JP2008143850A - New dihydroxytetracyclododecanecarboxylic acid, its ester and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dihydroxytetracyclododecanecarboxylic acid and its ester useful e.g. as a photosensitive resist raw material for semiconductor microfabrication, etc., and a resin raw material for optical materials having excellent optical properties, heat-resistance, moisture resistance, etc. <P>SOLUTION: The objective dihydroxytetracyclododecanecarboxylic acid and its ester expressed by general formula (1) is produced by oxidizing the unsaturated bond of tetracyclododec-3-ene-8-carboxylic acid or its ester with hydrogen peroxide in the presence of an acid catalyst (in the formula, R and R<SB>1</SB>to R<SB>3</SB>are each a hydrogen atom or an alkyl group). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a novel dihydroxytetracyclododecanecarboxylic acid or ester thereof and an industrially advantageous production method thereof.
In particular, may have an alkyl substituent, 3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acids or their primary alkyl esters In addition, the present invention relates to a method for producing dihydroxytetracyclododecanecarboxylic acids or esters thereof by using tetracyclododecenecarboxylic acids or esters thereof as raw materials and oxidizing them in a solvent in the presence of an acid catalyst.

  In recent years, crosslinked alicyclic hydroxycarboxylic acids or esters thereof are useful as photosensitive resist raw materials for semiconductor microfabrication and the like, as well as resin raw materials for optical materials having excellent optical properties, heat resistance, moisture resistance, etc. Sex is expected. In particular, as a resin material for an optical material, it is expected that a polyester composed of a crosslinked alicyclic compound has high transparency and a high glass transition temperature in terms of physical properties as compared with a general-purpose polyester resin. In particular, a polyester having a structure in which a carboxylic acid and an alcohol are directly bonded to a crosslinked alicyclic skeleton can be expected to have a higher glass transition temperature. However, the alcohol directly bonded to the alicyclic skeleton is a secondary alcohol and has poor reactivity (polycondensation) with a carboxylic acid and transesterification with an ester. As a result, it was difficult to obtain a high-purity and high-molecular-weight alicyclic polyester from a monomer using hydroxytetracyclododecanecarboxylic acid or its ester as a raw material because monomers and low-molecular weight substances remained in the resin. .

As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have paid attention to the number of hydroxyl groups of hydroxytetracyclododecanecarboxylic acid or its ester compound, and such groups are present in the molecule. A compound having a plurality can be expected to show high reactivity. In the case of the alkyl ester, since the ester group is relatively acid-stable, it can be used as a protective group when a hydroxyl group or a glycol group is reacted under acidic conditions.
However, as such hydroxy tetracyclododecane carboxylic acid or an ester thereof, conventional insofar as the present inventors know, 3,4-dihydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10]} dodecane-8-carboxylic acid t- butyl ester (U.S. Pat. No. 6265131B1 publications, U.S. Patent No. 6294309B1 publication), or 3 or 4-hydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10} ] Dodecane-8 carboxylic acid or its ester (JP-A-11-240851) is only known, and dihydroxytetracyclododecane carboxylic acid or its primary alkyl ester is not known.
Furthermore, an industrially advantageous production method for such compounds is not known.

US Pat. No. 6,265,131 US Pat. No. 6,294,309 Japanese Patent Laid-Open No. 11-240851

  The present invention has been made to meet the above-described demands, and an object thereof is to provide dihydroxytetracyclododecanecarboxylic acid or a primary alkyl ester thereof. Furthermore, it is intended to provide a method for producing dihydroxytetracyclododecanecarboxylic acid or a primary alkyl ester thereof easily from a commercially available alicyclic monoolefin carboxylic acid or a primary alkyl ester thereof as a raw material in good yield. Let it be an issue.

