JPS60104081A - 3,5,6-tricarboxynorbornan-2-acetic acid-5,6-anhydride - Google Patents

Abstract

NEW MATERIAL:3,5,6-Tricarboxynorbornan-2-acetic acid-5,6-anhydride shown by the formula I . USE:A raw material for heat-resistant polyimide resin, plasticizer for polyvinyl chloride, epoxy heat-curing agent, water-soluble polyester, etc. PREPARATION:Carbon-carbon double bond of diester is oxidized and cleaved to give 3,5,6-tricarboxynorbornan-2-acetic acid-5,6-diester shown by the formula II, ester group of the compound is hydrolyzed, to give 3,5,6-tricarboxynorbornan- 2-acetic acid shown by the formula III, and then a compound shown by the formula I is obtained. The hydrolysis is preferably carried out by the use of an ordinary acid (e.g., aqueous solution of Cl, H2SO4, etc.) or an alkali (e.g., solution of NaOH, KOH, etc. in water-alcohol).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 45,6-tricarboxynorbornane-2-acetic acid-5,6-anhydride (hereinafter abbreviated as monoanhydride) represented by structural formula (1). be.

The compound of the present invention is a new compound, and this family of tetracarboxylic acids is generally used as a raw material for polyimide resins for heat resistance purposes, plasticizers for polyvinyl chloride, curing agents for epoxy resins, and water-soluble polyesters. used in the field.

However, the currently widely used aromatic tetracarboxylic acids, such as pyromellitic acid and benzophenone tetracarboxylic acid, have high melting points, poor solubility in solvents, and are too reactive, resulting in poor workability. There was a problem. Furthermore, it is expensive, and a new type of tetracarboxylic acid with improved costs has been long awaited.

The compounds of the present invention are cycloaliphatic tetracarboxylic acids that can be prepared by two routes as shown in the following scheme.

In addition, it is an economical tetracarboxylic acid derivative that can be produced in a short number of steps using inexpensive dicyclopentadiene (DCPD) as a starting material. moreover.

Due to the characteristics of alicyclic compounds, improved performance such as lower melting point, improved solubility in solvents, and relaxation of reactivity is expected.

The method for producing the diester, which is the starting material for the present compound (Japanese Patent Application No. 190429/1982), is synthesized by the diesterization reaction of dicyclopentadiene, which was discovered by the present inventors.

(H: Alkyl, cycloalkyl, benzene-substituted alkyl, which may contain O or Ni atoms internally.) The conodiesterification method is a Wallaker-type reaction using a palladium chloride-copper chloride and/or oxygen catalyst system at room temperature and normal pressure. The process proceeds easily even under mild conditions, and the yield is extremely high.

There are two methods for producing monoanhydrides from diesters of .

One is to oxidatively cleave the carbon-carbon double bond of the diester to produce a 3,5,6-to-4+carboxynorbornane-2-acetic acid-S, /)-diester (hereinafter DB, DC) represented by the structural formula [1]. ) is abbreviated as i0. Subsequently, the ester group is hydrolyzed to form 3, which is represented by the structural formula (Ill).
5.6-) One route is to obtain a monoanhydride via IJ carboxynorbornane-2-acetic acid (hereinafter abbreviated as tetracarboxylic acid), and the other route is to first hydrolyze the ester group of diester to obtain dicarboxylic acid. This route is followed by oxidative cleavage of the carbon-carbon double bond to obtain the monoanhydride via the tetracarboxylic acid.

Hydrolysis of ester groups by these two routes easily proceeds in the presence of ordinary acids or alkalis.

When using an acid, use an aqueous solution such as hydrochloric acid or sulfuric acid; when using an alkali, use an aqueous solution such as sodium hydroxide or potassium hydroxide.
Preferably, an alcohol solution is used.

Next, as a method for oxidative cleavage of carbon-carbon double bonds, a method using nitric acid is generally used [Industrial Chemistry Magazine, Vol. 74! +97 pages (
1971)], permanganate method [Journal of the American Chemical Society (1971)], permanganate method [Journal of the American Chemical Society (1971)]
J, Ann, Cbem, Soc, ) Volume 82, 63
42 pages (1960)] Liquid phase catalytic co-oxidation method using metal catalyst [JP-A-55-1
62737), and ozone oxidation method [Journal of the American Chemical Society (J
, Am, Chem, Soc, ) Volume 81 4273
Page (1959)] are known.

