JPH0368539A - Preparation of 3,3',4,4'-biphenyltetracarboxylic acid and preparation method for its derivative - Google Patents

Abstract

PURPOSE: To obtain 3,3',4,4'-biphenyltetracarboxylic acid or its derivative with high purity, by coupling a 4-phthalic ester under the existence of a catalyst composed of a trialkyl phosphine, Ni chloride, Zn powder and an alkali metal halide in a polar neutral solvent.

CONSTITUTION: A compd. of formula II is obtd. by coupling a 4-phthalic ester of formula I, where R = a 1-6C alkyl), under the existence of a catalyst composed of a compd. of the formula (R'₃P)₂N:Cl, (where R' = a 1-12C cyclic alkyl, a 6-10C aryl, an alkyl or an alkoxy-substd. aryl), Zn powder and an alkali metal halide in a solvent. The trialkyl phosphine/Ni chloride catalyst can be easily removed from the reaction product, hence product of high purity is obtained. Heat generation is low when using the trialkyl phosphine complex and temperature control is easy.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing 3,3',4,4'-biphenyltetracarboxylic acid and its derivatives.

Tetracarboxylic acids and their dianhydrides are useful chemical intermediates for the further preparation of a variety of compounds including salts, esters, acyl halides, amides, imides, and the like. The compound 3.3',4.4'-biphenyltetracarboxylic acid (hereinafter referred to as biphenyltetracarboxylic acid) and the corresponding dianhydride can be synthesized with a suitable diamine such as ethylene shea or phenylene shea. It is particularly useful in the production of high performance solids by condensation. Additionally, the biphenyltetra acids and dianhydrides produced by the present invention are useful as curing agents for epoxy resins.

The production of biphenyltetraic acid using a palladium catalyst is described in the literature (Japanese Patent Nos. 7352749 and 8014141).
No. 7, No. 8551151, No. 8020705). Furthermore, Ni(○) catalyst and reducing agent (
Campling reactions of halogenated aromatic compounds using Zn, Mn, Mg) are disclosed. For example, 19
In 1981, Union Carbide
Colon et al. (Bide) reported the camplation reaction of monochlorides of aromatic and heteroaromatic compounds using triphenylphosphine, nickel chloride, zinc powder as a reducing agent, and an inorganic salt as a promoter. No. 3,263,466 (1981)
). However, these did not apply to the method for directly producing biphenyltetraic acid. Subsequent report [Colon et al., Journal of Organic
Chemistry (Journal of Organic
Chemistry), Vol.

51, Reference 14 (1986), pp. 2627-2637], chloroaromatics using both triarylphosphines and trialkylphosphines as ligands in a reaction mixture containing nickel chloride, a sodium halide promoter, and zinc. Coupling reactions of family compounds are disclosed. The authors found that triarylphosphine was the best ligand. Trialkylphosphines gave much slower reactions and lower yields even when large excesses of the ligand were used.

In 1984, K. Takagi et al. also carried out a cambling reaction using a previously prepared trialkylphosphine-nickel halide catalyst, potassium iodide as a promoter, a bromoaromatic compound, and an iodoaromatic compound. reported that good results were obtained (Bul
I, Chem, Soc, + Japan, 5th edition, 1887 (1984)). However, they report that the yield of the coupling product is very low when using chlorobenzene as the starting material. 1986
In , Hitachi Company developed halogenated O-benzenedicarboxylic acid ester as a starting material, tetrakis(triphenylphosphine)nickel(○) complex as a catalyst, tetrakis(triphenylphosphine)palladium(○), and A coupling reaction using zinc as a reducing agent was reported. Next, the coupling product was hydrolyzed to obtain biphenyltetraic acid (Japanese Patent No. 6122034).

