JPH07138205A - Dialkoxycarbonylation of norbornenes - Google Patents

Abstract

PURPOSE:To obtain a norbornane compound with high Pd activity in a high yield by reacting a norbornenes compound with an alcohol, CO and O2 using a catalyst containing Pd metal or its compound, a copper compound, a chlorine compound and a Mn or Zn compound. CONSTITUTION:A norbornene of formula I [R1 and R2 are each H or methyl; R3 and R4 are each H COOR5 (R5 is H or 1-3C alkyl)] is reacted with carbon monoxide and oxygen to afford a norbornane compound of formula II. In this reaction, as a catalyst, a catalyst consisting of palladium metal or its compound (e.g. palladium acetate), a copper compound [e.g. copper(II) acetate], a chlorine compound (e.g. hydrogen chloride) and a manganese or zinc compound [e.g. manganese(II) acetate] is preferably used. A gram atomic ratio of a chlorine atom in the reaction mixture liquid to a copper atom is preferably <2. As the norbornane compound, especially bicyclo[2,2, 1]heptane-2,3,5,6-tetracarboxylic acid tetraester is preferable.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a norbornene compound, an alcohol, carbon monoxide and oxygen, and two carboxylic acid ester groups (--C) on the carbon-carbon double bond of the norbornene compound.
The present invention relates to a method for producing norbornanes having an OOR group) introduced therein. These compounds and their derivatives are important compounds as raw materials for various compounds and additives to resins. Further, the general formula (1) [Chemical formula 3]

[0002]

[Chemical 3] (In the formula, R ₁ and R ₂ are each a hydrogen atom or a methyl group and may be the same or different, R ₃ and R ₄ may be a hydrogen atom or a —COOR ₅ group and may be the same or different, and R ₅ is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms), when the substituents R ₃ and / or R _{4 of the} raw norbornenes represented by the formula) are a carboxyl group or a carboxylic acid ester group, the product norbornane The classes can be converted into compounds having 3 or 4 carboxylic acids or their derivatives, which are important compounds as raw materials for imide resins and amide imide resins.

[0003]

2. Description of the Prior Art The carbon-carbon double bond of norbornenes is 2
There are several examples in which one carboxylic acid ester group is introduced. For example, in Japanese Unexamined Patent Publication No. 63-57557, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid diester is used as a starting material with a palladium catalyst and an oxidizing agent (copper compound or iron compound). 2 for norbornenes
In the presence of a double molar amount) to react with alcohol and carbon monoxide to give bicyclo [2.2.1] heptane-2,3,2.
5,6-tetracarboxylic acid tetraester has been obtained,
Further, in JP-A-60-104039, dicyclopentadiene, carbon monoxide, alcohol and / or its derivative acetal, ketal and alkyl orthoformate are added in the presence of a palladium catalyst, a copper or iron compound and / or oxygen. To [5.2.1.0 ^2,6 ] dece-3-ene-
8,9-dicarboxylic acid diester is obtained.

[0004]

However, in any of these methods, the reaction results are not sufficiently satisfactory, and especially the activity of the palladium catalyst is extremely low, and the application to industrial processes is at a level as much as desired. There was no. The object of the present invention is to react norbornenes with alcohol, carbon monoxide and oxygen, and to introduce two carboxylic acid ester groups into the carbon-carbon double bond of the norbornenes with high catalytic activity without impairing the reaction results. It is to provide a method for producing the prepared norbornanes.

[0005]

Means for Solving the Problems As a result of continuing studies on a catalyst system to achieve the above-mentioned object, the present inventors have found that norbornenes and alcohols, carbon monoxide and oxygen
When reacted in the presence of a catalyst containing (1) palladium metal or its compound, (2) copper compound, (3) chlorine compound and (4) manganese or zinc compound, the carbon-carbon double carbon of the norbornenes is obtained. The present invention has been completed by finding that norbornanes having two carboxylic acid ester groups introduced into the bond can be obtained with high reaction results and high catalytic activity of palladium. That is, the present invention has the general formula (1)
[Chemical 4]

[0006]

