JP3304638B2 - Alicyclic dicarboxylic acids and their esters, and methods for their production - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alicyclic dicarboxylic acid and a diester thereof, and a method for producing the same. More specifically, the present invention relates to a novel alicyclic dicarboxylic acid and a diester thereof useful as a raw material or an additive of a polyester monomer such as an optical material and a structural material, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polyester obtained from a monomer having an alicyclic structure such as an alicyclic dicarboxylic acid or an alicyclic diol as a raw material has been known for its transparency, heat resistance, chemical resistance, and dimensional stability. It is known to have excellent physical and chemical properties. Such polyesters are extremely useful polymer materials as various optical materials and structural materials, such as optical disks, substrates for optical cards, substrates for liquid crystal display elements, etc., utilizing the inherent properties of the alicyclic skeleton.

As a raw material of an acid component monomer of a polyester having an alicyclic skeleton, for example, JP-A-3-2
00830, JP-A-5-5026, JP-A-5-
Bicyclo [2.2.
1] heptane-2,3-dicarboxylic acid, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3,4-dicarboxylic acid, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0
^2,7 . [ ^09,14 ] Heptadecane-4,5-dicarboxylic acid and the like and diesters thereof are known. However, the alicyclic dicarboxylic acids and diesters thereof described in these publications have a steric hindrance to each other because a carboxylic acid group or an ester group thereof, which is a functional group, is bonded to a vicinal carbon, and a monomer is formed. Is poor in reactivity and it is difficult to increase the molecular weight. As a result, the obtained alicyclic polyester has a drawback that the molecular weight distribution is wide and a low molecular weight condensate remains.
Therefore, although conventionally known alicyclic polyesters have excellent transparency and mechanical strength as a polymer material, they have a problem that they do not sufficiently exhibit properties such as heat resistance, moisture resistance, and chemical resistance.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the conventional vicinal bond type alicyclic dicarboxylic acids and diesters thereof as described above.
An object of the present invention is to provide a novel alicyclic dicarboxylic acid and a diester thereof, and a method for producing the same.

That is, the present invention provides a compound represented by the general formula (1):

[0006]

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An alicyclic dicarboxylic acid represented by the general formula (2):

[0008]

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(Wherein R represents an alkyl group having 1 to 4 carbon atoms), an alicyclic dicarboxylic acid diester represented by the general formula (3):

[0010]

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An alicyclic cis-dicarboxylic acid represented by the general formula (4):

[0012]

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(Wherein R represents an alkyl group having 1 to 4 carbon atoms), an alicyclic cis-dicarboxylic acid diester represented by the general formula (5):

[0014]

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An alicyclic trans-dicarboxylic acid represented by the general formula (6):

[0016]

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(Wherein R represents an alkyl group having 1 to 4 carbon atoms), and an alicyclic trans-dicarboxylic acid diester represented by the general formula (7):

[0018]

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Hexacyclo [6.6.1.1] represented by
^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-as-heptadecene (hereinafter hexa cycloheptanone decene hereinafter) starting material is represented by the general formula, characterized by oxidative cleavage using an oxidizing agent The double bond moiety (3) A process for producing a cycloaliphatic cis-dicarboxylic acid,
A process for producing an alicyclic cis-dicarboxylic acid diester represented by the general formula (4), characterized by esterification with a monohydric alcohol of 4, and an alicyclic ring represented by the general formula (4) An alicyclic compound represented by the general formula (6), wherein a metal alkoxide is acted as a catalyst on the cis-dicarboxylic acid diester, and the ester groups are isomerized so that the ester groups have a trans configuration. The present invention relates to a method for producing a trans-dicarboxylic acid diester, and a method for producing an alicyclic trans-dicarboxylic acid represented by the general formula (5), which is hydrolyzed.

