JPH0368538A - Production of octahydrodimethanonaphthalene ring-containing compound - Google Patents

Abstract

PURPOSE:To obtain the title compound in a short time and good yield by inter mittently or continuously charging cyclopentadiene or dicyclopentadiene into a reaction system containing fumaric acid diester or maleic acid diester at a definite ratio and reacting the above-mentioned compounds at a specific tem perature. CONSTITUTION:Cyclopentadiene or dicyclopentadiene is intermittently or continu ously charged into a reaction system comprising a compound expressed by formula I (R<1> and R<2> are alkyl) at such amount as to finally become two or more times by mol that of the compound expressed by formula I and reaction temperature set to 200 deg.C to 250 deg. to provide the octahydromethanonaphthalene ring-containing compound (e.g. 1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8- dimethanonaphthalene-trans-2,3-dicarboxylic acid dibutyl ester) expressed by formula II. The compound expressed by formula 11 is used as a raw material for high polymer compound useful as various structural material and functional material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a compound having an octahydrodimethanonaphthalene ring.

The compounds produced by the method of the present invention are used as raw material compounds for polymeric compounds useful as various structural materials and functional materials.

[Conventional technology]

Conventionally, 1.2.3.4.4a, 5.8.88-octahydro-14:5.8-dimethanonaretalene-2,3
-berhydro-1 derived from dicarboxylic acid ester
,4:5.8-dimethanonaphthalene-2,3-dicarboxylic acid ester or perhythmyl:I-1,4:5,8-
Polyester obtained using dimanonaphthalene-2,3-dimethanol as a raw material has a high glass transition temperature, excellent dimensional stability, and is known to be used as a base for photographic films (U.S. National Defense Agency). Patent No. 896,03
No. 3 specification button and Journal of Polymer Science: Polymer Chemistry Editorial E 7 (J
internal of Polymer 5science
:Polymer Chemistry Editi
on), vol. 10, atc++'1 (1972)). These documents include diethyl fumarate and cyclopenmediene or Diels-Alder.
der) 1.2.3.4.4a by reaction.

A method for obtaining diethyl 5,8.8a-octahydro-1,4:5,8-dimethanonaphthalene-2,3-dicarboxylate is disclosed.

[Problem to be solved by the invention]

Diethyl fumarate and cyclopentadiene color 1゜2, 3
．． 4.4a, 5.8.8a-octahyto O-1,4:
The above method for producing 5,8-dimethanonaphthalene-2,3-dicarboxylic acid ester requires a long reaction time of 18 hours at a reaction temperature of 180°C, and the desired yield is only 22 % is low. As described above, in the conventionally proposed methods, it is necessary to carry out the reaction for a long time, and the yield of the target compound is low.

An object of the present invention is to provide a method for advantageously producing a dicarboxylic acid ester having an octahydrodimethanonaphthalene skeleton. , the above object is achieved by the following general formula (I) (% formula %) (wherein R1 and R2 each represent an alkyl group).

) When reacting the compound represented by cyclopentadiene or dicyclopentadiene, the reaction temperature is set at 200°C.
The temperature is maintained within the range of ~250°C, and the cyclopentadiene or hasycyclopentadiene is converted into cyclopentadiene, and the compound represented by the general formula (1) is finally mixed with more than 2 moles of soybean and cyclopentadiene. When reacting pentadiene enrichment or synchropentadiene, the reaction system is charged with the following formula (tl) (wherein R1j? and R2 are the constant product of the above.) This is accomplished by providing a method for producing the compound.

The alkyl group represented by R1 and R2 in general formula (1) & general formula (Il) is preferably an alkyl group having 1 to 8 carbon atoms.Specific examples include the following.

CHa CHa CH3 -CH2(CI(2)5CH3, -CH2- and H(CH
2) 3CH3 The compound represented by the general formula (1) may be a trans form, a cis form, or a mixture thereof. Also.

- The compound represented by the form (ri) may be one compound or two or more types of compounds.

In the method of the present invention, the amount of cyclopenmediene or dicyclopentadiene charged must be at least 2 times the amount of the compound represented by general formula (1) in terms of cyclopentadiene. There is.

