JP3102282B2 - Alicyclic diol compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel alicyclic diol compound and a method for producing the same. More specifically, the present invention relates to polyesters such as optical materials and structural materials, polycarbonates, and alicyclic diol compounds useful as additives 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.

The alcohol component of the polyester having an alicyclic skeleton is disclosed, for example, in JP-A-3-200.
830, JP-A-5-5026, JP-A-5-17
Bicyclo [2.2.1] described in 560 Publication
Heptane-2,3-dimethanol, tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3,4-dimethanol, hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 .
[0 ^9,14 ] alicyclic diol compounds such as heptadecane-4,5-dimethanol. However, the alicyclic diol compounds described in these publications all have a steric hindrance because the hydroxymethyl group, which is a functional group, is bonded to the vicinal carbon, resulting in poor monomer reactivity and high reactivity. It is difficult to reduce 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 diol compounds as described above, and a novel alicyclic diol in place of this is provided. It is intended to provide a compound and a method for producing the compound.

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

[0006]

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(Wherein n represents 0 or 1), an alicyclic diol compound represented by the general formula (2):

[0008]

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(Wherein n represents 0 or 1), and an alicyclic cis-diol compound represented by the general formula (3):

[0010]

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(Wherein n represents 0 or 1), and an alicyclic trans-diol compound represented by the general formula (4):

[0012]

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(Wherein n represents 0 or 1) Starting from an alicyclic monoolefin represented by the following formula, the double bond is oxidatively cleaved using an oxidizing agent to obtain a compound represented by the general formula (5) ):

[0014]

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(Wherein n represents 0 or 1) to obtain an alicyclic cis-dicarboxylic acid, which is then esterified with a monohydric alcohol having 1 to 4 carbon atoms to obtain a compound represented by the general formula (6) ):

[0016]

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(In the formula, n represents 0 or 1, and R represents an alkyl group having 1 to 4 carbon atoms.)
A method for producing an alicyclic cis-diol compound represented by the general formula (2), wherein the dicarboxylic acid diester is further subjected to catalytic hydrogen reduction in the presence of a hydrogenation catalyst; A metal alkoxide is acted as a catalyst on the alicyclic cis-dicarboxylic acid diester of the formula (6), and isomerization is performed so that the ester groups are in a trans configuration to each other, thereby obtaining a compound represented by the general formula (7):

[0018]

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(Wherein n represents 0 or 1 and R represents an alkyl group having 1 to 4 carbon atoms). The alicyclic trans-dicarboxylic acid diester represented by the formula: The present invention relates to a method for producing an alicyclic trans-diol compound represented by the above general formula (3), which comprises performing catalytic hydrogen reduction in the presence of a catalyst.

The alicyclic monoolefin represented by the general formula (4) used as a starting material of the present invention can be produced by a known method. That is, it can be obtained by a Diels-Alder reaction between cyclopentadiene or dicyclopentadiene which is a diene compound and ethylene or norbornene which is an alicyclic dienofile compound. For example, in the case of a reaction between cyclopentadiene and norbornene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (n is 0 in the general formula (4)), and hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0
^2,7 . 0 ^9,14] -4-heptadecene (in the general formula (4) n is 1) is obtained. The alicyclic monoolefin represented by the general formula (4) can improve the reaction selectivity to the target product by appropriately selecting the molar stoichiometric ratio of the charged diene compound and dienophile compound and the reaction conditions. It is generally known to improve and can be easily isolated by distillation under reduced pressure.

The alicyclic cis-diol compound represented by the general formula (2) of the present invention is obtained by using the alicyclic monoolefin represented by the above general formula (4) as a starting material, and Oxidative cleavage using an oxidizing agent gives an alicyclic cis-dicarboxylic acid represented by the general formula (5).
Alicyclic cis-dicarboxylic acid diester represented by the above general formula (6) by esterification with a monohydric alcohol of (1) to (4), and further obtained by catalytic hydrogen reduction in the presence of a hydrogenation catalyst. Can be.

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 (5) of the present invention, these known oxidative cleavage reactions can be directly employed.