The hexacycloheptadecene represented by the general formula (7) used as a starting material of the present invention can be produced by a known method. That is, cyclopentadiene or dicyclopentadiene which is a diene compound, and norbornene or tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
It can be obtained by a Diels-Alder reaction with dodecene. The reaction product is a mixture of various Diels-Alder adducts (for example, in the case of a reaction between cyclopentadiene and norbornene, a 1: 1 mixture of both raw materials).
The adduct tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, hexacycloheptadecene which is a 2: 1 adduct of the desired product, and octacyclo [8.8.0.1 ^2,9 . ^14,7 . 1 ^11,18 . 1
^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene), but by appropriately selecting the molar stoichiometric ratio of the charged diene compound and dienophile compound and the reaction conditions, the desired product, hexacycloheptadecene, can be obtained. It is generally known to improve the reaction selectivity of, and can be easily isolated by distillation under reduced pressure.

The isolated hexacycloheptadecene has the following structural formula:

[0022]

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There are several kinds of geometrical isomer mixtures containing a compound having a steric structure represented by the following formula as a main component. In the present invention, these geometrical isomer mixtures can be used without any problem. When a single geometric isomer represented by the above structural formula is required,
It can be easily purified by recrystallization.

The alicyclic cis-dicarboxylic acid represented by the general formula (3) of the present invention is obtained by oxidative cleavage of the double bond portion of hexacycloheptadecene represented by the general formula (7) using an oxidizing agent. Can be obtained.

A method for obtaining a dicarboxylic acid by oxidative cleavage of a carbon-carbon double bond in one step using an oxidizing agent includes the following:
For example, the method using permanganate [Journal
Of Chemical Society Parkin Trance
1 (J. Chem. Soc., Perkin. Tran)
s. 1) p. 806 (1973)], a method using a dichromate [Organic Synthesis (Org. Syn)
th. Vol. 4, p. 698 (1963)], a method using periodate in the presence of a ruthenium metal catalyst [Journal of Organic Society (J. Org.
Chem. 46, 19 (1981)], a method using nitric acid (JP-A-59-190945), and a method using ozone [Journal of American Chemical Society (J. Am. Chem. Soc.)]. 81, p. 4273 (1959)].
In the production of the alicyclic cis-dicarboxylic acid represented by the general formula (3) of the present invention, these known oxidative cleavage reactions can be directly employed.

The present inventors have conducted various studies on the above-mentioned oxidative cleavage reaction. In the method using permanganate, dichromate or nitric acid as an oxidizing agent, the target was represented by the general formula (3). The yield of the resulting cycloaliphatic cis-dicarboxylic acid was low. On the other hand, in both the method using periodate as the oxidizing agent and the method using ozone, the alicyclic cis-dicarboxylic acid represented by the general formula (3), which is the target product, can be obtained in high yield. However, it was also found that the reaction treatment was complicated or the reaction reagent was expensive, which was disadvantageous from the viewpoint of industrial production.

The present inventors have conducted intensive studies on the oxidative cleavage reaction. As a result, if the oxidative reaction was carried out under acidic conditions using permanganate as an oxidizing agent, the desired product could be obtained in a very high yield. It was newly found that an alicyclic cis-dicarboxylic acid represented by the general formula (3) was obtained. The general formula (3) utilizing the new oxidative cleavage reaction of the present invention
The method for producing an alicyclic cis-dicarboxylic acid represented by the general formula (1) is performed by setting the alkali to neutral conditions under which an oxidative cleavage reaction is usually performed under acidic conditions under which the oxidizing power of permanganate increases. Things. Hereinafter, a method for producing the alicyclic cis-dicarboxylic acid represented by the general formula (3) will be described with respect to such a new oxidative cleavage reaction of the present invention.

As the permanganate used as the oxidizing agent, potassium permanganate is generally used. Since the oxidative cleavage reaction is a stoichiometric reaction, the amount of permanganate used is usually at least 1 mole equivalent, preferably at least 1 mole equivalent to 1 mole of hexacycloheptadecene represented by the general formula (7). It is preferred to use 2 to 4 molar equivalents.

