JP2001139638A - Novel alcohol, (meth)acrylate thereof, resin thereof, and their production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin having a low moisture absorption and a good heat resistance, a (meth)acrylate used as a raw material monomer for the resin, a raw material alcohol for the (meth)acrylate, and efficient production methods for them. SOLUTION: 3-Hydroxymethyltetracyclo[4.4.0.12,5.17,10] dodecanes represented by formula I (wherein R1 is H or methuyl), (meth) acryloyloxymethyltetracyclo[4.4.0.12,5.17,10] dodecanes represented by formula II (wherein R1 and R2 are each H or methyl), and a resin prepared by (co) polymerizing a compound represented by formula II are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodecane such a manufacturing method thereof, and, 3-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^7,10 ] Derived from dodecane, it has excellent properties such as transparency, heat resistance, and low moisture absorption, and is expected to be used for optical applications such as optical fibers, optical discs, and plastic lenses, in particular. (Meth) acryloyloxymethyl Tetracyclo [4.4.0.1 ^2,5 .
[ ^1,7,10 ] dodecanes and a method for producing the same.

[0002]

2. Description of the Related Art Polymethyl methacrylate, which is a thermoreversible transparent resin, has advantages of excellent transparency, low refractive index, weather resistance and moldability. However, polymethyl methacrylate has high hygroscopicity and lacks heat resistance. Therefore, a resin that improves this point is strongly desired.

As a specific method for improving hygroscopicity, it has been proposed to homopolymerize or copolymerize a (meth) acrylic acid ester of a low hygroscopic alcohol. For example, a method of copolymerizing methyl methacrylate with cyclohexyl methacrylate, benzyl methacrylate and other higher alkyl methacrylates is disclosed in JP-A-58-5354, JP-A-58-11515, and JP-A-58-11515. No. 13652, JP-A-59-1
No. 22509 proposes this.

[0004]

However, although the copolymer obtained from such a monomer can realize low moisture absorption, its performance is not always sufficient, and the heat resistance may be reduced in some cases. There is also an example in which (meth) acrylic acid ester having a norbornane structure in the molecule is copolymerized to realize low moisture absorption without lowering heat resistance (Japanese Patent Publication No. 43-9069). Heat resistance higher than that of poly (methyl meth) acrylate has not yet been realized.

Accordingly, the present invention provides a resin having both low moisture absorption and heat resistance, a (meth) acrylic acid ester as a raw material monomer thereof, and a raw material alcohol for the (meth) acrylic acid ester, and their efficiency. It is intended to provide a simple manufacturing method.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a 3-hydroxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodecane,

[0007]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) (Meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane,

[0008]

Embedded image (In the formula, R ¹ and R ² each represent a hydrogen atom or a methyl group.) (Meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 . [ ^1,7,10 ] dodecane (co) polymerized resin.

Further, the present invention provides a 2-hydroxymethylbicyclo represented by the formula (4) obtained by aldehyde reduction of 2-formylbicyclo [2.2.1] -5-heptene represented by the formula (3). [2.2.1] A Diels-Alder reaction between -5-heptenes and cyclopentadiene is carried out to give 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . ^1-7,10 ] -8-dodecenes are obtained and further subjected to a hydrogenation reaction, wherein 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] a process for producing dodecanes, and

[0010]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

[0011]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

[0012]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

By the Diels-Alder reaction between the 2-formylbicyclo [2.2.1] -5-heptene represented by the formula (3) and cyclopentadiene, the 3-formyltetracyclo [represented by the formula (6) is obtained. 4.4.0.
^12.5 . 1 ^7,10 ] -8-dodecenes, which are further subjected to a hydrogenation reaction.
-Hydroxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] a process for producing dodecanes, and

[0014]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

[0015] shown as 3-hydroxymethyl-tetracyclo by the formula ^{(1) [4.4.0.1 2, 5} . [ ^7,10 ] dodecane is esterified, the above formula (2)
(Meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10]} is a manufacturing method of dodecane such.