The inventors of the present invention have conducted various studies on the above-mentioned oxidative cleavage reaction, and found that the method using permanganate, dichromate or nitric acid as the oxidizing agent results in the alicyclic ring represented by the general formula (5). The yield of formula cis-dicarboxylic acid was low.
On the other hand, in the method using periodate as the oxidizing agent and the method using ozone, it was found that the alicyclic cis-dicarboxylic acid represented by the general formula (5) can be obtained in high yield, 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 inventors of the present invention have conducted intensive studies on the oxidative cleavage reaction. As a result, if the oxidizing reaction is carried out under acidic conditions using permanganate as an oxidizing agent, the general formula can be obtained in an extremely high yield. It was newly found that an alicyclic cis-dicarboxylic acid represented by (5) was obtained. The new method for producing an alicyclic cis-dicarboxylic acid represented by the general formula (5) using the oxidative cleavage reaction of the present invention is carried out under the conditions where alkali oxidative cleavage reaction is usually carried out under alkaline to neutral conditions. This is done under acidic conditions that increase the oxidizing power of the acid salt. Hereinafter, regarding the production of the alicyclic cis-dicarboxylic acid represented by the general formula (5), such a new oxidative cleavage reaction of the present invention will be described.

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, per mole of the alicyclic monoolefin represented by the general formula (4). ,
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 per 1 mol of the alicyclic monoolefin represented by the general formula (4),
Preferably, it is used in the range of 0.4 to 2 molar equivalents.
When the amount is less than 0.2 molar equivalent, the yield is low, and when the amount exceeds 3 molar equivalents, a decomposition product due to acid is produced as a by-product, and any 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 (4) in consideration of the solubility of the alicyclic monoolefin represented by the general formula (4) and the permanganate. It is preferable to use 1 part by weight or more per 1 part by weight of the alicyclic monoolefin. More preferably water: acetone 1: 9
It is preferable to use a mixed solvent of up to 9: 1 (weight ratio) in an amount of 3 parts by weight or more based on 1 part by weight of the alicyclic monoolefin represented by the general formula (4).

In the oxidative cleavage reaction of the present invention, the alicyclic monoolefin, permanganate and acid represented by the general formula (4) may be charged and reacted together with a solvent from the beginning. May be added continuously or intermittently to the system. Further, only the permanganate alone is dissolved or suspended in the solvent first, and then the alicyclic monoolefin represented by the general formula (4) and the acid are continuously or intermittently added to the reaction system. Alternatively, only the alicyclic monoolefin represented by the general formula (4) is dissolved or suspended in a solvent first, and then the permanganate and the acid are continuously or intermittently introduced into the system. In addition, you may make it react. Further, the alicyclic monoolefin represented by the general formula (4) and the acid may be charged first, and then the permanganate may be continuously or intermittently added to the system to cause a reaction. The manganate and the acid may be charged first, and then the alicyclic monoolefin represented by the general formula (4) may be continuously or intermittently added to the system and reacted. May be charged first, and then the acid may be added continuously or intermittently to the system for reaction.

The reaction temperature is usually -20 to 100 ° C, preferably 0 to 40 ° C. The reaction time depends on the stoichiometric ratio of the alicyclic monoolefin represented by the general formula (4) and the permanganate and the reaction temperature, but is usually preferably 2 to 24 hours.

The alicyclic cis-dicarboxylic acid diester represented by the general formula (6) of the present invention is obtained by using the obtained general formula (5)
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 (5).
The above is required.

The alicyclic cis-diol compound represented by the general formula (2) of the present invention is obtained by converting the alicyclic cis-dicarboxylic acid diester represented by the general formula (6) obtained above into a hydrogenation catalyst. Can be obtained by catalytic hydrogen reduction in the presence of Examples of the hydrogenation catalyst include a copper-chromite catalyst, a platinum-tin catalyst, a rhodium-tin catalyst, a ruthenium-tin catalyst, a palladium-zinc catalyst, and the like. Among these, a copper chromite catalyst is preferable. For catalytic hydrogen reduction from diester compounds to corresponding diol compounds,
The use of copper chromite as a catalyst has been known for a long time [for example, see Organic Reaction (Or).
g. React. Vol. 8, pp. 1-27 (1954)
)], And various grades of copper chromite catalysts are used industrially. As the copper / chromite catalyst, commercially available ones may be used as they are, or other tin, rhodium, molybdenum, palladium, and other metal-based reduction catalysts may be mixed and prepared as cocatalysts. May be used.