（式中、Ｒは水素原子または炭素原子数１〜６の一級アルキル基を示し、Ｒ_１〜Ｒ_３は各々独立して水素原子または炭素原子数１〜６のアルキル基を示す。）
で表されるジヒドロキシテトラシクロドデカンカルボン酸又はそのエステルが提供される。 According to the present invention,
General formula (1)

(In the formula, R represents a hydrogen atom or a primary alkyl group having 1 to 6 carbon atoms, and R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The dihydroxytetracyclododecane carboxylic acid represented by these, or its ester is provided.

一般式（２）
（式中、Ｒ_１〜Ｒ_３は一般式（１）のそれと同じである。） In the general formula (1), when R is a hydrogen atom, the compound represented by the general formula (1) of the present invention is dihydroxytetracyclododecanecarboxylic acid represented by the following general formula (2). .

General formula (2)
(In the formula, R _{1 to} R ₃ are the same as those in the general formula (1).)

In the general formula (1) or general formula (2), the alkyl group having 1 to 6 carbon atoms represented by R _{1 to} R ₃ is a linear, branched or cyclic alkyl group. Preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. Most preferred R _{1 to} R ₃ are a hydrogen atom or a methyl group.

３，４−ジヒドロキシ−８−メチル−テトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸

３，４−ジヒドロキシ−９−メチル−テトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸

更に、
３，４−ジヒドロキシ−８、９−ジメチル−テトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸
３，４−ジヒドロキシ−９、９−ジメチル−テトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸
３，４−ジヒドロキシ−９−イソプロピルーテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸
３，４−ジヒドロキシ−８−メチル−９−エチルーテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸
等があげられる。 Accordingly, in the general formula (1), when R is a hydrogen atom, the dihydroxytetracyclododecanecarboxylic acid represented by the general formula (2) is
Specifically, for example,
3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid

3,4-dihydroxy-8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid

3,4-dihydroxy-9-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid

Furthermore,
3,4-dihydroxy-8,9-dimethyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid 3,4-dihydroxy-9,9-dimethyl - tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid 3,4-dihydroxy-9-isopropyl over tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane-8-carboxylic acid 3,4-dihydroxy-8-methyl-9-ethyl chromatography tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid and the like .

In the general formula (1), when R is a primary alkyl group having 1 to 6 carbon atoms, the compound represented by the general formula (1) of the present invention is dihydroxytetracyclododecanecarboxylic acid ester. is there.
As R when the R is a primary alkyl group having 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, an n-pentyl group, An isopentyl group, an n-hexyl group, a 4-methylpentyl group, and the like are mentioned. Among these, a methyl group, an ethyl group, and an n-propyl group, which are primary alkyl groups having 1 to 3 carbon atoms, are preferable, and a methyl group is particularly preferable. Is preferred.

３，４−ジヒドロキシ−８−メチル−８−メトキシカルボニルテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン、

３，４−ジヒドロキシ−９−メチル−８−メトキシカルボニルテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン

更に
３，４−ジヒドロキシ−８、９−ジメチル−８−メトキシカルボニルテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン
３，４−ジヒドロキシ−９、９−ジメチル−８−メトキシカルボニルテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン
３，４−ジヒドロキシ−８−エトキシカルボニルテトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン
等が挙げられる。 Therefore, in the above general formula (1), when R is a primary alkyl group having 1 to 6 carbon atoms, as the dihydroxytetracyclododecane carboxylic acid ester compound represented by the above general formula (1) of the present invention, Specifically, for example,
3,4-dihydroxy-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane

3,4-dihydroxy-8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane,

3,4-dihydroxy-9-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane

Further 3,4-dihydroxy-8,9-dimethyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane 3,4-dihydroxy-9,9-dimethyl -8 - methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane 3,4-dihydroxy-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^{7, 10} ] dodecane and the like.

