JP5157839B2 - Novel naphthol compounds and process for producing the same - Google Patents

Description

  The present invention relates to a novel naphthol compound having a tricyclodecane skeleton useful as a raw material for producing various industrial chemical raw materials, optical functional materials and electronic functional materials, and a method for producing the same.

  Phenolic resins and / or naphthol resins are for electrical insulation materials, resist resins, semiconductor sealing resins, printed wiring board adhesives, electrical laminates and prepreg matrix resins, build-up laminate materials, and fiber reinforced plastics It can be used for a wide range of applications such as resins, sealing resins for liquid crystal display panels, paints, various coating agents, and adhesives.

  As a resist resin, a lithography technique using an ArF (193 nm) excimer laser as a light source has been developed in place of the conventional KrF (248 nm) excimer laser with the recent fine processing. When conventional resist resin is applied to this ArF excimer laser, the optical properties (absorption coefficient and refractive index) of the material are not compatible, and development of a resist resin compatible with ArF excimer laser is necessary. .

In recent years, resins using polycyclic aromatic hydrocarbons typified by naphthalenes and naphthols have been developed as resist materials for ArF excimer lasers (Patent Documents 1 to 3), but optical properties for ArF excimer lasers have been developed. It does not have performance that satisfies the requirements. Therefore, development of an optical material that satisfies the required optical characteristics is expected.
JP 54-86593 A JP 2004-91550 A JP 2002-14474 A

An object of the present invention is to provide a tricyclodecane skeleton-containing naphthol compound (hereinafter sometimes abbreviated as a novel naphthol compound) useful as a resin material for a resist resin corresponding to a lithographic technique using an ArF excimer laser as a light source. . That is, a resist resin using a novel naphthol compound as a resin raw material exhibits excellent characteristics in terms of optical characteristics (absorption coefficient and refractive index). Moreover, the novel naphthol compound is useful as a raw material for producing various industrial chemical raw materials, optical functional materials and electronic functional materials.

  As a result of intensive studies, the present inventors have found that a tricyclodecane skeleton-containing naphthol compound improves optical properties, and have completed the present invention.

で表されるエステル化合物をフリース転位反応させる工程を含む、下記式（１）

で表されるトリシクロデカン骨格含有ナフトール化合物の製造方法、
[2]下記式（１）で表されるトリシクロデカン骨格含有ナフトール化合物、

[3]フッ化水素の存在下、トリシクロ［５．２．１．０^２，６］デカ−３−エンと一酸化炭素とを２０〜４０℃で反応させ、下記式（３）

で表わされるアシルフロライドを得、得られたアシルフロライドと１−ナフトールとを２０℃以下でエステル化反応させる工程を含む、下記式（２）

で表されるエステル化合物の製造方法、
[4]下記式（２）で表される新規エステル化合物、

に関するものである。 That is, the present invention
[1] Formula (2) below

Including the step of reacting the Fries rearrangement of the ester compound represented by the following formula (1):

A method for producing a tricyclodecane skeleton-containing naphthol compound represented by:
[2] A tricyclodecane skeleton-containing naphthol compound represented by the following formula (1):

[3] In the presence of hydrogen fluoride, tricyclo [5.2.1.0 ^2,6 ] dec-3-ene and carbon monoxide are reacted at 20 to 40 ° C. to obtain the following formula (3):

And a step of esterifying the obtained acyl fluoride and 1-naphthol at 20 ° C. or lower.

A method for producing an ester compound represented by:
[4] A novel ester compound represented by the following formula (2):

It is about.

When the novel naphthol compound represented by the formula (1) of the present invention is used as a resin material for a resist resin, the material exhibits excellent optical properties (absorption coefficient and refractive index). Moreover, the novel naphthol compound is useful as a raw material for producing various industrial chemical raw materials, optical functional materials and electronic functional materials. For example, the extinction coefficient can be suppressed to 50% or less, and the refractive index can be improved by 20% or more as compared with a normal phenol novolac resin.

The synthesis of the novel naphthol compound represented by the formula (1) of the present invention comprises the following three steps. That is, the first step is the synthesis of the acyl fluoride represented by the formula (3) by the carbonylation reaction of tricyclo [5.2.1.0 ^2,6 ] dec-3-ene, the second step is the synthesis of the acyl fluoride and 1- Synthesis of the ester compound represented by the formula (2) by esterification reaction with naphthol, and the third step comprises the synthesis of the naphthol compound represented by the formula (1) by Fries rearrangement of the ester compound.

