JP3342942B2 - Method for dialkoxycarbonylation of norbornenes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a process for producing two carboxylic acids from a norbornene and an alcohol, carbon monoxide and oxygen for each carbon-carbon double bond contained in the bicyclo [2.2.1] ring of the norbornene. Acid ester group (-COOR
Group) has been introduced.
These compounds and their derivatives are important compounds as raw materials for various compounds and as additives to resins. When the norbornanes of the product can be converted into a compound having four carboxyl groups or a derivative thereof, they are important compounds to be used as a raw material of an imide resin or the like.

[0002]

2. Description of the Prior Art Bicyclo [2.2.
1) There are some examples in which two carboxylate groups are introduced for each carbon-carbon double bond contained in the ring. For example, in JP-A-63-57557, bicyclo [2.2.
1] Hept-5-ene-2,3-dicarboxylic acid diester is reacted with an alcohol and a monoxide in the presence of a palladium catalyst and an oxidizing agent (a copper compound or an iron compound, etc., which is required to be twice as much as the starting norbornenes). Reacting with carbon to form bicyclo [2.2.1] heptane-2,3,5,6
-A tetracarboxylic acid tetraester is obtained. JP-A-60-104039 discloses that dicyclopentadiene, carbon monoxide, alcohols and / or their derivatives, such as acetals, ketals and alkyl orthoformates, are reacted with a palladium catalyst, a copper or iron compound and / or oxygen. To obtain tricyclo [5.2.1.0 ^2,6 ] dec-3-ene-8,9-dicarboxylic acid diester.

[0003]

However, in each of these methods, the activity of the palladium catalyst is extremely low in any case, and the application to an industrial process is not at all as desired. An object of the present invention is to react norbornenes with an alcohol, carbon monoxide and oxygen to obtain a palladium catalyst having a high catalytic activity without impairing the reaction results, and to reduce the carbon content contained in the bicyclo [2.2.1] ring of the norbornenes. An object of the present invention is to provide a method for producing norbornanes in which two carboxylic acid ester groups are introduced per one carbon double bond.

[0004]

Means for Solving the Problems The present inventors have intensively studied a catalyst system to achieve the above object, and as a result, have found that norbornenes and alcohols, carbon monoxide and oxygen are
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 bicyclo [2. 2.1] The inventors have found that norbornanes having two carboxylic acid ester groups introduced per one carbon-carbon double bond contained in the ring can be obtained with extremely high palladium catalytic activity, and completed the present invention.

That is, the present invention relates to norbornadiene,
Dicyclopentadiene or bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, norbornenes, and alcohol, carbon monoxide and oxygen are reacted with (1) palladium metal or Reacting in the presence of a catalyst containing the compound, (2) a copper compound, (3) a chlorine compound, and (4) a manganese or zinc compound, wherein the norbornene bicyclo [2.2. 1] A method for producing norbornanes in which two carboxylic acid ester groups are introduced for each carbon-carbon double bond contained in the ring.

The norbornenes used as raw materials in the process of the present invention are norbornadiene (ie, bicyclo [2.2.
1] hepta-2,5-diene), dicyclopentadiene (that is, tricyclo [5.2.1.0 ^2,6 ] deca-3,
8-diene) and bicyclo [2.2.1] hept-5
Selected from -ene-2,3-dicarboxylic anhydride. These are easily obtained by the Diels-Alder reaction. Alcohols include alcohols such as methanol, ethanol, propanol, butanol, pentanol, octanol, cyclopentanol, cyclohexanol, phenol, benzyl alcohol, ethylene glycol, polyethylene glycol and propylene glycol, and further include halogen and alkoxy groups. And other alcohols having a substituent that does not inhibit the reaction. The use amount of these alcohols is not particularly limited, but is usually 2 mol or more based on 1 equivalent of the carbon-carbon double bond contained in the bicyclo [2.2.1] ring of norbornenes. Ranges from 2.5 to 250 moles,
More preferably, it is 5 to 100 mol. The alcohol may be used not only as a reaction raw material but also as a solvent.