一般式（３）
（式中、Ｒ及びＲ_１〜Ｒ_３は一般式(１)のそれと同じである。） The purity of the dihydroxytetracyclododecanecarboxylic acid or ester thereof of the present invention is not particularly limited, but as a product, it is usually 80% or more, preferably 90% or more, more preferably, in gas chromatography analysis. 95% or more. In particular, when used as a polyester raw material or a photosensitive resist raw material, 98% or more is preferable.
The production method of the dihydroxytetracyclododecanecarboxylic acid or ester thereof represented by the general formula (1) of the present invention is not particularly limited, however, preferred production that can be produced easily and with high purity industrially. As a method, an unsaturated bond of tetracyclododec-3-ene-8-carboxylic acid represented by the following general formula (3) or an ester thereof is oxidized with hydrogen peroxide in a solvent in the presence of an acid catalyst. Thus, dihydroxytetracyclododecanecarboxylic acid represented by the general formula (1) of the present invention or an ester thereof can be obtained.

General formula (3)
(In the formula, R and R _{1 to} R ₃ are the same as those in the general formula (1).)

  In the above production method, when tetracyclododec-3-ene-8-carboxylic acid is used as a raw material, a corresponding dihydroxytetracyclododecanecarboxylic acid is obtained, and tetracyclododec-3-ene-8-carboxylic acid is used as a raw material. When the acid primary alkyl ester is used, the corresponding primary alkyl ester of dihydroxytetracyclododecanecarboxylic acid is obtained.

反応式（１）
又、テトラシクロ［４.４.０.１^２,５.１^７,１０］−ドデカ−３−エン−８―カルボン酸メチルエステルを原料とし、溶媒中、酸触媒の存在下に過酸化水素で酸化して３、４−ジヒドロキシ−テトラシクロ［４.４.０.１^２,５.１^７,１０］ドデカン−８−カルボン酸メチルエステルを得る場合の反応式は、下記の反応式（２）で示される。

反応式（２） For example, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] - dodecamethylene-3-ene-8-carboxylic acid as the starting material, solvent, and oxidizing with hydrogen peroxide in the presence of an acid catalyst Te 3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] Scheme in obtaining a dodecane-8-carboxylic acid is represented by the following reaction formula (1).

Reaction formula (1)
Further, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] - dodecamethylene-3-ene-8-carboxylic acid methyl ester as a starting material, in a solvent, with hydrogen peroxide in the presence of an acid catalyst oxidized to 3,4-dihydroxy - reaction formula in the case of obtaining a tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid methyl ester, the following reaction formula (2) Indicated by

Reaction formula (2)

Moreover, in the raw material compound represented by the above general formula (3) used in the preferred production method of the dihydroxytetracyclododecanecarboxylic acid represented by the general formula (1) of the present invention or an ester thereof, in the formula, R and R _{1 to} R ₃ are the same as those in the general formula 1. Therefore, as the tetracyclododec-3-ene-8-carboxylic acid or ester represented by the general formula (3) of the present invention, specifically, For example,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 8-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 9-methyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 8,9-dimethyl - tetracyclo [ 4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 9-isopropyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca - 3-ene-8-carboxylic acid 8-methyl-9-ethyl - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 8-methyl-8-methoxycarbonyltetracyclo [4.4. .1 ^2,5 .1 ^7,10] dodeca-3-ene 9-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene 8, 9-dimethyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, and the like.

In a preferred method for producing dihydroxytetracyclododecanecarboxylic acid or its ester represented by the general formula (1) of the present invention, the raw material tetracyclododec-3-ene-8-carvone represented by the above general formula (3) The purity of the acid or ester thereof is not particularly limited, but is usually 80% or more, preferably 90% or more, more preferably 90% or more in the gas chromatography analysis method for reasons such as improvement of productivity and suppression of by-products. Is preferably 95% or more.
The hydrogen peroxide used in the reaction is not particularly limited in its properties, but preferably a hydrogen peroxide solution having a concentration of about 30 to 40% is used. The amount of hydrogen peroxide is usually in the range of 1.0 to 1.5 moles, preferably 1.1 to 1.3 moles, per mole of the starting carboxylic acid or ester thereof.

