JPS59170038A - Bicyclo(3,3,0)octane-2,3,6,8-tetracarboxylic acid and its preparation - Google Patents

Abstract

NEW MATERIAL:The 5,6-tricarboxynorbornane-2-acetic acid of formula I . USE:A raw material of heat-resistant polyimide resin, plasticizer for polyvinyl chloride resin, hardener for epoxy resin, a water-soluble polyester, etc. PREPARATION:The objective compound of formula I can be prepared by (1) using the 3,5,6-tricarboxynorbornane-2-acetic acid 5,6-diester of formula II (R is alkyl, cycloalkyl or benzene-substituted alkyl which may contain O or N atom therein) as a starting material, (2) opening the double bond by oxidation, and (3) hydrolyzing the ester group of the resultant 3,5,6-tricarboxynorbornane-2-acetic acid of formula III.

Description

Detailed Description of the Invention The present invention provides bicyclo[3,3,O]octa-2,5,6,8-tetracarboxylic acid (hereinafter abbreviated as tetracarbo/acid) represented by the structural formula [I] and The present invention relates to a manufacturing method thereof.

The compound of the present invention is a new compound, and generally this family of tetracarboxylic grains is used as raw materials such as +ffrl thermal all-purpose polyimide resin, polyvinyl chloride plasticizer, epoxy resin hardening oki 1, and water bathing polyester. It is used for a wide range of packaging purposes.

However, the currently widely used aromatic tetracarboxylic acids, such as pyromellit 1 and benzophenone tetracarboxylic acids, have a high melting point, poor solubility in solvents, and are highly reactive, resulting in poor workability. There was a problem. father,
Since they are expensive, a new type of tetracarboxylic acid that improves these problems has been long awaited.

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

Also, cheap 11jtl dicyclopentadiene i DOP
It is a pre-prepared tetracarboxylic acid that can be produced in a short number of steps using D+ as a starting material. Furthermore, improvements such as lowering the melting point of alicyclic compounds and moderating the two reactivity of solubility in solvents are also expected.

The starting material of the present invention, the diester, is produced by the diesterization of dicyclopentadiene, which the present inventors have developed. (1 (niargyl, cycloalkyl, benzene direct alkyl, which may contain 0 or N atoms internally) The process proceeds easily even under mild conditions at room temperature and pressure, and the yield is extremely commercial.

The method for producing tetracarphone from this diester includes the aforementioned 7uO (there are two methods).

One is to connect the carbon and carbon-based bonds of the diester with an acid (HIMJ).
'J to obtain DEDC'i, followed by hydrolysis pH of this ester group to obtain tetracarboxylic acid,
The other route is to first hydrolyze the ester group of the diester to obtain the dicarboxylic compound, and then oxidatively cleave the carbon-carbon double bond to obtain the tetracarboxylic compound.

Hydrolysis of the ester group in these two routes proceeds in the presence of a normal acid or alkali.

When using an acid, use a water bath solution such as hydrochloric acid or mineral acid, or alkali +77.
．． When used, it is preferable to use a water-alcoholic solution of sodium hydroxide, sodium hydroxide, potassium hydroxide, or the like.

Next, as a method for oxidative cleavage of carbon-carbon double bonds, a method using nitric acid is generally used [Journal of Industrial Chemistry, Vol. 74, 697 (1'
971)], the permanganate method [Journal of American Chemical Nozayati (J.
Am, chem, Sac l vol. 82 6642 p. 1
960)] Liquid phase catalytic co-oxidation method using a metal catalyst [JP-A-55-
No. 162757], and ozone oxidation method [Journal of the American Chemical Society ((
J, Am, C! ] xem,, Soc l No. 81
Volume 4275 Sada (1959)] etc. are well known.

The present inventors independently investigated these cleavage reactions for diesters and dicarboxes r'+8, and found that the desired product could not be obtained by the method using nitric acid or permancanate.
Although it is difficult, it has been found that the co-oxidation method or the ozone oxidation method gives a higher yield, and the ozone oxidation method in particular gives a better result.

Ozonated Acid Ihi Method To be more specific, the ozone generation method is preferably carried out using a normal ozone generator in a cylinder, and if air is used, the arsenic oxide is removed by total alkali cleaning after ozonation. After drying, it is necessary to use it.

As a solvent, a hydrocarbon or a 10-genated hydrocarbon is used.

