TW201945331A - Method for producing alicyclic alcohol and aldehyde - Google Patents

Abstract

The present invention provides: a method for producing 3-hydroxymethyltetracyclo[4. 4. 0. 12, 5. 17, 10]dodecane, which is characterized by subjecting tetracyclo[4. 4. 0. 12, 5. 17, 10]-3-dodecene to a hydroformylation reaction and subsequently to a hydrogenation reaction; and the like.

Description

Production method of alicyclic alcohol and aldehyde

The present invention relates to a polymer of a raw material used in the optical material, electrical, electronic materials such as 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane manufacturing method, etc. .

Polymers such as poly (meth) acrylates, epoxy resins, polycarbonates, polyesters, cycloolefin polymers, cycloolefin copolymers, and ethylene-based alicyclic hydrocarbon polymers have transparency, heat resistance, and low moisture absorption Excellent physical properties such as properties, used in optical materials such as lenses and films.
Are known for improving the heat resistance and low moisture absorption of the above polymer, the 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane as a raw material of the above polymer, in the previous 3-hydroxymethyl-tetracyclo ^[2,5 .1 ^7,10 4.4.0.1] dodecane of the manufacturing method, using Di ear Disabled - Alder reaction. For example, Patent Document 1 discloses a method of carrying out 2-hydroxymethylbicyclo [2.2.1] -5- obtained by hydrogenating a 2-methylfluorenylbicyclo [2.2.1] -5-heptene. heptene with cyclopentadiene of the ear disabilities Di - Alder reaction to give 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -8- dodecene, secondly, it was hydrogenated Reaction, or the Diels-Adel reaction of 2-methylfluorenylbicyclo [2.2.1] -5-heptene and cyclopentadiene to obtain 3-methylfluorenyltetracycline [4.4.0.1 ^2,5 . 1 ^7,10] -8-dodecene, secondly, so the hydrogenation reaction, thereby producing 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane.
Further, Patent Document 2 discloses a method for producing a 3-hydroxyl by performing a Diels-Adel reaction of dicyclopentadiene and allyl acetate, subjecting the obtained product to a hydrogenation reaction, and then performing a hydrolysis reaction. methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane.
However, the above patent document discloses 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane method of manufacturing the yields were insufficient. Further, the above patent document has no description about the specific 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of the stereoisomers.
On the other hand, Patent Document 3 discloses the following method: by making methoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene hydrosilyl acylation reaction Secondly Hydrogenation reaction to produce a bifunctional compound having a reduced alkyl skeleton.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-139638
[Patent Document 2] International Publication No. 2016/152310
[Patent Document 3] International Publication No. 2016/153018

[Problems to be solved by the invention]

The object of the present invention is to provide a 3-hydroxymethyltetracycline, which is a raw material for producing polymers used in optical materials, electrical and electronic materials, etc., in a form with high selectivity to specific stereoisomers. [4.4.0.1 ^2,5 .1 ^7,10] dodecane and the like.
[Technical means to solve the problem]

The present invention provides the following [1] to [5].
[1] A 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane production method of, wherein: making tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-Dodecene is subjected to a hydroformylation reaction, followed by a hydrogenation reaction.
[2] [1] according to the method of manufacturing, wherein the 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of formula (1)

The compounds represented, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene of the formula (2)

The indicated compound.
[3] A 3-acyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane production method of, wherein: making tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-Dodecene undergoes a hydroformylation reaction.
[4] [3] The production method according to which acyl 3-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of formula (3)

The compounds represented, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene of the formula (2)

The indicated compound.
[5] The production method according to any one of [1] to [4], wherein the hydroformylation reaction is a reaction performed in the presence of a rhodium-based catalyst or a cobalt-based catalyst.
[6]
A compound represented by the formula (1)

Indicated.
[Effect of the invention]

According to the present invention, it is possible to provide a 3-hydroxymethyltetracycline that can be used as a raw material for polymers used in optical materials, electrical and electronic materials, etc., in a form with high selectivity to specific stereoisomers. [4.4.0.1 ^2,5 .1 ^7,10] dodecane and the like.

Hereinafter, the compound represented by formula (1) is referred to as compound (1). The same applies to other compounds of the formula number.
Produced by the production method of the present invention the 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane (hereinafter referred to as hydroxymethyl body) may have any stereostructure or the Etc., but is preferably a compound (1) having a single stereo structure, or a compound (1) and a methylol body having a stereo structure other than the compound (1) (hereinafter, referred to as the compound (1) Isomers), more preferably compound (1).
Produced by the production method of the present invention the 3-acyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane (hereinafter referred to as acyl body A) may have any stereostructure or such Mixture, but is preferably a compound (3) having a single stereo structure, or a formamidine matrix containing the compound (3) and a stereo structure other than the compound (3) (hereinafter, referred to as the isomerization of the compound (3) Mixture), more preferably compound (3).