The acid catalyst used together with hydrogen peroxide is not particularly limited as long as it can act on hydrogen peroxide to oxidize unsaturated bonds and add hydroxyl groups. For example, tungstic acid, vanadium oxide, Examples include selenium and osmium tetroxide. Of these, the preferred acid catalyst is tungstic acid.
The usage-amount of an acid catalyst is the range of 1.0-10 mol% normally with respect to 1 mol amount of raw material carboxylic acid, Preferably it is the range of 2-5 mol%.
The solvent used in the reaction is not particularly limited as long as it can dissolve the raw material tetracyclododecenecarboxylic acid or its ester. For example, lower saturated aliphatic carboxylic acid such as ethyl acetate and n-butyl acetate is used. Examples thereof include acid alkyl esters, aromatic hydrocarbons such as benzene or alkyl-substituted benzenes such as toluene and xylene, and mixtures thereof.
Such a reaction solvent is usually used in a range of 1 to 10 parts by weight, preferably in a range of 3 to 6 parts by weight with respect to 1 part by weight of the raw material tetracyclododecenecarboxylic acid or ester thereof. However, the amount of the reaction solvent is not limited to the above.
The oxidation reaction is usually performed at a temperature in the range of 0 to 100 ° C, preferably in the range of 40 to 60 ° C.

In the reaction, the reaction operation method is not particularly limited, and a known method can be appropriately selected. For example, a raw material tetracyclododecenecarboxylic acid or its ester, an acid catalyst and a solvent are charged into a reaction vessel, and hydrogen peroxide solution is dropped at the above reaction temperature with stirring in an inert gas to complete the reaction. The end point of the reaction can be confirmed by liquid chromatography analysis or gas chromatography analysis.
Under such reaction conditions, the reaction is usually completed in about 1 to 10 hours.
After completion of the reaction, a known method can be appropriately used as a purification method for obtaining the target product from the reaction mixture. For example, a reducing agent such as sodium hydrogen sulfite is added to the reaction mixture and the unreacted hydrogen peroxide is deactivated. Thereafter, the acid catalyst is filtered off, the oil layer obtained by further separating the aqueous layer is washed with water, the reaction solvent and the like are separated by distillation and the like, and the target product can be obtained as a distillation residue after distilling off. it can. The crude product can be further purified by an appropriate method such as thin layer chromatography or recrystallization as necessary to obtain a purified product.
According to the said method, the yield of the target object with respect to raw material tetracyclododecenecarboxylic acid or its ester is about 50-80 mol% normally (reaction yield about 80-90%).

  The dihydroxytetracyclododecanecarboxylic acid or its ester of the present invention has two hydroxyl groups (glycol group) and carboxyl group or its primary alkyl ester group highly reactive to the alicyclic skeleton at the molecular end, so it can be used as a raw material for polyester. If so, a high molecular weight polyester can be easily obtained. Furthermore, when used as a raw material for optical material resins, etc., it can be expected to improve optical properties, heat resistance, transparency, moisture resistance, and use the reactivity of its glycol group and / or carboxyl group or its primary alkyl ester group. For example, these hydroxyl groups are esterified by a known method using other carboxylic acids or the like, or ketones are reacted with glycol groups, or other hydroxyl groups are acrylated and polymerized, and then an aqueous alkaline solution is used. Since the ester group (COOR group) can be modified by hydrolysis, it can also be used as an intermediate material for producing a compound having various functional groups in the alicyclic skeleton. Alternatively, since one of the glycol groups can be left as an unreacted hydroxyl group, a polyester having a hydrophilic group can be expected.

(Example)
Hereinafter, the present invention will be described with reference to examples.

