WO1999067260A1 - Procede pour synthetiser des composes metallocenes - Google Patents

Procede pour synthetiser des composes metallocenes Download PDF

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Publication number
WO1999067260A1
WO1999067260A1 PCT/JP1998/002819 JP9802819W WO9967260A1 WO 1999067260 A1 WO1999067260 A1 WO 1999067260A1 JP 9802819 W JP9802819 W JP 9802819W WO 9967260 A1 WO9967260 A1 WO 9967260A1
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WO
WIPO (PCT)
Prior art keywords
compound
bis
meta
sendai
halide
Prior art date
Application number
PCT/JP1998/002819
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English (en)
Japanese (ja)
Inventor
Yuichi Kitagawa
Koji Otaka
Tomoya Kubo
Eiji Takeichi
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Priority to US09/486,273 priority Critical patent/US6175025B1/en
Priority to PCT/JP1998/002819 priority patent/WO1999067260A1/fr
Publication of WO1999067260A1 publication Critical patent/WO1999067260A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • the present invention relates to a method for synthesizing a meta-acene compound which can be used for hydrogenation of an organic synthesis catalyst, a polymerization catalyst, a low molecular weight compound or a high molecular weight compound, and the like.
  • the meta-opensene compound is useful as a catalyst, and various meta-opensene compounds are known.
  • a method for synthesizing an aryl metallocene compound a method known in the art is known in which a meta-mouth Sendai halide and an aryl metal compound are reacted at room temperature for a certain amount of reflux S to be used.
  • a side reaction such as reduction of the meta-mouth atom occurs, and the desired product cannot be obtained in high yield, and a high arylmetallocene conjugate is obtained.
  • a purification process such as recrystallization is required, which is not economical, whereas, in an aqueous medium, a meta-mouth Sendai halide (eg, a metallocene dichloride) and an aryl metal (eg, Aryl metal) and the metallocene Methods of synthesizing compounds are known (flat 2-34360, Japanese Patent Publication 63-60027,
  • the arylmetacene compound, which is the objective compound, is an industrially useful catalyst for the production of a high molecular compound having high steric fiber IJ properties and a hydrogenation catalyst. There is a strong need for a product that can be easily worked up and obtained in high yield.
  • a method in which a di-substituted dimethyl metallocene compound is prepared by reacting meta-mouth Sendai halide with a methyldarinyl reagent at 25 ° C in THF-nada (TS per et al., J. Inorg. Nucl. Chem., 3, 104 (1956). ].
  • this method yields a very low yield of 1%
  • WO97 / 09336 states that META-mouth Sendai halide is methyldarinyl for 10 minutes at -5 ° C or 1 at -5 ° C. It has been reported that a di-substituted dimethylmetacene compound can be obtained with a high yield by adding a drug.
  • an object of the present invention is to solve the above-mentioned problems in the synthesis of a meta-opencane compound, and to provide an aryl group which can be obtained safely, inexpensively, in a simple manner and in a high yield, This is to refer to the synthetic method of 2-position ⁇ ) meta-sensing ⁇ ! With benzyl group or diarylphosphinomethylene group. Disclosure of the invention
  • the present inventors have surprisingly found that by specifying reaction conditions and reacting metallocene dihalide with Grignard fiber, the above-mentioned 2-substituted metallocene compound can be obtained in high yield.
  • the present invention was made. sand By the way,
  • a method for producing a metallocene compound which comprises producing a disubstituted metallocene compound by subjecting a meta-mouth Sendai halide to a compound represented by KMgX.
  • R represents an aryl group, benzinole group or diarylphosphinomethylene group which may have a substituent, and X represents a nodogen element.
  • SiS is carried out under conditions in which the secondary metal is infrequent, and the meta-acene compound described in (1) is synthesized.
  • a metallocene compound described in (a) to (4) or (4) above which is metal nuclear power i, Zr, or Hf of a meta-mouth Sendai halide.
  • the compound of Alkyri metal which has been a conventional problem, can be used, and the halogen of meta-mouth Sendai halide can be removed without any problem. It can be substituted with substituents such as 1-/-, benzyl /-, and di-phosphinomethylene groups.
  • substituents such as 1-/-, benzyl /-, and di-phosphinomethylene groups.
  • the meta-mouth compound is obtained by reacting a meta-modi Sendai halide with a compound represented by the general formula 0) (hereinafter sometimes referred to as Grignard / drug) under the condition that no side reaction occurs.