Although inert solvents such as ethers and esters may also be used, it is preferable to use protic active solvents such as alcohols and carboxylic acids due to the risk of abnormal reactions.

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

Temperature coagulation with ozone is preferably carried out at a low temperature in order to suppress abnormal reactions, and a temperature around -78'C provides knitting selectivity. The chemical decomposition of the obtained ocinide is carried out using phosphorous, but it can also be carried out using peroxylic acid, peroxyacid, taFt hydrogen hydride, and the like.

Next, the liquid-phase Nl oxidation method is carried out by contacting molecular oxygen-containing M gas in the presence of a catalyst and co-oxidizing agent, but in addition to pure oxygen, an inert gas such as nitrogen or argon is used. Diluted oxygen mixture or air can also be used. Gas can be supplied using two methods: bubbling in a normal pressure flow system and under pressure in 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, metals such as ruthenium metal, ruthenium oxide, ruthenium halide, ruthenium water, and ruthenium complexes can be used. Specifically, ruthenium divalent, ruthenium divalent, ruthenium tetrachloride, ruthenium chloride, Ruthenium bromide, ruthenium iodide, etc. are preferred. .

The amount used is about 0.01 to 0.01 gram atom of ruthenium gold per mole of diester or dicarbonate raw material.

The aldehyde or ketone used as the co-oxidizing agent may be either aliphatic or aromatic. Specific examples include formaldehyde, paraformaldehyde, acetaldehyde, paraldehyde, glyoxal, brochionaldehyde, benzaldehyde, tolualdehyde, methyl ethyl ketone, methyl isobutyl ketone, biacetyl, cyclohexone, and methyl benzyl ketone. Among these, aliphatic aldehyde is preferred, and acetaldehyde is economical and excellent at 2%.

The historical doses of these aldehydes or keto/.

Approximately 0.5 to 100 moles per mole of raw material diester or dicarboxylic acid are preferable.

Although this reaction is possible without using a solvent.

It is usually preferable to carry out the reaction in the presence of a solvent. As a solvent, a wide range of solvents can be used as long as they are oil-free for the reaction.
Examples include halogenated hydrocarbons, aromatic hydrocarbons, esters, carboxylates, ethers, alcohols, ketones, etc.

Among these solvents are acetone and ethyl alcohol.

It is preferable to use acetic acid, methanol, etc.

Further, it is preferable that the temperature of the reel 6 is 0°C to 2000°C.

When the raw material is a diester, the oxidative cleavage products obtained by the ozone halide method and the liquid phase co-acid addition method are processed through the entire hydrolysis of the ester group as described above (7), and when the raw material is a dicarboxylic acid, , the desired tetracarboxylic acid is obtained.

The production of tetracarboxylic acid can be carried out by the following method.

Tetracarboxylic acid is dehydrated by heating under reduced pressure.
Bicyclo[5,5゜0]octane-2,6-carboxylic anhydride-6,8-dicarboxylic acid (abbreviated as monoanhydride) shown by the structural formula rlV] Then, the δ-crystal is formed (and the crystal of the dianhydride is obtained.

Next, is this pure monoanhydride product? A pure tetracarboxylic plate was obtained by washing with water in the presence or absence of tfC.

When the monoanhydride is hydrated, the reaction can be completed in a short time by adding a small amount of water such as hydrochloric acid or nitric acid to 1 mol or more of water and reacting with 1 mol of the monoanhydride. Even in the absence of an acid, hydration can be easily achieved by reacting at 70 to 80°C.

After the reaction was completed, pure white tetracarboxylic acid was obtained by removing excess water and acid.

Hereinafter, the entire history of the present invention will be explained in detail with reference to examples, but the present invention is not intended to be overshadowed by these in any way.

Reference Example 1 Synthesis of dimethyl ester (under pressure) Dicyclopentadiene (DOPD) 3.95P15 D mmot) in a 1007 Hastelloy autoclave
+ Palladium chloride 0.2677 (1,5rnnno/
-) r anhydrous chloride 2nd wJ (pure 1i, 95X) 10
．． 4g (73m+not) r Methanol 242 total preparation.

- After pressurizing with carbon oxide at 65 kg/c using a G-shape, stirring was started at room temperature (25C). - Carbon oxide absorption begins immediately and after 15 minutes 5 kq/tyl-G
Absorption stopped. The reaction was exothermic and the autoclave reached a strict temperature of 48°C.

After 60 minutes of starting the reaction, stirring was stopped, the temperature was returned to room temperature, carbon monoxide was removed, and the reaction mixture was taken out.

