JP2985085B2 - Organic platinum compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organoplatinum compound, and more particularly, to an organoplatinum compound such as metal platinum produced by thermal decomposition. In particular, the organoplatinum compound of the present invention has high solubility in carbitol solvents such as butyl carbitol acetate, and other solvents, and is an improved organoplatinum compound that maintains its solution state for a long time. The solution-type paste composition containing the organoplatinum compound can be used as a decoration made of a metal platinum thin film on a substrate, or to form a conductive circuit made of a metal platinum thin film on a substrate, or to form a metal on a substrate. It can be used to form various electrodes made of a platinum thin film.

Further, the organoplatinum compound of the present invention is mixed with a gold paste such as metal gold produced by thermal decomposition, by mixing with a palladium paste such as metal palladium produced by thermal decomposition, or By mixing with a mixture of the above, respectively, to decorate a thin film of platinum-gold alloy, platinum-palladium alloy, or platinum-gold-palladium alloy on the substrate, or to form a conductive circuit, or It can also be used to form various electrodes.

[0003]

2. Description of the Related Art As a method for forming a metal platinum thin film on a substrate, Japanese Patent Application Laid-Open No. Sho 51-86451 discloses a solution of bis (cis, cis-cycloocta-1,5-diene).
A method is described in which platinum is applied to a carrier, and then the carrier is heated to decompose bis (cis, cis-cycloocta-1,5-diene) platinum and deposit metallic platinum on the carrier.

In addition, the publication discloses the following general formula [II] Pt (Q) ₃ --- [II] (wherein Q is an olefinic compound such as olefin, arene, acetylene, or substituted olefin) Or acetylene 2
It represents a compound having at least one heavy bond or triple bond. )) Is applied to a carrier, and then the carrier is heated to decompose the compound represented by the general formula [II] to deposit metal platinum on the carrier. ing.

[0005] Japanese Patent Laid-Open No. 3-247772, the following general formula ^{[III] Pt (R 3 -C≡C} -R 4) 2 ------- [III] ( wherein, R ³ and R ⁴ represents a phenyl group, a 4-methylphenyl group or a 4-methoxyphenyl group, and R ³ and R ⁴
May be the same or different. ) Is applied to a substrate, and then the substrate is heated to decompose the compound represented by the general formula [III] to form a metal platinum thin film on the substrate. Have been.

[0006]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 51-8 / 1980
No. 6451, a solution of bis (cis, cis-cycloocta-1,5-diene) platinum is applied to a carrier, and the carrier is heated to form bis (cis, cis-cycloocta-1,5-diene). In the method of decomposing diene) platinum and depositing platinum on a carrier, bis (cis, cis-cycloocta-
(1,5-diene) platinum is unstable and a paste of constant quality cannot be obtained. In particular, it is quickly decomposed even at low temperatures in air, so it is difficult to handle. Further, since the solubility of bis (cis, cis-cycloocta-1,5-diene) platinum in a solvent is low, a paste of high concentration cannot be obtained. For that reason,
There is a limit in increasing the content of platinum, the thickness of the platinum film is limited, and the selection and amount of additives for improving applicability and adhesion between the platinum film and the substrate are significantly restricted. You. Further, by coating a compound represented by the general formula [II] described in the publication on a carrier, and then heating the carrier to decompose the compound represented by the general formula [II], platinum is formed on the carrier. In the method of depositing, a paste of constant quality cannot be obtained because the compound represented by the general formula [II] is unstable. In addition, there is no description in this publication regarding the solubility of bis (cis, cis-cycloocta-1,5-diene) platinum and the platinum compound represented by the general formula [II]. Therefore, there is no description about a paste containing the platinum compound for forming a thin film of metallic platinum.

Although a thin film having high uniformity can be obtained by the method disclosed in Japanese Patent Application Laid-Open No. 3-247772, pinholes and cracks are frequently generated, and it is highly probable that disconnection occurs when fine wiring is provided. The present invention is an improvement over the above-mentioned problems of the prior art, in which a uniform and continuous platinum thin film without pinholes or cracks can be obtained by heating the coating film, and corrosion of halogen atoms, sulfur atoms and the like can be obtained. It is an object of the present invention to provide an organoplatinum compound which does not contain a disadvantageous atom which causes generation of a reactive gas.