Hereinafter, the manufacturing method of this invention is demonstrated.
That the body may be by hydroxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter referred to as the starting olefin) acylation reaction with hydrogen methyl methyl hydrogen obtained by acylation reaction The product is then produced by subjecting the obtained hydroformylation reaction product to a hydrogenation reaction. Hydroformylation is carried out in the presence of a catalyst and a mixed gas of carbon monoxide and hydrogen.
The aforementioned hydroformylation reaction product can be obtained as a formamidine matrix or a mixture of a formamidine matrix and a methylol group.
The formazan substrate can be produced by subjecting a raw olefin to a hydroformylation reaction.
The raw material olefin in the present invention may be a commercially available one, or may be produced according to a known method. In the case of manufacturing by a known method, for example, the method described in SB Soloway, J. Am. Chem. Soc., 1952, 74 (4), pp 1027-1029 can be used, and Diene is produced by the Diels-Adel reaction.

In the hydroformylation reaction, conventional catalysts used for the hydroformylation reaction, such as cobalt-based catalysts, rhodium-based catalysts, and platinum-based catalysts, can be used. Among them, a cobalt-based catalyst or a rhodium-based catalyst is preferred in terms of reaction rate and yield. As the metal catalyst, a metal carbonyl complex, any compound capable of forming a metal carbonyl complex in the reaction system, and the like can be used, and a suitable carrier such as a metal supported on silicon rubber or activated carbon can also be used. catalyst. Specific examples of such metal catalysts include the oxides of the above metals, acetamidine pyruvate, various carboxylates, sodium salts, chlorides, carbonyl complexes, triphenylphosphine complexes, and the like. More specifically, Co ₂ (CO) ₈ , Co ₄ (CO) ₁₂ , Co ₆ (CO) ₁₆ , NaCo (CO) ₄ , CoH (CO) ₄ , [Co (CO) ₃ (C ₅ H ₅ )] ₂ (where C ₅ H ₅ represents cyclopentadienyl), cobalt oxide, cobalt acetate, cobalt 2-ethylhexanoate, Rh ₄ (CO) ₁₂ , Rh ₆ (CO) ₁₆ , acetic acid Rhodium, rhodium 2-ethylhexanoate, rhodium stearate, Rh (acac) ₃ (where acac represents acetamylacetone; the same applies below), Rh (acac) (CO) ₂ , Rh (acac) (cod ) (Wherein cod represents 1,4-cyclooctadienyl), RhCl ₃ , RhCl (PPh ₃ ) ₃ , (wherein, Ph represents phenyl; the same applies below), RhH (CO) (PPh ₃ ) ₃ Wait. These metal catalysts can be used alone or in combination of two or more.

Regarding the catalyst concentration in the case of using a rhodium-based catalyst, in terms of reaction speed, economy, etc., it is usually 0.1 to 1000 ppm, preferably 0.5 to 500 ppm, based on the weight concentration of the rhodium atom in the reaction mixture. And more preferably within a range of 1 to 100 ppm. The catalyst concentration in the case of using a cobalt-based catalyst is usually 10 to 5000 ppm, preferably 50 to 4000 ppm, based on the weight concentration of cobalt atoms in the reaction mixture, in terms of reaction speed and economy. And more preferably in the range of 100 to 3000 ppm.
Moreover, it is possible to coexist an organic phosphorus compound in excess with respect to these catalysts. The organic phosphorus compound is not particularly limited, and examples thereof include a phosphine represented by the general formula R ¹ ₃ P or a phosphite represented by the general formula (R ² O) ₃ P. The three R ¹ and three R ² may be the same or different, and are, for example, an aromatic hydrocarbon group, an aliphatic hydrocarbon group, and the like. Specific examples include: an alkyl group having 1 to 12 carbon atoms; a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a fluorenyl group; An alkyl group of 8 or an alkoxy-substituted alicyclic alkyl group having 1 to 8 carbon atoms is not particularly limited. Here, examples of the alicyclic alkyl group include cyclohexyl and the like. Moreover, you may use a bicyclic heterocyclic phosphine. More specifically, triphenylphosphine, tricresylphosphine, tris (2-methylphenyl) phosphine, sodium triphenylphosphine trisulfonate, tricyclohexylphosphine, tri-n-butylphosphine, 9 -Phosphabicyclo [3.3.1] nonane, 8,9-dimethyl-2-phosphobicyclo [3.3.1] nonane, 2-phosphobicyclo [3.3.1] nonane, triphenyl phosphite Ester, tris (nonylphenyl) phosphite, tris (2-third-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris ( 2-methylphenyl) ester, tris (3-methyl-6-tert-butylphenyl) phosphite, tris (3-methoxy-6-tert-butylphenyl) phosphite, etc. Among these, triphenylphosphine or triphenylphosphite is preferred. These organic phosphorus compounds may be used alone or in combination of two or more.
In terms of catalyst life, reaction selectivity, etc., the amount of these organic phosphorus compounds used is usually 1-2000 mol times, preferably 3-1000 mol times, more It is preferably in the range of 5 to 500 mol times.