In order to bring the reaction system under acidic conditions, usually,
Various inorganic and organic acids such as sulfuric acid, hydrochloric acid, acetic acid, and nitric acid are used. Among these acids, inorganic acids such as sulfuric acid and hydrochloric acid are preferred from the viewpoint of less generation of decomposition products due to the acid and inexpensiveness. These acids may be diluted with water and used as an aqueous solution, or may be used without dilution. The amount of the acid to be used is generally 0.2 to 3 molar equivalents, preferably 0.4 to 2 molar equivalents, per 1 mol of hexacycloheptadecene represented by the general formula (7). . If less than 0.2 molar equivalent, the yield is low,
If the molar amount exceeds 3 molar equivalents, a decomposition product due to acid is produced as a by-product, and either case is not preferable.

The solvent in the oxidative cleavage reaction of the present invention is not particularly limited as long as it is a solvent inert to the reaction, and examples thereof include water, acetone; ethers such as tetrahydrofuran and dioxane; benzene, toluene, xylene and the like. Aromatic hydrocarbons; aliphatic hydrocarbons such as hexane and heptane; and halogenated hydrocarbons such as methyl chloride, dichloromethane and chloroform. Among these solvents, a mixed solvent of water and an organic solvent is represented by the general formula (7) in consideration of the solubility of hexacycloheptadecene and the permanganate represented by the general formula (7). It is preferable to use 1 part by weight or more based on 1 part by weight of hexacycloheptadecene. More preferably, a mixed solvent of water: acetone (1: 9 to 9: 1 (weight ratio)) is added to 3 parts by weight of hexacycloheptadecene represented by the general formula (7).
It is preferable to use at least part by weight.

In the oxidative cleavage reaction of the present invention, hexacycloheptadecene, permanganate and acid represented by the general formula (7) may be charged and reacted together with a solvent from the beginning. The reaction may be performed continuously or intermittently while being added to the system. Further, only permanganate alone is dissolved or suspended in a solvent first, and then hexacycloheptadecene and an acid represented by the general formula (7) are continuously or intermittently added to the system to cause a reaction. Alternatively, only hexacycloheptadecene represented by the general formula (7) is first dissolved or suspended in a solvent, and then permanganate and an acid are continuously or intermittently added to the system. You may make it react. Furthermore, the general formula (7)
The hexacycloheptadecene and the acid represented by may be charged first, and then the permanganate may be added continuously or intermittently to the reaction system, and the permanganate and the acid may be charged first. Then, hexacycloheptadecene represented by the general formula (7) may be continuously or intermittently added to the reaction system, and the reaction may be performed. The manganate may be charged first, and then the acid may be added continuously or intermittently to the reaction system.

The reaction temperature is usually -20 to 100 ° C, preferably 0 to 40 ° C. The reaction time depends on the stoichiometric ratio of hexacycloheptadecene and permanganate represented by the general formula (7) and the reaction temperature.
4 hours is recommended.

The alicyclic cis-dicarboxylic acid diester represented by the general formula (4) of the present invention is obtained by using the obtained general formula (3)
Easily obtained by a very common method such as esterification of an alicyclic cis-dicarboxylic acid represented by the formula with a monohydric alcohol having 1 to 4 carbon atoms in the presence of an acid catalyst such as p-toluenesulfonic acid or sulfuric acid. Can be. Specific examples of the monohydric alcohol include methanol, ethanol, n- or iso.
-Propanol, n-, sec- or tert-butanol. In addition, esterification is usually performed by 1
The reaction is carried out in a polyhydric alcohol, and the monohydric alcohol is 3 times the weight of the alicyclic cis-dicarboxylic acid represented by the general formula (3).
The above is required.

The alicyclic trans-dicarboxylic acid diester represented by the general formula (6) of the present invention can be produced by isomerizing the obtained alicyclic cis-dicarboxylic acid diester of the general formula (4). The isomerization occurs easily and in high yield by using a metal alkoxide as a catalyst. In general, a compound having a hydrogen atom at the α-position of a carbonyl group can be converted to a “keto-enole-form” in the presence of a basic catalyst.
It is known that the compound has a fast equilibrium type, and the isomerization reaction of the present invention is a technique applying this fact. However, the cis-formation of a diester group substituted by a polycyclic aliphatic compound as in the present invention is performed. The present invention has been found for the first time by the inventors of the present invention, for example, as the catalyst for the isomerization reaction.
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal amides such as lithium diisopropylamide (LDA) have been tried. And did not produce good results.

