JP2001029794A - Ruthenium metathesis catalyst and method for producing olefin reaction product by metathesis reaction using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely and easily provide a ruthenium metathesis catalyst in a mass production usable as a catalyst for a carbon-carbon bond formation reaction by a metathesis reaction. SOLUTION: This ruthenium metathesis catalyst comprises a compound having formula I and a compound having formula II or III. Formula I is [RuX12(arene)(PR1R2R3)]2, formula II is R4CHX2, and formula III is R5ACC (wherein X1 and X2 separately denote a halogen atom; arene denotes a benzene ring-containing hydrocarbon; R1 to R3 separately denote an alkyl group, a cycloalkyl group, or an aryl group optionally having substituents; R4 denotes an alkyl group optionally having an ether bond or an ester bond and the like; and Ace denotes ethenyl.). Alternatively, the metathesis catalyst comprises compounds having formulas IV, V, and III. Formula IV is [RuX12(arene)]2, formula V is PR1R2R3, and formula III is R5ACC (wherein X1, arene, R1, R2, R3, R5, and Ace are the same as defined above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel ruthenium metathesis catalyst and a method for producing an olefin reaction product using the same. More specifically, the present invention relates to a ruthenium metathesis catalyst used as a catalyst for a carbon-carbon bond formation reaction using a metathesis reaction, particularly a metathesis reaction, and a method for producing a cyclic olefin, an internal olefin, or a polyolefin using the same.

[0002]

2. Description of the Related Art Conventionally, many transition metal complexes have been used as catalysts for organic synthesis reactions. Among them, a metathesis reaction of olefins catalyzed by a transition metal complex has been studied particularly in polymerization reactions of olefins (RH Grubbs, W. Tumas, Science, 1989, 243, pp 9).
07-915). This reaction has traditionally been based on tungsten-based catalysts (WC
l ₆ / EtAlCl ₂ or WCl ₆ / Cp ₂ TiMe ₂ (Et is an ethyl group, Me is a methyl group and Cp is a cyclopentadienyl group) or a titanium-based catalyst (Cp ₂ Ti (Cl) CH ₂ ) AlMe ₂ ) has been used for the synthesis of bioactive natural products such as civetone, D ⁹ , ¹⁰ -capnellan and 9-trichocene (Grubbs e).
etal. Acc. Chem. Res. 1995, 28, pp 446-452), generally the reaction selectivity, yield or stability to various functional groups is not always good.

Recently, it has been reported that the ring-closing metathesis of non-conjugated dienes and enones proceeds with high selectivity and efficiency using a molybdenum carbene complex catalyst (RH Grubbs).
etal. Acc. Chem. Res. 1995, 28, pp 446-452). However, this catalyst has very poor stability to many functional groups and to oxygen and moisture. Thus, ruthenium carbene complexes that are relatively stable to air and moisture have been developed (WO 93/20111, WO 96/04289, WO 97/06185, F. Oza
wa et al. 44th Symposium onOrganometallic Chemistr
y, Japan. Abstracts, 1997, pp 74-75). This catalyst is effective for ring-closing metathesis reaction of non-conjugated dienes, metathesis ring-opening polymerization of cyclic olefins, and the like, but requires many steps for catalyst preparation. As a method for preparing a catalyst with a shortened process, metathesis ring-opening polymerization of norbornene and cyclooctene is performed using in situ (A.
F. Noels et al., J. Chem. Soc., Chem. Commun., 199
5, pp 1127-1128; Macromolecules, 1997, 30, pp 3127
-3136). However, since these methods use unstable compounds (for example, diazo compounds), it is very difficult to produce a large amount of a catalyst in actual industrialization, and the metathesis reaction using the catalyst is on an industrial scale. There was a disadvantage that it could not be used.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a ruthenium metathesis catalyst which is safe, simple and can be obtained in large quantities by using a stable precursor and mixing the precursor in a system. Another object of the present invention is to provide a method for efficiently producing a cyclic olefin, an internal olefin or a polyolefin in a short time by performing a metathesis reaction of an olefin and a ring-opening metathesis polymerization reaction of an olefin using the catalyst.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, when a ruthenium compound having an alkyl group-substituted benzene ring is employed, the ruthenium metathesis can be carried out by a safe and simple method. It has been found that the catalyst can be prepared. Moreover, the metathesis catalyst has the same catalytic activity as a conventionally known metathesis catalyst, and can be widely used as a catalyst for a metathesis reaction, and a metathesis reaction of a non-conjugated diene, a cross-metathesis reaction of a terminal olefin and an olefin When used as a catalyst for the ring-opening metathesis polymerization reaction of
The inventors have found that internal olefins and polyolefins can be produced, and have completed the present invention.