In the present invention, the hydroformylation reaction can also be performed without using a solvent, but a solvent may also be used. The solvent is not particularly limited as long as the raw material olefin, the metal catalyst, and the organic phosphorus compound can be dissolved. Specific examples include alcohols such as ethanol, isopropanol, butanol, 2-ethylhexanol, and 2-octanol; butyl acetate, cyclohexyl acetate, dibutyl phthalate, and benzene Esters such as bis (2-ethylhexyl) dicarboxylate, diisononyl phthalate, diisodecyl phthalate, triisononyl trimellitate, pentane, hexane, heptane Saturated aliphatic hydrocarbons such as octane, isooctane, decane, dodecane, tetradecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, cyclododecane , Alicyclic hydrocarbons such as decahydronaphthalene, aromatic hydrocarbons such as benzene, toluene, xylene, alkylnaphthalene, ethers such as dibutyl ether, tetrahydrofuran, and nitriles such as acetonitrile and propionitrile. These solvents may be used alone or in combination of two or more.

In the present invention, the temperature of the hydroformylation reaction is usually within a range of 40 to 180 ° C, preferably 60 to 170 ° C, and more preferably 80 to 160 ° C. If the temperature is 40 ° C or higher, the reaction speed is increased, which is more preferable. In addition, it is more preferable to carry out at a temperature of 180 ° C or lower because the amount of by-products generated is reduced and the reaction yield is increased.
The hydroformylation reaction is preferably carried out under pressure from a mixed gas of carbon monoxide and hydrogen (hereinafter, referred to as a synthesis gas). At this time, carbon monoxide and hydrogen may be introduced into the reaction system independently, or a synthesis gas may be prepared in advance and introduced into the reaction system. The molar ratio (= CO / H ₂ ) of the synthesis gas introduced into the reaction system is usually in the range of 0.2 to 5.0, preferably 0.5 to 2.0, and more preferably 0.7 to 1.5. Furthermore, in the reaction system, a gas inert to the hydroformylation reaction can also coexist, such as methane, ethane, propane, nitrogen, helium, argon, carbon dioxide, and the like.

In the present invention, the hydroformylation reaction is usually preferably carried out under a pressure in the range of 0.2 to 40 MPaG. For example, when the catalyst precursor is used without using an organic phosphorus compound, the pressure is usually within a range of 10 to 30 MPaG, preferably 15 to 28 MPaG, and more preferably 18 to 26 MPaG. By setting the pressure to 10 MPaG or more, the catalyst is further stabilized and a sufficient reaction speed can be obtained. In addition, by setting the pressure to 30 MPaG or less, the cost of equipment with excellent pressure resistance can be further reduced, which is desirable.
On the other hand, when an organic phosphorus compound and a catalyst precursor are used in combination, the pressure is usually within a range of 0.3 to 30 MPaG, preferably 0.5 to 20 MPaG, and more preferably 0.7 to 10 MPaG. By setting the pressure to 0.3 MPaG or more, the catalyst is further stabilized and a sufficient reaction speed can be obtained. In addition, by setting the pressure to 20 MPaG or less, the cost of equipment with excellent pressure resistance performance is further reduced, which is desirable.

In the present invention, the reaction form of the hydroformylation reaction is not particularly limited, and it can be carried out in a batch manner using a well-known reaction device or in a continuous manner. Specifically, it can implement in any one of a stirred reaction tank, a tower-type reaction tank, or a tube-type reaction tank.
The hydroformylation reaction product obtained after the hydroformylation reaction can be directly used as a raw material for the hydrogenation reaction in the next step, or it can be purified by a known method to separate or remove the formamidine matrix and hydroxymethyl body. And a part or all of the catalyst is used as the raw material for the hydrogenation reaction in the next step. As a purification method in the case where purification is performed by a known method, for example, methods such as adsorption or extraction, neutralization with water washing, distillation, and crystallization may be used, and these methods may be appropriately combined and used.
In the case of using a cobalt-based catalyst, it is preferable to go through a neutralization and washing step. For example, an aqueous solution of an alkali metal compound or an alkaline earth metal compound can be added to the system after the hydrogen methylation reaction is completed to extract the cobalt-based catalyst. Remove it. Examples of the alkali metal compound or the alkaline earth metal compound include hydroxides, metal salts, and the like of lithium, sodium, potassium, magnesium, and calcium.