[0008]

Means for Solving the Problems The organoplatinum compound of the present invention has the following general formula [IA]

[0009]

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(In the formula, a represents a number of 1 or 2. When a = 1, R ¹ represents a tert-butyl group at the 3- or 4-position.
And R ² represents a hydrogen atom. When a = 2, R ¹ and R ² are a hydrogen atom, a carbon atom number
Hydrocarbon groups of 10 or less or alcohols of 10 or less carbon atoms
Represents an xy group, and R ¹ and R ² may be different and are the same
It may be. This is an organoplatinum compound obtained by reacting dihalogeno (1,5-cyclooctadiene) platinum with a base in the presence of the compound of formula (1).

[0011] Examples of the above general formula [IA] is, 4-tert
-Butoxyphenylphenylacetylene, 3-tert-butoxyphenylphenylacetylene , diphenyldiacetylene, di (4-ethylphenyl) diacetylene, di (3-ethylphenyl) diacetylene, di (4-normalpropylphenyl) diacetylene, Di (3-normalpropylphenyl) diacetylene, di (4-isopropylphenyl) diacetylene, di (3-isopropylphenyl) diacetylene, di (4-normalbutylphenyl) diacetylene, di (3-normalbutylphenyl)
Diacetylene, di (4-isobutylphenyl) diacetylene, di (3-isobutylphenyl) diacetylene, di (4-tert-butylphenyl) diacetylene, di (3-
tert-butylphenyl) diacetylene, di (4-normalpentylphenyl) diacetylene, di (4-normalhexylphenyl) diacetylene, di [4- (2ethylhexyl) phenyl] diacetylene, 4-ethylphenylphenyldiacetylene , 3-ethylphenylphenyldiacetylene, 4-normalpropylphenylphenyldiacetylene, 3-normalpropylphenylphenyldiacetylene, 4-isopropylphenylphenyldiacetylene, 3-isopropylphenylphenyldiacetylene, 4-normalbutylphenylphenyldiethyl Acetylene, 3-normalbutylphenylphenyldiacetylene, 4-isobutylphenylphenyldiacetylene, 3
-Isobutylphenylphenyldiacetylene, 4-tert
-Butylphenylphenyldiacetylene, 3-tert-butylphenylphenyldiacetylene, 4-normalpentylphenylphenyldiacetylene, 4-normalhexylphenylphenylphenyldiacetylene, [4- (2ethylhexyl) phenyl] phenyldiacetylene, (3 −te
rt-butylphenyl) (4-ethylphenyl) diacetylene, di (4-ethoxyphenyl) diacetylene, di (3-ethoxyphenyl) diacetylene, di (4-normalpropoxyphenyl) diacetylene, di (3-normal (Propoxyphenyl) diacetylene, di (4-isopropoxyphenyl) diacetylene, di (3-isopropoxyphenyl) diacetylene, di (4-normal butoxyphenyl) diacetylene, di (3-normal butoxyphenyl) diacetylene, Di (4-isobutoxyphenyl) diacetylene, di (3-isobutoxyphenyl)
Diacetylene, di (4-tert-butoxyphenyl) diacetylene, di (3-tert-butoxyphenyl) diacetylene, di (4-normalpentyloxyphenyl) diacetylene, di (4-normalhexyloxyphenyl)
Diacetylene, di [4- (2-ethylhexyloxy) phenyl] diacetylene, 4-ethoxyphenylphenyldiacetylene, 3-ethoxyphenylphenyldiacetylene, 4-normalpropoxyphenylphenyldiacetylene, 3-normalpropoxyphenylphenyldiacetylene , 4-isopropoxyphenyl phenyl diacetylene, 3-isopropoxy phenyl phenyl diacetylene, 4-normal butoxy phenyl phenyl diacetylene, 3-normal butoxy phenyl phenyl diacetylene, 4-isobutoxy phenyl phenyl diacetylene, 3-isobutoxy Phenylphenyldiacetylene,
4-tert-butoxyphenylphenyldiacetylene, 3
-Tert-butoxyphenylphenyldiacetylene, 4-
Normal pentyloxyphenylphenyldiacetylene, 4-normalhexyloxyphenylphenyldiacetylene, [4- (2-ethylhexyloxy) phenyl] phenyldiacetylene, (3-tert-butoxyphenyl) (4-ethoxyphenyl) diacetylene, ( 3-
tert-butylphenyl) (4-ethoxyphenyl) diacetylene; Two or more of these compounds can be used as a mixture in the organoplatinum compound of the present invention.