The carbon monoxide and oxygen used in the method of the present invention are preferably diluted with a gas that does not hinder the reaction, such as nitrogen, argon or carbon dioxide, in order to avoid an explosion range. Air can also be used as the oxygen source. The partial pressure of carbon monoxide carried out by the method of the present invention is:
5 MPa or less (absolute pressure, the same applies hereinafter), preferably in the range of 0.0005 to 4 MPa. The partial pressure of oxygen is 5 MPa or less, preferably 0.0002
Or 3 megapascals. The required amounts of carbon monoxide, oxygen and diluent gas may be charged to the reactor all at once, or a method of continuously or intermittently adding the required gas, or a method of continuously or intermittently adding a mixture thereof. It may be a method of distributing it to. The mixed gas to be subjected to the reaction may be freshly prepared each time, but the residual gas used in the reaction once or the exhaust gas in the method of flowing may be used repeatedly after adjusting the concentration of each component gas.

In the reaction according to the method of the present invention, alcohol as a raw material can be substantially used as a solvent, but a solvent can be used as long as it does not hinder the reaction. Such solvents include, for example, 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, etc. 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, nitriles such as acetonitrile and benzonitrile, amide compounds such as dimethylformamide, and sulfone compounds such as sulfolane.

As the palladium metal or the compound thereof as the first component of the catalyst of the present invention, for example, palladium metal is 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 palladium dibenzylideneacetone complex or tetrakis (triphenylphosphine) palladium, palladium chloride, Palladium halides such as palladium bromide, palladium sulfate,
Inorganic salts of palladium such as palladium phosphate or palladium nitrate, palladium acetate, organic acid salts of palladium such as palladium propionate or palladium benzoate,
Or a divalent palladium compound such as a complex of palladium such as bis (acetylacetonato) palladium, cyclooctadienedichloropalladium, palladium chloride benzonitrile complex, or palladium chloride ammine complex.

The amount of the palladium metal or its compound used is 0.05 gram atom as palladium atom with respect to 1 equivalent of the carbon-carbon double bond contained in the bicyclo [2.2.1] ring of the norbornene starting material. Is the following,
Preferably it is in the range of 5 × 10 ^-7 to 1 × 10 ^-2 gram atoms. Examples of the compound of copper as the second component of the catalyst of the present invention include copper halides such as copper chloride and copper bromide;
Inorganic acid salts of copper, such as copper carbonate and copper nitrate; organic acid salts of copper, such as copper acetate, copper propionate, copper stearate or copper benzoate; or copper, such as copper acetyltonate or copper benzoylacetonate And the like. The valence of copper in these compounds may be monovalent or divalent. These copper compounds may be used alone or in combination of two or more. It is preferable that these copper compounds are dissolved in the reaction mixture, but some copper compounds may remain insoluble. The amount of these copper compounds used is not more than 2 gram atoms per liter of the reaction mixture as copper atoms, and is preferably 0.00
It is in the range of 05 to 0.5 atoms. However, when copper chloride is used as the chlorine compound as the third component of the catalyst, the copper compound is used in such a manner that the copper atom of this compound is also included in the above range.

Examples of the chlorine compound as the third component of the catalyst include 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 or the like. Organic chlorinated compounds that easily generate chloride ions such as acid chlorides such as benzoyl chloride,
Chlorine-containing carbonic acid derivatives such as phosgene and methyl chloroformate,
Phosphorus chloride, such as phosphorus pentachloride; phosphorus oxychloride, such as phosphoryl trichloride; tellurium chloride, such as tellurium tetrachloride; thionyl chloride; and Group 4A, such as titanium and zirconium; Group 5A, such as vanadium and tantalum; 6A group such as molybdenum, 7A such as manganese
Group 8 such as iron, cobalt, nickel, ruthenium, palladium and platinum; Group 1B such as copper; Group 2B such as zinc and cadmium; 4B such as germanium and tin
And chlorides or oxychlorides depending on the valence of the Group 5B metal such as antimony and bismuth. Of these, chlorine, hydrogen chloride, phosphorus pentachloride, phosphoryl trichloride, vanadium oxytrichloride, chromium trichloride, manganese chloride, iron chloride, copper chloride, zinc chloride,
Tin chloride and bismuth chloride are preferred. These may be used alone or as a mixture of two or more. When the other catalyst component is a chlorine compound, it can also serve as part or all of the chlorine compound of the third component of the catalyst. The amount of these chlorine compounds used is not more than 1 gram atom per liter of the reaction mixture as chlorine atom, preferably in the range of 0.0001 to 0.1 gram atom. However, when a compound containing a chlorine atom is used as the other catalyst component, the amount is in the range including the chlorine atom.