In the present invention, a methylol body can be produced by subjecting a hydroformylation reactant or the like obtained in the aforementioned hydroformylation reaction to a hydrogenation reaction. The hydrogenation reaction can be carried out by reacting a reducing agent that generates a hydride such as sodium borohydride with a hydroformylation reactant, but industrially, in the presence of a catalyst, it is advantageous to react hydrogen with a hydroformylation reactant.
The catalyst used when reacting hydrogen with a hydrogen methylation reaction product or the like is not particularly limited, and a known catalyst can be used. For example, it is preferable to contain one or more elements selected from Group 6 to Group 12 transition metals in the periodic table of the elements. Specifically, examples include Rayleigh metals such as Raleigh nickel, Raleigh cobalt, and Raleigh copper. , Reduced nickel supported catalyst, reduced cobalt supported catalyst, copper-chromium oxide based catalyst, copper-zinc oxide based catalyst, copper-iron oxide based catalyst, palladium black, platinum black, ruthenium black Palladium-supported silicon dioxide, palladium-supported alumina, palladium-supported activated carbon, platinum-supported silicon dioxide, platinum-supported alumina, platinum-supported activated carbon, ruthenium-supported silicon dioxide, and ruthenium-supported oxidation Precious metal supported catalysts such as aluminum, ruthenium supported activated carbon, rhodium supported activated carbon, iridium supported activated carbon, and osmium supported activated carbon. The amount of the catalyst used when reacting hydrogen with a hydrogen methylation reaction product is not particularly limited, and it can be appropriately selected depending on the type of the catalyst, the reaction form, and the like.

In the present invention, the hydrogen gas used when reacting hydrogen with a hydroformylation reactant or the like can be diluted by a gas inert to the reaction, such as nitrogen, helium, argon, and the like, and then supplied to the reaction system. The hydrogen pressure is not particularly limited, but is usually within a range of 0.1 to 20 MPaG, preferably 0.3 to 10 MPaG, and more preferably 0.5 to 7 MPaG.
In the present invention, the hydrogenation reaction can be performed without using a solvent, but a solvent may also be used. The solvent is not particularly limited as long as it dissolves a methylol group and a formamidine matrix. Specific examples include alcohols such as ethanol, isopropanol, butanol, 2-ethylhexanol, and 2-octanol; esters such as butyl acetate and cyclohexyl acetate; pentane, hexane, and heptanol. Saturated aliphatic hydrocarbons such as alkane, octane, isooctane, decane, dodecane, tetradecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclooctane, cyclododecane Alicyclic hydrocarbons such as alkane and decalin, aromatic hydrocarbons such as benzene, toluene, xylene, alkylnaphthalene, and ethers such as dibutyl ether and tetrahydrofuran. These solvents may be used alone or in combination of two or more.
The temperature of the hydrogenation reaction can be appropriately set according to the type or amount of the catalyst used, taking into consideration the reaction speed and yield, and is usually 30 to 250 ° C, preferably 50 to 200 ° C, and more preferably 70 to 170 ° C. Within range.
The reaction form of the hydrogenation reaction is not particularly limited, and it can be carried out in a batch manner using a known reaction device or in a continuous manner. Specifically, it can implement in any one of a stirred reaction tank, a tower-type reaction tank, or a tube-type reaction tank.
The methylol group-containing mixture obtained after the end of the hydrogenation reaction can be purified by a known method to isolate the methylol group. The purity of the isolated methylol body is preferably 80 area% to 100 area% based on the purity when analyzed by gas chromatography using a hydrogenated flame ionization detector. 90 area% to 100 area%, and more preferably 95 area% to 100 area%. As a purification method in the case where purification is performed by a known method, for example, methods such as adsorption or extraction, neutralization with water washing, distillation, and crystallization may be used, and these methods may be appropriately combined and used.

According to the production method of the present invention, not only can methylol and formamidine substrates be produced from raw material olefins in high yield, but also can be produced in a form having high selectivity to specific stereoisomers. It is more preferable to use a compound (2) as a raw material olefin from a viewpoint of availability.
The methylol body obtained by the production method of the present invention can be reacted with unsaturated fatty acids or their derivatives, glycidyl halides, vinyl ethers, vinyl esters, alkynes, and the like to make polymerizable monomers. The polymerizable monomers It can be used as a raw material for polymers such as poly (meth) acrylate, epoxy resin, and polyvinyl ether.
Specific examples of the unsaturated fatty acid or its derivative include acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, methyl acrylate, methyl methacrylate, and the like, as the glycidyl halide. Specific examples include epichlorohydrin, epibromohydrin, 2-chloromethyl-3-methylethylene oxide, 2-chloromethyl-2-methylethylene oxide, and the like, as the vinyl ether. Specific examples include butyl vinyl ether, halogenated alkyl vinyl ether, and the like. Specific examples of the vinyl ester include vinyl acetate and the like, and specific examples of the alkyne include acetylene and the like.

