JPS60104080A - Tricyclo(5,2,1,02,6)dec-3-ene-8,9-dicarboxylic acid anhydride and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I . USE:An intermediate raw material for a heat-resistant polyimide of addition type, epoxy heat-curing agent, polyester resin, etc. A precursor for agricultural chemicals and drugs. PREPARATION:Dicyclopentadiene is reacted with CO, an alcohol and/or acetal, ketal, or orthoformic acid alkyl ester, a derivative of the alcohol in the presence of a copper or iron compound and/or oxygen to give a compound shown by the formula II, which is hydrolyzed to give a free acid, which is dehydrated to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tricyclo[5,2,1,02.6]gus-3-ene-a9-dicarboxylic acid anhydride represented by the structural formula:

The compound of the present invention is a novel ornament, and this type of dicarboxylic acid anhydride is generally used as an intermediate raw material for epoxy thermosetting agents, polyester resins, polyimide resins, etc., as well as agricultural chemicals such as antibacterial agents, central nervous system acting drugs, and circulating drugs. As a precursor for pharmaceuticals such as active agents, its applications are extremely wide-ranging.

In particular, for the use of polyimide resin for heat resistance,
A new addition that improves the drawbacks of conventional condensation polyimide
It is expected to have novel properties as an intermediate raw material for polyimide.

The compound of the present invention is produced by the route shown by the following formula.

socyclopenotadiene tricyclo['5.2.1.0'-61 dec-3-enone ester tricyclo[5,2,1,0216] dec-3-en-
Dicarboxylic acid tricyclo[5,2,L 02.6]des-6-en-a? -Dicarboxylic anhydride (abbreviated as dicarboxylic anhydride) Conventionally, direct diesterification of cycloolefins has been carried out by JK Steel (J, K, St;
), etc., Journal of the American Society (J, fi-111, Ohem, sac, '
1, Vol. 98, No. 7, p. 1810 ('1976), cyclomonoolefins are discussed, but the number is extremely small, and furthermore, no examples of direct diesterification of cyclodiolefins have been reported.

The present inventors have conducted intensive studies on a method for selectively directly diesterizing one double bond of dicyclopentadiene, which is the base of cyclodiolefin, as a result of 1. ＠<What should be done is to find out the complete reaction to selectively diesterize only the double bond of norbornene while leaving the double bond of cyclobentene, and then to hydrolyze this diester. A dicarboxylic acid was obtained, which was further dehydrated to obtain its dicarboxylic anhydride.

Furthermore, the present inventors also discovered that dicarboxylic acid anhydride can be synthesized in one step by diesterizing dicyclopentadiene using a specific alcohol. 9 Completed the present invention. This is what led to this.

Dicyclobenotadie/, which is the raw material of the present invention, is contained in a considerable proportion in the C% fraction obtained by cracking naphtha, and since there is currently a large surplus in large quantities, there is an industrial significance to its effective utilization. Next, embodiments of the method for producing the compound of the present invention will be described.

First of all, the diesterization of the present invention is based on the basic VC haPd2+
This was made possible by the acid specific addition reaction of
It has also been found that the diesterification reaction can proceed even when radium is generally used as a catalyst or even in the absence of palladium.

The forms of palladium include inorganic acid salts, organic acid salts, 4
11! Palladium attached, colloidal metals, etc., form IF
The knee can be used without being removed.

Specifically, palladium chloride and palladium nitrate.

Examples include palladium sulfate, palladium acetate, palladium globionate, palladium-carbon, palladium-silica dipalladium-alumina, palladium monocarbonate, palladium black, and colloidal palladium.

The amount used is 0.00% based on the raw material dicyclopentadiene.
When the amount is 1 mole or more, diester can be obtained in high yield.

Furthermore, in the single reaction, since Pd2+ is reduced to Pd0 by the reaction, an oxidizing agent is required to return this to Pd2+. As the oxidizing agent, a metallized adduct having a low redox potential is preferred, and in particular, a copper or iron compound is used.