The present inventors conducted various studies on the oxidative cleavage reactions of diesters and dicarboxylic acids, and found that it was difficult to obtain the desired product using methods using nitric acid or permanganate, but high yields were obtained using the co-oxidation method or ozone oxidation method. We found that the ozone oxidation method in particular gave excellent results.

First, regarding the ozone oxidation method, the ozone generation method is preferably carried out using oxygen in a cylinder using a normal ozone generator.If air is used, nitrogen oxides are removed after ozonation by washing with alkaline, etc. It must be dried after removal before use.

The solvent -C is a hydrocarbon or a halogenated hydrocarbon.

Inert solvents such as needles and esters can also be used, but since there is a risk of abnormal reactions, alcohols, carbon
It is preferable to use a protic active solvent such as f.

In particular, alcohols are preferred because they allow reaction at low temperatures, and specifically, methanol, ethanol, propatool, butanol, etc. give particularly good results.

It is preferable to heat the ozone at a low temperature in order to suppress abnormal reactions, and in particular, a temperature of -78° C. provides high selectivity. The oxidative decomposition of the obtained oscinide is carried out mainly with oxygen, but it can also be carried out with peracetic acid, performic acid, hydrogen peroxide, etc.Next, the liquid phase catalytic oxidation method Although this is carried out by contacting with an oxygen-containing gas, in addition to pure oxygen, an oxygen mixed gas or air diluted with an inert gas such as nitrogen or argon can also be used. The gas can be supplied either by bubbling in a normal pressure circulation system or under pressure using an autoclave.

As the catalyst, metals such as ruthenium and osmium or compounds thereof can be used. However, osmium is not practical due to its toxicity.

As ruthenium, metal ruthenium, ruthenium oxide, ruthenium halide, ruthenium hydroxide, ruthenium complex, etc. can be used, and specifically, ruthenium sesquioxide, ruthenium dioxide, ruthenium tetroxide, ruthenium chloride, ruthenium bromide, iodide, etc. Ruthenium and the like are preferred.

The amount used is ruthenium metal equivalent Q, 0001 to 0.01 per mole of raw material diester or dicarboxylic acid.
A gram atom is sufficient.

The aldehyde or ketone used as the co-oxidizing agent may be either aliphatic or aromatic. Specifically 6
-L, polyalnahyde, paraformaldehyde, acetaldehyde, paraaldehyde, glyoxal, globionaltehyde, benzaldehyde, tolualdehyde, methyl ethyl ketone, methyl isobutyl ketone, biacetyl, cyclohexanone, methyl benzyl ketone, etc. Among these, aliphatic alfhydes are preferred, and acetaldehyde is particularly economical and elegant.

How much of these aldehydes or ketones should be used?

It is preferable that α5 is about 100 moles per mole of raw material diester or dicarboxylic acid.

Although this reaction Q is possible without using a solvent.

It is usually preferable to carry out the reaction in the presence of a 7u medium. A wide range of solvents can be used as long as they are inert to the reaction, and examples include halogenated hydrocarbons, aliphatic and aromatic hydrocarbons, esters, carboxylic acids, ethers, alcohols, and ketones. . - Among these solvents acetone, ethyl acetate.

Particular preference is given to using acetic acid, methanol and the like.

Further, the reaction temperature is preferably from 0°C to 200°C.

The oxidative cleavage products obtained by the ozone oxidation method and the liquid phase co-oxidation method are produced by the hydrolysis of the ester group as described above when the raw material is a diester, or by the hydrolysis of the ester group as described above when the raw material is a dicarboxylic acid. Acid is obtained.

Subsequently, the tetracarboxylic acid can be dehydrated by heating under reduced pressure F and converted into the desired monoanhydride.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these in any way.

Reference example 1 Synthesis internal volume of dimethyl ester (under pressure) 1
Dicyclopentadiene (DCFD) 595f (50mmot) in a 00ml Hastelloy autoclave
, palladium chloride 0.267r (1,5mmOf-)
, anhydrous cupric chloride (purity 95%) 1 [14f (73
ff+m0t), methanol 24f was charged, and after pressurizing to 65Kg/Cd-G with -carbon oxide, it was heated to room temperature (25℃
) to start stirring. - Absorption of carbon oxide started immediately and stopped at 5 Kg/r, rl-G after 15 minutes. The reaction is exothermic.