[Chemical 4] (In the formula, R ₁ and R ₂ are each a hydrogen atom or a methyl group and may be the same or different, R ₃ and R ₄ may be a hydrogen atom or a —COOR ₅ group and may be the same or different, and R ₅ is hydrogen. Atom or an alkyl group having 1 to 3 carbon atoms), and an alcohol, carbon monoxide and oxygen, (1) palladium metal or a compound thereof, (2) a copper compound, (3) chlorine compound and (4) reaction in the presence of a catalyst containing a compound of manganese or zinc, represented by the general formula (2)

[0007]

[Chemical 5] (In the formula, R ₁ and R ₂ are each a hydrogen atom or a methyl group and may be the same or different, R ₃ and R ₄ may be a hydrogen atom or a —COOR ₅ group and may be the same or different, and R ₅ is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms, R ₆ is an alcohol R ₆ used in the reaction
The organic residue of OH is shown. ) Is a method for producing norbornanes in which two carboxylic acid ester groups are introduced into the carbon-carbon double bond of the norbornenes.

The general formula (1) of the raw materials in the method of the present invention
Examples of the norbornenes represented by are, for example, bicyclo [2.2.1] hept-2-ene (common name norbornene), 5-methyl-bicyclo [2.2.1] hept-2.
-Ene, bicyclo [2.2.1] hept-5-ene-2
-Carboxylic acid, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid methyl, ethyl or propyl ester, 2-methyl-bicyclo [2.2.1] hept-
5-ene-2-carboxylic acid, 2-methyl-bicyclo [2.2.1] hept-5-ene-2-carboxylic acid methyl, ethyl or propyl ester, bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboxylic acid or bicyclo [2.2.1] hept-5-ene-2,3-
Examples include dimethyl, diethyl or dipropyl esters of dicarboxylic acids, many of which are easily produced by the Diels-Alder reaction.

Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, octanol, cyclopentanol, cyclohexanol,
It may be an alcohol such as phenol, benzyl alcohol, ethylene glycol, polyethylene glycol or propylene glycol, and may be an alcohol having a substituent such as a halogen or an alkoxy group which does not inhibit the reaction. The amount of these alcohols to be used is not particularly limited, but is usually 2 mol or more, preferably 2.5 to 250 mol, and more preferably 5 to 100 mol, per 1 mol of norbornenes. is there. Alcohol may be used as a solvent as well as a reaction raw material.

The carbon monoxide and oxygen used in the method of the present invention are preferably diluted with a gas such as nitrogen, argon or carbon dioxide which does not interfere with the reaction in order to avoid an explosive range. Air can also be used as the oxygen source. The partial pressure of carbon monoxide carried out by the method of the invention is
It is not more than 5 megapascals (absolute pressure, the same applies hereinafter), and preferably in the range of 0.0005 to 4 megapascals. The partial pressure of oxygen is 5 MPa or less, preferably 0.0002
To 3 megapascals. The required amount of these carbon monoxide, oxygen and diluent gas may be charged into the reactor all at once, or the required gas may be added continuously or intermittently, or a mixed gas thereof may be continuously or intermittently added. Alternatively, the method of distribution may be used. The mixed gas to be subjected to the reaction may be freshly prepared each time, but it is also possible to repeatedly use the residual gas once used in the reaction or the exhaust gas in the method of circulating after adjusting the concentration of each component gas.

In the reaction according to the method of the present invention, the starting alcohol can be substantially used as a solvent, but a solvent can be used as long as it does not inhibit the reaction. Examples of such a solvent include ethers such as diethyl ether, dipropyl ether, methyl ethyl ether, phenyl ethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether or triethylene glycol dimethyl ether, acetone, methyl ethyl ketone or acetophenone. Ketones, esters such as methyl acetate, ethyl acetate or methyl propionate, benzene,
Aromatic hydrocarbons such as toluene, p-xylene, ethylbenzene, chlorobenzene or dichlorobenzene or substituted compounds thereof, aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane, isooctane or cyclohexane, propylene carbonate And carbonates such as dimethyl carbonate, nitrites such as acetonitrile and benzonitrile, amide compounds such as dimethylformamide, and sulfone compounds such as sulfolane.