Specifically, cupric chloride, cupric nitrate, cupric sulfate, cupric formate, cupric acetate, and ferric chloride.

Nitsu! ! Ferric iron, ferric sulfate, ferric formate, ferric vinegar, etc. are used, and copper compounds in particular give excellent results. For all of these compounds, diesters can be obtained in higher yields when they are anhydrous, and the yield is lower when they are hydrated.

The amount of these oxidizing agents to be used is a theoretical amount based on the raw material H, and when a so-called catalytic amount of hackradium catalyst is used in the diesterification reaction of the present invention, it is necessary to use 2 times the mole of dicyclopentadiene as the raw material. It is.

On the other hand, it is used as an oxidizing agent! It is also possible to use molecular oxygen without using a proboscis, and a combination of a metal compound and molecular oxygen can also be used.

When using 9 molecular oxygen as the oxidizing agent, use methyl orthoformate, which is also an alcohol derivative.

Dehydrating agents such as methyl orthoacetate, orthoacetic acid fk, and 1,1-dimethoxycyclohexane can be added! F is low, and as a result, a significant improvement in yield can be seen.

In addition, in the present invention, it was unexpectedly discovered that even a metal compound as an oxidizing agent alone causes an oxidative addition reaction and a diesterification reaction proceeds.

Under these conditions, the reaction rate is lower than when a palladium catalyst and a metal compound are combined, but the selectivity of the diester tossed like LJ is high.

Therefore, from an industrial perspective, /! This may be an effective condition for reducing LiM costs.

Alcohols, which are another raw material for diesterification, include alkyl alcohols, unsaturated alkyl alcohols, cycloalkyl alcohols, benzene-equivalent alkyl alcohols, benzene/l&, m not! Alkyl and unsaturated argyl alcohols may contain 0 or N atoms, regardless of whether they are 11 or more alcohols.

Specifically, methanol, ethanol, butanol, nonanol, tridecanol, cyclohexanol, benzyl alcohol, allyl alcohol, cinnamyl alcohol, furfuryl alcohol, propargyl alcohol,
Geraniol, nerol, ethylene glycol, propa/diol, glycerin, ethanolamine.

Examples include glopanolamine.

Father, alcohol can also be used in the form of its derivatives acetal, ketal, ortho-alkyl.
The reaction proceeds in the same way.

In other words, methyl ortho-fermented and methyl ortho-acetate.

When using 1.1-dimethot'cyclohexy-7 or the like, dimethyl ester can be mixed in the same manner as when methanol is used.

Furthermore, pentane, n-hexane as a fl medium.

Hydrocarbons such as cyclohexano and hegetane can be used, but alcohol, which is one of the raw materials, acetal, ketal, alkyl orthoformate, etc., which are one of the raw materials, can be used.
In addition to theory 1j or more for 1 Pe/Taj Ln, 1 as it is
Molten 1? - can also be used.

Father, water, acetic acid, N,N-dimethylformamide (D
M P' ) and the like are not suitable as bath media because the diester yield decreases.

There is no particular limit to the amount of bath medium, but dicyclobe/Taje/
A base is preferably present in order to remove the acid by-produced from the catalyst and oxidizing agent during the reaction, and it is also possible to suppress the conversion of by-products such as halides. Bases include sodium acetate and thorium gropionate.

Fatty acid salts such as butyric acid (butyric acid) are preferred.The reaction proceeds satisfactorily at around room temperature, but it can also be carried out at 100°C or higher.

- There is no particular limit to the pressure of carbon oxide, but the latent pressure ~5 L
l kg/, yl G is preferred. 1 for low pressure
The reaction time becomes longer and the selectivity of the diester tends to decrease.

Carbon monoxide does not need to be of high purity, and 6# with hydrogen,
Oxo gas, which is a secondary gas, can also be used in the same way as carbon monoxide, and is also industrially advantageous.

The reaction time is a function of the catalyst dispersion, the carbon pressure, etc., but it usually takes about 15 minutes to 2 hours to complete, but under conditions where the reaction time is longer, the yield of diester is generally lower. decreases.