Autoclave 1l-J: The maximum temperature reached 48°C.

Stirring was stopped 30 minutes after the reaction started, and after the temperature was returned to room temperature, carbon monoxide was removed and the reaction product was drained.

After removing the solvent from the reaction product, extraction was performed with n-hexane. As a result of analyzing this 11-hexane solution with a gas chromatograph, no dicyclopentadiene as a raw material remained and a monopeak of 11 was detected as a product.

Therefore, the 2-water reaction was repeated 5 times in exactly the same way.

The n-hexane solution for 5 reactions was concentrated and further distilled under reduced pressure to 140-bH? Dimethyl ester 631 (purity 98%) was obtained.

Reference Example 2 Synthesis of dimethylnisder (under normal pressure) 2t (D
Dicyclobetaji xy (DC
PD) 2129 (1,6m0A).

Palladium chloride 4. Of/ (α025 mol-)
, anhydrous cupric (purity 95%) 465? (3
, 5moA).

Methanol 8001 was charged, the temperature was raised to 50°C, and carbon monoxide was blown into the reactor at a flow rate of 2 A/min under normal pressure for 2 hours with stirring.

After the reaction, the two reactants were cooled and extracted with n-hexane while removing the solvent. This hexane solution was concentrated and distilled under reduced pressure to obtain 165-b1 (purity 98%).

Reference Example 3 Synthesis of dicarboxylic acid 64 f (1,6 mob) of sodium hydroxide was added to 1 part of water.
50- was dissolved in dimethyl ester 102r.
(Purity 98%) (0.4mot) dissolved in ethanol 4002 was mixed and refluxed at 78°C for 3 hours, after which the ethanol was removed.

After adding 1,652 ml of pure hydrochloric acid to the residue, it was concentrated to remove water.

By extracting the resulting concentrate with acetone and concentrating the acetone solution,! Dicarboxylic acid 852 was obtained.

By recrystallizing this with an acetonitrile solvent, white crystals of the desired dicarboxylic acid were obtained. Melting point 1
67-168℃.

Example 1 Synthesis of monoanhydride from dimethyl ester Diester 5 was placed in a 500 ml glass cylindrical gas absorption tube.
1v (purity 98%) ((L 2 mat ) and 500f of methanol were charged and cooled to -78°C.

Ozone generation tl'& (1-1 bottles ozone■ manufactured by company 0-1-
Type 2.

45 t/hr of ozone-containing oxygen was blown into the reactor at a voltage of 100 V) and reacted for 12 hours.

This reaction solution was concentrated under reduced pressure at 50° C. or lower to obtain a water syrup-like ocinide. This oscinide was dissolved in formic acid 6062, and
When 60% hydrogen peroxide is added at around 0°C, reflux begins soon.

When the reflux stopped, 1 trough 202 of 60% hydrogen peroxide was added, the bath temperature was gradually raised to 120°C, and reflux was continued for 2 hours. After completion, remove the solvent under reduced pressure and DF3DC
I got it.

An aqueous solution of ethanol 2001 and sodium hydroxide 522 dissolved in 100v of water was added to DE3DC, and the bath temperature was 1.
Refluxing was continued for 5 hours while stirring at 20°C.

Then remove the ethanol and add concentrated hydrochloric acid (35% HCl)
851 was added to remove the neutralized drain water. This residue was extracted with acetone, and the acetone solution was concentrated to obtain crude tetracarboxylic acid crystals 522.

Subsequently, this crude crystal was heated at around 100° C. under reduced pressure for 2 hours. This reaction product was crystallized from an acetone-ethyl acetate solvent to obtain pure white crystals 692.

The following analysis was performed on this crystal.

Engineering R (KBr): 5200-2500.1775.17
00.14351220, 1085.9M5 (, Tl
+-') Infrared absorption of carboxylic acid anhydride is 1775 cm
-', it can be seen that it is a 5-membered cyclic acid anhydride, that is, a 2.3-position carboxylic acid anhydride.

"C-NMR (CD, C0CD,): 175.9.
17&7.46.2.45.5゜45.1.44.6.
44.3.57.1.55.7.52.7 (p迦) Remas spectrum: Measured after cyclization with bis(trimethylcycle)acetamide.