This time, in order to obtain biphenyltetracarboxylic acid, we used a pre-prepared nickel complex of triphenylphosphine and/or trialkylphosphine as a catalyst, zinc powder as a reducing agent, and an alkali metal halide as a promoter. It has been discovered that biphenyltetracarboxylic acid esters and their derivatives can be produced by a cambling reaction of 4-halogen-substituted 0-benzenedicarboxylic acid esters carried out in a neutral polar solvent. The ester can then be hydrolyzed in a basic solution to yield the biphenyltetraic acid. When this acid is heated or boiled with acetic anhydride, biphenyl dianhydride is obtained.

Pre-produced (Art P) z NiX2 or (AI
kzP) z N1Xz catalyst (in the above catalyst, X is chlorine or bromine, Ar is aryl, and Alk is alkyl) is more stable in air than (Ph3P) 4 Ni (○). This is an advantage of the invention. In the prefabricated catalysts used in the present invention, only 2 equivalents of triarylphosphine or trialkylphosphine are required per mole of nickel halide. It is therefore a particular advantage of the present invention that no excessive amounts of expensive triphenylphosphine or trialkylphosphine ligands need to be added during the reaction.

4-Halogen Substitution for the Method of the Invention. -Benzenedicarboxylic acid ester starting materials can be conveniently prepared by reaction of the corresponding 4-halogen-substituted phthalic anhydride with a lower alcohol under acid-catalyzed conditions.

This ester was then converted to (Ars P) in a neutral solvent.
z N5Xz or (Alki P) z Ni X
Cuffbling according to the invention using z as a pre-prepared catalyst. The yield of biphenyltetraic acid ester can reach more than 90%. The corresponding tetraacid can be obtained by hydrolyzing and acidifying this tetraester in a basic solution. Biphenyldianhydride is produced by heating or boiling this tetraacid with acetic anhydride.

The starting material for the process of the invention is an ester of 4-halophthalic acid. These starting materials are typically prepared in the presence of a mineral acid such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, etc.
Reaction of 4-halophthalic anhydride, preferably 4-chloro- or 4-bromophthalic anhydride, with a suitable alcohol, preferably an alkanol of 1 to 6 carbon atoms, at a temperature of from 0' to 160't: It can be conveniently manufactured by

The coupling reaction of the present invention is represented by the following formula.

In the above formula, R is preferably an alkyl group of 1 to 6 carbon atoms, most preferably an alkyl group of 1 to 4 carbon atoms, and R' is an alkyl group, a cyclic alkyl group, an aryl group, an alkyl group. or an alkoxy-substituted aryl group,
The alkyl or alkoxy group here has 1 to 12 carbon atoms and the aryl group has 6 to IO carbon atoms. Preferably R' is an alkyl group of 1 to 4 carbon atoms and MX is an inorganic salt, preferably an alkali metal halide, most preferably bromide.

Inorganic salts are typically used in amounts of about 100 to 600 mole percent based on the amount of 4-halophthalate starting material. The solvent used is preferably dimethylformamide (DMF), dimethylacetamide (DMAC)
, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMS○), hexamethylphosphoramide (HI
vlPA) and other polar, neutral solvents.

Preferably, the solvent is used in an amount of about 1-10 mole % g reactant. The zinc is in powder form, preferably about 100-40% based on the amount of 4-halophthalate starting reactant.
It is used in an amount of 0 mol%. The temperature at which the coupling reaction is carried out can vary considerably, but is typically about 2
It ranges from 0 to 100°C, preferably about 40 to 100°C, most preferably 40 to 60°C. For example, the reaction time is 4
It can be as long as 8 hours or more, but typically about 1
~8 hours.

The amount of (R':+P)zNiCIt catalyst is preferably about 1 to 10 mole percent based on the amount of 4-halophthalate starting reactant. The catalyst can be purchased commercially or can be prepared in a known manner, for example by reaction of triphenylphosphine or trialkylphosphine with nickel chloride in a suitable solvent such as ethanol.

A method for preparing catalysts suitable for use in the process of the invention is described by Jensen et al., Acta Chem.
, 5cand.