The diester thus obtained is then hydrolyzed.

Hydrolysis, diaphragmation, a method using an acid such as lIf acid, or a method using a base such as an aqueous solution of sodium hydroxide or potassium hydroxide can be used, but it can be easily performed by using a base. The reaction progressed like a military song, and tricyclo [5, 2, I, [12.6] Dessay 6-F-
An 8,9-dicarbonate alkali salt is obtained.

Hydrolysis using bases converts raw material diester into ethanol,
A solution of monogamma alcohol such as glopanol A' + HCg, and a slightly excess alkaline water bath solution compared to the theoretical M' are added and stirred for 1 to 2 hours at around the reflux temperature of alcohol Ima 1 (reaction Vi is easily completed from C). Arca 9 was fucked like this
The target dicarboxylic acid can be obtained by treating one word with an acid such as 14 fl liters.

This dicarboxylic acid is used as a medium such as acetonitrile.
By crystallizing one hand and loading it, it becomes white crystal (J
It will be done.

In general, when this dicarboxylic acid is reacted with a dehydrating agent, 1]
The right dicarboxylic acid anhydride is interesting. Dehydration Ha1
Examples of 1 include acid anhydrides such as anhydrous vinegar, gropionic anhydride, and succinic anhydride.

The amount used is 2 to 2 to the theoretical molar amount based on the raw material dicarboxylic acid.
The reaction proceeds more quickly when it is present in amounts 5 times or more. A reaction temperature of about 100 to 150°C is sufficient, and the reaction is completed in 1 to 5 hours.

After the reaction, the reaction solution was evaporated as it was, and the residue was dried under reduced pressure to obtain crystals of the dicarboxylic anhydride.
By recrystallizing this with a bath medium such as cyclohexa 7, high purity crystals can be obtained.

Moreover, it has been surprisingly found that in the diesterification reaction of the present invention, the desired dicarboxylic acid anhydride can be directly obtained by using a tertiary alcohol as the alcohol while keeping other reaction conditions the same. Examples of the 6th alcohol include L-phthyl alcohol and t,-amyl alcohol.

Borneol, linalool, etc. can be used.

Furthermore, it has been found that when allyl alcohol gold is used as the alcohol, diester is produced as the main product, but dicarboxylic acid anhydride is also produced to a large extent.

Father, in the case of VC ball tyrene glycol, additives and [
2. By applying spinal pressure to fatty acid salts.

-C dicarbonoic anhydride is formed as the main product.

It was found that some diester was also produced as a by-product.

In the case of ethylene glycol, the dicyclopentadiene conversion rate and dicarboxylic anhydride selectivity are both high, and therefore the dicarboxylic anhydride yield is high.

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

Actual IJj1j Example 1 (dimethyl ester) internal volume + 0
0 me hastelloy mate crepe, zinc chloride: c7 (1) (! P l) ) 3.95j
i' (!I Om1nc))j)r Palladium chloride o, 2b7y (1,5auto/, ), anhydrous cupric chloride (pure U 95%) 10.41 (75 mmol
'1. Charged 24ff of methanol, -55 with carbon oxide
After pressurizing to kg/ra ti, the reaction was started at room temperature (25 Cj. - Carbon oxide absorption started immediately and 1
After 5 minutes, the pressure became I''15 kq/, II!G and absorption stopped.

The reaction was exothermic and reached a maximum temperature of 48°C VC.

After stirring for an additional 15 minutes, the reaction was stopped, the autoclave was returned to room temperature, carbon monoxide was removed, and one reaction solution was taken out.

After removing the solvent from the reaction solution by concentrating the reaction product, one reaction product was extracted with rhohexane.As a result of analyzing this n-hexane solution by gas chromatography, the raw material dicyclopentadiene did not remain. Almost a single peak was detected as the product.

Therefore, we repeated the two-tube reaction five times in exactly the same way.

After concentrating the reaction solution, 5 batches of q-hexane extract were added and concentrated, and further distilled under reduced pressure to 140-145℃/
Fraction 567 of Q, 7 wx IQ was obtained.