The (meth) acrylic acid ester can be produced according to, for example, a method described in Japanese Patent Laid-Open No. 2001-139638, but is not limited to these.
Similarly, the production of glycidyl ether can be performed according to, for example, a method described in Japanese Patent No. 5249549, but is not limited to these.
Similarly, the production of vinyl ether can be performed according to, for example, a method described in Japanese Patent Laid-Open No. 2005-23049, but is not limited to these.
Polymerization of a polymerizable monomer produced from a methylol body obtained by the production method of the present invention can be performed according to a known method. Examples of the known method include Japanese Patent Laid-Open No. 2005-255956 and Japanese Patent. The methods described in, for example, Japanese Patent No. 5951286, Japanese Patent Laid-Open No. 2009-79015, Japanese Patent No. 5249549, Japanese Patent No. 5009115, International Publication No. 2016/152310, and the like are not limited thereto. Wait.
In the polymer obtained from the above-mentioned polymerizable monomer, the composition range of the polymerizable monomer can be changed within an arbitrary range according to the performance required for its application.
The polymer obtained from the above polymerizable monomer has low yellowing resistance, heat resistance, low hygroscopicity, transparency, light resistance, high refraction, low birefringence, mechanical properties, electrical properties, chemical properties, and formability. It is excellent in workability, etc., and is therefore useful for optical materials, electrical, and electronic materials. Examples of applications using this polymer include the use of information transmission bodies such as plastic optical fibers, the use of information recording media such as optical discs, the use of optical components such as optical lenses and optical films, and light-emitting diodes (LEDs). ), Etc.), flat panel displays (organic EL (Electroluminescence) elements, etc.), resin applications such as electronic circuits, optical circuits (optical waveguides), resist materials such as solder resists for printed circuit boards, and color filters Light sheet, printing ink, sealant, coating, coating agent, adhesive, etc. for all electrical and electronic materials.
[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.
The purity and isomer ratio of the products were analyzed by gas chromatography with a hydrogen flame ionization detector. The stereo structure of the product was identified by NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance). The cobalt concentration was measured by a spectrophotometer.
[Gas chromatography with hydrogen flame ionization detector]
<Measurement conditions during purity analysis>
・ Apparatus: GC-14B gas chromatograph manufactured by SHIMADZU
・ Column: HP-5 manufactured by Agilent Technologies (column length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm)
・ Temperature rise: After being held at 60 ° C for 0.5 minutes, the temperature was raised to 320 ° C at a rate of 15 ° C per minute and then held for 17 minutes.
・ Temperature of sample injection part and detector: 320 ℃
＜ Measurement conditions for isomer ratio analysis ＞
・ Device: Gas Chromatograph GC-14A manufactured by SHIMADZU
・ Column: DB-WAX manufactured by Agilent Technologies (column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)
・ Temperature rising conditions: After holding at 60 ° C for 0.5 minutes, the temperature is increased to 230 ° C at a heating rate of 8 ° C per minute, and then held for 20 minutes.
・ Temperature of sample injection part and detector: 230 ° C
[NMR]
＜ Measurement conditions ＞
・ Equipment: JNM-ECA 500 made by Japan Electronics Co., Ltd.
・ Measurement solvent: Chloroform-d 99.8%, 0.05 Vol% tetramethylsilane ・ Resonant frequency: 500 MHz
[Spectrophotometer]
・ Installation: SPECTROPHOTOMETER UVmini 1240 manufactured by SHIMADZU

[Example 1]
[Manufacture of formazan substrate (hydroformylation reaction using rhodium catalyst)]
A compound (2) (manufactured by Tokyo Chemical Industry Co., Ltd.) 180 g (1.12 mol), diisononyl phthalate (manufactured by J-PLUS), 20 g, Triphenyl phosphate (manufactured by Kanto Chemical Co., Ltd.) 0.35 g (1.12 mmol) and Rh (acac) (CO) ₂ (manufactured by NE CHEMCAT) 0.0029 g (0.0112 mmol). Nitrogen was substituted in the reaction system. The temperature in the system was raised to 50 ° C, and while maintaining the temperature, stirring was performed for 10 minutes. Thereafter, the inside of the system was replaced with a synthesis gas (mole ratio of CO / H ₂ = 1) and the pressure was increased to 0.8 MPaG. Thereafter, the temperature of the system was increased to 90 ° C, and the temperature and pressure were maintained at 6 After an hour, the reaction was stopped to obtain 219.5 g of a crude product containing a formazan matrix. Low-boiling components were removed by distilling the crude product under reduced pressure at 110 ° C and 0.4 kPa. High-boiling components were removed by thin-film distillation of the obtained distillation residue at 95 ° C and 0.05 kPa to obtain 169.1 g of a formazan substrate.
As a result of analysis by gas chromatography, the purity of the formazan matrix obtained was 96.8 area%. Based on the compound (2), the yield was 79.1%.

[Example 2]
[Production of hydroxymethyl body (hydrogenation reaction)]
300 g (1.58 mol) of formazan substrate, 150 g of isopropyl alcohol, and 6 g of reduced nickel supported catalyst were placed in an autoclave with a volume of 1000 ml, and the system was replaced with hydrogen. After the pressure in the system was increased to 3.0 MPaG with hydrogen, the temperature in the system was adjusted to 150 ° C, and the internal pressure was adjusted to 5.0 MPaG. While maintaining the temperature and pressure, the reaction was stopped after 4 hours, and the reduced nickel-supported catalyst was removed by pressure filtration. The solvent was distilled off from the obtained reaction solution to obtain 240.0 g of a methylol compound.
As a result of analysis by gas chromatography, the purity of the obtained methylol group was 97.5 area%, and the yield was 79.2% based on the formamidine matrix.
The isomer ratio of the methylol group obtained by gas chromatography analysis revealed that the component corresponding to the retention time of the compound (1) of 25.5 minutes was 99.8 area%.