In the above isomerization reaction, the metal alkoxide used as a catalyst includes, for example, methoxide, ethoxide, n-propoxide, iso-propoxide, alkali metal such as lithium, sodium or potassium.
n-butoxide, sec-butoxide, tert-butoxide, pentoxide and the like. As these alkali metal alkoxides, those synthesized separately may be used, or they may be synthesized and used in the same system of the present isomerization reaction (for example, in a solvent used for the isomerization reaction or in the reaction). An alcohol is reacted with an alkali metal or alkali metal hydride in an inert and appropriate solvent to synthesize the solution, and the solution is used for the reaction as it is.) These metal alkoxides may be used alone,
A plurality of the alkoxides may be used as a mixture. The amount of the catalyst used is not particularly limited, but is preferably used in the range of 0.05 to 0.5 molar equivalent per 1 mol of the alicyclic cis-dicarboxylic acid diester represented by the general formula (4). preferable. When the amount of the catalyst is less than 0.05 molar equivalent, isomerization does not occur or progress is extremely slow, which is not practical. On the other hand, if it is more than 0.5 molar equivalent, there is a danger that various side reactions may occur at the same time because the catalyst is strongly alkaline.

The above-mentioned isomerization reaction can be performed without a solvent, but it is usually better to use a suitable solvent. The solvent used is not particularly limited as long as it can completely or partially dissolve the alicyclic trans-dicarboxylic acid diester represented by the general formula (4) and is inert to the reaction. Examples of such a solvent include ethers such as diethyl ether, tetrahydrofuran, and dioxane; benzene,
Aromatic hydrocarbons such as toluene and xylene; hexane;
Organic solvents such as aliphatic hydrocarbons such as heptane; alcohols such as methanol and ethanol. Aprotic organic solvents such as ethers such as tetrahydrofuran and dioxane are preferred. Although a good result can be sufficiently obtained by using a commercially available solvent as it is, it is more preferable to use a simple or dehydrated solvent.

The reaction temperature for the isomerization is usually -50 to 100
C, preferably -10 to 50C. The reaction time is such that the isomerization
As it progresses, therefore, in most cases less than 5 hours is sufficient.

The alicyclic trans-dicarboxylic acid represented by the general formula (5) of the present invention is obtained by hydrolyzing the obtained alicyclic trans-dicarboxylic diester represented by the general formula (6). Can be manufactured. The hydrolysis can be easily carried out under both conditions in the presence of a general acid catalyst or in the presence of an alkali catalyst. Examples of the acid catalyst include hydrochloric acid and sulfuric acid, and examples of the alkaline catalyst include sodium hydroxide,
Examples include potassium hydroxide.

[0039]

According to the present invention, there are provided novel alicyclic dicarboxylic acids and diesters thereof, and methods for producing them. Such alicyclic dicarboxylic acids and diesters thereof of the present invention are useful as monomer raw materials and additives for polyesters such as optical materials and structural materials. In particular, since the carboxylic acid group or its ester group, which is a functional group, is not bonded to the vicinal carbon, steric hindrance hardly occurs when used as a raw material for alicyclic polyester. Further, according to the present invention, only the cis-form represented by the general formulas (3) and (4) or the trans-form represented by the general formulas (5) and (6) can be selectively produced. Therefore, only the cis or trans alicyclic skeleton can be introduced into the polyester. In addition, the novel alicyclic dicarboxylic acid and its diester of the present invention can be used as a racemic form without being limited to a cis or trans form as represented by the general formulas (1) and (2). It is.

[0040]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The following apparatus was used for measuring the physical properties, spectra, etc. of each alicyclic dicarboxylic acid or its diester.

Melting point: Trace melting point measuring device MP-S3
(Manufactured by Yanaco Equipment Development Laboratory). NMR: BRUKER ARX300 (manufactured by Bruker). IR: FT-IR FTS-7 (manufactured by Bio-Rad). Elemental analysis: Elemental analyzer 2400CHN
(PerkinElmer).