The present invention further relates to (meth) acryloyloxymethyltetracyclo [4.
4.0.1 ^2,5 . [ ^1,7,10 ] dodecane (co) polymerized resin.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 3-hydroxymethyltetracyclo [4.4.0.1] represented by the above formula (1).
^2,5 . 1 ^7,10 ] dodecane (hereinafter, referred to as a compound of the formula (1)).

Examples of the method for producing the compound of the formula (1) include the following two methods.

In the first production method, 2-formylbicyclo [2.2.1] -5-heptene represented by the formula (3) (hereinafter, referred to as a compound of the formula (3)) is subjected to aldehyde reduction. Thus, 2-hydroxybicyclo [2.2.1] -5-heptene represented by the formula (4) (hereinafter, referred to as a compound of the formula (4)) is obtained, and is subjected to a Diels-Alder reaction with cyclopentadiene. The 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecenes (hereinafter referred to as compounds of formula (5))
And a subsequent hydrogenation reaction to obtain a compound of the formula (1) (hereinafter referred to as Production Method A). This manufacturing method is represented by the following chemical reaction formula.

[0020]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

In the production method A, in the first step, the compound of the formula (3) is reduced with an aldehyde to produce the compound of the formula (4). As a method for reducing only an aldehyde in the presence of an olefin, a method using a metal hydride or a metal hydride complex compound is usually employed.

Among the compounds represented by the formula (3), 2-formylbicyclo [2.2.1] -5-heptene is, for example, Diels-cyclopentadiene and acrolein.
Although it can be synthesized by an Alder reaction, a commercial product sold by Sigma-Aldrich Japan Co., Ltd. or Tokyo Chemical Industry Co., Ltd. may be used. 2-formyl-2-methylbicyclo [2.2.1] -5-heptene is obtained by the Diels-Alder reaction of cyclopentadiene and methacrolein described in Tetrahedron, 49, 4073-4084 (1993). Can be synthesized.

Examples of the metal hydride or metal hydride complex used to reduce the aldehyde in the presence of the olefin include borane dimethyl sulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, Potassium borohydride, zinc borohydride, lithium aluminum hydride, tri-hydride
lithium t-butoxyaluminum, sodium bis (methoxyethoxy) aluminum hydride, and the like,
Sodium borohydride is particularly preferred because of easy handling and mild reaction conditions.

When sodium borohydride is used, the amount of sodium borohydride used is determined by the amount of compound 1 of the formula (3).
The amount is preferably 0.5 to 1 mol per mol. The reaction temperature of reduction with sodium borohydride is preferably -20 to 60 ° C, and 0 to 40 in consideration of the reaction rate and suppression of side reactions.
More preferably, the reaction is carried out at a temperature of 0 ° C. The solvent for the reduction reaction is not particularly limited as long as it is an alcohol, ether, or halogenated hydrocarbon solvent, but an alcohol solvent is preferable. Specific examples of the alcohol-based solvent include methanol, ethanol, and 2-propanol. Among them, ethanol is particularly preferable because it suppresses the decomposability of sodium borohydride.

The compound of the formula (4) obtained by the reduction reaction can be used for the next reaction without purification, but may be purified by silica gel column chromatography or precision distillation.

In the second step, a Diels-Alder reaction between the compound of the formula (4) and cyclopentadiene is carried out to obtain a compound of the formula (5). This reaction is preferably performed under heating conditions in a closed system replaced with an inert gas. Examples of the inert gas used here include nitrogen, argon, and the like. The reaction temperature is preferably 140 ° C. or higher because the higher the reaction speed, the faster the reaction rate. The lower the reaction temperature, the lower the reverse reaction and the higher the yield. Since the boiling point of cyclopentadiene is 41.5 ° C. at normal pressure and the difference from the reaction temperature is large, the reaction system is preferably a closed system, and it is preferable to use an autoclave for the reaction device. If the preparation is small, it can be carried out by taking it in a glass tube, replacing with an inert gas, and sealing the tube. Note that dicyclopentadiene starts to decompose into cyclopentadiene at about 140 ° C. under normal pressure, and its decomposition point is 170 ° C. Therefore, by setting the reaction temperature to 170 to 200 ° C., the dicyclopentadiene is thermally decomposed to form cyclopentadiene. There is no need to provide a separate step of obtaining pentadiene, and there is an advantage that readily available dicyclopentadiene can be used as a raw material.