Examples of the palladium metal or its compound which is the first component of the catalyst of the present invention include palladium metal, activated carbon, silica gel, alumina, silica alumina,
Supported on a carrier such as diatomaceous earth, magnesia, pumice or molecular sieve, palladium metal such as palladium black, zero-valent palladium complex such as dibenzylideneacetone complex of palladium and tetrakis (triphenylphosphine) palladium, palladium chloride or Palladium halides such as palladium bromide, paraum sulfate,
Inorganic acid salts of palladium, such as palladium phosphate or palladium nitrate, organic acid salts of palladium, such as palladium acetate, palladium propionate or palladium benzoate,
Alternatively, a divalent palladium compound of a palladium complex such as bis (acetylacetonato) palladium, cyclooctadiene dichloropalladium, a palladium chloride benzonitrile complex or a palladium chloride ammine complex may be used. The amount of the palladium metal or its compound used is 0.05 gram atom or less, preferably 5 × 10 ⁻⁷ to 1 × 10 ⁻² gram atom, per 1 mol of the norbornenes as the raw material, as palladium atoms. . Examples of the copper compound as the second component of the catalyst of the present invention include copper halides such as copper chloride and copper bromide, copper carbonate, copper inorganic acid salts such as copper nitrate, copper acetate, copper propionate, and the like. Examples thereof include an organic acid salt of copper such as copper stearate or copper benzoate, or a complex compound of copper such as copper acetylattonate or copper benzoylacetonate. The valence of copper in these compounds may be monovalent or divalent.

Even if these copper compounds are used alone,
Alternatively, two or more kinds may be mixed and used. These copper compounds are preferably dissolved in the reaction mixture, but it does not matter if some of them remain insoluble. The amount of these copper compounds used is 2 gram atoms or less per 1 liter of the reaction mixture as copper atoms, and preferably 0.0005.
To 0.5 atom. However, when copper chloride is used as the chlorine compound as the third component of the catalyst, the copper atom of this compound is also included in the above range and the copper compound is used.

The chlorine compound which is the third component of the catalyst includes, for example, chlorine or a solution thereof or hydrogen chloride or a solution thereof, and a tertiary alkyl chloride such as tertiary butyl chloride or tertiary amyl chloride or acetyl chloride. Chlorinated carbonic acid derivatives such as phosgene and methyl chloroformate, phosphorus chloride such as phosphorus pentachloride, phosphorus oxychloride such as phosphoryl trichloride, tetrachloride Tellurium chloride such as tellurium chloride, thionyl chloride, and also Group 4A such as titanium and zirconium, 5A such as vanadium and tantalum.
Group, 6A group such as chromium and molybdenum, 7A group such as manganese, 8 group such as iron, cobalt, nickel, ruthenium, palladium and platinum, 1B group such as copper, 2B group such as zinc and cadmium, germanium and tin, etc. Group 4B and 5B such as antimony and bismuth
Examples thereof include chlorides and oxychlorides corresponding to the valences of group metals. Of these, chlorine, hydrogen chloride, phosphorus pentachloride, phosphoryl trichloride, vanadium oxytrichloride,
Chromium trichloride, manganese chloride, iron chloride, copper chloride, zinc chloride, tin chloride, bismuth chloride and the like are preferable. These may be used alone or in combination of two or more.
When the other catalyst component is a chlorine compound, it can also serve as a part or all of the chlorine compound of the third catalyst component. The amount of these chlorine compounds used is
The chlorine atom content is 1 gram atom or less, preferably 0.0001 to 0.1 gram atom, per liter of the reaction mixture. However, when a compound containing a chlorine atom is used as the other catalyst component, the range is the amount including the chlorine atom.

In the method of the present invention, it is more preferable to use the chlorine compound as the third component of the catalyst so that the chlorine atom present in the reaction mixture is less than 2 in atomic ratio to the copper atom also present. . More preferably 0.05 to
The range is 1.90. Examples of the compound of manganese or zinc which is the fourth component of the catalyst in the present invention include inorganic compounds such as oxides, hydroxides, chlorides or carbonates of manganese or zinc, acetic acid, propionic acid, stearic acid, succinic acid. , A salt of a monovalent or divalent organic acid such as phenylacetic acid, benzoic acid, phthalic acid or toluenesulfonic acid, or a complex compound such as an acetylacetonate complex, a cyclopentadienyl complex or a carbonyl complex. These compounds may be used alone or in combination of two or more. These compounds are preferably dissolved in the reaction mixture, but some of them may be insoluble. The amount of the compound of the fourth component of the catalyst used is such that the gram atom ratio of the contained metal atom to the copper atom present in the reaction mixture is in the range of 0.01 to 50, preferably in the range of 0.05 to 10.