<Hydride>
The tricyclo [5.2.1.0 ^2,6 ] dec-3-ene (hereinafter abbreviated as DHDCPD) of the present invention is usually prepared by hydrogenating dicyclopentadiene (hereinafter abbreviated as DCPD) by a conventional method. There is no limit. It can be produced by a known method, for example, a hydrogenation method described in JP-A-2003-128593.

<First stage: acyl fluoride>
The carbonyl reaction of DHDCPD is carried out under pressure of carbon monoxide (hereinafter sometimes abbreviated as CO) in the presence of hydrogen fluoride (hereinafter abbreviated as HF), and the acyl fluoride represented by the formula (3) To obtain a carbonylation reaction solution containing the acyl fluoride. At this time, the CO may contain an inert gas such as nitrogen or methane. Although it does not specifically limit about CO partial pressure, Usually, it is about 0.5-5 MPa, and 1-3 MPa is more preferable. When the CO partial pressure is in the above range, the carbonylation reaction proceeds sufficiently, side reactions such as disproportionation and polymerization are suppressed, and a large equipment cost is not required.

<Second stage: ester compound>
HF may be separated from the carbonylation reaction solution containing the acyl fluoride represented by the formula (3) and then reacted with 1-naphthol. However, since HF acts as a catalyst in the esterification reaction, Without separation, it is reacted with 1-naphthol to synthesize an ester compound represented by formula (2) (hereinafter sometimes abbreviated as an ester form) to obtain a reaction solution containing the ester compound.

<Third stage: naphthol compound>
By raising the temperature of the reaction solution containing the ester compound, the Fries rearrangement of the ester compound proceeds, and a new naphthol compound represented by the formula (1) (hereinafter sometimes abbreviated as the Fries rearrangement) is generated. To do. Even in this rearrangement reaction, HF acts as a catalyst.

After separating HF from the carbonylation reaction solution obtained in the first stage, the ester reaction of the second stage acyl fluoride and 1-naphthol again in the presence of HF, the Fries rearrangement reaction of the ester compound in the third stage. It is also possible to produce a novel naphthol compound by proceeding with the above, but usually, the second stage esterification reaction with 1-naphthol without separating HF from the carbonyl reaction solution, and the third stage ester compound fleece rearrangement reaction Is continuously progressed to produce a novel naphthol compound.

  The reaction temperature of the second-stage carbonylation reaction is particularly important because it acts sensitively on the yield of the novel naphthol compound having a tricyclodecane skeleton represented by the formula (1) and the yield changes. As a result of investigation on the yield and the reaction temperature, it has been found that the condition of the reaction temperature of high yield is around 30 ° C. Therefore, in the present invention, the reaction temperature of the carbonylation reaction is 20 ° C. or more and less than 40 ° C., preferably 25-25 ° C. The reaction is carried out in the range of 35 ° C.

  In the first to third stages, HF acts as a catalyst. HF is preferably substantially anhydrous. The amount of HF used is such that the carbonyl reaction proceeds sufficiently and side reactions such as disproportionation and polymerization can be suppressed, and from the viewpoints of HF separation cost, volumetric efficiency of the reactor, etc., relative to 1 mol of raw material DHDCPD. In general, it is used in the range of about 4 to 12 times mol, preferably 6 to 10 times mol.

  There is no restriction | limiting in particular about the reaction form of a 1st-3rd step, Any may be semi-continuous type, a continuous type, etc.

In the second stage esterification reaction, the reaction temperature is preferably −40 to 20 ° C. from the standpoint of inhibiting the decomposition of the produced ester compound and suppressing the by-product of water by the dehydration reaction of the added alcohol. More preferably, it is -20-10 degreeC, More preferably, it is -10-10 degreeC. Depending on the reaction temperature, a third-stage fleece rearrangement, which will be described later, may proceed, but there is no particular problem.
The amount of 1-naphthol used is, as a guideline, preferably 0.1 to 3 times mol, more preferably 0.3 to 2 times mol, and still more preferably relative to DHDCPD used in the first stage. It is 0.3-0.8 times mole.

  The reaction temperature of the third stage Fries rearrangement reaction is preferably −10 to 40 ° C., more preferably −10 to 30 ° C., further preferably −10 to 25 ° C., and particularly preferably −10 to 10 ° C. It is preferably 20 ° C. and the reaction time is preferably maintained for 6 to 40 hours. However, the speed of the third stage fleece rearrangement reaction is faster as the temperature is higher, but since an equilibrium composition exists between the fleece rearrangement and the ester, the ratio of the fleece rearrangement is maintained at a temperature of 20 ° C. for 1 to 3 hours. , And then cooled to 0 ° C. and held for 8 to 10 hours to further increase the ratio of the fleece rearrangement, whereby a novel naphthol compound that is a fleece rearrangement can be obtained efficiently.