Example 1 Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
Synthesis of pentadecane-cis-10,12-dicarboxylic acid (alicyclic cis-dicarboxylic acid represented by general formula (3)) Acetone in a 5-L separable flask equipped with a stirrer, a cooler, a thermometer, and a dropping funnel. 2L, water 700mL, sulfuric acid 3
5.5 mL (0.67 mol), potassium permanganate 3
After charging 02 g (1.91 mol) and stirring at 10 to 15 ° C., 144 g (0.64 mol) of hexacycloheptadecene represented by the general formula (7) was added dropwise over 1 hour.
Further, the reaction was performed at room temperature for 24 hours. Then, after removing manganese dioxide generated from the reaction mixture, the filtrate was concentrated under reduced pressure to obtain 151 g of crude crystals of an alicyclic cis-dicarboxylic acid represented by the general formula (3). Recrystallization from a mixed solvent of 140 mL of dimethyl sulfoxide (DMSO) and 115 mL of water gave 125 g of white crystals having a melting point (decomposition) of 256 to 258 ° C (collection from hexacycloheptadecene represented by the general formula (7)). 67 mol%, hereinafter simply referred to as%). The crystals were identified by ¹ H-NMR, ¹³ C-NMR, IR and elemental analysis, and confirmed to be the desired alicyclic cis-dicarboxylic acid represented by the general formula (3). The following shows the spectrum data.

¹ H-NMR (DMSO-d ₆ ): 0.8
9-0.93 (m, 4H), 1.37-1.42 (m, 4H)
3H), 1.57 (s, 2H), 1.66 (dt, 1
H), 1.72 (d, 1H), 2.03 (s, 4H),
2.16 (q, 1H), 2.56 (d, 2H), 2.8
8-2.98 (m, 2H), 12.05 (s, 2H)
(Ppm).

¹³ C-NMR (DMSO-d ₆ ): 17
4.05, 49.65, 47.02, 44.06, 4
3.73, 38.70, 35.63, 34.79, 3
2.57, 30.98 (ppm).

IR (KBr): 2959, 1719, 1
687, 1265, 1202 (cm ^-1 ).

Elemental analysis (C ₁₇ H ₂₂ O ₄ ) Calculated: C, 70.32, H, 7.64, Found: C, 70.25, H, 7.54.

Example 2 In Example 1, acetone, water and potassium permanganate were initially charged, and then sulfuric acid and a compound of the general formula (7)
Was carried out in exactly the same manner as in Example 1 except that hexacycloheptadecene represented by the formula was changed from a separate dropping funnel into the reaction system over 1 hour. As a result, 130 g of white crystals were obtained after recrystallization (yield 70%). ¹
By H-NMR, ¹³ C-NMR, IR and elemental analysis,
It was confirmed that the compound was the same as the alicyclic cis-dicarboxylic acid represented by the general formula (3) in Example 1.

Example 3 The procedure of Example 1 was repeated except that the amount of sulfuric acid was changed to 18 mL (0.34 mol). As a result, 122 g of white crystals were obtained after recrystallization (yield 66%). ^{By 1} H-NMR, ¹³ C-NMR, IR and elemental analysis, it was confirmed that the compound was the same as the alicyclic cis-dicarboxylic acid represented by the general formula (3) in Example 1.

Example 4 Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
Synthesis of dimethyl pentadecane-cis-10,12-dicarboxylate (alicyclic cis-dicarboxylate diester represented by the general formula (4) and R is a methyl group) 5 L equipped with a stirrer, a thermometer, and a cooler In a separable flask, 375 g (1.30 mol) of the alicyclic cis-dicarboxylic acid represented by the general formula (3) obtained in Example 1 and p-
14.5 g (76 mmol) of toluenesulfonic acid and 3.5 L of methanol were charged, and an ester reaction was performed at a reflux temperature of methanol for 12 hours. After completion of the reaction, methanol was distilled off under reduced pressure to obtain 415 g of pale yellow powder. This was recrystallized from methanol to obtain 381 g of white crystals having a melting point of 142 to 143 ° C (yield 92%). This crystal is ¹ H-N
Identified by MR, ¹³ C-NMR, IR and elemental analysis,
It was confirmed that the desired dimethyl was an alicyclic cis-dicarboxylate represented by the general formula (4). The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.95
(Dd, 2H), 0.97 (d, 1H), 1.03
(D, 1H), 1.42-1.50 (m, 2H), 1.
57 (bs, 1H), 1.61 (bs, 2H), 1.6
8 (d, 1H), 1.88 (dt, 1H), 1.96
(S, 2H), 2.13 (s, 2H), 2.52 (q,
1H), 2.69 (d, 2H), 2.95-3.08
(M, 2H), 3.72 (s, 6H) (ppm).