[Identification of the three-dimensional structure of 3-hydroxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane]
The three-dimensional structure of the hydroxymethyl body obtained in Example 2 was confirmed by identification using various NMR. From the results of the NMR analysis of FIGS. 1 and 2, it was confirmed that the hydroxymethyl body obtained in Example 2 was the compound (1).
¹ H-NMR (CDCl ₃ , δ ppm); 3.38 (1H), 3.29 (1H), 2.19 (2H), 2.09 (2H), 1.98 (1H), 1.74-1.62 (4H), 1.50 (1H), 1.45 (2H), 1.26 (1H), 1.13 (1H), 1.01-0.90 (3H), 0.84 (1H)
In NOESY (Nuclear Overhauser Effect Spectroscopy) -NMR, the methylene hydrogen (1.26 ppm) and hydroxyl group at the 11th position of the methylene cross-linking site on the alicyclic structure of the compound (1) were confirmed Methylene methylene hydrogen (3.38 ppm), and methylene hydrogen (1.26 ppm) in the 11th position and methine hydrogen (1.74-1.62 ppm) in the alicyclic structure .
From the above results, it was confirmed that the formazan substrate obtained in Example 1 was the compound (3).

[Example 3]
[Continuous production of methylol body (hydroformylation using rhodium catalyst)]
Put compound (2) (made by Tokyo Chemical Industry Co., Ltd.) 200 g (1.25 mol), isopropyl alcohol 100 g, and triphenyl phosphite (made by Kanto Chemical Co., Ltd.) 0.39 g at room temperature into an autoclave with a volume of 500 ml. (1.25 mmol) and Rh (acac) (CO) ₂ (manufactured by NE CHEMCAT) 0.0032 g (0.0125 mmol), and the system was purged with nitrogen. The temperature in the system was raised to 50 ° C, and while maintaining the temperature, stirring was performed for 10 minutes. Thereafter, the inside of the system was replaced with a synthesis gas (mol ratio of CO / H ₂ = 0.8) and the pressure was increased to 5.0 MPaG. Thereafter, the temperature of the system was raised to 100 ° C, and the temperature and pressure were maintained at 2 The reaction was stopped after hours. The reaction liquid was analyzed by gas chromatography. As a result, the purity of the formazan matrix obtained was 85.6 area%.
4 g of reduced nickel supported catalyst was added thereto, and the system was replaced with hydrogen. After the pressure in the system was increased to 3.0 MPaG with hydrogen, the temperature in the system was adjusted to 150 ° C and the internal pressure was adjusted to 5.0. MPaG. While maintaining the temperature and pressure, the reaction was stopped after 4 hours, and the reduced nickel-supported catalyst was removed by pressure filtration to obtain a crude product containing a methylol body. Low-boiling components were removed by vacuum distillation of the crude product at 150 ° C and 1.4 kPa. 151.0 g of methylol body was obtained by thin-film distillation of the obtained distillation residue at 95 ° C. and 0.02 kPa. As a result of analysis by gas chromatography, the purity of the obtained methylol group was 97.9 area%. Based on the compound (2), the yield was 61.5%.
The ratio of the isomers of the obtained methylol group was analyzed by gas chromatography. As a result, the component corresponding to the retention time of the compound (1) of 25.5 minutes was 99.8 area%.

[Example 4]
[Continuous production of methylol body (hydroformylation using cobalt catalyst)]
Into a 500 ml glass flask with a nitrogen substitution in the system, 76 g of an aqueous solution of NaCo (CO) _{4 with a} cobalt concentration of 0.7 wt%, 162.5 g of compound (2) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 87.5 g of nonane (manufactured by KH Neochem) was stirred at room temperature to obtain a solution separated into two layers of an aqueous solution (lower layer) and an isononane solution (upper layer) of the compound (2). Further, while stirring at room temperature, 4.0 g of a 30 wt% sulfuric acid aqueous solution was added dropwise to produce cobalt tetracarbonyl hydride in a glass flask, and the cobalt tetracarbonyl hydride was extracted into an isononane solution of compound (2). The cobalt concentration of the isononane solution of the compound (2) after the extraction was measured, and it was 0.2 wt%. Next, 200 g of the isononane solution of the extracted compound (2) (containing 0.68 mol of the compound (2)) was placed in an autoclave having a volume of 1000 ml, and nitrogen was substituted. After that, the inside of the system was replaced with a synthesis gas (mol ratio of CO / H ₂ = 0.8) and the pressure was increased to 16 MPaG. Thereafter, the temperature in the system was raised to 130 ° C, and the internal pressure was adjusted to 18 MPaG. After 2 hours, 80.0 g of a 1.1 wt% sodium hydroxide aqueous solution was added to the system and stirred for 20 minutes. After the reaction solution was cooled, the pressure was released, and the contents were taken out. Thereafter, 100 g of isononane was added to the content, and then the organic phase was washed with water to obtain 232.3 g of a crude product containing a formazan matrix. Next, the obtained crude product containing the formazan matrix was transferred to an autoclave with a volume of 500 ml, and 2.6 g of reduced nickel supported catalyst was added to replace the hydrogen in the system, and the pressure in the system was increased to 3.0 by hydrogen. After MPaG, the temperature in the system was adjusted to 150 ° C, and the internal pressure was adjusted to 5.0 MPaG. While maintaining the temperature and pressure, the reaction was stopped after 2 hours, and the reduced nickel-supported catalyst was removed by pressure filtration. 201.0 g of the obtained crude product containing the methylol group was analyzed by gas chromatography. As a result, the purity of the methylol group containing the solvent was 36.3 area%. The yield was based on the compound (2). It was 55.8%. The isomer ratio of the obtained methylol group was analyzed by gas chromatography. As a result, the component corresponding to the retention time of the compound (1) of 25.5 minutes was 99.0 area%.