After completely removing the solvent from the reaction mixture, extraction was performed with n-hexane. As a result of gas chromatograph analysis of this n-hexane bath for 7 nights, it was found that no dicyclopentadiene as a raw material remained and a nearly monopeak was detected as a product.

Therefore, one reaction was repeated five times in exactly the same way.

Dimethyl ester 362 (1i98X)i was obtained at 14.0 to 145°C at 107η4HjL by diluting the reaction mixture in an n-hexane bath fLk for 5 times and then distilling it under reduced pressure.

Reference Example 2 Synthesis of dimethyl ester (under normal pressure) Dicyclopentadiene (DCP
D) 212 S' (1,617 IO/-).

Palladium chloride 4.0? (0,023 mot), anhydrous cupric chloride (purity 95X) 465? (3,5
After pouring methanol into the flask, the mixture was heated to 50° C., and then carbon monoxide was blown into the flask for 2 hours under normal pressure with stirring at a flow rate of 2 t/min.

After the reaction, the reactant was completely cooled, bath I& was removed, and extraction was performed with n-hexane. This rhohexane solution'f
f: 135-145℃10.5 by vacuum distillation after concentration
Dimethyl ester 2841 (theta degree 98X) was obtained with a water weight of H/.

Reference Example 3 Synthesis of dicarboxylic acid Sodium hydroxide 64 y I 1.6 mat, )
of dimethyl ester dissolved in 150 ml of water and dimethyl ester 102 mm (, l + 11! degrees 98
t) A bath solution dissolved in ethanol 4001 was mixed and refluxed at 78°C for 3 hours, after which the ethanol was removed.

Concentrated hydrochloric acid 1652 was added to the residue and concentrated to remove water. The obtained concentrate was extracted with acetone, and the acetone solution was concentrated to obtain crude dicarbonate 851. By recrystallizing this with all acetonitrile solvent, white crystals of dicarboxylic acid were obtained. Melting point 167-168c0 Example 1 Synthesis of tetracarboxylic acid from dimethyl ester 500 - In a glass cylindrical gas absorption tube, dimethyl ester 5iy (purity 98X) (0.2 mol) and methanol 500? and cooled to -78°C.

Ozone generator (Japan Ozone ■ 0-1-2 type 1oov
) 45 L/hr of ozone-containing oxygen was blown in from 12
Allowed time to react.

This reaction solution was concentrated under reduced pressure at 50° C. or lower to obtain a starch syrup-like osinide. Is this oscinide formic acid 606? #understand, 50
6'OX dispersion water accumulation around ℃ 25? Adding 1￥11
If you lose it, it will flow back.

When the reflux stopped, 60% hydrogen peroxide 202 was further added, and the temperature was gradually raised to 1120° C. and the reaction was continued for 2 hours.

After the reaction, the solvent was removed under reduced pressure to obtain a still viscous liquid. The analysis results of this product were as follows.

Engineering R (KBr): 3000-2900, 1700,
1200 (Cn+-') mass spectrum: Measured after silylation with bis(trimethylsilyl)acetamide.

[%(X)]: 458 (2), 443 (100),
56B +12)3! +5 (35), 185 (50),
From above 73(30), this highly viscous liquid is bicyclo[3
,3°0]octane-2,3-diester-48-dicarboxylic acid (hereinafter abbreviated as DEDO). This is DEDC! Add ethanol 2002 and sodium hydroxide 622 io to water.

The aqueous solution (g) that had been bathed in 2 was placed, and reflux was continued for 3 hours with stirring at a bath temperature of 1201:.

Next, remove ethanol and add concentrated hydrochloric acid (3sXHcz) 862
Add neutralized water and completely distill off. This residue was extracted with acetone and completely concentrated in an acetone bath to obtain 522 crude crystals of the desired tetracarboxylic acid.

Subsequently, the parent crystal was heated at around 100°C under total vacuum for 2 hours, and then recrystallized from an acetone-ethyl acetate solvent to obtain bicyclo[3,5,0)octane-2,6-carboxylic anhydride-6,8 - A pure product (100% purity) of dicarboxylic acid (monanhydride) 691 was obtained.

Next, monoanhydride 10f? Add 3 oya of water.

After stirring at 100°C for 2 hours, the mixture was completely dissolved and became homogeneous. Subsequently, excess water was removed to obtain pure white crystal 102. The following analysis was performed on this crystal.