17 (1963) lk4 and Dough
ty) et al., Journal of the American Chemical Society4
American Chemical Society)
101:10 (1979),
These descriptions are incorporated herein by reference. A preferred catalyst is a complex of trialkylphosphine and nickel chloride, most preferably when the alkyl group is 1
~4 carbon atoms. Trialkylphosphine/nickel chloride catalysts have been found to be particularly effective due to the ease of removal of catalyst residues from the reaction products. This is particularly important for the production of high purity biphenyltetraate esters and derivatives for subsequent use in the production of high performance polyimides. Furthermore, it has been found that the use of trialkylphosphine complexes produces less exotherm during the reaction, thus making it easier to control the reaction temperature.

The following examples are presented to illustrate the invention and methods of carrying out the invention. It is understood, however, that the specific details shown in the examples are chosen for illustrative purposes only and are not to be considered as limitations on the invention. In the examples, unless otherwise specified, all parts and percentages are by weight, and all temperatures are in degrees Celsius.

Example 1 4-chlorophthalic anhydride (80 g, purity 95%) and 3
A mixture of 20- and methanol was heated to reflux in a round bottom flask. Anhydrous H (l) gas was slowly added into this solution with stirring. After 6 hours, the addition of HCJ was stopped and most of the methanol was removed by distillation. After adding 500 ml of H2O to the residue. , CHIz
Extracted with. The organic layer was saturated three times with saturated NazCO3 and saturated NaCj! After washing twice with water, it was dried over anhydrous MgSO3. Remove CHCl5 with a rotor evaporator,
The residue was distilled under reduced pressure and 95.07 g of dimethyl 4-chlorobenzenedicarboxylate (yield 95%, boiling point 110 - ) and 25n11 of glacial acetic acid were added. The mixture was heated under nitrogen to remove all the pH.
, dissolved p. The solution was cooled to room temperature and 2.37 g of NiC7! in H2O of 2-! □・6H20(1
0 mmol) was added. Glacial acetic acid (50 mO) was added. A large amount of olive green crystals precipitated from this solution.

The solution was stirred constantly overnight.

The crystals turned dark blue. The mixture was filtered, and the precipitate was washed twice with glacial acetic acid and dried in vacuo to give 5.5 g (84% yield).
) of (Phi P )z ・N+ Cj! I got z.

2. 4.50 g (20 mmol) dimethyl 4-chlorobenzenedicarboxylate (CBDM), 5.2 g (20 mmol) anhydrous NaBr, under a nitrogen atmosphere into a reaction flask flushed with nitrogen. 68 g (40 mmol) of zinc powder and 0.52 g (0.8 mmol) of (
Ph3P)z・N1CA'z was added.

The mixture was dried over molecular sieves while maintaining a nitrogen atmosphere. DMAC30- was added. The mixture was heated to 80° C. for 1 hour with stirring. The color of the solution changed from blue-green to brown in 0.5 hours. 4 hours later,
The solution was cooled, filtered, and the solvent removed on a rotary evaporator. Chloroform was added and the solution was filtered again. The filtrate was washed three times with saturated NaCl aqueous solution, and CHC
a. was removed. To the residue was added 50-20% NaOH solution and the mixture was heated to reflux for 4 hours. The mixture was filtered and the filtrate was acidified with concentrated hydrochloric acid. The white precipitate formed was filtered, washed several times with N20, and dried at 100 °C in a drying bed.
to obtain 3.2 g of biphenyltetracarboxylic acid (yield 97%). Gradually add this tetraic acid to 210 to 22
Dehydration was achieved by heating to 0°C to obtain biphenyldianhydride, melting point 299-302°C.