  • a meta-modi Sendai halide means that one molecule of a central metal is coordinated with two molecules of a cyclopentadiene ring or a cyclopentadiene ring having a substituent, and two halogen atoms are further coordinated. Things.
  • the disubstituted meta-mouth compound refers to a meta-open-sene compound in which all the two halogens of the meta-mouth Sendai halide are replaced by the general 3 ⁇ 4 (R in R).
  • R in R the general 3 ⁇ 4
  • S ⁇ is less than 25 ° C to -30 ° C, considering the yield and key of the target compound. , Preferably 15 to -25 ° C, more preferably -5 to -20 ° C, and the dropping time is 3 to 20 hours, preferably 5 to 15 hours, more preferably 10 hours. Before and after is more preferred.
  • the target product obtained by the synthesis method of the present invention contains a compound which is relatively weak at high or low temperature, the reaction is completed in order to further suppress the decomposition of the target product and the like. Therefore, it is preferable that the temperature at the time of dropping is within the above range.
  • the dropping time is less than 3 hours, there is a tendency for the reaction to be insufficient and the impurities to be removed, and the quality of the product to be deteriorated. This is thought to be due to the presence of a large amount of the Grignard reagent relative to the meta-mouth Sendai halide, whereby the reduction reaction of the transition proceeds together with the halogen substitution reaction.
  • the dropping time is too short, the mSiS is sufficiently placed and the rf tends to generate a mixture of ⁇ 2 substitution and 1 fiber, which is not substituted only by 1 substitution.
  • the dropping time exceeds 20 hours, Although it is thought that the halogen of dihalide is properly replaced by the R group in the general formula (I) by the Grignard reagent, the dropping time is too long, and there is a problem that the synthesized product deteriorates with time. Tend.
  • the Grignard reagent of the general formula 0) is used in an amount of 0.9 to 1.5 mol times the physics ft, preferably 0.95 to 1.05 times the ⁇ ! ; *; L20 mol times, more preferably 1.10 times the meta-mouth Sendai halide. force s preferably reacted by adding ⁇ 1.15mol times.
  • the molar ratio of the amounts of Grignard and meta-mouth Sendai halide used in the present invention is 2: 1 [Theoretical amount of this is that all halogens of meta-mouth Sendai halide are equal to R in 1; 0). Is replaced. ].
  • the added general G (G) when the added general G (G) is 0.9 mol, the presence of an unstable reaction intermediate tends to cause a side reaction, which results in a decrease in quality and yield.
  • the Grignard reagent of general formula 0) to be added exceeds 1.5 mol times of the Grignard reagent ifi, a separate step is required to connect Grignano, which complicates the production, and further increases the crystal quality. Since a large amount of Mg remains inside, the quality of the target compound produced tends to decrease.
  • the Grignard ⁇ ⁇ ⁇ which is a compound of the general formula 0
  • the Grignard ⁇ ⁇ ⁇ which is a compound of the general formula 0
  • the Grignard ⁇ ⁇ ⁇ which is a compound of the general formula 0
  • R in the general formula 0) may be the same or different and may have one or more substituents, such as an aryl group, a benzyl group or a di / rephosbuinomethylene group.
  • the substituent having a substituent on the aryl group, benzyl group (the benzene ring of the benzyl group) and the diarylphosphinomethylene group represented by R in the general formula (0) has a carbon number of 1 to 20 straight-chain or branched alkyl groups and alkoxy groups, aryloxy groups, alkylsilyl groups, arylsilyl groups, alkoxysilyl groups, aryloxyxyl groups, and the like.
  • the aryl group represented by R in the general formula (0) include aryl groups having 6 to 14 carbon atoms, which may have one or more substituents which may be the same or different.
  • aryl groups include phenyl, trinole, ethylphenyl, butylphenyl, dimethylphenyl, trimethylphenyl, methoxyphenyl, dimethoxyphenyl and ethoxy.
  • Examples of the benzyl group represented by R in general (0) include a benzyl group which may have one or more substituents which may be the same or different on a benzene ring, and a specific example of a benzyl group is benzyl. And methylbenzyl, methoxybenzyl, phenylbenzyl, phenoxybenzyl, trimethylsilylbenzyl and the like.
  • the diarylphosphinomethylene group represented by R in the general 3 ⁇ 40 includes one ⁇ -CR 2 m'R "(R 7 and R" may have one or more substituents which may be the same or different.) And represents an aryl group having 6 to 14 carbon atoms.) Specific examples thereof include dipheninophenomethylene, bismethoxyphen-norrefosphinomethylene, and bisphenoxyphenylphosphinomethylene. No.
