, 6H, Me ), 1.365 ( s, 6H, Me ), 1.30 (s, 6H, Me ), 1.23 (s, 6H, Me ), 1.07 (s, 9H, tBu ).
¹³ C { ¹ H} NMR (CDCl ₃ ): δ 154.05 (Ti-O- C ), 146.4, 146.1, 145.1, 140.2, 137.06, 136.96, 126.0, 123.9, 123.6, 122.1, 117.6, (unsaturated C ), 35.4 , 35.3, 34.9, 34.8, 34.2, 32.2, 32.1, 31.6, 29.9.
FD-MS: 589 (M +).

≪ (2,4-di-tert-butyl-6- (1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro Synthesis of -1H-dibenzo [b, h] fluoren-12-yl) -phenoxy) titanium dichloride >>
[Potassium (2,4-di-tert-butyl-6- (1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12- Synthesis of Octahydro-1H-dibenzo [b, h] fluoren-12-yl) -phenoxide)]
A rotor was placed in a sufficiently dry and nitrogen-substituted reaction vessel, and 2,4-di-tert-butyl-6- (1,1,4,4,7,7,10,10-) obtained by the above reaction was obtained. Octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluoren-12-yl) phenol (0.16 g, 0.28 mmol), and potassium hydride ( 0.022 g, 0.55 mmol) was added, and toluene (10 mL) was added thereto and reacted at room temperature with stirring for 20 hours. The target product was quantitatively obtained by drying the resulting beige suspension. The result of NMR analysis of the obtained product was as follows.
¹ H NMR (THF-d ₈ ): δ 7.83 (s, 2H, Fluorenyl), 7.48 (s, 2H, Fluorenyl), 6.85 (s, 1H, Phenoxy), 6.25 (d, 1H, Phenoxy), 1.68 (s , 8H, C H ₂ ), 1.50, (s, 9H, tBu ), 1.32 (s, 6H, Me ), 1.31 (s, 6H, Me ), 1.26 (s, 6H, Me ), 1.21 (s, 6H , Me ), 0.96 (s, 9H, tBu ).
[(2,4-di-tert-butyl-6- (1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro Synthesis of -1H-dibenzo [b, h] fluoren-12-yl) -phenoxy) titanium dichloride]
Put the rotor in a well-dried, nitrogen-substituted reaction vessel, and put titanium tetrachloride (0.01 mL) and deuterated methylene chloride (0.3 mL) in this reaction vessel. (2,4-di-tert-butyl-6- (1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- 1H-dibenzo [b, h] fluoren-12-yl) -phenoxide) (4.6 mg, 6.8 μmol) in a deuterated methylene chloride solution (0.4 mL) was slowly added dropwise at room temperature. The reaction was allowed to stir for 10 minutes. The obtained brown suspension was dried to obtain a mixture of the target compound and potassium chloride quantitatively.
The results of analyzing the obtained product by NMR and FD-MS were as follows.
¹ H NMR (CD ₂ Cl ₂ ): δ 7.93 (d, J = 2.38 Hz, 1H, Phenoxy), 7.16 (d, J = 2.61 Hz, 1H, Phenoxy), 7.11 (s, 2H, Fluorenyl), 6.81 ( s, 2H, Fluorenyl), 1.66, (s, 9H, tBu ), 1.66-1.59 (br, 8H, C H ₂ ), 1.38 (s, 9H, tBu ), 1.271 (s, 6H, Me ), 1.267 ( s, 6H, Me ), 1.21 (s, 6H, Me ), 1.14 (s, 6H, Me ).
¹³ C { ¹ H} NMR (CD ₂ Cl ₂ ): δ 197.3 (Ti-O- C ), 169.4, 168.4, 150.4, 149.8, 147.4, 142.0, 141.2, 140.5, 136.4, 127.4, 127.0, 124.9 (unsaturated C ); 37.6, 36.5, 35.5, 34.8 (Quaternary C ); 34.18, 34.15 ( C H ₂ ); 31.15, 31.10, 30.5, 30.3, 29.7 ( C H ₃ ).
FD-MS: 706 (M +).