These known means can be employed as they are in the catalytic hydrogen reduction of the present invention. The amount of the hydrogenation catalyst used is usually in the range of 0.01% by weight to 15% by weight based on the alicyclic cis-dicarboxylic acid diester represented by the general formula (6). If it is less than this range, it takes a long time for reduction, and if it is more than this range, side reactions may occur at the same time, which is not preferable from the viewpoint of industrial production.

The catalytic hydrogen reduction reaction is usually performed in a solvent. The solvent to be used is not particularly limited as long as it is a solvent inert to the reaction. Examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene and cumene, aliphatic hydrocarbons such as hexane, heptane and octane, and other alcohol-based solvents. Solvents, ether solvents and the like can be used. The amount of the solvent used is preferably in the range of 0.1 to 50 parts by weight based on 1 part by weight of the alicyclic cis-dicarboxylic acid diester represented by the general formula (6).

The pressure of hydrogen used in the catalytic hydrogen reduction reaction may be any pressure above normal pressure. Usually 10kg / cm ²
It is better to do the above. When a copper-chromite catalyst is used, it is preferably at least 100 kg / cm ² . More preferably, it is 200 kg / cm ² or more. If the pressure is lower than these, the progress of the catalytic hydrogen reduction reaction is extremely slow, which is disadvantageous from the viewpoint of industrial production. The reaction temperature is higher from the viewpoint of industrial production as the temperature is higher as long as side reactions do not occur, which is advantageous from the viewpoint of industrial production.
It is good to carry out in the range of 300 ° C. Preferably, 170-
It is good to carry out in the range of 300 ° C. The reactor is not particularly limited as long as it is a pressure-resistant reactor used for general catalytic hydrogen reduction.

Next, a method for producing the alicyclic trans-diol compound represented by the general formula (3) will be described.
The alicyclic trans-diol compound represented by the general formula (3) is obtained by reacting a metal alkoxide as a catalyst with the alicyclic cis-dicarboxylic acid diester represented by the general formula (6) to form an ester group. After being isomerized so as to have a trans configuration relationship with each other, an alicyclic trans-dicarboxylic acid diester represented by the general formula (7) is obtained.
Further, it can be obtained by catalytic hydrogen reduction in the presence of a hydrogenation catalyst.

The isomerization occurs easily and in high yield by using a metal alkoxide as a catalyst. In general, it is known that compounds having a hydrogen atom at the α-position of the carbonyl group have a fast keto-enolate type equilibrium in the presence of a basic catalyst. However, there is no example of using cis-trans isomerization of a diester group substituted with a polycyclic aliphatic compound as in the present invention, and such isomerization of the present invention is performed by the present inventors. It is the first thing I found. The present inventors have tried alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkali metal amides such as lithium diisopropylamide (LDA) as catalysts for the isomerization reaction. As compared with the system catalyst, the isomerization rate was low or side reactions occurred at the same time, so that good results could not be obtained.

The metal alkoxide used as a catalyst in the above isomerization reaction includes, for example, methoxide, ethoxide, n-propoxide, iso-propoxide and the like of alkali metals such as lithium, sodium and 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 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 (6). 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.

Although the above-mentioned isomerization reaction can be carried out without a solvent, it is usually better to use a suitable solvent. The solvent to be 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 (6) 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-diol compound represented by the general formula (3) of the present invention is obtained by converting the alicyclic trans-dicarboxylic acid diester represented by the general formula (7) in the presence of a hydrogenation catalyst. Can be obtained by catalytic hydrogen reduction. Various reaction conditions for the catalytic hydrogen reduction are as follows: the alicyclic cis-dicarboxylic acid diester represented by the general formula (6) is catalytically hydrogen-reduced to form the alicyclic cis represented by the general formula (2). -The conditions under which the diol compound was produced can be applied as is.

[0041]

According to the present invention, a novel alicyclic diol compound and a method for producing the same are provided. Such alicyclic diol compounds of the present invention are useful as raw materials for polyesters and polycarbonates such as optical materials and structural materials, and as additives. In particular, since the hydroxylmethyl group, which is a functional group, is not bonded on the vicinal carbon, steric hindrance hardly occurs when used as a raw material of an alicyclic polyester or the like. Further, according to the present invention, since only the cis-form represented by the general formula (2) or the trans-form represented by the general formula (3) can be selectively produced, the alicyclic skeleton of the cis-form or the trans-form is provided. Only can be introduced into polymers such as polyesters. 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 the cis or trans form as represented by the general formula (1).