Namely, the present invention, the table in the formula _{^{(1) RuX 1 2 (arene}} ) (PR 1 R 2 R 3) (1) a ruthenium compound and formula represented by ^{(2) R 4 CHX 2 (} 2) Or a terminal alkyne represented by the formula (3) R ⁵ Ace (3) (wherein X ¹ and X ² represent a halogen atom, arene represents a hydrocarbon having a benzene ring, R ¹ , R ² and R ³ may be the same or different and each may be an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group which may have a substituent (substituents having 1 to 8 carbon atoms) R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms, or a halogen atom. Having a bond Alkyl group, an optionally substituted aryl group or a cycloalkyl group having a carbon number of 3 to 8 (the substituent is a halogen atom or a hydroxyl group),
R ⁵ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and which may have an ether bond or an ester bond, an aryl group, or a cycloalkyl group having 3 to 8 carbon atoms (substituted Is a halogen atom or a hydroxyl group), and Ace represents an ethynyl group), or a metathesis catalyst comprising

[0007] Equation _{^{(4) [RuX 1 2 (}} arene)] 2 ruthenium compound represented by (4), Equation ^{(5) PR 1 R 2 R} 3 (5) represented by phosphine and the formula in (3) R Terminal alkyne represented by ⁵ Ace (3) (wherein, X ¹ , arene,
R ¹ , R ² , R ³ , R ⁵ , and Ace are the same as described above), and an olefin substrate is subjected to a metathesis reaction in a reaction solution into which the respective metathesis catalysts have been added to produce an olefin reaction. A method of manufacturing a product,
It is.

[0008]

First ruthenium metathesis catalyst of the embodiment of the present invention _{^{is, RuX 1 2 (arene) (}} PR 1 R 2 R 3) (1) a ruthenium compound and formula (2) represented by R ⁴ CHX ² (2) dihalogeno compound represented by or _{^{RuX 1 2 (arene) (PR}} 1 R 2 R 3) ruthenium compound represented by (1), and ends the formula (3) R ⁵ Ace (3) Consists of alkyne. A first component constituting the catalyst RuX ¹ ₂ (arene) (PR
Specific examples of X in ¹ R ² R ³ ) include chlorine, bromine and iodine. A preferred example of (arene) is benzene or benzene having a substituent, and the substituent is preferably an alkyl group or an alkoxy group having 1 to 4 carbon atoms. Specifically, benzene, p-cymene, methoxybenzene, hexamethylbenzene and the like can be mentioned.

Further, R ¹ , R in (PR ¹ R ² R ³ )
Examples of the alkyl group having 1 to 8 carbon atoms of ² and R ³ include:
Methyl, ethyl, propyl, isopropyl, butyl, 1-methylpropyl, pentyl, 2-ethylpropyl, 1-methylbutyl, hexyl, 1-
There are methylpentyl group, 1-methylhexyl group, 1-methylheptyl and the like, and as a cycloalkyl group having 3 to 8 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. And an aryl group which may have a substituent includes a phenyl group, a 2-methylphenyl group,
Methylphenyl group, 2,6-dimethylphenyl group, 4-
Examples include a biphenyl group, a 4-methoxyphenyl group, a 4-dimethylaminophenyl group, a 4-chlorophenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Specific examples of phosphine (PR ¹ R ² R ³ ) include triisopropylphosphine and tri (butane-
2- (yl) phosphine, tri (pentan-2-yl) phosphine, tri (pentan-3-yl) phosphine, tri (hexane-2-yl) phosphine, tri (heptane-2-yl) phosphine, tri (octane- 2-yl)
Phosphine, diisopropylphenylphosphine, di (butan-2-yl) phenylphosphine, di (pentan-2-yl) phenylphosphine, di (pentane-3)
-Yl) phenylphosphine, di (hexane-2-yl) phenylphosphine, di (heptane-2-yl) phenylphosphine, di (octane-2-yl) phenylphosphine, isopropyldiphenylphosphine, butan-2-yldiphenylphosphine Pentane-2-yldiphenylphosphine, pentan-3-yldiphenylphosphine, hexane-2-yldiphenylphosphine, heptane-2-yldiphenylphosphine, octane-2-yldiphenylphosphine, tricyclopropylphosphine, tricyclobutylphosphine , Tricyclopentylphosphine, tricyclohexylphosphine, tricycloheptylphosphine, tricyclooctylphosphine, dicyclopropylphenylphosphine,
Dicyclobutylphenylphosphine, dicyclopentylphenylphosphine, dicyclohexylphenylphosphine, dicycloheptylphenylphosphine, dicyclooctylphenylphosphine, cyclopropyldiphenylphosphine, cyclobutyldiphenylphosphine, cyclopentyldiphenylphosphine, cyclohexyldiphenylphosphine, cycloheptyldiphenylphosphine, And cyclooctyldiphenylphosphine.