[Comparative Example 1]
<< Synthesis of (2,4-di-tert-butyl-6- (9H-fluoren-9-yl) -phenoxy) titanium dichloride >>
Place the rotor in a Schlenk-type reaction vessel that has been thoroughly dried and purged with nitrogen, and put titanium tetrachloride (1.0 M toluene solution; 0.98 mL, 0.98 mmol) in it, and add toluene (10 mL). While stirring, 2,4-di-tert-butyl-6- (9H-fluoren-9-yl) phenol (0.37 g, 0.98 mmol) obtained by the method described in WO2006 / 022355A1 was slowly added at room temperature. The mixture was added dropwise, and after completion of the addition, the mixture was allowed to react with stirring at room temperature for 1 hour. The obtained red solution was cooled to −78 ° C. with a dry ice-acetone bath, and normal butyl lithium (1.56 M hexane solution; 1.26 mL, 1.97 mmol) was slowly added dropwise thereto. The mixture was stirred and reacted at room temperature for 10 hours and then at 100 ° C. with stirring for 3 hours and 30 minutes to obtain a brown suspension. The suspension was filtered through a glass filter filled with celite under a nitrogen atmosphere, and the resulting black solid was washed with toluene (4 mL), and the washing was mixed with the filtrate. This solution was concentrated and dried, and recrystallized with toluene to obtain 0.13 g of a brown solid containing the target product. The results of analyzing the obtained product by NMR and FD-MS were as follows.
¹ H NMR (C ₆ D ₆ ): δ 7.70-6.05 (m, 10H, aromatics); 1.44 (s, 9H, C Me ₃ ), 1.38 (s, 9H, C Me ₃ ).
FD-MS: 486 (M +).

  According to the present invention, the transition metal compound (A) represented by the general formula (4) can be easily synthesized with high yield and high purity, which is extremely useful industrially.

Claims (5)

The following [Step 1] and [Step 2] are carried out sequentially, and the method for producing a transition metal compound (A) is characterized.
[Step 1]: By reacting the ligand (l) represented by the following general formula (1) with one or more potassium compounds selected from the group consisting of potassium alkoxide and potassium hydride, the following general formula A step of converting to a dianionic ligand (L) represented by (2),
[Step 2]: By reacting the dianionic ligand (L) obtained in the above [Step 1] with the transition metal compound (a) represented by the following general formula (3), the following general formula The process of preparing the transition metal compound (A) represented by (4).

(In the above formula (1), R ^{1 to} R ¹² may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a silylated hydrocarbon group, an oxygen-containing group or nitrogen. 2 groups adjacent to each other among the atoms or groups represented by R ^{1 to} R ¹² are bonded to each other to form an aromatic ring, an aliphatic ring or a heterocyclic ring together with the carbon atoms to which they are bonded. at best, Q is showed SansoHara child, ^{R a} and ^{R b} is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

(In the above formula (2), R ^{1 to} R ¹² and Q each represent the same atom or group as in formula (1).)

(In the above formula (3), M represents a transition metal atom of Group 4 of the periodic table having a divalent, trivalent or tetravalent valence state , and X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen atom. A hydrocarbon group, an oxygen-containing group or a nitrogen-containing group, m is a number satisfying the valence of M, and when m is 2 or more, a plurality of atoms or groups represented by X are the same or different from each other A plurality of groups represented by X may be bonded to each other, or may form a conjugated linear diene, a conjugated branched diene, a non-conjugated linear diene or a non-conjugated branched diene, In addition, a plurality of groups represented by X may be bonded to each other to form a ring, and may further form an aromatic ring, an aliphatic ring, a conjugated cyclic diene, or a non-conjugated cyclic diene.

(In the above formula (4), M and X represent the same atom or group as in formula (3), L represents a dianionic ligand represented by the above general formula (2), and n represents M When n is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other, A conjugated linear diene, conjugated branched diene, non-conjugated linear diene or non-conjugated branched diene may be formed, and a plurality of groups represented by X are bonded to each other to form a ring. In addition, an aromatic ring, an aliphatic ring, a conjugated cyclic diene, and a non-conjugated cyclic diene may be formed with each other. The method for producing a transition metal compound (A) according to claim 1, wherein the potassium compound is potassium hydride. The method for producing a transition metal compound (A) according to claim 1 or 2 , wherein the transition metal atom M is a titanium atom and the valence state thereof is divalent, trivalent or tetravalent. The transition according to any one of claims 1 to 3 , wherein m is 2 or more, and a plurality of groups represented by X are conjugated, non-conjugated acyclic, or cyclic dienes in which the groups are bonded to each other. The manufacturing method of a metal compound (A). The method for producing a transition metal compound (A) according to any one of claims 1 to 3, wherein the transition metal atom M is a titanium atom, X is a chlorine atom, and m is 4.