¹³ C-NMR (CDCl ₃ ): 173.3
8, 51.46, 50.18, 47.70, 44.8
9, 44.33, 39.07, 36.05, 35.1
6, 32.71, 31.35 (ppm).

IR (KBr): 2943, 1735, 1
726, 1439, 1381, 1245, 1189, 1
150 (cm ^-1 ).

Elemental analysis (C ₁₉ H ₂₆ O ₄ ) Calculated: C, 71.67, H, 8.23, Found: C, 71.55, H, 8.33.

Example 5 Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
Synthesis of pentadecane-trans-10,12-dicarboxylate (alicyclic trans-dicarboxylate diester represented by the general formula (6) and R is a methyl group) Stirrer, thermometer, dropping funnel, and nitrogen introduction 2 with tube
The dimethyl alicyclic cis-dicarboxylate represented by the general formula (4) obtained in Example 4 was placed in an L-separable flask.
74 g (0.86 mol), 1 L of tetrahydrofuran and 19.3 g (0.17 mol) of potassium tert-butoxide were charged and stirred at 0 ° C. for 2 hours. After quenching by adding 50 mL of water, the reaction mixture was concentrated under reduced pressure to about 300 mL, and further separated and extracted with 1 L of water and 1 L of ethyl acetate. The obtained organic layer was concentrated under reduced pressure to obtain 268 g of a pale yellow solid. This solid was recrystallized from hexane,
255 g of white crystals having a melting point of 52-53 ° C. were obtained (yield 9).
3%). The crystals were analyzed by ¹ H-NMR, ¹³ C-NMR, IR
And it was identified by elemental analysis, and it was confirmed to be the target dimethyl alicyclic trans-dicarboxylate represented by the general formula (6). The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.92
(D, 1H), 0.98 (dd, 2H), 1.10
(D, 1H), 1.32 (d, 1H), 1.45 (d,
2H), 1.55 (d, 1H), 1.68 (s, 2
H), 1.94 (t, 1H), 2.04-2.12
(M, 1H), 2.14 (S, 2H), 2.23 (s,
2H), 2.23-2.35 (m, 2H), 2.49
(D, 2H), 3.69 (s, 6H) (ppm).

¹³ C-NMR (CDCl ₃ ): 175.1
6, 51.68, 49.18, 48.96, 46.8
5, 45.25, 36.27, 35.93, 35.0
6, 33.90, 31.27 (ppm).

IR (KBr): 2950, 1736, 1
726, 1438, 1367, 1251, 1194, 1
143 (cm ^-1 ).

Elemental analysis (C ₁₉ H ₂₆ O ₄ ) Calculated: C, 71.67, H, 8.23, Found: C, 71.64, H, 8.35.

Example 6 Example 5 was repeated except that the amount of potassium tert-butoxide was changed to 9.7 g (0.09 mol).
The same was done. As a result, after recrystallization, 248 g
Was obtained (91% yield). ¹ H-NMR, ¹³ C
-By NMR, IR and elemental analysis, it was confirmed that the compound was the same as the alicyclic trans-dicarboxylate dimethyl represented by the general formula (6) in Example 5.

Example 7 In Example 5, 9.18 g of sodium methoxide was used in place of potassium tert-butoxide as a catalyst.
(0.17 mol), except that Example 5 was used. As a result, after recrystallization, 248 g of white crystals were obtained (yield: 91%). ¹ H-NMR, ¹³ C-NMR,
By IR and elemental analysis, it was confirmed that the compound was the same as the dimethyl alicyclic trans-dicarboxylate represented by the general formula (6) in Example 5.