[-(% Month: 412 (10), 17 (100).

369 (15), 322 (25), 294 (30)
Elemental analysis'<yl(+zOz=26""'!:
Melting point: 228-250°C It was found that the 92 crystals were 3.5.6-) 7-norbornane-2-acetic acid.

In addition, the yield from dimethyl ester to monoanhydride is 7
It was 6chi.

Example 2 Synthesis of monoanhydride from dicarboxylic acid 500-
22v dicarboxylic acid (purity 1) in a glass cylindrical gas absorption tube
00%) (C1mot) and methanol 3001, and 45 tons of ozone-containing oxygen from an ozone generator at -78℃.
/hr and allowed to react for 5 hours.

Next, this reaction solution was concentrated under reduced pressure at 50° C. or lower to obtain a starch syrup-like osinide. Subsequently, this oscinide is dissolved in formic acid 1507, and 60% hydrogen peroxide 202 is added at around 50° C., and reflux begins shortly after. When the reflux stopped, the bath temperature was raised to 120°C and reflux was continued for 2 hours.

Next, when the solvent was distilled off under reduced pressure, white nato-2 carboxylic acid crude crystals 26? was gotten. Subsequently, C2 This crude crystal was heated under reduced pressure.
After heating at around 00°C for 2 hours and cooling, the reaction product was recrystallized from an acetone-ethyl acetate solvent to obtain Simonoanhydride 2.
22 (purity 100%) (yield 82) was obtained.

Example 6 Synthesis of monoanhydride from dimethyl ester Acetaldehyde was placed in a 600 mm glass reaction flask with 252 mm. Ruthenium dioxide (Ruo2・2H20) α1
2. Prepare acetone 1001 and add 30% oxygen gas at 40℃
Blow for 1.5 hours at a rate of t/hr.

Subsequently, 5. dimethyl ester was added to this solution. Or(C02m
A solution of u, c) dissolved in Ahiton 207 was added dropwise over 1 hour, and the mixture was further stirred for 2 hours 4id.

After the reaction, the ruthenium catalyst was removed, and 30 g of water was added to the solution and stirred for 2 hours at a bath temperature of 60°C.

Concentrate the reaction solution, dissolve DEI)C in 201 of ethanol, dissolve 5.2 r of hydroxide in 107 of water, add aqueous solution of methane, and stir at a bath temperature of 120°C. Refluxing was continued for 2 hours.

After the completion of the reaction, remove the ethanol and remove the drained water which has been neutralized by adding concentrated hydrochloric acid (65 f(Cz)'a3?).The residue is dissolved in acetone and the acetone solution is concentrated. 5.2y of crude carboxylic acid crystals were obtained.Subsequently, the crude crystals were heated at around 100°C under reduced pressure for 2 hours, cooled, and then recrystallized from an acetone-ethyl acetate solvent to obtain a monoanhydride (purity 10 (1 ) 3.51 (yield 66 cm from dimethyl ester) was obtained.

Example 4 Synthesis of monoanhydride from dicarboxylic acid 300-
Acetaldehyde 252.
Ruthenium dioxide (RuO2・2H20) 0.1 ? ,
7 Setone I C1Or was prepared and oxygen gas was added at 40°C.
Blow for 1.5 hours at a rate of 0 t/hr. Subsequently, a solution of dicarboxylic acid 4.51 (cLo 2 mot) dissolved in acetone 201 was added dropwise to this solution over 1 hour, and the mixture was further stirred for 2 hours.

After the reaction, the ruthenium catalyst was removed, 60% of water was added to ii'e, and the mixture was stirred for 2 hours at a bath temperature of 60°C. When this reaction solution is concentrated, 4.82 g of crude crystals of tetracarboxylic acid are obtained.

Subsequently, the crude crystals were heated at a reduced pressure near F100°C for 2 hours, cooled, and then recrystallized from an acetone-ethyl acetate solvent to obtain anhydrous! /l (100% purity) 5.89
(Yield 71 from dicarboxylic acid) is 1 (1).

Patent applicant: Nissan Chemical Industries, Ltd.

Claims (1)

[Claims] 45,6-tricarboxynorbornane-2-acetic acid-5,6-anhydride represented by structural formula (1)