The amount to be charged is preferably in the range of 2 to 6 times the mole, and 2 to 4 times the mole.
A range of multiple moles is more preferable. When the amount of cyclopentadiene or dicyclopentadiene charged is less than 2 moles relative to the compound represented by general formula (1), 1 mole of cyclopentadiene and the compound represented by general formula (1) The addition product of pair 1, i.e. 5-norbornene-2,3-
As a result of the increase in the amount of dicarboxylic acid ester produced, - form (
The yield of the compound represented by II) decreases. On the other hand, if the amount charged is more than 6 moles, for example, an addition product of 3 pairs of cyclopentadiene and the compound represented by the general formula (1), that is, 1.2.3.4.4 & , 5
．． 8.8a, 9.9a.

10.1011-dodecahyte el-1,4: 5,8
: 9.1 (+-) Rimetanoanthracene-2,3
- As a result of the increase in the amount of dicarboxylic ester produced, the yield of the compound represented by the - format (fl) decreases, and the increase in the amount of cyclopentadiene oligomer produced increases the viscosity of the reaction solution or the formation of precipitates. , which is not preferable as it may make the reaction operation difficult. - Cyclopentadiene or dicyclopentadiene with a CI+E of 2 moles or more of the compound shown by Monka (1) is not charged all at once at the start of the reaction, but after the internal temperature of one reaction vessel reaches a predetermined temperature. When reacting with intermittent fractionation or synchropentadiene, the yield of the compound represented by the general formula ([[) can be increased by charging it to the reaction system. Preparation time is preferably about 10 minutes to 10 hours, more preferably about 10 minutes to 8 hours, particularly preferably about 10 minutes to 6 hours. If the preparation time is longer than 10 hours, it is not preferable that the generated compound represented by the general formula A part of the cyclopentadiene or synchropentadiene may be charged in advance into the reaction vessel at the start of the reaction and then turned off.This charge is preferably about 90% or less of the total charge of cyclopentadiene or synchropentadiene. When cyclopentadiene or synclopentadiene is charged when reacting syncropentadiene, the rate of feeding may be kept constant or may be varied. An appropriate liquid feeding bonder may be used for the preparation. If you use it intermittently, use cyclobenmadiene'!
Alternatively, it is preferable to divide the total charge amount of synchropentagene into two or more appropriate number of fractions and charge them within the above-mentioned charge time. In this case, an appropriate liquid feeding pump may be used for charging. This can also be done after the internal temperature of the reaction vessel has been cooled to about room temperature. Reaction time is usually about 30
minutes to 15 hours.

Preferably for 30 minutes to 10 hours, more preferably for 1 hour.
The duration ranges from 1 hour to 10 hours.

In the method of the present invention, the degree of reaction p has a large effect on the reaction rate p and the yield of the compound represented by the general formula (n). The reaction is carried out at a temperature ranging from 200<0>C to 250<0>C. The reaction temperature is preferably in the range of 200°C to 240°C, and 2
The range of 10°C to 240°C is more preferable. The reaction source is 25
If the temperature is higher than 0°C, the generated compound represented by the general formula (It) is consumed by polymerization or decomposition, and the raw material cyclopentadiene or synclopentadiene is polymerized, resulting in its loss. Becomes large. On the other hand, if the reaction temperature is lower than 200° C., the reaction rate will drop significantly and the yield of the target compound represented by the general formula (■) will drop.

Although the reaction between cyclopentadiene or synclopentadiene and the compound represented by the general formula (1) can be carried out in the absence of a solvent, it is preferable to carry out the reaction in the presence of a suitable reaction solvent. It is preferable in that the yield of the compound shown in 1) is good.As the reaction solvent, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; tetrahydrofuran and 1,4-dioxane. Ethers such as; alcohols such as methanol, ethanol, propanol, butanol; methylene chloride,
Halogenated hydrocarbons such as chloroform; nitrogen-containing compounds such as N,N-dimethylformamide and N-methylpyrrolidone are used; among these, aromatic hydrocarbons and aliphatic hydrocarbons are represented by the general formula (n). It is preferable in that the yield of the compound represented by is good, and aromatic hydrocarbons are particularly preferable. The reaction solvent is usually 0% for all raw material compounds.
．． It is used in amounts ranging from 1 to 100 magnifications. The amount of reaction solvent to be used is preferably in the range of 0.2 to 50 times the weight of the total raw material compounds, and more preferably in the range of 0.2 to 10 times the weight!
Yes. If the amount of reaction mts used is less than 0.1 times by weight, the yield of the compound indicated by -monya (n) may decrease, and if the amount used exceeds 100 times by weight, 1 reaction rate may decrease, and either case is unfavorable.