In the process 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 has an atomic ratio of less than 2 to the copper atom also present. . More preferably 0.05 to
It is in the range of 1.90.

The compound of manganese or zinc which is the fourth component of the catalyst in the present invention includes inorganic compounds such as oxides, hydroxides, chlorides or carbonates of manganese or zinc, acetic acid, propionic acid and stearic acid. And salts of monovalent or divalent organic acids such as succinic acid, phenylacetic acid, benzoic acid, phthalic acid and toluenesulfonic acid, and complex compounds such as acetylacetonate complex, cyclopentadienyl complex and carbonyl complex. Can be These compounds may be used alone or in combination of two or more. These compounds are preferably dissolved in the reaction mixture, but may be partially insoluble. The amount of the compound of the fourth component of the catalyst is such that the gram atomic 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 0.05 to 10. The compounds of the first, second, third, and fourth components of the catalyst described above may be combinations of compounds that generate such compounds in the reaction system.

The reaction type of the method of the present invention is a batch type,
Either a semi-batch type or a continuous flow type may be used. The total pressure of the reaction in the process according to the invention depends on the partial pressure of the carbon monoxide, oxygen and diluent gas used, but is usually below 50 megapascals, preferably in the range from 0.1 to 30 megapascals. The reaction temperature is 200 ° C. or less, preferably 40 ° C.
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.

[0015]

The present invention will be described below with reference to examples. Example 1 In a glass cylindrical container, 3.14 milligrams (0.0140 millimoles) of palladium acetate, 699 milligrams (3.50 millimoles) of cupric acetate monohydrate, and 1.03 manganese acetate tetrahydrate were added.
Gram (4.20 mmol) was weighed, 80 g of methanol was added thereto, and then bicyclo [2.2.1] hept-5-
23.0 grams (140 mmol) of ene-2,3-dicarboxylic anhydride were weighed. A solution in which hydrogen chloride gas whose concentration was measured immediately beforehand was absorbed in methanol (concentration 0.50
N) in 3.5 ml (the amount of hydrogen chloride is 1.75 mmol)
In addition, another 150 grams of methanol was added. This container was inserted into a 1 liter autoclave. The stirring blade of the autoclave is made of fluororesin, and the temperature measuring tube is also protected by glass.

In the autoclave, while maintaining the total pressure at 4 MPa, the partial pressure ratio of carbon monoxide: oxygen: nitrogen is 8.7.
: 6.2: 85.1 The mixture was allowed to react at 110 ° C. for 9 hours while continuing stirring while passing the mixed gas at 0.7 liter / minute (standard state). During this time, the outlet gas was discharged through a reflux condenser. After the reaction was completed, the pressure was cooled and the pressure was released, and the reaction solution taken out was analyzed by gas chromatography. As a result, there was no starting material, and two methyl carboxylates were attached to the double bond between the 5- and 6-positions of the bicyclo [2.2.1] ring. An ester group is introduced,
39.2 g of bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid tetramethyl ester in the form of the anhydride of the carboxylic acid at the 2-position and 3-position converted to its methyl ester by methanol during the reaction. (119.4 mmol). The yield was 85.3% and the number of moles of the desired product formed per gram atom of palladium (hereinafter abbreviated as Pd turnover) was 8,530.