  In the reaction of the first to third stages of the present invention, a reaction solvent having the ability to dissolve the raw material DHDCPD and inert to DHDCPD and HF, for example, saturated aliphatic hydrocarbons such as hexane, heptane, decane, etc. May be used. In the case of using a solvent, the polymerization reaction is further suppressed and the yield is improved. When a large amount of solvent is used, the volumetric efficiency of the reaction apparatus is lowered, and at the same time, the energy intensity required for the solvent separation is deteriorated. When using a solvent in a 1st step, it is preferable that it is 0.5-1 times mass with respect to the sum total of DHDCPD and HF. In the second stage, when the solvent used in the first stage is used as it is, it is preferable to add 0.5 to 1.5 times the mass of 1-naphthol. In the third stage, if a solvent is used in the first and second stages, there is no need to add another solvent.

  After distilling off HF from the reaction solution containing the novel naphthol which is the fleece rearrangement obtained in the first to third stages, the total of the ester and fleece rearrangement is obtained by rectification separation according to a conventional method such as distillation. A fleece rearrangement (a novel naphthol compound) having a ratio of fleece rearrangement to 80 mol% or more can be obtained.

The tricyclodecane skeleton-containing naphthol represented by the formula (1) includes Endo and Exo isomers, and the present invention includes these isomers.

There is no particular limitation on the ratio of Endo isomer / Exo isomer of the tricyclodecane skeleton-containing naphthol represented by the formula (1). At the first stage carbonylation temperature of 30 ° C., the ratio of Endo isomer / Exo isomer is 0. 4 to 0.6.

Hereinafter, the method of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
<Gas chromatography analysis conditions>
For gas chromatography, GC-17A manufactured by Shimadzu Corporation and DBWAX (0.32 mmφ × 30 m × 0.25 μm) manufactured by J & W were used as the capillary column. The temperature was raised from 100 ° C. to 250 ° C. at 5 ° C./min.
^<1 H-NMR spectrum>
The measurement was performed with an AL-400 apparatus manufactured by JEOL Ltd. Tetramethylsilane was used as the internal standard substance.

<Preparation Example 1 of Hydride>
Using a Cu—Cr hydrogenation catalyst, 2000 g of DCPD (manufactured by Maruzen Petrochemical Co., Ltd., purity 99%) was reacted at a hydrogen pressure of 2 MPa and a reaction temperature of 90 ° C. for about 5 hours until no hydrogen absorption was observed. The Cu—Cr hydrogenation catalyst was removed by filtration and then purified by distillation to obtain 1850 g of hydride DHDCPD with a purity of 98.5%.