Examples of dihalogeno (1,5-cyclooctadiene) platinum include dichloro (1,5-cyclooctadiene) platinum, dibromo (1,5-cyclooctadiene) platinum, and diiodo (1,5) -Cyclooctadiene) platinum and the like. Although there is no particular limitation on the base used, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, Strong bases such as potassium tert-butoxide, sodium borohydride and the like are preferred.

The organoplatinum compound of the present invention is, for example, a ratio of 2 to 10 mol of the compound of the above formula [IA] and 2 to 10 mol of the base per 1 mol of dihalogeno (1,5-cyclooctadiene) platinum. In an inert organic solvent in a ratio of 0.1 to 50 g of the inert organic solvent to 1 g of the mixture.
By stirring at a temperature of 0 to 80 ° C. for 0.1 to 24 hours, the compound 2 of the general formula [IA] is preferably added to 1 mol of dihalogeno (1,5-cyclooctadiene) platinum.
To 3 moles of the base and 2 to 5 moles of the base are obtained by stirring for 0.5 to 5 hours at a temperature of 30 to 70 ° C. in 1 to 10 g of an inert organic solvent per 1 g of the mixture. Can be

Examples of the inert organic solvent include alcohol solvents such as methanol and ethanol, aromatic solvents such as benzene and toluene, and ether solvents such as tetrahydrofuran. Examples of the solvent include halogenated hydrocarbon solvents such as chloroform, methylene chloride, and aliphatic hydrocarbon solvents such as hexane and heptane.

After the above-mentioned stirring, the organic platinum compound of the present invention is obtained by washing with water and removing the solvent. If necessary, it can be purified by reprecipitation or the like.

[0016]

The organoplatinum compound of the present invention comprises dihalogeno (1,
5-cyclooctadiene) atomic platinum by platinum and base the reaction is generated, then the platinum atom is coordinated immediately compound represented by the general formula [IA] present in the reaction system It is believed that the strong base formed and preferably used in this reaction accelerates the rate of this reaction and efficiently forms the organoplatinum compound of the present invention.

In this reaction, a reaction product of a base and a halogen and a product derived from cyclooctadiene are considered to be by-produced. These by-products can be removed by a purification method such as washing with water and reprecipitation. Depending on the purification, the amount of halogen and the amount of alkali metal contained as impurities in the organoplatinum compound of the present invention can be reduced to 10 ppm or less.

The purified organoplatinum compound of the present invention and an initially formed precipitate obtained by dissolving the organoplatinum compound in a good solvent, gradually adding a poor solvent to form a precipitate in a stepwise manner, and No difference was found in the results of elemental analysis with any of the precipitates formed in 1 ) , which is consistent with the composition of the compound consisting of 2 mol of the compound of the above general formula [IA] and 1 mol of platinum atom used in the synthesis.

No difference is observed between the infrared absorption spectrum (hereinafter referred to as IR spectrum) of the compound of the formula [IA] used in the reaction and the specific absorption peak of the IR spectrum of the organoplatinum compound of the present invention. As described above, in the organoplatinum compound of the present invention, one platinum atom has the general formula [IA]
The following general formula [IB] coordinated to two molecules of the compound represented by

[0020]

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(In the formula, a represents a number of 1 or 2. When a = 1, R ¹ represents a tert-butyl group at the 3- or 4-position.
And R ² represents a hydrogen atom. When a = 2, R ¹ and R ² are a hydrogen atom, a carbon atom number
Hydrocarbon groups of 10 or less or alcohols of 10 or less carbon atoms
Represents an xy group, and R ¹ and R ² may be different and are the same
It may be. ) Or a = 1
In this case, the following general formula [IC]