Example 4 2.28 g (10 mmol) CBDM, 2.6 g (20 mmol) NaB into a reaction flask under nitrogen
r, 0.67 g (10 mmol) zinc powder, 0
．． 26 g (0.4 mmol) of Ni CI12 (PP
h3) Added 2 and 20 ml of dry DMAC. The mixture was heated to 80° C. for 18 hours with stirring, then cooled and filtered. DMAC was removed under reduced pressure and C3(1
3 was added and the mixture was filtered again. The filtrate was diluted with saturated Na(
J! Washed three times with hot solution and dried over anhydrous MgSO.

GC analysis of sample shows biphenyltetraester 93.9%
, CBDMl, 8% and benzene diester (reduction product) 4.3%.

4.56 g (20 mi'J) into the reaction flask under nitrogen.
mol) (DCBDM, 6.6 g (401'J% le) of anhydrous KI, 1.34 g (20,S mol) of zinc powder and 0.52 g (0,8 mmol) of (Phz P)z
- Added NiC1z. CaH, NMP distilled over
(40tR1) was added to this mixture.

This solution was heated to 80°C for 7 hours. The brown mixture was mixed with dilute HC&solution and extracted with CHCl. The organic layer was washed three times with saturated NaCl solution, dried over anhydrous Mg5O, and filtered. CHC with rotary evaporator
l, was removed. The residue was hydrolyzed with 50-20% NaOH and then acidified to yield 2.2 g of biphenyltetraic acid (66.6% yield).

Implementation Group-1 The operation of Example 5 was repeated. However, (Phi P) Ji Cj! 0.29 instead of t
g (0.8 mmol) of triethylphosphine nickel chloride (Ets P) t NiCl! z was used. The final yield is Bifenyl Tetra! 2.1g (yield 63.6%
)Met.

Large construction-1 Into a reaction flask, under N2, 22.8 g (100 mmol) of CBDM, 26 g (200 mmol) of anhydrous NaBr, 13.4 g (mmol) of zinc powder and 2
．． 6g (4,0t remol) of CPh5P)z ・Ni
Cj! Added z. To this mixture was added 150-dry DMAC. The solution was heated to 60°C with stirring for 1 hour and kept at 60°C for 4 hours. The mixture was then filtered and the filter cake was washed three times with DMAC. DMAC was removed from the filtrate. Loomf to the residue
of anhydrous EtOH and a small amount of activated carbon were added. The mixture was heated to boiling, filtered hot, and the filtrate was cooled.

The resulting white crystals were recrystallized twice in EtOH and dried to yield 16 g of biphenyltetraester (83%), melting point 97-99°C.

Large facility-1 According to the procedure of Example 3, 2.7 in DMAC of 20-
3 g (10 mmol) of 4-promobenzenedicarboxylic acid methyl ester, 0.26 g (0.4 mmol) of (
PhzP)z・NiC1z, 2.6g (20 mmol)
of NaBr and 1.38 g of biphenyltetraic acid (83,6%) from 1.34 g (20 mmol) of zinc powder
, melting point 297-301°C.

Daitoyo-ban - To Eufrask, 4.56 g (20 mol) of dimethyl 4-chlorophthalate, 5.2 g (20 mmol) of anhydrous sodium bromide, 2.68 g (40 sz limole) of zinc powder, and 0.27 g (0 , 8 mmol) of bis(tributylphosphine)nickel chloride was added.

After purging with nitrogen, syringe 30-
was added. The mixture was heated to 70°C with stirring for 1 hour.
and reaction conditions were maintained for an additional 5 hours. After cooling, the reaction mixture was filtered, and the filtrate was distilled under reduced pressure to remove DMAC. Chloroform was added and the mixture was filtered again. The filtrate was washed three times with aqueous sodium chloride solution. Yield of tetraester 70.6% by gas chromatography
was measured.

1-Ll from Previous 1 The following method was carried out for comparison. 0.11 g (0,
17 mmol) anhydrous nickel chloride, 0.49 g (0,
6 mmol) of tributylphosphine, 5.2 g (20
mmol) of anhydrous sodium bromide and 2.86 g (40
A mixture of ξ mol) of zinc dust was added to the flask. After purging with nitrogen, 10 d of dry DMAC was added via syringe. The mixture was stirred and kept at room temperature for 0.5 hours. 2
A solution of 4.56 g (20 mmol) of dimethyl 4-chlorophthalate in o-dry DMAC was added slowly.