[Comparative Example 1]
[Production of hydroxymethyl body (previous method)]
350 g (2.82 mol) of 5-norbornene-2-methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 187 g (1.41 mol) of dicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a 1000 ml autoclave. The system was hermetically sealed, and the system was purged with nitrogen. While stirring at 700 rpm, the inside of the system was heated to 180 ° C, and the temperature was maintained. The internal pressure was 1.3 MPaG at 180 ° C. Since After 7 hours After incubation, the reaction was stopped to obtain a reaction solution comprising 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -8- of dodecene. At 125 ℃ / 3.0 kPa was removed by distillation from the reaction mixture under reduced pressure the unreacted 5- drop-2-methanol with dicyclopentadiene to give 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ⁷ 201 g of crude product of ¹⁰ ] -8-dodecene.
And obtain the 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecene -8- crude product was dissolved in 201 g of 200 g of toluene, was added palladium on carbon (Tokyo Chemical Industry Co. (Manufactured) 17.9 g (5% Pd / 55% water-containing product), put in an autoclave with a volume of 1000 ml, sealed, and replaced the system with hydrogen. The system was heated to 100 ° C under a hydrogen pressure of an initial pressure of 2.0 MPaG. After 1.5 hours, palladium on carbon was removed by filtration to obtain 339 g of a reaction solution containing a methylol group. This was performed twice to obtain 711 g of a reaction solution containing a methylol body, and then the solvent was distilled off to obtain 333 g of a crude product of the methylol body. Thereafter, the crude product of the methylol body obtained was subjected to vacuum distillation at a pressure of 0.1 kPa in the range of an oil bath temperature of 135 to 190 ° C [filler Helipak-No. 2: equivalent to the number of theoretical plates 15 plates] to obtain 200 g of a distillate from which high-boiling components have been removed. Further, cyclopentadiene oligomer was separated from the distillate by silica gel column chromatography to obtain 155 g of methylol.
As a result of analysis by gas chromatography, the purity of the obtained methylol group was 99.3 area%, and based on 5-norene-2-methanol, the yield was 14.4%.
The isomer ratio of the obtained methylol group was analyzed by gas chromatography. As a result, the component (isomer of compound (1)) with a retention time of 25.2 minutes was 55.0 area%, and the retention time was The component (isomer of compound (1)) of 25.9 minutes was 43.0 area%.

[Reference Example 1]
[Bing Xixi yloxymethyl methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of Manufacturing]
50.1 g (260.7 mmol) of the methylol group obtained in Example 2, 33.7 g (391.9 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyclohexane (manufactured by FUJIFILM Wako Pure Chemical) were placed in a reactor. 152.5 g, p-toluenesulfonic acid monohydrate (manufactured by FUJIFILM Wako Pure Chemical) 1.2 g (6.5 mmol), 4-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.2 g (1.4 mmol), heated, Cyclohexane was discharged under reflux, and the reaction was carried out for 12 hours. Processed in the order of water washing, NaHCO ₃ aqueous solution washing, and water washing. After removing the acid catalyst and excess methacrylic acid, the organic layer was filtered through silica gel, and the solvent was distilled off under reduced pressure. Bing Xixi oxymethyl group tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane 62.8 g (241.3 mmol). As a result of analysis by gas chromatography, the purity was 96.6 area%. The evaluation results of the structure are shown below.
¹ H-NMR (CDCl ₃ , δ ppm): 6.09 (1H), 5.54 (1H), 3.89 (2H), 2.24 (1H), 2.19 (2H), 2.11 (2H), 1.94 (3H), 1.70 (4H ), 1.47 (2H), 1.33 (1H), 1.17 (1H), 0.96 (4H).