The ruthenium complex represented by the above formula (1) can be obtained, for example, by the method of Can. J. Chem., Vol. 50, 3063 (1972). As a specific method, for example, dichloro (p-cymene) triphenylphosphineruthenium (RuCl ₂ (p-cymene) PPh ₃ ) is
μ-chlorobis [(p-cymene) chlororuthenium]
It is obtained by refluxing ([RuCl ₂ (p-cymene)] ₂ ) and triphenylphosphine in an organic solvent.

The present invention has one feature in using the ruthenium complex. That is, for example, a ruthenium complex containing cyclooctadiene instead of arene does not bring about the effects of the present invention.

Specific examples of the 1,1-dihalide represented by the formula (2) as the second component constituting the catalyst include 1,1-dihalides such as ethylidene chloride, ethylidene bromide and ethylidene iodide. Dihalogenoalkyl aromatic compounds such as halogenoalkanes, benzal chloride, benzal bromide, and benzal iodide; dihalogeno fatty acid esters such as methyl dichloroacetate, methyl dibromoacetate, methyl diiodoacetate, ethyl dichloroacetate, ethyl dibromoacetate, and ethyl diiodoacetate And the like. The 1,1-dihalide used in the present invention may be at least twice the molar amount of the ruthenium complex represented by the above formula (1), and can be used as a reaction solvent. These dihalides can be used commercially or can be prepared by a known method.

The second component constituting the catalyst may be a terminal alkyne represented by the formula (3). Specific examples of the terminal alkyne include phenylacetylene, 4-methylphenylacetylene, 4-chlorophenylacetylene, aromatic acetylenes such as 3-phenyl-1-propyne, 1-pentyne, 1-hexyne, 1-heptin, -Octin, 1-
Desine, 3,3-dimethyl-1-butyne, 5-chloro-1
-Aliphatic acetylenes such as pentyne, propargyl alcohol, 3-butyn-2-ol, 2-methyl-3-
Alcohols such as butyn-2-ol, 3-butyn-1-ol, 2-propynyl acetate, 2-methyl-3 acetate
Esters such as -butyn-2-yl and methyl acetylenecarboxylate; carbonates such as propargylmethyl carbonate; and ethers such as propargylmethyl ether. The terminal alkyne used in the present invention may be at least twice the molar amount of the ruthenium complex represented by the above formula (1), and can also be used as a reaction solvent. These terminal alkynes can be used commercially or can be prepared by known methods.

The first metathesis catalyst of the present invention comprises the above ruthenium complex (1) and a dihalogeno compound (2) or the above ruthenium complex (1) and a terminal alkyne (3). This metathesis catalyst is prepared by adding the ruthenium complex (1) and the dihalogeno compound (2) or the terminal alkyne (3) to a reaction vessel which has been replaced with an inert gas such as nitrogen and stirring the mixture in a solvent. Can be easily obtained. Examples of the solvent used include halogenated organic solvents such as methylene chloride, methylene bromide, 1,2-dichloroethane, and chlorobenzene, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ethyl acetate, butyl acetate, and methyl benzoate. Esters,
Dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran and the like can be mentioned. In preparing the catalyst, the amount of the ruthenium complex (1) to be present in the solvent is preferably adjusted to be 0.001-1 mol concentration.

A second metathesis catalyst of the present invention, in formula _{^{(4) [RuX 1 2 (}} arene)] 2 (4) ruthenium compound represented by the formula ^{(5) PR 1 R 2 R} 3 (5) terminal alkyne (where represented by represented by phosphine and the formula ^{(3) R 5 Ace (3} ), X 1, arene,
R ¹ , R ² , R ³ , R ⁵ and Ace are the same as described above). X and (arene) of the ruthenium compound represented by the formula (4), which are the first components constituting the second metathesis catalyst, are as described above.