[0042]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the following devices were used for measurement of physical properties, spectra, and the like of each alicyclic diol compound.

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 (i) Tricyclo [5.2.1.0 ^2,6 ] decane-
Synthesis of dimethyl 3,3,5-dicarboxylate (an alicyclic cis-dicarboxylate diester represented by the general formula (6), where n is 0 and R is a methyl group) Stirrer, cooler, thermometer, dropping In a 5 L separable flask equipped with a funnel, acetone 2 L, water 700 mL, sulfuric acid 3
5.5 mL (0.67 mol), potassium permanganate 3
02g (1.91 mol), and tetracyclo [4.4.0.1 ^2,5 . 1
103 g (0.64 mol) of ^7,10 ] -3-dodecene (an alicyclic monoolefin represented by the general formula (4), where n is 0) was added dropwise over 1 hour, and further reacted at room temperature for 24 hours. Was done. Thereafter, manganese dioxide generated from the reaction mixture was removed, and the filtrate was concentrated under reduced pressure to obtain 99 g of crude crystals of an alicyclic cis-dicarboxylic acid (general formula (5), n = 0). Dimethyl sulfoxide (DMSO) 110 mL,
Recrystallized from a mixed solvent of 90 mL of water, melting point = 250-2.
85 g of 55 ° C. white crystals were obtained.

Next, 5 equipped with a stirrer, thermometer and cooler
In the L-separable flask, the alicyclic cis-
85 g of dicarboxylic acid (in the general formula (5), n is 0) (0.
38 mol), 4.3 g of p-toluenesulfonic acid (22 m
Mol) and 850 mL of methanol, and esterified at a reflux temperature of methanol for 12 hours. After completion of the reaction, methanol was distilled off under reduced pressure to obtain 95 g of a pale yellow powder. This was recrystallized from methanol to obtain 86 g of white crystals having a melting point of 98 to 100 ° C. (yield from raw alicyclic monoolefin: 53 mol%, hereinafter simply referred to as%). This crystal is ¹
The compound was identified by 1 H-NMR, ¹³ C-NMR and IR, and the target tricyclo [5.2.1.0 ^2,6 ] decane-cis-
It was confirmed to be dimethyl 3,5-dicarboxylate .

(Ii) Tricyclo [5.2.1.0
Synthesis of ^2,6 ] decane-cis-3,5-dimethanol (cycloaliphatic cis-diol compound represented by the general formula (2), n = 0) The reaction was carried out in a 300 mL autoclave equipped with a magnetic stirrer. The tricyclo [5.2.1.0 obtained in Example 1 (i)
^2,6 ] dimethyl-decane-cis-3,5-dicarboxylate (30 g, 0.12 mol), dioxane (150 mL) and copper chromite (0.5 g) were charged, and the system was sufficiently purged with hydrogen gas. cm ² of hydrogen gas was charged and stirred at 200 ° C. for 20 hours. After the completion of the reaction, the system was cooled to 60 ° C. or lower, the catalyst was filtered off, and dioxane was distilled off under reduced pressure. The obtained pale yellow powder was recrystallized from a mixed solvent of methanol and ethyl acetate to obtain 19.8 g (yield: 85%) of white crystals having a melting point of 115 to 117 ° C. This crystal is ¹ H
-NMR, ¹³ C-NMR, IR
Tricyclo [5.2.1.0 ^2,6 ] decane-cis-
It was confirmed to be 3,5-dimethanol . less than,
3 shows spectral data.

¹ H-NMR (CDCl ₃ ): 0.96
(Q, 1H), 1.04 (dt, 1H), 1.09 (d
d, 2H), 1.21 (dt, 1H), 1.36-1.
48 (m, 4H), 1.82 (dt, 1H), 2.11
(Dt, 2H), 2.23 (bs, 2H), 2.22-
2.36 (m, 2H), 3.67 (bt, 2H),
76 (bt, 2H) (ppm).

¹³ C-NMR (CDCl ₃ ): 61.7
5, 49.48, 44.97, 36.27, 35.2
6, 29.32 (ppm).

IR (KBr): 3268, 2946, 2
868, 1479, 1458, 1082, 1037, 1
012 (cm ^-1 ).