The reaction in the method of the present invention can be carried out in accordance with the usual Diels-Alder reaction.

That is, a reaction vessel made of metal or pressure-resistant glass is charged with the compound represented by the general formula (1), cyclobenmediene or dicyclopentadiene, and an appropriate reaction solvent if necessary, and heated to a predetermined temperature of a degree. and react. Although the reaction can be carried out in air, it is preferably carried out in an inert gas such as nitrogen, argon or carbon dioxide. Also 1
Mechanical stirring is usually preferred. Among these, dicyclopentadiene easily decomposes into cyclopentadiene and reacts under the temperature conditions of the production method of the present invention.

It is not necessarily necessary to use cyclopentadiene as a raw material. After completion of the reaction, the compound represented by the general formula 1■> can be isolated from the reaction mixture by distilling the reaction mixture, or by precipitating the compound represented by the general formula (n) from the reaction mixture depending on the type of reaction solvent used. This is done by filtering off the indicated compound.

By subjecting the compound represented by the general formula (U) obtained by the method of the present invention to a double bond hydrogenation reaction, diberhydro-1,4: 5,8-dimethanonaphthalene-2,3-
A dicarboxylic acid ester is produced, and this perhydro-1
, 4:5.8-dimethanonaphthalene-2,3-dicarboxylic acid ester is subjected to a reduction reaction of the ester moiety to produce behydro-1,4:5゜8-dimethanonaphthalene-2,3-dimethanol. Manufactured. In this case, by reacting the compound represented by the general formula (II) in a pressurized hydrogen atmosphere in the presence of a copper-chromium catalyst, for example, rubberhydro-1°425.8-dimethanonaphthalene-2
, 3-dimethanol can also be produced directly. The thus obtained perhydro-1,4:5.8-dimethanonaphthalene-2,3-dicarboxylic acid ester ti is perhydro-1,4:5,8-dimethanonaphthalene-2,3-
Dimethanol is extracted into various structural materials according to known methods.

It can be easily derived into polyester, polycarbonate or polyester carbonate useful as functional materials. It was a cabinet. The compound represented by the general formula (■) becomes a homopolymer through vinyl polymerization.

It is also possible to form a copolymer with other compounds having double bonds, such as maleic anhydride, vinyl acetate, acrylonitrile, etc.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Autoclaved diptyl 7malate 171f (0.75 mol) of content 11 with a magnetic stirrer.

Dicyclopentadiene 99 (0.75 mol) &! hip
- 300f of xylene was charged and the system was replaced with nitrogen gas. Next, the internal temperature of the autoclave was raised to 230°C, and the mixture was reacted at the same temperature for 2 hours with stirring. At this point, using a metering pump, dicyclopentadiene 92f (0,70
mol) over 30 minutes, and then for an additional hour 3
It was allowed to react for 0 minutes.

After the completion of the reaction, the reaction mixture was analyzed by gas chromatography, and the results were as follows: 1.2.3.4.4a, 5.8.8
1! L-octahydro-1,4:5,8-dimethanonaphthalene-trans-2,3-dicarboxylic acid dibutyl is 1
It was confirmed that 81 was generated. From this reaction mixture, 1.2.3.4.4&, 5.
8.8a-octahydro-1,425,8-dimethanonaphthalene-trans-2,3-dicarboxylic acid dibutyl 1
43t was obtained. The yield based on diptyl fumarate was 53%.

Example 2 In the autoclave used in Example 1, 1 dimethyl 7 malate was added.
08F (0.75 mol) and p-xylene 3002 were charged and the gold in the system was replaced with nitrogen gas.

Next, the internal temperature of the autoclave was raised to 210°C, and dicyclopentadiene 99F (
After adding 0.75 mol) over 1 hour, the mixture was reacted for 1 hour. After that, 50 ml of dicyclopentadiene (
0.38 mol) was added over 1 hour using a metering pump, and the mixture was reacted for 1 hour.

After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and the results were as follows: 1.2.3.4.4&, 5.8.8
&-octahydro-1,4:5.8-dimethanonaphthalene-trans-2,3-dicarboxylic acid dimethyl is 122
It was confirmed that f was being generated. From this reaction mixture, 1.2.3.4.4 &, 5.8.8
a-octahydro-1,4:5,8-dimethanonaphthalene-trans-2,3-dicarboxylic acid dimethyl 103f
I got it. The yield based on dimethyl fumarate was 50%.