[Reference Example 2]
[Bing Xixi yloxymethyl methyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] manufacture and evaluation of a polymer of dodecyl]
Reference Example 1 using the obtained methyl Bing Xixi yloxymethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane, by following the polymerization, the molded molding acquisition was evaluated.
＜ Polymerization and molding method A ＞
The obtained tetracyclic Reference Example 1 methyl Bing Xixi yloxymethyl [4.4.0.1 ^2,5 .1 ^7,10] dodecane mixture over 3.6 g tert-butyl ester 2-ethylhexanoate peroxide (LUPEROX 26, manufactured by Arkema Yoshitomi) 0.018 g. After the monomer composition was obtained by stirring, the monomer composition was poured into an aluminum cup with an inner diameter of 2.8 cm, and heated in an oven at 100 ° C for 3 hours under a nitrogen atmosphere. Then, it was heated at 120 ° C. for 1 hour, and after polymerization and molding, it was cooled to room temperature, thereby obtaining a transparent molded article.
＜ Polymerization and molding method B ＞
The obtained tetracyclic Reference Example 1 methyl Bing Xixi yloxymethyl [4.4.0.1 ^2,5 .1 ^7,10] dodecane mixing 2.0 g of peroxide, 0.01 g tertiary butyl-2-ethylhexanoate Esters (LUPEROX 26, manufactured by Arkema Yoshitomi). After the monomer composition is obtained by stirring, the monomer composition is flowed into a shallow glass dish having an inner diameter of 5.0 cm, and in an air oven at 100 ° C. After heating for 3 hours, followed by heating at 160 ° C for 1 hour, after polymerization and molding, it was cooled to room temperature to obtain a transparent molded article.
(1) Yellowness (YI)
For a molded article having a thickness of about 5 mm obtained by the polymerization and molding method A, the yellowness (YI) was calculated according to the method described in JIS K-7373 using a "Spectrophotometer SE2000" manufactured by Nippon Denshoku Industries.
(2) The glass transition temperature is such that the molded article obtained by the polymerization and molding method B is pulverized into a granular or powdery form, and about 10 mg is taken as a test sample. For this test sample, a "differential scanning calorimeter DSC-220" manufactured by Hitachi High-Tech Science Co., Ltd. was used, and the temperature was raised to 160 ° C at a temperature increase rate of 10 ° C / min, and the mixture was held for 10 minutes to be melted, and then the temperature was increased to 10 ° C. After being rapidly cooled to 40 ° C / min, the temperature was lowered to -50 ° C, and then again raised to 250 ° C at a heating rate of 10 ° C / min, and the glass transition temperature was determined according to the method described in JIS K-7121.
(3) Water absorption: Approximately 1 g of a test piece was cut from a molded article having a thickness of about 1 mm obtained by polymerization and molding method B. This test piece was vacuum-dried at 60 ° C for 12 hours, and the dried test piece was weighed (the weight at this time was set to W0). Wet the dried test piece in a constant temperature and humidity tank at a temperature of 85 ° C and a relative humidity of 85% for 1 week. After humidification, wipe off the moisture attached to the surface and weigh it (set the weight at this time as W). Let (W-W0) / W0 be the water absorption.
(4) Refractive index and Abbe number Cut a test piece having a length of about 40 mm and a width of about 8 mm from a molded article having a thickness of about 1 mm obtained by polymerization and molding method B. About this test piece, the "Abbe refractometer DR-M2" manufactured by Atago Co., Ltd. was used to measure the refractive index n _{D at} 23 ° C and D rays (589 nm) in accordance with the method described in JIS K-7142. Similarly, the refractive indices n _F and n _{C at} F-rays (486 nm) and C-rays (656 nm) were obtained, and the Abbe number ν _{D was} calculated according to the following formula.
ν _D = (n _D -1) / (n _F －n _C )
The evaluation results of (1) to (4) are shown in Table 1.
[Table 1]
Ring obtained in Reference Example 2 of methyl Bing Xixi yloxymethyl [4.4.0.1 ^2,5 .1 ^7,10] dodecane of the polymer obtained is low yellowing, and a high glass transition temperature, water absorption Lower refractive index and Abbe number are also good.
[Industrial availability]

According to the present invention, it is possible to provide a 3-hydroxymethyltetracycline that can be used as a raw material for polymers used in optical materials, electrical and electronic materials, etc., in a form with high selectivity to specific stereoisomers. [4.4.0.1 ^2,5 .1 ^7,10] dodecane and the like.

FIG. 1 is a ¹ H-NMR chart of the compound obtained in Example 2. FIG.

2 is a NOESY-NMR chart of the compound obtained in Example 2. FIG.

Claims (6)

One 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane production method of, wherein: making tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 -After dodecene is subjected to a hydroformylation reaction, a hydrogenation reaction is performed. The manufacturing method of the requested item 1, wherein 3-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of formula (1) The compounds represented, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene of the formula (2) The indicated compound. One 3-methyl acyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane production method of, wherein: of tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 -Dodecene applies a hydroformylation reaction. The manufacturing method of the requested item 3, wherein the 3-acyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane of formula (3) The compounds represented, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene of the formula (2) The indicated compound. The manufacturing method according to any one of claims 1 to 4, wherein the hydroformylation reaction is a reaction performed in the presence of a rhodium-based catalyst or a cobalt-based catalyst. A compound represented by the formula (1) Indicated.