Elemental analysis (C ₁₂ H ₂₀ O ₂ ) Calculated: C, 73.43; H, 10.27; Found: C, 73.18, H, 10.39.

Example 2 (i) Tricyclo [5.2.1.0 ^2,6 ] decant
Lance-3,5-dicarboxylate (general formula (7)
Synthesis of alicyclic trans-dicarboxylic acid diester represented by the formula: n = 0, R = methyl group) 5 equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen inlet tube.
The tricyclo [5.2.1.0 ^2,6 ] decane-cis- obtained in Example 1 (i) was placed in a 00 mL four-necked flask.
55.0 g of dimethyl 3,5-dicarboxylate (0.218
Mol), 300 mL of tetrahydrofuran, potassium te
4.80 g (0.043 mol) of rt-butoxide was charged and stirred at 0 ° C. for 2 hours. After quenching by adding 20 mL of water, the reaction mixture was concentrated under reduced pressure to about 100 mL, and further separated and extracted with 300 mL of water and 300 mL of ethyl acetate. The obtained organic layer was washed with water, and then concentrated under reduced pressure.
54 g of a pale yellow solid were obtained. This solid was recrystallized from methanol to obtain 49 g of white crystals having a melting point of 57 to 59 ° C (89% yield). This crystal was analyzed by ¹ H-NMR, ¹³ C-N
The target tricyclo [5.2.
1.0 ^2,6 ] decane-trans-3,5-dicarboxylic
It was confirmed to be dimethyl acid .

(Ii) Tricyclo [5.2.1.0
Synthesis of ^2,6 ] decane-trans-3,5-dimethanol (an alicyclic trans-diol compound represented by the general formula (3), n = 0) The reaction was carried out in a 300 mL autoclave equipped with a magnetic stirrer. The tricyclo [5.2.1.0 obtained in Example 2 (i)
^2,6 ] decane-trans-3,5-dicarboxylic acid dime
After charging 30 g (0.12 mol) of chill , 150 mL of dioxane and 0.5 g of copper chromite, and then sufficiently replacing the inside of the system with hydrogen gas, charging 200 kg / cm ² of hydrogen gas and stirring at 200 ° C. for 20 hours did. After the reaction,
The system was cooled to 60 ° C. or lower, the catalyst was filtered off, and dioxane was distilled off under reduced pressure. The obtained pale yellow powder was recrystallized with a mixed solvent of methanol and ethyl acetate to obtain 18.5 g (yield 79%) of white crystals having a melting point of 125 to 130 ° C. This crystal
^The compound was identified by ¹ H-NMR, ¹³ C-NMR and IR, and the target tricyclo [5.2.1.0 ^2,6 ] decane- tola was obtained.
-3,5-dimethanol . The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.75
(Q, 1H), 0.91 (d, 1H), 0.98 (d
d, 2H), 1.32 (d, 1H), 1.40-1.4
9 (m, 4H), 1.42 (s, 2H), 1.65-
1.71 (m, 1H), 1.98 (s, 2H), 3.2
9-3.43 (m, 4H), 4.35 (t, 2H) (p
pm).

¹³ C-NMR (CDCl ₃ ): 65.0
7, 51.29, 47.52, 39.53, 34.5
0, 32.82, 28.27 (ppm).

IR (KBr): 3316, 2929, 2
873, 1476, 1452, 1091, 1056, 1
013 (cm ^-1 ).

Elemental analysis (C ₁₂ H ₂₀ O ₂ ) Calculated: C, 73.43, H, 10.27; Found: C, 73.28, H, 10.33.

Example 3 (i) Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] dimethyl pentadecane-cis-10,12-dicarboxylate (an alicyclic cis-dicarboxylate diester represented by the general formula (6), wherein n is 1 and R is a methyl group) Stirrer, cooling Acetone 2L, water 700mL, sulfuric acid 3 in a 5L separable flask equipped with a vessel, thermometer and dropping funnel
5.5 mL (0.67 mol), potassium permanganate 3
02g (1.91 mol) was charged and hexacyclo [6.6.1.1 ^3,6 . 1
^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene (formula (4 represented by alicyclic mono-olefins in), n is 1) 1
44 g (0.64 mol) was added dropwise over 1 hour, and the reaction was further performed at room temperature for 24 hours. After removing manganese dioxide generated from the reaction mixture, the filtrate was concentrated under reduced pressure to obtain 151 g of crude crystals of alicyclic cis-dicarboxylic acid (general formula (5), n = 1). Recrystallized from a mixed solvent of 140 mL of dimethyl sulfoxide (DMSO) and 115 mL of water, 125 g of white crystals having a melting point of 256 to 258 ° C.
I got