<Example 1>
First stage (acyl fluoride)
The experiment was conducted using a stainless steel autoclave having an internal volume of 500 ml, which was equipped with a Nack drive type stirrer, three inlet nozzles at the top and one extraction nozzle at the bottom, and the internal temperature could be suppressed by the jacket.
First, after replacing the inside of the autoclave with carbon monoxide, 189 g (9.4 mol) of hydrogen fluoride was introduced, the liquid temperature was set to 30 ° C., and the pressure was increased to 2 MPa with carbon monoxide.
While maintaining the reaction temperature at 30 ° C. and maintaining the reaction pressure at 2 MPa, 236 g of n-heptane solution in which 141.1 g (1.05 mol) of DHDCPD was dissolved was supplied from the top of the autoclave to carry out the carbonylation reaction. . After completion of the supply of DHDCPD, stirring was continued for about 10 minutes until no absorption of carbon monoxide was observed.
The production of acyl fluoride was confirmed by the production of the corresponding ethyl ester. Specifically, a part of the obtained reaction solution was sampled in cooled ethanol, water was added, and the oil phase and the aqueous phase were separated. After the oil phase was neutralized and washed with water, the resulting oil phase was analyzed by gas chromatography. The main product was found to be ethyl exo-tricyclo [5.2.1.0 ^2,6 ] decane-2-carboxylate and endo-tricyclo. It was [5.2.1.0 ^2,6 ] decane-2-carboxylic acid ethyl, and the ratio of Endo isomer / Exo isomer was 0.53.
Second stage (ester)
Subsequently, a stainless-steel autoclave having an internal volume of 1000 ml, equipped with a Nack drive type stirrer, three inlet nozzles at the top and one extraction nozzle at the bottom and capable of suppressing the internal temperature by the jacket, was charged with 83.4 g of 1-naphthol ( 0.58 mol) and 83.4 g of n-heptane were introduced, cooled to 0 ° C., and the reaction solution containing the acyl fluoride previously synthesized was added by pipe connection under stirring.
Formation of the ester was confirmed by gas chromatography. Specifically, a part of the obtained reaction solution was sampled in ice water to separate the oil phase and the aqueous phase. After the oil phase was neutralized and washed with water, the resulting oil phase was analyzed by gas chromatography. As a result, the total purity of the Fries rearranged product and the ester product was 75.1% (Fries rearranged product / ester product = 4.3 / 95). 7).
Moreover, the target component was isolated by rectification using a rectification column having 20 theoretical plates, and analyzed by GC-MS. As a result, the molecular weight 306 of the ester was shown. Moreover, the chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated chloroform solvent is 1.24 (m, 3H), 1.50 (m, 2H), 1.70 (m, 5H). 2.09 (m, 2H), 2.55 (m, 2H), 2.65 (m, 1H), 7.25 (d, 1H), 7.46 (t, 1H), 7.50 ( m, 2H), 7.71 (d, 1H), 7.86 (m, 1H), and 7.92 (m, 1H). From this result, the ester was identified as 1-naphthyl tricyclo [5.2.1.02,6] decane-2-carboxylate.
Third stage (Fleece rearrangement)
Subsequently, the temperature of the reaction solution was raised to 20 ° C., and this temperature was maintained for 2 hours to perform a Fries rearrangement reaction.
The formation of the Fries rearrangement was confirmed by gas chromatography. Specifically, a part of the obtained reaction solution was sampled in ice water, and after separating the oil phase and the aqueous phase, the oil phase was washed twice with 100 ml of 2% by weight aqueous sodium hydroxide solution and 2 times with 100 ml of distilled water. Washed twice and dehydrated with 10 g of anhydrous sodium sulfate. When the obtained oil phase was analyzed by gas chromatography, a reaction result having a total purity of 70.9% (Fries rearranged body / ester body = 72.2 / 27.8) of the Fries rearranged body and the ester body was obtained. .
Furthermore, the reaction liquid temperature was cooled to 0 ° C., and this temperature was maintained for 8 hours to proceed the Fries rearrangement reaction.
The reaction solution is extracted from the bottom of the autoclave into ice water, and the oil phase and the aqueous phase are separated. Then, the oil phase is washed twice with 100 ml of 2% by weight aqueous sodium hydroxide solution and twice with 100 ml of distilled water, and 10 g of anhydrous sodium sulfate And dehydrated. When the obtained oil phase was analyzed by gas chromatography, a reaction result having a total purity of 73.8% (Fries rearranged body / ester body = 81.3 / 18.7) of the Fries rearranged body and the ester body was obtained. .
Simple distillation When the obtained liquid was subjected to simple distillation, a main fraction portion having a total purity of 92.4% (Fries rearrangement / ester = 80.8 / 19.2) of the fries rearrangement and ester was 142. 1 g (yield 40.7%, based on DHDCPD) was obtained. There was no change in the ratio of the fries rearrangement / ester by simple distillation.
Further, the target component was isolated by rectification using a rectification column having 20 theoretical plates and analyzed by GC-MS. As a result, the molecular weight 306 of the fleece rearrangement of the target product was shown. The chemical shift values (δ ppm, TMS standard) of ¹ H-NMR in deuterated chloroform solvent are 0.91 (m, 1H), 1.21 (m, 4H), 1.30 (m, 1H), 1.49 (m, 1H), 1.66 (m, 1H), 1.78 (m, 2H), 2.06 (d, 2H), 2.45 (q, 1H), 2.85 (d , 1H), 2.99 (t, 1H), 7.23 (d, 1H), 7.51 (t, 1H), 7.61 (t, 1H), 7.74 (d, 1H), 7 .93 (d, 1H), 8.48 (d, 1H), 14.53 (s, 1H). From this result, the Fries rearrangement was identified as 2- (tricyclo [5.2.1.02,6] decane-2-carbonyl) -1-naphthol.

Claims (4)

Following formula (2)

Including the step of reacting the Fries rearrangement of the ester compound represented by the following formula (1):

The manufacturing method of the tricyclodecane frame | skeleton containing naphthol compound represented by these. A tricyclodecane skeleton-containing naphthol compound represented by the following formula (1).

In the presence of hydrogen fluoride, tricyclo [5.2.1.0 ^2,6 ] dec-3-ene and carbon monoxide are reacted at 20 to 40 ° C. to obtain the following formula (3):

And a step of esterifying the obtained acyl fluoride and 1-naphthol at 20 ° C. or lower.

The manufacturing method of the ester compound represented by these. A novel ester compound represented by the following formula (2).