Example 3 Diethyl maleate 129f (0.75 mol)% cyclobentashev 99 was added to the autoclave used in Example 1.
F (0,75 mol) &! and p-xylene 300F, and the system was purged with nitrogen gas.

Next, the internal temperature of the autoclave was raised to 220°C, and the reaction was carried out at the same temperature for 2 hours with stirring. after that.

Dicyclopentadiene 30F (0.23 mo/') was added over 30 minutes using a metering pump and reacted for 1 hour. Furthermore, dicyclopentadiene 2Qf (0.15 mol)
was added over 30 minutes using a metering pump.

The reaction was carried out for 1 hour and 30 minutes. Results of analyzing one reaction mixture by gas chromatography after the completion of the reaction.

1, 2.3.4.4a, 5.8.8a-octahydro-1,4:5,8-simethanonaphthalenesis-2,3
It was confirmed that 1122 diethyl dicarboxylates were produced. buttons, 1.2.3.4.4a, 5 at the same time
．． 8. It was observed that 13f of diethyl ga-octahydro-1,4:5.8-dimethanonaphthalene-trans-2,3-dicarboxylate was produced. This reaction mixture is distilled under reduced pressure. s 1+ 2+ 3+ 4+
48. ri, s, sa-octahydro-1,4:
Diethyl 5.8-dimethanonaphthalene-cis-2,3-dicarboxylate 94f was obtained. Yield based on dimethyl maleate was 41%.

Comparative Example 1 Dimethyl fumarate 1 was added to the autoclave used in Example 1.
08f (0.75 mol), synchropentadiene 189
F (1,43 mol) p and p-xylene 300F were charged, and the system was purged with nitrogen gas.

Next, the internal temperature of the autoclave was raised to 180°C, and the reaction was carried out at the same temperature for 4 hours with stirring. After the reaction is completed, 1, 2.3.4.4 is obtained by subjecting the reaction mixture to vacuum distillation.
B, 5.8.88-octahito l:'-1,4:5,
14 t of dimethyl 8-dimethanonaphthalene-trans-2,3-)h rubonate was obtained. The yield based on dimethyl fumarate was 7.5%. The reaction and distillation were carried out in the same manner as above except that one reaction time was 24 hours. Based on dimethyl fumarate in this case, (1, 2, 3
,4,4&,5.8.8a-octahydro-1,4:
The yield of dimethyl 5.8-dimethanonaphthalene-trans-2,3-dicarboxylate was 25%.

1, 2.3.4.4&, 5.8.8&-octahydro-1,4:5.8-dimethanonaphthalene-trans- obtained in Example 1 was placed in the autoclave used in Reference Example 1. Diptyl 2°3-dicarboxylate 40', 1,4-dioxane 400d and copper-chromium catalyst 21 were charged.

After fully replacing 10,000 yen with hydrogen gas, replace 250 yen with hydrogen gas.
The mixture was charged at atmospheric pressure and stirred at 200°C for 24 hours.

After cooling, the reaction solution was taken out and the catalyst was filtered off.

1.4-Dioxane was removed. The residue was recrystallized from acetone to obtain 15 ft of white crystals.

The IH-NMR spectrum of the obtained crystal was as follows, and it was confirmed that this crystal was berhydro-1,4:5,8-dimethanonaphthalene-trans-2,3-dimethanol.

0.8-2.0 ppm: 12H 2,0-2.3 ppm: 4H (proton at the bridgehead position of the norbornane skeleton) 3,0-3.8 ppm: 6 H (bond t to the oxygen atom, *of the methylene group) [Effects of the Invention] According to the uninvented method, the reaction time was shorter and the yield was better than that of the conventionally proposed method.
．． a, 5.8.8a-octahuman I:I-1.4:5
．． 8-dimethanonaphthalene-2,3-dicarboxylic acid ester is produced.

Claims (1)

[Claims] The following general formula (I) R^OOC-CH=CH-COOR^2 (I) (In the formula, R^1 and R^2 each represent an alkyl group.)
When reacting the compound represented by cyclopentadiene or synchlopentadiene, the reaction temperature is set at 200°C.
The temperature is maintained within a range of ~250°C, and the cyclopentadiene or syncropentadiene is intermittently heated in an amount equivalent to cyclopentadiene so that the final amount is at least 2 times the mole of the compound represented by general formula (I). Or the following general formula (II), which is characterized by being continuously charged into the reaction system ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 are as defined above.) A method for producing a compound represented by