[0022]

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(Wherein R ¹ is tert-butyl at the 3- or 4-position
And R ² represents a hydrogen atom. ) Is a polymer having a repeating unit, or when a = 2, the following general formula [ID]

[0024]

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(Wherein R ¹ and R ² represent a hydrogen atom, a carbon atom
Hydrocarbon group having 10 or less atoms or 10 or less carbon atoms
Represents an alkoxy group, and R ¹ and R ² may be different
And may be the same. ) Or a polymer having the following general formula [IE]

[0026]

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(Wherein R ¹ and R ² represent a hydrogen atom, a carbon atom
Hydrocarbon group having 10 or less atoms or 10 or less carbon atoms
Represents an alkoxy group, and R ¹ and R ² may be different
And may be the same. ) Is considered to be a polymer having repeating units. Here, the above IR spectrum
Wherein the compound of the general formula [IA] used in the reaction is
IR spectrum and IR spectrum of the organoplatinum compound of the present invention.
Because there is no difference in the specific absorption peak of
The organoplatinum compound of the present invention is identified by the general formula [IB].
You. When the organoplatinum compound of the present invention is heated to about 450 ° C., metallic platinum is produced in an amount corresponding to the above identification formula. The organic platinum compound of the present invention is methyl ethyl ketone,
Ketones such as cyclohexanone, ethyl acetate, amyl acetate, benzyl acetate, dibutyl oxalate, dibutyl itaconate, benzyl benzoate, dibutyl phthalate, dioctyl phthalate, butyl carbitol acetate, dioxane, ethyl cellosolve, dipentene oxide Ethers such as butanol and cyclohexanol, aromatic hydrocarbons such as toluene and xylene, nitro-substituted aromatic hydrocarbons such as nitrobenzene and nitrotoluene, terpenes such as pinene and terpineol, and lavender oil. It is highly soluble in essential oils such as linseed oil, rosemary oil and the like and mixtures thereof, is stable for several months and does not form a precipitate.

[0028]

【Example】

Example 1 A reaction flask was charged with 36.37 g (0.53 mol) of sodium ethoxide, 87.18 g (0.43 mol) of diphenyldiacetylene,
80 g of dichloro (1,5-cyclooctadiene) platinum (0.21
Mol), ethyl alcohol (300 ml) and toluene (450 ml) were stirred at 65 ° C. for 1 hour to obtain a black slurry. Thereafter, the slurry was cooled to room temperature, and the by-produced sodium chloride was removed by filtration. Then, ethanol was distilled off from the filtrate under reduced pressure, washed with water, and toluene was distilled off under reduced pressure to obtain 161 g of a crude product as a black powder. The crude product was dissolved in methylene chloride (160 ml), and 1600 ml of hexane was gradually added dropwise with stirring to form a precipitate.The precipitate was collected by filtration and dried under reduced pressure to obtain 120 g of a brown powder. .

No difference was found in the specific absorption peaks of the IR spectrum of the product and the IR spectrum of diphenyldiacetylene. Table 1 shows the results of elemental analysis of the product. The result of elemental analysis is the following formula [1B]

[0030]

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A compound represented by the following formula [1D]

[0032]

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A polymer of the above compound represented by the following formula or
[1E]

[0034]

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The composition of the polymer of the above compound (P
t 32.5%, C 64.1%, H 3.4%). IR spectrum of the product and diphenyl
Difference in specific absorption peak of IR spectrum of rudiacetylene
Since no difference was observed, the product was of the above formula
[1B] is identified. [Solubility test] 0.5 g of butyl carbitol acetate was added to 1 g of the product, and the mixture was allowed to stand at room temperature. As a result, a uniform solution was obtained. [Stability Test] The butyl carbitol acetate solution was left at room temperature for 1 year under light shielding, but no change was observed and no formation of a precipitate or the like was observed. [Separation precipitation test] 5 g of the product was dissolved in 5 ml of methylene chloride, and 5 ml of hexane was gradually added with stirring at room temperature to form a precipitate. The precipitate was filtered and dried to obtain a precipitate.
g of the first precipitate was obtained.