The analysis results of this distillate were as follows.

IR(NaO/j: 2930.1750.1450
．． 1200 (cm)'O-NMR (CI sword 1.):
174.1.175.9. +51.9. +31.5°52-5.51.5.46.4.44.5.4 i5.
451141.8. 5 &7.52.5 (δpot
n) Masubek i・ru(tsu(...do)I: 250(
M+, 251,218 (+00'l.

+24 (651, 66 (80) Elemental analysis' ``++ 11.AO, from the above, main distillate ii, l-link a [5, 2, +, 0'' 6] dehi uichi-ko/-a9-dicarbo/ It turned out to be acid dimethyl ester (abbreviated as dimethyl ester).

Further, 7 ftJ of +1-hequina solution was subjected to gas chromatography at a constant rate of 1 □t, and the reaction yield of dimethyl ester was 98%.

Real Mj[IJ2. 3 1 dimethyl ester): □ Example 1 Table 1 shows the results of the reaction carried out in the same manner except that part or all of the methanol used was changed to ortho...11 thyl.

Table 1 Examples 4 to 11 (Dimethyl ester) Table 2 shows the results of a reaction carried out in the same manner as in Example 1, except that the type of catalyst and oxidizing agent, the molar ratio of the catalyst and oxidizing agent, and the reaction time were changed. .

Table 2 *1 Reaction @ degree 60℃ *2 Reaction temperature 100℃ Examples 2 to 14 (Dimethyl ester) Example IV 1
．． - Molecular oxygen (
The procedure was carried out in the same manner as in Example 1, except that the oxygen pressure was changed to 201<9/cA (), IE is the initial reaction pressure of 55 kg/LJt), and the ratio of alcohol and dehydrating agent was changed.The results are shown in Table 3. .

Table 3 Examples 15 and 16 (Dimethyl ester) Table 4 shows the results of a reaction conducted in the same manner as in Example 1 except that the carbon monoxide pressure was changed.

& 4 * DOPI) Conversion rate 100% Examples 17 to 20 (Dimethyl ester) The catalyst in Example 1 was replaced with a palladium supported catalyst, the oxidizing agent and the temperature 2
Table 5 shows the results of the same reaction except that the time was changed.

Table 5 Examples 21 to 26 (Various diesters) Table 6 shows the results of the same reaction as in Example 1, except that the alcohol species and temperature were changed for 1 hour.

Cloth θ *1 Dicarboxylic I), Zeanhydride yield 28X*2 [
3,H,(X]ONa 5.8?(60mM)+i”V
J mouth, dicarboi Makisen kanamasa rate 58% Example 27
(Dicarboxylic acid) tricyclo[5,2,1,O'-6] ace-3-ene-8,9-dicarboxylic acid dimethyl ester 25F was mixed with ethanol 100F and 50% potassium hydroxide aqueous solution at 78°C. When refluxing was continued for 2 hours, crystals were deposited. After passing through the crystals, they were washed with hexane, resulting in crystal 281.
Chloroform 200? and 35X concentrated hydrochloric acid 602 to neutralize it. This lower layer chloroform solution was separated, washed with water, dehydrated, and concentrated to obtain crude crystals 207. 4
By recrystallizing this with an acetonitrile solvent, white crystals were obtained.

The crystals were dissolved in tetrahydrofuran and analyzed by gas chromatography, which revealed a single peak with a retention time different from that of the starting diester, and the retention time was shortened by the trimethylsilylation treatment.

Furthermore, the following analysis was performed on this crystal.

IR (kBr'): 2960.1700.1420
．． 1240.920 (cm-1) 130-NMI ((C
1),,(1[(): 177.5. +77.2.
132.7.152.5°56.5. 47.5. 4
5.3. 44.4. 44.1. 42.8゜u 9
1. 52.7 (δppl) mass spectrum (silylated with bis(trimethylsilyl)acetamide 6
1 set) (1 deficiency ('6)): 366 (10), 351 (71'
).