The ruthenium complex represented by the above formula (4)
Is, for example, the method of Can. J. Chem., Vol 50, 3063 (1972).
Can be obtained by As a specific method, for example
For example, di-μ-chlorobis [(p-cymene) chlororuthen
Um] ([RuCl_Two (P-cymene)]_Two ) Is ruthenium chloride
Refluxing of calcium and α-ferrandrene in ethanol
Obtained by As a specific example of the above ruthenium complex
Is [RuCl_Two (benzene)]_Two  [RuCl_Two (P-cymene)]_Two  [RuCl_Two (Hexamethylbenzene)]_Two  [RuCl_Two (Methoxybenzene)]_Two  [RuBr_Two (benzene)]_Two  [RuBr_Two (P-cymene)]_Two  [RuBr_Two (Hexamethylbenzene)]_Two  [RuBr_Two (Methoxybenzene)]_Two  [RuI_Two benzene)]_Two  [RuI_Two (P-cymene)]_Two  [RuI_Two (Hexamethylbenzene)]_Two  [RuI_Two (Methoxybenzene)]_Two  And the like.

The phosphine (5) as the second component constituting the second metathesis catalyst is as described above. It is advantageous from the viewpoint of reactivity and economy that the phosphine used in the present invention has an equivalent weight or more of the ruthenium complex represented by the above formula (4). Specifically, it is preferable to coexist 1.6 to 2 times the molar amount of the ruthenium complex. The terminal alkyne (3) as the third component constituting the second metathesis catalyst is as described above.

The metathesis catalyst composed of the ruthenium complex (4), phosphine (5) and terminal alkyne (3) is obtained by adding each of the above components to a reaction vessel which has been replaced with an inert gas such as nitrogen. Can be easily obtained by stirring. Examples of the solvent used include halogenated organic solvents such as methylene chloride, methylene bromide, 1,2-dichloroethane, and chlorobenzene, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ethyl acetate, butyl acetate, and methyl benzoate. And dimethylformamide, dimethylsulfoxide, dioxane, tetrahydrofuran and the like. In preparing the catalyst,
The amount of the ruthenium complex (4) to be present in the solvent is 0.001.
Preferably, the concentration is -1 mol.

The thus obtained metathesis catalyst of the present invention has extremely high catalytic activity and can be widely used as a catalyst for a metathesis reaction for preparing a metathesis reaction product from a metathesis reaction substrate.

As the metathesis reaction substrate, any substrate can be used as long as it is a metathesis reaction substrate known before the present application, and specifically, the formula (5) CH ₂ ＣＨCHR ⁷ (5) (R ⁷ is A hydrogen atom, an alkyl group, an alkenyl group, or an aryl group having 1 to 20 carbon atoms, which may have a substituent, such as a hydroxy group, a carboxy group, a keto group, a silyl group, or an alkoxy group; A terminal olefin represented by a group, an aryloxy group, an amino group, a halogen atom, an aryl group, an ester bond or an amide bond.

Formula (7) R ⁸ CH ＝ CHR ⁹ (7) (R ⁸ and R ⁹ are a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group having 1 to 20 carbon atoms, and they have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a keto group, a silyl group, an alkoxy group, an aryloxy group, an amino group, a halogen atom, an aryl group, and a group containing an ester bond or an amide bond. )
An internal olefin represented by the formula (8)

Embedded image
(8) (R ¹⁰ is an alkyl group, an alkenyl group, or an aryl group which may contain an oxygen atom, a nitrogen atom, or the like having 3 to 20 carbon atoms, and these may have a substituent.
Examples include a hydroxy group, a carboxy group, a keto group, a silyl group, an alkoxy group, an aryloxy group, an amino group, a halogen atom, an aryl group, and a group containing an ester bond or an amide bond. )).