In the obtained reaction solution containing the compound of the formula (5), the compound of the formula (4) as a raw material remains unreacted, and tricyclopentadiene and tetracyclopentadiene as by-products are left unreacted. And the like. It is considered that the cyclopentadiene oligomer was formed by the continuous Diels-Alder reaction between cyclopentadienes. Therefore, equation (5)
The reaction is carried out in such a manner that the production of the compound of formula (4) is promoted as much as possible to reduce the residual amount of the compound of formula (4) as a raw material, and that the production of cyclopentadiene oligomer as a by-product is suppressed as much as possible. It is necessary to adjust the amount of cyclopentadiene or dicyclopentadiene charged to the compound (4). The amount of cyclopentadiene charged per mole of the compound of the formula (4) is preferably 0.5 or more because the amount of the compound of the formula (5) increases as the amount increases, and the amount of the cyclopentadiene oligomer decreases as the amount decreases. 1.0 mol or less is preferable. The same applies to the charged amount of dicyclopentadiene per 1 mol of the compound of the formula (4). The larger the amount, the larger the amount of the compound of the formula (5) formed. Is preferably 0.5 mol or less, since the amount of

Although the reaction solution of the second step can be used as it is in the subsequent reaction, it may be purified by silica gel column chromatography or precision distillation, if necessary. The compound of the formula (4) recovered during the purification can be reused in the Diels-Alder reaction for obtaining the compound of the formula (5).

By subjecting the thus obtained compound of the formula (5) to a hydrogenation reaction, the olefin can be reduced to obtain the compound of the formula (1).

Examples of the catalyst for catalytic hydrogenation when reducing olefins include palladium carbon, Raney nickel, platinum oxide, ruthenium carbon, rhodium carbon, rhodium alumina, copper chromite, nickel boride, iridium black,
Chlorotristriphenylphosphine rhodium and the like. The catalyst used here is easy to handle,
Palladium carbon is particularly preferred because it is easily available and inexpensive. The use amount of palladium carbon is preferably 5 to 10% by weight of the compound of the formula (5).

The reaction temperature of the hydrogenation reaction is preferably from 0 to 50 ° C., and the hydrogen pressure is preferably from 100 to 500 kPa. Examples of the solvent for the hydrogenation reaction include methanol, ethanol, ethyl acetate, acetic acid, diethyl ether, benzene, toluene, hexane, dioxane, dichloromethane, trichloromethane, carbon tetrachloride and the like. However, in consideration of the solubility of the raw materials, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane, trichloromethane and carbon tetrachloride are particularly preferable as the solvent.

In the second production method, the compound of formula (3) is subjected to a Diels-Alder reaction with cyclopentadiene to give 3-formyltetracyclo [4.4.0.1 ^2,5 represented by formula (6)]. . [ ^7,10 ] dodecenes (hereinafter, referred to as a compound of the formula (6)) and a hydrogenation reaction to obtain a compound of the formula (1) (hereinafter, referred to as a production method B). This manufacturing method is represented by the following chemical reaction formula.

[0033]

Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.)

In the production method B, a Diels-Alder reaction between the compound of the formula (3) and cyclopentadiene is carried out in the first step to produce a compound of the formula (6). This reaction is performed under a heated condition in a closed system replaced with an inert gas. Examples of the inert gas used here include nitrogen, argon, and the like. The reaction temperature is preferably from 140 to 200 ° C., and dicyclopentadiene can be used instead of cyclopentadiene.
200 ° C. is particularly preferred. Further, it is preferable to use an autoclave for the reaction apparatus.