The reaction was carried out at 70°C for 10 hours. The reaction mixture was worked up as described in Example 3 to yield 0.7 g (21.2%) of biphenyltetracarboxylic acid.

Back application - above 30, 12.6 g diptyl 4-chlorophthalate, 8.2 g anhydrous sodium bromide in 0 g DMF, 4.
0g zinc dust and 1.0g tributylphosphine-
Nickel chloride ((BIJ3P) 2 Ni (II)
The mixture of Cl1z) was heated and kept at 50°C with stirring for 9 hours. Gas chromatographic analysis of the reaction mixture showed 86.69% (g, c, area %) biphenyltetrabutyl ester.

Large Breath Spot - Soil 1 The procedure of Example 11 was repeated except that the reaction temperature was kept at 60°C, and the reaction product was analyzed after 6 hours of reaction time.
% (g, c, area %) of biphenyltetrabutyl ester.

The procedures of Examples 11 and 12 were repeated, except that the sterile-container reaction was run at 70°C for 6.25 hours. The reaction product is
It contained 86.52% biphenyltetrabutyl ester in g, c0 area%.

Large site - 4.5 g of 4 in 3 g of dimethylformamide 28, 4
- dimethyl chlorophthalate, 0.6 g sodium chloride, 2.7 g zinc dust and 0.3 g pre-prepared triethylphosphine-nickel chloride catalyst ((Eb P )
2NiClx ) was heated with stirring in a nitrogen atmosphere and kept at 80° C. for 5 hours to obtain a reaction mixture containing 77.4% biphenyltetramethyl ester in g, c, area %. Raise the temperature to 100°C and hold for an additional hour, g, c.

A reaction product containing 86.7% by area of biphenyltetramethyl ester was obtained.

Large facility - soil I The following method was performed for comparison. 45.0 g dimethyl 4-chlorophthalate, 7.3 g sodium chloride, 15.4 g in 70.8 g dimethylformamide
A mixture of zinc powder, 0.5 g of nickel chloride and 3.5 g of triethylphosphine was heated with stirring in a nitrogen atmosphere and kept at 77-80°C for 5.5 hours to obtain g, c,
A reaction product containing 13% by area of biphenyltetramethyl ester was obtained.

Claims (1)