The above-mentioned olefin substrates may be used alone or in combination of two or more. The appropriate combination of substrates is determined by the chemical structure of the desired olefin product. Further, a cross metathesis reaction, a ring-opening metathesis polymerization reaction and the like can also be used. Although the metathesis reaction product obtained in the present invention is not particularly limited, the following are typical metathesis reaction products. First,
Examples of the terminal olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
Hydrocarbons such as 1-decene, styrene, 4-chlorosterene, 4-methoxystyrene, 2-propen-1-ol (allyl alcohol), 4-penten-2-ol, 5-hexene-1
-All, 2-methyl-6-hepten-2-ol, 9-decene
-1-ol, 9-decene-2-ol, 10-undecene-1-
Alcohols such as oar, 2-propenyl acetate,
Esters such as 5-hexen-1-yl acetate, 9-decene-1-yl acetate, 10-undecen-1-yl acetate, methyl acrylate, methyl 3-butenoate, methyl 9-decenoate, methyl 10-undecenoate,
Examples include acids such as 9-decenoic acid and 10-undecenoic acid.

Examples of the internal olefin include hydrocarbons such as 2-butene, 2-pentene, 3-hexene, 3-heptene, 4-octene, 5-decene and 9-octadecene, and 2-butene-1,4. Alcohols such as -diol, acids such as 9-octadecene-1,18-dicarboxylic acid, 10-eicosene-1,20-dicarboxylic acid, dimethyl 9-octadecene-1,18-dicarboxylate, 10-eicosene-1, Esters such as dimethyl 20-dicarboxylate. Examples of the cyclic olefin include hydrocarbons such as cyclopentene, cyclohexene, and cyclooctene; 3-cyclopentene-
Esters such as diethyl 1,1-dicarboxylate, 10-tetradecene-14-olide, 10-pentadecene-15-olide,
Lactones such as 4-pentadecene-15-olide and 10-eicosene-20-olide. Examples of the polyolefin include poly (cyclooctene), poly (norbornene), and poly (7-oxanorbornene).

In order to carry out a metathesis reaction using the catalyst of the present invention, the above-mentioned metathesis catalyst and the solvent used are mixed at 0 ° C.
~ 140 ° C, preferably room temperature ~ 80 ° C for about 10 minutes ~ 1
After stirring for a time, the reaction substrate may be directly charged into the solution containing the catalyst. Alternatively, the components constituting the metathesis catalyst and the reaction substrate may be simultaneously charged to perform the metathesis reaction in a solvent. Further, a part of each component constituting the metathesis catalyst may be added, and the remaining catalyst components may be further added.Alternatively, the reaction substrate may be first added to the solvent, and then the catalyst components may be added. Good. As the solvent used,
Although it is advantageous to use the same solvent employed when preparing the metathesis catalyst, it is not necessary that it be the same solvent.
The temperature of this metathesis reaction is 0 ° C to 140 ° C.
And the reaction time is preferably 30 minutes to 40 hours. The amount of the ruthenium complex used in the present invention is 0.001 to 50 mol%, preferably 0.01 to 30 mol%, more preferably 0.05, based on the reaction substrate.
~ 20 mol% can be used.

[0026]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following examples, the following instruments were used for measuring the physical properties of the obtained compounds. Table 1
The results of Examples 1 to 5 and Examples 7 to 8 are shown in FIG. ¹ H-NMR spectrum: DRX-500 apparatus (manufactured by Bruker) Internal standard substance; tetramethylsilane ³¹ P-NMR spectrum: DRX-500 apparatus (manufactured by Bruker) External standard substance: 85% phosphoric acid molecular weight : D-2520 GPC Integrater (Hitachi, Ltd.
(Made by Co., Ltd.)

Reference Example: Synthesis of dichloro (p-cymene) tricyclohexylphosphine ruthenium Di-μ-chlorobis [(p-cymene) chlororuthenium] 1.86 g (3.0 mmol), methylene chloride 20 ml under a nitrogen stream
The solution of tricyclohexylphosphine 1.567
g (5.59 mmol) in 15 ml of methylene chloride was added dropwise, and the mixture was stirred at room temperature for 1 hour and concentrated to about 15 ml.
70 ml of hexane was added thereto, and the mixture was allowed to stand for 2 hours. The precipitated solid was filtered, and the residue was washed with hexane and dried with a vacuum pump to obtain 2.89 g of the desired product. 82.3% yield. ¹ H-NMR (CD ₂ Cl ₂ ) δ: 1.1 (d, 6H, J = 7 Hz), 1.85
(s, 3H), 2.78 (sept, 1 H, J = 6.9 Hz), 4.99 (d, 2
H), 5.19 (d, 2H) 7.35-7.39 (m, 6H), 7.40-7.42 (m,
3H), 7.77-7.81 (m, 6H) ³¹ P-NMR (CD ₂ Cl ₂ ) δ: 25.77 (s)