In the thus obtained reaction solution containing the compound of the formula (6), the compound of the formula (3) as the raw material remains unreacted, and the cyclopentadiene oligomer as a by-product is left unreacted. Is included. For the same reason as in the case of the Diels-Alder reaction in the second step of production method A,
The charge amount of cyclopentadiene is preferably 0.5 to 1.0 mol, and the charge amount of dicyclopentadiene is preferably 0.25 to 0.5 mol per 1 mol of the compound of the formula (3). The obtained reaction solution can be used as it is in the subsequent reaction, but it may be purified by silica gel column chromatography or precision distillation, if necessary. The compound of the formula (3) recovered during the purification can be reused in the Diels-Alder reaction for obtaining the compound of the formula (6).

In the second step, the compound of the formula (6) thus obtained is subjected to a hydrogenation reaction, whereby the olefin and the aldehyde are simultaneously reduced to obtain the compound of the formula (1).

Examples of catalysts for the hydrogenation reaction in the simultaneous reduction of olefins and aldehydes include platinum oxide, palladium carbon, Raney nickel, ruthenium carbon, rhodium carbon, rhodium alumina, copper chromite, chlorotristriphenylphosphine rhodium and the like. No. Among them, platinum oxide, which has a high reducing power for both olefin and aldehyde functional groups and is easy to handle, is particularly preferable.

The reaction temperature of this hydrogenation reaction is 0 to 50 ° C.
Is preferable, and the hydrogen pressure is preferably 100 to 500 kPa. Examples of the solvent for the hydrogenation reaction include methanol, ethanol, ethyl acetate, acetic acid, trifluoroacetic acid and the like. However, acetic acid is particularly preferred in terms of reaction rate.

The present invention also relates to a compound represented by the above formula (2).
-(Meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane (hereinafter referred to as compound of formula (2)). The compound of the formula (2) is obtained by reacting the compound of the formula (1) with a (meth) acrylic acid halide, (meth) acrylic acid or (meth) acrylic ester to form an ester.

When esterifying with (meth) acrylic halide, a base is usually used. The base used here is not particularly limited as long as it neutralizes the generated acid, and examples thereof include triethylamine, pyridine, and sodium hydrogen carbonate. At this time, alcohol:
The molar ratio of (meth) acrylic acid halide: base was 1: 1.
2 to 2.0: preferably 1.3 to 2.4. -80 ° C because the higher the reaction temperature, the faster the reaction rate
The above is preferable, and particularly preferable is -20 ° C or higher. Also,
Since the side reaction decreases as the reaction temperature decreases,
The temperature is preferably 100 ° C. or lower, particularly preferably 60 ° C. or lower.

When esterifying with (meth) acrylic acid, an acid is usually used. As the acid used here,
For example, sulfuric acid, paratoluenesulfonic acid monohydrate, acidic ion exchange resin and the like can be mentioned. At this time, the molecular weight ratio of alcohol: (meth) acrylic acid: acid is preferably 1: 1.02 to 2.0: 0.001 to 0.20,
More preferably 1: 1.05 to 1.20: 0.01 to
0.05. The reaction is usually carried out using a decanter or the like while removing water, and hexane or toluene is used as an azeotropic solvent. The reaction temperature is usually from 0 to 170 ° C, but preferably from 40 to 150 ° C, more preferably from 60 to 130 ° C, in order to obtain a significant reaction rate. In order to prevent polymerization at high temperatures, it is preferable to use a polymerization inhibitor. As the polymerization inhibitor, for example,
Phenolic compounds such as hydroquinone and paramethoxyphenol, N, N ^* -diisopropylparaphenylenediamine, N, N ^* -di-2-naphthylparaphenylenediamine, N-phenyl-N ^* -(1,3-dimethylbutyl) Amine compounds such as paraphenylenediamine, 4
And N-oxyl compounds such as -hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl. During the reaction, air bubbling may be performed if necessary.