Example 8 Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ]
Synthesis of pentadecane-trans-10,12-dicarboxylic acid (alicyclic trans-dicarboxylic acid represented by the general formula (5)) Example 1 was prepared in a 1-L four-necked flask equipped with a stirrer, a cooler, and a thermometer. 5 g (0.16 mol) of the dimethyl alicyclic trans-dicarboxylate represented by the general formula (6) obtained in 5 above, 20 g of sodium hydroxide, and 500 ml of water were charged and stirred vigorously at 105 ° C. for 2 hours. After the reaction, p
Concentrated hydrochloric acid was added until H1, and the precipitated white crystals were separated by filtration, washed with water and dried (46 g: yield 99%, melting point (decomposition) = 240 to 242.5 ° C). The crystals ¹ H-
It was identified by NMR, ¹³ C-NMR, IR and elemental analysis, and it was confirmed that it was the target alicyclic trans-dicarboxylic acid represented by the general formula (5). The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.87-
1.01 (m, 4H), 1.37-1.51 (m, 4
H), 1.62 (q, 1H), 1.64 (bs, 2
H), 1.93 (quin, 1H), 2.05 (s, 2
H), 2.12 (s, 2H), 2.17-2.26
(M, 2H), 2.32 (d, 2H), 12.08
(S, 2H) (ppm).

¹³ C-NMR (CDCl ₃ ): 175.8
7, 48.69, 48.51, 46.40, 44.8
3, 35.89, 35.64, 34.64, 33.7
7, 30.88 (ppm).

IR (KBr): 2944, 1728, 1
700, 1278, 1205 (cm ^-1 ).

Elemental analysis (C ₁₉ H ₂₆ O ₄ ) Calculated: C, 70.32, H, 7.64, Found: C, 70.25, H, 7.80.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 67/475 C07C 67/475 69/753 69/753 Z // C07B 61/00 300 C07B 61/00 300

Claims (12)

(57) [Claims] 1. General formula (1): An alicyclic dicarboxylic acid represented by the formula: 2. General formula (2): (Wherein, R represents an alkyl group having 1 to 4 carbon atoms). 3. A compound of the general formula (3): An alicyclic cis-dicarboxylic acid represented by the formula: 4. A compound of the general formula (4): (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) An alicyclic cis-dicarboxylic acid diester represented by the formula: 5. A compound of the general formula (5): An alicyclic trans-dicarboxylic acid represented by the formula: 6. A compound of the general formula (6): (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) An alicyclic trans-dicarboxylic acid diester represented by the formula: 7. A compound of the general formula (7): Hexacyclo [6.6.1.1 ^3,6 . 1
^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene as the starting material, according to claim 3, wherein the alicyclic cis, characterized in that the double bond moiety to oxidative cleavage using an oxidizing agent - method for producing dicarboxylic acids. 8. Using permanganate as an oxidizing agent,
The method according to claim 7, wherein the oxidative cleavage is performed under acidic conditions. 9. A compound of the general formula (7): Hexacyclo [6.6.1.1 ^3,6 . 1
^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene as a starting material, the double bond moiety to oxidative cleavage, according to claim 4, further this is characterized in that esterified with monohydric alcohol having 1 to 4 carbon atoms A process for producing an alicyclic cis-dicarboxylic acid diester. 10. The process according to claim 9, wherein oxidative cleavage is performed under acidic conditions using permanganate as an oxidizing agent. 11. General formula (4): (Wherein, R represents an alkyl group having 1 to 4 carbon atoms). A metal alkoxide is acted as a catalyst on the alicyclic cis-dicarboxylic acid diester represented by 7. The process for producing an alicyclic trans-dicarboxylic acid diester according to claim 6, wherein the isomerization is performed. 12. A compound of the general formula (4): (Wherein, R represents an alkyl group having 1 to 4 carbon atoms). A metal alkoxide is acted as a catalyst on the alicyclic cis-dicarboxylic acid diester represented by 6. The process for producing an alicyclic trans-dicarboxylic acid according to claim 5, wherein the isomerization is carried out so as to obtain an alicyclic trans-dicarboxylic acid.