Example 1
3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] Synthesis stirring blade dodecane-8-carboxylic acid, a thermometer, a nitrogen inlet tube, a 1L volume equipped with a cooling pipe four-necked flask, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene-8-carboxylic acid 80.0 g, ethyl acetate 400.0g and tungstate 2.9g Prepared.
Next, the temperature of the solution was raised to 50 ° C., and 45.7 g of 35% aqueous hydrogen peroxide was added dropwise over 1 hour while maintaining the temperature.
After completion of the dropping, stirring was continued for 5 hours at the same temperature to complete the reaction.
After completion of the reaction, 45.7 g of a 10% aqueous sodium hydrogen sulfite solution was added dropwise to the resulting reaction mixture to inactivate excess hydrogen peroxide.
Next, after tungstic acid was filtered off, the aqueous layer was separated and removed from the obtained filtrate to obtain an oil layer containing the desired product.
After adding water to the obtained oil layer and washing with water, the solvent was distilled off from the oil layer after washing with water to obtain 59.2 g (purity: 81.4%, by gel permeation chromatography) as a distillation residue. .

Molecular weight: 237 (M−H) ⁻ (mass spectrometry APCI ⁻ )
1H-NMR analysis result (400 MHz, solvent: DMSO-d6, reference substance: tetramethylsilane)
1.00-1.36 (m, 4H), 1.51-2.13 (m, 8H), 2.32-2.40 (m, 1H), 2.51-2.59 (m, 1H), 3.61 (m, 1H), 4.54 (d, 2H), 11.93 (s, 1H) (ppm)
¹³ C-NMR analysis result (400 MHz, solvent: DMSO-d6, reference substance: tetramethylsilane)
176.18,176.14,175.07,76.19,75.97,75.90,75.58,75.42,75.37,75.32,50.93,50.87,50.52,49.83,49.79,49.60,49.45,46.89,46.71,46.37,46.04,45.93,44.81,44.74,44,69 44.51,43.56,43.48,42.81,42.73,42.02,40.94,40.83,40.73,40.68,39.99,39.93,39.79,39.57,39.37,39.16,38.95,38.86,38.77,38.21,37.89,34.73,34.41,34.31,34.19, 32.77,32.32,21.06,20.99,14.04

(Reference example)
Comparison of self-esterification reactivity of dihydroxytetracyclododecanecarboxylic acid and monohydroxytetracyclododecanecarboxylic acid (Table 1)

Reference Example 1
To a 4-liter flask having a capacity of 1 L equipped with a stirring blade, a thermometer, a nitrogen inflow pipe, and a Dean-Stark condenser, 3,4-dihydroxy-tetracyclo obtained in Example 1 [4.4.0.1 ^{2, 5.1 7,10]} dodecane-8-carboxylic acid 11.1 g, was charged toluene 22.2g and p- toluenesulfonic acid 1.1 g.
Thereafter, this solution was heated to 110 ° C. and reacted for 4 hours with stirring. When the obtained reaction liquid was analyzed by gel permeation chromatography, the molecular weight of the produced polyester was 53770 in terms of polystyrene-equivalent weight average molecular weight.

Comparative Reference Example 1
Reference Example 1, 3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] in place of dodecane-8-carboxylic acid, 3 or 4-hydroxy - tetracyclo [4.4 0.1, ² , ^{5.1 7,10} ] The reaction was performed in the same manner as in Reference Example 1 except that dodecane-8-carboxylic acid was charged.
When the obtained reaction liquid was analyzed by gel permeation chromatography, the molecular weight of the produced polyester was 2280 in terms of polystyrene-equivalent weight average molecular weight.

Claims (4)

General formula (1)

(In the formula, R represents a hydrogen atom or a primary alkyl group having 1 to 6 carbon atoms, and R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Dihydroxytetracyclododecanecarboxylic acid represented by General formula (2)

(In the formula, R _{1 to} R ₃ are the same as those in the general formula (1).)
The dihydroxytetracyclododecanecarboxylic acid of Claim 1 represented by these. 3,4-dihydroxy - tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane-8-carboxylic acid. Dihydroxytetracyclododecanecarboxylic acid according to claim 1, characterized in that tetracyclododecenecarboxylic acid represented by the following general formula (3) or an ester thereof is used as a raw material and is oxidized in a solvent in the presence of an acid catalyst. A method for producing an acid or an ester thereof.

General formula (3)
(In the formula, R and R _{1 to} R ₃ are the same as those in the general formula (1).)