The compounds of the first, second, third, and fourth components of the catalyst described above may be a combination of compounds that produce such compounds in the reaction system. The reaction system of the method of the present invention may be a batch system, a semi-batch system or a continuous flow system. The total pressure of the reaction in the method of the present invention depends on the partial pressures of carbon monoxide, oxygen and diluent gas used, but is usually 50 megapascals or less, and preferably in the range of 0.1 to 30 megapascals. The reaction temperature is 200 ° C or lower, preferably in the range of 40 to 160 ° C. The reaction time varies depending on the reaction conditions, but is usually 0.
01 to 24 hours, preferably 0.05 to 15 hours.
After completion of the reaction, the product can be taken out by a conventional separation method such as distillation, extraction, reprecipitation or recrystallization.

[0017]

EXAMPLES The present invention will be described below with reference to examples. Example 1 In a cylindrical glass container, 3.14 mg (0.0140 mmol) of palladium acetate, 699 mg (3.50 mmol) of cupric acetate monohydrate, and 1.03 of manganese acetate tetrahydrate were added.
Gram (4.20 mmol) was weighed, 80 g of methanol was added thereto, and bicyclo [2.2.1] hept-5 was added.
29.4 grams (140 mmol) of -ene-2 endo, 3 endo-dicarboxylic acid dimethyl ester was weighed out. To this, 2.5 ml (hydrogen chloride amount: 1.75 mmol) of a liquid (concentration: 0.7 N) in which hydrogen chloride gas whose concentration had been measured immediately before was absorbed in methanol was added, and further 150 g of methanol was added. The container was inserted into a 1 liter autoclave. The stirring blade of the autoclave is made of fluorine resin, and the temperature measuring tube is also protected by glass.

While maintaining the total pressure at 5 megapascals in the autoclave, the partial pressure ratio of carbon monoxide: oxygen: nitrogen was 8.8.
A mixture gas of: 6.0: 85.2 was passed through at a rate of 0.5 liter / min (standard state), and stirring was continued to react at 100 ° C. for 9 hours. During this time, the outlet gas was discharged through the reflux condenser. After the reaction was completed, the pressure was cooled and released, and the reaction liquid taken out was analyzed by gas chromatography.
It contained 2.3 grams (129 mmol) of bicyclo [2.2.1] heptane-2 endo, 3 endo, 5 exo, 6 exo-tetracarboxylic acid tetramethyl ester. Yield 92.1%
The number of moles of the desired product formed per gram atom of palladium (hereinafter abbreviated as Pd turnover) was 9210, which was an extremely high value.

Comparative Example 1 The procedure of Example 1 was repeated, except that manganese acetate / tetrahydrate was not used. The conversion rate of the raw material was 23.1%, and the bicyclo [2.2.1] heptane-2 endo, 3 endo, 5 exo, 6
The yield of exo-tetracarboxylic acid tetramethyl ester is
It was 8.7%. The Pd turnover is 870.

Comparative Example 2 The procedure of Example 1 was repeated except that hydrogen chloride was not used. The conversion rate of the raw material is 15.2%, and the bicyclo [2.2.1]
Heptane-2 endo, 3 endo, 5 exo, 6 exo-tetracarboxylic acid tetramethyl ester was in traces.