[0027]

Example 1 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate In a 5 ml flask under a nitrogen stream, 0.293 g (1.22 mmol) of diethyl diallylmalonate and 0.036 g of dichloro (p-cymene) tricyclohexylphosphine ruthenium (0.061 mm
ol), toluene 1.5 ml, methyl dichloroacetate 0.006 ml
(0.061 mmol), and the mixture was stirred at 80 ° C. for 2.5 hours. Conversion rate 89.3%. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (toluene) to obtain 0.224 g.
Was obtained. Yield 76.6%. ¹ H-NMR (CDCl ₃ ) δ: 1.24 (t, 6H, J = 7.2 Hz), 3.00 (s,
4H), 4.19 (q, 4 H, J = 7.2 Hz), 5.60 (s, 2H)

[0028]

Example 2 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate Under a nitrogen stream, 0.539 g (2.246 mmol) of diethyl diallylmalonate and 0.066 g of dichloro (p-cymene) tricyclohexylphosphine ruthenium were placed in a 10 ml flask in a nitrogen stream. (0.112
mmol), toluene 3 ml, benzal chloride 0.015 ml (0.112
mmol), and the mixture was stirred at 80 ° C for 3 hours.
The desired product was obtained in a yield of 54.6%.

Example 3 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate Same as Example 1 except that 0.0067 ml (0.061 mmol) of phenylacetylene was used in place of methyl dichloroacetate and the mixture was stirred for 18 hours. 95.5 conversion rate
%, Yield 80.9%.

[0029]

Example 4 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate Same as Example 1 except that in Example 1, 0.0059 g (0.061 mmol) of propargyl acetate was used in place of methyl dichloroacetate and stirred for 20 hours. 91.8% conversion rate
The desired product was obtained with a yield of 66.0%.

Example 5 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate In Example 1, 0.0059 ml (0.061 mmol) of propargyl bromide was used in place of methyl dichloroacetate.
The same operation as in Example 1 was carried out except that the mixture was stirred for an
The desired product was obtained in 1.1% and a yield of 57.3%.

[0030]

Example 6 Synthesis of polyoctene by metathesis ring-opening polymerization of cyclooctene Under a nitrogen stream, 0.025 g (0.043 mmol) of dichloro (p-cymene) tricyclohexylphosphine ruthenium, 1 ml of toluene, 0.0043 ml of methyl dichloroacetate (0.043 mmo)
l) and 2.8 ml (21.5 mmol) of cyclooctene were added and stirred for 18 hours. The reaction product was dissolved in 5 ml of methylene chloride, poured into 150 ml of methanol and reprecipitated to obtain 1.90 g of polyoctene. The yield was 80.2%, the weight average molecular weight was 81,200, and the number average molecular weight was 68,900. ¹ H-NMR (CDCl ₃ ) δ: 1.00-1.75 (m, 10H), 1.75-2.10 (m,
2H), 5.20-5.50 (m, 2H).

[0031]

Example 7 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate 0.056 g (0.2 mmol) of tricyclohexylphosphine and di-μ-chlorobis ((p
-Cymene) chlororuthenium) 0.06 g (0.1 mmol), toluene 5 ml, phenylacetylene 0.02 ml (0.2 mmol),
0.91 g (3.79 mmol) of diethyl diallylmalonate was added, and the mixture was stirred at 80 ° C. for 23 hours. The conversion was 93.0%. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (toluene) to obtain 0.81 g of the desired product. The yield was 89.0%. ¹ H-NMR (CDCl ₃ ) δ: 1.24 (t, 6H, J = 7.2 Hz), 3.00
(s, 4H), 4.19 (q, 4H, J = 7.2 Hz), 5.60 (s, 2H)

[0032]

Example 8 Synthesis of diethyl 3-cyclopentene-1,1-dicarboxylate In Example 7, 2-methyl-3-butyn-2-ol (0.02 ml, 0.2 mmol) was used instead of phenylacetylene.
The same operation as in Example 7 was carried out except that the mixture was stirred for 0 hour, and the conversion was
The desired product was obtained with a yield of 79.8% and a yield of 57.8%.