When transesterifying with (meth) acrylic acid ester, a catalyst for transesterification reaction is used. The catalyst used here may be a general transesterification catalyst, for example, a titanium-based catalyst such as tetrabutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, or a tin catalyst such as dibutyltin oxide or dioctyltin oxide. And the like. In the case of a titanium-based catalyst,
The molar ratio of alcohol: (meth) acrylate: catalyst is preferably from 1: 1.5 to 20.0: 0.0001 to 0.05, and especially from 1: 2.0 to 5.0: 0.0005 to
0.03 is preferred. In the case of a tin-based catalyst, the molar ratio of alcohol: (meth) acrylate: catalyst is 1:
1.5 to 20.0: preferably 0.0005 to 0.1,
In particular, 1: 2.0-5.0: 0.001-0.03 is preferable. The reaction temperature is usually −30 to 150 ° C., but preferably 60 to 150 ° C. to obtain a significant reaction rate excluding alcohol by-produced. In order to prevent polymerization at a high temperature, it is preferable to use a polymerization inhibitor and perform air bubbling.

The compound of the formula (2) thus obtained may be purified by silica gel column chromatography, distillation or the like, if necessary.

The compound of the formula (2) is polymerized by a conventional method (co) with a homopolymerizable or copolymerizable monomer to obtain a thermoreversible transparent resin having excellent transparency, low refractive index, weather resistance and moldability. can get.

[0045]

The present invention will be described below in detail with reference to Examples, but it should not be construed that the invention is limited thereto. The analysis in the examples was performed by gas chromatography (hereinafter referred to as GC).

The purity was calculated from the peak area of GC according to the following equation. Purity (%) = (A / B) × 100 where A represents the peak area of the target product, and B represents the sum of all peak areas.

The actual yield was calculated by the following equation. Actual yield (%) = (C / D) × 100 where C is the number of moles of the target product (calculated by multiplying the weight of the target product containing impurities by the purity and dividing by the molecular weight of the target product). ) And D represent the number of moles of the reference raw material.

Example 1 Sodium borohydride 1
8.9 g (0.5 mol) was dissolved in 400 ml of ethanol, and 2-formyl-2-methylbicyclo [2.2.
13] -5-heptene (136.2 g, 1.0 mol) was added little by little. After stirring for 6 hours, 200 ml of water was added, dilute hydrochloric acid was added dropwise until the reaction solution became neutral, ethanol was distilled off, and the mixture was extracted three times with 300 ml of ethyl acetate. The organic layers were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution, dried over magnesium sulfate, and then ethyl acetate was distilled off to give 2-hydroxymethyl-2-methylbicyclo [2.
2.1] -5-Heptene 126.1 g was obtained.

The purity of the obtained 2-hydroxymethyl-2-methylbicyclo [2.2.1] -5-heptene was 9
8.3%, actual yield 89.6% (2-formyl-2-
Methylbicyclo [2.2.1] -5-heptene).

Next, 2-hydroxymethyl-2-methyl
Bicyclo [2.2.1] -5-heptene 27.6 g
(0.2 mol) and 13.2 g of cyclopentadiene
(0.2mol) in a 200ml autoclave
The vessel was sealed and the inside was replaced with nitrogen. Up to 180 ° C in the system
Heat and stir at 150 rpm while maintaining this temperature
Was. At 180 ° C, the internal pressure should be 1,750 kPa
Adjusted. The reaction was stopped after 8 hours from the start of the heat retention,
3-hydroxymethyl-3-methyltetracyclo [4.
4.0.1.^2,5. 1^7,10] White anti-containing containing 8-dodecene
A solution was obtained. Vacuum the reaction solution at 120 ° C / 0.4 kPa
Unreacted 2-hydroxymethyl-2-methyl
Excluding rubicyclo [2.2.1] -5-heptene, distillation
The residue was purified by silica gel column chromatography.
The clopentadiene oligomer is separated and white crystalline 3
-Hydroxymethyl-3-methyltetracyclo [4.
4.0.1. ^2,5. 1^7,108.4 g of -8-dodecene
Was.

The obtained 3-hydroxymethyl-3-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] −8−
The purity of dodecene is 95.1%, the actual yield is 19.6%
(2-hydroxymethyl-2-methylbicyclo [2.
2.1] -5-heptene).