[Claims] 1. A method for producing biphenyltetracarboxylic acid ester of the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R is an alkyl group having 1 to 6 carbon atoms) (1) Pre-produced (R'_3P)_2NiCl_2 catalyst (in the above catalyst, R' is an alkyl group, or 1 to 12
(2) zinc powder; and (3) an alkali metal halide; , in a polar neutral solvent, the formula: ▲ Formula,
There are chemical formulas, tables, etc. ▼ A manufacturing method that includes coupling reaction of 4-phthalic acid ester represented by (in the above formula, R is as defined above). 2. The pre-prepared catalyst is represented by the formula (R'_3P)_2NiCl_2 (in the above formula, R' is a phenyl group),
2. The method according to claim 1, which is a complex of triphenylphosphine and nickel chloride. 3. The manufacturing method according to claim 2, wherein the 4-halophthalic ester is 4-chlorophthalic ester. 4. A claim that the 4-halophthalic ester is a 4-chlorophthalic ester of the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R is an alkyl group having 1 to 4 carbon atoms) The manufacturing method according to item 3. 5. The manufacturing method according to claim 4, wherein the 4-chlorophthalic acid ester is dimethyl 4-chlorophthalate. 6. The manufacturing method according to claim 4, wherein the alkali metal halide is sodium bromide. 7. The manufacturing method according to claim 4, wherein the alkali metal halide is sodium chloride. 8. The pre-prepared catalyst is a complex of nickel chloride and triphenylphosphine represented by the formula (R'_3P)_2NiCl_2 (in the above formula, R' is an alkyl group of 1 to 12 carbon atoms). A manufacturing method according to claim 1. 9. The manufacturing method according to claim 8, wherein the 4-halophthalic acid ester is a 4-chlorophthalic acid ester. 10. Claim 9, wherein the halophthalic acid ester is a 4-chlorophthalic acid ester of the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R is an alkyl group having 1 to 4 carbon atoms) Manufacturing method described. 11. The manufacturing method according to claim 8, wherein the 4-halophthalic acid ester is dimethyl 4-chlorophthalate. 12. The production method according to claim 9, wherein the 4-halophthalic acid ester is diptyl 4-chlorophthalate. 13. The manufacturing method according to claim 9, wherein the 4-chlorophthalic acid ester is diethyl 4-chlorophthalate. 14. The production method according to claim 10, wherein the alkali metal halide is sodium bromide. 15. The method of claim 1, which is carried out at a temperature of about 20-100<0>C. 16. Claim 1, further comprising an additional step of hydrolyzing the produced biphenyltetracarboxylic acid ester in a basic solution to produce the corresponding biphenyltetracarboxylic acid.
Manufacturing method described. 17. The production method according to claim 15, wherein the produced biphenyltetracarboxylic acid is dehydrated to produce the corresponding biphenyl dianhydride. 18. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R is an alkyl group of 1 to 4 carbon atoms) A method for producing biphenyltetracarboxylic acid ester represented by ( 1) previously prepared (R'_3P)_2NiCl_2 catalyst (in the above catalyst, R' is phenyl), (2) zinc powder, and (3) alkali metal bromide, in the presence of and in a polar neutral solvent, the formula : ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A manufacturing method that includes coupling reaction of 4-chlorophthalic acid ester represented by (in the above formula, R is as defined above). 19. The method of claim 18, which is carried out at a temperature of about 40-100<0>C. the catalyst is present in an amount of about 1 to 10 mole percent, based on the amount of 20,4-chlorophthalate starting reactant;
20. The method of claim 19, wherein zinc is present in an amount of about 100-400 mole percent and the alkali metal bromide is present in an amount of about 100-600 mole percent. 21. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, R is an alkyl group of 1 to 4 carbon atoms) A method for producing biphenyltetracarboxylic acid ester, comprising: (1) (R'_3P)_2NiCl_2 catalyst (in the above catalyst, R' is alkyl of 1 to 4 carbon atoms), (2) zinc powder, and (3) alkali metal bromide, in the presence and polarity of a previously prepared (R'_3P)_2NiCl_2 catalyst. A production method comprising coupling a 4-halophthalic acid ester represented by the formula: ▲Mathematical formula, chemical formula, table, etc.▼ (in the above formula, R is as defined above) in a neutral solvent. . 22. The method of claim 21, which is carried out at a temperature of about 40-100<0>C. 23. Claim 2, wherein the solvent is dimethylformamide.
1. The manufacturing method described in 1. Based on the amount of 24,4-chlorophthalate starting reactant, the catalyst is present in an amount of 1 to 10 mole percent, zinc is present in an amount of about 100 to 400 mole percent, and the alkali metal bromide is present in an amount of about 23. A process according to claim 22, wherein the compound is present in an amount of 100 to 600 mol%. 25. The production method according to claim 24, wherein the alkali metal bromide is sodium bromide. 26. The manufacturing method according to claim 24, wherein the 4-chlorophthalic acid ester is dimethyl 4-chlorophthalate. 27. The manufacturing method according to claim 24, wherein the 4-chlorophthalic acid ester is diethyl 4-chlorophthalate. 28. The manufacturing method according to claim 24, wherein the 4-chlorophthalic acid ester is diptyl 4-chlorophthalate.