Next, a 2 equipped with a stirrer, thermometer and cooler was used.
The alicyclic cis-dicarboxylic acid obtained in Example 3 (i) (in the general formula (6), n is 1) 1 is placed in an L-separable flask.
25 g (0.43 mol), p-toluenesulfonic acid4.
83 g (25.3 mmol) and 1.2 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 138 g of a pale yellow powder. This was recrystallized from methanol to obtain 127 g of white crystals having a melting point of 142 to 143 ° C (yield: 62%). This crystal was analyzed by ¹ H-NMR, ¹³ C-NM
R and IR, and the target pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane-cis-1
It was confirmed to be dimethyl 0,12-dicarboxylate.

(Ii) Pentacyclo [6.5.1.1]
^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane-cis-10,1
Synthesis of 2-dimethanol (alicyclic cis-diol compound represented by general formula (2), n = 1) In a 300 mL autoclave equipped with a magnetic stirrer, the pentacyclo obtained in Example 3 (i) was added. [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane-cis-10,1
38.2 g (0.120 mol) of dimethyl 2-dicarboxylate, 150 mL of dioxane and 0.5 g of copper chromite
, Followed by sufficient replacement of the inside of the system with hydrogen gas,
200 kg / cm ² of hydrogen gas was charged, and 200 ° C.
Stirred for 0 hours. After the completion of the reaction, the system was cooled to 60 ° C. or lower, the catalyst was filtered off, and dioxane was distilled off under reduced pressure. The obtained pale yellow powder was recrystallized from hexane to give a melting point of 125 to 13.
22.3 g (71% yield) of white crystals at 0 ° C. was obtained. The crystals were identified by ¹ H-NMR, ¹³ C-NMR and IR, and the target pentacyclo [6.5.1.1 ^3,6 . 0
^2,7 . [0 ^9,13 ] pentadecane-cis-10,12-dimethanol. The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.90-
1.03 (m, 4H), 1.07 (d, 1H), 1.2
3 (d, 1H), 1.41-1.49 (m, 2H),
1.62 (s, 2H), 1.75-1.93 (m, 4
H), 2.09 (bs, 2H), 2.25-2.38
(M, 2H), 2.25 (bs, 2H), 2.45
(D, 2H), 3.61 (dd, 2H), 3.71 (d
d, 2H) (ppm).

¹³ C-NMR (CDCl ₃ ): 61.6
2, 50.12, 44.55, 43.51, 41.3
3, 39.69, 36.68, 35.79, 31.18
(Ppm).

IR (KBr): 3293, 2947, 2
875, 1484, 1457, 1017, 903 (cm
^-1 ).

Elemental analysis EA (C ₁₇ H ₂₆ O ₂ ) Calculated: C, 77.82, H, 9.99; Found: C, 77.85, H, 10.11.

Example 4 (i) Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] pentadecane-trans-10,12-dicarboxylate (an alicyclic trans-dicarboxylate diester represented by the general formula (7), wherein n is 1 and R is a methyl group)
1 equipped with a stirrer, a thermometer, a dropping funnel, and a nitrogen inlet tube.
L separable flask was charged with the pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ⁹ 9,13] pentadecane-cis-10,12-dicarboxylate (86.0 g, 0.270 mol), tetrahydrofuran 5
00 mL, potassium tert-butoxide 6.06 g
(54.0 mmol) and stirred at 0 ° C. for 2 hours.
After quenching by adding 10 mL of water, the reaction mixture is
The mixture was concentrated under reduced pressure to 00 mL, and further separated and extracted with 400 mL of water and 400 mL of ethyl acetate. The obtained organic layer was concentrated under reduced pressure to obtain 83 g of a pale yellow solid. The solid was recrystallized from hexane to obtain 78.2 g of white crystals having a melting point of 52 to 53 ° C (yield: 91%). The crystals ¹ H-
The compound was identified by NMR, ¹³ C-NMR and IR, and the target pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . [0 ^9,13 ] pentadecane-trans-10,12-dicarboxylate.