  • meta-mouth Sendai halide a commercially available one can be used, and in general, it may be synthesized by removing ⁇ !
  • Examples of the metal of the meta-mouth Sendai halide used in the present invention include a fourth period, a fifth synchronous transition, and a sixth period transition.
  • the components include titanium, vanadium, chromium, iron, cobalt, nickel, zirconium, ruthenium, and nornium.
  • Examples of the halogen of the meta-mouth Sendai halide include bromine, chlorine, iodine and the like, and preferably bromine.
  • the cyclopentagenenyl ring of the meta-mouth Sendai halide used in the present invention may have a substituent or may be cross-linked, and the substituent has 1 to! And a silyl group having 1 to 12 carbon atoms. Any substituent may be used as long as it does not inhibit the present invention.
  • These substituents may be cyclopentadene / ⁇ in which mono-, di-, tri-, tetra-, and penta-substituted cyclopentadienyl rings are substituted.
  • 1 to 12 carbon groups such as a hydrocarbon group of Includes hydrogen group, moon hydride group, and TK ⁇ kTK element group, and also has 1 to 1 carbon atoms!
  • RET R "Si- or -SiRET- (, IT, R” each represents an alkyl S having 1 to 12 carbon atoms), which forms a ring on the same cyclopentagenino
  • Furuoreniru, Indeyuru, Tetorahi Doroindeyuru, methylene, ethylene, -C (CH3) 2 -, -C (C 2 H5) 2 -, -Si (CHs) 2 -, -S (C 2 H 5) 2 - and the like Are mentioned.
  • an anhydrous organic solvent can be used, and preferably, a chain ether, a cyclic carbon, a mixed solvent thereof and the like can be used.
  • chain ethers include getyl ether and 1,2-dimethoxetane, and cyclic hydrocarbons are substituted with cyclohexane, benzene, toluene, xylene, and one or more halogens. Tiff self-fragrance! ⁇ More preferred are fi xylene, toluene, and 1,2-dimethoxyethane.
  • Example 1 do bis- (dipheninolefos fuinomethylene) -bis (-cyclopentane) was carried out in the same manner as in Example 1 except that diphen2 / refosfuinomethylene magnesium chloride was used as Grignard ⁇ . An orange crystal of (Jeninole) titanium was obtained. The yield is 62.5%, and the quality is satisfactory.
  • Example 1 the synthesis and treatment were carried out in the same manner as in Example 1 except that R) ⁇ tanada was changed to 1,2-dimethoxyethane, and di-P. Tolylbis (7J-cyclopentagel) was obtained. 8294g (yield; 65.0%) of orange crystals of titanium were obtained; ⁇ o The i content of the obtained crystals was 13.23% (S ⁇ ; 13.29%), the difficult Mg content was lppm, and the C1 content was 5ppm. Yes, the quality was satisfactory enough.
  • Example 1 was carried out in the same manner as in Example 1 except that the internal temperature was 24 ° C and the Grignard drug was dropped in 2 hours.
  • the product contained many impurities and was purified by repeated recrystallization.
  • the yield of di-P-tolylbis (77-cyclopentapentaenyl) titanium was 35%.
  • Example 1 was carried out in the same manner as in Example 1 except that the internal temperature was 25 ° C and the Grignard reagent was dropped in 1.5 hours.
  • the product is very high in impurities and repeats recrystallization
  • the yield of di-P-tolylbis ( ⁇ -cyclopentapentageninole) titanium, which was the target compound, was 3%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des composés métallocènes disubstitués, de grande qualité, peuvent être entièrement synthétisés à faible coût pour des rendements élevés, au moyen d'un procédé facile mettant en réaction un dihalide métallocène avec un réactif de Grignard dans des conditions spécifiques. Ledit dihalide métallocène est un composé de la formule générale (I): RMgX dans laquelle R est aryle éventuellement substitué, benzyle ou diarylphosphinométhylène, et X est halogène.
PCT/JP1998/002819 1996-12-25 1998-06-24 Procede pour synthetiser des composes metallocenes WO1999067260A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/486,273 US6175025B1 (en) 1996-12-25 1998-06-24 Process for synthesizing metallocene compounds
PCT/JP1998/002819 WO1999067260A1 (fr) 1998-06-24 1998-06-24 Procede pour synthetiser des composes metallocenes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1998/002819 WO1999067260A1 (fr) 1998-06-24 1998-06-24 Procede pour synthetiser des composes metallocenes

Publications (1)

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WO1999067260A1 true WO1999067260A1 (fr) 1999-12-29

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH093085A (ja) * 1995-06-19 1997-01-07 Hoechst Ag 立体的に堅固なメタロセン化合物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH093085A (ja) * 1995-06-19 1997-01-07 Hoechst Ag 立体的に堅固なメタロセン化合物

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