Engineering H (KBr): 5200-2500.1700.
1420.12601220, 920 (crn-1
) ”0-NMRi[:!D, C0CD, ): 17
4.7.174.5.174.0.46, 245.8.
45.5.45.2.45.1.44.6.44.4.
44.1°37.9.57.4.57.1.55.8.
52.7 (ppm) 'Mass spectrum: Measured after silylation with bis(trimethylsilyl)acetamide.

C”/e (%l): 574 +151,559(
1001,484 (501394 (401 Elemental analysis: O,, H,, O, = 286.24 Melting point: 75-85℃ From the above, this crystal is bicyclo[3,3,0]]octa2
．． It turned out to be 3t 6.8-tetracarboxylic acid.

Example 2 Synthesis of tetracarboxylic acid from dicarboxylic acid.
1 and methanol 300yf, cooled to -78℃/Ozone-containing oxygen from Motosei Ikuyori 45/-/h
The reaction was continued for 5 hours.

This reaction mixture was concentrated under reduced pressure at a temperature below 50° C. to obtain a starchy oscinide gold. Subsequently, this oscinide was dissolved in 150 y of formic acid, and 60× hydrogen peroxide 20 ml was dissolved at around 50°C. When f is added, reflux occurs.

When the reflux stopped, the bath temperature was raised to 120°C and reflux was continued for 2 hours.

Next, the solvent was completely distilled off under reduced pressure to obtain white crude tetracarboxylic acid crystals 262.

The gold flakes obtained by gas chromatography of all the crude crystals were silylated with bistrimethylsilylacetamide and analyzed, and the yield was 88X.

implementation? 113 Synthesis of tetracarboxylic acid from dimethyl ester Acetaldehyde 252. Ruthenium dioxide (Hue, 2H, o l
O, 1y, acetate/1009f) At 40°C, oxygen gas f 50 L/hr17) At a rate of 1.5 tj4
-7)j] Infuse.

Next, this bath #! Dimethyl ester 5. Of (
0.02 moAl was reduced to 202% total acetone in 1 hour, and then 211. ! 1-11” 1 Stir.

After the reaction, the ruthenium catalyst was removed, 60 g of water was added to the P solution, and the mixture was stirred for 2 hours and 1 hour at a bath temperature of 6Q°C.

This reaction solution is concentrated and bathed in the obtained Dh:DC total ethanol 205'. To this ethanol solution, an aqueous solution of 3.2 P i of sodium hydroxide bathed in 102 ml of water was added, and reflux was continued for 2 hours with stirring at a bath temperature of 120°C.

After finishing, remove all ethanol, add a salt (65% Hct)
, l a 5 y is added to remove the neutralized water.

The remaining mass was extracted with all acetone and the acetone bath was concentrated to obtain 5.2 tons of crude crystals of the desired tetracarboxylic acid. The crude crystals were synthesized with bistrimethylcylinoacetamide using gas chromatography and analyzed, and the yield was 69%.

Example 4 Synthesis of tetracarboxylic acid from dicarboxylic acid A 500 ml glass reaction flask was charged with 252 ml of acetaldehyde. Ruthenium dioxide (Ru01.2H, O
) 0.1 r, acetone 100? and 1.5 +i at a rate of oxygen gas k 30 t/br at 40C,
j 1iiJ infuse. Subsequently, this bath 7M k dicarbon II 4.5 SF (0.02 mal l total acetone 201 was added dropwise to the τ6 solution for 1 hour, and further 2
time product.

After the reaction, remove the ruthenium catalyst and add 50ml of water to the P solution.
Add and stir for 2 hours + 1 > at a bath temperature of 60°C. This) also reaction liquid?
When concentrated, M Fj &
4.8y was not obtained. This crystal was silylated with bistrimethylsyl-17-gamma-cet-gammaide using gas chromatography, and the yield was 76X.

Example 5 In run flJ 1, raw material dimethyl ester 51F
was replaced with dibutyl ester 67 (pure I and 98%), and oxidized to total <Ir0iJ, )JD moisture γ
A crude crystal 497 of tetracarboxylic acid was obtained by performing a gold test.