Next, 5 ml of hexane was gradually added to the filtrate after filtration of the first precipitate while stirring at room temperature to form a precipitate, and the precipitate was filtered and dried to obtain about 1.5 g of the second precipitate. A precipitate was obtained. Further, the filtrate after the second precipitation filtration was dried under reduced pressure to obtain about 2 g of powder. Elemental analysis results of the powder before dissolution in methylene chloride, the first precipitate, the second precipitate, and the powder after drying under reduced pressure were all the same. [Film formation test] To 1 g of the product, 1 g of butyl carbitol acetate was added.
A uniform solution was prepared, and the solution was applied to the entire surface of an alumina substrate measuring 2 cm in length and width by a brush, and then the substrate was heated from room temperature to 800 ° C. over about 30 minutes, and then baked at 800 ° C. for 10 minutes.

As a result, a smooth platinum film with no pinholes or cracks having high adhesion was formed on the entire surface of the alumina substrate. Example 2 A crude product (169 g) was obtained in the same manner as in Example 1 except that 100.77 g (0.43 mol) of 4-tert-butylphenylphenylacetylene was used instead of diphenyldiacetylene.

The crude product is dissolved in 100 ml of methylene chloride, and 1600 ml of methyl alcohol is gradually added dropwise with stirring to form a precipitate. The precipitate is collected by filtration and dried under reduced pressure to obtain a brown powder. g was obtained. No difference was observed in the specific absorption peak between the IR spectrum of the product and the IR spectrum of 4-tert-butylphenylphenylacetylene.

The results of elemental analysis of the product are shown in Table 1.
The result of elemental analysis is the following formula [2B]

[0040]

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A compound represented by the following formula or the following formula [2C]

[0042]

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The composition of the polymer of the above compound (P
t 29.4%, C 65.1%, H 5.5%). IR spectrum of the product and diphenyl
Difference in specific absorption peak of IR spectrum of rudiacetylene
Since no difference was observed, the product was of the above formula
[2B] is identified. Using this product, the same [solubility test], [stability test], [separated sedimentation test], and [film-forming test] were performed as in Example 1, and the same results as in Example 1 were obtained. Obtained. However, in the fractional precipitation test, methyl alcohol was used instead of hexane as the poor solvent.

Example 3 A crude product (172 g) was obtained in the same manner as in Example 1 except that 100.77 g (0.43 mol) of 3-tert-butylphenylphenylacetylene was used instead of diphenyldiacetylene. The crude product was dissolved in 80 ml of methylene chloride, and 1600 ml of methyl alcohol was gradually added dropwise with stirring to form a precipitate. The precipitate was collected by decantation and dried under reduced pressure to give a brownish high-viscosity oil. 130g was obtained.

No difference was observed in the specific absorption peak between the IR spectrum of the product and the IR spectrum of 3-tert-butylphenylphenylacetylene. Table 1 shows the results of elemental analysis of the product. The following formula is a result of elemental analysis [3
B]

[0046]

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A compound represented by the following formula or the following formula [3C]

[0048]

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The composition of the polymer of the above compound (P
t 29.4%, C 65.1%, H 5.5%). IR spectrum of the product and diphenyl
Difference in specific absorption peak of IR spectrum of rudiacetylene
Since no difference was observed, the product was of the above formula
[3B] is identified. Using this product, the same [solubility test], [stability test] and [fractionation precipitation test] as in Example 2
And [film forming property test], the same results as in Example 2 were obtained. However, the precipitate and the dried product formed in the fractional precipitation test were high-viscosity oily substances. Therefore,
The precipitate was recovered by the decantation method.

Example 4 A crude product was produced in the same manner as in Example 1 except that the amount of diphenyldiacetylene was changed to 42.3 g (0.21 mol), and 55 g (0.23 mol) of 3-tert-butylphenylphenylacetylene was further added. 162 g of product were obtained. Methylene chloride
Dissolve in 100 ml and slowly add methyl alcohol with stirring.
The precipitate was collected by decantation, and dried under reduced pressure to obtain 126 g of a brown high-viscosity oily substance.