Comparative Example 1 The procedure was the same as in Example 1 except that no hydrogen chloride was used. The conversion of the raw material is 7.3%, and bicyclo [2.2.1]
Heptane-2,3,5,6-tetracarboxylic acid tetramethyl ester was not quantifiable.

Comparative Example 2 The procedure of Example 1 was repeated except that manganese acetate tetrahydrate was not used. The conversion of the starting material was 19.5%, the yield of bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid tetramethyl ester was 9.2%, and the Pd turnover was 920.

EXAMPLE 2 2.48 mg (0.0140 mmol) of palladium chloride, 527 mg (2.64 mmol) of cupric acetate monohydrate, 115.8 mg (0.861 mmol) of cupric chloride, 1.03 mg of manganese acetate tetrahydrate Grams (4.20 mmol) were weighed, and after adding a part of methanol, dicyclopentadiene (ie, tricyclo [5.2.1.0 ^2,6 ] deca-
18.5 grams (140 mmol) of 3,8-diene)
Further methanol was added to make the total amount 230 grams.
When the reaction was carried out in the same manner as in Example 1, the conversion of the raw materials was 10
0%, and two carboxylic acid methyl ester groups are introduced into the double bond of the bicyclo [2.2.1] ring, and the double bond of the five-membered ring is unchanged. Tricyclo [5.2.1. 0
^2,6 ] Dece-3-ene-8,9-dicarboxylic acid dimethyl ester was obtained in a yield of 81.6%. The Pd turnover was 8160.

Example 3 The procedure of Example 2 was repeated except that the raw material was changed to 12.9 g (140 mmol) of norbornadiene (ie, bicyclo [2.2.1] hept-2,5-diene). The total pressure was 10 megapascals, and the flow rate of the mixed gas was 1.2 liter / min (standard condition). Except for this, the reaction was carried out in the same manner as in Example 2 and Example 1. Bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid tetramethyl ester in which two carboxylic acid methyl ester groups are introduced at each of two double bonds of the bicyclo [2.2.1] ring Is obtained in a yield of 72.4%,
The Pd turnover was 7240.

Example 4-15 The reaction was carried out in the same manner as in Example 1 except that the types and amounts of the catalyst components shown in Table 1 were used. The results are shown in Table 1 together with the results of Example 1.

[0022]

[Table 1]

Example 16 In Example 1, a solution of hydrogen chloride in methanol (concentration: 1.
5N) was used in the same manner as in Example 1 except that 6.0 ml (the amount of hydrogen chloride was 9.0 mmol). The gram atomic ratio of chlorine atoms to copper atoms in the reaction mixture was 2.6 in Example 1 instead of 0.5.
As a result, the yield of bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid tetramethyl ester was 71.3%, and the Pd turnover was 7130.

[0024]

According to the method of the present invention, a norbornene is reacted with an alcohol, carbon monoxide and oxygen in the presence of a specific catalyst to form a bicyclo [2.
2.1] Norbornanes having two carboxylic acid ester groups introduced per carbon-carbon double bond contained in the ring can be produced with extremely high palladium catalytic activity.

Continuation of front page (56) References JP-A-63-57557 (JP, A) JP-A-63-57589 (JP, A) JP-A-62-16448 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C07C 67/38 C07C 69/753

Claims (3)

(57) [Claims] 1. Norbornadiene, dicyclopentadiene or bicyclo [2.2.1] hept-5-ene-
Norbornenes which are 2,3-dicarboxylic anhydrides;
Alcohol, carbon monoxide and oxygen in the presence of a catalyst containing (1) palladium metal or a compound thereof, (2) a copper compound, (3) a chlorine compound and (4) a manganese or zinc compound. A process for producing norbornanes wherein two carboxylic acid ester groups are introduced for each carbon-carbon double bond contained in the bicyclo [2.2.1] ring of the norbornenes. 2. The method according to claim 1, wherein the norbornenes are bicyclo [2.2.
1) The method according to claim 1, which is hept-5-ene-2,3-dicarboxylic anhydride. 3. The method according to claim 1, wherein the gram atomic ratio of chlorine atoms to copper atoms in the reaction mixture is less than 2.