Patent Applicant: Nissan Chemical Industries, Ltd. Procedural Amendment 8 (Voluntary) January 4, 1980 Commissioner of the Office of Time and Labor Affairs Kazuo Wakasugi RO, 3.0] Octane-2,5,6,8-tetracarboxylic acid and its manufacturing method Relationship with the person who makes the S3 amendment Patent applicant's address: 3F Kanda Nishiki-cho, Chiyoda-ku, Tokyo 101 No. 7, No. 14, column of the title of the invention in the application to be amended and claim number 4 of the specification (bureau and claim number 4 of the invention in the description) 5, content of the amendment 1 ) The name of the invention in the application (also, the specification) (first name, name of the invention, lines 5 to 4 from the bottom of the 5th line, lines 2 to 6 from the bottom of the 18th line of the application) ``...bicyclo[3, 3, OJ octane-2, ro, 6.8-tetracarboxylic acid + W2...-1 was corrected to [...3.5.6- tricarboquinonorbornane-2-acetic acid...] 2) Correct the amended scope of claims as shown in Attachment 1, 5) Delete page 5 of the specification (4, line 16, line 16 of Ino No. 5) and insert all of Attachment 2. do.

5) Page 12 of the specification, 5-5h, 17th page 13-14
Row 1 [...bicyclo[6ro0] octane-2,5-
``Carboxylic anhydride-6,8-dicarboxylic acid...'' was corrected to ``...ro, 5.6-dolycarpoquinonorbornane-2-acetic acid v -'5.6- anhydride °''. do.

6) Four layers [g, page 12, line 7, +1000 7) Ming #111, page 16, line 2 from the bottom to page 17, line 1
The line "...bicyclo(3,3,0:]]octane-25-diester-6,8-dicarboxylic acid..." is [...5.5.6-)lycarboxynorbornane. -2-acetic acid-5,6-dimethyl ester...'' is corrected.

Attachment 1 2. Claims (1) Represented by the structural formula [1], 5.6-) dicarboxynorbornane-2-acetic acid (
(hereinafter abbreviated as tetracarboxylic acid) (2) Structural formula [represented by a river (R & j: full, kyl, /chloroalkyl, benzene
Alkyl may contain ○ or N atoms inside. ) As a total starting material, this double bond is fully oxidized to obtain 111 acid (hereinafter abbreviated as IJ Ie I) C) represented by the structural formula, followed by 71FF ester-based hydrolysis. All characteristics of tetracarvone r-[! 2. Manufacturing method.

1:1lltlj Dragon style [abbreviation to be worn in one]
i? As a raw material, this two forces are combined, and Shunhi cleavage 1-Loko and all! A method for producing samurai-1 tracarboxylic acid.

+4. Oxidative cleavage of the double bonds of diethyl and dicarboxylic acids.A method for producing tetracarboxylic acids, which is carried out by the Hakura ozone oxidation method. A method for producing a tetracarboxylic acid, which comprises (1) co-oxidizing a ruthenium compound, an aldehyde or a ketone, and a molecular oxygen residue in a liquid phase.

Attachment 2 Carbon monoxide (DCPDI (diester) 5 carboxylic acid)

Claims (1)

[Scope of Claims] (11 Bicyclo[h40]octane-2 represented by structural formula [1); 5.6.8-tetracarboxylic acid (hereinafter abbreviated as tetracarboxylic acid) (2) Structural formula [■ ] (RFi alkyl, cycloalkyl, benzene-substituted alkyl which may contain O, NIQ molecules internally) Tricyclo[5,2,1,02"6] Demo-8-enme 4-diester ( (hereinafter abbreviated as diester) as a starting material, this double bond is cleaved with an acid to form bicyclo[3,0]octane-2,6-dinyster, which has the structural formula r system, with 8-dicarbonyl r-wave. (hereinafter abbreviated as DEDCi)
A method for producing a tetracarboxylic acid, which comprises obtaining a tetracarboxylic acid, followed by ester base hydrolysis to obtain ffi%. (3) Tricyclo[5,2,1,02°6]des-8-ene- expressed between the structural formulas
A method for producing a tetracarboxylic acid using 44-dicarboxylic acid (hereinafter abbreviated as dicarboxylic acid) as a raw material and cleaving this double bond with the acid. (4) A method for producing a tetracarboxylic acid in which the oxidative cleavage of the double bond of a diester and a dicarboxylic acid is carried out by an ozone oxidation method. (5) A method for producing a tetracarboxylic acid, which comprises carrying out oxidative cleavage of a double bond in a diester and a dicarboxylic acid by co-oxidizing the double bond in a liquid phase with ruthenium or a ruthenium compound, an aldehyde or a ketone, and molecular oxygen gas.