Example 2 Palladium chloride 2.48 mg (0.0140 mmol), cupric acetate monohydrate 527 mg (2.64 mmol), cupric chloride 115.8 mg (0.861 mmol), manganese acetate tetrahydrate 1.03 Gram (4.20 mmol) was weighed, and after adding a part of methanol, bicyclo [2.2.1]
23.3 g (140 mmol) of hept-5-ene-2-methyl-2-carboxylic acid methyl ester was taken, and further methanol was added to make the total amount 230 g. This raw material contains e of the carboxylic acid methyl ester at the 2-position of the bicyclo ring.
It has an ndo / exo ratio of 1 / 2.5. When the reaction was performed in the same manner as in Example 1, the conversion rate of the raw material was 100%, and the bicyclo [2.2.1] heptane-2 exo-methyl-2 endo, 5
Exo, 6 exo-tricarboxylic acid trimethyl ester is 25.8
% Yield, and bisiro [2.2.1] heptane-2 endo
-Methyl-2exo, 5exo, 6exo-tricarboxylic acid trimethyl ester was produced in a yield of 64.5%, and the total yield was 90.3%. The ratio of both isomers of the product is 1 / 2.5, which is the same as the isomer ratio of the raw material. The Pd turnover was 9030.

Example 3 The procedure of Example 2 was repeated except that the raw material of Example 2 was changed to 21.3 g (140 mmol) of bicyclo [2.2.1] hept-5-ene-2-carboxylic acid methyl ester. The raw material is carboxylic acid methyl ester at the 2-position of the bicyclo ring.
An endo / exo ratio of 3.2 / 1 is included. As a result, the raw material conversion rate was 100% and the bicyclo [2.2.1] heptane-
2 endo, 5 exo, 6 exo-tricarboxylic acid trimethyl ester yield 67.4%, and bisiro [2.2.1] heptane-
2 exo, 5 exo, 6 exo-tricarboxylic acid trimethyl ester was produced in a yield of 21.7%, and the total yield was 89.1%. The ratio of both isomers of the product is 3.1 / 1, which is not much different from the isomer ratio of the raw material. Pd turnover
It was 8910.

Example 4-14 With the types and amounts of catalyst components and reaction conditions shown in Table 1,
Reaction was carried out in the same manner as in Example 3. The results are shown in Table 1 together with the results of Example 3.

[0024]

[Table 1]

Example 15 In Example 1, hydrogen chloride in methanol (concentration
1.25 N) was used in the same manner as in Example 1 except that 7.0 ml (hydrogen chloride content was 8.75 mmol) was used. The gram atom ratio of chlorine atoms to copper atoms in the reaction mixture was 0.5 in Example 1, but was 2.5 here. As a result, bicyclo [2.2.1] heptane-2 endo,
The yield of 3 endo, 5 exo, 6 exo-tetracarboxylic acid tetramethyl ester was 80.4%, and the Pd turnover was
It was 8040.

[0026]

According to the method of the present invention, norbornenes in which two carboxylic acid ester groups are introduced into the carbon-carbon double bond of the norbornenes by reacting norbornenes with alcohol, carbon monoxide and oxygen. Can be produced with high catalytic activity of palladium and high reaction performance.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Rei Hara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (3)

[Claims] 1. General formula (1) [Chemical formula 1] (In the formula, R ₁ and R ₂ are each a hydrogen atom or a methyl group and may be the same or different, R ₃ and R ₄ may be a hydrogen atom or a —COOR ₅ group and may be the same or different, and R ₅ is hydrogen. Atom or an alkyl group having 1 to 3 carbon atoms), and an alcohol, carbon monoxide and oxygen, (1) palladium metal or a compound thereof, (2) a copper compound, (3) chlorine compound and (4) reaction in the presence of a catalyst containing a compound of manganese or zinc, represented by the general formula (2) [Chemical Formula 2] (In the formula, R ₁ and R ₂ are each a hydrogen atom or a methyl group and may be the same or different, R ₃ and R ₄ may be a hydrogen atom or a —COOR ₅ group and may be the same or different, and R ₅ is hydrogen. An atom or an alkyl group having 1 to 3 carbon atoms, R ₆ is an alcohol R ₆ used in the reaction
The organic residue of OH is shown. ) A method for producing norbornanes having two carboxylic acid ester groups introduced into the carbon-carbon double bond of the norbornenes represented by 2. The norbornenes are bicyclo [2.2.
1] a hept-5-ene-2,3-dicarboxylic acid diester in which norbornanes are bicyclo [2.2.1]
The method according to claim 1, which is heptane-2,3,5,6-tetracarboxylic acid tetraester. 3. The method according to claim 1, wherein the gram atom ratio of chlorine atoms to copper atoms in the reaction mixture is less than 2.