255 (46), 141 (76), 73 (+00) Elemental analysis ``HE (II o, melting point 1615-16aO℃) Therefore, this crystal is tricyclo[5,2,f, OZ'
It turned out to be 1-dec-8-ene-4-dicarboxylic acid.

Example 2B (Dicarboxylic anhydride) Trisifu O1'5.2.1+0216] Dec-8-ene-5,4-dicarboxylic acid 227 and acetic anhydride+013IP
was refluxed at 140°C for 2 hours.

Next, the solvent was distilled off and dried under reduced pressure to obtain crude crystals 20'f.

This was recrystallized with cyclohexane solvent to obtain pale yellow crystals. The crystals were dissolved in chloroform and analyzed by gas chromatography.
A single peak appeared at different retention time positions. Furthermore, the following analysis was performed on this crystal.

18 (kBr): 2960. +860.1790.
1218.1090°925(cm+13n-NMR(DDO Otsu): 174.6.
+74.2. +32.4.1310°51.7.45
．． 6.45.4.45.9.42.9.41.0゜56
．． 5,32, O (δppm1 Mass spectrum (layer (a)): 204 (M+, 15)
, 1z6 (4!5).

1!1D55), 66(+00) Elemental analysis "IIHIIOI" Melting point: 95.0-95.5℃ From the above, this crystal is tricyclo[5,2,+,02-
6] It was found that the product was 5-dicarboxylic anhydride.

Examples 2.) to 3,6 (Dicarboxylic anhydride) The entire reaction was carried out in the same manner as in Example 1 except that the methanol and temperature were shaken for 9 hours. The results are shown in Table 7.

Table 7

Claims (5)

[Claims] (1) Tricyclo[5,2,L 02+6] Demo-3-Engine represented by structural formula [1]
-a9-dicarboxylic anhydride. (2) Dicyclopentadiene, -acetal which is carbon oxide, alcohol and/or its derivative. A ketal, an alkyl orthoformate is reacted in the presence of a palladium catalyst, a copper or iron compound, and/or oxygen, and the structural formula [1
1] (RH alkyl, unsaturated alkyl, cycloalkyl, benzene-substituted alkyl, benzene-substituted unsaturated alkyl, the alkyl and unsaturated alkyl may contain O, N atoms) tricyclo[5,2, 1,0
216] de-3-ene-8,9-diester, which is then hydrolyzed to give tricyclo[5,2,1,02-' ]]de-3-ene-Ill, 9 - dicarboxylic acid is obtained, which is further dehydrated to obtain tricyclo[(2, L O
``' ]] A production method characterized by obtaining de-3-ene-a9-dicarboxylic acid anhydride. (3) Dicyclopentadiene, -acetal which is carbon oxide, alcohol and/or its derivative. Ketar. By reacting an alkyl orthoformate in the presence of a copper or iron compound, tricyclo[
5,2,1,0''6]dece5-ene-a9-diester, which is then hydrolyzed to give tricyclo[5,2,1,ro2,6]dece3, which is represented by the structural formula l]
-ene-a9-dicarboxylic acid was obtained, which was further dehydrated to give tricyclo[5゜2.1.0
2.6]] De-3-En-a9-Dical Castle/Makuanhydride A manufacturing method characterized by obtaining. (4) Dicyclopentage/, -carbon oxide is reacted with one or two adducts selected from 6th-class alcohol or allyl alcohol in the presence of a palladium catalyst, a copper or iron compound, and/or oxygen. , a manufacturing method characterized by directly obtaining tricyclo[5,2,16g2,6 ]]de-3-ene-8,9-dicarboxylic acid anhydride represented by the structural formula [1]. (5) Dicyclopentadiene, carbon oxide, and ethylene glycol are reacted in the presence of a palladium catalyst, a copper or iron compound, and/or oxygen, and a fatty acid salt to produce tricyclo[5゜2-1. 0216] Tesse 3-
A production method characterized by directly obtaining en-8,9-dicarboxylic acid anhydride.