[0033]

Example 9 Synthesis of 3-cyclopentenyl benzoate 0.53 g (1.9 mmol) of tricyclohexylphosphine and di-μ-chlorobis ((p
-Cymene) chlororuthenium) 0.62 g (1.0 mmol), toluene 50 ml, phenylacetylene 0.22 ml (2 mmol),
8.28 g of 1,6-heptadien-4-yl benzoate (38.3 mmo
l) and stirred at 80 ° C for 22 hours.
The extract was washed with an aqueous sodium hydroxide solution and saturated saline in this order, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was distilled under reduced pressure (73-74 ° C / mmHg) to obtain 5.00 g.
Was obtained. The yield was 69.4%. ¹ H-NMR (CDCl ₃ ) δ: 2.51, 2.59 (dd, 2H), 2.82, 2.9
0 (dd, 2H), 5.59-5.65 (m, 1H), 5.77 (s, 2H), 7.38
-7.58 (m, 3H), 8.00-8.05 (m, 2H)

[0034]

Example 10 Synthesis of polyoctene by metathesis ring-opening polymerization of cyclooctene 0.070 g of tricyclohexylphosphine under a nitrogen stream
(0.25 mmol), di-μ-chlorobis ((p-cymene) chlororuthenium) 0.065 g (0.125 mmol), toluene 1
ml, 0.0255 g (0.25 mmol) of phenylacetylene and 2.76 g (25 mmol) of cyclooctene were added, and the mixture was stirred for 22 hours. The solidified reaction product was dissolved in chloroform, and methanol was added.
Then, the solution was poured into 1.0 l and reprecipitated to obtain 1.77 g of polyoctene. The yield was 64.2%, the weight average molecular weight was 909,000, and the number average molecular weight was 529,000. ¹ H-NMR (CDCl ₃ ) δ: 1.00-1.75 (m, 10H), 1.75-2.10
(m, 2H), 5.20-5.50 (m, 2H).

[0035]

Comparative Example 1 Under a nitrogen stream, 0.078 g (0.28 mmol) of tricyclohexylphosphine, 0.078 g (0.28 mmol) of dichloro-1,5-cyclooctadiene ruthenium were placed in a flask.
Toluene 3.3 ml, phenylacetylene 0.03 ml (0.28mmo
l), diethyl diallymalonate 0.36 g (1.50 mmol)
Was added and the mixture was stirred at 80 ° C. for 4 hours, but the reaction did not proceed at all.

Comparative Example 2 Under a nitrogen stream, 0.059 g (0.21 mmol) of tricyclohexylphosphine, 0.055 g (0.21 mmol) of ruthenium trichloride trihydrate, 4 ml of toluene, 0.023 ml (0.21 mmol) of phenylacetylene, diallylmalone were placed in a flask. 0.27 g (1.13 mmol) of diethyl acid was added and the mixture was stirred at 80 ° C. for 4 hours, but the reaction did not proceed at all.

[Table 1]

[0036]

Industrial Applicability According to the present invention, a catalyst capable of causing a metathesis reaction to proceed efficiently can be prepared safely and easily. In the present invention, various metathesis reaction products can be prepared by selecting an olefin as a substrate, which is extremely advantageous industrially.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 69/74 C07C 69/74 69/78 69/78 C08G 61/08 C08G 61/08 // C07B 61 / 00 300 C07B 61/00 300 C07F 15/00 C07F 15/00 A (72) Inventor Tsutomu Hashimoto 1-4-11, Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Takasago International Corporation Co., Ltd. (72) Inventor Hagiwara Toshimitsu 4-4-1, Nishi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture F-term (reference) 4S0A AA06 AA09 BA27A BA27B BC70A BC70B BE02A BE02B BE26A BE26B BE37A BE37B BE45A BE46B CB59 FC02 4H006 AA02 AC29 BA BA39 BA44 BA48 BA49 BA81 BC32 BJ20 BJ50 BS30 4H039 CA19 CA40 CH40 CJ30 4H050 AA03 AB40 WB11 WB16 WB17 4J032 CA68 CD02 CE03

Claims (8)