(Ii) Pentacyclo [6.5.1.1]
^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane-trans-1
Synthesis of 0,12-dimethanol (the alicyclic trans-diol compound represented by the general formula (3), where n is 1) Obtained in Example 4 (i) in a 300 mL autoclave equipped with a magnetic stirrer. Pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane-trans-1
38.2 g of dimethyl 0,12-dicarboxylate (0.12
0 mol), 150 ml of dioxane and 0.1 ml of copper chromite.
5 g was charged, and then the inside of the system was sufficiently replaced with hydrogen gas, and then 200 kg / cm ² of hydrogen gas was charged.
For 20 hours. After the completion of the reaction, the system was cooled to 60 ° C. or lower, the catalyst was filtered off, and dioxane was distilled off under reduced pressure. The obtained pale yellow powder was recrystallized from hexane to give a melting point of 114 to
23.5 g (75% yield) of white crystals at 115 ° C were obtained.
The crystals were identified by ¹ H-NMR, ¹³ C-NMR and IR, and the target pentacyclo [6.5.1.1 ^3,6 . 0 ^2,
7 ． [0 ^9,13 ] pentadecane-trans-10,12-dimethanol. The following shows the spectrum data.

¹ H-NMR (CDCl ₃ ): 0.83
(Q, 1H), 0.91 (d, 1H), 0.98 (d
d, 2H), 1.04 (d, 1H), 1.38 (d, 2
H), 1.44 (d, 2H), 1.57 (d, 1H),
1.62-1.72 (m, 3H), 1.66 (bs, 2
H) 1.84-1.93 (m, 3H), 2.10
(D, 4H), 3.52-3.68 (m, 4H) (pp
m).

¹³ C-NMR (CDCl ₃ ): 67.1
8, 49.22, 47.77, 45.81, 45.2
9, 36.84, 36.46, 35.07, 34.1
7, 31.36 (ppm).

IR (KBr): 3316, 2947, 2
925, 2886, 2868, 1481, 1458, 1
040, 903 (cm ^-1 ).

Elemental analysis (C ₁₇ H ₂₆ O ₂ ) Calculated: C, 77.82, H, 9.99; Found: C, 77.75, H, 10.08.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C07M 7:00 (58) Investigated field (Int.Cl. ⁷ , DB name) C07C 31/27 C07C 51/31 C07C 61/06 C07C 61/12 C07C 69/753 C07C 69/757 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. General formula (1): (Where n represents 0 or 1). 2. General formula (2): (In the formula, n represents 0 or 1.) An alicyclic cis-diol compound represented by the formula: 3. A compound of the general formula (3): (In the formula, n represents 0 or 1.) An alicyclic trans-diol compound represented by the formula: 4. A compound of the general formula (4): (In the formula, n represents 0 or 1.) Using an alicyclic monoolefin represented by the following formula as a starting material, this double bond portion is oxidatively cleaved using an oxidizing agent to obtain a compound represented by the general formula (5): Formula 5 Wherein n represents 0 or 1. An alicyclic cis-dicarboxylic acid represented by the following formula, which is then esterified with a monohydric alcohol having 1 to 4 carbon atoms, is obtained by general formula (6): Formula 6 (In the formula, n represents 0 or 1, and R represents an alkyl group having 1 to 4 carbon atoms.) An alicyclic cis-dicarboxylic acid diester represented by the following formula: 3. The method for producing an alicyclic cis-diol compound according to claim 2, wherein catalytic hydrogen reduction is carried out. 5. Use of permanganate as an oxidizing agent,
The method according to claim 4, wherein the oxidative cleavage is performed under acidic conditions. 6. A compound of the general formula (6): (Wherein n represents 0 or 1 and 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 the following formula: The groups are isomerized so that they are in the trans configuration with respect to each other to give the general formula (7): (Wherein, n represents 0 or 1 and R represents an alkyl group having 1 to 4 carbon atoms). The alicyclic trans-dicarboxylic acid diester represented by the formula: 4. The method for producing an alicyclic trans-diol compound according to claim 3, wherein catalytic hydrogen reduction is carried out. 7. Using permanganate as an oxidizing agent,
7. The method according to claim 6, wherein the oxidative cleavage is carried out under acidic conditions.