3-hydroxymethyl-3-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0]} -8-dodecene 33.9 g (0.166 mol) of carbon tetrachloride 250m
Then, 1.7 g (5% Pd) of palladium carbon was added, and the mixture was sealed in an autoclave having a volume of 500 ml and subjected to a catalytic hydrogenation reaction for 32 hours while stirring under an initial pressure of 300 kPa of hydrogen. The palladium carbon was removed by celite filtration, and the solvent was distilled off. The residue was purified by silica gel column chromatography, and white crystalline 3-hydroxymethyl-3-methyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodecane (hereinafter referred to as compound A) 3
4.9 g were obtained.

[0053] Purity 98.0% of the obtained compound A, real TokuOsamuritsu 100.0% (3-hydroxymethyl-3-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] -8
-Dodecene standard). The ¹ H-NMR spectrum, ¹³ C-NMR spectrum and MS spectrum of compound A thus obtained are shown in FIGS.

Example 2 Compound 34.9 g (0.1
66 mol), 70 ml of methyl methacrylate (66.1)
g, 0.66 mol), 0.35 g of titanium tetrabutoxide and 0.02 g of hydroquinone were placed in a 200 ml three-necked flask, placed in an oil bath, and stirred at 105 ° C. for 8 hours to carry out a transesterification reaction. After completion of the reaction, 3.5 g of Celite and 3.5 g of water were added, and
Stir for hours, filter and dry the filtrate over magnesium sulfate. After adding 0.02 g of paramethoxyphenol and distilling off the solvent and purifying by silica gel column chromatography, a transparent liquid of 3-methacryloyloxymethyl-3-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7
, 10} ] dodecane (hereinafter referred to as compound B) 43.2 g
I got

The purity of the obtained compound B was 98.7%, and the actual yield was 93.6% (based on compound A). ¹ H-NMR spectrum of compound B thus obtained,
^{The 13} C-NMR spectrum and MS spectrum are shown in FIGS.
6 is shown.

Example 3 3-Hydroxymethyl-3-
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0} ]-
In the step of obtaining 8-dodecene, 13.2 g (0.1 mol) of dicyclopentadiene instead of cyclopentadiene
The reaction and purification were carried out in the same manner as in Example 1 except for using 3-hydroxymethyl-3-white crystal.
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
6.5 g of 8-dodecene were obtained.

[0057] The resulting 3-hydroxy-3-methyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] −8−
The purity of dodecene is 93.2%, the actual yield is 14.8%
(2-hydroxymethyl-2-methylbicyclo [2.
2.1] -5-heptene).

Example 4 27.2 g of 2-formyl-2-methylbicyclo [2.2.1] -5-heptene (0.2 g)
2 mol) and 13.2 g of cyclopentadiene (0.
(2 mol) was placed in an autoclave having a volume of 200 ml, the vessel was sealed, and the inside was replaced with nitrogen. The system was heated to 180 ° C. and stirred at 150 rpm while maintaining this temperature. 1
At 80 ° C., the internal pressure was adjusted to 1,750 kPa. After a lapse of 8 hours from the start of the heat retention, the reaction was stopped, and 3-formyl-3-methyltetracyclo [4.4.0.
^12.5 . 1 ^{7,1 0]} -8 to obtain a white reaction solution containing dodecene. The reaction solution was distilled under reduced pressure at 110 ° C./0.4 kPa to obtain unreacted 2-formyl-2-methylbicyclo [2.
2.1] Excluding -5-heptene, the distillation residue was subjected to silica gel column chromatography to separate cyclopentadiene oligomer, and white crystalline 3-formyl-3- was obtained.
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
8.8 g of 8-dodecene were obtained.

The obtained 3-formyl-3-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^{7,1 0]} -8 purity 94.2 percent dodecene, real TokuOsamuritsu 20.5% (2-formyl-2-methylbicyclo [2.2.1] -5-heptene reference) there were. 3-formyl-3-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -8-dodecene 3
0.3 g (0.15 mol) was dissolved in 250 ml of acetic acid, and 1.0 g of platinum oxide and 1.0 ml of 37% hydrochloric acid were added.
The autoclave was sealed in a 500 ml autoclave, and subjected to a catalytic hydrogenation reaction for 24 hours with stirring under an initial pressure of 300 kPa of hydrogen. The platinum oxide was removed by celite filtration, and the solvent was distilled off. The residue was purified by silica gel column chromatography to give a white crystalline compound A (25.0 g).
I got

[0060] Purity 95.9% of the obtained compound A, real TokuOsamuritsu 77.4% (3-hydroxymethyl-3-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] -8-
Dodecene standard).