[Claims] 1. A formula _{^{(1) RuX 1 2 (arene}} ) (PR 1 R 2 R 3) (1) a ruthenium compound and formula (2) represented by the dihalogeno compound represented by R ⁴ CHX ² (2) Or a terminal alkyne represented by the formula (3) R ⁵ Ace (3) (wherein X ¹ and X ² represent a halogen atom, arene represents a hydrocarbon having a benzene ring, R ¹ , R ² , R ^{And 3} is an alkyl group having 1 to 8 carbon atoms, which may be the same or different, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group optionally having a substituent (the substituent is an alkyl group having 1 to 8 carbon atoms) R 1 is an alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms or a halogen atom), and R ⁴ is an alkyl group having 1 to 8 carbon atoms and has an ether bond or an ester bond. Alkyl group, Cycloalkyl group aryl group or a C 3-8 which may have a group (substituent is a is a halogen atom or a hydroxyl group) indicates,
R ⁵ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and which may have an ether bond or an ester bond, an aryl group, or a cycloalkyl group having 3 to 8 carbon atoms (substituted A group represents a halogen atom or a hydroxyl group), and Ace represents an ethynyl group). Wherein formula (4) [RuX ¹ ₂ (arene)] ₂ ruthenium compound represented by (4), Equation (5) PR ¹ R ² R ³ phosphine represented by (5) and (3 ) Terminal alkyne represented by R ⁵ Ace (3) (wherein, X ¹ represents a halogen atom, arene represents a hydrocarbon having a benzene ring, and R ¹ , R ² , and R ³ are the same or different. An alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms and an aryl group which may have a substituent (the substituent is an alkyl group having 1 to 8 carbon atoms, An alkoxy group, an alkylamino group having 1 to 8 carbon atoms or a halogen atom), and R ⁵ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and has an ether bond or an ester bond. Alkyl and aryl groups Or a metathesis catalyst comprising a cycloalkyl group having 3 to 8 carbon atoms (substituent is a halogen atom or a hydroxyl group, and Ace is an ethynyl group). 3. The metathesis catalyst according to claim 2, wherein the phosphine is present in an amount of 1.6 to 2.0 moles per mole of the ruthenium complex. Wherein formula _{^{(1) RuX 1 2 (arene}} ) (PR 1 R 2 R 3) (1) a ruthenium compound and formula represented by (2) dihalogeno compound represented by R ⁴ CHX ² (2) Or a terminal alkyne represented by the formula (3) R ⁵ Ace (3) (wherein X ¹ and X ² represent a halogen atom, arene represents a hydrocarbon having a benzene ring, R ¹ , R ² , R ^{And 3} is an alkyl group having 1 to 8 carbon atoms, which may be the same or different, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group optionally having a substituent (the substituent is an alkyl group having 1 to 8 carbon atoms) R 1 is an alkyl group having 1 to 8 carbon atoms, an alkylamino group having 1 to 8 carbon atoms or a halogen atom), and R ⁴ is an alkyl group having 1 to 8 carbon atoms and has an ether bond or an ester bond. Alkyl group, Cycloalkyl group aryl group or a C 3-8 which may have a group (substituent is a is a halogen atom or a hydroxyl group) indicates,
R ⁵ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and which may have an ether bond or an ester bond, an aryl group, or a cycloalkyl group having 3 to 8 carbon atoms (substituted A group is a halogen atom or a hydroxyl group), and Ace represents an ethynyl group) in a reaction solution charged with a metathesis catalyst comprising olefins, to produce an olefin reaction product by subjecting the olefins substrate to a metathesis reaction. 5. The formula _{^{(4) [RuX 1 2 (}} arene)] 2 (4) ruthenium compound represented by a phosphine of the formula ^{(5) PR 1 R 2 R} 3 (5), and ( 3) Terminal alkyne represented by R ⁵ Ace (3) (in the formula, X ¹ represents a halogen atom, arene represents a hydrocarbon having a benzene ring, and R ¹ , R ² , and R ³ are the same or different. An alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group which may have a substituent (the substituent is an alkyl group having 1 to 8 carbon atoms, R ⁵ is an alkyl group having 1 to 8 carbon atoms which may have a substituent and has an ether bond or an ester bond. Alkyl group and aryl group Alternatively, a metathesis reaction of an olefin substrate is carried out in a reaction solution into which a metathesis catalyst comprising a cycloalkyl group having 3 to 8 carbon atoms (substituent is a halogen atom or a hydroxyl group) and Ace represents an ethynyl group). A olefin reaction product. 6. The method for producing an olefin reaction product according to claim 4, wherein the olefin substrate is a terminal olefin. 7. The method for producing an olefin reaction product according to claim 4, wherein the olefin substrate is an internal olefin. 8. The method for producing an olefin reaction product according to claim 4, wherein the olefin substrate is a cyclic olefin.