Using this product, the same [solubility test], [stability test], [separated sedimentation test] and [film formation test] were carried out in the same manner as in Example 3. The result was obtained. Comparative Example 1 1 g of butyl carbitol acetate was added to 1 g of bis [cis, cis-cycloocta-1,5-diene] platinum at room temperature but did not completely dissolve. Therefore, 20 g of butyl carbitol acetate was added to make a homogeneous solution. However, the solution was applied with a brush to the entire surface of an alumina substrate measuring 2 cm in length and width, and then the substrate was heated from room temperature to 800 ° C. in about 30 minutes. Was deposited and became non-uniform. And
Although calcination was performed at 800 ° C. for 10 minutes, only fine powdered metallic platinum was formed on the alumina substrate, and no metallic platinum thin film was formed.

Comparative Example 2 Using [bis [diphenylacetylene] platinum, the same [solubility test], [stability test] and [film formation test] as in Example 1 were performed. As a result, the [solubility test] and the [stability test] did not differ from the product of Example 1, but in the film-forming test, several tens of pinholes were formed on the alumina substrate, and A crack having a length of about 1 cm was observed in the vicinity.

[0053]

The organoplatinum compound of the present invention has excellent solubility and film-forming properties due to its special organic group structure. That is, when the organoplatinum compound of the present invention is thermally decomposed, metallic platinum is produced, and the organoplatinum compound of the present invention is:
Terpene alcohol solvents such as terpineol, solvents often used as screen printing solvents, aromatic solvents such as toluene, halogenated hydrocarbon solvents such as methylene chloride, ketone solvents such as methyl ethyl ketone, Highly soluble in solvents such as ethyl acetate, ester solvents such as butyl carbitol, and ether solvents such as tetrahydrofuran, and improved organoplatinum compounds that maintain the solution state for a long time. Then, a solution-type paste mixture containing the organoplatinum compound is applied to a ceramic or metal substrate by an ordinary method, and heated by an ordinary method to obtain a uniform adhesive layer without pinholes and cracks. A thin film made of metallic platinum is formed on the substrate.

In particular, the organoplatinum compound of the present invention does not contain a sulfur atom or a halogen atom, and does not generate corrosive gas such as sulfur oxides, halogens and hydrogen halides during thermal decomposition. Further, a uniform and continuous thin film free of metal platinum pinholes and cracks can be formed on a substrate on which a thin metal film is easily formed. Also,
There is no humus in the firing furnace or pollution of the surrounding environment.

Further, the organoplatinum compound of the present invention is economically advantageous because platinum metal is not lost by sublimation even when heated, and is a platinum thin film having a fixed size and a fixed thickness without pinholes and cracks. Can be easily obtained. The solution of the organoplatinum compound of the present invention and the paste composition containing the organoplatinum compound of the present invention can be decorated with a metal platinum thin film on a substrate, or various electric or electronic devices formed of a metal platinum thin film on a substrate. It is particularly useful for forming circuits or for forming various electrodes made of a thin film of metallic platinum on a substrate.

Further, the organoplatinum compound of the present invention can be mixed with a palladium paste such as metal palladium produced by thermal decomposition by mixing with a gold paste such that metal gold is produced by thermal decomposition taking advantage of the above characteristics. , Or by mixing with the above-mentioned paste mixture, a thin film of an alloy of platinum and gold, an alloy of platinum and palladium, or an alloy of platinum, gold and palladium can be formed on the substrate.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C07F 15/00 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The following general formula [IA] (In the formula, a represents a number of 1 or 2. When a = 1, R ¹
Represents a tert-butyl group at the 3- or 4-position, and R ² represents a hydrogen atom
Represents a child. When a = 2, R ¹ and R ² represent a hydrogen atom,
Hydrocarbon group having 10 or less carbon atoms or 10 or less carbon atoms
Represents the following alkoxy group, wherein R ¹ and R ² are different
Good and may be the same. The presence of a compound represented by), obtained by reacting a dihalogeno (1,5-cyclooctadiene) platinum and a base, the following general formula [IB] ## STR2 ## (Wherein a, R ¹ and R ² are the same as above) .