Example 5 20.6 g of compound A (0.1
0 mol), 36 ml of methyl acrylate (34.4 g,
0.40 mol), titanium tetrabutoxide 0.2
0 g and 0.01 g of hydroquinone were placed in a 100 ml three-necked flask, placed in an oil bath, and stirred at 85 ° C. for 8 hours to carry out a transesterification reaction. After completion of the reaction, 2.0 g of celite and 2.0 g of water were added, the mixture was stirred at 60 ° C. for 1 hour, filtered, and the filtrate was dried over magnesium sulfate. The solvent was distilled off by adding 0.01 g of paramethoxyphenol,
Purification by column chromatography gave a clear liquid, 3-acryloyloxymethyl-3-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane 25.
2 g were obtained.

The obtained 3-acryloyloxymethyl-
3-methyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -8-purity 98.4% dodecane, real TokuOsamuritsu 94.5% (3-hydroxymethyl-3-methyl-tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7, 10]} -8 it was dodecane reference).

[0063]

According to the present invention, a resin having both low moisture absorption and heat resistance, a (meth) acrylate ester as a raw material monomer thereof, and a raw material alcohol of the (meth) acrylate ester can be efficiently produced. We were able to.

[Brief description of the drawings]

FIG. 1 ¹ H-NMR of compound A obtained in Example 1
Spectrum.

FIG. 2 is a ¹³ C-NMR of compound A obtained in Example 1.
Spectrum.

FIG. 3 is an MS spectrum of the compound A obtained in Example 1.

FIG. 4 shows ¹ H-NMR of compound B obtained in Example 2.
Spectrum.

FIG. 5 is a ¹³ C-NMR of compound B obtained in Example 2.
Spectrum.

FIG. 6 is an MS spectrum of the compound B obtained in Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 45/69 C07C 45/69 47/445 47/445 67/40 67/40 69/54 69/54

Claims (6)

[Claims] 1. The method according to claim 1, wherein the 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodecanes. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) 2. A (meth) acryloyloxymethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodecanes. Embedded image (In the formula, R ¹ and R ² each represent a hydrogen atom or a methyl group.) 3. A 2-hydroxymethylbicyclo [2. 2] represented by the formula (4) obtained by aldehyde reduction of 2-formylbicyclo [2.2.1] -5-heptene represented by the formula (3). 2.1] -5-Heptenes and cyclopentadiene are subjected to a Diels-Alder reaction to give 3-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . ^3. The 3-hydroxymethyltetracyclo [4.4.] According to claim 1, wherein 1 ^7,10 ] -8-dodecenes are obtained and a hydrogenation reaction is further carried out.
0.1 ^2,5 . [ ^17,10 ] A method for producing dodecanes. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) (In the formula, R ¹ represents a hydrogen atom or a methyl group.) (In the formula, R ¹ represents a hydrogen atom or a methyl group.) 4. A 3-formyltetraformer represented by the formula (6) by a Diels-Alder reaction between a 2-formylbicyclo [2.2.1] -5-heptene represented by the formula (3) and cyclopentadiene. Cyclo [4.4.0.1
^2,5 . 1 ^7,10] -8-dodecene acids give, according to claim 1, further characterized in that the hydrogenation reaction of 3-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ]
A method for producing dodecanes. Embedded image (In the formula, R ¹ represents a hydrogen atom or a methyl group.) 5. The 3-hydroxymethyltetracyclo [4.4.0.1] represented by the formula (1) according to claim 1.
^2,5 . [ ^7,10 ] dodecane is esterified, (meth) represented by the formula (2) according to claim 2,
Acryloyloxymethyltetracyclo [4.4.0.
^12.5 . [ ^17,10 ] A method for producing dodecanes. 6. A (meth) acryloyloxymethyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] A resin obtained by (co) polymerizing dodecanes.